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1 Solidification Processing

Merton C. Flemings

Department of Materials Science and Engineering,


Massachusetts Institute of Technology, Cambridge, MA, U.S.A.

List of Symbols and Abbreviations 2


1.1 Solidification Mode 4
1.2 Plane Front Solidification and Crystal Growing 4
1.3 Heat Flow in Solidification of Castings and Ingots 8
1.4 Alloy Solidification - Traditional and Rapid Solidification Processes 12
1.5 Equiaxed Structures 16
1.6 Heat Flow and Mechanical Properties 20
1.7 Microsegregation in Novel Near-Rapid Solidification Processes 24
1.8 Alloy Solidification - Columnar Growth 26
1.9 Alloy Solidification - Heat Flow into the Bulk Liquid 29
1.10 Mixed Cases of Rapid Solidification 31
1.11 Macrosegregation 33
1.12 Deformation of Semi-Solid Dendritic Structures 38
1.13 Grain Refinement 42
1.14 Semi-Solid Slurries 44
1.15 Flow Characteristics of Semi-Solid Slurries 46
1.16 Semi-Solid Composite Slurries 50
1.17 Processing Non-Dendritic Semi-Solid Slurries 52
1.18 References 54

Materials Science and Technology


Copyright © WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
2 1 Solidification Processing

List of Symbols and Abbreviations

A surface area
a0 length scale related to interatomic spacing
C constant
C* composition of solid at the interface
CL, C o composition of a liquid, composition of the initial liquid
cm9 cs specific heat of the mold, specific heat of the solidified metal
d dendrite arm spacing
D, D s , DL solute diffusion coefficient, solute diffusion coefficient of a solid, solute dif-
fusion coefficient of a liquid
/ L , fs fraction liquid, fraction solid
gL volume fraction liquid
gr gravitational acceleration
Gs, GL temperature gradient in a solid, temperature gradient in a liquid
H heat of fusion
h casting surface heat transfer coefficient
K permeability
K consistency
k, k\ k0 partition ratio, effective partition ratio, equilibrium partition ratio
fc, /cs, kL thermal conductivity, thermal conductivity of a solid, thermal conductivity
of a liquid
Km9 Ks thermal conductivity of a mold, thermal conductivity of a solid
L length
l0 one-half of the dendrite arm spacing
mL slope of equilibrium liquidus line
n power law index
n rate of nucleus formation in growth direction
P pressure
R, RT growth rate, isotherm velocity
S thickness solidified
T temperature
t, tf time, total solidification time of casting
To mold temperature
TL, T{ equilibrium liquidus temperature, initial temperature
TM melting point of the metal being cast
V casting volume
v, vx velocity, velocity perpendicular to isotherms
z distance in growth direction

a, as thermal diffusivity, thermal diffusivity of solid metal


P solidification contraction
y constant
y shear rate
5 boundary thickness
List of Symbols and Abbreviations

S distance between nucleation events


g cooling rate
ji viscosity
£s> QL> Qm density of a solid, density of a liquid, density of a mold
T shear stress
KGT Kurz-Giovanola-Trivedi model
LKT Lipton-Kurz-Trivedi model
M.I.T Massachusetts Institute of Technology
SIMA strain-induced melt activation
U.T.S. ultimate tensile strength
1 Solidification Processing

1.1 Solidification Mode usual structure is columnar dendritic. For


steeper thermal gradient and slower growth
One way to categorize solidification rate, the structure may become cellular.
processes is by their "solidification mode." Lower thermal gradient, agitation, or grain
For the primary phase of usual, non- refinement alters the structure from colum-
faceting binary alloys which solidify over a nar dendritic to equiaxed dendritic. Vigor-
temperature range, there are six of these ous agitation or more effective grain refine-
(Fig. 1-1): columnar dendritic, cellular, equi- ment results in equiaxed non-dendritic
axed dendritic, equiaxed non-dendritic, sin- solidification. Sufficiently steep thermal gra-
gle-phase plane front, and two-phase plane dient at slow growth rate results in plane
front. front solidified alloys that are either single-
For alloys which freeze over a tempera- phase or two-phase, depending on the num-
ture range, and in which thermal gradient is ber of phases present at the equilibrium sol-
sufficiently steep and convection low, the idus of the alloy.
The three structures on the left of Fig. 1-1
Equiaxed Equiaxed are the most common in usual casting and
dendritic non-dendritic
crystal growing processes. The structures on
the right belong to processes of emerging or
potential commercial importance.

1.2 Plane Front Solidification


and Crystal Growing

Cellular Solidification with a plane front is ob-


tained in one of three ways: (1) with an
ideally pure metal, (2) with an alloy at suf-
ficiently high temperature gradient, G, and
low growth rate, R; or (3) at sufficiently
high R. The first way is of little interest
(except as a physical approximation for
treating heat flow in solidification or cast-
ing of ingots which solidify in a narrow
freezing range). (This topic is treated in
Plane Front Plane Front
(Single-Phase) (Two-Phase) Vol. 5, Chap. 10, Sees. 10.2.2 and 10.2.3.)
The third is of emerging interest in "rapid
solidification processing." The second is
the basic technology of crystal growing.
The basic heat flow objectives of all crys-
tal growing techniques are to (1) maintain
a positive thermal gradient across a liquid-
solid interface, and (2) independently con-
Figure 1-1. Types of solidification structure that can trol this gradient so that the liquid-solid
be obtained in directionally solidified binary alloys (of interface moves at a controlled rate. A heat
the non-faceting type). balance at a planar liquid-solid interface in
1.2 Plane Front Solidification and Crystal Growing

ooooooooo

Solid I Liquid To inert gas


source or vacuum
o o o o oQoooco o

Heating coils

Crystal

(a)

To inert gas
source or vacuum

Crystal withdrawal
and rotation
Crystal

To inert gas "Floating" liquid zone


source or vacuum
Heating coils

o Figure 1-2. Examples of


crystal-growing methods,
Heating coils
(a) Boat method; (b) crystal
pulling; (c) floating zone
(Flemings, 1974, courtesy
of McGraw-Hill Book
(b) (c) Company).

crystal growth from the melt is written The basic feature of all crystal growing
(Flemings, 1974) furnaces is, therefore, the ability to obtain
a controlled flux of heat across the liquid-
solid interface. Fig. 1-2 shows schemati-
where ks is thermal conductivity of the cally several types of furnaces to accom-
solid metal, kL is thermal conductivity of plish this (Flemings, 1974). Principles of
the liquid metal, Gs is temperature gradient crystal growing will be illustrated in the
in the solid at the liquid-solid interface, GL following sections with reference to the
is temperature gradient in the liquid at the type of furnace illustrated in Fig. 1-2 a, in
liquid-solid interface, QS is density of the which metal in a crucible of some length,
solid metal, and H is heat of fusion. L, is fully melted and then solidified by
Note from Eq. (1-1) that growth velocity "normal solidification" from one end to the
R is dependent, not on absolute thermal other.
gradient, but on the difference between In the limiting ideal case of "complete
ksGs and /cLGL. Hence, thermal gradients diffusion in the liquid" (or very vigorous
can be controlled independently of growth convection), no solid diffusion, and equilib-
velocity. This is an important attribute of rium interface kinetics, solute redistribu-
single-crystal-growing furnaces since grow- tion in crystal growth occurs as shown
ing good crystals of alloys requires that the schematically in Fig. 1-3. The liquid com-
temperature gradients be high and growth position during solidification is given by
rate be low. the well-known non-equilibrium lever rule
1 Solidification Processing

LIQUID

LIQUID

2
O
2
c0 Co
cs
kC 0
0 L
DISTANCE—*- DISTANCE •
(a) (b)

Figure 1-3. Solute redistri-


bution in solidification with
no solid diffusion and com-
plete diffusion in the liquid.
(a) At start of solidification;
(b) at temperature T*;
(c) after solidification; (d)
phase diagram (Flemings,
1974, courtesy of McGraw-
Hill Book Company).
kC(
DISTANCE - COMPOSITION •
(c) (d)

which, for constant partition ratio, fc, is In real crystal growing processes, diffu-
written sion in the liquid is not complete, and there
is some buildup of solute in a boundary
—c f^ (1-2)
layer in front of the liquid-solid interface.
where CL and fL are liquid composition When some convection is present, the
and fraction liquid, respectively, and C o is thickness of this boundary layer is taken to
initial liquid composition. This equation, be some value 8, usually small compared
also termed the Scheil equation, may be with the size of the liquid pool. Now, even
written in terms of the solid composition at though equilibrium is still maintained at
the interface, Cs*, and fraction solid, / s : the interface, the higher solute content in
the liquid at the interface leads to a higher
Cg* = fcC0(l-/,)<*"" (1-3)
solute content in the solid.
This equation also describes the final solid For convenience, we now define an "ef-
composition along the length of the crystal, fective partition ratio," k\ which is equal
since it is assumed that no diffusion occurs to the solid composition forming, Cs*, di-
in the solid during or after solidification. vided by the bulk liquid composition (the
1.2 Plane Front Solidification and Crystal Growing

liquid outside the boundary layer). The


relation between k! and k is (Burton et al.,
1953):
k
k (1 4 )

o
where DL is the solute diffusion coefficient
in the liquid. This expression is of consider- oC s M
able engineering usefulness because it re- o k'= 1.0
lates the composition of the solid forming c
o
in crystal growth to alloy composition and
growth conditions. It can be used to de-
scribe solute redistribution in crucibles of
finite extent, provided only that the thick-
ness 8 of the boundary layer is small com-
DISTANCE, x
pared with the length of the crucible. When
Figure 1-4. Final solute distributions for solidification
this is true, a dynamic equilibrium is at-
with limited liquid diffusion and different amounts of
tained between the bulk melt and growing convection (hence different "effective partition ratios,"
solid and equations identical to Eqs. (1-2) k!) (Flemings, 1974, courtesy of McGraw-Hill Book
and (1-3) are readily derived, except that Company).
the equilibrium partition ratio k is replaced
by the effective partition ratio k':
smooth interface which moves at constant
s* = fc'C0(l-/s)<*'-1) (1-5 a)
velocity. Because of the buildup of solute in
front of the crystal, the "melting point" (liq-
Here CL is the bulk liquid composition and uidus temperature of the alloy) increases
k' = C*/CL. Eqs. (1-5a) and (l-5b) consti- with distance from the interface as shown
tute a modified "normal segregation equa- schematically in Fig. 1-5. The actual tem-
tion." perature gradient must be maintained as
Fig. 1-4 shows some calculated distribu- steep or steeper than this to avoid super-
tions of solute for the alloy of the preceding cooling ("constitutional supercooling") in
examples, taking k! equal to fc, unity, and front of the interface. The basic condition
an arbitrary value between the minimum for this, the "constitutional supercooling
(k) and the maximum (unity). As seen from criterion," may be written (Tiller et al.,
Eq. (1-4), the minimum value occurs when 1953):
Rc5/DL<^1, that is, at slow growth rate, GL>_mLCs*(l-fc)
high liquid diffusivity, and maximum stir- (1-6)
ring, and so 5 is a minimum. At this limit, R kDL
solute distribution is described by the spe- where mL is the slope of the equilibrium
cial case given earlier where infinite diffu- liquidus line in the phase diagram.
sivity in the liquid was assumed. The max- As written, this equation is valid regard-
imum value of k! (equal to unity) is less of degree of stirring. For no stirring Cs*
obtained for RS/DL> 1. equals C o , and for very vigorous stirring it
The major single problem in crystal is the partition ratio times the bulk liquid
growing of alloys is maintaining a flat, composition. Eq. (1-6) illustrates directly
1 Solidification Processing

SOLUTE ENRICHED
LAYER IN FRONT OF
LIQUID-SOLID
INTERFACE
LIQUID CO

o
o

DISTANCE,
(a) (b)
Figure 1-5. Constitutional
supercooling in alloy solidi-
fication, (a) Phase diagram;
t
UJ
Ld
a: (b) solute-enriched layer in
or D front of liquid-solid inter-
ZD
\-
< or CONSTITUTIONALLY face; (c) stable interface;
u (d) unstable interface
QL c CL
SUPERCOOLED
REGION (Flemings, 1974, courtesy
TEM

of McGraw-Hill Book
Company).
DISTANCE, x1 DISTANCE, x ' -
(c) (d)

the reason for the requirement in crystal single crystals in that heat is rarely added
growing of controlling GL and R indepen- to the liquid during solidification, and so-
dently - it is the ratio of these two that lidification rates are usually much higher.
determines whether a plane front is main- Fig. 1-6 shows the general heat flow
tained. problem for solidification of a pure metal
The constitutional supercooling crite- in a mold, with temperature drops shown
rion, Eq. (1-6), remains today an engineer- across the various resistances to heat flow.
ing tool of great value, although we under- Fig. 1-7 is a similar plot, except for an alloy
stand that the conditions for breakdown of solidifying in columnar dendritic manner.
the plane front are more exactly specified (In this latter plot, mold-metal interface re-
by the stability analysis originally devel- sistance is assumed to be negligible, and
oped by Mullins and Sekerka, and that the mold is assumed to be very thick.) The
significant deviations may occur from this following description of casting processes
equation for faceting alloys or at very high is given for the case of a pure metal being
rates of solidification (Mullins and Sek- cast; differences for the treatment of alloys
erka, 1963; 1964; Sekerka, 1965). (See also are discussed later.
Vol. 15, Chap. 10, Sec. 10.2.4.) A number of important casting pro-
cesses employ mold materials that are rela-
1.3 Heat Flow in Solidification tively insulating compared with the metal
of Castings and Ingots being cast. In "sand casting" the mold is
made of sand, usually bonded with clay or
Solidification processing of castings and with a resin. The pattern to form the mold
ingots is basically different from that of cavity is usually reusable, made of wood,
1.3 Heat Flow in Solidification of Castings and Ingots

AIR SOLID LIQUID

SOLID LIQUID

X
*S L
^ _

LIQUIDUS
SOLIDUS

5
AT, iyAETAL-MOLD
INTERFACE
LJ

AT, MOLD-AIR To
INTERFACE
DISTANCE, x
DISTANCE

Figure 1-6. Temperature profile in solidification of a Figure 1-7. Unidirectional solidification of an alloy
pure metal (Flemings, 1974, courtesy of McGraw-Hill against a flat mold wall (Flemings, 1974, courtesy of
Book Company). McGraw-Hill Book Company).

COMPLETED
CASTING-
BROKEN OPEN
TO REVEAL
INTERIOR

Figure 1-8. Sketch of sand-


casting processes as used in
manufacture of a house-
hold radiator (Taylor et al.,
1959, courtesy of J. Wiley
and Sons, Inc.).
MOLD SECTION B

metal, or plastic (Fig. 1-8). In "investment thin mold is made by dipping the wax pat-
casting" the pattern is not reusable; it is tern alternatively into the ceramic slurry
made of wax or plastic. The pattern (or and then into a fluidized bed of dry ce-
group of patterns) is surrounded or "in- ramic. After the mold is made, it is fired to
vested" with a slurry of ceramic which is bond the ceramic and to melt and burn out
allowed to "set." In one method a relatively the pattern (Taylor et al., 1959).
10 1 Solidification Processing

The heat flow problem for casting in in- given mold surface area has a fixed ability
sulating molds is simplified by the fact that to absorb heat, it follows that in castings of
heat flow is usually limited primarily by the simple shape the volume of metal solidified
heat diffusion in the mold, as illustrated divided by the casting surface area may be
schematically in Fig. 1-9. When this is the substituted for S in Eq. (1-7). The result
case, and when mold and metal variables may be written as "Chvorinov's rule":
are constant, a simple expression relates
thickness solidified, S, to time t after cast- (1-8)
ing:
TM-T0 where V and A are casting volume and
S= t (1-7) surface area, respectively, C is a constant,
and t{ is total solidification time of the cast-
where TM is melting point of the metal be- ing.
ing cast, To is mold temperature, and Km, In a large number of casting processes,
gm, and cm are thermal conductivity, den- heat flow is controlled to a significant ex-
sity, and specific heat, respectively, of the tent by heat transfer resistance at the cast-
mold. This equation predicts a square-root ing surface. These processes include per-
relation of thickness solidified with time manent mold casting, die casting, liquid
that is proportional to certain metal vari- metal atomization, and thin strip casting.
ables and to the square root of the "heat The die casting process is illustrated in Fig.
diffusivity,"Km£mcm. 1-10, and several rapid solidification pro-
Heat flow into a concave mold surface is cesses in which heat flow is largely "/z-con-
divergent and therefore somewhat faster troiled" are illustrated in Fig. 1-11.
than into a plane surface, and heat flow When the surface heat transfer coeffi-
with a convex mold surface is slower. How- cient is overriding, the temperature distri-
ever, taking as a first approximation that a bution in the metal and mold is as in Fig.
1-12, and thickness solidified in a given
time t is:
TM-T0
S=h (1-9)
;| SAND $ SOLID LIQUID

where h is casting surface (usually metal-


mold) heat transfer coefficient. For castings
of simple shape, Eq. (1-9) can be general-
ized to yield the total solidification time, tf,
of the casting:
i
LU QsH
a. (1-10)
h(TM-T0) A
In the limiting case of ingot casting,
DISTANCE , x when sufficient solid metal has formed, the
mold-metal resistance to heat transfer be-
Figure 1-9. Approximate temperature profile in solid-
ification of a pure metal poured at its melting point comes negligible, and the temperature pro-
against a flat, smooth mold wall (Flemings, 1974, file becomes as in Fig. 1-13 a for a water-
courtesy of McGraw-Hill Book Company). cooled mold, and as in Fig. 1-13 b for
1.3 Heat Flow in Solidification of Castings and Ingots 11
Cover die Ejector die
Stationary platen \ Cores J Sliding platen
Ejector pins ye' -s~ + erf y =
\ 1 \ YA PC A/A I

Chamber

(TM-T0) (1-12)
HJK
___ Ejector Rack
and pinion
where ks, QS, and cs are thermal conductiv-
Sleeve Parting line Die Cavity Ejector block ity, density, and specific heat, respectively,
Gate of the solidified metal, and erf signifies the
(a) Metal ladled into chamber
error function.
Fig. 1-14 shows a plot of the solution to
Eqs. (1-11) and (1-12) for pure iron cast in
a cast iron mold. Also shown in this figure
are two other curves showing how solidifi-
cation is affected by varying degrees of
mold-metal interface resistance.
Analytic solutions such as those de-
(b) Metal forced into die cavity
scribed above are available for a limited
number of additional cases. Today, how-
ever, computer modeling is being used to
an increasing extent to analyze solidifica-
tion behavior of alloys, of complex shapes,
and of simple shapes with complex bound-
ary conditions (as continuous casting). The
basic equation used in most analyses is,
(c) Die opened, cores withdrawn
simply:
dT
= ocV2T (1-13)

where T is temperature and a is thermal


diffusivity. This equation is typically used
in the semi-solid region as well as in the
(d) Casting and excess metal ejected
fully solid region and in the mold material.
In the semi-solid region, the thermal diffu-
Figure 1-10. Die casting, cold chamber machine (Tay- sivity is adjusted to account for the heat of
lor et al., 1959, courtesy of J. Wiley and Sons, Inc.). fusion released at a given temperature, and
to refer to the thermal diffusivity of the
liquid-solid mixture (i.e., for alloy solidifi-
an uncooled thick mold. Thickness of cation as shown schematically in Fig. 1-1).
metal solidified is again proportional to In continuous casting, the equation is some-
the square root of time: times applied at steady state, in fixed coor-
dinates, for a casting withdrawal rate of R:
(1-n)
where as is the thermal diffusivity of the = 0 = aV2T-R-^ (1-14)
solid metal and 7 is a constant given by:
12 1 Solidification Processing

Metal Water

Non-rotating
tungsten electrode
Vacuum
Inert gas

- Collection port

(a) V- or cone-jet atomization (b) Rotating electrode process

Molten Liquid metal


Gas fired furnace
droplets Closed type
Nitrogen
atomizer
Gas T V - . . . \..l.-:r".[ / ^oo\ed Tractor Sray chamber
atomizer ^r' ' •"• •""vlV.V ' drum
Deposited strip
Flake d? cP
particles 0 **

\ \ \ \ \ \ \ \ \ \ \ \ \ s \ \ \
Exhaust system

(c) Production of splat particulate by (d) Multilayer spray deposition on to


impact of atomized droplets on a translating flat chill surface
a rotating cooled drum

Figure 1-11 a. Rapid Solidification - Spray Processes (Jones, 1982).

where z is distance in the growth direction. 10 4 Ks x for large ingots to nearly


Construction of a mathematical model 109 K s " 1 for surface treatments. Isotherm
for alloy solidification requires a detailed velocities range from as little as 10" 5 ms" l
model for solidification mode, and this is to more than 10ms" 1 . Table 1-1 lists ex-
discussed in subsequent sections. amples of the various solidification pro-
cesses and their respective regimes of cool-
ing rates. A region of growing industrial
1.4 Alloy Solidification - significance is that of "near-rapid" solidifi-
Traditional and Rapid cation, the range of about 1 to 103 K s " 1
Solidification Processes cooling rate, where dendrite arm spacings
in the range of 5 to 50 microns are ob-
Solidification processes involving den- tained. Here, casting structure is usually
dritic solidification are carried out com- fine-grained equiaxed, and segregate spac-
mercially over a range of cooling rates of ings are sufficiently fine that a high degree
more than 12 orders of magnitude - from of homogeneity can be obtained through
1.4 Alloy Solidification -Traditional and Rapid Solidification Processes 13

— Vacuum outlet Pressure

Melt RF coil

- Coolant

-Mold - Molten metal


cavity

Pistons Photocell Orifice Liquid stream

Heat removal

Injection tube
i Quenchant

Liquid-solid
interface

N
- Fibre (wire)
Aluminum foil

(a) Injection-chill mould (b) Two-piston method (c) Free-jet melt-spinning

Gas pressure

Ribbon
%— Heating source Heating
Winding
Melt

Tension -d

Rotating Ftokes
Fibre + sheath drum

(d) Taylor wire process (e) Chill-block melt-spinning (f) Twin-roll method

Melt stock

Product
Molten metal —
Fibre
Extraction disc

(g) Crucible melt-extraction (h) Pendant-drop melt-extraction (i) Melt-drag process

Figure 1-11 b. Rapid Solidification - Chill Processes (Jones, 1982).

subsequent thermal processing (or thermo- ing, spray casting, semi-solid forming, and
mechanical processing in the case of ingots metal matrix composite casting. At more
and continuous castings). Processes car- rapid rates, processes of fine powder atom-
ried out in this region of cooling rate in- ization, thin strip casting, laser surface
clude strip casting, die casting, coarse pow- melting, and others are becoming of in-
der atomization, "premium quality" cast- creasing importance. (Rapid solidification
14 1 Solidification Processing

TIME , MINUTES
16 36 100

SOLID LIQUID

TM
(a) NO INTERFACE RESISTANCE
(b)CARBON BLACK CHILL WASH
<
o:
LJ
Q.

DISTANCE, x
Figure 1-12. Temperature profile during solidification
against a large flat mold wall with mold-metal inter-
face resistance controlling (Flemings, 1974, courtesy
of McGraw-Hill Book Company).
2 4 6
SQUARE ROOT OF TIME, MINUTES172

Figure 1-14. Unidirectional solidification of pure iron


against a cast-iron chill, (a) No interface resistance;
(b) carbon-black chill wash [h assumed to be
0.04 cal cm' K *]; (c) thick insulating wash [h
(Flemings,
', MOLD / SOLID LIQUID 'MOLD ' SOLID LIQUID 1974, courtesy of McGraw-Hill Book Company).

''*-~VA

1 techniques are discussed in detail in


i Vol.15, Chaps. 2 and 3.)
1
TM _._ In considering alloy solidification of
LJ
~'~'A
/ 1 castings and ingots, we need first of all to
DC / i
Z> / 1
/ 1 distinguish between columnar and equi-
LJ
•L // 1i axed solidification, and secondly to distin-
/ 1
guish between cases in which heat flow
TEN

To
1
i direction during solidification is into the
DISTANCE DISTANCE bulk liquid, and those in which it is out-
wards through the growing semi-solid.
(a) (b)
Figs. 1-15 a and 1-15 b illustrate sche-
Figure 1-13. Temperature profiles for solidification matically the growth of equiaxed versus
against a flat mold wall when (a) resistance of solidify-
ing metal is controlling and when (b) combined resis-
columnar grains, with heat flow through
tance of metal and mold are controlling (Flemings, the growing dendrites. From the point of
1974, courtesy of McGraw-Hill Book Company). view of solute redistribution, the major dif-
1.4 Alloy Solidification -Traditional and Rapid Solidification Processes 15

Table 1-1. Range of cooling rates in solidification processes.

Range of cooling rate Production processes Dendrite arm dendrite


Designation (urn)

l ( T 4 t o 1(T2 Slow Large castings and ingots 5000 to 200


1(T2 to 1 Medium Small sand castings and ingots; 200 to 50
billet and bar continuous castings
1 to 103 Near-rapid Strip casting; die casting; coarse powder 50 to 5
atomization; "Premium Quality" casting;
spray casting; semi-solid forming;
metal matrix composite casting
103 to 109 Rapid Melt spinning; fine powder atomization; 5 to 0.05
thin strip casting; electron beam or laser
surface melting

Columnar Equiaxed
dendritic dendritic

Liquid Liquid

Figure 1-15. Solidification


of an alloy against a cold
chill wall, (a) Columnar so-
lidification; (b) equiaxed so-
(a) (b) lidification.

ference between these two cases is that, for The same is not true in columnar or cel-
the case of equiaxed grains, the velocity of lular growth. Here, isotherm velocity and
the isotherm where solidification begins, dendrite tip velocity must be very nearly
RT, can be much higher than the velocity of equal, and, at the more rapid rates of solid-
any given dendrite tip. It is: ification, we expect increasing deviation of
the dendrite tip temperature from the liq-
RT = Sn (1-15) uidus temperature.
Solidification of columnar or equiaxed
where 8 is linear distance in the growth structures when heat flow is into the bulk
direction between nucleation events, and n melt present a difficult set of problems for
is rate of nucleus formation in the growth the solidification scientist and engineer,
direction. Hence, even at high rates of and these are discussed in a later section.
movement of the solidification front, RT,
dendrite tip temperature can be quite close
to the liquidus temperature.
16 1 Solidification Processing

1.5 Equiaxed Structures of ripening or other remelting process on


growth. In differential form it is written
We first consider solidification where (Scheil, 1942):
heterogeneous nucleation is sufficient so
8CL
that undercooling before nucleation is low, - n (1-16)
and also that, regardless of the velocity of
solidification isotherms, dendrite tips grow The solution to this equation has been
at temperatures near the equilibrium liq- given earlier as Eq. (1-2). This result can be
uidus. Fig. 1-16 shows the model schemat- rewritten in terms of solid composition as
ically. Liquid composition at any tem- Eq. (1-3), which describes the microsegre-
perature within the liquid-solid zone, Fig. gation within fully solidified castings or in-
1-16 c, is given by the equilibrium liquidus gots. It is written for a binary alloy with
line, Fig. 1-16 b. Fraction liquid (or solid) constant partition ratio, k. Calculated re-
at any point within the liquid-solid zone, sults for a simple binary alloy are shown
Fig. l-16d, is calculated by the "Scheil schematically in Fig. 1-17.
equation" or one of its derivative analyses It has long been understood that diffu-
to be described below. In addition to the sion in the solid during dendritic solidifica-
assumptions of interfacial equilibrium and tion alters microsegregation in most real
negligible undercooling implicit in Fig. systems. This was first quantitatively ana-
1-16, the Scheil equation assumes no lyzed by Brody and Flemings (1966), who
macroscopic mass transport and no effect derived a simple approximate analytical

Equiaxed
dendritic Solid

Liquid

Solid
Distance

(a) (b)

Figure 1-16. Model of


equiaxed solidification (a)
dendrite structure; (b) tem-
perature profile; (c) compo-
sition at the liquid versus
distance; (d) fraction solid
Distance versus distance (Flemings,
1974, courtesy of McGraw-
(c) Hill Book Company).
1.5 Equiaxed Structures 17

kCQ

(b)

Figure 1-17. Formation of microsegregation. (a) Iso-


concentrates as seen in a cross-section of a primary
columnar dendrite arm after solidification, (b) Phase
diagram showing "solidification path." (c) Microseg-
kC regation, measured along a radial path from the cen-
ter of the dendrite.

expression (modified Scheil analysis) to ac- quite approximate, valid only for small val-
count for solid diffusion: ues of a. Calculated results from the same
k-1 work using a more exact numerical solu-
(1-17) tion are shown in Fig. 1-18 for Al-4.5%
Cu alloy.
and Since publication of the above work and
4Dstf its companion experimental study (Brody
a = • (1-18) and Flemings, 1966; Bower et al., 1966),
many refinements of the theory have been
where Ds is the diffusion coefficient of sol- developed. Ohnaka (1986) derived a simple
ute in the solid, tf is solidification time, and expression for an improved estimate of
d is dendrite arm spacing. This analysis is liquid composition during solidification.
18 1 Solidification Processing

and Poirier presented a computationally


Room temperature
efficient finite element method to calculate
Just below eutectic- the microsegregation (Yeum et al., 1989).
Just above eutectic-
Kirkwood (1984) and Ogilvy and Kirk-
1.38 wood (1987) first incorporated the phe-
7.1.3, nomenon of dendrite arm coarsening into
the microsegregation model, and Morten-
sen later derived an analytical expression
for this effect (Mortensen, 1989). Allen and
"0.61 Hunt (1976, 1979) first showed that den-
drite arms tend to "climb" up the tempera-
0.2 0M 0.6 0.8 1.0 ture gradient as a result of concentration-
Fractional distance along dendrite
driven solute diffusion. Others, most re-
Figure 1-18. Calculated composition across a den- cently Riedl and Fischmeister (1990), have
drite arm at different times during solidification,
showing effect of diffusion in the solid. Each curve
amply demonstrated the effect of dendrite
drawn extends from the center of the dendrite arm to arm climb and its influence on microsegre-
the position of the liquid-solid interface at the given gation. No attempt has yet been made,
time (Brody and Flemings, 1966). however, to incorporate this effect into the
more general microsegregation models de-
2.5
scribed above.
a = 0.2713
In equiaxed structures with heteroge-
/
k = 0.77 Eq.(1-23) ^ neous nucleation at low undercoolings, the
Scheil / main factor causing microsegregation to
/
deviate from that predicted by the Scheil
(3=2 equation appears to be diffusion in the
Ea( solid during solidification. Fig. 1-19 com-
* 2.0 pares calculated results on segregation of
c
o
Matsumiya- manganese in an Fe-1.52 wt.% Mn alloy,
rody
obtained using several of the different anal-
%&• ' yses referred to above. The analyses differ
Equilibrium
only in the analytic or computational
method used to account for solid diffusion
1.5
(including assumed dendrite geometry).
0.2 0M 0.6 0.8 1.0
Fraction solid
The extent of diffusion in the solid oc-
curring during solidification depends on
Figure 1-19. Comparison of calculated microseg-
regation for manganese in an Fe 1.52% Mn alloy solidification time and inversely on the
(Ohnaka, 1986). square of the diffusion distance (and hence,
interdendrite arm spacing). Since dendrite
arm spacing, as discussed below, depends
Clyne and Kurz (1981) presented an ana- on the cube root of solidification time, the
lytical expression that is also approximate result is a weak dependence of final micro-
but has the correct limit at high values of a. segregation on solidification time (i.e., for a
Kobayashi (1988) has recently developed given alloy or cooling rate). Fig. 1-20 is an
an improved analytic solution, although it example from work of Michael and Bever
is more difficult to use. Yeum, Laxmanan, (1954) in which severity of microsegrega-
1.5 Equiaxed Structures 19

tion is measured by amount of non-equi- sis of the solidification model discussed


librium eutectic in aluminum-copper al- above, considering the effect of solidifica-
loys. For the alloys studied, the amount of tion and coarsening (Brody and Flemings,
interdendritic eutectic increased by a fac- 1966; Bower et al., 1966; Basaran, 1981;
tor of two or more over the range of cool- Roosz et al., 1984; Sarreal and Abbaschian,
ing rates from 10" 2 K s " 1 to 102 Ks" 1 . At 1986; Haider et al., 1987; Jones, 1984).
the highest cooling rate employed, about While the degree of final segregation is
102 Ks" 1 , the amount of non-equilibrium not much influenced by cooling rate in
eutectic measured is about that predicted these equiaxed structures, even at the max-
by the Scheil equation. More recently, imum cooling rates studied, the segregate
these and similar experimental results have spacing (i.e., the dendrite arm spacing) is
been interpreted quantitatively on the ba- very much affected. Fig. 1-21 is a summary
of data from a wide range of investigations
4.79% for the binary alloy Al-4.5% Cu (Jones,
Cu
o 10 1984). The line through the points is:
o
3.97%
<D
Cu a — DK)8 U-iyj
D
<D 8
. -is— —
C c ^ ^
0) D 2.92%- where d is dendrite arm spacing (in mi-
dJ ,
Q. U
Cu crons) and s is cooling rate (Ks" 1 ). The
^
u> 2 2.05%.
factor determining dendrite arm spacing is
—-—-r- Cu now well understood to be ripening, which
n occurs during solidification (Mortensen,
0.01 0.05 0.1 0.5 1.0 5 10 50 100
Solidification index-degrees centigrade per second
1989; Kattamis et al., 1967). It is seen that
Figure 1-20. Weight percent eutectic vs. "solidifica- this relation, and hence the importance of
tion index" (cooling rate) for aluminum-copper alloys ripening, extends to well above the range of
(Michael and Bever, 1954). cooling rates of near-rapid solidification.

Figure 1-21. Dendrite arm


spacing versus cooling rate
for alloys of approximately
Al-4.5 wt.% Cu. Experi-
mental data are from a
number of different investi-
gations (Jones, 1984).
10 10b 1011
z K/s
20 1 Solidification Processing

Dendrite arm spacing is of engineering is left in sand castings after usual solution
importance primarily because it deter- treatments. On the other hand, modern
mines the distance over which solute ele- "Premium-Quality" aluminum foundries
ments must diffuse to obtain fully homoge- apply substantial chilling to their castings
neous material. For dendrite arm spacings to ensure that dendrite arm spacing stays
above those obtained in near-rapid solidi- below about 50 jim. Furthermore, they em-
fication (above about 50 jum), times re- ploy high-purity materials and carefully
quired for full homogenization in most controlled equipment so that they can so-
commercial alloys become prohibitively lutionize within 10 to 20 °C of the melting
long. Moreover, experience indicates that point (eutectic temperature) of the alloy
even extensive hot working of coarse den- being solution treated. A 2.5-h solution
dritic structures does not fully eliminate treatment at these temperatures is now
the compositional heterogeneities. more than ample to dissolve all the second
For example, Fig. 1-22 shows solution phase.
treatment calculations for Al-4.5% Cu al- It should be added that, in the solidifica-
loy (Flemings, 1974). Solution tempera- tion processes that occur at rates up to
ture, time, and segregate spacing (dendrite those of near-rapid rate, solidification be-
arm spacing) are the important variables havior (including microsegregation and
determining the effectiveness of a solution secondary dendrite arm spacing) is not in-
treatment. A moderate size sand casting, fluenced by grain size or by whether the
with dendrite arm spacing of 200 jim and grain structure is equiaxed or columnar.
given a standard commercial solution treat-
ment (10 h at 515 °C), will not have the
volume fraction of eutectic present reduced 1.6 Heat Flow and Mechanical
very much by the heat treatment. Accord- Properties
ing to Fig. 1-22, approximately 40 h would
be required to eliminate the second phase. Modern mathematical models of heat
This agrees with observations in practice flow in solidification of alloys are generally
which show that considerable second phase based on physical models similar to that of

1.0

0.8
Figure 1-22. Calculated rate
of solution of Al-4.5% Cu
0.6
alloy. The symbols g and
^-SOLVUS (515°C) g0 are final and initial vol-
0.4 ~\ \ v ume fractions of the second

A\
phase, respectively, /0 is
one-half of the dendrite
arm spacing, and t is time
0.2
(Flemings, 1974, courtesy
of McGraw-Hill Book
n \EUTECTIC\ Company).
\(548°C) 0.5 1.0 1.5 2.0
t/,2 x 10~9 sec/cm2
1.6 Heat Flow and Mechanical Properties 21

/TimT Al-4.5% Cu alloy

8 x 10" - 8x10 5
LU

\ & = 0.6
O
k O
- \

o
x Cooling rate
<u - a
L.
3 5
2x10' - - 2x10

0.2 0.A 0.6 0.8 1.0

- 2.0x10"'

a. 1.5x10"* Figure 1-23. Solidification


E
o of Al-4.5% Cu alloy
o against a water-cooled
o 1.0x10"' chill. Biot Number is 0.6.
Dimensionless distance is
measured from surface rela-
"5 0.5 xUT 4 0.5 o
tive to half-thickness of
metal (Flemings and Shio-
hara, 1985).
0.2 0.4 0.6 0.8 1.0
Dimensionless distance, X/L

Fig. 1-16 (Clyne, 1984; Rappaz, 1989). Fig. conductivity of the metal). Movement of
1-23 shows some calculated results from the dendrite tips and the liquidus isotherm
work of Campagna (Campagna, 1970; versus the square root of time are shown at
Flemings and Shiohara, 1985) in which his the upper left. Average cooling rate during
physical model was exactly that described solidification is shown in the center plot,
by Fig. 1-16 and for which the model alloy and dendrite tip velocity at the bottom. We
chosen was Al-4.5% Cu. The results plot- may use this and Fig. 1-21 (or Eq. (1-19)) to
ted are for solidification against a water- illustrate some engineering aspects of sev-
cooled chill, with a Biot number of 0.6 eral important commercial processes.
(where the Biot Number is defined as h L/k9 Consider first a 100 mm thick plate of
where h is the heat transfer coefficient at Al-4.5% Cu alloy, chilled on both sides.
the mold-metal interface, L is the half- Mold-metal interface resistance is typical
thickness of the metal, and k is the thermal of that encountered in casting processes
22 1 Solidification Processing

(about 0.04 cal cm " 2 s " x K x) so that the


Biot Number is about 0.6. From Fig. 1-23,
cooling rate varies from about 3.0 K s " 1 at
the surface to l.OKs" 1 at the centerline.
Corresponding dendrite arm spacings vary
from about 35 jim at the surface to 50 }im
at the center - a suitable range for good
mechanical properties, as seen by the ex-
perimental data in Fig. 1-24 for the alloy
after solution treatment, quench, and aging • - unchilled plates
treatment. Fig. 1-25 plots this expected o - chilled plates

variation in dendrite arm spacing and me- 30

chanical properties across the plate thick-


25
ness.
A casting of the same thickness cast in a
sand mold would solidify, of course, at a
much slower rate. An aluminum alloy cast- ELONGATION
510
ing this size would solidify throughout
at a cooling rate of about 0.02 Ks" 1 , or
50 times more slowly than the center of the o 30 40 50 60 70
DENDRITE ARM SPACING (urn)
above chilled plate. The dendrite arm spac-
Figure 1-24. Mechanical properties of Al-4.5% Cu
ing throughout this sand casting would be
alloy versus dendrite arm spacing. Alloy was solution
about 200 jim. Full homogenization would treated, quenched, and aged (Flemings and Shiohara,
be impossible (Flemings, 1974), and, as can 1985).
be inferred from Fig. 1-24, very poor prop-
erties would result.
The foregoing relationships are used heat transfer coefficients than do chilled
by foundrymen in producing "Premium sand castings, and we estimate that a die
Quality" castings (Flemings, 1974), in casting of about 3 mm thickness would so-
which high mechanical properties such as lidify with a Biot Number of about 0.6, so
those of Fig. 1-24 are reliably produced that we may use Fig. 1-23 to estimate its
throughout castings. In sand castings, this cooling rate during solidification. Cooling
is done by placing "metal chills" in the rate at the surface would be over 3 x
mold in appropriate locations and at ap- 10 3 Ks~ 1 and cooling rate at the center
propriately spaced intervals so that the about a third of that. Dendrite arm spacing
sand casting solidifies at rates comparable would be about a tenth of that of the chilled
to those of the chilled casting described sand casting described above, about 3 |im
above - and final dendrite arm spacings at the surface and 5 jim at the center.
are under about 50 |im. Dendrite arm Such high cooling rates would normally
spacing measurements from actual cast- be expected to result in excellent proper-
ings are sometimes requested by customers ties, but, for a number of reasons, high
as a measure of process control. mechanical properties are not obtained in
We may also consider solidification be- most of today's die castings. Reasons for
havior of a die casting. Die castings typi- this include entrapment of air and other
cally solidify with much higher mold-metal gases during mold filling, and difficulties in
1.6 Heat Flow and Mechanical Properties 23

50
fully feeding shrinkage. In addition, alloys

T
used for most die castings are not ame-
45 nable to development of high properties.
The alloys used are chosen for low cost and
40 • ease of casting.
It is clear, however, that the very high
35 Al-4.5% Cu alloy \ - cooling rates obtainable in die casting
10 cm thick plate \ could result in castings of high mechanical
Biot Number = 0.6 •
properties and reliability. Perhaps new pro-
30
^ - 3 - 2 - 1 0 1 2 3 4 cesses such as semi-solid forming ("Rheo-
Position Relative to Centerline (cm) casting") will permit die casting to reach its
potential for high-performance products.
As an example of solidification at the
very high rates characteristic of rapid rate
bU •
processes, we may consider the example of
a "splat cooled" 100 jim thick sample of
50" Ssv \U.T.S.
Al-4.5% Cu solidifying from both sides.
The high heat transfer coefficient here will
40"
again result in a Biot Number of 0.6, so
we can again use Fig. 1-23 to calculate
Yield cooling rate. Now cooling rate is about 3 x
30"
106 Ks"* at the surface and a third of that
at the center. Dendrite arm spacing, from
20-
Fig. 1-21, varies from 0.35 ^im at the sur-
I 10"
""^^^ Elongation
\ ^ _
face to 0.5 jim at the center.
It should be added that, in solidification
processes above that of the "near rapid"
- 5 - 4 - 3 - 2 - 1 0 1 2 3 4 5 range, it becomes increasingly unlikely that
Position Relative to Centerline (cm) nucleation frequency will be sufficiently
Figure 1-25. Calculated dendrite arm spacings and high so that dendrite tip growth rate can
mechanical properties across the thickness of a remain a low value. In such cases, the
100 mm chilled plate, Al-4.5% Cu alloy. Scheil equation becomes invalid and we

Table 1-2. Cooling rates and dendrite arm spacings for some practical examples. Al-4.5% Cu Alloy. Equiaxed
solidification.

Example Surface Center

Cooling rate DAS Cooling rate DAS


(Ks- 1 ) (urn) (Ks- 1 ) (um)

100 mm thick sand casting 0.02 184 0.02 184


100 mm thick chilled casting 3.2 35 1.2 47
3 mm thick die casting 3.6 xlO 3 3.3 1.3 xlO 3 5
100 urn thick splat-cooled droplet 3.2 x 106 0.35 1.2 xlO 6 0.5
24 1 Solidification Processing

must turn to the analysis of a later section would be expected from a direct linear cor-
of this paper to describe the dendrite relation of dendrite arm spacing with the
growth process. logarithm of solidification time (Mathur
Table 1-2 summarizes the cooling rate etal., 1989).
and dendrite arm spacing calculations out- In semi-solid forming (Rheocasting)
lined in the previous paragraphs. (Flemings, 1974; Flemings and Young,
1978), Fig. 1-27, solid particles initially
present in the metal may be relatively large
1.7 Microsegregation in Novel (50 jim or more), but solidification in the
Near-Rapid Solidification Processes last stages (i.e., in a metal mold), may
be very rapid. Microsegregation, and ho-
It is of interest to consider several pro- mogenization of that microsegregation, are
cesses which are often practiced in the only now being studied in these alloys
near-rapid range of cooling rates but in (Molenar and Kool, 1989).
which cooling behavior is greatly different A third process in this category is casting
from that in the more conventional pro- of metal matrix composites. In one type of
cessing described above. One of these is such casting, metal is infiltrated into a ce-
"spray casting," shown schematically in ramic preform. If the preform is cooler
Fig. 1-26, in which metal is spray atomized, than the liquidus temperature of the alloy,
partially solidified in flight, and then de- initial solidification of the advancing front
posited in plate form or other shape. The is very rapid; subsequent solidification is
first part of this solidification may involve then determined by heat extraction to the
some undercooling, and certainly involves mold (Mortensen et al., 1989; Masur et al.,
rapid rate; the last part of solidification is 1989). The amount of dendrite coarsening
slower, depending on heat extraction to the that can occur in these composites is, how-
substrate or surroundings. Final segregate ever, limited, since (at least in the alloys
spacing is found to be somewhat less than studied to date) coarsening ceases when

MOLTEN METAL TUNDISH / CRUCIBLE

Figure 1-26. Schematic of


the Osprey™ process (Ma-
SPRAY CHAMBER thur et al., 1989).
1.7 Microsegregation in Novel Near-Rapid Solidification Processes 25

CONTINUOUS
ALLOY FEED

INGOT SECTIONED ^ - MOLD


INTO "CHARGES"
[7771^—^ WJ
RHEOCAST p
, INGOT ^

SLURRY IN
SHOT CHAMBER SLURRY INJECTED
INTO DIE

Figure 1-27. Rheocast Process (Flemings and Young, 1978).

dendrite size becomes about that of the


interstices of the preform. Final microseg-
regation in these cases can therefore be
much less than in conventional solidifica-
tion (Mortensen et al., 1988). Fig. 1-28
shows the coarsening process in a fibrous
composite schematically. Fig. 1-29 illus-
trates that, for local solidification times
above a critical value (which depends on
size of the interstices in the composite) dur-
ing directional solidification, the dendritic
structure has disappeared as a result of
solid state diffusion into arms which are
limited in their ability to coarsen by the
ceramic fibers. Note that the time for dis-
appearance of the second phase in this case
can be very short compared with the time
required to eliminate it by conventional
solution treatment. For example, the time
A V \ I
w
8! p Figure 1-28. Schematic rendition of coarsening in (a)
a usual casting or ingot; (b) the interstices between
7 fibers in a metal matrix composite (Mortensen et al.,
(b) 1988).
26 1 Solidification Processing

3
E 10 -, LIQUIDUS ISOTHERM
Average for the

iDUS ISO!"HI
CT

unreinforced alloy \U\ 1
c
o
o
Q.
1

• m
mmm
tc
1
~^
o
tf
[
B
V)
Q. SOLID
E 102- _ •
1
0) 3
o
<D

H


• - A
i
L
i
~
n>
J

(a) CHILL CAST (b) LASER MELTING-, WELDING

TJ i o
c •
0)
Q
] i
1 |
1
10° 1o 10 2 10
Local solidification time Ms
Figure 1-29. Dendrite arm spacing versus solidifica- SPINNING WHEEL
tion time in a directionally solidified, aligned fiber
( c ) MELT SPINNING
metal matrix composite. Dendrite structure (and mi-
crosegregation) are eliminated when dendrite arms Figure 1-30. Examples of rapid solidification pro-
coarsen to the maximum size permitted by the inter- cessing with columnar dendritic growth; heat flow
stices between fibers (Mortensen et al., 1988). through the growing solid.

in Fig. 1 -29 required to eliminate the inter- Equilibrium Liquidus = 918 K


920
dendritic eutectic is less than 100 s whereas
910
many hours of conventional solution treat-
900
ment would be required for material with a Al-4.5% Cu
comparable dendrite arm spacing. G=o

1.8 Alloy Solidification - Equilibrium Solidus = 844 K


Columnar Growth 840
10 "4 io "^ io"^ io -1 io° io x Mr
R(m/s)
In "constrained" columnar growth Figure 1-31. Dendrite tip temperature versus tip ve-
(growth with heat flow through the semi- locity. Columnar growth of Al-4.5% Cu calculated
solid region), dendrite tip temperature can using the KGT model (Kurz et al., 1986) with k = k0.
fall significantly below the liquidus iso-
therm, as illustrated in the practical exam-
ples of Fig. 1-30. Calculation of the extent the Ivantsov solution for the diffusion field,
of tip undercooling has occupied the atten- the shortest marginally unstable wave-
tion of solidification scientists for a num- length for determining the tip radius, and a
ber of years. growth rate dependent partition ratio, k
It has long been understood that den- (Kurzetal, 1986).
drite tip undercooling can arise from three Fig. 1-31 shows results of calculations
sources: the effect of interface curvature on of dendrite tip temperature versus growth
equilibrium melting point; diffusion of heat velocity for Al-4.5% Cu alloy using the
and/or solute from the growing tip; and KGT model with k = k0. The calculations
interface kinetics. A recent model, that of assume growth into an isothermal melt
Kurz, Giovanola, and Trivedi (the "KGT at the tip temperature, so are drawn for
model") incorporates all three effects using (G/R) = 0.
1.8 Alloy Solidification - Columnar Growth 27

However, the curve is essentially un- solute trapping can be important. For
changed even if G is much increased. For Al-4.5% Cu alloy, it is possible, as indi-
example, solidification of Al-4.5% Cu cated above, that some significant trapping
with a Biot Number of 0.6 (the example can occur at velocities as low as about
of Fig. 1-23) occurs, regardless of solid- lms"1.
ification rate, with a value of (G/R) = 1.5 x Fig. 1-32 a shows the variation produced
10 6 Ksm~ 2 . Fig. 1-31 is not visibly in tip composition for the cases outlined
changed by using this value of G/R. above, for equilibrium k. Tip composition
The curve of Fig. 1-31 assumes equilib- varies from k0 C o at the lowest velocities to
rium interface kinetics. Note that signifi- C o when absolute stability is reached. Fig.
cant tip undercooling is present at tip ve- l-32b shows the calculated final microseg-
locities as low as 10~ 3 ms~ 1 . The under- regation, using the recent empirical formu-
cooling increases with increasing tip ve- lation of Giovanola and Kurz (1990) to
locity, reaching a maximum at about "patch" the KGT solution at the tip to the
6.3 ms" 1 , the "limit of absolute stability" Schell relation behind the tip. Table 1-3
first described by Mullins and Sekerka summarizes some calculations of tip un-
(Mullins and Sekerka, 1964). At this veloc- dercooling for several examples of this type
ity, solidification is with a plane front of of solidification for Al-4.5% Cu. It should
uniform solid composition C o . be understood, however, that these cal-
From a simple kinetic argument we ex- culations are probably valid only up to a
pect that, at sufficiently high growth veloc- velocity of a few tenths of a meter per sec-
ities, the partition ratio will differ signifi- ond. At higher velocities, we expect k no
cantly from the equilibrium ratio as a longer to equal k0 due to "solute trapping."
result of "solute trapping." A functional re- The predicted deviation of k from k0 at
lationship initially proposed by Aziz (Aziz, the dendrite tip is apparently substantiated
1982) and incorporated in the KGT model by experimental work on rapidly solidified
for dendritic growth is: Ag-15wt.% Cu alloy (Boettinger et al,

k = (1-20) Table 1-3. Calculated tip undercoolings for some


1+ practical examples. Columnar growth of Al-4.5% Cu
D alloy.
where k and k0 are the kinetic and the Example* Tip Tip under-
Cooling
equilibrium partition ratios, respectively, velocity rate cooling
D is the solute diffusion coefficient at the (ms' 1 ) (K)
interface, and a0 is a length scale related to
100 mm thick 2.5x10" 1.5 7
the interatomic spacing. Eq. (1-20) predicts
chilled casting
a rising k from k0 to unity over a range of 3 mm thick 0.09 2xlO 3 25
velocities. For the Al-4.5% Cu alloy used die casting
as example here, it is over the range of 100 jam thick 2.5 1.5 xlO 6 67
about 1 to 100 ms" 1 , assuming ao = 0.5 nm. splat-cooled
For a sufficiently dilute alloy, we expect droplet
the limit of absolute stability to be at a * Calculation in each case is for a location halfway
lower velocity than that where solute trap- between the surface and center of the casting; colum-
ping occurs, but for higher solute contents nar growth assumed with Biot Number equal to 0.6.
28 1 Solidification Processing

5 i i i i i i

C
0
4
J

ity Limit
Al-4.5% Cu /
3 G=o /
/
2
1
J3

10 "6 10' 5 10 "4 10 "3 10 "2 10 * 10° 10x


R(m/s)

Figure 1-32. Microsegregation in Al-4.5% Cu, calcu-


lated using the KGT model (Kurz et al., 1986) with
k = k0. (a) Dendrite tip composition as a function of
tip velocity, (b) Solute redistribution as measured out- 0.0 0.2 0.4 0.6 0.8 1.0
ward from the center of a dendrite arm, calculated
using the empirical patching relation of Giovanola
and Kurz (1990).

25 'I
/
/
Ag-15wt% Cu /
/
20 -" V = 12cm/s / /
/ /

- 15
1
% -•••,'•••;.
GK^ _
/
O y y
10 -- Range of
V.QC measured
values

0
0.01 1 10 100 0.2 0.4 0.6 0.8 1.0
V[cm/s]

(b)
(a)

Figure 1-33. Microsegregation in rapidly solidified similar model with k = k0. (b) Solute redistribution.
Ag-15 wt.% Cu. (a) Dendrite tip composition. Data Solid curve calculated from KGT model using ex-
from Boettinger et al. (1987). Solid curve, KGT model perimental patching (Giovanola and Kurz, 1990).
(Kurz et al., 1986). Dashed curve, calculation using a Dashed curve, Brody and Flemings (1966).
1.9 Alloy Solidification - Heat Flow into the Bulk Liquid 29

1987). The KGT analysis with k = k0 pre-


dicted a tip composition substantially less
than that observed (Fig. 1-33 a), while as-
suming a velocity-dependent k resulted in
close agreement of the KGT theory with
experiment (Kurz and Giovanola, 1988).
DISTANCE —*>
The resulting solute distribution across the
(a) SOLIDIFYING DROPLET (b) TEMPERATURE ACROSS
dendrite arm is shown in Fig. 1-33 b. DROPLET DIAMETER

1.9 Alloy Solidification -


Heat Flow into the Bulk Liquid
When heat flows from the bulk liquid
directly to the surroundings before or dur- TIME —+-
ing solidification, conditions prevail that (c) AVERAGE DROPLET
after solidification behavior in an impor- TEMPERATURE
VERSUS TIME
tant way. Heat then flows from the grow-
Figure 1-34. Solidification of an undercooled alloy
ing dendrite tips into the liquid, and reca- droplet. 7j is initial temperature.
lescence occurs (at least locally). We some-
times see a small amount of this recales-
cence at the beginning of solidification in numerical results of dendrite tip velocity
conventional castings and ingots. We can versus undercooling are very close to those
obtain much larger undercoolings in small calculated earlier, as shown in Fig. 1-35 for
droplet or bulk specimens, or in continu- Al-4.5% Cu alloy using the LKT model
ous processes, by employing clean molten (Lipton et al., 1987). Superimposed on the
metal and solidifying it without contact model is the curve of Fig. 1-31 (KGT
with materials which catalyze crystalliza- model) which is for growth into a non-un-
tion. dercooled melt (constrained growth).
In Fig. 1-34, for example, a liquid drop- Many workers are now studying den-
let is originally undercooled to a tempera- drite growth in undercooled alloys, and
ture T{ below the equilibrium liquidus, TL. comparing experimental results with these
Nucleation occurs at the left of the droplet and other analyses. Results of one such
and dendrites grow from left to right. Tem- study by Wu et al. (1987) are summarized
perature across the droplet at this time is as in Fig. 1-36.
shown in Fig. l-34b with heat flowing pre- Solidification of this "unconstrained"
dominantly into the liquid. Movement of type is obtained in continuous processes
the dendrite front across the specimen is when heat flow from the liquid is rapid and
quite rapid at high undercoolings, and so nucleation is hindered. Fig. 1-37, for exam-
the rate of local recalescence can be very ple, shows equipment for direct casting of
rapid indeed. steel wire developed at Michelin several
The growth velocity of dendrites into an decades ago (Massoubre and Pflieger,
undercooled melt is treated in a manner 1978). The molten steel is ejected from a
similar to the constrained growth dis- small orifice at speeds up to about 15ms" 1
cussed in the previous section. Moreover, and solidifies before Rayleigh breakup oc-
30 1 Solidification Processing

I i lilMj

I Ni-25% Sn
: Al-4 5%Cu /
LKT & BC
model

: o KGT

LKT 1 Experimental
• • High-speed cinematography.-?'
& o Thermal measurement
• Thermal measurement
o
o 10° = [9 mm dia. droplet] °
o
o
8
9 ~ 10"
8
8
9 10"
II
o

o
10-
8
io " 4 r s l I I i iml l i i i mill i i
o9 10"
o 10 100 1000
c Bulk undercooling, K
o

Figure 1-36. Dendrite tip velocity vs. undercooling in


Ni-25 wt.% Sn alloy. Experimental results and com-
AT (K) parison with predictions of three dendrite growth
models (Wu et al., 1987).
Figure 1-35. Comparison of predictions of growth ve-
locity versus undercooling for the models of Kurz
et al. (1986), KGT, and Upton et al. (1987), LKT, for
constrained and free dendritic growth, respectively,
Melt
assuming k = k0.
Gas inlet-
Crucible
Induction coil — Pressurised vessel
curs. The wire is only about 200 |im in di- (Maxi pressure: 30bars)
ameter, so radial temperature differences, ~0rifica
Gas inlet —*•
even at these high velocities, are small.
Solidification, in the usual case, occurs by
axial dendritic growth, Fig. 1-38, and so, at > Cooling
steady state, dendrite growth velocity is vessel

just equal to the ejection speed. Fig. 1-39


shows results of actual experimental tem-
perature measurements in wire spinning
for a range of ejection velocities. Dendrite
tip undercooling is seen to increase with
.Take-up
increasing tip velocity and to be significant device
at these tip velocities of some meters per
second. The undercoolings, in fact, are
quite close to those of the Ni-25% Sn al- Figure 1-37. Apparatus for spinning steel wire from
loy of Fig. 1-36. the melt (Massoubre and Pflieger, 1978).
1.10 Mixed Cases of Rapid Solidification 31

Dendritic growth is treated in detail in ation. For example, consider the wire spin-
Vol. 5, Chap. 10, Sees. 10.4 and 10.5.4. ning operation shown schematically in Fig.
1-38 at steady state, and suppose that at a
time, t, a large number of effective hetero-
1.10 Mixed Cases of Rapid geneous nuclei are continuously intro-
Solidification duced into the molten stream. The "up-
stream front" then moves quickly up to the
The classes of rapid solidification cited liquidus and subsequent solidification is by
above are not necessarily mutually exclu- heat flow through the liquid-solid zone,
sive with respect to any given casting oper- comparable to the schematic example of
Fig. 1-30. In the unsteady state, there re-
main two additional solidification fronts
which grow together as shown schemati-
cally in Fig. 1-40. This phenomenon is ob-
served in melt spinning (Massoubre and
Pflieger, 1978).
Mixed types of solidification can also oc-
cur when a thermal boundary layer reaches
LIQUIDUS TEMPERATURE the surface of a casting, as can occur in
solidification of atomized powders or in
AT \ melt spinning. Fig. 1-41 illustrates this for
melt spinning. Growth is assumed to occur
I only by columnar growth of existing grains,
with no nucleation at the growing inter-
DISTANCE
face. Hence, substantial undercooling must
occur in the melt to propagate growth up-
Figure 1-38. Solidification of spun cast wire. At steady
state, wire moves to right with velocity R and den- stream, and growth is rapid. But if the strip
drites grow at constant velocity R into liquid metal thickness is small compared with the ther-
undercooled an amount AT. mal boundary layer, then this type of solid-

C =0.4%
j Si = 3.5%
T°C
'LIQUIDUS
1500
V= II.I m s - 1
AT= ^ V=l3.8ms-'
\ 190°
' 0~* V = l 6 . 4 m s " '
1400 :=r
AT= ^ ^ - ^ _ 4 - * - V = 19ms" '
2301°
265<
1300 V=l2.4ms-1
^ = 15.1 ms-'
Figure 1-39. Measured tem-
perature distributions
V = 17.7 ms'
1200
along spun wire during
steady state solidification
at different velocities (Mas-
I 100 soubre and Pflieger, 1978).
300
LENGTH FROM O R I F I C E mm
32 1 Solidification Processing

of workers and described and explained


by Chu etal. (Chu et al, 1988; Chu and
L I Q U I D ;". |,
•I*
LIQUID
mmm -++ Granger, 1990).
Figs. 1-42 a and l-42b are from that
work, and employ the theory of Lipton
etal. (1987) to interpret the two distinct
LIQUIDUS TEMPERATURE
regions observed in Al-Fe alloy melt-spun
strip of 100 jiim thickness. Fig. 1-42 a shows
calculated growth velocity, assuming 75 K
undercooling at the start of solidification,
and Fig. l-42b shows calculated dendrite
(or cell) tip radius. Note that this radius
increases by nearly an order of magnitude
DISTANCE
over the first 20 |im of growth (as under-
Figure 1-40. Schematic illustration of transient solidi- cooling is dissipated) and stays relatively
fication resulting when nuclei are introduced to the constant as further growth is limited by
melt stream in wire casting. Three solidification fronts heat transfer to the surroundings. The
result. points in Fig. l-42b indicate experimental
estimates of tip radius and agree quite well
with calculations.
ification can occur only in the bottom por- It should be added that in this case the
tion of the strip. In later stages of solidifica- very narrow freezing range of the Al-Fe
tion, the undercooling in the bulk liquid alloy, combined with a Biot number that is
will be depleted, tip temperature will rise, not too low, apparently permitted this fine
and tip velocity will slow to that which structure to be retained. In other instances,
results from external heat extraction. The if ripening takes place more uniformly
result is a strip of two distinct regions - an throughout a specimen, it may not be pos-
outer fine structure and an inner, much sible to distinguish as readily between the
coarser structure, as observed by a number two regions of solidification.

LIQUIDUS
Figure 1-41. Mixed solidifi-
cation in melt spinning.
Two distinct regions form
in the microstructure dur-
ing solidification. Top: So-
lidifying structure. Bottom:
Temperature in the metal
| LIQUIDUS TEMPERATURE
near mold surface, assum-
ing /i-controlled heat trans-
fer to the mold. Tempera-
ture distribution at the top
surface would be similar in
form, but displaced slightly
to the right.
DISTANCE
1.11 Macrosegregation 33

Al-2 wt % Fe
AT = 75K
= 105w/m2-K

uu

Figure 1-43. Sketch of an ingot solidifying in a metal


80 mold (shaded) with a refractory "hot top." The center
of the ingot (dotted) is fully liquid; the outer portion
AI-2wt%Fe
(white) is fully solid. A semi-solid region exists be-
60 tween the two.
h = 105w/m2-K
L = 100 pm
2 A = observation
only over very small distances. One way in
which the physical displacement can occur
20 -
" / is by floating or settling of precipitated
phases early in solidification (e.g., kishing
n i i i of graphite in cast iron, or settling of fine
0.2 0.4 0.6 0.8 1.0 grains early in ingot solidification). Most
X/L
(b)
macrosegregation, however, is caused by a
different mechanism - the flow of liquid
Figure 1-42. Dendrite tip velocity and tip radius ver-
sus dimensionless distance from the wheel surface for
through the interdendritic channels in the
melt-spun Al-2 wt.% Fe alloy. Curves are calculated liquid-solid zone.
from Lipton et al. (1987). Triangular points on Fig. Fig. 1-43 shows schematically solidifica-
l-42b are experimental (Chu et al., 1988). tion of an ingot. The character of the liq-
uid-solid zone is described quantitatively
in three ways using appropriate thermal
1.11 Macrosegregation relations combined with the Scheil equa-
tion (Eq. (1-2)) or one of its various modifi-
The cause of macrosegregation in cast- cations described earlier (Flemings, 1974).
ings and ingots is now understood to be The liquid-solid region is permeable to
physical movement of liquid or solid phases liquid flow, as illustrated by the schematic
during solidification. Diffusional transport, "volume element" shown in Fig. 1-44. The
in the times available, can be significant interdendritic liquid flows through the ele-
34 1 Solidification Processing

tion equation" (Flemings and Nereo, 1967;


Flemings et al., 1968; Mehrabian et al.,
1970 a)
0L
(1-22)
acL
where ft is solidification contraction and 8
is rate of temperature change.
The physical significance of Eq. (1-22)
can be seen by considering steady state
solidification with planar isotherms mov-
ing with velocity R in the x direction. Eq.
(1-22) then becomes:

8CL
Figure 1-44. Fluid flow through a solidifying "volume
element" (Flemings and Nereo, 1967). where vx is isotherm velocity perpendicu-
lar to isotherms. Eq. (1-23) reduces to the
Scheil equation when vx and /? both equal
ment with a velocity v given by: zero. It also reduces to the Scheil equation
K (written in terms of volume fraction) when
v= — (1-21)
P
vv = — l - p R (1-24)
where K is permeability; /i, gL, and QL are
viscosity, volume fraction, and density, re- This flow is just that required to feed solid-
spectively, of the interdendritic liquid; P is ification shrinkage, and in steady state so-
pressure; and gY is gravitational accelera- lidification the result is no macrosegrega-
tion. tion. Flow with a speed greater than (down
The flow may be driven by gravity acting the temperature gradient from) that of Eq.
on a fluid of varying density within the liq- (1-24) results in negative segregation; a
uid-solid zone, by solidification shrinkage, speed that is less, or in the opposite direc-
by convection in the bulk liquid, which can tion, results in positive macrosegregation.
influence flow within the liquid-solid zone, Fig. 1-45 shows results, compared with
especially near the dendrite tips, or by elec- theory, for an early experiment conduct-
tromagnetic forces or centrifugal accelera- ed to verify Eq. (1-22). Solidification of
tion. Tt may also be influenced by solid Al-4.5 wt.% Cu was carried out horizon-
movement, as in bulging in continuous tally with approximately planar isotherms.
casting. Gravity and solidification shrinkage cause
Because the liquid composition varies the interdendritic flow shown in Fig. l-45b.
spatially within the liquid-solid zone, any The resulting calculated and experimental
interdendritic flow other than that parallel macrosegregation are shown in Fig. l-45c.
to an isotherm must alter the composition A schematic illustration of application of
of the volume element. Conservation of these principles to continuous casting is
solute requires modification of the Scheil shown in Fig. 1-46. No segregation results
equation to a new "local solute redistribu- if interdendritic flow lines are all vertical.
1.11 Macrosegregation 35

Miyazawa and Schwerdtfeger (1981)


were the first to demonstrate the foregoing
by quantitative calculation of segregation
during bulging in continuous casting. Fig.
1-47 a illustrates their model, and Fig.
l-47b several calculated flow fields within
the liquid-solid zone. Resulting carbon and
manganese macrosegregation is shown in
Fig. 1-48.
Another limiting condition of Eq. (1-23)
(a) occurs when

I.U i
f >1 (1-25)
A x = 10cm that is, when flow is in the same direction
_, 0.8 \ L=10cm as, and is greater than, isotherm velocity.
\\ Co= 4.35% copper
\\
\\ tG/s=-3x10"*cm/s In this case, as temperature continues to
en
°V fall (and so local liquid composition in-
<D
0.6 — V -
-C
creases), local melting occurs, rather than
~o
c
o
solidification. It is this local melting that
"o 0.4 _ \ results in the channel segregates known in
o
\\
\\ their various manifestations as "freckles,"
theoretical \\ "A" segregates, and "V" segregates. The
0.2 experimental \\°
\\ basic relation of Eq. (1-25) was first under-
\\
\\ stood qualitatively on the basis of labora-
0 I tory experiments (McDonald and Hunt,
-1.0 -0.5 0 0.5 1.0 1970; Copley et al., 1970) and later inter-
AC S ,% copper
preted analytically with the aid of Eq. (1-22)
(c)
(Mehrabian et al, 1970 b).
Figure 1-45. Macrosegregation in a horizontal unidi-
rectionally solidified ingot, (a) Sketch of mushy zone,
(b) calculated flow lines in mushy zone, (c) macroseg-
regation (Flemings, 1974, courtesy of McGraw-Hill
Book Company).

Negative segregation at mid-radius would


result from flow lines such as those of Fig.
l-46b, and positive segregation at the cen-
terline would result from flow lines such as
those of Fig. l-46c. It can easily be visual-
ized that "bulging" will result in greater (a) (b) (c)

downward flow, and in particular, greater Figure 1-46. Interdendritic fluid flow in a continuous
casting, (a) No segregation, (b) negative segregation at
downward flow toward the centerline (as mid-radius, (c) positive segregation at centerline
illustrated in Fig. l-46c), thus enhancing (Flemings, 1974, courtesy of McGraw-Hill Book
centerline segregation. Company).
36 1 Solidification Processing

In the early analytical work of Flemings


solid mushy . and coworkers cited above, steady state
shell zone •
solidification was assumed with the ther-
mal field given a priori, either from an
uncoupled calculation, or from measure-
ments. In addition, Eqs. (1-21) and (1-22)
were uncoupled for ease of solution, and
the bulk liquid in front of the growing
dendrites was assumed to be quiescent.
A simple relation between permeability,
dendrite arm spacing, and fraction solid
was assumed, with permeability being iso-
tropic. Refinements in these and other re-
spects have been incorporated in subse-
quent papers on the subject (Miyazawa
sotidus and Schwerdtfeger, 1981; Kou et al, 1978;
line U
Dilawari and Szekely, 1977; Asai and
surface center Muchi, 1978; Fujii et al, 1979; Mori et al,
1979; Ridder et al, 1981; Tacke et al, 1981;
(a) Ohnaka and Fukusoko, 1981; Petrakis

center center

'Ml
' ' M M I
heterogeneous
1 0 2 1
CO

Distance from center x (cm)

(b)
Figure 1-47. Effect of bulging on interdendritic flow in vertically continuous cast carbon steel (Miyazawa and
Schwerdtfeger, 1981). (a) Schematic model of half-thickness of continuous casting, (b) Left is flow assuming only
bulging; right is flow including effects of both bulging and solidification shrinkage.
1.11 Macrosegregation 37

Center Center Fig. 1-49 a shows flow vectors during


0.72 0.72 horizontal solidification of an ingot of
NH 4 Cl-70wt.% H 2 O. This material was
Carbon Manganese chosen because of the many laboratory
5
max
studies which have been conducted using
0.68- 0.68- (mm) it. Solutally driven upflows are seen within
1 the mushy region; these penetrate the liq-
2
uidus front in the upper one-third of the
3
cavity. Note the formation of discrete flow
"channels" within the mushy region out-
c 0.64- 0.64-
lined by the dashed lines. The higher up-
ward velocities within these outlined zones
result from the local remelting and there-
fore higher permeability in the channel re-
0.60 0.60—
gion.

0.56 0.56
1 0 2 1
Distance from center x(cm)

Figure 1-48. Macrosegregation of carbon (left) and


of manganese (right) for three different degrees of
bulging in carbon steel (Miyazawa and Schwerdt-
feger, 1981).

etal, 1981; Ramachandran et al., 1981;


Chang and Brown, 1983; Yao etal., 1984;
Nomura etal., 1981; Maples and Poirier,
1984; Ohnaka and Kobayashi, 1986; Yeum
et al., 1988; Bennon and Incropera, 1987 a,
1987 b, 1987 c; Beckermann and Viskanta,
1988; Nandapurkar et al, 1989; Mori et al,
1989; Heinrich etal, 1989).
Fig. 1-49 is an example of results obtain-
able from the current advanced methods of
mm
calculation. The figure is from work of — 0.55 /s
Bennon and Incropera (1987 b), who solved 0.47-0.56
0.56-0.64
the solute continuity equation (including 0.64 - 0.72
both advection and diffusion mechanisms) 0.72 - 0.80
simultaneously with equations for energy (a) (b)
and momentum. In this way they were able Figure 1-49. (a) Flow vectors during solidification,
to show by calculation an irregular den- and (b) macrosegregation after complete solidification
drite front and to account for a mushy re- in NH 4 Cl-70 wt.% H 2 O ingot (Bennon and Incrop-
gion substructure (e.g., channel formation). era, 1987 c).
38 1 Solidification Processing

Fig. 1-49 b shows the resulting macro-


segregation schematically. At the given
time during solidification, the entire re- -
maining liquid is enriched above its initial \
y^~~~~
70 wt.% H 2 O. The liquid channels within U -II -
\
.1
the mushy zone are clearly visible, and 1
zones of negative segregation, especially
toward the lower left, are present to make I/I
the solute balance. These results appear to
be the first quantitative prediction of the
,/r^B d| = 300/i.m
// I
formation of channel segregates.
At the time of the initial quantitative
-14
work on macrosegregation in castings and 0.0 0.2 0.4 0.6 0.8 1.0
ingots (Flemings and Nereo, 1967; Flem-
ings et al., 1968; Mehrabian et al., 1970 a), (a)
the data available for permeability in liq-
1
uid-solid zones were limited to those of /
/
Piwonka and Flemings (1966). Since that -10 - /"
time, many experimental studies have been /
/

conducted, as summarized and used by y /


y
y
Poirier (1987) to develop correlations for y* __
macrosegregation calculations. Fig. 1-50 \
\
shows examples of results of permeability C—^
calculations for flow through columnar
structures.
The macrosegregation theory outlined
above, including the improved analyses
V
now available, serves as the foundation to- -* '/i
_

day for design of laboratory experiments i/i d, = IOO/i.m


ii
on macrosegregation. It serves also as the i i d 2 = 40^.m
-1 i
starting point for control of macrosegrega- I I
i '
tion in practice. A few examples are given '; '
i i i i i i
-16
below. 0.0 0.2 0.4 0.6 0.8 1.0
The theory predicts that macrosegrega-
tion will occur at abrupt changes in cross- (b)
section in directional solidification. Fig. Figure 1-50. Calculations for permeability through
1-51 shows experimental confirmation of columnar dendrites versus volume fraction liquid for
flow normal to primary dendrite arms, (a) Primary
this for carbon steel (Nomura et al., 1981) and secondary dendrite arm spacings are 300 and 125
and for a Mar M200 alloy (Sellamuthu microns, respectively, (b) Spacings are 100 and 40
etal., 1986). microns, respectively. A, B, and C represent three dif-
In agreement with calculations, elimina- ferent correlations which give comparable results in
tion of bulging, plus a slight amount of their range of validity. Extrapolation C is the most
realistic since this has the correct physical result at
additional reduction ("soft reduction") can high fraction liquid. dt and d2 are primary and sec-
reduce and even eliminate centerline segre- ondary dendrite arm spacings, respectively (Poirier,
gation in continuous casting. Fig. 1-52 is 1987).
an example (Izutani et al., 1988).
1.12 Deformation of Semi-Solid Dendritic Structures 39

Calcd.

0.2 6
o u_ 1.0
°\ / "D O O O °
o 024
\ / o
u
-- 0.9
7.O0.25
0.22
•/•Si = 0.2 5
o

0.20 t i - 0.8
-15 -10 -5 0 5 10 15

Distance! mm)

Bottom area -•—1-»- Neck area

(a)

In addition to work done relating theo-


Mar M2OO + 2..O%Hf retical understanding of experiments on
13.1 - channel formation in transparent alloys,
13.0
1 some work has been done also in metal
12.9 systems (Mehrabian et al., 1970 b; Shaw
12.8
et al., 1986). Fig. 1-53 shows graphically
12.7

12.6
/I that the severity of channel segregates in a
laboratory test increases with increasing
change in liquid density during the solidifi-
- 12.5
c
cation process (in agreement with theory).
1 \
itio

12.4 The figure also shows that the direction of


o 12.3 the channel segregate depends on the sign
Q.
E
/ \ of the density change (also in agreement
o 12.2 z
u 12.1 I
with theory).

12.0 -
II.9
Change In
1.12 Deformation of Semi-Solid
11.8 if 1 Croit-ffldlon - Dendritic Structures
11.7 • -
• i i i i i t i t t When a casting of equiaxed grains solid-
0 1 2 3 4 5 6 7 8 9 10 ifies in "mushy" fashion, the top surface of
the casting can be seen to settle more or
Distance , cm
less uniformly in the early stages of solidifi-
(b) cation. Early in solidification, the grains
are free to move (to "settle"). At some crit-
Figure 1-51. Macrosegregation at abrupt section
changes in directional solidification, (a) Carbon steel
ical local solid fraction, the grains form a
(Nomura et al, 1981); (b) Mar M200 alloy (Sella- network and this stage of "mass feeding"
muthuetal., 1986). ceases. The fraction solid at which the den-
40 1 Solidification Processing

Reduction zone

o
o

o Xn100°/o
"5

1.1

Middle carbon steel


C = 0.15-0.16%
High carbon steel O
to C= 0 . 5 0 - 0 . 5 5 %

50 100
x = k. x 100 %
X%

Figure 1-52. Relation between macrosegregation in continuous cast steel and "soft reduction." (Reduction is that
calculated to have occurred near the centerline within the range of fraction solid from 0.4 to 0.7 as shown on right)
(Izutani et al., 1988).

I I I I I
40
3CS15 DCS16
(inverted
channel)

20 -
D
Cooling rate 0.015 Ks" 1
A Cooling rate 0.044Ks" 1

0 - -

CS18A a CS14
CS136
-20 _ OCS17 -
"0 0.10.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Fraction solid, fs
• CS9
-40 _ Figure 1-54. Isothermal shear strength of semi-solid
dendritic aluminum alloys. Shear stress plotted is that
a CS10 after a small amount of shear (6.25 mm shear at a
CS19 a CS12 strain rate of 0.049 mm s"1). Insert at upper right
en
-DU shows test specimen (Metz and Flemings, 1970).
• CS7

CS8 •
an
30
I I I I i drites form a cohesive network, and at
30 60 90 120 150 170
Area of channels, mrrr
which the network begins to develop some
strength, must depend on dendrite size and
Figure 1-53. Relation between liquid density change
and area of channel segregate formation in some car- morphology, but a number of studies in
bon steels, in a laboratory experiment (Shaw et al., different alloys show it to be in the range of
1986). about 0.1 to 0.2 and occasionally higher.
1.12 Deformation of Semi-Solid Dendritic Structures 41

Rotating outer
cylinder

Figure 1-55. Isothermal shear strength of


semi-solid dendritic S n - 1 5 wt.% Pb al-
100 - loy. Shear stress is the maximum mea-
sured (at a shear rate of 0.16 s" 1 ). Insert
at upper right shows test arrangement
(Spencer et al., 1972).
o o
0 0.2 0.4
Fraction solid, fs

As one example, Metz and Flemings iso- alloys. Measurable strength began to de-
thermally sheared small blocks of alumi- velop at a fraction solid of about 0.2.
num alloys and found negligible strength Typical isothermal stress-strain curves
below about 0.2 fraction solid (Metz and for Spencer's semi-solid alloy are shown in
Flemings, 1969, 1970). Above 0.2 fraction Fig. 1-56. At a given strain rate, stress in-
solid, shear strength increased with in- creases with displacement to a maximum,
creasing fraction solid, Fig. 1-54. Shear after which it falls to a low value. Maxi-
strength was found also to increase some- mum strength increases with increasing
what with increasing strain rate and with fraction solid. Deformation at fractions
increasing grain size. In well-grain-refined solid up to about 0.9 is primarily by grain
alloys, strength did not begin to develop boundary sliding with some dendrite dis-
until 0.4 fraction solid. tortion. The increase of stress with initial
Spencer et al. (1972) carried out similar strain is probably because strain increases
tests on Sn-15% Pb alloy. His test ap- the number of contacts (the "welds") be-
paratus consisted of two grooved counter- tween particles. At sufficiently high strain,
rotating cylinders, as shown at the upper continuous fissures open, and so stress falls
right of Fig. 1-55. Maximum stresses ob- to a low level. The fissures become filled
tained in the tests were qualitatively simi- with liquid except at very high fractions
lar to the results of Metz on aluminum solid.
42 1 Solidification Processing

At sufficiently high solid fractions (above


about / s = 0.9) liquid can no longer flow to
compensate for thermal or other strains in
400 -
the solidifying metal. Then, if stresses are
large enough to overcome the strength of
the partially solid material, internal or
open "hot tears" result. Fig. 1-58 shows re-
sults from a typical type of "hot tear" test
casting employed by foundrymen. When a
casting is sufficiently long and the mold is
sufficiently rigid, the casting tears apart
during solidification. Hot tear susceptibil-
ity is strongly alloy-sensitive. Alloys most
prone to hot tearing are those which solid-
ify over a wide temperature range, but with
a relatively small amount of residual liquid
at the eutectic temperature (Rosenberg
et al, 1960; Clyne and Davies, 1979). As
shown in Fig. 1-58, greatest hot tear sus-
ceptibility in Al-Cu alloys is at about
80 5 wt.% Cu.
Angular displacement in degrees
Figure 1-56. Isothermal shear test results, semi-solid
Sn-15% Pb alloy (Spencer et al, 1972). 1.13 Grain Refinement

Strains such as the foregoing, with re- Columnar grains in castings and ingots
sulting liquid flow, result in localized re- may be many centimeters long. Their di-
gions of macrosegregation in actual cast- ameter may range from less than 0.1 mm to
ings and ingots. A common source of the 1 cm or more. Generally, the diameter of
strain is thermal contraction of the solidi- columnar grains increases progressively as
fying metal, hindered by mold constraint solidification proceeds, since those grains
(Rosenberg et al, 1960; Clyne and Davies, which have a preferred growth direction
1979). Centerline segregation in continu- oriented near the heat flow direction tend
ous casting can be visualized as having a to "crowd out" less favorably oriented
similar root cause, resulting from thermal grains.
contraction of the solid, accentuated by Equiaxed grains typically also range in
"bulging" of the casting due to metallo- size from less than 0.1 mm to over 1 cm.
static head (Miyazawa and Schwerdtfeger, Effective grain refiners (heterogeneous nu-
1981). Detailed analysis of compositional cleating agents) are available for most non-
variations across a casting cross-section ferrous alloys. Through the use of these it
such as this requires analysis of the full is possible in practice (especially with alu-
thermal and interdendritic flow fields dur- minum and magnesium alloys) to obtain
ing solidification (Flemings, 1974; Flem- grain sizes consistently under about 0.1 mm.
ings and Nereo, 1967). Fig. 1-57 is an ex- Grain refiners have been developed for fer-
ample. rous and nickel-base alloys which are effec-
1.13 Grain Refinement 43

tive as mold coatings for thin-section cast- favored over columnar grains by low
ings, but their effective life is not sufficient- pouring temperature (low "superheat"). As
ly long for refinement of sections more pouring temperature is lowered further, the
than a few millimeters thick (Flemings, equiaxed grains become finer. We now un-
1974). To achieve smaller grain sizes than derstand that the major cause of the fore-
can be achieved with available grain refin- going is convection at low pouring temper-
ers, and especially to refine the grain size of ature: the convection associated with the
metals for which grain refiners are not mold filling itself remains strong as solidi-
available, we need to turn to other meth- fication commences. With high pouring
ods. temperatures, on the other hand, the forced
Vibration (ultrasonic and sonic) has convection dissipates before solidification
been shown to influence formation of new begins, so that solidification proceeds in a
grains, and there has been much specula- relatively quiescent melt. Columnar grains
tion as to the mechanism. An interpreta- (or large equiaxed grains) are favored at a
tion favored by many some decades ago given pouring temperature when convec-
was that the vibration promoted heter- tion is minimized by application of a mag-
ogeneous or even homogeneous nuclea- netic field (Uhlmann et al., 1966), or by
tion (Richards and Rostoker, 1956). Others casting in a thin section within which con-
(Southin, 1966) were inclined to the earlier vection is quickly dissipated (Bower and
explanation of Schmid and Roll (1939) that Flemings, 1967).
the grain refinement derived from fragmen- More importantly from a practical
tation of primary crystallites, providing an standpoint, introducing convection by me-
artificial source of more nuclei. This second chanical or electromagnetic means during
one is the prevalent view today. the early stages of solidification favors for-
Foundrymen and ingot casters have mation of fine, equiaxed grains. There are
long understood that equiaxed grains are many references in the older cast metals

center
center
solid mushy !
shell zone ' I
• » 1
1
1 11
» 1 t 1 I
t I
~*
1
< I
'TT'I <
\ \ :X
on

» t

\ \;^^^ o
<u

1 \ x-x
\ • *
/ / 1
JOI

' ' *
/ / 1
\
solid\ i > i
1 11
Qi

\ 1 1 l
heterogeneous' '
1
2 1 0 0.56
surface Distance from center in cm
Distance from center in cm

Figure 1-57. Centerline segregation due to "bulging" in continuous casting, (a) Schematic, (b) interdendritic flow
lines, (c) resulting macrosegregation (Miyazawa and Schwerdtfeger, 1981).
44 1 Solidification Processing

60
1 I " mechanism is. (It must be added also that
we cannot rule out the possibility that in
some cases the convection may also en-
933 K hance the effectiveness of heterogeneous
L
50
• — .

-»_ nucleation agents.) Some possible dendrite


-—-».
\
• — - ^
• — • —
fragmentation mechanisms are:
X (a) Dendrite arm fracture. Arms shear
821 K
K
\ z off as a result of the force on the arm from
/ /
/ - the fluid flow (Garabedian and Strickland-
X
/ O
Constable, 1972, 1974).
X 1 X X / O
/
(b) Remelting of the arm at its root as
0 /
a result of normal coarsening (Kattamis
30
/

/
\
1 et al., 1967). The function of the fluid flow
0 \x
r
XX
X XX
XX
X
X
/
/X
/ o
O
in this case is simply to carry the dendrite
arm away from its "mother grain" to where
f it can grow as a new grain.

/i
5 20 - o —
vxxX X X X O
\ (c) Remelting as above, enhanced by
\ thermal perturbations which occur with
^ X XX /
O\\ / turbulent convection in a liquid which is
/ not at uniform temperature.
10 ~ O >

O o (d) Remelting as above, but where the


x -- torn casting melting at the root is accelerated by the
O -- no visible tears stress introduced at the dendrite root as a
| |
result of the force of the fluid flow.
5 10 15
(e) As in (c) above, but where the melting
Wt. % copper
at the root is further enhanced by a high
Figure 1-58. Hot tear testing of Al-Cu alloy. Plot solute content in the solid at the dendrite
shows maximum length test casting that can be made root (Uhlmann et al., 1966).
without visible tears (Rosenberg et al., 1960).
(f) Recrystallization as a result of the
stress introduced by the force of the fluid
flow, with rapid liquid penetration along
literature as to the effect of such convection the new grain boundaries (Vogel, 1978;
on grain structure. Mold oscillation, for ex- Apaydinetal, 1980).
ample, was sometimes employed to achieve
fine grains in sand castings, and stirring
with a cold rod was used to refine the struc- 1.14 Semi-Solid Slurries
ture of ingots. Today, electromagnetic stir-
ring is widely practiced in continuous cast- During the course of his doctoral thesis
ing to achieve fine grain size. research in early 1971, Spencer was con-
There is general agreement today that ducting the hot tearing tests on Sn-15%
vibration, low pouring temperature, and Pb alloy discussed earlier (Figs. 1-55 and
externally induced convection all promote 1-56) (Spencer, 1971). In the course of those
grain refinement primarily by a dendrite experiments, he decided to use the same
fragmentation mechanism, although there apparatus to conduct a quite different type
is not yet agreement on what this basic of test. Instead of partially solidifying the
1.14 Semi-Solid Slurries 45

Solid
Liquid
Rotating
outer
cylinder

0.8

0.6

0.4
Figure 1-59. The Spencer experiment. Experi-
mentally determined viscosity and shear stress
versus fraction solid for Sn-15 wt.% Pb alloy
0.2 cooled at 0.006 Ks" 1 with a shear rate of
200 s" 1 . Inset at upper right is a schematic illus-
fi-3'S tration of the test specimen (Spencer et al.,
06 1972).
0.2 0.4 0.6 0.8

Fraction solid, fs

alloy before beginning shear, he began the tion solid, / s , is calculated from the Scheil
shear above the liquidus and then slow- equation based on actual temperature
ly cooled his alloy into the solidification measurements. The grain structure ob-
range while it was being sheared. tained in these early experiments was non-
The results were surprising. When shear dendritic, as shown schematically at the
rate was relatively high, stress increased upper right of Fig. 1-59, and it was evident
only very slowly as temperature was de- that shearing in the material was taking
creased below the liquidus. The shear place more or less uniformly throughout
stress measured at a given temperature be- the sample. The material was behaving as
low the liquidus was orders of magnitude a liquid-like slurry, to which an apparent
less than when the samples were cooled to viscosity could be assigned, as has been
the given temperature before shear. Com- done in Fig. 1-59 (Spencer, 1971; Spencer
parison of Figs. 1-55 and 1-59 provides an et al., 1972). We came, in our early work
example of this remarkable reduction in at M.I.T., to call the process of obtaining
shear stress. In both of these figures, frac- these new structures "Rheocasting" to sig-
46 1 Solidification Processing

nify the distinctive rheological behavior of extent to which the morphology evolves
the material. along the spectrum from that of Fig. 1-60 a
Vigorous agitation as solidification be- to that of Fig. 1-60 e increases with increas-
gins results in formation of new grains by ing shear rate and amount of solidification,
one or another of the mechanisms de- and with decreasing cooling rate. The size
scribed in the previous sections, presum- of the individual grains (dendrites or ro-
ably by dendrite fragmentation. The early settes) appears to depend only moderately
growth of each dendrite fragment then ap- on shear rate above some given minimum
parently continues dendritically, as shown value, but depends strongly on cooling rate
schematically in Fig. 1-60 a and b. With - at least cooling rate during the initial
continuing shear and time during solidifi- stages of solidification.
cation, the dendrite morphology becomes
that of a "rosette" (Fig. l-60c), as a result of
ripening, shear, and abrasion with other 1.15 Flow Characteristics
grains. Ripening proceeds during further of Semi-Solid Slurries
cooling, Fig. l-60d. With sufficiently slow
cooling and high shear, the particles be- When viscosity of such a slurry is mea-
come spheroidal (or in some cases ellip- sured during continuous cooling, it is
soidal), usually with a small amount of en- found to be a strong function of shear rate,
trapped liquid, as shown in Fig. l-60e. The decreasing with increasing shear rate, Fig.
1-61. One effect of the shear is to produce
denser, more rounded particles which
(a)
move more easily past one another; i.e., to
accelerate the irreversible structural evolu-
tion illustrated in Fig. 1-60. The major ef-
fect of cooling rate on viscosity can be un-
derstood in a similar way. Viscosity in-
Structure evolution in rheocasting creases with increasing cooling rate, as il-
lustrated in Fig. 1-62, primarily because
the higher cooling rate results in less dense,
Increasing shear rate
less spheroidal particles (Flemings, 1991).
(c) Increasing time
Decreasing cooling rate
Shear rate affects structure in an impor-
tant way in addition to that sketched in
Fig. 1-60. A larger scale "structure" can
build in these slurries by collision and co-
Id) alescence of favorably oriented particles, as
sketched in Fig. 1-63. The extent of this
larger structure will depend on a balance
between the rate of structure buildup and
(e) its breakdown from shear (Rames et al.,
1989). We expect this structure buildup and
breakdown to be more or less reversible
Figure 1-60. Schematic illustration of evolution of
structure during solidification with vigorous agita- with changing shear rate.
tion, (a) Initial dendritic fragment, (b) dendritic In rheological terms, these semi-solid
growth, (c) rosette, (d) ripened rosette, (e) spheroid. slurries are said to exhibit "pseudoplastic-
1.15 Flow Characteristics of Semi-Solid Slurries 47

(a) (b)

Figure 1-61. Effect of shear rate on apparent viscosity of semi-solid alloys, (a) Sn-15wt.% Pb (Joly and
Mehrabian, 1976); (b) Al-4.5% Cu-1.5 wt.% Mg (Kattamis and Piccone, 1990).

ity." Empirical equations developed to de- Fig. 1-64 plots results from recent thesis
scribe the full range of viscosity of pseudo- work at M.I.T. by Moon (1990) on Al-
plastic materials require at least four pa- 6.5 wt.% Si alloy. Viscosity is shown at
rameters. However, a simple and widely 0.4 fraction solid as a function of shear rate
used relation that is often useful over wide for a number of different initial conditions.
ranges of shear rate is the well-known Note that viscosity at a given shear rate
"power-law" model: can vary by over an order of magnitude.
Data for the top curve were obtained by
fi = Kyn~i (1-26) cooling to fs = 0.4 and recording the vis-
where \i is viscosity, y is shear rate, n is cosity obtained immediately on reaching
called the "power law index," and K the this fraction solid; cooling time from the
"consistency." The smaller the power law liquidus to this fraction solid was approxi-
index, the greater the pseudoplasticity. We mately 5 min. The middle curve shows
may use this simple model to help under- measurements obtained after continuing
stand the effects of process variables on the shear at / s = 0.4 for an extended period
viscosity of semi-solid alloys. (90 min). For longer holding times, change
48 1 Solidification Processing

10 i i
I I I I
7
Al-4.5%Cu-1.5%Mg
Sn-15%Pb
y0=330s"1
_
6 - 8 -
0.33 Ks"1
continuously - -
5 - cooled
OJ
Q_
c •E 6 -
>^ 4 ~
<7>
o

i
i-t
\A

c=0.42Ks"1-^
c 3 -
c- AH -

i
<u m
ro
Q.
a
< £- 0.017 Ks"1 0.03 Ks"'

i
2 -

2 -
/ c= 0.0055
1 -
/ VKs"1
w I I
c= 0.008 Ks"1

i i

0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8


Fraction solid, f% Fraction solid, fs

(a) (b)

Figure 1-62. Effect of cooling rate on apparent viscosity of semi-solid alloys, (a) Sn-15wt.% Pb (Joly and
Mehrabian, 1976); (b) Al-4.5 wt.% Cu-1.5% Mg (Kattamis and Piccone, 1990).

in viscosity with time was very slow, and so


we expect this as the "steady state" curve.
The large drop in viscosity resulting as
the "steady state" is approached during
isothermal shearing is due to the irrevers-
ible morphological evolution occurring
with time, as sketched in Fig. 1-60. Note
the difference between the apparent shear
thinning behavior in these two cases. The
power-law exponent is substantially higher
for the steady state case (indicating less
shear thinning).
Approximately reversible pseudoplastic
behavior appears to be typical for "steady
Figure 1-63. "Structure" buildup from collision and state" curve experiments such as the two in
coalescence. Schematic (a) rosettes, (b) spheroids. Fig. 1-64. That is, "structure" of the type
1.15 Flow Characteristics of Semi-Solid Slurries 49
10
A Continuously cooled, 0.075 Ks"1
steady state value. The difference between
A Continuously cooled, 0.0083Ks"1 this curve of "instantaneous viscosity" and
• Steady state
O Viscosity immediately after the steady state curve is a measure of the
shear rate abruptly changed
from 900 s"1 to value shown thixotropy of the slurry.
This structural buildup is further en-
hanced by solidifying and then partially
remelting the semi-solid material in the
process we have come to call "Thixocast-
ing." Measurements on viscosities of "thixo-
cast" Sn-15% Pb alloy were made by
Laxmanan (1980) using a modified parallel
plate plastometer (essentially a compres-
sion test) at low shear rates. Viscosities in
the range of 107 Pa • s were obtained for
0.1
material at about 50% solid, as shown in
Fig. 1-65. These viscosities are several or-
ders of magnitude greater than those ob-
tained for the same alloy with the same
Fraction solid = 0.4 initial spheroidal structure after vigorous
agitation, and enable small samples to be
lifted and handled like solids (Kenney
0.01
100 200 500 1000 etal., 1988).

Shear rate in s 1

Figure 1-64. Viscosity versus shear rate for Al-


6.5 wt.% Si alloys (Moon, 1990).

illustrated in Fig. 1-63 builds and is de-


stroyed depending on shear rate. There is,
however, a time dependency (thixotropy),
so that when shear rate is abruptly changed,
the new steady state viscosity is attained
only after some time at that shear rate.
This effect is illustrated by the bottom
curve of Fig. 1-64, in which instantaneous
viscosity is given after dropping the shear
rate from 900 s~* to the shear rate plotted.
This instantaneous viscosity is less at any "-5 - 4 - 3 - 2 - 1 0 1
given shear rate than the "steady state" f, shear rate in s"1

value, because the "structure" has not had


Figure 1-65. Viscosity versus shear rate for Sn-
time to adjust to that of the new shear rate. 15 wt.% Pb alloys. Solid lines at the upper left are
With time, agglomerates build and the vis- for "Thixocast" materials (Laxmanan and Flemings,
cosity at a given shear rate approaches the 1980).
50 1 Solidification Processing

Results qualitatively similar to those de- Table 1-4. Viscosities of semi-solid alloys and of some
scribed above for Sn-15% Pb alloy and familiar materials.
two aluminum alloys have been described Approx.
for a large number of other aluminum and viscosity
low melting point alloys. Similar results Pas
have also been obtained for a wide range of Silicate glass in its temperature 10 4 -10 8
other metal alloys including copper-base range for forming
alloys, cast iron, steels, and superalloys. Semi-solid alloys, 50% solid, 107
During an extended program at M.I.T. in shear rate 1 0 " 3 s - 1
the 1970's, alloys studied included hypo- Molten silicate glass 103 104
eutectic cast irons, several copper-base Molten polymers 103
alloys, a cobalt-base superalloy, a nickel- Liquid honey 101
base superalloy, several stainless steels, Yogurt, shear rate 10 s" 1 101
and a low alloy steel. References to these Semi-solid alloys, 50% solid, lO0-^1
works are given in a recent summary paper shear rate 200 s" 1
(Flemings, 1991). Glycerol 10°
We may gain more familiarity with the Yogurt, shear rate 200 s ~1 lO" 1
properties of semi-solid metal alloys by Water, liquid metals io~ 3 -io- 2
comparing them with some well-known
materials. Vigorously agitated metals at 40 than 1 mm in a ten second period. Re-
to 50% solid have viscosities typically in quired viscosity can be calculated from the
the range of 0.1 to 10 Pa • s. This is two to simple equation defining viscosity:
four orders of magnitude higher than the
viscosities of water or fully liquid metal, x = iiy (1-27)
and in the range of glycerol, liquid honey,
where T is shear stress. The result is a vis-
and machine oil (Table 1-4). Yogurt ex-
cosity of approximately 106 Pa • s. Semi-
hibits the same range of viscosities; from
solid thixocast alloys at 40 to 50% or more
about 1 to 10 Pa • s, depending on shear
solid easily reach this viscosity, permitting
rate. At higher viscosities, molten polymers
them to be handled as if they were solids.
and molten silicate glass are in the range of
103 to 104 Pa • s. At this viscosity, the ma-
terials still flow readily under gravity or 1.16 Semi-Solid Composite Slurries
moderate pressure.
A material behaves as a "solid" in our It was recognized early in the Rheocast-
vocabulary when it undergoes negligible ing research at M.I.T. that the high and
deformation during a time that is of inter- controllable viscosity of semi-solid slurries
est to us. We can begin to handle these made them excellent starting materials for
semi-solid alloys as if they were solids processing metal matrix composites. It was
when their viscosity rises much above found that a variety of ceramic particulates
106 Pa • s, as is seen by the following order could be added to the semi-solid slurry and
of magnitude calculation. A 50 mm cube kept in suspension without floating or
of semi-solid aluminum is imagined to be settling (Mehrabian et al., 1974; Flemings
held between two parallel plates. Gravity et al., 1976 b). Other researchers have shown
produces a shear force. Suppose now that that particles can be similarly added to fully
we arbitrarily wish no more displacement liquid metal (Rohatgi et al, 1979; 1986), but
1.16 Semi-Solid Composite Slurries 51

10

Matrix: Al-6.5wt.%Si
Steady state at 973K

30 vol.% SiC

20voL%SiC
0.1

10vol.%SiC continuously cooled


SiC/Al-6.5wt.%Si
Cooling rate: 0.075 Ks'1
Shear rate: 180 s'1

0.01
100 200 500 1000
1
Shear rate in s" Total volume fraction
of (primary solid + SiC)

(a) (b)

Figure 1-66. (a) Viscosity versus shear rate for Al-6.5 wt.% Si alloy with SiC. (b) Viscosity versus total volume
fraction solid during cooling through the liquid-solid zone of Al-6.5 wt.% Si alloy. Contains 0, 0.1, and 0.2
volume fraction SiC (Moon, 1990).

that a semi-solid metal slurry provides bet- shear rate for Al-6.5 wt.% Si with 0.1, 0.2,
ter wetting and dispersion (McCoy et al., and 0.3 volume fraction SiC. Fig. l-66b
1988). The ease with which particles are shows viscosity during cooling in the liq-
entrained in the melt is a sensitive function uid-solid range with 0, 0.1, and 0.2 volume
of surface chemistry (e.g., magnesium in an fraction SiC. It is of interest that the vis-
aluminum alloy greatly aids incorporation cosity for a given total volume fraction of
and retention of SiC particles; whereas solids is less when a portion of that volume
chlorine degassing causes expulsion of the fraction is ceramic particles. This is possi-
particles). bly because the ceramic particles prevent
Rheological properties of these slurry the metal particles from joining and coales-
composites have been studied by a number cing as readily as in the fully metal slurry.
of investigators (Girot, 1987; Loue and This conclusion is supported by the obser-
Kool, 1989; Mada and Ajersch, 1990; vation that both the pseudoplasticity and
Moon, 1990). Most find that the com- thixotropy also appear to be reduced in
posites (with or without some solidified aluminum slurries by the addition of the
metal) exhibit thixotropic behavior quali- particulate SiC. It may also be that the
tatively similar to that of partially solidi- presence of the ceramic accelerates the
fied fully metallic slurries. Fig. 1-66 is an morphological evolution of the solidified
example from recent thesis work of Moon metal particles toward more perfect spher-
(1990). Fig. 1-66 a shows viscosity versus oids.
52 1 Solidification Processing

1.17 Processing Non-Dendritic et al., 1976 a; Riek et al., 1975; Young et al.,
Semi-Solid Slurries 1976; Flemings and Young, 1978).
The third type of process, Fig. l-67c, is
The main processes used to date for vigorous electromagnetic stirring of con-
achieving non-dendritic structures are il- tinuous castings (to produce billets for sub-
lustrated schematically in Fig. 1-67. Fig. sequent thixocasting) (Kenney et al., 1988;
1-67 a is a simple "batch rheocaster," in Young et al., 1984). This is a process of con-
which a crucible of molten liquid is me- siderable technological importance today
chanically mixed while being cooled. This since it permits production of large ton-
type of stirrer was used in early M.I.T. nages using a variant of a well-established
work on casting of metal and composite technology, and it is applicable to high
components and in exploratory studies by temperature metals such as steel.
others. It has been incorporated in vacuum There are other routes as well to produc-
or inert atmosphere chambers for use with tion of non-dendritic material. In one, the
high melting point metals or to reduce air shear is obtained by rapid electromagnetic
entrapment. pulse discharge (Nakada et al., 1990). In
A second type of process which has been another, the slurry structure is obtained by
employed is the "continuous rheocaster" of flow of cooling metal within a tortuous
Fig. 1-67 b, in which (1) higher shear is channel to achieve the shear needed for
readily achievable, (2) the stirring is well dendritic breakup (Brook, 1982; Antona
below the surface of the metal, thus mini- and Moschini, 1986). Another relies solely
mizing air entrapment, and (3) cooling rate on long thermal treatment of fine grain
can be high so as to achieve a fine struc- structures in the semi-solid temperature re-
ture. This type of rheocaster has been used gion; one notable starting material in this
in the course of much of the practical pro- process is spray-deposited metal (Ogilvy,
cess development at M.I.T. for low melting 1990). Nature is kind in a very few alloys,
point metals, copper-base alloys, and steels in which the grain refiners employed in
(Flemings and Mehrabian, 1973; Flemings usual casting processes are so powerful

Figure 1-67. Schematic dia-


grams of methods of pro-
ducing non-dendritic struc-
tures, (a) Batch, (b) con-
tinuous, (c) electromagnetic
stirring with continuous
(a) (b) (0 casting.
1.17 Processing Non-Dendritic Semi-Solid Slurries 53

that the original grain structure is non-


dendritic. One such case is zirconium-
refined magnesium-zinc alloy (Flemings,
1974).
A completely different approach has o 1 1
o nrTT-n
1 o
o
been termed SIMA (Strain-Induced Melt o
o
o
o m
Activation). In this case, an alloy billet or o o
0 o
bar (usually of relatively small cross-sec- o o
tion) is cold worked a critical amount so o [I JU o
that, on reheating to the liquid-solid zone,
the desired spheroidal structure is obtained
(Kenney et al., 1988; Young et al., 1983). CZ2
Critical steps in this process appear to be
obtaining a fine grain structure in the billet
or bar and then achieving grain boundary
melting on reheating.
The step of solidifying the original slurry
in either a continuous casting or shaped
casting has been termed "Rheocasting."
When a rheocast billet is reheated for sub-
sequent shaping, the process is termed
"Thixocasting" or, at higher fraction solid,
"Thixoforging." Today, industrial interest
focuses primarily on these "Thixoforming"
process routes. Small billets cut from con-
1
tinuous castings with the rheocast struc-
oooooc

1 L_
ture are reheated and formed, usually by FT

a process which resembles either die cast-


ing (Fig. 1-68 a) or closed die forging (Fig. o
l-68b). Other types of processes have also o _
been shown to be suitable for shaping the ur
semi-solid material, including extrusion
and rolling.
Present manufacturing processes, such
as that shown schematically in Fig. 1-68,
are now highly automated, with billets be-
ing progressively heated under computer
control and then transported by robot
arms to the forming operation for auto-
matic shaping and subsequent removal
from the die. Current applications for the
process are primarily to produce parts of Figure 1-68. Parts manufacture by semi-solid form-
higher integrity than die castings and lower ing: (a) by equipment similar to die casting; (b) by
cost than other competing methods. equipment similar to closed die forging.
54 1 Solidification Processing

1.18 References Flemings, M.C. (1974), Solidification Processing.


New York: McGraw-Hill.
Flemings, M.C. (1991), Edward Campbell Memorial
Allen, D.J., Hunt, J.D. (1976), Metall. Trans. 7 A, Lecture, ASM International Fall Meeting, Detroit,
161-110. MI. Metall. Trans. B (in press).
Allen, D.J., Hunt, J.D. (1979), Solidification and Flemings, M . C , Nereo, G.E. (1967), Trans. AIME
Casting of Metals. London: The Metals Society, 239, 1449-1461.
Book 192, pp. 39-43. Flemings, M . C , Mehrabian, R., Nereo, G.E. (1968),
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2 Rapid Solidification

C. Suryanarayana

Institute for Materials and Advanced Processes, University of Idaho,


Moscow, ID, U.S.A.

List of Symbols and Abbreviations 59


2.1 Introduction 60
2.2 Rapid Solidification Techniques 62
2.3 Spray and Droplet (Atomization) Methods 63
2.3.1 Gas Atomization 64
2.3.2 Water Atomization 65
2.3.3 Ultrasonic Gas Atomization 66
2.3.4 Rotating Atomization Processes 67
2.3.4.1 Centrifugal Atomization 67
2.3.4.2 Laser Spin Atomization 68
2.3.4.3 Electron Beam Rotating Disk Process 68
2.3.4.4 Rotating Electrode Process (REP) 69
2.3.4.5 Rapid Spinning Cup (RSC) Process 69
2.3.4.6 Perforated Rotating Cup (PRC) Process 70
2.3.5 Soluble Gas Atomization 70
2.3.6 Electrohydrodynamic Atomization (EHDA) 71
2.3.7 The Drop Tube Method 71
2.3.8 The Spark Erosion Technique 71
2.3.9 Twin Roll Atomization 71
2.3.10 Vibrating Electrode Atomization 72
2.3.11 The Duwez "Gun" Technique 72
2.3.12 Spray Deposition Methods 74
2.3.12.1 Spray Rolling 74
2.3.12.2 Spray Forging 74
2.3.12.3 Centrifugal Spray Deposition 75
2.3.12.4 The ALCOA Flake Process 75
2.3.12.5 Plasma Spray Deposition 75
2.4 Chill Methods 76
2.4.1 The Die Method 76
2.4.2 The Piston-and-Anvil Technique 76
2.4.3 Twin-Roller Quenching 78
2.4.4 Melt Spinning Process 80
2.4.4.1 Free-Flight Melt Spinning 80
2.4.4.2 Chill-Block Melt Spinning (CBMS) 82
2.4.4.3 Centrifuge Melt Spinning 86

Materials Science and Technology


Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
58 2 Rapid Solidification

2.4.4.4 Planar Flow Casting Process 86


2.4.5 In-Rotating Water Spinning (INROWASP) 88
2.4.6 Taylor Wire Process 88
2.4.7 Melt Extraction Process 89
2.4.7.1 Crucible Melt Extraction (CME) 89
2.4.7.2 Pendant Drop Melt Extraction (PDME) 91
2.4.8 Melt Drag Process 92
2.4.9 Melt Overflow Process 93
2.4.10 Comparison of Rapid Solidification Techniques 93
2.5 Laser Surface Treatment 93
2.6 Cooling Rates in Rapid Solidification 96
2.7 Consolidation Methods 99
2.7.1 Shock Wave (Dynamic) Compaction 100
2.7.2 Hot Compaction 101
2.8 Concluding Remarks 102
2.9 References 104
List of Symbols and Abbreviations 59

List of Symbols and Abbreviations

A constant
a constant
D diameter
d eutectic lamellar spacing
h heat transfer coefficient
K material constant
L length
n, n2 material constants
t solidification rate
Tm melting temperature
V wheel velocity
z section thickness
X secondary dendrite arm spacing
ALCOA Aluminum Company of America
CBMS chill-block melt spinning
CME crucible melt extraction
CSC centrifugal shot casting
CW continuous wave
EREP electron beam rotating electrode process
EBSQ electron beam splat quenching
EDM electric discharge machining
EHDA electrohydrodynamic atomization
FFMS free-flight melt spinning
HIP hot isostatic pressing
INROWASP in-rotating water spinning
LREP laser rotating electrode process
PREP plasma arc rotating electrode process
PDME pendant drop melt extraction
PDRSC pendant drop rapid spinning cup process
PFC planar flow casting
PRC perforated rotating cup process
PSV pulverisation sous vide
r.f. radio frequency
REP rotating electrode process
ROC rapid omnidirectional compaction
RS rapid solidification
RSC rapid spinning cup process
RSR rapid solidification rate
VHP vacuum hot pressing
60 2 Rapid Solidification

2.1 Introduction solidify metallic melts has heralded a new


era in materials science by vastly expand-
Scientific investigations by metallurgists ing the processing window for a variety of
and materials scientists have been continu- existing materials and enabling processing
ously directed towards improved perfor- of entirely novel compositions. This simple
mance of materials in ever increasing hos- technique involved rapid heat removal by
tile environments. Thus, stronger, tougher, conduction from a thin liquid layer shot
hotter and corrosion-resistant materials onto a good heat conducting substrate
are required. These properties for materials such as copper. Good thermal contact with
have been traditionally achieved through the substrate and small thickness of the
chemistry modifications and conventional melt resulted in solidification rates ap-
thermal, mechanical and thermo-mechani- proaching 10 6 Ks~ 1 and achievement of
cal processing treatments. In fact, materials relatively large (hundreds of degrees) un-
processing occupies a central place in the dercooling of the melt before significant
interplay of internal structure, external amounts of a solid phase could form.
properties and performance in service. Rapid solidification processing has now
Quenching of steels from the austenitic come to be recognized to result in charac-
phase field to produce the strong and hard teristic constitutional and microstructural
martensitic phase and subsequent tem- changes. The constitutional changes in-
pering to control the microstructure and clude (a) extension of solid solubility lim-
properties is a classic example of heat its, (b) formation of new non-equilibrium
treatment. Enhancing the mechanical be- crystalline or quasicrystalline intermediate
havior through precipitation hardening by phases, and (c) production of metallic
producing metastable transition phases glasses. Interestingly, all these effects were
through aging a supersaturated solid solu- first observed by Duwez and his colleagues
tion is another example. during the first year of the use of the "gun"
Independently of the details, all these technique (Duwez et al., 1960; Klement
methods to improve the performance of et al., 1960). The microstructural effects in-
materials in general, and metals and alloys clude changes in the morphology and re-
in particular, involve transforming the ma- finement of dimensions of microstructural
terials into a metastable condition either features (the size, shape and location of
by quenching from a high temperature (but grains and phases present). The change is
still in the solid state), deformation or ir- in the direction of a more uniform and finer
radiation. A major limitation in all these microstructure with a large reduction in
methods is the extent of metastability scale of solute segregation effects. Addi-
(departure from equilibrium) achieved; it tionally, all these effects lead to increased
is limited essentially by the low cooling chemical homogeneity of the material.
(solidification) rates, reaching only about In comparison with conventional ingot
103 K s ~ l , obtained during solid-state materials, rapidly solidified materials ex-
quenching. These low solidification rates hibit greatly reduced segregation levels.
arise through the inherent limited heat Thus, the grain size, dendrite arm spacing,
transfer efficiency of the convection and and the size of constituent particles, precip-
radiation modes. itates and dispersoids are refined leading to
The advent of the "gun" technique by significant reduction in diffusion times for
Duwez and his associates (1960) to rapidly homogenization. As an example, it has
2.1 Introduction 61

been shown (Cohen et al., 1980) that at effects in a variety of alloy systems, the
1600 K, the time required to reach 99% 1970's witnessed enhanced activity in the
homogenization of tungsten in nickel in field of metallic glasses. This increased ac-
conventional solidification is 16 h when tivity on glassy alloys was due to the devel-
the segregate spacing is 100 jim. On the opment of techniques to produce long and
other hand, in rapidly solidified alloys continuous tapes with uniform cross sec-
when the segregate spacing is only about tion. The unusual soft magnetic properties
1 jim, the corresponding time is only 6 s. (reasonably high saturation magnetiza-
Hence, chemical homogeneity can be tion, very low coercivity, zero magne-
achieved much more easily in rapidly so- tostriction and high electrical resistivity) of
lidified materials. metallic glasses prompted extensive re-
The metastable effects mentioned above search into this field and also development
confer beneficial properties on the rapidly of applications for these novel magnetic
solidified materials. A vast amount of liter- materials, especially as transformer core
ature, amounting to over 20000 publica- materials (Egami, 1984). However, metallic
tions, is available today on various aspects glasses crystallize during annealing at high
of rapidly solidified materials. A major temperatures and lose all the beneficial ef-
source of this literature is the proceedings fects. Thus, during the 1980's, there was a
of the international conferences on Rapidly resurgence of activity in the area of rapidly
Quenched Metals held once in three years solidified microcrystalline alloys - espe-
regularly since 1975 (the seventh in the se- cially those based on light metals - for pos-
ries was held in Stockholm, Sweden, dur- sible application in the aerospace industry.
ing August 13-17, 1990). In addition, sev- The discovery of quasicrystalline phases
eral books, bibliographies, reviews and (Shechtman et al., 1984; Suryanarayana
other conference proceedings give state-of- and Jones, 1988) has given a short-lived
the-art situation on structure, properties added impetus to this field.
and applications of rapidly solidified mate- The metastable effects of rapid solidifica-
rials (Jones, 1982; Anantharaman and tion can be achieved in other ways also.
Suryanarayana, 1987; Jones and Suryana- The starting material in these non-RSP
rayana, 1973; Suryanarayana, 1980; Gun- techniques can be in the form of either a
therodt and Beck, 1981; Beck and Giin- solid, liquid, or vapor. By their very nature,
therodt, 1983; Luborsky, 1983; Ananthara- the quenching rates obtained in the solid
man, 1984). state are not high and the metastable ef-
In comparison to conventional materi- fects therefore are limited. The quantity of
als, rapid solidification processing has pro- the materials that can be produced per run
duced materials with greatly superior is low when the starting material is in the
strength properties, improved corrosion vapor phase. (Recently, however, it has
resistance and a highly desirable combina- been shown (Bickerdike et al., 1986; Gar-
tion of magnetic properties. In addition to diner and McConnell, 1987) that large
a general improvement in the properties, sheets can be produced by consolidating
rapid solidification processing allows pro- the product after physical vapor deposition
duction of materials with compositions or vacuum evaporation methods.) None
otherwise impossible. While the 1960's saw of these techniques can easily compete with
the emergence of the rapid solidification rapid solidification processing in rate of
principles and observation of metastable production. Therefore, in the present chap-
62 2 Rapid Solidification

ter, techniques such as thermal vapor de- to achieve striking non-equilibrium effects,
position (Chopra, 1969), sputtering (Dahl- these can be considered the precursors of
gren, 1978), chemical vapor deposition the present-day rapid solidification tech-
(Bryant, 1977), electrodeposition (Brenner, niques. The techniques of rapid quenching
1963), electroless deposition (Bonetti et al, from the melt have been reviewed periodi-
1981), ion or electron irradiation (Rechtin cally in recent years with emphasis on dif-
etal, 1978; Fujita and Mori, 1988), rapid ferent aspects (Duwez, 1968; Ananthara-
pressure application (Reddy etal., 1986; man and Suryanarayana, 1971; Chen et al.,
Ponyatovsky, 1988), ion implantation (Bor- 1980; Jones, 1982; Liebermann, 1983;
ders, 1979), ion beam mixing (Liu, 1988), Savage and Froes, 1984; Fleetwood, 1987;
solid-state diffusion reactions (Yeh et al., Anantharaman and Suryanarayana, 1987).
1983; Johnson, 1986), etc. will not be con- High enough cooling rates during solidi-
sidered, even though these may have spe- fication can be achieved when two impor-
cific advantages in particular cases. Some tant requirements are satisfied. The solidi-
of these alternative techniques are treated fication rate, T, during ideal cooling is
by Follstaedt in Chap. 6 of this volume. related to the section thickness, z (in mm)
Ever since the advent of the "gun" tech- through the relation
nique, a great variety of techniques have
been developed to achieve rapid solidifica- t = 10 4 z~ 2 (2-1)
tion of metals and alloys. Most of these
techniques are capable of producing grain suggesting that the solidification rate in-
refinement and inducing one or more of the creases by two orders of magnitude for a
metastable effects referred to earlier. The decrease in section thickness by one order
present chapter is devoted to a brief de- of magnitude. Thus, firstly, the molten
scription of the important techniques avail- metal must be delivered in a stream which
able today for rapid solidification of metal- is thin enough in at least one dimension
lic melts, resulting in the formation of pow- and have a high surface area to volume
ders, fibers, tapes, flakes, wire, etc. Vari- ratio to allow rapid heat removal. Second-
ables that affect the solidification rates and ly, rapid heat removal can be achieved
product parameters are also discussed. by maximizing the contact area between
The special features of laser treatment of the melt and the cooling medium by
solid surfaces are covered in Chap. 3 of this rapidly increasing the liquid alloy surface
volume. A more general treatment of solid- area. This may be effected either by alter-
ification will be found in Chap. 1 of this ing the shape of the melt during processing
volume, while the underlying physical the- (e.g., spreading it as a thin layer on a sub-
ory of solidification is treated in Chap. 10 strate) or by physically disintegrating the
of Volume 5. melt into small droplets (e.g., by atomiza-
tion). Fig. 2-1 presents combinations of
three possibilities which are used in prac-
2.2 Rapid Solidification Techniques tice and also lists the major processes to
which they apply. As can be clearly seen,
Jones (1981) has presented a historical the molten metal can be delivered in the
survey of the early techniques developed to form of either droplets, cylindrical stream
rapidly solidify metallic melts. Although or ribbon stream and the melt stream can
these methods were not designed primarily be cooled by gas, liquid or solid.
2.3 Spray and Droplet (Atomization) Methods 63

Droplets Gas Rapid solidification methods have been


classified into various categories by differ-
ent authors. For example, Jones (1982)
classifies them into three categories -
(i) spray methods involving fragmentation
of melt into droplets prior to quenching,
Cylindrical stream Liquid (ii) chill methods preserving continuity of
the melt up to and during quenching, and
(iii) surface methods which involve rapid
melting and solidification of a limited
depth at the surface of a more substantial
Ribbon stream Solid
thickness of material acting as the heat
sink. On the other hand, Savage and Froes
(1984) classify the methods into two
1. Atomization processes, rapid solidification rate
(RSR), rotating electrode process (REP) groups, viz., Atomization and Non-Atom-
2. Water atomization, rapid spinning cup (RSC) ization, depending on whether atomization
3. Duwez gun, piston-and-anvil, drum splat, electron
of a melt stream into droplets is involved
beam splat quenching, controlled spray deposition, or not. Although each of these classifica-
spray deposition, Osprey tions has its advantages, we shall follow the
former classification and describe the tech-
4. Taylor wire, free-flight melt spinning niques accordingly in the following pages.
5. Free-flight melt spinning, in-rotating water spin-
ning
6. Melt extraction, pendant drop melt extraction 2.3 Spray and Droplet
7. Melt spinning, planar flow casting, melt drag, melt
(Atomization) Methods
overflow
In these methods, a continuous stream
Figure 2-1. Combinations of molten metal stream and of liquid metal is atomized, i.e., broken
cooling medium used in the principal rapid solidifica- down into fine droplets by means of a gas
tion processes. or a liquid. The resultant product after so-
lidification is powder. The mechanism of
achieving atomization and the means of
The shape, size and nature of the prod- cooling can be different in different tech-
ucts which result from the different combi- niques.
nations of molten metal stream and cool- For large-scale applications of rapidly-
ing medium depend essentially on what solidified alloys, the preferred form for con-
happens to the metal stream before it solid- solidation is powder, because of its nearly
ifies. For example, droplets which are al- equiaxed geometry. The deformation pro-
lowed to solidify individually form pow- cesses which occur during the consolida-
ders or flakes, whereas droplets which land tion of powder are characterized by large
on top of one another before they have amounts of relative motion between parti-
solidified coalesce into solid shapes. Sim- cles and the flow of individual particles.
ilarly, a continuous cylindrical stream The high degree of interfacial shear that
solidifies as wire, but a stream which is results helps to disrupt oxide films provid-
broken up solidifies as fibers. ing clean surfaces across which good inter-
64 2 Rapid Solidification

particle bonding can occur. Because of this, impingement point. A representative con-
atomization techniques have become the figuration is shown in Fig. 2-2 a. Details of
preferred methods of rapid solidification recent developments of this process can be
for commercial exploitation (see Chap. 4 in found in the annual conference proceed-
this volume). ings of the various powder metallurgy soci-
Atomization is not a very new technique. eties.
The Merchant's Shot Tower in Baltimore, The overall process of gas atomization is
MD, USA, was continuously used between governed by several interrelated operating
1828 and 1892 to produce some half-mil- parameters: jet distance, jet pressure, noz-
lion 25 lb bags of spherical lead shot each zle geometry, velocity and mass flow rate
year (Adam, 1986). In recent years several of gas and metal, metal superheat, angle of
versions of the atomization techniques impingement, metal surface tension and
have been developed and some overviews metal melting range. Consequently, rigor-
of these different techniques have been pre- ous interpretation of experimental data is
sented from time to time (Lawley, 1977, difficult even though empirical expressions
1978,1981; Grant, 1983; Miller, 1983; Aller have been proposed relating the particle
and Losada, 1990). size distribution to the atomization condi-
tions (Lubanska, 1970; Kim and Marshall,
1971). The solidification rate depends on
2.3.1 Gas Atomization the melt droplet size and on the type of
Conventional gas atomization of liquid atomization medium. Higher solidification
metals has been in continuous use since rates are achieved with smaller particle
the 193O's to produce a variety of metallic sizes and lighter gases. For example, he-
powders for diverse applications. Each lium provides more rapid cooling than ar-
space shuttle launch, for example, con- gon. In practice, nitrogen, hydrogen, ar-
sumes 160000 kg of atomized aluminum gon, or air is used even though mixtures of
powder as part of the solid fuel propellent these gases and helium are also effective.
mixture (NASA, 1980). If sufficient superheat is provided and the
Gas atomization involves breaking atmosphere is neutral to the alloy, the final
down of a continuous stream of liquid powder product is a sphere. The range of
metal by one or more high-velocity jets of powder sizes is broad with the mean par-
air or any other gas. Atomization occurs ticle diameter around 100 |im (Fig. 2-3),
by kinetic energy transfer from the atomiz- even though Unal (1990) reported a mean
ing medium to the metal. The small liquid diameter of 12 to 15 jim for gas-atomized
particles solidify in flight by convection or zinc powder. This technique has been em-
radiation. The solidification rate depends ployed for atomizing a wide range of alloys,
on the particle size, with higher rates asso- including superalloys, high-alloy steels and
ciated with smaller particle sizes. The num- aluminum alloys. With aluminum, how-
ber and geometry of gas/metal configura- ever, a special problem exists. When alu-
tions used in commercial practice are very minum powders are handled in moist air,
varied. Typically, two or more jets, or a hydrates tend to form on their surfaces.
ring, are positioned around the axis of the These, if not removed, tend to form blisters
metal stream. The axes of the gas jets are on subsequent solution annealing.
equally inclined to the metal stream axis Inert gas atomization is currently the
and intersect this axis at the geometrical primary process for the production of su-
2.3 Spray and Droplet (Atomization) Methods 65

Melt Melt

Gas jets Gas jets


Liquid jets

'/rWW ^Atomized Powder


powder slurry Figure 2-2. Schematic
showing the principle of
(a) gas atomization and
(b) gas-water atomization.

Argon
atomized

Rotating
electrode
process Figure 2-3. Representative
particle size distribution for
powders prepared by vari-
ous atomization methods.
10 60 80100 400 600 800 1000
Particle size

peralloy, titanium and other reactive metal 2.3.2 Water Atomization


powders (Moll and Yolton, 1986; Hoh-
mann and Jonsson, 1990). This process suf- This is similar to gas atomization except
fers from a very low overall energy effi- that water jets are used instead of gas jets
ciency (~3%) and is expensive if inert to atomize the metal stream. Further, the
gases other than nitrogen have to be used. water pressure used is higher than the
The yield is about 80% for - 35 mesh pow- pressure employed in gas atomization and
der. Typical solidification rates achieved the angle of impingement is smaller. Water
are 10 2 -10 3 K s " 1 . Hopkins (1987) has re- atomization has been used extensively to
cently given insight into the critical areas make powders of tool and low-alloy steels,
of atomizer design affecting powder mor- copper, tin, and iron. Excess oxide on the
phology, fineness and purity. particle surfaces can be subsequently re-
66 2 Rapid Solidification

moved or minimized in amount by hydro- droplets in streams of high-velocity water


gen reduction. Trial production of steels (Miller and Murphy, 1979) (Fig. 2-2 b). By
(Dunkley, 1982) and superalloys (Tracey this combined technique an amorphous
and Cutler, 1981) has shown that reactive phase could be produced in 100 jim diame-
components tend to oxidize, making it dif- ter Cu 60 Zr 40 powder particles. The pro-
ficult to achieve oxygen contents below cess offers some degree of control over par-
1000 ppm, as against 100 ppm typical of ticle geometry by the relative placement of
gas-atomized superalloy powders. Repre- the gas and liquid jets.
sentative operating conditions for these Oil atomization of iron-base alloys has
two types of atomization are listed in Table recently been tried out (Kainer and Mor-
2-1. dike, 1989) to produce powders in the size
Attempts have also been made in recent range of 10-150 jim. The solidification
times to achieve more effective atomization rates achieved (about 105 K s " 1 at 20 jim
(Fortman and Ullman, 1984; Smith, 1985; powder size) are comparable to those ob-
Couper and Singer, 1985) to achieve higher tained in water atomization. However, a
yields of fine powders. A similar effect has decisive advantage is the low oxygen con-
also been claimed with the use of higher tent of the oil-atomized powders.
gas pressure (Ricks and Clyne, 1985).
Water atomization requires large quan-
tities of energy to supply the water at high 2.3.3 Ultrasonic Gas Atomization
pressures. Consequently, the overall en- This method is again similar to gas at-
ergy process efficiency is less than about omization except that the impinging gas is
4%. The particles are irregular in shape at a very high velocity (up to Mach 2.5).
and the average solidification rate is in the Further, while the gas jets flow in a contin-
range of 10 2 -10 4 K s " 1 . uous manner in normal gas atomization,
Higher solidification rates of 10 5 - they are pulsating at a high frequency of
10 6 Ks~ 1 for 20 jam particles have been 80-100 kHz in ultrasonic gas atomization.
achieved by quenching the gas-atomized The pulsations are provided by the incor-
poration of a series of Hartman shock
wave tubes in the gas passage of the atom-
Table 2-1. Typical operating conditions for gas and
izing die (Anand et al., 1980). This causes
water atomization processes. the molten stream to break up more effi-
ciently, producing finer, more uniform par-
Parameter Gas Water ticles quenched at higher average rates. It
atomization atomization
is claimed that droplet formation in ultra-
Pressure (MPa) 1.4-4.2 3.5-21 sonic gas atomization is a one-step process
Velocity (m s"1) 50-150 40-150 in contrast to the three-stage mechanism of
Superheat (°C) 100-200 100-250 conventional gas and water atomization.
Angle of 15-90° ^30° The average particle size is about 20 |im
impingement (with a narrow size distribution) and the
Particle size (urn) 50-150 75-200 cooling rates estimated are of the order of
Particle shape Smooth and Irregular and 105 K s " 1 . The yields are in excess of 90%
spherical rough surface and this technique has been successfully
Yield 40% at 60% at exploited for producing aluminum and su-
— 325 mesh — 35 mesh
peralloy powders (Grant, 1983) and Ti-Al
2.3 Spray and Droplet (Atomization) Methods 67

powders (Sastry et al., 1983), Because of the Cooling gas


large specific surface area, care must be
exercised in safe handling of these powders.

2.3.4 Rotating Atomization Processes


2.3.4.1 Centrifugal Atomization Fine
Rotary particles
Centrifugal atomization is a technique, atomizer disk
the different variants of which involve dis-
integration of liquid metal at the rim or
Figure 2-4. Schematic of the rapid solidification rate
edge of a rapidly rotating container (disk, centrifugal atomization technique.
cup, crucible, or plate which may be flat or
concave). The liquid metal is supplied to
the rotating part by pouring from a cru-
cible or tundish, or by melting the end of a
disk/cup presents other problems at very
bar in situ. Owing to the centrifugal force,
high centrifugal speeds.
the molten metal is forced out to the edge
In the related Centrifugal Shot Casting
of the container where it is atomized, eject-
(CSC) process, an electric arc between a
ing particles of molten metal. The drop-
stationary electrode and a rotating cruci-
lets spheroidize and solidify in flight. The
ble containing the charge melts the metal
whole process - melting, atomization and
(Fig. 2-5). Owing to the centrifugal force,
solidification - takes place in an inert at-
the molten metal is forced out through the
mosphere.
edge of the crucible where it is atomized,
In the Rapid Solidification Rate (RSR)
ejecting particles of the molten metal (Sut-
Centrifugal Atomization process as prac-
cliffe and Morton, 1976).
ticed by Pratt and Whitney (Cox et al.,
1976), the melt stream is usually bot-
tom-poured on to the center of a water-
cooled horizontal disk, spun at speeds up
to 35 000 rpm. The liquid metal is mechan- Electrode
ically atomized and thrown off the edges of
the spinning disk. Solidification takes place
in flight, and can be speeded up by blasting
the emerging particles with a stream of he-
lium (Fig. 2-4). The helium atmosphere can Atomization rim
also minimize oxidation. The particles are (spin off)

spherical and the solidification rates are of


the order of 104 -10 6 K s ~1 for particle size Powder
particles
of 25-80 jum (Fig. 2-3). Nickel, aluminum,
Alloy
titanium and superalloy powders have material
been produced by this technique. Rotating
crucible
Rapid erosion of the crucible orifice at
high temperatures results in coarser pow- Electrode
ders and lower solidification rates. The de- Figure 2-5. Schematic of the centrifugal shot casting
formation and overall life of the spinning process.
68 2 Rapid Solidification

2.3.4.2 Laser Spin Atomization Electron Alloy bar


beam guns Electron
beam gun
This process (Konitzer et al., 1984; Peng
etal., 1985 a) is similar to the Pratt and
Whitney process, but a high-power laser
beam is used to melt the top surface of
a rod rotating at 10000-30000 rpm. The
molten droplets expelled by centrifugal
force from the circumference of the rod are
cooled by flowing helium gas before they
impinge on the walls of the apparatus. The
droplets solidify predominantly as spheri-
cal particulates, although 10-30 wt.% of Rotary water cooled
copper crucible
the yield was in the form of needles with
diameters of 0.1 to 1.0mm (Peng etal.,
1985 b). Figure 2-6. Schematic of the electron beam rotating
Typical solidification rates of 105 K s " 1 disk process.
are achieved for 100 jum powders using this
technique; different cooling rates can be
obtained by controlling the rotational
speed and gas flow which result in different (Fig. 2-6). Using this process, it is possible
powder diameters. Two particularly signifi- to manufacture metal powders of highly
cant advantages of this process are (i) the reactive materials. The powder size is be-
high power laser beam causes high super- tween 30 and 50 |im and the particle shape
heats so that most second-phase particles is spherical with clean surfaces.
are dissolved in the melt and (ii) the tech- In a slightly different variation of this
nique is of the local melting type, so that process known as Electron Beam Splat
contamination during atomization can be Quenching (EBSQ), an electron beam is fo-
kept to a minimum. This process has been cused on to the end of an alloy rod where
extensively used to produce titanium alloy it melts the surface and produces molten
powders (Sastry et al., 1983). droplets (Sastry et al., 1984; Seshadri et al.,
1988). The molten droplets fall onto a
rotating disk and are stretched into thin
flakes under the combined actions of a
2.3.4.3 Electron Beam Rotating Disk
high angular velocity and the centrifugal
Process
force of the rotating disk. It has been re-
In this variation of the method (Wahlster cently reported (Seshadri et al., 1988) that
etal., 1980) a vertically fed, slowly rotat- as the substrate angle increases, the shape
ing cylindrical bar form is drip melted by of the flake changes from elongated to
several electron beams. The droplets run nearly circular and that the lower substrate
down the pencil-shaped bar and drop into angles yield thinner flakes solidified at a
the center of the rotating disk. Molten higher cooling rate. The flake thickness
metal particles are thrown off the rim, and hence the solidification rate are
preferably within a horizontal angle be- controlled by varying the rotational speed
tween 60° and 80° and are deflected down- of the copper disk. Typical cooling rates
wards by a water-cooled copper shield achieved vary from 104 to 106 K s " 1 .
2.3 Spray and Droplet (Atomization) Methods 69

2.3.4.4 Rotating Electrode Process (REP) A method similar to the PREP method
is Pulverisation Sous Vide (PSV) (or pow-
In this process, a rod of the material to
der under vacuum) process, in which the
be atomized is rapidly rotated while it is
ingot to be converted into powder is placed
simultaneously melted at one end by an
in an ingot mold with vertical axis, rotating
electric arc issuing from a non-consum-
at a slower speed (1000-4500 rpm) than in
able tungsten electrode (Friedman, 1976;
the PREP process. An electron gun melts
Loewenstein, 1981). Fig. 2-7 shows a sche-
the tip of the ingot, the droplets from which
matic diagram of this process. Molten
are ejected and solidify into spheres (Devil-
metal spins off the bar and solidifies before
lard and Herteman, 1980). Special mea-
hitting the walls of the chamber filled with
sures are taken to prevent the powder par-
an inert gas. The process is used fairly
ticles from flattening against the cold walls
widely for the atomization of reactive
of the chamber during solidification by
metals, e.g., high-purity, low-oxygen Ti, Zr,
use of carbonaceous shields. This process
Nb, Ta, V and their alloys, and Ni and Co
generates a larger particle size (>90% is
superalloys.
+ 125 jim) than the PREP process. The
Tungsten contamination from the sta-
carbonaceous shield may cause slight con-
tionary electrode is possible in REP, but
tamination of the powder.
can be avoided by replacement with a tita-
nium cathode or by melting the bar by
plasma arc (PREP), laser (LREP), or elec- 2.3.4.5 Rapid Spinning Cup (RSC) Process
tron beam (EREP).
In this process, developed at Battelle,
REP powders are usually spherical, of
Columbus, OH, USA, the molten metal
high surface quality, but have a large aver-
particles fall into a cup with a rotating
age particle diameter, generally more than
liquid, usually water. The cup with the
200 jim (Fig. 2-3), and so the solidification
quenching liquid is rotated at high speeds
rates are only about 102 K s " 1 . Typically,
(8000-16000 rpm) and the liquid forms a
yields run 75% for —35 mesh powder.
thick layer on the vertical interior side of
the cup. The force of the rotating liquid
Inert gas Vacuum layer improves the heat transfer condi-
tions, increasing the solidification rates
Rotating
consumable and acting also as an atomizer. A wide
electrode variety of steels, superalloys, aluminum,
copper and many other alloys have been
processed by this method. Fig. 2-8 shows a
schematic of the rapid spinning cup pro-
cess (Raman et al., 1984). The pendant
drop rapid spinning cup (PDRSC) process
Non-rotating is a variant in which a droplet is generated
tungsten by melting of the rod-end and falls on the
electrode
rotating liquid.
The powder produced by this method
Collection port has a narrow size distribution (Fig. 2-3)
Figure 2-7. Schematic of the rotating electrode pro- and a high yield of fine powder. Most of the
particles are spherical in shape and the
70 2 Rapid Solidification

Molten metal with sharper ends) are typically 1000-


5000 jim long and 1000 jim in diameter,
Spinning cup and are subsequently introduced into a
Powder
particles rolling mill and consolidated directly as
sheet at rates up to 60 m min" 1 . The pro-
cess can be made continuous and has been
employed to fabricate sheets of relatively
low-melting alloys such as aluminum, lead,
zinc, etc. Since the canning and outgassing
steps during consolidation are eliminated,
the economics might be very attractive.

23.5 Soluble Gas Atomization

Figure 2-8. Schematic of the rapid spinning cup pro-


In this process, also known as the vac-
uum atomization process, and developed
by Homogeneous Metals Co., a crucible of
liquid metal supersaturated with a gas
particle surfaces are clean and oxide-free. under pressure is suddenly exposed to a
The RSC process (i) produces rapidly so- vacuum. Under these conditions, the gas
lidified powders, including highly alloyed expands, comes out of solution and causes
microcrystalline and glassy alloys, (ii) con- the metal to be atomized (Wentzell, 1974).
trols the size distribution in the particles Various gases, including nitrogen, argon,
produced from very narrow to very broad, and hydrogen have been used. Alloy pow-
(iii) varies the particle shapes from irregu- ders based on Ni, Cu, Co, Fe, and Al have
lar-to-spherical-to-elongated, (iv) controls been vacuum atomized with hydrogen as
the oxygen, nitrogen and hydrogen con- the gas. The powders are mostly spherical
tamination and (v) does not produce air- (but can be a mixture of powders and flakes
borne fines. The solidification rates are in depending on the actual disintegration
the range of 10 4 -10 6 K s " 1 (see also Sec- process), clean and are of high purity. The
tion 2.4.5).

2.3.4.6 Perforated Rotating Cup (PRC)


Process
An important commercial variant of the
Centrifugal Atomization is the Perforated
Rotating Cup process developed by Rey-
nolds Metals Co. (Daugherty, 1964). In this
method the molten metal is poured into
a deep rotating cup with holes in the
side (Fig. 2-9). Centrifugal force causes the Collect and transfer
molten metal to flow through the holes.
The streams created break up in flight and Coil
solidify at rates of about 10-10 2 Ks~ 1 . Figure 2-9. Schematic of the Reynold's perforated ro-
These acicular powders (rice-shaped but tating cup process.
2.3 Spray and Droplet (Atomization) Methods 71

cooling rates are low (about 102 Ks *). A 2.3.8 The Spark Erosion Technique
1000 kg/run production plant is in opera-
This method, patterned after the electric
tion.
discharge machining (EDM) method, in-
volves maintaining a repetitive spark dis-
2.3.6 Electrohydrodynamic Atomization charge between two electrodes immersed
(EHDA) in a dielectric fluid. The electrodes are
made of the material whose powder is to be
This method was developed to produce
produced. Each spark melts or vaporizes a
rapidly solidified powders and coatings for
minute quantity of the material which im-
characterization studies (Perel et al., 1980,
mediately freezes or condenses to powder
1981). An intense electric field, typically
particles (Yamaguchi and Narita, 1977;
105 V/m, is applied to the surface of liquid
Berkowitz and Walter, 1980). The powder
metal contained in a capillary emitter. Un-
is usually contaminated with breakdown
der these high field strengths, surface ten-
particles of the dielectric fluid and for this
sion forces are overcome and the droplets
reason inert gas cryogenic fluids have been
are emitted. The charged droplets are ac-
used (Cogan et al., 1978). Amorphous and
celerated towards a collector and may
microcrystalline powders have been pro-
impact while still liquid to produce foils,
duced by this technique, at a rate of 1 to
flakes or a coating, or may solidify in flight
20 g per 6 h run.
to give spherical powders. Particles rang-
ing from 0.1 |nm to 100 |im in diameter can
2.3.9 Twin-Roll Atomization
be produced and the solidification rates
can be as high as 107 K s " 1 for very fine This is a novel process to produce pow-
particles of 0.01 (im diameter (Perel et al., der by atomizing the molten stream fed
1980). Amorphous and microcrystalline between two high-speed rolls rotating in
powders of Al-Si, Al-Cu, aluminum- opposite directions (Singer and Roche,
coated Ti- and Fe-base alloys have been 1977). The rolls are coated with a carbon
produced. The advantages of this process paste to reduce heat transfer and prevent
lie in it being a continuous process, having solidification in the nip of the rolls. As the
no vital moving parts, and it can include liquid metal emerges from the far side of
radiation, convection and splat cooling the rollers, it cavitates and is thrown off
techniques. as droplets (Fig. 2-10). The droplets are
quenched in a water bath, located within
25 mm of the roller nip. Elongated flakes of
2.3.7 The Drop Tube Method 200 jim thickness can be produced at solid-
There has been a revival of interest in ification rates of 10 5 -10 6 K s " 1 (Durand
recent times in this method (Steinberg etal, 1976; Murty and Adler, 1982; Ishii
et al., 1981; Evans et al., 1986; Vinet et al., et al., 1982). This method is capable of con-
1991), wherein droplets generated at the verting a wide range of metals into flake,
top of a vertical column are allowed to fall acicular, irregular, or spherical particles.
freely to different distances and in different At present the process is limited by its in-
environments. Useful fundamental knowl- ability to produce small liquid metal drop-
edge can be gained from these studies lets, as only 2 to 3% of the powder pro-
about the mode and kinetics of solidifica- duced is below 37 jim in diameter (Ishii
tion from deeply undercooled melts. etal., 1982).
72 2 Rapid Solidification

2.3.11 The Duwez "Gun" Technique

This technique, used for the first time


by Duwez and his associates in 1959 to
quench small quantities of liquid alloys
rapidly, remained the most popular of all
RS techniques until the advent of conti-
nuous production techniques in the 1970's.
Even to-day, it retains the distinction of
being a simple, elegant and versatile labo-
ratory technique for producing small (mg)
quantities of rapidly solidified metals and
alloys.
Fig. 2-11 shows a schematic of the"gun"
apparatus (Duwez and Willens, 1963). Es-
sentially, a small quantity (up to 100 mg) of
the metal or alloy is melted by induction or
Liquid/Solid resistance heating in a graphite crucible
interface
with an orifice of about 1 mm in diameter
Molten at the bottom. Because of high surface ten-
droplets
sion the melt does not fall through the ori-
Figure 2-10. Schematic of the twin-roll atomization fice. Ejected by means of a shock wave, the
process. molten metal passes through the orifice,
is atomized and cools rapidly on contact
with a copper substrate in the form of a
thin foil (up to about 15 jam in thickness).
2.3.10 Vibrating Electrode Atomization The shock wave is generated by the rup-
ture of a thin mylar diaphragm located be-
In this process, an electrode having one tween the high- and low-pressure cham-
end free is continuously moved between bers, by an inert gas let into the high-pres-
rollers towards a slowly rotating copper sure chamber with increasing pressure.
disk in a vacuum or inert-gas filled cham- Graphite appears to be the best material
ber. Atomization takes place in the arc for the container for metals and alloys
struck between the water-cooled disk and which do not react with carbon. In case of
the vibrating end of the electrode. The reactive and refractory metals like tanta-
droplets are made to fall off by causing this lum, tungsten and titanium, either a ce-
electrode to resonate by means of a trans- ramic insert can be kept at the bottom of
ducer (Matei et al., 1977). Spherical parti- the crucible or the metal can be melted
cles are formed whose size and size distri- with concentrated r.f. induction heating
bution can be controlled by changing the over a silver hearth (Willens and Beuhler,
length of the resonant rod. The narrowest 1966; Ruhl and Cohen, 1969). Because of
size distribution is obtained at the resonant the rapid heating rate, even alloys with
frequency of the electrode. This method is high vapor pressure constituents can be
not widely used and shows little potential melted with a minimum change in compo-
for scale up. sition. Although the "gun" devices are gen-
2.3 Spray and Droplet (Atomization) Methods 73

Clamping pin
High pressure
chamber
Helium
0-Rings
Argon
Mylar diaphragm
Low pressure
chamber Clamp for
graphite
Water — container
Tantalum
Water cooledi
induction coil

Graphite
container

Figure 2-11. Schematic of the Duwez "gun" technique.

2 cm

erally operated in air, versions operating liquid globule strikes the substrate at a
under controlled atmospheres or vacuum glancing angle to improve the thermal con-
have been described (Shingu et al., 1968; tact. The substrate can be maintained at
Ruhl and Cohen, 1969; Lohberg and low temperatures, if desired. This helps in
Muller, 1969; Davies and Hull, 1972). The retaining those metastable phases which
shock wave can also be generated with the decompose rapidly at ambient tempera-
help of an explosive (Predecki et al., 1965). tures (Kane et al., 1966). Glass substrates
Cahn et al. (1976) produced the shock have been used to quench oxide melts (Sar-
wave by means of vanes rotating rapidly at jeant and Roy, 1967) and diamond was
speeds up to 13 000 rpm and the alloy was used in another investigation (Ramachan-
levitation melted. drarao et al., 1972) to take advantage of its
The substrate should have a high ther- substantially increased conductivity at liq-
mal conductivity to extract the heat rapid- uid nitrogen temperatures.
ly. Therefore, copper is most commonly The product of this technique, popularly
used. In the earliest version (Duwez et al., called splat, the technique itself referred to
1960), the globule was received on the in- as "splat cooling", is of varying thickness
side of a rotating cylinder located at about (0.1 to 15 |im in different portions of the
1.2 cm from the exit of the graphite con- same splat) and porosity and is at best a
tainer. Because of the geometry of the cru- few cm in size. Although best suited for
cible orifice, the full impact of the shock structural characterization by electron mi-
wave could not be realized. The substrate croscopy (near the edges and holes, the
takes the form of a "Ski-Slide" in the later foils are electron transparent) and X-ray
version (Duwez and Willens, 1963) and the techniques, these splats are not suitable for
74 2 Rapid Solidification

evaluating the physical and mechanical Holding furnace


properties. Nitrogen
Solidification rates in the range of 106 to
108 K s " 1 and 104 to 1010 K s " 1 have been
measured (Predecki et al., 1965) and calcu-
lated (Ruhl, 1967) for this technique. It was
suggested that higher solidification rates
can be achieved by improving the thermal
contact between the splat and the substrate
and decreasing the thickness of the splat.
Quenching the melt in an inert atmosphere
(Davies and Hull, 1974) or in vacuum
(Boswell and Chadwick, 1976) has been re- Substrate
ported to result in higher rates of solidifica- Figure 2-12. Schematic of the spray rolling process
tion. with a rotating substrate.
Successful operation of this technique
involves (a) restricting the quantity of the
molten alloy, (b) atomizing it rapidly into on to the roughened surface of a wide, in-
very small droplets, and (c) expelling the ternally-cooled, slowly-rotating drum (Fig.
atomized stream over a short distance and 2-12). The droplets solidify on impact, with
time interval to make high speed impact subsequent droplets building up the thick-
with the quenching substrate. ness. This layer is peeled off from the drum
and fed directly into a rolling mill to pro-
2.3.12 Spray Deposition Methods duce a strip. Strips of 18 mm thickness and
0.5 m width have been produced so far.
In these methods, atomized melt parti-
Solidification rates as high as 10 6 Ks~ 1
cles get deposited on a cooled solid sub-
have been claimed for this process, which
strate, where the droplets solidify to make
can be made continuous and where pow-
a more or less dense deposit, which may be
der handling is completely avoided. Parti-
several millimeters in thickness. The de-
cle sizes vary widely depending on circum-
posit can be removed from the substrate
stances, but a typical size is 150 |tim. The
and subjected to further processing to den-
main difficulty in spray rolling is in ensur-
sify it. The solidification rate experienced
ing that a spray deposit is uniformly thick
by the initial deposit is much higher be-
across the width of the strip. Variations in
cause of conduction cooling, whereas the
thickness should not be more than ± 2 %
later deposits cool relatively slowly. Singer,
for industrial exploitation. A further refine-
who formulated the concept of spray form-
ment of spray rolling is spray peening, in
ing (Singer, 1968) has reviewed the spray
which spray deposition is accompanied by
forming of solid materials (Singer, 1982,
1983). Its application presently includes (a) simultaneous shot peening to consolidate
spray rolling, (b) spray forging, and (c) cen- the spray deposit as it forms (Singer, 1978).
trifugal spray deposition.
2.3.12.2 Spray Forging
2.3.12.1 Spray Rolling In this process, a spray of gas-atomized
In this process (Singer, 1970), a gas-at- metal is directed into a mold or, in some
omized molten stream is sprayed directly cases, onto a flat substrate or collector
2.3 Spray and Droplet (Atomization) Methods 75

which is moved in an appropriate manner Molten


droplets
under the spray by a manipulator. In the
case of a mold, the shape is replicated in
reverse, whereas in the case of a movable
flat collector, the preform shape is deter-
mined by the motions of the manipulator.
A high spray density ensures that the
porosity is only about 1 % and so the pre-
form can be subsequently forged. This pro-
cess has been adopted by Osprey Metals
Ltd. in South Wales, U.K. to produce alloy
steels and superalloys (Brooks et al., 1977).
The spray-forged materials have been Figure 2-13. The ALCOA process to produce splat
shown to have better mechanical proper- particulate by impact of atomized droplets on a rotat-
ties and to be far more isotropic than con- ing cooled drum.
ventional drop forgings.

2.3.12.3 Centrifugal Spray Deposition


cles, and rates up to 106 K s i appear pos-
sible. The particle, or flake, size is quite
This method involves centrifugally gen- variable. Handling and pouring are not as
erating the spray to produce metal prod- easy as with spherical powders, but these
ucts having axial symmetry together with a flakes are subjected to higher quench rates
central hole (Singer and Kisakurek, 1976). than most of the spherical particulates and
With this method, it is also possible to have therefore, a wide range of alloy composi-
very fine-grained non-segregated products tions can be processed.
to be produced under strict atmosphere
control. This could be especially useful for 2.3.12.5 Plasma Spray Deposition
materials such as titanium. A 2-ton com-
Very hot, highly ionized plasma jets are
mercial scale plant is already in operation
commonly employed to melt and to spray
to produce tool and high alloy steels (Rick-
prealloyed powder onto cold substrates
inson et al., 1981). This process has now
(Moss, 1968; Moss and Schuster, 1969;
been renamed Liquid Dynamic Compaction
Jackson etal., 1981; Apelian et al., 1983;
(Ogata etal., 1986) presumably to associ-
Herman, 1988). In one pass of the spray, a
ate it with the solid-state dynamic com-
layer typically 100 jim thick may be de-
paction technique practised on rapidly so-
posited, and thicker deposits can be pro-
lidified powders (Morris, 1980 b).
duced by continuing the deposition pro-
cess. However, there is possibility of self-
2.3.12.4 The ALCOA Flake Process annealing and to minimize this effect a ro-
In this process, gas atomized particles tating water-cooled substrate may be ad-
impinge on the cooled surface of a rotating visable. A jet of inert gas can also be helpful
drum (Fig. 2-13). Here, they form small in diverting the hot gases away from the
splats that leave the drum surface after so- substrate (Cahn, 1978). Metal droplet ve-
lidification and are subsequently collected locities can reach up to 1000 m s " 1 and
and screened. Quench rates depend upon cooling rates approximately 107 K s " 1 . All
the size and velocity of the molten parti- types of metastable effects achieved by
76 2 Rapid Solidification

rapid quenching from the melt have been small cross section through vacuum (Groe-
obtained by flame or plasma spraying also ber and Haneman, 1937), gravity (Serita
(Krishnanand and Cahn, 1976; Giessen et al., 1970) and pressure plus vacuum
et al., 1977; Shingu et al., 1979; Miura et al., (Hinesly and Morris, 1970). A schematic
1982). Further, oxides and ceramic materi- representation of the process is shown in
als can also be easily deposited by spray- Fig. 2-14. Melt penetration is difficult in
ing. Nearly fully dense microstructures view of solidification at the entrance of the
with much lower oxygen content than air mold. However, the unique advantage of
plasma spraying have been produced using this method is that wires of predetermined
a low-pressure environment (Jackson et al., cross-section (mostly circular) can be ob-
1981). These showed substantial improve- tained. A tapering (wedge) mold has also
ments in mechanical properties, but with been used to obtain controlled changes of
limited ductility. section (and thus cooling rate) within a
Two major problems have been encoun- single sample (Falkenhagen and Hofmann,
tered in plasma spraying technology. First, 1952; Esslinger, 1966; Burden and Jones,
the strength of the bond between the sub- 1970 a; Ichikawa et al., 1971). The cooling
strate and the deposit is not always accept- rates measured are 104 K s " 1 at thickness
able in situations involving dissimilar ma- of 0.7 mm and 107 K s~1 at 0.2 mm (Arm-
terials. The problem is particularly acute strong and Jones, 1979).
when the coated part is subjected to ther-
mal cycling, which rise to high stresses at
the coating-substrate interface. Second, the 2.4.2 The Piston-and-Anvil Technique
mechanical properties of the as-deposited Shortly before the Duwez gun technique
material are far from ideal owing to the was perfected, Salli (1958) (Miroshnichen-
presence of internal stresses and micropo- ko and Salli, 1959) proposed the method of
rosity. thinning of a molten droplet by squeezing
it between a stationary anvil and a moving
piston. The melt was transferred to the
anvil by means of a lever and spring device
2.4 Chill Methods in a graphite crucible, allowing the melt
droplets to be caught between a stationary
Rapid solidification is achieved in these anvil and a fast-moving piston. Several
methods by bringing the melt into contact modifications to this basic technique have
with a chill substrate. The various methods been tried out.
involve injecting the melt into a die cavity,
Unlike in the "gun" technique, the foil
or forming the melt into a thin section by
produced in the piston-and-anvil appara-
forging between a hammer or piston and
tus has a uniform cross-section, is devoid
anvil, or extruding the melt on to a chill
of porosity and has a few cm2 in area. This
surface or extraction of melt by contact
technique has been used quite extensively
with a rotating disc. These will be de-
for many scientific investigations.
scribed below.
The crucible used for melting has been
either graphite (sometimes a ceramic in-
2.4.1 The Die Method
sert is introduced) or fused silica. The alloy
These methods involve forcing a liquid can be melted by any conventional method
metal into copper chill-mold cavities of - induction heating (Pietrokowsky, 1963),
2.4 Chill Methods 77

Vacuum outlet

Insulated coolant
container

Coolant bath

Copper mold

Mold cavity

O-Ring

Base plate

Compression nut

Injection tube

Figure 2-14. Schematic of


the liquid quench injection
mold used for rapid solidi-
Aluminum foil fication studies.

levitation melting (Baker et al., 1969) 1967; Baker et al., 1969; Blank, 1972),
(which also has the advantage of eliminat- spring (Ohring and Haldipur, 1971) pendu-
ing the crucible problems in the study of lum (Wang, 1970; Caryll and Ward, 1967),
reactive alloys) or even resistance heating electromagnetic (Harbur et al., 1969) and
(Dixmier and Guinier, 1967; Laine et al., magnetic yoke (Cahn et al., 1976) drives
1971). Gas flame (Pietrokowsky, 1963), have also been employed. Other modifica-
electron beam (Galasso and Vaslett, 1966), tions have also been described in the litera-
plasma jet (Zboril and Posedel, 1970) and ture (Booth and Charles, 1966; Beghi et al.,
arc (Wang, 1970; Ohring and Haldipur, 1969; Tonejc and Bonefacic, 1969; Bletry,
1971) have also been used. 1970; Williams and Jones, 1974). Two
The molten droplets can be released by moving pistons were employed in some
switching off the r.f. generator (in levitation cases instead of one stationary anvil and
melting) or by applying a small gas pres- one moving piston. Fig. 2-15 shows the ba-
sure to the melt container. The falling sic principle of the piston-and-anvil appa-
droplet intercepts a beam of light between ratus.
a source and a photocell and thus triggers The solidification rates achieved in this
the solenoid which in turn releases the technique are typically about 10 5 Ks~ 1 .
piston, through an adjustable delay cir- Even though cooling takes place from both
cuit. Although solenoids have been gener- the sides of the foil (and thus the cooling
ally used to release the piston, hydraulic rate should have been higher), the thick-
(Pietrokowsky, 1963; Dixmier and Guinier, ness of the foil is generally large (up to
78 2 Rapid Solidification

tion. It was found that the higher the pis-


ton velocity and the higher the splat-sub-
strate heat transfer coefficient, the faster
are the attainable cooling rates, although
there is a tendency to approach limiting
values.

2.4.3 Twin-Roller Quenching


This process involves rolling of a melt
stream between two conducting rolls ro-
tating in opposite directions (Chen and
Miller, 1970; Babic et al, 1970 a). The melt
stream is directed vertically downwards
1. Fixed anvil 5. Susceptor
2. Fast-moving piston 6. Finger into the nip of the rolls (Fig. 2-16). Short
3. Copper discs 7. Light source strips of about 10 to 200 |im thickness
A. Silica tube 8. Photo cell
quenched at approximately 105 K s " 1 are
Figure 2-15. Schematic of the piston-and-anvil appa- generally produced. By controlling the pa-
ratus.
rameters carefully, it is possible to produce
very long filaments. Variables in the pro-
cess include the material and diameter of
300 |im) and therefore, the cooling rate is the roller, the roller gap and the speed of
lower. rotation.
The higher cooling rates of the gun tech- The rolls should be hard enough for
nique and the uniform cross-section of the durability and the surface must be ma-
foils produced in the piston-and-anvil ap-
paratus have been achieved simultaneous-
ly by introducing a pressure switch. The
Heater
stream of molten metal ejected from the
gun is caught between the piston-and-anvil Melt
assembly, by synchronizing the release of
the piston with the rupture of the dia- Rollers
phragm (Ramachandrarao et al., 1970). The
foils so produced are 6-7 cm in diameter
and about 100 }im in thickness (Hanuman-
tha Rao et al., 1985).
Modeling of the piston-and-anvil
quenching process has been done (Miya-
zawa and Szekely, 1979). Allowance has
been made for fluid flow effects regarding
the spreading of the slug, convective heat
flow and the actual movement of the piston
after the impact. In representing heat flow,
allowance has been made for the two-di-
mensional transient temperature fields and Figure 2-16. Schematic of the twin-roll quenching ap-
the existence of a mushy zone on solidifica- paratus.
2.4 Chill Methods 79

chined to close tolerances. They are gener- report (Chen and Miller, 1970) indicates
ally made of hardened steel (Chen and that this technique is for the preparation of
Miller, 1970), chromium-plated steel (Babic amorphous solids. However, thicker sec-
etal., 1970 b), copper (Murty and Adler, tions of non-equilibrium crystalline phases
1982) or brass. The two rolls, 5-15 cm in are easy to produce. This contact time can
diameter, are held together with a pressure be increased by introducing a third roller
ranging from 20 to 90 kg and so the ribbon (Budaira and Suito, 1979) on the exit side
is prone to deformation. This can be mini- of the twin rollers or a flexible belt (Sakata
mized by incorporating a silicon rubber and Ishibachi, 1982) running between the
damping pad (Lewis et al., 1979) between rollers.
the core and periphery of the rollers or by Although there is no limit on the quan-
spring loading (Murty and Adler, 1982) to tity of melt that can be continuously rolled,
allow the rollers to be run in mutual con- normally only a small quantity is pro-
tact without application of excessive pres- duced. Durand et al. (1976) reported a ver-
sure. The rollers can be cooled by liquid sion designed to produce up to 4.5 kg lots
nitrogen for continuous operation. The per run via a tundish.
rollers can rotate at speeds ranging from
100 to 6000 rpm. For a successful operation of the twin-
Variations of this standard configura- roll quenching apparatus, very stringent
tion have been reported. These help in pro- control is necessary in comparison with
ducing splat flakes (Sankaran and Grant, single roller melt spinning. Surface crack-
1980; Singer and Roche, 1980; Lakshmiku- ing of the foils produced in the twin-roller
mar et al., 1980) or continuous lengths of apparatus appears to be a problem. Fur-
ribbon (Lewis et al., 1979; Murty and Adler, ther, as in melt spinning and melt extrac-
1982; Fujiwara et al., 1982). The process tion methods, roller life is another prob-
has been carried out with the roller axes of lem.
rotation vertical instead of horizontal to Process modeling of the twin-roller tech-
permit lateral dispersal of furnace debris nique has been carried out (Miyazawa and
(Leontic et al., 1978) or excess liquid metal Szekely, 1981; Murty and Adler, 1982) to
which otherwise accumulates between the optimize the parameters that yield the best
rollers above the roll gap. results. It has been shown that the most
A serious problem associated with this important variables are (a) roller gap, (b)
technique is the very short contact length angular velocity of the rollers, (c) feed rate
between the melt and the rollers. It has of the material, and (d) physical properties
been estimated that for a jet of 1 mm dia of the material. If all the parameters are
and a roller dia of 80 mm, the contact considered, there exists only a narrow
length is only 6.3 mm which, for a roll range of these parameters that gives a sta-
speed of 6000 rpm gives a contact time of ble mode of operation. It was demon-
about 0.25 ms (Davies, 1978). Because of strated that the diameter of the circular jet
this, the sample may still be hot and cools is a critical parameter governing to a great
by radiation (at rates < 103 K s~x) (Davies extent the nominal width and thickness of
et al., 1978), losing thereby the benefits of the resultant foil product. Further, to get a
rapid quenching. Amorphous phases can- continuous foil, the ratio of the jet velocity
not be produced easily by this technique to the roller velocity should be between 0.5
(Davies et al., 1978), although the very first and 1.0.
80 2 Rapid Solidification

2.4.4 Melt Spinning Process mine the experimental conditions which


will allow the fabrication of a continuous
Melt spinning is the most commonly
wire, i.e., to prevent the breakdown of the
used method now-a-days to produce long
molten jet into droplets before it solidifies.
and continuous ribbons. In fact, the devel-
Typically, the orifices used to create the
opment of this technique has been mainly
liquid jets are circular with diameters rang-
responsible for the accelerated progress of
ing from about 50 to 1250 jim. The pres-
rapid solidification technology since the
sure required to eject the molten metal
1970's. A wide variety of materials includ-
from the orifice increases as the orifice area
ing steels, aluminum, copper, titanium-base
decreases. This aspect, plus the inherent
alloys and superalloys have been success-
difficulties in keeping small orifices open
fully cast as filaments using this process.
and free streaming, sets the lower size limit
The melt spinning process derives its
for the orifices. The upper size limit is pri-
name from the fact that it involves the ex-
marily set by the length of the column re-
trusion of molten metal to produce fine
quired to solidify large streams with most
fibers in a way which is akin to that used
of the quenchants used.
for the manufacture of synthetic textile
The orifices (nozzles) are made of a suit-
fibers. The melt spinning process can be
able refractory material, the exact nature of
broadly divided into two categories de-
which depends on the type of metal to be
pending upon whether an orifice is in-
processed. Successful long-term operation
volved or not. Each one of these processes,
requires that the orifices (and crucible) be
in turn can be further subdivided into two
stable (i.e., non-reacting, non-eroding) with
variants depending on whether the molten
respect to the alloy being cast. For exam-
metal stream is solidified in flight or against
ple, the best orifice material for aluminum
a chill. These will be, in subsequent sec-
and its alloys has been found to be alumina
tions, referred to as free-flight melt spin-
with a silica content of <0.5%. Table 2-2
ning (FFMS) and chill-block melt spinning
presents a list of suitable orifice materials
(CBMS), respectively (Hubert et ah, 1973).
for different metals and alloys.
The liquid metal jet is free-streamed into
2.4.4.1 Free-Flight Melt Spinning a chamber containing an atmosphere suit-
This process (Pond, 1959, 1961) consists able to generate a very thin film around the
of creating and subsequently solidifying a
stable liquid metal jet. Generally, the stable
jet is created by ejecting the liquid through Table 2-2. Orifice materials for melt spinning.
an orifice and the metal is then solidified
Metal Orifice material
by passage through a gaseous or liquid
quenching medium. Fig. 2-17 a illustrates Aluminum Alumina
the principle. Owing to the relatively high Tin Oxidized steel, pyrex glass,
surface tension and low viscosities of liquid graphite
metals, the small diameter jets typically Lead Steel, pyrex glass, graphite,
used in the process will form droplets un- alumina
less solidified and/or stabilized within a Zinc and alloys Pyrex and vycor glass, mullite,
alumina, SiC
short distance from the orifice. Thus, the
Magnesium Armco iron
major question governing the successful
Grey iron Dense alumina, sapphire
performance of this technique is to deter-
2.4 Chill Methods 81

Pressure Pressure

— Molten metal Molten metal

Liquid stream
Orifice Orifice « — Liquid stream
Heat removal
Quenchant
Liquid solid-Interface Fiber (ribbon) Figure 2-17. Schematic illus-
tration of the (a) free-flight
Fiber (wire) Chill block melt spinning and (b) chill-
block melt spinning tech-
(a) (b) niques.

liquid jet, thereby preventing its break-up the critical extrusion velocity decreases
before it is fully solidified. A stopper rod or from 12 to 3 m s " 1 , as the orifice diameter
surface tension of the melt may be used to increases from 50 to 300 jum.
prevent pouring until melting is complete. The temperature profiles in the solidify-
The simplest technique uses ambient air, ing liquid jet under FFMS have been ana-
which is most efficiently introduced as a lyzed (Ostroumov, 1959; Kavesh, 1978). As
pressurized stream which accelerates the with all casting processes, the quench rates
solidification process. Further, the high increase as the product dimension (in this
pressure, if it exceeds the partial pressure case, diameter) decreases. Typically, the
of the alloying elements, can prevent their quench rate associated with 50 (im diame-
vaporization. This was found to be the case ter metal jet is about 105 Ks~ x and de-
in suppressing zinc evaporation during creases to 10 K s~1 when the jet diameter is
melt spinning of brass. Air-water fog quen- 1250 jim. A cooling rate of about 104 K s~1
chants have also been successfully used was claimed for 150 jim diameter glassy
with cast iron. Liquid quenchants (Kavesh, filaments of Fe 38 Ni 39 P 14 B 6 Al 3 (Kavesh,
1978) and liquid nitrogen (Shepelskii and 1974). A detailed account of this process
Zhilkin, 1969), inert gases (Mottern and has been given by Pond et al. (1976).
Privott, 1973) and brine have also been Both microcrystalline and amorphous
used to both stabilize the molten metal jet filaments have been produced by this pro-
and to accelerate its cooling rate. cess. Microcrystalline wires generally ex-
For a given diameter, experimental and hibit a bamboo-type structure wherein a
theoretical considerations dictate a mini- single grain extends across the entire cross-
mum jet speed which is required to obtain section of the wire. The filament surface
a continuous jet. For a given liquid and exhibits a microscopically rough, dendrit-
orifice diameter, the stable length of the ic-type pattern.
jet increases with increasing velocity. Typi- The basic advantage of this technique,
cally, a jet is ejected from the orifice with a sometimes also known as melt extrusion,
velocity of 2 to 10ms" 1 , yielding filament in addition to its obvious simplicity, is to
production rates of about 1 to 10 g s " 1 per allow the production of continuous fila-
stream. Multiple orifices can be used to ments with a circular cross section, more or
increase the productivity of a given stream. less directly usable in wire-type applica-
Available data suggest that for aluminum, tions. Monsanto Corporation have devel-
82 2 Rapid Solidification

oped this technique for, among other ap- ness, while thinner tapes could be pro-
plications, production of ferrous-base tire duced at speeds of about 10000 rpm. Bos-
cord. well and Chadwick (1976) used a cup of
380 mm diameter and the whole process
was carried out in vacuum. It was claimed
2.4.4.2 Chill-Block Melt Spinning (CBMS) that the vacuum promoted formation of
Originally patented by Strange and Pirn more uniform ribbons by minimizing aero-
(1908), this process involves directing a dynamic disturbances. A further variant
molten metal jet onto a cold, moving heat involves jetting on to the cylindrical sur-
sink where the jet is reshaped and solidi- face of a disk or roll rotating about a hor-
fied. The jet on impingement with the disk izontal axis (Liebermann and Graham,
forms a melt puddle, of thickness approxi- 1976). Glassy ribbons of about 10 to 40 |im
mately equal to and length about double thickness were produced in Fe-Ni-B al-
that of the jet. As solidification begins, the loys at speeds of 20 to 40 m s~*. Chen and
ribbon is expelled from the surface of the Miller (1976), on the other hand, cast the
wheel, as schematically illustrated in Fig. jet on to the convex inner surface of a
2-17 b. Since the orifice can be placed very quench wheel rotating about a horizontal
close to the chill block, and the jet stream- axis. This imparts radial acceleration to the
ing distance thereby minimized, jet stabil- ribbon which provides forced contact with
ity is not quite as critical in CBMS as in the chill surface, but has only a limited
FFMS. contact time with the chill, allowing con-
In the original version of Pond (1958), tinuous operation. The process, however,
the chill block, rotating about a vertical suffers from the disadvantage that the rib-
axis, had a shallow concave impression. bon solidifies with a curvature, reflecting
Long and continuous filaments with 1 to the disk diameter and the angle of sloping
100 |im thickness could be produced at surface. The cooling rates in all the above
speeds of 15 to 300 m s " 1 . Pond and Mad- variants can reach up to 10 6 Ks~ 1 , thus
din (1969) changed the design by ejecting making it possible to produce glassy phases
the melt through a fine orifice to impinge in a large number of alloy systems.
onto the inner surface of a rapidly rotating The most common method of CBMS, in
crucible. The orifice traverses rapidly par- which the molten metal stream impinges
allel to the axis of rotation, thus producing on the outer rim of a rotating disk, was
a helix of rapidly solidified filament. The developed by Bedell (1975). Here, the cen-
radial acceleration imparted by the cruci- trifugal force acts to throw the ribbon off
ble to the liquid results in efficient spread- the chill surface at rates of about 50 m s ~1
ing of the stream and promotes good ther- and by internally water cooling the disk,
mal contact between the melt and the heat the process can be made continuous. De-
sink. Following the successful application tailed accounts of the CBMS process have
of this method to produce specimens suit- been given by several workers (Hilzinger
able for mechanical testing (Masumoto and Hock, 1981; Jech et al., 1984; Lieber-
and Maddin, 1971), this technique has mann, 1984 a). The following paragraphs
been continuously used by Masumoto and deal with the methods of optimizing the
his group in Japan. A crucible diameter of several parameters involved in CBMS.
100 mm and rotation speeds of about Crucibles: Selection of crucible material
5000 rpm yielded tapes of 20-40 \im thick- is based on chemical compatibility with the
2.4 Chill Methods 83

melt, temperature capability, thermal placed by arc melting the alloy sample on
shock resistance, low thermal conductivity the orifice of a water-cooled copper anode.
and low porosity (gas permeability). Expulsion of the melt on to the rotat-
Crucibles can be made by dipping a wax ing chill block was achieved with applied
mandrel in commercial shell mold refrac- pressure differences, preferably exceeding
tory slurry. Repeated dippings build the about 0.5 bar. The newer version incorpo-
crucible wall to the desired thickness. Intri- rates an arrangement to feed, automati-
cate nozzle geometries may be molded in cally, solid granules of alloy into the melt
wax and duplicated in the shell mold. Alu- zone in order to process larger quantities
mina shell mold crucibles are thermal continuously into ribbon or flake, depend-
shock-resistant, have low thermal conduc- ing on the conditions. Masumoto et al.
tivity and are compatible with most engi- (1980) used levitation melting to melt nio-
neering alloys. The major disadvantage of bium, chromium and titanium-base alloys
the shell mold crucible is that it is not fully in a chamber filled with argon. When melt-
dense and therefore becomes permeable to ing was complete, the alloy was ejected by
pressurizing gases. switching off the current to the levitation
Dense alumina is commercially avail- coils and allowing the melt to drop because
able and nozzles can be shaped by ultra- of the difference in pressure between this
sonic abrasive machining. Fine holes with chamber and the one containing the wheel
circular, clean and sharp edges can be pro- (Fig. 2-18). The ejection of the molten
duced. These dense alumina crucibles are metal was achieved in some cases by melt-
gas tight and are usable up to temperatures ing a fuse plug (usually Mo over Ti) over
in excess of 1600°C. The major disadvan- the nozzle (Rowe and Amato, 1987). Other
tage is susceptibility to cracking when in- designs have also been reported (Ray and
ternally heated at a high rate. This can be Clemm, 1986).
minimized by using a susceptor to heat Wheels: Wheels for melt spinning have
the crucible externally or by jacketing the been made from a variety of materials, al-
crucible to reduce thermal gradient. though copper is the most popular one.
Quartz crucibles are useful for tempera- Primarily, the aim is to select a wheel mate-
tures below 1400°C. They are thermally rial which will extract heat from the ribbon
shock-resistant, relatively inexpensive and as quickly as possible, while allowing the
can be readily purchased with nozzles in puddle to wet the wheel and form the rib-
place. Temperature limitations and possi- bon. Cooling of the wheel is desirable for
ble reactivity with the melt are the major long runs such as would be necessary in
disadvantages. commercial operations.
Attempts have been made in recent times Wheel surface texture and cleanliness
to quench reactive melts, such as those influence both product quality and form
based on titanium, molybdenum, chro- (Huang and Fiedler, 1981). The wheel side
mium, and niobium. The system devised by of vacuum cast ribbon is almost an exact
Whang and Giessen (1983) (Whang, 1984) replica of the wheel surface. Progressive
is similar to the one used to melt spin wear of the chill surface is a serious prob-
lanthanum-based alloys (Tutzauer et al., lem, but can be counteracted by refinishing
1980). In this apparatus, the conventional the wheel during every turn. The casting
arrangement of r.f. melting and pressurized equipment may also be designed to delay
expulsion from a quartz nozzle was re- the wear of the wheel, by carrying out the
84 2 Rapid Solidification

Specimen chamber

Argon gas inlet


Stainless steel
vessel

Molten alloy

Copper levitation (Cooling water)


coil

— Supporting stand
Shutter
of specimen
Quartz nozzle
Argon gas inlet

Figure 2-18. Schematic il-


lustration of the melt-spin-
ning apparatus used by
— Stainless steel Masumoto and his group
vessel in Japan.

casting in such a way as to minimize the et al., 1973; Mitera et al., 1979; Jech et al.,
ratio of product tape area to the chill sur- 1984), chromium (Narasimhan, 1979) and
face area. This can be done by employing a molybdenum (Ray, 1979).
larger wheel diameter, or by continuously Chamber Atmosphere: Spinning can be
displacing the crucible-nozzle unit along carried out in vacuum, air, inert atmo-
the vertex of the cylindrical quenching sphere, or reactive gas depending upon the
body during the operation so that the worn chemical and physical properties of the
track spirals along the wheel. Both these charge. Alloys susceptible to oxidation can
measures offer the additional benefit of re- be cast in vacuum or inert gas. Chamber
duced surface temperature. atmosphere influences ribbon quality with
The hardness of the substrate is found to respect to surface smoothness and edge
be one of the factors that influences the definition. Many alloys cast in vacuum
wear resistance because a roll made of age- have regular, smooth edges and wheel-side
hardened Cu-2% Be alloy showed com- surfaces which are almost exact replicas of
paratively little wear even after much the wheel surface. The same alloys cast in
longer service than pure copper (Hilzinger helium may have ribbon edges with a
and Hock, 1981). Moreover, all tapes cast rough 'saw-tooth' appearance and wheel-
on copper show perceptible traces of cop- side surfaces with pits and irregularities.
per on their contact side, which is entirely Casting in argon aggravates the condition
absent in the tape cast on the Cu-Be (Jechetal., 1984).
wheel. Other wheel materials used to date Ejection Pressure: Ejection of the melt
are steel (Chen and Miller, 1970; Hubert from the crucible is accomplished by gas
2.4 Chill Methods 85

pressurization. Although an inert gas is as a function of melt ejection pressure, tem-


generally used, any gas compatible with perature, flow rate, wheel velocity, atmo-
the melt can be used. Ejection pressures of sphere, etc.
5-70 kPa have been used depending upon In all the models described in the litera-
the desired melt delivery rate. ture, the ribbon is visualized as having
The use of high ejection pressure results formed by transport of momentum and/or
in improvement of the wetting pattern and heat between the melt puddle and the chill
hence better thermal contact between the surface. Two limiting cases and a mixed
melt puddle and the rotating substrate case can be distinguished: (a) thermal trans-
(Huang, 1982). port control, (b) momentum transport con-
Wheel Speed: Increasing the wheel speed trol, and (c) coupled thermal and hydro-
leads to the formation of thinner ribbons. dynamic regime. Further, the liquid puddle
For example, an Fe 4 0 Ni 4 0 B 2 0 alloy cast on is visualized as consisting of a "bound-
a 250 mm diameter copper wheel rotating ary layer" zone in which the thermal and
at a substrate velocity of 26.6 ms""1 pro- momentum effects of the chill surface are
duced a ribbon of 37 jim thickness, while at strongly felt and an outer zone where the
a velocity of 46.5 m s " 1 , the ribbon thick- effects of the chill surface have not yet pen-
ness was only 22|im (Liebermann, 1980 a). etrated.
The time of contact of the solidifying If thermal transport is much faster than
material on the chill block is of decisive momentum transport, a solid boundary
importance in the fabrication of amor- layer will form adjacent to the chill surface
phous metallic filaments. If the filament de- and propagate into the melt puddle to
taches from the disk too soon, crystalliza- form the ribbon. In this case, material
tion and phase decomposition may occur within the "frozen" layer will be in motion
during secondary cooling from the melt in at a velocity equal to that of the chill sur-
the solid state. In extended operations, this face. A sharp transition in velocity occurs
can be avoided by deliberately increasing just outside of the frozen layer; the width of
the filament contact time by employing a this transition zone depends on the viscos-
spring-loaded auxiliary disk in contact ity-temperature characteristic of the alloy.
with the main melt-spinning disk (Bedell, In the outermost zone, the melt will experi-
1975). ence cooling but only slight momentum
The nozzle tip is usually about 3 mm transport (see Figure 3 of Kavesh, 1978).
from the wheel surface although much On the other hand, if momentum trans-
shorter gaps (about 0.35 mm) have also port from the chill surface is much faster
been used. The optimum direction of melt than thermal transport, a liquid boundary
jet impingement has been found to be 6 to layer will be dragged out of the melt puddle
15° from the local substrate normal at the by the moving substrate to solidify farther
point of jet impingement. downstream. In this case, the velocity gra-
Modeling of the CBMS process has been dient will be continuous across the depth
done both empirically and theoretically of the puddle.
(Kavesh, 1978; Pavuna, 1981; Huang, 1982; Determination of which of the limiting
Katgermann and Van den Brink, 1982; cases is likely to exist is based on the trans-
Takeshita and Shingu, 1983,1986). Empiri- port properties of the melt. Although till
cal relationships have been established, recently the thermal transport mechanism
with little scatter, for the ribbon geometry has been considered to be of importance
86 2 Rapid Solidification

because of the small value of the Prandtl ing rates. Thus, the centrifuge melt spinning
number of liquid metals (which means the technique has been developed, the merits
large thermal boundary layer thickness in and limitations of which have been sum-
comparison with the momentum bound- marized very recently (Baram, 1990).
ary layer thickness), it is now recognized In this technique (Rosen et al., 1986 a,
that a combined thermal-momentum trans- 1987), a rotating disk holds the rotating
port model explains the experimental ob- crucible. The melt is ejected from the cru-
servations more satisfactorily. Although cible by centrifugal force, through an ori-
these approaches have partial success in fice in the crucible wall, and impinges on
describing the experimental results, the the inner surface of the copper rim, which
complex nature of the ribbon formation serves as the quenching substrate and ro-
process and the factors which control it are tates in a direction opposite to the disk
still to be described by a physically consis- holding the crucible. The rotational veloc-
tent model. ities of both the disk and the rim can be
The solidification rates achieved in this adjusted, as also the crucible orifice diame-
process are typically about 1 0 6 K s " 1 ter and the distance from the rim. In con-
(Shingu and Ozaki, 1975; Davies and Lewis, trast to conventional CBMS, centrifuge
1976) and the ribbon is only a few mm melt spinning employs higher metal ejec-
wide. Pavuna (1981, 1982) has suggested tion pressures (up to 280 kPa) together
methods by which good quality tapes can with higher extraction velocities (up to
be produced. 95 ms" 1 ) (Rosen etal., 1986b). Paramet-
CBMS has been modified to produce he- rization (Rosen etal., 1986a) and mathe-
lical glassy alloy ribbons (Liebermann, matical modeling studies (Baram, 1988 b,
1981), composite alloys and multilayer de- 1990) have shown that this new technique
posits (Tenwick and Davies, 1984; Soder- produces ribbons solidified at rates of
hjelm and Mandal, 1985; Liebermann, 108 K s~1 and with better dimensional uni-
1985). formity and improved wetting pattern than
in conventional melt spinning methods.

2.4.4.3 Centrifuge Melt Spinning


2.4.4.4 Planar Flow Casting Process
All the variants of the chill block melt
spinning techniques described above suffer The continuous production of tapes by
from some inherent problems. Some of the chill block melt spinning (CBMS) pro-
these are (i) short contact times between cess has been widely used. However, since
the wheel and the melt leading to poor heat a circular orifice is used, the tapes so pro-
transfer, (ii) restricted wetting of the casting duced have a width not much greater than
rim by the liquid metal (at low ejection the jet diameter and necessarily there is a
pressures) due to the formation of an air limit up to which the width can be in-
boundary layer (Baram, 1988 a) and (iii) "ca- creased. Accordingly, the width of the
tastrophic sticking" (Liebermann, 1984 b) tapes produced by the CBMS process is
at high substrate velocities. Although these limited to a few mm (typically about 5 mm).
can be overcome by increasing the ejection To produce wider ribbons of uniform
pressure (Huang, 1982), this leads to an cross-section, a rectangular melt puddle is
increased ribbon thickness (Kavesh, 1978; required and that cannot be produced by a
Liebermann, 1981) and hence lower cool- cylindrical jet (Anthony and Cline, 1978,
2.4 Chill Methods 87

1979). Further, rectangular jets degenerate


rapidly in a complicated fashion (Cline and Nozzle wall
Anthony, 1979), owing to the low viscosi-
ties and high surface tensions of metallic
Substrate
melts. This problem was solved by Nara-
simhan (1979), who invented the Planar
Flow Casting (PFC) Process. In this pro-
Substrate motion
cess, illustrated in Fig. 2-19, the molten
metal is forced through a slotted nozzle in Figure 2-19. Schematic of the planar flow casting pro-
cess.
close proximity (about 0.5 mm) to a rotat-
ing chill substrate. The melt puddle is con-
strained to a stable, rectangular shape by preparation of wide tapes with teeth or
the lips of the nozzle and the substrate. other geometries have been made without
Flow is basically pressure controlled, but it the need to punch the teeth out with a
is also critically dependent on the substrate die. The teeth were formed by casting a
surface speed, nozzle width (parallel to the low-thermal-conductivity pattern onto the
direction of ribbon motion) and nozzle- wheel, causing the ribbon to be brittle and
substrate gap. easily separated from the very tough non-
An important feature of the PFC pro- brittle remainder of the ribbon (Luborsky
cess is that it is intrinsically scalable. It has et al., 1983). Another novel variation is the
been reported that ribbons up to 300 mm preparation of helical rather than straight
in width have been produced by this pro- ribbons (Liebermann, 1981). The helical
cess (Heineman, 1985), which can also be ribbon can be wound without producing
used in an inert atmosphere or vacuum. the degradation in properties associated
The tape comes away from the roller at with the bending stresses produced on
a speed of 900-1800 m min" 1 and so winding up straight ribbon into a core. By
winding of this into a coil could be a prob- combining this helical-ribbon technique
lem. A system has now been devised (Nara- with the technique for producing a cut-out
simhan et al, 1981) to capture the ribbon pattern, electric motor stators can be pre-
in a winder in a matter of seconds after the pared directly from the cast ribbon without
initiation of a cast. the need for punching.
PFC has a few distinct advantages over Gutierrez and Szekely (1986) analyzed
the CBMS process. Firstly, moving the the PFC process using a mathematical
nozzle closer to the substrate increases uni- model based on the principles of lubrica-
formity of quench rate and secondly, the tion theory, capillary fluid dynamics and
melt puddle is stabilized and suffers less solidification heat transfer. The model sug-
perturbation. The thickness of the tapes gests that the most important parameters
varies from 20 to 100 ^m and cooling rates of the PFC process are (a) the melt flow
achieved are about 10 6 Ks~ 1 . However, rate, (b) the wheel velocity, (c) the nature of
care must be exercised to maintain a fixed the mechanical and thermal contact at the
nozzle-substrate gap because it signifi- splat-wheel interface, (d) the geometry of
cantly affects ribbon dimensions, smooth- the system and (e) the material properties.
ness and quench rate. It has been shown that satisfactory perfor-
Some improvements have been effected mance of the PFC process depends on a
to the basic PFC process. For example, delicate balance between capillary pro-
88 2 Rapid Solidification

cesses in the meniscus and solidification dendritic structure in these wires is often
phenomena underneath the puddle. along the direction of the wire unlike in
It should be noted that perturbation of melt-spun ribbons where they tend to grow
the melt on the wheel by the gas boundary transverse to the casting direction. The
layer (Huang and Fiedler, 1981) and sur- cooling rates achieved are reported to be
face roughness of the wheel etc. are sub- about l O ^ s " 1 (Ohnaka et al., 1985). A
stantially reduced because of the con- wide variety of ferrous and non-ferrous al-
straint of the melt imposed by crucible. It loys have been cast into amorphous or mi-
has been calculated that a momentum, crocrystalline wires.
rather than a thermal, boundary layer con- This process has the advantage of pro-
trols the ribbon dimensions (Vincent et al., ducing wires of even those alloys which
1982). are difficult to draw by the conventional
methods. The wires produced by this pro-
cess have been extensively characterized
2.4.5 In-Rotating Water Spinning for their microstructural, mechanical and
(INROWASP) magnetic properties by many Japanese
This is a modification of the melt spin- teams.
ning technique in that instead of allowing
the stream to impinge on to the interior of
2.4.6 Taylor Wire Process
a rotating drum, the melt stream is ejected
into rotating water. In this process (Ohna- This technique can be used to produce
ka, 1985; Masumoto et al., 1981; Ohnaka fine wires of uniform cross section (Taylor,
et al., 1985), a jet of molten metal is ejected 1924). In this process, a metallic rod con-
through a quartz nozzle (80 to 200 |am di- tained in a glass tube is melted. The glass is
ameter) into a liquid cooling layer (usually softened due to contact with the molten
water) formed by centrifugal force on the metal and it can then be drawn, while act-
inner surface of a rotating drum of 400 to ing as a continuous mold crucible during
600 mm dia. The speeds of the coolant and the solidification of the metal, ensuring
of the melt jet are controlled by the rota- regular surface and diameter of the wire
tion of the drum and by the ejection gas (Fig. 2-20). The composite product ob-
pressure, respectively. In this process, tained, consisting of a metallic wire in a
which is somewhat similar to the Rapid glass sheath, is collected on a rotating
Spinning Cup process described earlier for drum at speeds of about 5 m s~1. A critical
the production of powder (see Section aspect of this technique concerns the
2.3.4.5), a wire can be formed by making availability of sheath material having a
sure that the jet solidifies before being sub- sufficient chemical inertness towards the
jected to disturbance. molten metal used, as well as a softening
The distance between the nozzle tip and temperature consistent with the melting
the coolant surface and ejection angle, the point of that metal. In addition, the neces-
depth of the coolant layer and the coolant sity of removing the sheath by a relatively
temperature are some of the important simple treatment might place further limi-
variables which need to be controlled and tations upon the choice of the glass mate-
varied depending on the alloy being cast. rial to be used.
The product of this technique is a con- Cooling in this process is predominantly
tinuous wire of round cross section. The by convection and the rates are in the
2.4 Chill Methods 89

2.4.7 Melt Extraction Process


As mentioned earlier, the melt spinning
Metal rod methods can produce fibers and ribbons
continuously. However, the material com-
Glass tube patibility problems (of melt with crucibles,
orifice, or stream stabilizing sheaths) in-
Heating coil crease enormously as the melt temperature
and reactivity increase. The melt extrac-
tion methods overcome some of these
Tension problems (Pond, 1959; Pond et al, 1976;
Maringer and Mobley, 1974, 1978 a, b;
Fiber and sheath Maringer et al, 1976; Collings et al, 1978;
Robertson et al, 1978).
Figure 2-20. Schematic illustration of the Taylor wire Melt extraction differs substantially
process. from melt spinning in that no orifice and
no liquid jet is involved. It is a process
wherein the periphery of an appropriately-
shaped, rotating heat-extracting disk con-
tacts a source of molten metal. The metal
solidifies over the area of contact and ad-
range of 104 to 106 K s " 1 for wires of 50 heres to the disk for a short residence time
down to 2 jim diameter (Bunge, 1976). (of the order of milliseconds), and then it is
Fibers from a wide range of metals have spontaneously released and thrown free in
been produced in this way including steels, the form of a filament or staple fiber. There
copper and noble metals as well as low- are several variants of the process. For ex-
melting metals (Manfre et al., 1974; Bunge, ample, if the melt is contained in a crucible,
1976; Pardoe et al, 1978). The production, as schematically shown in Fig. 2-21 a, the
properties and uses of "microwires" made process is called Crucible Melt Extraction
by this process have been reviewed by (CME). On the other hand, if the crucible
Donald (1987). is eliminated by melting the end of a rod to
A modified version of this technique has produce a molten pendant drop, shown in
been used by Goto and coworkers for a Fig. 2-21 b, it is called Pendant Drop Melt
variety of alloys. A major problem in this Extraction (PDME).
technique is the contamination of the ma-
terial by the glass sheath. This can be
2.4.7.1 Crucible Melt Extraction (CME)
avoided by choosing a glass compatible
with the material in terms of chemistry, Crucible Melt Extraction is a process
viscosity and melting temperature. Micro- wherein the periphery of a rotating heat
structure, mechanical and superconduct- extraction disk is brought into contact
ing properties of a variety of microcrystal- with the surface of a source of molten metal
line and amorphous alloys (copper, steels, (Fig. 2-21 a). The disk is normally water
stainless steel, iron, silver, gold and silver- cooled and is rotated about an axis perpen-
copper alloys, Pd-Si alloys, F e - P - C - B dicular to the plane of the disk and parallel
alloys) have been evaluated (Goto et al, to the plane of the molten surface. The melt
1974, 1977). surface is contacted by the disk either by
90 2 Rapid Solidification

Clean, quiet, flat


melt surface , Wiper Pendant drop Melt stock
Rotating extracting disc
Filament
Heat source

Filament

Induction
furnace Rotating Wiper
extracting disc

(a) (b)
Figure 2-21. Sketches illustrating the principles of (a) crucible melt extraction and (b) pendant drop melt
extraction.

lowering the disk or raising the crucible. As The disk has a wedge type periphery.
the periphery of the disk passes through The wedge angle is 90° and the periphery is
the molten metal, the metal solidifies onto normally slightly rounded. For the same
and adheres to the disk. This solidified area of contact between the melt and the
metal is extracted from the melt, still cling- disk, greater speed limits the time during
ing to the disk periphery, and continues to which solidification can occur and, there-
cool. As a result of thermal contraction fore, limits the thickness of the product. A
and centrifugal force, the metal in the form decrease in the depth of penetration of the
of a fiber, is then spontaneously thrown free disk into the melt will lead to the produc-
off the disk after a short residence time. tion of a smaller (and rounder) product.
Materials with high surface tensions (e.g. The materials used for the disk include
steels) give coarse fibers and large particu- aluminum, copper, brass, various steels,
lates, while finer fibers/particulates can be nickel and molybdenum. Copper has been
produced in alloy systems with low surface the most popular material in view of its
tensions (e.g. lead-base alloys). The solidifi- high thermal conductivity, easy machin-
cation rate for stainless steel has been mea- ability, durability and relative cheapness.
sured as about 5 x 104 K s " 1 . Fiber shapes can be controlled by disk
The important elements of the process geometry as well as by the extraction
are (i) the melting system, (ii) the disk drive, parameters of disk speed and depth of im-
(iii) the disk geometry and properties, (iv) mersion. Fiber in the shape of ribbon, or
the feed system and (v) the surface chemis- with C-, D-, and L-shaped cross sections
try of the melt. can be cast simply by altering the shape of
The disk of about 20 cm diameter is ro- the disk periphery. Staple fibers of any par-
tated smoothly at controlled speeds rang- ticular length can be cast by putting suit-
ing from 200 to 2000 rpm. The fiber is thus able indentations in the periphery at de-
produced at rates of 1.5 to 15ms" 1 . The sired spacings.
disk has to be water cooled to extract the The source of molten metal should have
heat from the solidifying fibers and also a clean, stable surface to have uniform
from the bath radiation. rapid solidification processing and for uni-
2.4 Chill Methods 91

form product dimensions. It is essential to for filaments having effective diameters be-
use a wiper to remove the metal debris low 25 (im, the quench rate can exceed
from the disk edge. 1 0 6 K s " 1 (Maringer and Mobley, 1979).
(The effective diameter is the diameter of a
circle of the same cross-sectional area as
2.4.7.2 Pendant Drop Melt Extraction the irregularly shaped filament.)
(PDME)
The major disadvantage of PDME is
Pendant Drop Melt Extraction is very that it is unsuitable for bulk production
similar to CME except for the way in since the process relies heavily on the equi-
which the molten metal is supplied to the librium droplet size governed by surface
disk periphery. Here, the end of a rod of tension forces.
material 6 to 25 mm in diameter is melted Although CME and PDME share the
to form a pendant drop, as shown schemat- ability to produce fibers and filaments of a
ically in Fig. 2-21 b. When the droplet con- wide variety of metals and alloys, there are
tacts the edge of the heat extracting disk, some recognizable differences. CME lends
the filament is formed in the same way as itself to the casting of heavier cross-sections
in CME. Once fiber production has begun, because the massive melt supply enables
the intensity of heating and the feed rate one to exert considerable control over the
are adjusted to stabilize a continuous cast- area of contact between the melt and the
ing process. By adapting a carousel to the disk surface. CME also lends itself to the
system (Stewart et al., 1974), the filament use of multiple edges, since the extent of
can be collected as a continuous coil. Like the melt surface can be easily expanded
in CME, by notching the disk, staple fiber through the use of larger crucibles.
can be produced. Such fibers can be made PDME, on the other hand, easily pro-
of almost any length and diameter (L/D) duces fine fiber, is readily adaptable to vac-
ratio. These are know as L/D powders. If uum or inert gas enclosed systems and is
L/D is 10 : 1 or less, the particles flow freely ideally suited to produce small quantities
and may be handled as powder. of reactive materials for which suitable
The greatest single advantage of PDME crucibles are not readily available. How-
is the elimination of the crucible and thus ever, it is very difficult to get a suitable
it is possible to produce fibers of high-melt- droplet from alloys with a large liquidus-
ing-point and highly reactive materials solidus range, or with a miscibility gap in
with little difficulty. Further, green powder the liquid phase. It is also difficult to main-
compacts, either pre-alloyed or mixed as tain a pendant drop with materials such as
elemental powders, may also be used as silver or copper, which have exceptionally
starting materials. A great variety of metals high thermal conductivities.
and alloys, including titanium alloys and The interrelationship between various
superalloys, have been converted to fiber process variables and product dimensions
by this method. The effective diameters has been evaluated largely on a predictive/
range from 15 to 1500 jim. theoretical basis (Maringer and Mobley,
Quench rates associated with the melt 1978 b).
extraction process depend strongly on the Maringer et al. (1978) produced L/D
thickness of the cast filament. For steel types of powders of Ti-6 A1-4V by PDME
filaments of 300 jiim effective diameter, and subjected them to vacuum hot press-
the quench rate is 102 to 103 K s ~ \ while ing or hot-isostatic pressing to produce
92 2 Rapid Solidification

sound billets with acceptable mechanical This method has several technological
properties. Thus, melt extracted staple advantages over classical continuous cast-
fibers may provide an alternative to the ing. This requires no fabricated, lubricated
types of metal or alloy powder currently in or reciprocating molds nor any complex
use. roller guide system for withdrawing the
CME has been brought into commercial cast product.
production. Some hundreds of tons of The width of the product is equal to the
CME mild and stainless steels are used ev- width of the slot and strips exceeding
ery year for reinforcing refractories and 25 cm in width have been cast. In this
concrete. sense, this process is similar to the PFC
process. However, in the latter, the thick-
ness is somewhat lower. The thickness in
2.4.8 Melt Drag Process
the melt drag process can vary from 25 to
The Melt Drag process takes its name 1000 jim, with the foils cooling at rates
from its main feature, viz., the molten metal from 106 to 103 K s " 1 . Another important
is dragged from an orifice onto a cooled difference between the PFC and melt-drag
rotating cylinder, as shown schematically processes is that while the melt is pressure-
in Fig. 2-22. The process involves bringing fed to the nozzle in PFC, it is only gravity
the meniscus of liquid metal protruding fed in the melt drag process.
from a slot nozzle into contact with the The dimensions of the wire or tape are
periphery of a rotating substrate. The me- determined in this process essentially by (a)
niscus is partially solidified by contact with circumferential speed of the drum, (b) vis-
the rotating drum which rapidly drags cosity of the molten metal, and (c) surface
away the solidifying metal to form a con- tension of the molten metal with respect
tinuous wire or ribbon (King, 1967; Hubert to the drum, which in turn depends on
et al, 1973). After the solidification is com- the nature of protective atmosphere, if any,
pleted, the final product is removed from and the superheat of the molten metal.
the drum after about one-third of its cir- This process has been used to cast alu-
cumference, and then coiled. minum, steel, armco iron, solders and

Crucible
Heating coil

Water-cooled
rotating drum

Fiber

Figure 2-22. Sketch illus-


trating the melt drag pro-
cess.
2.5 Laser Surface Treatment 93

others. It allows for a simple and inexpen- moval is primarily controlled by the melt
sive technology and is particularly suited flow rate which in turn is normally ad-
to the requirements of relatively small scale justed by displacing the liquid metal in the
production. crucible behind the overflow lip.
The fine fibers that are produced can
2.4.9 Melt Overflow Process have variable lengths by having indenta-
tions at different positions in the wheel.
In this process, the molten material is
The fibers produced in the Melt Overflow
allowed to flow over a lip in the side of
process are apt to have a variable cross-
a furnace on to a rotating water-cooled
section and have been described as having
wheel. The melt is not constrained on the
a sector shape. This results in a flat heat
upper surface as in the orifice methods of
extraction surface and this, coupled with a
planar flow casting and melt drag. Fig.
longer dwell time on the wheel, leads to
2-23 a shows a schematic of the technique.
cooling rates of > 1 0 6 K s " 1 . The overall
The nature of the shear zone (shown
fiber thickness is between 20 and 25 jim.
shaded in Fig. 2-23 b) is governed by the
Details of this process can be found in the
melt properties (viscosity, surface tension)
literature (Gaspar et al., 1986; Boulby and
and wheel speed. The rate of material re-
Wood, 1986; Wood and Boulby, 1986).

la) 2.4.10 Comparison of Rapid Solidification


Filament Techniques
Table 2-3 presents a summary of the var-
ious rapid solidification techniques and
their product parameters (Savage and
Froes, 1984).

2.5 Laser Surface Treatment


All the techniques described in the pre-
(b) ceding sections involve complete melting
of the alloy prior to rapid solidification. An
alternative is to locally melt the surface (the
depth ranging from 10 to 1000 \im) of bulk
material followed by rapid solidification
and subsequent solid-state cooling (Breinan
and Kear, 1976; Breinan et al., 1976). This
process has also been referred to as self
quenching, laser annealing, laser glazing,
layer glazing, etc. However, in order to
avoid possible confusion with other similar
Figure 2-23. (a) Schematic illustration of the melt
overflow technique, (b) Shows details of the melt pool
terms used in metallurgy, the term laser
shape and nature of the shear region at the overflow surface treatment has been suggested by
lip-wheel contact point. Cahn (1983) (see also Chapter 3).
94 2 Rapid Solidification

Table 2-3. Rapid solidification techniques and product parameters.


Technique Product tpye Typical Typical cooling Comments
dimensions (um) rateCKs"1)
Gas atomization Smooth, spherical 50-150 dia. 10 2 -10 3 Inert gas (nitrogen, argon)
powder used where oxidation
is a problem
Water atomization Rough, irregular 75-200 dia. 10 2 -10 4 Used on tonnage scale
powder
Ultrasonic gas Smooth, spherical 10-50 dia. up to 106 Narrow size distribu-
atomization powder tion, high efficiency
Centrifugal Smooth, spherical 25-80 dia. 10 5 Low oxide, clean powder
atomization powder
Electron beam splat Elongated splats 40-100 thick 10 4 -10 7 Applicable to reactive
quenching metals
Rotating electrode Smooth, spherical 125-200 dia. 10 2 Low cooling rate, low
process powder contamination
Rapid spinning cup Variable, spherical < 50 dia., 10 4 -10 6 Narrow size distribu-
to irregular possible tion possible
Perforated rotating Acicular granules 1000-5000 long 10 1 Very economical
cup x 1000 dia.
Soluble gas Spherical powder 20-100 dia. lO1-^2 Very clean, satellite-free
atomization powder
Electrohydrodynamic Powder, flake or 0.01-100 dia. up to 107 Excellent powder size
atomization coating control
Spark erosion Spherical or 0.5-30 dia. 10 5 -10 6 Little control of
irregular powder size
Twin roll atomization Variable, powder 200 thick flake 10 5 -10 6 Economical
to flake
106_108
"Gun" technique Foils 0.1-10 thick Widely applicable
Spray deposition Thick deposit > 1 mm thick 10 3 -10 6 Short process route
to thick section
Plasma spray Coherent deposit > 1 mm thick <10 7 Has potential to produce
deposition near-net shape
Chill methods Wedge or cylinder 200-1000 thick 10 4 Widely applicable
possible
Piston-and-anvil Splat 50 mm dia. 10 4 -10 6 Widely used laboratory
x 5-300 thick technique
Free-flight melt Circular section 100-200 dia. 10 2 -10 4 Restricted application
spinning filament wire
Chill-block melt Rectangular section 10-100 thick 10 5 -10 7 Very widely used
spinning tape up to 3 mm wide
Planar flow casting/ Wide rectangular 20-100 thick up 10 5 -10 6 Widely applicable
melt drag section tape to 300 mm wide
In-rotating water Circular section 60-200 dia. 10 5 -10 6 Widely applicable
spinning wire
Taylor wire Circular section 20-100 dia. 10 3 -10 6 High risk of contamina-
wire tion of melt
Crucible melt Filament of fiber 20-100 thick 10 5 -10 6 Applicable to reactive
extraction/pendant melts
drop melt extraction
Melt overflow Sector shape fiber 20-25 thick >10 6 Widely applicable
2.5 Laser Surface Treatment 95

The process of laser surface treatment is which may grow so rapidly that they dis-
accomplished by concentrating on alloy rupt the amorphous layer. Secondly, when
surfaces extremely high power densities of vitrifying a large surface area with overlap-
about 10 6 Wcm~ 2 in a small spot, typi- ping passes, recrystallization of the amor-
cally 0.1 to 1.0 mm diameter for short phous material starts in the heat-affected
durations of about 10 5 s. Although lasers zones (Sepold and Becker, 1986). An im-
have been very commonly used, one can portant difference between rapid solidifica-
also use electron beams (Kadalbal et al, tion from the melt and laser surface treat-
1980; Lewis et al., 1980; Tucker and Ayers, ment is that in the latter technique, it
1980) to achieve similar results. has been possible to produce amorphous
Two different types of lasers have been phases in metal-metalloid systems even at
used - pulsed ruby, neodymium glass or as low a concentration as 5 at.% of the
other solid-state lasers and continuous- metalloid (Lin and Spaepen, 1983).
wave (CW)-gas (CO2). The former are used Practical applications of laser surface
in stationary mode, whereas the latter are melting (Steen, 1985) include:
used in conjunction with a rapid scanning
(a) Surface remelting to reconstitute, ho-
of the alloy surface perpendicularly to the
mogenize, or refine the surface to achieve
beam. If such scanning is combined with
special properties at the surface,
slow transverse translation of the laser
(b) Surface alloying in which preplaced
beam, then successive strips of melted ma-
or injected alloying additions are incorpo-
terial can cover the whole surface (Breinan
rated into the surface (Draper and Poate,
and Kear, 1978). The melted layer solidifies
1985),
immediately after the heat source moves
(c) Particle injection in which a disper-
on or after it is switched off because the
sion of second phase is incorporated, with-
liquid layer is in good thermal contact with
out being remelted, into the remelted zone
the bulk of the material. Cooling rates of
at the surface (Ayers etal., 1980; Cooper
1 0 6 - 1 0 8 K s " 1 have been reported (Tuli
and Ayers, 1985).
et al., 1978; Strutt et al, 1980; Kear et al,
(d) Surface cladding in which a metal or
1981) for these processes.
alloy is fused on to the underlying material
Early studies on laser surface treatment
with a minimum of dilution by the under-
were concerned with the production of
lying material (Powell and Steen, 1982),
metastable phases such as extension of
and
solid solubility limits (Elliott et al, 1973)
(e) Laser layer technique for joining
and formation of metastable crystalline
amorphous materials to produce thick foils
phases (Laridjani et al, 1972). Later, it was
(Sepold and Becker, 1986).
also possible to produce quasicrystalline
phases (Schaefer et al, 1986) and amor- Alternate elemental layers (composition-
phous phases in "easy" glass-forming sys- ally modulated films) totalling less than
tems (Sepold and Becker, 1986; Lin and 1 \\m in thickness have been remelted and
Spaepen, 1986). There are, however, two solidified on a surface to produce very high
possible effects which may prevent the for- cooling rates of 10 1 0 -10 1 3 K s " 1 (von All-
mation of a glassy phase in many systems. men et al, 1984). This resulted in the for-
Firstly, the underlying crystalline material mation of glassy phases in much wider
being in contact with the melt serves as a composition ranges than had been possible
nucleation site for the crystalline phases with rapid solidification processing (Lin
96 2 Rapid Solidification

and Spaepen, 1983; von Allmen, 1983; von cooling rates. Further, the magnitude of
Allmen et al., 1984). the cooling rate and its variation aids in
Research in the area of laser surface interpreting the microstructures obtained.
treatment is prompted mainly by two con- It is, therefore, not surprising that several
siderations, viz., (i) it requires possibly ex- attempts have been made to estimate, mea-
pensive alloying elements to be present sure or calculate the cooling rates during
only in a very thin surface layer which can rapid solidification in the laboratory or the
be easily achieved by laser surface treat- industry.
ment, and (ii) it offers a way of working In most rapid solidification processes,
with bulk materials, which is not possible the thin dimension of the product is typi-
with the usual rapid solidification tech- cally ^100 |im, with a corresponding cool-
niques. ing rate of ^ 1 0 5 K s " 1 . Thus, the solidifi-
Laser surface treatment has been found cation and cooling are complete in a mat-
to increase fatigue, erosion and wear resis- ter of a few milliseconds. Actual recording
tance. This process can also be used for of temperature variations in such a short
coating a cheap base material with a more interval of time naturally poses serious ex-
expensive, harder or corrosion-resistant perimental difficulties. All the same, some
surface. The technique of electron beam measurements have been carried out. On
melting and solidification has been ele- the other hand, microstructural features of
gantly employed to study the basic princi- the solidification product such as sec-
ples of solidification structures and condi- ondary dendrite arm spacing or eutectic
tions for solid solubility extensions (Ben- lamellar spacing can be used to estimate
dersky and Boettinger, 1981; Boettinger the cooling rate at the point of solidifica-
et al., 1984) and formation of quasicrys- tion fairly easily. However, this approach
talline phases (Schaefer et al., 1986). (A sep- fails when the product of rapid solidifica-
arate chapter on Laser Surface Modifica- tion is glassy in nature.
tion by B. L. Mordike follows the present Under conditions of non-equilibrium
chapter in this book, and may be consulted cooling many solid solution alloys solidify
for further details.) in a dendritic fashion. Relationships can
be developed between the cooling rate (T)
and the primary or secondary dendrite arm
spacings. However, primary dendrite arm
2.6 Cooling Rates spacings are neither uniform nor at all suit-
in Rapid Solidification able for estimating T, since the nucleation
of a primary dendrite can take place rather
The rate of cooling of a metallic melt randomly anywhere in the melt. However,
before, during, and after solidification can, once the primary dendrite is nucleated, the
in principle, be calculated and also mea- spacings of the secondary dendrite arms
sured experimentally. A knowledge of such are dictated by the solidification condi-
cooling rates helps in the first instance in tions. Therefore, the secondary dendrite
evaluating the relative efficiencies of differ- arm spacing can be used and has been
ent quenching techniques. An understand- widely used as a very convenient measure
ing of the variables affecting the rates of oft.
cooling enables one to optimize the condi- At low cooling rates, the secondary den-
tions to achieve the maximum possible drite arm spacing, X is related to t through
2.6 Cooling Rates in Rapid Solidification 97

the relationship and aluminum alloys. It may be noted that


the slopes are different for different alloys.
(2-2)
Burden and Jones (1970 b) used the rela-
where K and n are constants for a given tionship between eutectic lamellar spacing,
material, n has been shown to have a value d to estimate the cooling rates from the
of about 1/3. A plot relating X and T up to relation
about 3 x 104 K s ~1 was first developed by
d= (2-3)
Dean and Spear (1966). By measuring the
cooling rates in rapidly solidified alloys, where A is a constant (1.04 x 10 5 cm 3/2
this plot was extended to higher values of s~1/2) and n2 = 0.5 for an Al-Cu eutectic
t (Matyja et al, 1968). This method has alloy. A knowledge of the splat thickness is
since been frequently used to measure and necessary for these estimates, which was
grade the cooling rates (Suryanarayana avoided in estimation of cooling rates from
and Anantharaman, 1970; Mehrabian, the eutectic cell spacings (Chattopadhyay
1978; Duflos and Stohr, 1982). For exam- etal., 1980).
ple, the cooling rate was measured as Although very convenient for estimating
2 x l O 6 K s ~ 1 when Al-Ge alloy melts the order of cooling rates, these indirect
were quenched by the "gun" technique, methods suffer from the following limita-
while it was only 4 x 104 K s " 1 when the tions:
melt was dropped on to a copper substrate (a) they are not applicable to glass-form-
(Suryanarayana and Anantharaman, 1970). ing alloy compositions,
The variation of dendrite cell spacing mea- (b) they can only give an average cooling
sured directly on rapidly solidified Ni-Al rate,
and Fe-Ni alloys with cooling rate were (c) each family of alloys requires a sepa-
also found to follow the above equation rate calibration, and
(Hayzelden et al., 1983; Gillen and Cantor, (d) the dendrites may coarsen after solid-
1985). Fig. 2-24 shows a plot relating the ification and so yield misleading results.
dendrite arm spacing to the cooling rate For these reasons, direct measurement
for stainless steels, maraging steels, copper, of cooling rates is desirable.

1000

• 100

Copper alloys
10
Maraging
1 .steels
Austenitic Figure 2-24. Secondary
stainless steels dendrite arm spacing as
0.1
a function of cooling rate
Aluminum alloys for steels, copper and alu-
0.01 minum alloys.
10-3 10° 103 10e 109
Solidification rate (K/s)
98 2 Rapid Solidification

The earliest measurement of cooling of the solidification point, V is the wheel


rates in "gun"-quenched alloys was by Pre- velocity and a is a constant (=1.2x
decki etal. (1965). In their method, the x 104 Km" 1 ). The above equation is vir-
splat was allowed to land on a pair of dis- tually independent of melt-spun ribbon
similar metals kept close to one another in material or other melt spinning variables.
an insulating base, thus forming the hot Other methods for measuring the cool-
junction of a thermocouple. The e.m.f. gen- ing rates in rapid solidification have also
erated was recorded on an oscilloscope been used, e.g., recording of infra-red radi-
and making some assumptions (not all of ation emitted from the solidifying melt
them justifiable), they calculated the cool- (Lohberg and Muller, 1970).
ing rate to be 1 to 5 x 108 K s " 1 for silver Irrespective of the technique used to
and 106 K s" 1 for an Au-14 at.% Sb alloy. measure the cooling rates, it should be
Measurements have been made on pis- borne in mind that the cooling rate varies
ton-quenched liquid alloys using either substantially between the freezing point
the above principle (Harbur et al., 1969) or and ambient temperature. Thus, at 1500°C,
by embedding a temperature sensor such near the freezing point, the cooling rate
as a photo-electric (Strachan, 1967) or a for piston-quenched steel or iron samples
thin junction conventional thermocouple 25-50 fim in half-thickness is 1 0 5 -
(Duflos and Cantor, 1982; Nishi etal., 107 K s " 1 . The cooling rate at 1000°C is
1982). Pyrometry of the droplet has also about 10 times slower than at 1500°C, and
been employed (Kattamis et al., 1973). In at 500°C it is 2 - 3 times slower again. The
all these cases, it has been shown that the cooling rates in single-roller melt spinning
efficiency of the cooling process increases appear to be lower than in piston-and-
with increasing piston velocity. anvil quenching (Hayzelden, 1984). It is
Cooling rate measurements have also generally accepted that the twin-roller
been made on melt-spun ribbons using quenching is even slower than single-roller
photographic techniques. A calibration be- melt spinning, in spite of the fact that heat
tween film density and surface temperature is extracted from both the sides. This is
has been established, using which the tem- because the ribbon is in contact with the
perature profiles along the ribbon have rolls for a very short duration. However,
been evaluated using either color (Hayzel- the initial cooling rate is very high (Davies
den et al., 1983; Gillen and Cantor, 1985) et al., 1978).
or black-and-white (Warrington et al., 1982; Direct measurements of cooling rates us-
Cantor, 1986) photographic techniques. ing thermocouples are subject to the uncer-
From these investigations also it could be tain effects of response-time lag arising
established that the cooling rate increases from imperfect contact between the melt
with higher wheel velocities and also with and the thermocouple and, in the "gun"
lower specimen thickness. technique, due to the effects of material
A remarkable feature noted by Cantor overlapping at different stages of cooling.
(1986) is that the cooling rates in melt spin- These can result in reduced e.m.f. readings
ning can be represented by a simple rela- and the measured cooling rates can thus be
tion of the type substantially lower than the actual values.
T = aV (2-4) Cooling rates have also been calculated
using the heat-flow models (Ruhl, 1967).
where t is the cooling rate in the vicinity These have been based on one-dimen-
2.7 Consolidation Methods 99

sional heat flow and depending on the na- result in coarsening of the ultrafine struc-
ture of contact between the specimen and tures and/or elimination of other meta-
the substrate, one can consider "ideal cool- stable effects produced by rapid solidifica-
ing" (where the heat transfer coefficient h tion processing and this leads to reduced
has a value of oo) or "Newtonian cooling" mechanical property levels. Thus, to realize
(where h is quite small) or "intermediate the full potential of rapid solidification
cooling". Using these concepts, for "gun"- products (i.e., refined microstructures, su-
quenched 1 jim thick iron splat, the cooling persaturation of solute atoms and for-
rate has been calculated a s 8 . 1 x l O 9 K s ~ 1 mation of metastable intermediate phases
for ideal cooling and 6.9xlO 7 Ks~ 1 for and consequent improved physical and
Newtonian cooling. Refined treatments of mechanical properties), the consolidation
these models have also been published temperature must be relatively low. How-
(Mehrabian, 1982; Levi and Mehrabian, ever, it is difficult to achieve the appro-
1982; Clyne, 1984; Cantor, 1986). priate particle deformation in the high-
In addition to the above-mentioned the- strength powders with full densification
oretical estimates or experimental calcula- and inter-particle bonding that is neces-
tions, one can also use structural parame- sary to achieve the desired properties in the
ters of the quenched product for compar- consolidated structure at low tempera-
ing two different techniques. For example, tures. Thus, the challenge is to achieve the
if one technique can produce a homoge- necessary integrity at a relatively low tem-
neous solid solution throughout the com- perature.
position range in the Cu-Ag system and The consolidation of rapidly solidified
another technique cannot, then obviously powders can be carried out in different
the former technique can produce higher ways depending on whether the chemical
cooling rates (Franetovic et al., 1979). Sim- homogeneity or the metastable effects in
ilarly, the extent of supersaturation (Cahn the rapid solidification products is more
et al., 1976) and the formation of an amor- important. If chemical homogeneity is the
phous phase can also be used as criteria in primary benefit sought, then time, tem-
this regard. perature and pressure may be chosen in
such a way as to produce a nearly porosity-
free, fully dense and metallurgically well-
2.7 Consolidation Methods bonded product. On the other hand, if the
other virtues of rapid solidification (e.g.,
For rapid solidification technology to unique microstructures and metastable
become commercially viable and a strong phases) have to be retained, then the con-
competitor to the existing technology, the solidation parameters have to be much
rapid solidification product (powder, rib- more carefully controlled. The temperatures
bon, flake, fiber, etc.) needs to be consoli- may have to be low especially when metallic
dated into larger, more usable, fully dense glasses are concerned and their crystalliza-
forms that are adequate in size and shape tion has to be avoided at all costs.
for required applications. Conventional Several methods have been in use for
consolidation techniques and processes consolidating powders in conventional
used in powder metallurgy require applica- powder metallurgy technology. These
tion of pressure at relatively high tempera- methods can also be used to consolidate
tures. This high-temperature exposure may rapidly solidified powders or flakes with
100 2 Rapid Solidification

, Sealed Heat
I\container) / (

\ RamO
pressure Extruded
(b)

Laser or
electron beam
Figure 2-25. Four consoli-
Powder or
wire feed dation methods related to
Rapidly solidified
rapid solidification process-
Projectile Powder
deposit ing, (a) Hot isostatic press-
ing, (b) hot extrusion, (c)
Gas incremental solidification,
pressure
and (d) dynamic com-
(c) Gun barrel I (d) paction.

appropriate modifications. The most com- The shock-wave concept involves appli-
mon methods used for consolidating cation of a very high pressure or stress
rapidly solidified powders are hot isostatic pulse for a short duration. The wave trav-
pressing (HIP), hot pressing, vacuum hot els through the medium at supersonic ve-
pressing (VHP), and hot extrusion. Some locities (about 105 cms" 1 or Mach 3) and
other methods like cold isostatic pressing, greatly accelerates matter in the shock front
hydrostatic extrusion, forging, rolling and into a region of the medium which is in a
dynamic compaction have also been em- static state. This produces a marked inter-
ployed. However, HIP seems to be the best action of the atoms or particles. The im-
method to get a near-net shape. Fig. 2-25 portant parameters to be considered in this
shows schematically four of the commonly process are pressure and pressure dura-
used consolidation methods. Grant (1985) tion, stress state and history, particle size,
and Flinn (1985) have recently summarized shape and distribution, and precompac-
the present status of consolidation meth- tion density. Pressure-densification curves
ods for rapidly solidified products. for different amorphous and microcrys-
talline materials have been reported (Mor-
ris, 1980 a).
2.7.1 Shock-Wave (Dynamic) Compaction
Amorphous metallic ribbons or strips
Metallic glasses have been usually com- have been consolidated by explosive com-
pacted by cold compaction methods. Very paction methods (Clauer et al., 1980; Murr
often, the glassy tapes are subjected to et al., 1981) and the results indicate that
comminution before consolidation. Be- bonding of successive layers of amorphous
cause of the high strength of these mate- strips is rather difficult to achieve (Clauer
rials and the necessity of preserving the etal., 1980). Powders produced by atom-
glassy structure, shock-wave (high-energy- ization techniques or obtained by com-
rate forming) techniques are preferred. minution of strips/ribbons have also been
These involve explosive forming, explosive compacted (Cline and Hopper, 1977; Cline
bonding, electrohydraulic forming, electro- etal., 1978; Morris, 1980b). Cline etal.
magnetic forming, etc. (1978) were able to achieve full densifica-
2.7 Consolidation Methods 101

tion and also good bonding between amor- a variety of titanium-base alloys (Mahajan
phous metallic filaments and conventional et al., 1985). In this process the powder
crystalline material substrates. Rapidly so- contained in a thick-walled container
lidified Al-6% Si alloy (Gourdin, 1984), (made of a material which acts as an in-
MAR-M 200 (superalloy) (Meyers et al., compressible fluid when subjected to an
1981), and stainless steel powders were also external pressure) is subjected to isostatic
compacted. pressure developed in a conventional forg-
Although some investigations have been ing press.
carried out using shock waves, the results Hot extrusion is much more commonly
are not easy to analyze because the process applied to consolidate rapidly solidified
is very complex. Optimization of structure/ powders. Preparation of the powder is
property correlation in terms of consoli- done in a manner similar to that for HIP
dation parameters is still to be carried out (the can used has a thicker wall). The pow-
systematically. However, this technique der-filled billet is heated to approximately
seems to hold great potential. 0.6-0.7 Tm prior to extrusion. The princi-
pal variables in this process are (a) extru-
sion ratio, (b) deformation velocity, and (c)
2.7.2 Hot Compaction
working temperature. This process has
These techniques have been employed been used extensively for superalloys and
when chemical homogeneity is more im- aluminum alloys. Warm extrusion has
portant than retention of metastable phases been shown to be superior to warm uni-
and fine microstructures in the rapidly so- axial die pressing since extrusion confers
lidified products. Although several meth- substantial shear components resulting in
ods are possible, hot isostatic pressing breaking-up of surface oxide layer and im-
(HIP) and hot extrusion are the most fa- proved adhesion between neighboring par-
vored techniques. Hot isostatic pressing is ticles (Liebermann, 1980 b). Tables 2-4 and
favored because of its near-net-shape pro- 2-5 show the process correlations with
cessing capabilities and potential for re- principal parameters for powder consoli-
ducing manufacturing costs, while hot dation and the extent of retention of rapid
extrusion is favored for control of micro- solidification virtues, respectively (Flinn,
structures. 1985). The advantages and disadvantages
The HIP process of rapidly solidified of different consolidation methods are pre-
powders involves (i) complete filling of a sented in Table 2-6.
container to achieve maximum possible In addition to the methods mentioned
packing efficiency, (ii) degassing to remove above, one can also use incremental depo-
any residual gases, (iii) hermetical sealing sition methods like spray forming tech-
of the container, and (iv) hot isostatic niques to obtain large quantities of rapidly
pressing by choosing the appropriate pres- solidified material. This can be later sub-
sure, temperature and time cycles. Grain jected to rolling or extrusion. In some of
growth in HIP-consolidated powders is the cold consolidation methods, addition
very slow compared to conventional heat of other powders can also be made before
treatments (Kelly et al., 1982). extrusion (Austen et al., 1986).
Recently, the Rapid Omnidirectional
Compaction (ROC) process has been used
to produce fully recrystallized structures in
102 2 Rapid Solidification

Table 2-4. Process correlations with principal parameters for powder consolidation.

Consolidation Principal parameter characteristic


method
Pressure Bulk temperature Time Densification rate

Inert gas hot pressing Low-medium High Long Low


Vacuum hot pressing Low-medium High Long Low
Hot isostatic pressing Low-medium High Long Low
Forging Medium-high Medium-high Short Medium-high
Rolling Medium-high Medium-high Short-medium Medium-high
Extrusion High Medium-high Short High
Shock/Dynamic Very high Low-medium Very short Very high

Table 2-5. Expected retention of rapid solidification virtues for the various consolidation processes.

Consolidation Rapid solidification virtues


method Chemical Refined Extended solid Metastable
homogeneity microstructures solubility phases

Inert gas hot pressing High Medium Low-medium Low


Vacuum hot pressing High Medium Low-medium Low
Hot isostatic pressing High Medium Low-medium Low
Forging High Low-medium Low-medium Low
Rolling High Low-medium Low-medium Low
Extrusion High Medium-high Medium Low
Shock/dynamic High High High High

2.8 Concluding Remarks However, caution has to be exercised in


comparing the properties of materials ob-
The salient features of the remarkable tained by different methods, especially the
range of techniques available for rapidly rapid solidification and other non-equilib-
solidifying metallic melts have been re- rium processing techniques, since the mech-
viewed. While the rapid solidification prod- anisms of formation of the non-equilib-
uct can be powder, ribbon, tape, wire, etc., rium structures are quite different in differ-
the solidification rates achieved can vary ent techniques. It should also be realized
from as low as 102 to as high as 10 8 - that differences in the structure and prop-
109 K s ~*. The exhaustive list of references erties of the same alloys have been noted
at the end of the Chapter can be consulted even when they were prepared by rapid
for the specific details of any process. With solidification techniques. These can be at-
a proper choice of the technique, the de- tributed to the differences in the quenching
sired metastable effects can be easily conditions, which in turn calls for a great
achieved in a given alloy system. In fact, control on the experimental variables for
rapid solidification processing combined obtaining reproducible results.
with a subsequent heat treatment can con- The large amount of experimental data
fer properties on a material which are oth- available should make the rapid solidifica-
erwise difficult to attain or unattainable. tion process amenable to rigorous mathe-
2.8 Concluding Remarks 103

Table 2-6. Some apparent advantages and disadvantages of powder consolidation processes for rapidly solidified
materials.

Consolidation Apparent advantages Apparent disadvantages


processing

Inert gas hot pressing Containerless operation High temperatures, tendencies for porosity,
possible nonhomogeneous consolidation
Vacuum hot pressing Containerless operation, in situ High temperatures, possible nonhomo-
outgassing, less tendency for porosity geneous consolidation
Hot isostatic pressing Uniform pressure - homogeneous High temperatures, requires containeriza-
consolidations; more flexibility in tion, and substantial degassing, porosity
parametric cycling
Simple operation Requires thick wall container and degassing,
Forging
nonuniform consolidation and structure
gradients, parametric control in gross,
requires several billet reheats
Established operation High temperatures, nonuniform consolida-
Rolling tion and structure gradients, relative thick
wall container and degassing, requires
several workpiece reheats
Extrusion Established one-step operation, High temperature, requires containeriza-
very high-restrictive deformation tion and degassing, some nonuniformity
in consolidation and structure
Shock/dynamic Low bulk temperatures Shock physics and material response not
understood, very high work-hardened
conditions, size limitations

matical modeling. Efforts have already been systems investigated, the quantity of mate-
made in this direction with partial success. rial produced, the wide spectrum of tech-
For the successful exploitation of the niques developed, and the commercial ex-
rapidly solidified alloys, tonnage quantity ploitation of rapid solidification products
of the material is required. At the present, are indeed remarkable. The U.S. market
the different variants of the atomization for rapidly solidified materials is expected
process appear to be the only choice. The to reach $ 290 million by 1993. Significant
solidification rates achieved in these meth- improvements in combinations of tensile
ods, however, are low and so the extent of strength, fatigue, fracture toughness, elec-
non-equilibrium effects achieved is also trical conductivity and corrosion resis-
limited. Development of innovative con- tance have been responsible for the in-
solidation methods is also required to re- creased acceptance of these alloys for
tain the rapid solidification virtues in bulk high-performance applications. The cost of
forms made from the as-quenched mate- these products is also expected to come
rial. down with increased tonnage production.
Rapid solidification technology has Thus, it can be concluded that rapid solid-
come a long way from the 1960's when ification technology will pave the way for
only a few milligrams of the product could new materials and metal processing tech-
be produced at a time. The variety of alloy nologies in the future.
104 2 Rapid Solidification

2.9 References (Eds.). Baton Rouge, LA: Claitor's Pub. Div.,


pp. 294-305.
Adam, C M . (1986), in: Mechanical Behavior of Bickerdicke, R.L., Clark, D., Easterbrook, J.N.,
Rapidly Solidified Materials: Sastry, S.M.L., Hughes, G., Mair, W.N., Partridge, P.G., Ranson,
MacDonald, B. A. (Eds.). Warrendale, PA: Metall. H.C. (1986), Internat. J. Rapid Solidification 2,
Soc. AIME, pp. 21-39. 1-19.
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Rapidly Solidified Metals: A Technological Over-
3 Surface Modification by Lasers
Barry L. Mordike

Institut fur Werkstoffkunde und Werkstofftechnik, Technische Universitat Clausthal,


Clausthal-Zellerfeld, Federal Republic of Germany

List of Symbols and Abbreviations 112


3.1 Introduction 113
3.2 Fundamental Considerations 113
3.2.1 Reflectivity and Absorption 113
3.2.2 Methods of Increasing Absorptivity 114
3.2.2.1 Preheating 114
3.2.2.2 Surface Coatings 114
3.2.2.3 Surface Roughening 114
3.3 Applications of CO2 Lasers 114
3.4 Surface Modification Processes 115
3.4.1 Transformation Hardening in Iron-Base Alloys 116
3.4.2 Surface Melting 117
3.4.3 Constitutional Effects 117
3.4.4 Surface Melting of Cast Iron 120
3.4.5 Surface Melting of Aluminium-Silicon Alloys 121
3.4.6 Surface Alloying and Surface Cladding 122
3.4.6.1 Surface Alloying 123
3.4.6.2 Laser Cladding 126
3.4.7 Surface Treatment of Ceramic Materials 127
3.5 Wear Properties of Laser-Treated Surfaces 129
3.5.1 Transformation Hardening 129
3.5.2 Surface Melting and Surface Alloying 129
3.5.3 Cladding 130
3.6 Other Effects of Laser Treatment 131
3.6.1 Internal Stresses 131
3.6.1.1 Transformation Hardening Stresses 131
3.6.1.2 Cladding Stresses 131
3.6.2 Effect on Bulk Properties, in Particular, Fatigue Life 132
3.7 Industrial Applications 133
3.8 Acknowledgements 135
3.9 References 135

Materials Science and Technology


Copyright © WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
112 3 Surface Modification by Lasers

List of Symbols and Abbreviations

A absorptivity
c A ,c B equilibrium solubilities
liquid and solid concentrations
D diffusion constant
G temperature gradient
intensity
distribution coefficient
T temperature
T melting temperature
£ quenching rate
r Gibbs-Thomson coefficient
HV On Vickers hardness under load 0.
NdYAG neodymium aluminium garnet
3.2 Fundamental Considerations 113

3.1 Introduction to the lattice. Photons are absorbed and


electrons are excited into higher energy
Lasers have been used for several years states. Assuming that the incident beam
in industry for cutting and welding appli- energy is insufficient to expel an electron,
cations. More recently, with the advent of it imparts its energy to the lattice and lat-
high power lasers, not only CO 2 but also tice defects, thus increasing the lattice vi-
neodymium aluminum garnet (NdYAG) brations or temperature. There are many
and excimer lasers, attention has been paid factors which limit the overall efficiency of
to developing methods of surface modifi- the photon energy -• heat energy transfer.
cation of components. The problems in in- The first stage is the absorption of the pho-
troducing laser surface treatment into in- tons. Here losses may occur owing to re-
dustry are three-fold; obtaining a surface flectivity or plasma formation.
structure capable of withstanding the con-
ditions obtaining in service (mechanical
3.2.1 Reflectivity and Absorption
loading, chemical attack, etc.); develop-
ment of handling systems to treat the com- The reflection losses are often the limit-
plicated shapes of components; establish- ing factor in overall efficiency in many la-
ing the deleterious effects of laser surface ser applications in the processing of mate-
treatment, if any, on the bulk properties of rials. The absorptivity A = {\-reflectivity).
the components, e.g., the effect of residual The heating effect of a beam with a known
stresses on the fatigue life and treatment at intensity Io (watts m~ 2 ) is AI0. Although
an economical price. Nevertheless some there are methods of calculating the re-
applications have been successfully taken flectivity (Johnson and Christy, 1975;
up by industry, although mainly for high Shavarew etal., 1978) and hence the ab-
cost components, turbine blades (Mac In- sorptivity A, the simplest approach is to
tyre, 1986), ships' diesel cylinder liners measure A directly during laser excitation.
(Amende, 1990). Figure 3-1 shows the wavelength depen-
The present article discusses the applica- dence of the absorptivity A for some
tions of CO 2 lasers to the surface treat- metals. The wavelengths of CO 2 , NdYAG
ment of materials. There are three main and excimer lasers are also shown. It is
aspects - fundamental considerations, sur- immediately apparent that the absorption
face treatment of components and proper-
ties of laser-treated surface and compo-
0.7
nents. Some general aspects of laser sur- — Excimer
i

face treatment are also discussed in Chap. 0.6 - NdYAG


2, Sec. 2.5. 0.5 C02-

Fe--
>
3.2 Fundamental Considerations e-o.3 **v Stainless
o
U) \ . steel
_Q l-Cu
< 0.2
The initial stage in all laser processing
0.1
applications involves the coupling of laser
radiation to the material. The majority of 0.0
0.1 1
applications involve metallic materials and A in pm

the electrons ensure the transfer of energy Figure 3-1. Wavelength dependence of absorptivity.
114 3 Surface Modification by Lasers

of CO 2 (infrared) light, of wavelength defects and not the surface topography per
10.6 jim is significantly less efficient than se and these anneal out at elevated temper-
that of the NdYAG and excimer lasers. atures (Weiting and De Rosa, 1979).
This is especially marked in the case of Cu A plasma on the surface dramatically
and Al. The wavelength dependence of the increases the coupling of energy. If too
absorptivity suggests that certain applica- high a power is used, however, the plasma
tions might better be carried out with lifts off from the surface and effectively
NdYAG or excimer lasers. Now that shields the surface from the incident beam.
higher power NdYAG and CO 2 lasers are
becoming available, this possibility may be
realizable.
3.3 Applications of CO 2 Lasers
3.2.2 Methods of Increasing Absorptivity
Figure 3-2 shows the fields of applica-
3.2.2.1 Preheating tion of lasers according to the energy den-
sity of the laser and interaction time. The
Increasing the absorptivity is necessary
surface treatments lie on a straight line
for many applications, particularly with
ranging from transformation hardening to
CO 2 lasers. As A usually increases with
shock hardening. Transformation harden-
temperature, preheating by conventional
ing and melting rely on the introduction of
heat sources may improve the efficiency of
heat into the material whereas in shock
laser treatment. Independently of this,
hardening the laser pulse induces an elastic
there may be other advantages in preheat-
wave which causes local plastic deforma-
ing.
tion.
The important parameters in laser treat-
3.2.2.2 Surface Coatings
ment are the energy density and interac-
Oxide coatings or deliberately added tion time. There are limitations in the
coatings have a significantly different com- choice of parameters depending on the ap-
position from the metal substrate. The plication required. This is illustrated in
change in reflectivity can be calculated if Figs. 3-3 and 3-4.
the optical constants are known (Heavens,
1965). Such effects depend also on the
wavelength. Nevertheless, several coatings
have been found to be successful for IR
wavelengths.

3.2.2.3 Surface Roughening


It has been observed that the surface
topography has an effect on the absorp-
tion. Roughening the surface by sandblast-
ing or emery cloth increases A by an
amount of the order of 30%. This im-
provement disappears at elevated tempera- 10~8 10~6 10"A 10~2 10°
tures. The improvement observed in A is Interaction time in s
probably due to the formation of surface Figure 3-2. Applications of lasers according to ener-
gy density and interaction time.
3.4 Surface Modification Processes 115

3500 3500
A P . 6 0 0 0 W ; P//
A t = 10S
melted depth = 2.04nm
melted depth = 3.31mm
3000 vaporised = 40}jm 3000
2
o P= 3000 W ; P/A = 3820 W-cnrff o t = 3.33 s
melted depth= 0.96mm melted depth = 0.18mm
2500 vaporised = 0 pm 2500
• P= 1000 W ; P/A = 1273 W • cm" 2 Df=1.0s
.melted depth = 0 mm melted depth = 0.0mm
2 2000 vaporised = 0 pm

M500

1000^

500
293
0.00 0.80 1.60 2.40 3.20 4.00 0.00 0.80 1.60 2.40 3.20 4.00
Depth x in mm Depth x in mm

Figure 3-3. Temperature profile for cast iron for var- Figure 3-4. Temperature profile for iron for various
ious energy densities at constant interaction times. interaction times at constant energy densities.

These figures show the temperature pro- The conclusions which can be drawn are:
file generated in a material by a laser beam the penetration depth at high energy densi-
10 mm in diameter for various energy den- ties is limited by evaporation from the sur-
sities and interaction times. The calcula- face. Long exposure times and low energy
tions were for simplification made for one- densities are required for thick heat treated
dimensional heat flow. layers. Other low energy density sources
Figure 3-3 shows the temperature pro- are much cheaper than lasers and may be
files for cast iron for 3 different energy able to carry out such treatments satisfac-
densities for an interaction time of 1 sec- torily. The laser is thus more likely to be
ond. applied for applications where relatively
It is apparent that for interaction times thin heat-treated layers are required.
of 1 second there is a limit to the power
density which can be used. 40 jim of the
surface have evaporated for the highest 3.4 Surface Modification Processes
power. Reducing the energy density re-
duces the temperature gradient and also The following processes have been de-
the depth to which the heat penetrates. The veloped for treatment of surfaces:
broken line shows the melting point of cast • transformation hardening in iron-base
iron. The depth melted for the higher den- alloys
sity was about 2 mm whereas at the lower • surface melting
energy density about 1 mm is melted. At • surface alloying
lower energy densities still, no melting oc- • cladding
curs. Figure 3-4 shows the influence of in- • amorphisation.
teraction time. A low energy density was
chosen. Increasing the interaction time dis-
placed the curves to higher temperatures.
116 3 Surface Modification by Lasers

3.4.1 Transformation Hardening displaces the transformation temperatures


in Iron-Base Alloys to higher temperatures. This can be by as
much as 100-150 °C. The time spent above
Transformation hardening of iron base
A 3 is very short and this limits carbon dif-
alloys involves austenitization and self-
fusion and dissolution of carbides result-
quenching. For the purposes of discussion
ing in a heterogeneous structure.
it will be assumed that the coupling of the
laser energy into the workpiece is assured The initial micro structure is very impor-
and that it is massive enough to ensure tant in determining the suitability for laser
quenching. Laser treatment involves rapid transformation hardening. Microstruc-
heating with a short austenitization time. tural heterogeneities, coarse carbides or
On subsequent rapid cooling the harden- pearlite exacerbate the problem of homog-
ing will depend on the degree of austeni- enization. Ideally, the microstructure in
tization which had been achieved. The re- addition to the composition should be
sults can thus be significantly different specified for alloys which are to be laser
from those obtained for the alloy using transformation hardened.
conventional hardening processes. This In practice, the beam must be defocused
is illustrated by the time-temperature - to obtain a spot of the required size. In
austenitization curve (Fig. 3-5) (Orlitsch some cases, special optics are necessary to
etal., 1973). For the composition chosen obtain rectangular spots with a homoge-
the areas for homogeneous austenite, in- neous energy distribution. The energy acts
homogeneous austenite, ferrite + pear- only for a short time and hence the beam
lite + austenite are shown. It is obvious must be moved accurately and with a con-
that the rapid rate of heating effectively stant speed. The depth of hardening and
the temperature profile are determined by
choice of energy density and spot speed.
Heating rate in °C-s~ 1 The method can be applied to all materials
1300
2400 260 65 13 2.6 0.55 0.05 which can undergo a martensitic transfor-
Steel B mation with the limitation imposed by the
effect of rapid heating. Steels or irons with
1200
largely pearlitic or heat treated matrices
are better suited than those with high frac-
: 1100 homogeneous austenite tions of ferrite or stable carbides. Figure
3-6 shows the heating curves for different
depths below the surface. These curves are
B 1000
dependent on the energy density.
Figure 3-7 shows schematically the na-
900 ture of the hardened zones. If higher ener-
gy densities are used, not only is there a
800 bigger difference in heating rates between
the surface and interior but where higher
700
rates of heating are experienced the trans-
10 seconds formation temperatures are displaced to
Time
10° 1
10 102 minutes higher temperatures. Figure 3-8 shows the
Figure 3-5. Time-temperature austenitization curve hardness profile for a transformation-
for a low chromium steel. (After Orlitsch et al., 1973). hardened grey cast iron. Transformation
3.4 Surface Modification Processes 117
1200

1100

1000 | transformation
\ temperature
900 ^ (rapid heating)

i
800
o
c 700
0)

B 600
o 250 500 750 1000
Distance from surface in pm
I 500 \
<v Figure 3-8. Hardness profile for a transformation-
*~ U)0
hardened grey cast iron.

300

200 cooling
\m / cycle cycle 3.4.2 Surface Melting
100
0 Applications involving surface melting
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Time in s
rely for improvement of the surface prop-
Figure 3-6. Heating curves for different depths below
erties on one or more factors. In the case of
the surface. cast materials, remelting the surface en-
ables casting defects (e.g., porosity, cold
shuts) to be eliminated. The main reason
for laser surface melting is to obtain better
properties as a result of the rapid solidifi-
cation. The quenching rates can be as high
as those achieved in other techniques, e.g.,
melt spinning, powder atomization (Pond
et al., 1976; Lawley, 1977). The aim of sur-
face melting is thus to reproduce the im-
provements obtained in rapidly quenched
powders and ribbons on massive mate-
rials.

3.4.3 Constitutional Effects


Rapid quenching influences the nature
Distance from surface and stability range of phases, also their
Figure 3-7. Micro structural changes at different size, morphology and distribution. The fi-
depths for a given heating rate. nal microstructure depends on the process
parameters and obviously on the nature of
the system. The phases which are produced
hardening has been successfully applied to may be non-crystalline (amorphous) or
carbon and alloy steels, tool steels, case crystalline (stable or metastable). Indepen-
carburized steels and cast irons (Amende, dently, there may be an extension in the
1990). stability range of solid solubility.
118 3 Surface Modification by Lasers

Equilibrium diagrams can only be em-


ployed as an aid when considering the pos-
sible outcome of laser surface treatment.
The equilibrium diagram, Fig. 3-9, shows
the relationship between free energy and
composition and the resultant solubility
limit for a chosen temperature 7\, for a
eutectic system. The tangent defines the
equilibrium solubilities CA and CB for the
terminal solid solutions a and /?. The inter-
sections of the liquid and solid free energy
curves show the corresponding maximum
possible metastable solubilities for a and /?.
The locus of C c and CD provides the well
known To curve. It represents the highest
interface temperature at which the parti- C
HCB 1
tion coefficient can be unity (Jones, 1973). Composition Q
Generally, further kinetic undercooling is Figure 3-9. Relationship between free energy and
necessary for partitionless solidification composition at the temperature T (schematic).
(solute trapping). Extension of solid solu-
bility must be avoided if an amorphous
structure is to be possible. Figure 3-10
shows the range of compositions of solid
solution which can form from a liquid at
the interface of composition CL. In case
(a), partitionless solidification is possible
but not in case (b) (Boettinger, 1981). How
the solidification in fact proceeds depends
on the kinetic conditions, the speed with
which the solidification front moves. This
is determined by the relative speed of laser
beam and workpiece. The conditions in la-
ser melting are such that growth occurs
usually by cellularly or dendritic mecha-
nisms, which involve segregation. At suffi-
ciently high growth rates the solidification
front remains planar and segregation-free
growth is possible. The condition for this is
that the speed exceeds D AT/FK0 where F
is the Gibbs-Thomson coefficient (ratio of
Composition
Interfacial Energy: Entropy of Melting), D
is the diffusion coefficient, AT is the tem- Figure 3-10. The shaded areas show the range of sol-
id solubility Cs which can form from a liquid at the
perature difference between liquidus and
interface of composition CL at different interfacial
solidus, Ko is the distribution coefficient temperatures. Solidification without segregation is
(Coriell and Skeraka, 1980). Such growth possible in case (a) but not in case (b).
3.4 Surface Modification Processes 119

Figure 3-12. Effect of energy density on the mi-


crostructure for a Fe-13%Cr-2.1%C steel, a) Low
energy density, b) High energy density. Transverse
speed constant.

geneously. Thereafter, there are the vari-


ous possible forms of growth. Examples of
different nucleation forms are given in
Figs. 3-1 la, b and c (Bergmann et al.,
1984).
The solidification behaviour is influ-
Figure 3-11. Different nucleation modes in laser-
melted surfaces; a) from substrate (Mag. 25 x); b) enced mainly by three parameters -
within the melt (Mag. 100 x); c) from the surface quenching rate, s, solidification rate, R,
(Mag. 50 x). and the temperature gradient, G. These
three parameters are interrelated in the ex-
pression 8 = RG. The temperature gradi-
rates are possible with lasers or electron ent in laser surface melting depends on the
beams. energy density and the solidification rate,
The microstructure which is produced in and apart from stationary pulsing, on the
laser surface melting is the result of many displacement rate. Figure 3-12 shows the
competing processes. There is nucleation, effect of increasing the energy density
which can occur either heterogeneously on whilst maintaining the solidification rate
the substrate or within the melt, or homo- constant.
120 3 Surface Modification by Lasers

The influence of increasing the solidifi-


cation rate while maintaining the energy
density constant is shown in Figs. 3-13 a, b,
c, d. The type of growth changes from near
planar to cellular to dendritic. The me-
chanical properties are correspondingly
different.

3.4.4 Surface Melting of Cast Iron


Iron-carbon alloys can solidify accord-
ing to the metastable iron-Fe3C phase dia-
gram or the iron-graphite equilibrium
phase diagram. The relative stability of ce-
mentite and graphite is affected by alloying
additions. Most cast irons are grey cast
irons, containing graphite in a matrix
which is usually pearlite, or ferrite. In-
creasing the cooling rate favours the for-
mation of cementite, a fact used in the pro-
duction of chill-hardened irons. If grey
cast iron is surface-melted, the layer solid-
ifies rapidly and thus in the form of ledebu-
rite - i.e., austenite and cementite. The
properties, particularly wear resistance,
and strength are much better than those of
grey cast irons. Simple surface remelting
can thus convert a cheap material with rel-
atively poor properties into a high perfor-
mance material. There are many compo-
nents made from cast iron, e.g., cam fol-
lowers, brake drums, supports, engine
blocks, camshafts, cylinder liners. The
loading and operating conditions are very
different but in each case surface melting
can improve the wear resistance consider-
ably. Figures 3-14 a and b show the struc-
ture obtained on remelting lamellar and
spheroidal cast iron, respectively.

Figure 3-13. Different microstructures in lamellar


cast iron surface remelted with increasing solidifica-
tion rate and constant temperature gradient; (a) has
the lowest solidification rate, and (b) the highest.
3.4 Surface Modification Processes 121

Depending on the conditions of melting,


the thickness and hardness of the layer can
be determined (Fig. 3-15). The heat-affect-
ed zone also depends on the parameters
and also on the type of cast iron used, e.g.,
ferritic or pearlitic. This zone can show
martensite which can induce cracking in
the layer on cooling or during subsequent
grinding operations. It is customary to pre-
heat to about 350 °C before laser treatment
to prevent martensite forming.

3.4.5 Surface Melting


of Aluminum-Silicon Alloys
Aluminum-silicon alloys are widely used
as casting alloys in the automobile and re-
lated industries, in particular Al-13Si or
Al-(8 Si + 3 Cu). They rely for their strength-
ening on the eutectic precipitation of sili-
con and primary aluminum. The silicon
phase is coarse and acicular and to im-
prove the properties it is customary to add
sodium to the melt to "modify" the silicon
Figure 3-14. Surface-melted lamellar (a) and spheroi- morphology. Rapid cooling produces a
dal (b) cast irons (Mag. 100 x). similar effect.

Figure 3-15. Hardness pro-


file of lamellar cast iron
remelted with different la-
ser parameters.
500 1000 1500 2000
Distance from the surface in pm
122 3 Surface Modification by Lasers

200 £00 600 800 1000 1200


Distance from surface in urn
Figure 3-17. Hardness profile corresponding to
Fig. 3-16.

by elements soluble in the bulk material


and accomplished during laser surface
melting, then it is termed laser surface al-
loying. Laser dispersion hardening is the in-
jection of insoluble particles into the laser
Figure 3-16. Surface-melted aluminium-silicon alloy
(Mag. 50 x). melted surface layer. If the properties are
still insufficient then the surface must be
clad, i.e., a different alloy must be melted
onto the surface much in the same way as
Surface melting produces a very fine eu-
deposits are laid on surfaces using stan-
tectic on the surface of both modified and
dard welding procedures. When a laser is
unmodified Al-Si alloys (Pelletier et al.,
used, this is termed laser-cladding.
1989; Mordike, 1989). Figure 3-16 shows
It is convenient to discuss these tech-
an example of surface melting with un-
niques together as the processes are very
modified A1-13SL The surface was covered
similar. A change in the surface composi-
by a raster and the individual tracks can be
tion can be brought about by melting a
discerned. No difficulties were encoun-
deposit on the surface into the surface
tered in laser treatment. The use of a line
(laser-alloying) or onto the surface with
focus instead of a point focus improves the
minimal substrate melting (laser-clad-
coupling and also the surface quality. The
ding). These are two-stage processes and
hardness profile is shown in Fig. 3-17.
involve first coating the surface and then
laser-treating it. The initial coating can be
3.4.6 Surface Alloying
applied by thermal spraying, electrodepo-
and Surface Cladding
sition or affixing foil to the surface, for
Surface melting alone is often insuffi- example, The thickness of the coating is
cient to provide the properties required. chosen so that when the desired depth is
Consequently it is necessary to change the laser melted, the mixing with the substrate
composition of the surface. If this is done provides the desired composition in the
3.4 Surface Modification Processes 123

(a) . laser
\ beam

wder-
. , ,. . , <'.y/:/ injection
mjeCTK
cladding ^^Uykv nozzle

- Feed direction

(b) yx\ laser , ^


Y/} beam ' / / y
^— nozzle
shield^
gas y\ r
remelted layer coating

' / 7 / molten pool


^ , , ,
substrate / / /

^ Feed direction

Figure 3-18. Schematic drawing of a) one- and b) Figure 3-19. Powder injection head.
two-stage coating processes.

surface layer. The alternative is to add the This determines also the flight time in the
alloying element or dispersed phase at the laser beam and hence the degree of pre-
same time as the surface is melted as part heating. The rate of powder feed can be
of a single-stage process. The alloying ele- continuously varied. Typical rates are 2.5 g
ment may be added in the gaseous form, min" 1 . Powder injection in various forms
powder or wire. Hard metals can be added has become a standard technique at least
by injecting powder into the surface with in the laboratory or small scale produc-
or without bond metal, with or without tion. The alternative method of supplying
coating or enclosing it in wire. Figure 3-18 the addition in the form of wire or filled
shows the two processes schematically. wire is more elegant and less wasteful of
It is possible to coat or alloy virtually material. The refinement of preheating the
any substrate with a very wide range of wire (Burchards and Hinse, 1990) provides
materials. Laser coating/alloying is thus an the opportunity of a significant increase in
extremely versatile and potent technique in deposit rate and hence economic viability.
matching component performance to ser-
vice requirements. Success depends criti-
3.4.6.1 Surface Alloying
cally on the coating parameters and coat-
ing devices used. Figure 3-19 shows a pow- Examples will be discussed of alloying
der injection head. The angle at which the from the gas phase or by melting a deposit-
powder strikes the surface can be varied. ed layer into the substrate. These examples
124 3 Surface Modification by Lasers

suffice to illustrate the potential of the Ti-N


method. There are numerous other exam- 2 5 10 15 22.6
3000
ples and the reader is referred to the litera-
ture.
Laser Gas Alloying 2600 -

Laser gas alloying is the term applied to


changing the composition of the surface by 2200 -
melting it in a stream of gas which will
react with the substrate material. Solid
state reactions are slow and hence it is nec- 2 1800
essary to melt the surface. Laser gas al-
loyed layers are much thicker than those
obtained by solid state reactions even after uoo -
long treatment times. This has particular
advantages for some metals, e.g., titanium. 1000
Although titanium transforms martensiti-
cally on quenching and although this can
be influenced by alloying, no improvement 600
0 10 20 30 40 50 60
in properties is observed, as is the case
for many iron-based alloys. An alternative Figure 3-20. Phase diagrams for systems Ti-N.
means of improving the strength must be
sought, e.g., by a dispersion of a second
hard phase. By laser melting in the pres-
ence of nitrogen nitride dendrites precipi-
tate out, producing a surface layer consist-
ing of TiN in an a-Ti matrix (Mordike,
1987). The process of gas alloying can be
employed for several systems, e.g., Ti-N,
Ti-C, Zr-C, Fe-C. The precise mechanism
of absorption/desorption depends in each
particular case on the nature of the metal-
gas system. The behaviour can in general
be described by the law of mass action. In
applying this law to gaseous systems, the
concentrations can be replaced by the par-
tial pressures.
In the case of nitriding titanium, nitro-
gen is mixed with an inert carrier gas. The
partial pressure of nitrogen and the tem-
perature and nitrogen concentration in the
titanium will determine the rate and direc-
tion of the reaction.
The phase diagrams for TiN is shown
below Fig. 3-20. TiN forms at tempera- Figure 3-21. Microstructure of laser-gas alloyed Ti.
3.4 Surface Modification Processes 125

0.66-105W cm 2 • 0.5 m/min


RT A 1 m/min
40Vol.-% N2 * 2 m/min
60Vol.-% Ar D 3 m/min
overlap 75% • 5 m/min

Figure 3-22. Relationship between TiN


layer hardness and displacement rate.
100 200 300 400 500 600 700 800 900 1000
Distance from the surface in pm

tures in excess of 2600 °C. The microstruc- cally or plasma-deposited, into the surface
ture of the nitrided surface is shown in of Al alloy will produce a fine dispersion of
Fig. 3-21. The dendrite size depends on the intermetallic precipitates throughout the
partial pressure of nitrogen and interac- melted layer. The addition of nickel has
tion time, which can be the sum of several been investigated by several groups (Pel-
passes. Under appropriate conditions a letier et al., 1989; Mordike and Veit, 1988;
continuous TiN layer can be produced. Bergmann etal., 1988).
This can pose problems in practice with Three intermetallic phases are likely to
thick layers due to cracking. Figure 3-22 form, Al3Ni, Al 3 Ni 2 and Al-Ni. Their
shows the relationship for a given nitrogen structure and composition range are given
partial pressure between thickness of the in Table 3-1.
layer as determined by the hardness and Figure 3-23 shows the surface of
displacement rate. AlSi9Cu surface alloyed with 19.6 at.
%Ni. Increasing the nickel content to 25%
Surface Alloying of Aluminum Alloys
increases the hardness in the surface layer
Aluminum alloys, apart from Al-Si, suf- to values between 900 and 1000 HV. This
fer from poor wear resistance and even results in significant increase in load bear-
Al-Si alloys have insufficient load-bearing Table 3-1. Intermetallic compounds in Al-rich Al-Ni
capacity. The problem is thus initially one
alloys.
of increasing the strength. It is found that
the increase in strength obtained by simply Inter- Crystal Composition Melting
remelting Al-Si alloys was only modest. metallic structure at.% Ni point
compound
There is no possibility of increasing this as
changing the silicon content produces un- Al3Ni ortho- 25.0 Melts
acceptable changes in the bulk properties. rhombic incongruently
Any increase in the number of dispersed at 854 °C
particles must come from direct addition Al3Ni2 hexagonal 36.3-40.8 Melts
or reaction with aluminum. Many metals incongruently
at 1120°C
form intermetallic compounds with alu-
AINi B2 type 45-60 1638°C
minum. Melting a metal coating, galvani-
126 3 Surface Modification by Lasers

'"•"' -Vv<

Figure 3-23. AlSi9Cu layer alloyed with 19.6 at.% Figure 3-24. Laser-melted deposited WC-Co layer.
Ni. Substrate Ck45 steel (Mag. 100 x).

ing capacity and at the same time a reduc-


tion in abrasive wear.

3.4.6.2 Laser Cladding


The most commonly applied cladding
materials are stellites or hard metals (Steen,
1987). They are applied by one of the
methods previously discussed. The method
initially adopted was to laser-melt plasma- 500 1000 1500 2000 2500
Distance from the surface in urn
deposited layers. Ideally the laser power
should be set to melt the deposited layer Figure 3-25. Hardness profile of a laser-melted WC-
Co layer.
onto the substrate so as produce a good
bond without dilution of the layer. In the
case of hard metals, it is unavoidable that
the carbide particles are largely dissolved, Figure 3-26 shows a layer of TiC laser-
which may deleteriously affect proper- melted on to a carbon steel substrate. The
ties. Figure 3-24 shows the structure of a difference in structure from that obtained
surface-melted WC-Co plasma-deposited by melting predeposited coatings is appar-
layer. The structure apart from individual ent. The carbides are retained rather than
undissolved carbide is very fine, essentially dissolved. The structure is therefore a true
free of pores and crack free. The final composite with hard particles in an essen-
thickness of such layers is typically less tially ductile matrix. To prevent oxidation,
than 1.0 mm. Increasing the thickness in- the carbide particles can be coated, in the
creases the tendency to cracking. This lim- above case by nickel.
its the maximum thickness possible with The TiC particle size in the powder used
the technique. The average hardness of the was 45-90 jim. After spraying and laser
layer is about 650HV 0<1 (Fig. 3-25). The melting the size measured (circular inter-
layers are extremely well bonded to the cept) was about 10% smaller. This ignored
substrate and exhibit good thermal shock the fine reprecipitated particles in the ma-
and impact resistance. trix which became visible at high magnifi-
3.4 Surface Modification Processes 127

3.4.7 Surface Treatment


of Ceramic Materials

Plasma-sprayed ceramic coatings on


hot-section components of gas turbines of-
fer significant advantages by increasing the
operating temperatures and thus efficien-
cy. Research is directed to improving these
coatings. Most of the coatings are based
on zirconia as it has a lower thermal con-
ductivity and higher coefficient of thermal
Figure 3-26. TiC particles in a Ni matrix, optimum
melting conditions. Substrate, carbon steel (Mag.
expansion than other ceramics. The main
100 x). life-limiting factor of such plasma-sprayed
coatings is oxidation of the metallic bond-
ing coat by corrosive gases and molten
Table 3-2. Hardness values of TiC-Ni layer.
salts able to penetrate the interconnected
Microstructure HV0.3 porosity of sprayed coatings. The metallic
TiC particles 2300 coat ensures a good bond to the ceramic
Ni-rich phase 470 coating and should also limit corrosion.
Heat-affected zone 800
Substrate (CK45)
Porosity in sprayed coatings is unavoid-
230
able and in many respects desirable since
porosity increases the thermal insulation
and resistance to thermal cycling.
cations. Table 3-2 lists the hardness values Surface melting of porous layers would
measured for the various phases and improve the performance considerably.
zones. The densification of the surface layer
Martensite has formed in the heat-af- would prevent access to gas whilst at the
fected zone. The macro hardness value of same time retaining the heat insulation of
650 HV0 3 in this layer shows this. the porous substrate. Various workers
Cobalt alloys are suitable layers to com- have reported results on surface melting of
bat wear, particularly where high tempera- ceramics (Galasso and Veltri, 1983;
tures are involved. Stellites are easy coat- Zaplatiynsky, 1982; Iwamoto, 1982;
ing materials and find wide application for Adamski and McPherson, 1986; Havrda
valve seats. The layers produced have a et al., 1986). The problem is crack forma-
fine dendritic structure with a hardness tion due to anisotropic thermal expansion
of ^470 HV (Mordike and Burchards, combined with low toughness. Apart from
1989). sealing the pores, laser-melting can
Injection of powder on to the surface or provide a smoother surface and hence re-
laser wire cladding of metals has similarly duce aerodynamic losses. Sivakumar and
been studied and perfected by several Mordike (1988) studied the problem of
groups (Steen, 1987; Amende, 1991; Beck- crack formation in surface melting of ce-
er etal., 1988; Burchards and He, 1991; ramics based on ZrO 2 , A12O3 and TiO 2 .
Kahrmann, 1988; Mordike and Bur- The tendency to cracking can be reduced
chards, 1989). The reader is referred to the by using the pulsed mode and high energy
literature for detailed information. densities as this is more suitable for melt-
128 3 Surface Modification by Lasers

ing a thin layer with a high temperature form cooling of the melted spot which pro-
gradient. The rate of cooling during solidi- duces elastic thermal stresses. At tempera-
fication is directly proportional to the en- tures above ^0.5 Tm these stresses can be
ergy density but an upper limit is imposed relieved by plastic deformation, but below
as the surface temperature should not ex- this temperature they build up on cooling
ceed the boiling point. and since they are tensile in character
In the case of all three ceramics, surface cause fracture when the fracture strength is
melting on specimens at room temperature exceeded. On the basis of considerations of
was not possible without some cracking. cooling of thin discs it is possible to esti-
ZrO 2 was worst and A12O3 best. In all cas- mate the maximum stress developed, using
es, melting thin layers produced transverse known or estimated values of the coeffi-
cracks which can possibly be tolerated. On cient of thermal expansion, the modulus of
increasing the thickness, a point is reached elasticity and the range of temperature
when longitudinal cracks form. These fa- during cooling in which the stresses cannot
cilitate spalling and can not be tolerated be relieved. If the surface is preheated, the
under any circumstances. Figure 3-27 temperature range in which the stresses
shows a cross-section of a surface-melted can build up can be reduced. For example,
layer of ZrO 2 -7Y 2 O 3 . The problem of for A12O3, which is plastic above 1000°C
cracking arises mainly from the non-uni- (Dorre and Hubner, 1984), treatment with
specimens at room temperature would re-
sult in a maximum stress of 1488 MPa,
which is much higher than quoted values
of the fracture strength (220 to 310 MPa).
By preheating to 800 °C, the effective cool-
ing range is reduced to 200 and the maxi-
mum stress developed is only « 305 MPa.
No cracking is observed in surface melting
of A12O3 preheated to 800 °C. Similar cal-
culations for ZrO 2 show that preheating
temperatures of 1050 °C must be employed
ta) which is too high for current substrate ma-
terials. Consequently, for ZrO 2 some mod-
ification to the ceramic composition is nec-
essary to increase the fracture strength
and/or fracture toughness.
The benefits in practice which may be
achieved by laser surface melting are
shown by hot corrosion tests. In a test used
by Sivakumar (1988), only crack-free spec-
imens (i.e., made by laser treatment of pre-
heated specimens) withstood the test. In
(b) fact, the specimen treated at room temper-
Figure 3-27. Cross sections of laser-melted ZrO2- ature was worse than the plasma-sprayed
7Y 2 O 3 . a) Thin layer melted on top. b) Entire coating specimen although few cracks were present
melted (Mag. 25 x). (Fig. 3-28). Zaplatiynsky (1982) showed
3.5 Wear Properties of Laser-treated Surfaces 129

component wear. In engineering systems,


the tribological conditions are complex
and more than one wear mechanism is op-
erative which make compromise solutions
0 1 2 3
necessary.
Figure 3-28. Appearance of A12O3 coatings after hot
salt corrosion. 0 As sprayed. 1 Lasered at room tem-
The methods of laser treatment previ-
perature, 2, 3 Lasered at 800 °C. ously discussed, i.e., transformation hard-
ening, surface alloying and cladding, in-
volve structural changes which must be
that in burner-rig tests, i.e. simulated jet exploited in a particular wear situation.
engine conditions, where the salt deposi- Hardness measurements are universally
tion conditions were different and the used as a mean of establishing the depth
probability of salt penetration lower due to and extent of a laser surface treatment. It
the smaller number of cracks, laser-treat- is wrong to believe, however, that to com-
ment at room temperature also improved bat wear, hardening the surface of the en-
the corrosion resistance. dangered partner is all that is necessary.
This one example suffices to demon- The microstructure and not the hardness is
strate the problems and possible solutions the prime consideration.
associated with surface melting of ceram-
ics. 3.5.1 Transformation Hardening
Steels and cast irons are often hardened
3.5 Wear Properties by laser treatment to combat wear. Such
treatment does not automatically imply an
of Laser-Treated Surfaces increase in wear resistance, although there
is in general an increase in resistance to
The main reason for surface treatment is
abrasion and also surface fatigue (pitting),
to improve the wear resistance and hence
the latter by increasing the load-bearing
useful service life of components. Compo-
capability. The hardness has no influence,
nents in general engineering use are subject
however, either on the coefficient of wear
to different types of loading simultaneous-
(Burwell and Strang, 1952) or on the rate
ly and indeed different parts of the compo-
of wear in the case of adhesion wear.
nent can experience completely different
For the latter it is better to produce multi-
conditions. Wear is the result of frictional
phase microstructures with a lower hard-
processes between components or compo-
ness than a predominantly martensitic
nents and materials in relative motion.
structure. Typical applications of trans-
Consequently wear is a function of the sys-
formation hardening are cylinder liners
tem and not a material constant. Improve-
(Amende, 1990), cog teeth (Miller and
ment of the wear resistance of a compo-
Winemann, 1978) and shafts.
nent requires a knowledge of the system,
the material, environmental conditions
3.5.2 Surface Melting
and the dominant wear mechanisms, e.g.,
and Surface Alloying
adhesion, tribo-oxidation, abrasion and
surface fatigue. It is against this back- Melting the surface provides the chance
ground that an appropriate laser treatment of removing surface defects, modifying
must be selected or developed to reduce and refining the surface. Elimination of
3 Surface Modification by Lasers

3.5.3 Cladding
Abrasive wear is best combatted by pro-
ducing a surface harder than the abrading
medium. This is best achieved by coating
the surface with hard particles, usually car-
bides. The carbide or other hard material
can be chosen for ease of application and
also the expected conditions. The wear oc-
curs by the matrix material being removed
until the carbide particle breaks out. If the
mean free path of the carbide particles is
less than the diameter of the abrading
medium, then wear of the matrix is more
difficult. The mean free path depends on
20 40 60 80
Time in h
the size and volume fraction of carbide
particles. Figure 3-30 shows the abrasive
Figure 3-29. Improvement in rolling wear in TiA16V4
achieved by gas alloying. Driving roll • •: laser gas wear measured on untreated TiA16V4 and
nitrided, • not ground, Q ground, HV0 3 850-1010. TiC-coated TiA16V4. The wear was mea-
Driving roll •: annealed ground, HV0 3 375. Driven sured by the pin and disc method
roll: 42CrMo4, hardened ground, HV0 3 630. RPM (Mordike, 1990). Different microstruc-
300 m~ 1 , surface pressure 63 N mm~ 2 , ship 10%, no
lubrication.
tures result for the single- and two-stage
cladding processes and this affects the
wear behaviour. The one-stage process is
capable of producing much thicker layers
surface defects has been shown to marked-
ly improve rolling wear resistance (Mor-
dike, 1988). Modifying and refining the 50
surface microstructure also increases the
resistance to rolling wear by increasing the
yield stress. In addition, a fine distribution uncoated
of phases as obtained by laser treatment
improves the adhesive wear resistance.
This has been observed for a wide range of
materials. Figure 3-29 shows the improve-
ment in rolling wear achieved on TiA16V4
by gas alloying to form TiN in the surface
layer (Mordike, 1990).
On increasing the contact pressure from
63 MPa to 89 MPa an abrupt increase in
wear rate was observed. This is due to the TiC/Ni (70/30)
fact that at 89 MPa the layer is no longer TiC
able to withstand the Hertzian pressure 10 20 30 40 50 60 70 80
and hence the predominant mode of wear Load in g -cm
changes from abrasive wear to fatigue Figure 3-30. Abrasive wear in TiA16V4 before and
wear. after cladding by TiC.
3.6 Other Effects of Laser Treatment 131

and is capable of being varied more by mation hardened steels and also made
choice of particle size and composition. some measurements on clad specimens.
Erosive wear is similar to abrasive wear
but very much more complex. Depending 3.6.1.1 Transformation Hardening Stresses
on the impact angle and impact velocity of
the eroding particles, the nature of the In transformation hardening, the pur-
wear can change. Abrasive wear predomi- pose of the treatment is to induce a phase
nates at small angles of incidence whereas change. The coarseness of the microstruc-
for normal incidence, fatigue failure and ture and the heating rate as already dis-
ablation predominate. cussed determines the degree of austeni-
tization and hence hardness. The intensity
and distribution of the residual stresses re-
flect this (Fig. 3-31). Furthermore, in mul-
3.6 Other Effects tipass-treated surfaces the previous pass is
of Laser Treatment modified by subsequent passes. The degree
of overlap is important in determining the
3.6.1 Internal Stresses magnitudes and distribution of residual
stresses. Generally the surface is in com-
In all laser processing, problems may be
pression as a result of the transformation.
caused by the formation of residual stress-
es. These can cause distortion or even
3.6.1.2 Cladding Stresses
cracking. Although laser treatment is bet-
ter in this respect than many other tech- In this case a material with different
niques, the dependence of residual stresses properties is applied to the surface. The
on the production procedure and their in- elastic properties, thermal expansions and
fluence on the bulk properties of the com-
ponent must both be understood if laser
600
surface treatment is to be accepted in in-
dustry.
There are currently two methods used £00 - tempered
for determining the residual stresses, X-ray £00 °C
annealed
methods (Maeder etal., 1981) and the
Leluan method (Leluan, 1969). The X-ray 200 -
method is difficult to apply if the surface is
rough or if a texture is present (see Chap. Q_

10, Sec. 10.3.7). The Leluan method in-


volves sequential chemical machining and
measuring the shape relaxation after each -200
machining operation. The stress values ob-
tained are therefore average values. The
origin of the internal stresses lies in the -£00

nonuniform cooling together with any sol-


id state transformations which may occur.
-600
Chabrol and Vannes (1986) have carried Depth in mm
out a comprehensive study of the develop- Figure 3-31. Residual stress distribution for different
ment of internal stresses in laser transfor- microstructures.
132 3 Surface Modification by Lasers

surface

Figure 3-32. Residual stress field


of stellite-clad steel.
substrate cladding

temperature dependence of the mechanical ed stresses obviously influence the me-


properties are factors which must be con- chanical behaviour and corrosion proper-
sidered when matching coating and sub- ties. They must be added to any stresses
strate materials. Figure 3-32 shows a typi- which arise in service. The stresses arising
cal profile for a laser clad substrate. Stellite from surface treatment can fluctuate wild-
powder was injected into the laser beam as ly and also change in sign in different re-
the substrate was a martensitic steel. gions. It is impossible to predict such
The results show that tensile residual stresses and their influence. This is one of
stresses are induced in the clad layer and the aspects of laser treatment which has
again in the substrate. An intermediate been insufficiently studied. It has been
zone is characterized by a peak in tensile shown that the distribution of residual
strength. stresses depends on the microstructure of
the substrate and the laser parameters.
Methods are being developed of producing
3.6.2 Effect on Bulk Properties,
adaptive layers, i.e., layers designed to
in Particular, Fatigue Life
minimize the residual stresses whilst at the
A problem to be resolved before a laser- same time preserving the layer properties.
treated component can be put into service Attempts are also being made to predict
is whether the treatment has affected the the formation of residual stresses by mod-
bulk properties and if so, how this would elling.
influence the performance. The remarks Ultimately, in any case, the components
on residual stresses show that all laser must be tested under operational condi-
treatments produce stresses and an influ- tions. It has been shown (Bergmann, 1986;
ence on the properties is unavoidable. Amende, 1990; Mordike, 1986) using stan-
There are the obvious effects such as dard fatigue specimens that the fatigue re-
cracking of the layer which can arise dur- sistance is changed by laser treatment. In
ing laser treatment or subsequently on me- those cases where compressive stresses can
chanical working, e.g., grinding, and there be generated in the surface there is an im-
is also the problem of the associated dis- provement in fatigue resistance and in
tortion which often arises. These associat- those cases where tensile stresses are in-
3.7 Industrial Applications 133

duced there is a reduction in fatigue resis-


tance. If components have been mechani-
cally worked or heat-treated, then there is
the complicating effect of surface anneal-
ing which can affect the fatigue resistance.
Fortunately, for many applications fatigue
considerations are not critical (e.g., form-
ing tools and dies) but for moving parts
subjected to fluctuating stresses fatigue
tests are necessary.

Figure 3-33. Transformation hardening of a press


3.7 Industrial Applications tool (Courtesy of MAN Neue Technologie).

Surface engineering applications of laser


treated surfaces are confirmed to harden-
ing and isolated cases of cladding. The
breakthrough to mass production will be
made in 1991 when Volkswagen (Ger-
many) start to laser surface-treat cam-
shafts following development (Mordike,
1988) at the Technical University, Claus-
thal, Germany.
Components which are ideal for laser
treatment are those with highly stressed Figure 3-34. Transformation hardening of pearlitic
regions which represent only a small frac- cast iron cylinder blocks. (Courtesy of BIAS Bre-
tion of the total volume of the component. men).
It is then possible to treat the required sur-
face without too much application of heat
and hence little danger of distortion. production are hardening of cylinder lin-
MAN (Germany) Neue Technologie has ear sealing surfaces (Mordike and Bur-
undertaken a number of interesting appli- chards, 1989), shafts and splines, racks
cations. Hardening has been applied to for rack and pinions.
hardening of cylinder liners for car, lorry The applications demonstrate that lasers
and ships' diesels (Amende, 1990). are ideally suited to local treatment of
Figure 3-33 shows a press tool in the large components not amenable to harden-
process of being hardened. The hardening ing by other methods, and local hardening
tracks are clearly visible. Figure 3-34 of small components which show excessive
shows hardening of cast iron cylinder lin- distortion when hardened by conventional
ers. The liners are large enough for the methods.
hardening optics to be inserted. By con- Cladding is an expensive process and it
trolling the insertion of the optics and ro- is not surprising that applications have to
tating the liner it is possible to achieve any be selected carefully. Figure 3-35 shows the
desired hardening pattern. Other examples localized cladding of a valve seat for a
reported of transformation hardening in large diesel motor. Powder is sprayed into
134 3 Surface Modification by Lasers

beam onto the cylinder ring groove. Other


applications are internal surfaces of tubes
(Sepold, 1990) and turbine blades (Rolls
Royce (U.K.) and Pratt and Whitney
(U.S.A.)). Such applications result in con-
siderable saving owing to the high price of
the component and absence of competitive
techniques.
This is not the case in the motor industry
where economic considerations play a ma-
jor role in determining which processes are
employed.
It has been shown that surface melting
using lasers is feasible. The use of lasers
depends on whether the required proper-
ties can be attained and whether the pro-
duction brings technical and economic ad-
vantages. It is not sufficient to consider
simply using the laser to replace an existing
hardening process. The whole production
process must be analyzed to see where it
can be modified to benefit from the advan-
Figure 3-35. Cladding of diesel motor valve seat.
tages offered by laser treatment. Another
(Courtesy of MAN Neue Technologie).
problem is the caution demonstrated by
manufacturers with regard to the introduc-
tion of a new technology when failure
could involve very high costs. Testing pro-
cedures are thus extensive and time-con-
suming. Many components have been sur-
face-melted, e.g., camshafts, rocker arms,
brake drums, spring supports and axle
supports. The most demanding applica-
tion is surface-melting of camshafts. This
became possible only after lasers of suffi-
cient power became available so that, with
Figure 3-36. Cladding of piston-ring grooves. (Cour- appropriate beam-forming, a track of the
tesy of BIAS Bremen). required width could be method in a single
pass. (Previously, the surface had been te-
diously remelted by laying narrow tracks
the laser beam and melts onto the surface side by side until the required area had
with a minimum of mixing with the sub- been treated. The production rate was too
strate. Another interesting application de- slow for the method to be economic.) Fig-
veloped by BIAS Fig. 3-36 is the cladding ure 3-37 shows a camshaft surface-melted
of piston ring grooves in large pistons. In using a 6 kW Heraeus laser equipped with
this application wire is fed down the layer a line focus optical system.
3.9 References 135

Figure 3-37. Surface-melted camshaft.

Production rates of camshafts higher Bergmann, H. W, Barton G., Mordike, B. L., Fritsch,
than those of competitive processes as- H. U. (1984), Rapidly SolidifiedMetastable Materi-
als. Amsterdam: Elsevier, pp. 28, 29.
sured its acceptance in principle. This was Bergmann, H. W., Gundel, P. H., Kalinitchenko, A. S.
followed by a comprehensive laboratory (1988), Optoelektronik4, 510-517.
and field testing programme before the fi- Boettinger, W.J. (1981), in: Rapidly Solidified Amor-
phous and Crystalline Alloys, Vol. 8: Kear, B.H.,
nal decision was made. Giessen, B.C., Cohen, M. (Eds.). New York/
This indicates that the acceptance of la- Amsterdam/Oxford: North Holland, pp. 15-31.
ser surface treatment is dependent on the Burchards, D., He, X. (1991), Journal of Lasers in
Materials Engineering (in press).
application and industry involved. Wide Burchards, D., Hinse, A. (1990), in: ECLAT '90,
acceptance in mass production will be a Bergmann, H.W., Kupfer, R. (Eds.). Diisseldorf:
slow and tedious process. DVS, pp. 439-450.
Burwell, J.T., Strang, C D . (1952), J. Appl. Phys. 23,
18-28.
Chabrol, C , Vannes, A.B. (1986), in: Laser Surface
Treatment of Metals: Draper, C.W., Mazzoldi, P.
3.8 Acknowledgements (Eds.). NATO Advanced Science Institutes Series.
Dordrecht/Boston/Lancaster: Martinus Nijhoff
Publishers, pp. 435-450.
The author is indebted to Dr. Amende, Coriell, S.R., Skeraka, R.R (1980), in: Rapid Solid-
MAN (Germany) Neue Technologie, and ification Processing, Principles and Technology II,
to Prof. Sepold, Bremer Institut fur Ange- Mehrabian, R., Kear, B.H., Cohen, M. (Eds.).
wandte Strahlenphysik, for supplying pho- Baton Rouge, LA: Claitors, pp. 35-49.
Dorre, E., Hiibner, H. (1984), Aluminia 103. Berlin:
tographs of the treatment of components Springer Verlag.
which are in industrial service. Galasso, F. S., Veltri, R. (1983), Ceramic Bull. 62, 253.
Havrda, M. (1986), Proc. 11th Int. Thermal Spraying
Conf. 1986. Oxford: Pergamon Press, p. 569.
Heavens, O. S. (1965), Optical Properties of Thin Sol-
id Films. New York: Dover.
3.9 References Iwamoto, N. (1982), Thin Solid Films 95, 563.
Johnson, P.B., Christy, R. W. (1975), Phys. Rev. B 11,
Adamski A., Me Pherson, R. (1986), Proc. 11th Int. 1315.
Thermal Spraying Conference 1986. Oxford: Perga- Jones, H. (1973), Rep. Prog, in Physics 36, 1425-
mon Press, p. 555. 1497.
Amende, W. (1990), in: Der Laser in der industriellen Kahrmann, W. (1988), ECLAT '88. Diisseldorf: DVS,
Fertigungstechnik: Treiber, H. (Ed.). Darmstadt: pp. 119-120.
Hoppenstedt Verlag, pp. 193-233. Lawley, A. (1977), Int. J. Powd. Met. 13, 169-188.
Becker, R., Binruth, C , Sepold, G. (1988), ECLAT Leluan, A. (1969), Revue du Garni, Mechanique Juin-
'88. Diisseldorf: DVS, pp. 121-124. Juillet, 19-24.
Bergmann, H. W. (1986), in: Laser Surface Treatment Mac Intyre, R. M. (1986), in: Laser Surface Treatment
of Metals: Draper, C. W., Mazzoldi, P. (Eds.). NA- of Metals: Draper, C. W, Mazzoldi, P. (Eds.). NA-
TO Advanced Science Institutes Series. Dordrecht/ TO Advanced Science Institute Series. Dordrecht/
Boston/Lancaster: Martinus Nijhoff Publishers, Boston/Lancaster: Martinus Nijhoff Publishers,
pp. 351-368. pp. 545-550.
136 3 Surface Modification by Lasers

Maeder, G., Lebrun, XL., Sprauel, J.M. (1981), Ma- Orlitsch, J., Rose, A., Weist, P. (1973), Atlas zur
teriaux et Techniques Avril-Mai, 135-149. Wdrmebehandlung der Stdhle. Dusseldorf: Verein
Miller, J.F., Winemann, J. A. (1978), Metal Processes Deutscher Eisenhiittenleute, Vol. 3.
III, 38. Pelletier, J.M., Bonnet-Jobez, S., Vannes, A.B.,
Mordike, B. L. (1986), in: Laser Surface Treatment of Gobin, P. F. (1989), in: Laser 4, Ghosh, S. K. (Ed.):
Metals: Draper, C. W, Mazzoldi, P. (Eds.). NATO Tech. Trans. Series. Paris: Int. Inst. of Techn.
Advanced Science Institutes Series. Dordrecht/ Transfer, 143-152.
Boston/Lancaster: Martinus Nijhoff Publishers, Pond, R.B., Maringer, R.E., Mobley, C.E. (1976),
pp 389-412. New Trends in Materials Fabrication. Cleveland,
Mordike, B.L. (1987), Oberflachentechnik Surtec, Ohio: Amer. Soc. Metals, pp. 128-164.
Miinchen: Hanser, pp. 153-158. Sepold, G. (1990). Bremer Institut fur Angewandte
Mordike, B.L. (1988), Opto Elektronik 4, 482-490. Strahlentechnik, Private Communication.
Mordike, B.L. (1989), Oberflachentechnik Surtec, Shavarew, K.M. (1978), High Temp. Res. 16, 441.
Miinchen: Hanser, pp. 571-578. Sivakumar, R., Mordike, B.L. (1988), Surface Engi-
Mordike, B.L. (1990), in: Laser 6, Mordike, B.L., neering 4, 127-140.
Vannes, A.B. (Eds.). Paris: Int. Inst. of Techn. Steen, W.M. (1987), Oberflachentechnik Surtec.
Transfer, 9-20. Miinchen: Hanser, pp. 159-166.
Mordike, B.L., Veit, S. (1988), ECLAT '88. Diissel- Weiting, T.T., De Rosa, J.L. (1979), J. Appl. Physics
dorf: DVS, pp. 95-96. 50, 1071.
Mordike, B.L., Burchards, D. (1989), in: Laser 5, Zaplatiynsky, I. (1982), Thin Solid Films 95, (3), 275.
Ghosh, S.K. (Ed.). Paris: Int. Inst. of Techn.
Transfer, 157-172.
4 Powder Metallurgy

V.S. Arunachalam * and R. Sundaresan2


1
Scientific Adviser to the Minister for Defence, New Delhi, India
2
Defence Metallurgical Research Laboratory, Hyderabad, India

List of Symbols and Abbreviations 139


4.1 Introduction 142
4.2 Production of Powders 143
4.2.1 Mechanical Methods 144
4.2.1.1 Comminution 144
4.2.1.2 Mechanical Alloying 146
4.2.2 Chemical Methods 148
4.2.2.1 Reduction 148
4.2.2.2 Decomposition 149
4.2.2.3 Precipitation 150
4.2.2.4 Self Propagating High Temperature Synthesis 150
4.2.3 Electrochemical Methods 151
4.2.4 Physical Methods 151
4.2.4.1 Principles of Atomization 152
4.2.4.2 Gas and Water Atomization 154
4.2.4.3 Centrifugal Atomization 156
4.2 A A Ultrasonic Gas Atomization 157
4.2.4.5 Vacuum Atomization 158
4.2.4.6 Rapid Solidification 158
4.3 Characterization of Powders 159
4.4 Compaction of Metal Powders 161
4.4.1 Pressureless Compaction 162
4.4.1.1 Vibratory Compaction 162
4.4.1.2 Slip Casting 163
4.4.1.3 Injection Molding 163
4.4.2 Unidirectional Compaction 163
4.4.3 Cold Isostatic Compaction 165
4.4.4 Explosive Compaction 167
4.4.5 Powder Rolling 169
4.5 Sintering 170
4.5.1 Solid State Sintering 170
4.5.1.1 Equations of Sintering 171
4.5.1.2 Pore Closure and Development of Microstructure 173
4.5.1.3 Sintering Mechanism Maps 173
4.5.2 Liquid Phase Sintering 173

Materials Science and Technology


Copyright © WILEY-VCH Verlag GmbH & Co KGaA. Allrightsreserved.
138 4 Powder Metallurgy

4.5.3 Activated Sintering 176


4.6 Deformation Processing at High Temperatures 176
4.6.1 Principles of Pressure Sintering 177
4.6.2 Hot Isostatic Pressing 179
4.6.3 Uniaxial Hot Pressing 180
4.6.4 Powder Forging 181
4.6.5 Powder Extrusion 182
4.6.6 Special PM Processes 183
4.6.7 Post-Consolidation Operations 184
4.7 Applications 185
4.8 References . 189
List of Symbols and Abbreviations 139

List of Symbols and Abbreviations

a particle radius
a,d constants
A constant
A, creep constant
As surface area
b compression coefficient
B constant
B magnetic flux density
Bs microstructure based constant
c vacancy concentration
C slope of the deformation resistance against temperature curve
c ps heat capacity
d average particle size
d diameter
dx diameter of the liquid metal stream
D melt pool diameter
e emissivity
E free energy
f propellant force
/a flow rate of air
/. flow rate of liquid
/v cyclic force
peak vibratory compaction force
F
P
direct force
K amplitude of cyclic force
9 acceleration due to gravity
h half distance of approach of the particle centers
H magnetic field
AH droplet cooling
AH0 enthalpy of formation
k constant
kB Boltzmann constant
K constant
AL linear shrinkage
Lo initial length
m, n sintering parameters
creep constant
Nu Nusselt number
Pu2 partial pressure of hydrogen
PH2O partial pressure of water vapor
P vapor pressure
P pressure
applied pressure, effective pressure
140 4 Powder Metallurgy

extrusion pressure
pressure of liquid metal, pressure of atomizing atmosphere
particle radius
principal radii of curvature
R extrusion ratio
R gas constant
Re Reynold's number
s Stefan-Boltzmann constant
s, s0 solubilities
t time
T temperature
Tad adiabatic temperature
Td9 T w , I,g temperature of the droplet, temperature of the chamber wall,
temperature of the gas
V velocity
V volume
AV reduction of volume
v0 initial volume
K volume of propellant gases for unit mass propellant
w powder mass
W Weber number
w punch assembly mass
X radius of the neck
ag grain growth parameter
y surface tension
s charge density
Co.

total creep rate


fix, Zy> K strain rates in x9 y9 z direction
er9 e09 ez radial strain, circumferential strain, axial strain
n coefficient of viscosity
kinematic viscosity of liquid metal, kinematic viscosity of gas
0 volume porosity
6 densification rate
jl chemical potential
V Poisson ratio
Q density
^app apparent density of powder
tccomp density of compacted mass
O stress
creff effective stress
°y yield stress
CO rotation rate
Q atomic volume
List of Symbols and Abbreviations 141

APT ammonium paratungstate


CAP consolidation by atmospheric pressure
CSC centrifugal shot casting
EBRD electron beam rotating disk process
FEM finite elements method
HIP hot isostatic pressing
MA mechanical alloying
PM powder metallurgy
PREP plasma rotating electrode process
PSV pulverisation sous vide
REP rotating electrode process
ROC rapid omnidirectional compaction
RRP rotating rod process
RS rapid solidification
RSP rapid solidification processing
142 4 Powder Metallurgy

4.1 Introduction other instances where particulates were


heated and bonded to form desired objects.
Powder metallurgy is an ancient tech- The famous Damascus sword with co-
nology. Our ancestors used it extensively bonded layers of iron-carbon alloys of dif-
when they did not possess the required ferent compositions and the platinum jew-
knowledge or wherewithal to melt metals, elry of the Inca civilization typify this
or even reduce ores. They therefore heated approach.
the metal nuggets they collected and beat Powder metallurgy (PM) received a ma-
them together to form the required shapes. jor boost in this century from the growth of
Later they used chunks of ores that were the electrical industry. Wires made from
reduced by charcoal under heat and high melting metals and alloys were
bonded together. A classic example of such needed to replace the carbon heating ele-
an effort is the Iron Pillar of Delhi which ments of incandescent lamps; tungsten
was fabricated during the reign of Emperor metal produced by powder metallurgy met
Ashoka in the second century B.C. As the need. This metal was later replaced by
monuments go, it is a large one weighing tungsten alloys containing dispersoids to
over six tons and it has withstood the rav- increase the life of the filaments. Other re-
ages of time rather well (Fig. 4-1). There are fractory metals needed for similar applica-
tions were also produced by powder metal-
lurgy. In fact, until the middle of this
century, PM was exclusively used either for
producing parts from refractory metals
and compounds, or for fabricating struc-
tures with controlled porosity or disper-
soids.
As in the case of conventional electrical
power, the emergence of nuclear power
also brought in new challenges to PM. Fis-
sile materials for nuclear fuel were needed
as ceramic compounds because of their
high temperature strength and environ-
mental compatibility. PM techniques were
so successful that practically all nuclear
fuels are currently produced using the PM
route (see Volume 10, Chapters 1-3).
With melting temperatures for all metals
well within reach, PM techniques are now
widely employed for their other attributes.
PM is in itself a complete materials pro-
cessing route. Often the process begins
with the reduction of ores to produce pow-
der and the mixing of appropriate alloying
additions. The homogeneity of composi-
tion is also assured down to the size of the
Figure 4-1. Delhi iron pillar. powder particle itself. The powder agglom-
4.2 Production of Powders 143

erates are then shaped into products with tion of powder; compaction and sintering,
the application of pressure and tempera- or hot pressing where compaction and sin-
ture. When necessary, some additional tering are combined into a single step.
processing steps such as forging are intro- Where necessary, these steps are followed
duced as finishing operations. by further deformation processing. In the
Today, PM is used for manufacturing a following Sections, we shall discuss these
variety of products. Powders can often be steps in some detail, as also the applica-
the end products in themselves and are tions of PM in many areas of materials
used in many industrial applications. Pro- processing.
duction of porous products such as self-
lubricating bearings and filters is made
easy because of PM. Refractory metal 4.2 Production of Powders
products and composite structures such as
cemented carbides are also produced using The size, shape and purity of the powder
this route. A recent application is in the are important parameters in determining
more demanding area of aerospace tech- the quality of a PM product. Considerable
nology where PM is preferred not only for effort has therefore gone into developing
the attractive high-temperature properties a variety of techniques to manufacture
and desirable microstructures, but for the metal and alloy powders with the required
near-net shape of the end products as well. properties. Even though it is possible to
PM is intrinsically economical in the use fabricate PM products from powders of
of raw materials as only minimum scrap is any size, practical considerations dictate
generated during processing. Further, the that the particles should be small and their
consumption of energy is less compared to size distribution appropriate to pack the
conventional ingot metallurgy. This is es- volume of the preform efficiently. The
pecially true when products are needed in voids in a powder agglomerate have a geo-
very large numbers. In spite of these attrac- metrical relationship to the particle size:
tions, there are some limitations imposed the finer the particle size, the smaller is the
both by the processing equipment such as size of the void. These voids are to be filled
presses and furnaces, and by the large sur- during compaction and sintering. As sin-
face areas of powder aggregates. Large- tering is a diffusion-controlled process,
sized products are more easily produced small pores are more easily filled, thus
by conventional metallurgical operations making small particles attractive starting
than by PM. There is also some resistance materials for PM processing. There is also
to the use of PM products in critical load- an additional advantage: the specific sur-
bearing applications; this is due more to face energy of fine particles is large com-
the non-availability of reliable quality as- pared to that of coarse ones, and this pro-
surance techniques for detecting small re- vides an increased driving force for sin-
sidual pores and other defects than to the tering. But there are also instances where
processing route. In many applications, large surface areas result in extensive for-
this resistance has been overcome by fin- mation of thin oxide films which may ad-
ishing the PM processing with forging or versely affect the properties of the resulting
extrusion. PM products. Relatively coarse powders
PM can broadly be divided into the fol- around 100-300 (im diameter are pre-
lowing processing steps (Fig. 4-2): produc- ferred in such cases.
144 4 Powder Metallurgy

Electro- Chemical Mechanical Physical Synthesis


chemical Methods Methods Methods
Methods

POWDER

Lubricants -JBLENDINGU_ Additives

COLD COMPACTION HOT CONSOLIDATION

Die Cold Other Hot Hot Other


Compaction Isostatic Methods Pressing Isostatic Methods
Pressing Pressing
Rolling Extrusion
Extrusion Pseudo-
Explosive Isostatic
CocnpocHon
Injection
Molding

SINTERING

FINISHING OPERATIONS FORGING

Coining Infiltration

FINISHED PM PARTS Figure 4-2. Basic processing


steps in powder metallurgy.

The shape of the powder is also an im- sition and atomization from the melt. The
portant parameter. Some applications choice of the technique is determined by
such as porous filters specifically demand the properties of the metal, the application
spherical particles while irregular particles in view, the desired purity and economics.
are adequate for many other applications. Table 4-1 gives a summary of the methods
Spherical particles are difficult to compact used in the manufacture of different metal
and are therefore used only with large powders and these methods are discussed
compacting pressures or in hot pressing, in the following sections.
where high temperatures and pressures are
simultaneously applied. 4.2.1 Mechanical Methods
Metal powders are produced by a vari-
4.2.1.1 Comminution
ety of techniques which include mechanical
comminution, chemical synthesis, decom- Mechanical comminution processes such
position or precipitation, electrolytic depo- as crushing and grinding are perhaps the
4.2 Production of Powders 145

Table 4-1. Processes used in the manufacture of pow- type of mill, the grinding elements can be
ders, (a) Mechanical comminution; (b) Chemical: re- hardened balls or even rods. Tumbler ball
duction; (c) Chemical: decomposition; (d) Chemical:
precipitation; (e) Electrochemical; (f) Physical: atom- mills containing appropriately chosen
ization. grinding media are most commonly used
for comminution. Comminution can be
Material Process carried out either in wet or dry conditions.
(a) (b) (c) (d) (e) (f) The limiting particle size that can be ob-
tained depends on the size and shape of the
Al/Al alloys X grinding media, and other milling condi-
Be X x
tions. Several high-energy milling pro-
Co X
Cu X X X X
cesses are also used effectively for size re-
Cu alloys X duction. These include vibratory ball mills,
Fe X X X X X attrition ball mills and large-diameter tum-
Steels X bler ball mills (see Chapter 5, Sec. 5.2). The
Mo X
comminution efficiency and the limiting
Ni X X X
Ni alloys X
particle size depend on the equipment used
Ag X X X and these are shown in Fig. 4-3 (Kuhn
Ta X X etal., 1984).
Sn X Even ductile metals can be powdered by
Ti X X X
mechanical comminution though they may
Ti alloys X X
W X
first have to be made brittle before grind-
Zr X ing. For instance, titanium is hydrided to
the friable hydride, or stainless steel sensi-
tized before comminution. The milling
oldest ones for the production of powder processes are also used for an effective mix-
and are still used in many PM plants. The ing of the components in a powder blend.
metal to be powdered is usually milled in a Particle shapes resulting from mechani-
vessel containing appropriate grinding ele- cal comminution are generally irregular,
ments for comminution. Depending on the but the shape can be controlled to some
Jaw crusher

Vibratory mills

Ring roller mill

Ball mill

Hammer mill

Attritor

Fluid energy mills


Figure 4-3. Comminution
range of different classes of
equipment.
105 104 103 102 101 10° 10'
Product size, urn
146 4 Powder Metallurgy

extent by the milling conditions: wet can reach such fine levels that interparticle
milling, for instance, leads to more flaky spacing between dispersoids can be well
powders than dry milling. There are also below 0.5 jam, and alloying may even ap-
limitations to the level of purity that can be pear homogeneous under X-ray diffrac-
maintained in mechanical milling because tion. The welding, rewelding and homoge-
of the wear of the grinding media. There- neous blending take place on the surface of
fore mechanical comminution is used only the grinding media during the impact of
in those applications where the resulting the powder with the media. This is seen by
shape and purity are acceptable. However, the change of particle size with increasing
some special grinding processes are avail- comminution time; it may also so happen
able to maintain purity during mechanical that after prolonged comminution, the
milling. Gas-jet pulverizing techniques particle size increases, confirming the weld-
lead to better purity by avoiding grinding ing of impacted particles on the surface of
media such as steel balls. These methods the grinding media. As comminution and
employ collision between powder particles mechanical alloying take place in a high
themselves or between powder and targets energy mill, a large quantity of heat is gen-
of the same composition for grinding. En- erated, and this in turn enhances diffusion
ergy for collision is provided by gas jets. In among the components and promotes re-
such a fluidized-bed counterflow jet mill, crystallization of the deformed powder.
particles are ground by mutual collision in Recent experiments (Bhagiradha Rao,
a fluidized bed, the kinetic energy being 1989) have also confirmed the postulated
provided by a number of high-speed gas mechanisms of diffusion and recrystalliza-
jets (Joensson and Hohmann, 1987). This tion. These experiments were carried out in
technique is often used in the comminution a nickel-chromium alloy with and without
of high purity powders that are obtained dispersoids. Results of this study confirm
from rapid solidification of melts (Sec. that true alloying does indeed take place
4.2.4.6), which are generally too coarse to during mechanical alloying, because of en-
be used directly for PM processing. hanced diffusion due to cold work and re-
crystallization cycles (Fig. 4-5). As recrys-
tallization is retarded in alloys containing
4.2.1.2 Mechanical Alloying dispersoids, mechanical alloying is found
A novel extension of mechanical com- to be correspondingly slower for the same
minution was developed by Benjamin alloy with dispersoids.
(1976) for producing alloyed and disper- Because of the heavy cold work, me-
sion hardened materials from powder chanically alloyed powders are not easy to
blends. This process, known as mechanical consolidate. They are therefore compacted
alloying (MA) is carried out in attritors or at elevated temperatures by hot pressing,
other high energy ball mills. In these ball hot extrusion or hot rolling. This is further
mills, the powder is welded, broken and followed by thermomechanical processing
rewelded repeatedly during comminution to yield elongated grain structures that
leading to a homogeneous dispersion of give high-temperature creep resistance.
the constituents. The various stages of me- At present, mechanical alloying is em-
chanical alloying are described by Gilman ployed mainly in the production of oxide
and Benjamin (1983) and are shown sche- dispersion strengthened nickel-, iron- and
matically in Fig. 4-4. The dispersion in MA aluminum-base alloys. Because of their
4.2 Production of Powders 147

100 pm

Metal A ntermetallic 100 urn

Concentration
vX of metal B
Dispersoid
Metal B -l ° ^ -
• • a t
0
"JL Remnant of
* P fj intermetallic
0.5pm

(a) / Equilibrium
t precipitate
Concentration
of metal A Dispersoids

0.5 pm

(c)

Heat
(Consolidation)

100 | 100pm 100 pm

Metal A
Metastable phase
Dispersoids
Interdiffusion
Intermetallic
Dispersoids
Dispersoids Precipitate phase

0.5|jm

(d)

Figure 4-4. Stages in mechanical alloying: (a) intense cold welding in the first stage, (b) rapid fracturing in the
intermediate stage and (c) moderate cold welding in the final stage lead to (d) extremely deformed structure in
completely mechanically alloyed powder with fine grained structure and equilibrium distribution of dispersoids
(Sundaresan and Froes, 1987).
148 4 Powder Metallurgy

(a) (b)

Ni
Figure 4-5. Mechanical al-
loying of Ni-20Cr (a) with
ThO2 addition and (b) with-
out ThO 2 . EPMA line
scans show low degree of
alloying in the presence of
Cr ThO2 (Bhagiradha Rao
et al., 1986).

high-temperature properties, mechanically lic ores, or in the synthesis, precipitation


alloyed superalloys find applications in air- or decomposition of metallic compounds.
craft and industrial gas turbines, in power The governing chemical equations for
generation equipment, and in heat treat- these reactions are the following:
ment furnaces. Mechanically alloyed alu- Reduction by carbon monoxide or hy-
minum-base alloys are currently entering drogen:
into some applications. These alloys incor- MO + H 2 ^ M + H 2 O (4-1)
porate organic process control additives,
resulting in dispersions of A12O3 and MO + CO -> M + CO 2 (4-2)
A14C3. Decomposition of carbonyls or hydrides:
Lately several new facets of mechanical
alloying have been recognized (Sundaresan Fe(CO) 5 -*Fe + 5Co (4-3)
and Froes, 1987). Liquid-immiscible and TiH 2 -+Ti + H 2 (4-4)
solid-immiscible systems which are diffi-
cult and often impossible to process by Precipitation from liquid solutions or gas-
conventional methods of solidification eous compounds:
processing can be obtained in the solid CuSO 4 + H 2 -> Cu + H 2 SO 4 (4-5)
phase with a homogeneous distribution of
the second phase by using mechanical al- ZrCl 4 + 4 Na -* Zr + 4 NaCl (4-6)
loying. Superconducting Nb 3 Sn, supercor- Synthesis from constituents:
roding Mg-Fe/Cu/Cr/Ti and hydrogen-
storing Mg-Ti/Ce alloys are examples of MoO 3 + 2Al + 2 S i ^ M o S i 2 + Al 2 O 3 (4-7)
this kind. Because of the heavy cold work Several factors have to be considered in
involved in the process, mechanical alloy- selecting an appropriate reaction for pow-
ing is known to produce amorphous der production. Thermodynamics and ki-
phases and this is now being explored in netics of the reaction dictate the feasibility
some multicomponent systems. Mechani- and economics, while nucleation and
cal alloying is also treated in Chapter 5, growth parameters determine the resulting
Sec. 5.5, of this volume. powder characteristics.

4.2.2 Chemical Methods 4.2.2.1 Reduction


Chemical reactions often offer attractive One of the early developments in PM
routes to produce metal powders. These was the production of iron powder by the
reactions can be in the reduction of metal- Hoganaes process (Goetzel, 1949). The
4.2 Production of Powders 149

process was developed using the high pu- duction is carried out using akali or alka-
rity iron ore mined in Sweden, and pro- line earth metals. For instance, titanium
duces good quality iron powder of high oxide can be reduced by a calciothermic
purity and excellent flow characteristics reduction:
needed for good compaction and sintering.
TiO 2 + 2 Ca -• Ti + 2 CaO (4-8)
In this process, the magnetite concentrate
Fe 3 O 4 is mixed with coke, and limestone The reduced metal comes out as powder
to absorb sulfur, and reduced at tempera- because of CaO which separates metallic
tures around 1475 K. Part of the required agglomerates. As this reaction is highly
heat is generated by burning CO produced exothermic and difficult to control, cal-
during the reduction. Pure iron powder is cium hydride is used as a reducing agent:
produced by separating the sponge iron
TiO 2 + CaH 2 -*Ti + Ca(OH) 2 (4-9)
produced in the reduction, pulverizing the
sponge and annealing the powder in hy- By using excessive reductant, it is possible
drogen. to control the reaction and the powder
Iron powder is also produced by the hy- particle size. However, these reactions are
drogen reduction of millscale. This reac- of limited importance as the products are
tion takes place at a lower temperature generally impure and are therefore only
compared to the Hoganaes process useful where non-critical and non-load
(1300 K), but the requirement of critical bearing applications are envisaged. Selec-
partial pressures demand that a continu- tive reduction of oxides is also employed to
ous countercurrent flow of hydrogen is produce complex powders with oxides dis-
maintained when the oxide charge is con- persed in a metallic matrix, as in thoria-
tinuously or semicontinuously fed. dispersed or yttria-dispersed nickel and
An industrially important hydrogen re- nickel-chromium alloys.
duction reaction is in the production of
tungsten powder (Borchers, 1979). This
4.2.2.2 Decomposition
forms part of a complex processing route
that includes purification of the ore con- Both nickel and iron powders are pro-
centrate and its conversion to high purity duced by a decomposition reaction of their
ammonium paratungstate (APT) by a se- respective carbonyls. The process (Fig. 4-6)
ries of dissolution and re-precipitation re- consists of first preparing the carbonyl by
actions. Subsequently, APT is thermally passing high pressure CO over the heated
decomposed to a suboxide of tungsten metal and condensing the vapor as liquid
(WO3_X) which is then reduced in a coun- under pressure. The liquid is purified by
tercurrent of dry hydrogen in a tubular fractional distillation and is then decom-
furnace with semicontinuous feed. The ra- posed at temperatures around 400 K at at-
tio of partial pressures (PU2/PH2O) provides mospheric pressure to produce fine, high
an effective tool for controlling the reac- purity metal powder (Queneau et al, 1969).
tion rate and the particle size of the re- To ensure purity and suitable particle
duced powder. This ratio is determined by shape, reaction conditions are optimized
the rate of gas flow, the reducing tempera- so that the decomposition is spontaneous
ture, oxide bed height and its feed-rate. within the heated space and not nucleated
In some cases, where the oxides are not on the walls of the container. Complex car-
reducible by carbon or hydrogen, the re- bonyls such as Pt(CO) 2 Cl 2 and organo-
150 4 Powder Metallurgy

Iron as hydrogen:
Reaction
Chamber M+ + + H 2 ^ M ° + 2H+ (4-10)
Synthesis of
(CO^ with an equilibrium constant given by
+
Purification of ]p H 2 (4-11)
carbonyl
Fractionating
Column CO recycle Both nickel and copper powders are pro-
to synthesis
Pure duced directly from the leached ores using
this route. Various organic surface-active
agents are used as additives to control the
I Vaporization
powder characteristics. An extension of
NH this process is the precipitation of com-
3 —I Decomposition
posite particles by suitably seeding the sec-
i ond phase particles in the solution.
Carbonyl
iron powder Precipitation from the vapor phase is
also sometimes used to produce metal
"2 ->| Reduction | | Blending |
powder. A case in point is the production
j i of fine, spherical powders of the refractory
I Soft grades | | Hard grades |
metals W and Mo from their gaseous
Figure 4-6. Flowsheet for the manufacture of car- hexafluorides.
bonyl iron powder.

4.2.2.4 Self-Propagating
High Temperature Synthesis
metallic compounds have also been used to
produce metal powders by decomposition. Self-propagating high temperature syn-
Decomposition of the hydride is also an thesis of powders of ceramic and refractory
effective method for producing titanium compounds and alloys is a recent innova-
and zirconium powders via the hydride- tion. In this process, a porous compact
dehydride route. The ductile metal or its made from a mixture of the reagents is
alloy is first converted to its hydride by brought into contact with a hot tungsten
reaction with hydrogen at 700-900 K un- coil. This initiates an exothermic reaction
der pressure. The friable hydride is easily which continues as a self-sustaining com-
crushed to powder of the required fineness bustion wave propagating through the po-
and then decomposed to the metallic pow- rous mass and converting it into the reac-
der by heating under vacuum. tion products. The scheme of the reaction
synthesis is shown in Fig. 4-7 (Crider,
1982). Depending on the temperature of
4.2.2.3 Precipitation
the reaction, synthesis can be entirely in
Copper powder is sometimes produced the solid state as gasless combustion,
by displacing the copper ion in the salt partly in the gaseous state as filtration
solution (generally copper sulfate) by iron. combustion, or entirely in the gaseous state
The extent of precipitation is controlled by as condensed combustion. Of these, gasless
factors such as the pH value of the solu- combustion can be used for the production
tion. Precipitation of metals from salt solu- of powders suitable for PM applications
tions can also be achieved with gases such (Munir and Anselmi-Tamburni, 1989).
4.2 Production of Powders 151

Rate of n

k
thermal \J 1 s— Temperature
release j I

\ - D e p t h of
Direction transformation

y IK
of wave
Figure 4-7. Equilibrium
adiabatic structure of a
self-propagating high tem
perature synthesis wave
(Crider, 1982).
Initial Zone of Zone of Final product
substances heating synthesis

The synthesis can be designed on the This method is mainly used in the produc-
basis of the adiabatic temperature of com- tion of copper and iron (Willis and
bustion, the combustion wave velocity and Klugston, 1959). Fused salt electrolysis has
activation energy for the compound for- also been used for the production of tanta-
mation. For a useful reaction, the adiabatic lum and beryllium powders (Miller, 1958).
temperature Tad must be lower than the The factors that promote powdery de-
melting temperature of the reaction prod- posits are high current densities, weak
uct (Munir, 1988). The value of Tad of a metal concentrations, low temperatures,
compound can be computed on the basis and surfactants to promote high viscosi-
of its enthalpy of formation {AH0) and its ties. All these factors also lead to low depo-
heat capacity Cps and compared with the sition rates and high costs. With increasing
melting temperature to evaluate the feasi- energy costs, electrochemical methods of
bility of the reaction. powder production are being phased out
The process has relatively low energy (see also Chapter 11).
requirements and is highly cost-effective.
With an exothermic reaction, the process- 4.2.4 Physical Methods
ing time at high temperatures is short and
Atomization is a process of breaking up
the purity of the powder can be main- liquid metal or alloy into fine droplets and
tained. Metastable phases such as cubic allowing them to solidify as powder. Be-
TaN and composites such as MoS 2 /Nb cause of the versatility, purity and the con-
can be made by this process. The process is trol of powder shape inherent in the pro-
already in use in the USSR for the produc- cess, atomization is becoming increasingly
tion of TiC abrasive powders, TiNi mem- popular as a route for large scale manufac-
ory alloys and MoSi2 heating elements. ture with attendant reduction in costs.
Many techniques are available for
4.2.3 Electrochemical Methods
breaking up a liquid metal stream into fine
Metals of high purity can be precipitated droplets which are then allowed to solidify
from aqueous solutions on the cathode of by exchange of heat with the surroundings.
an electrolytic cell in a spongy form to pro- Most common among these are the im-
duce powder by subsequent comminution. pingement of high speed jets of gas or wa-
152 4 Powder Metallurgy

ter on the liquid metal stream. This tech- small sizes (Shinde and Tendulkar, 1977;
nique is limited to metals and alloys that Lawley, 1977).
do not chemically react with the impinging The liquid metal stream has a velocity v
gas or water. There are also variations given by
where the liquid metal stream is directly
= A[2g(Pl-Pg)/Q] 0.5 (4-12)
fragmented by centrifugal forces. These are
used for producing powder from reactive where A is a geometric constant and g, the
metals and superalloys which are sensitive acceleration due to gravity; Px is the injec-
to gas contamination. There are also other tion pressure of the liquid metal, Pg the
techniques like vacuum atomization and pressure of the atomizing atmosphere and
ultrasonic atomization which are used in Q is the density of the liquid. The shearing
special cases. forces in atomization that lead to the for-
mation of ligaments from the liquid metal
4.2.4.1 Principles of Atomization depend on the Reynold's number, Re,
which in turn, is related to the size and
In conventional atomization, a liquid
velocity of the stream and the density and
metal stream is produced by pouring
viscosity of the liquid metal.
molten metal through a tundish which is
There are several empirical equations for
then broken into droplets by the impinge-
calculating the average particle size in at-
ment of high pressure gas or water. This
omization. The most frequently used one
disintegration of the liquid is shown sche-
for determining the average particle size d
matically in Fig. 4-8. The interaction be-
is given by
tween the jets and the liquid stream begins
with the initiation of small disturbances at
d=A y
the liquid surface which grow into shearing
forces that fragment the liquid into liga-
ments. The energy of the jets is so large that 0.45 /•M.5
the broken ligaments are further frag- 1000 y (4-13)
mented into droplets which can reach very

Stage I Stage II Stage III


Growth of waves Fragmentation Breakdown of Figure 4-8. Mechanism of
on liquid sheet and formation ligaments into droplet formation in atom-
of ligaments drops ization (Lawley, 1981).
4.2 Production of Powders 153

where Q is the density of the liquid, y, the for instance, even with high surface ten-
surface tension, rj, the coefficient of viscos- sion, aluminum and zinc tend to solidify as
ity and v, the relative velocity between the irregular particles because of oxidation ef-
liquid and gas jets; /, is the flow rate of fects.
liquid, / a , the flow rate of air and A and B The mechanism of centrifugal atomiza-
are constants. tion is different because of the process de-
Another empirical equation for the par- sign. In this technique, the molten pool is
ticle size is rotated at high speed till the liquid flows
over the rim of the container and is frag-
0.5
mented by the centrifugal force acting on
(4-14)
Wr,. it. As the cooling rate in this process is slow
in the absence of gas jets, centrifugally at-
where Wis the Weber number of the metal omized powders tend to be spherical. It
stream, vg, the velocity of the atomizing may also happen that the time of flight of
medium, du the diameter of the liquid the liquid droplet to hit the chamber walls
metal stream; rjx and r\% are the kinematic is smaller than the time required for solid-
viscosity of the liquid metal and gas, and ification. In such instances, the particles
K, a constant. appear as flat discs solidified on impact
Both these equations show the particle with the walls.
size to decrease with decreasing surface Because of the rotation of the molten
tension of the liquid metal and increasing pool, the liquid metal spreads towards its
velocity of the atomizing medium. In prac- periphery and forms a toroidal rim. Owing
tice, for a given nozzle design, the average to instability at the rim, the sheet of the
particle size is controlled by the pressure of liquid breaks up into fine threads, which in
the atomizing medium and also by the turn break into droplets surrounded by
apex angle between the axes of the gas jets. smaller droplets known as satellites. The
Higher apex angles lead to smaller particle mean diameter d of the main drop can be
sizes. estimated by balancing the surface tension
The particle shape in gas or water atom- force against the centrifugal force and is
ization depends largely on the surface ten- given by (Hodkin et al, 1973)
sion and the solidification rate (Lawley,
1977). While the surface tension of the drop
(4-15)
tends to spheroidize it, the cooling rate lim-
its the time available for this process. If, for
instance, the time for solidification is larger where co is the rotation rate, y, the surface
than the time required for spheroidization, tension and D, the melt pool diameter. The
then spherical particles will result. For pro- above equation is strictly valid only for the
ducing fine spheres, it is necessary for the main droplets, and it is difficult to calculate
solidification to be as late as possible be- either the particle size or the distribution of
fore the droplets hit the chamber wall. Be- the satellite sizes as the mechanisms under-
cause of this condition, iron and copper lying their formation are not fully under-
solidify readily as fine spherical powders, stood.
while lead and tin solidify as irregularly Since the flight of the atomized droplets
shaped powders. There are also other fac- is entirely dictated by friction and gravity
tors that contribute to the particle shape: opposing the centrifugal momentum, the
154 4 Powder Metallurgy

trajectory can be easily calculated. The


droplet cooling AH in time At is given by
AH=-nKdNu(Td-Tg)At +
T(t-T*)At (4-16)
where Td, Tg and Tw are the temperatures of
the droplet, the gas and the chamber wall
respectively; e is the emissivity of the
droplet, s the Stefan-Boltzmann constant
and Nu the Nusselt number of the cooling
gas flow. On the basis of Eq.(4-16), it is
possible to design the cooling parameters
and chamber size appropriately for cen-
trifugal atomization.

4.2.4.2 Gas and Water Atomization


A typical atomization unit consists of a
melting facility, an atomizing chamber,
and powder drying and collection unit
(Gummeson, 1972) as shown in Fig. 4-9.
Typical atomization parameters are given
in Table 4-2, and some atomized powders
are shown in Fig. 4-10. Any of the standard
Inert gas atomization plant melting furnaces is acceptable for produc-
ing the liquid metal. However, complex al-
loys prone to contamination are usually
Vacuum melting
melted in a vacuum induction furnace or
by skull melting with an electron beam.
The molten metal is then poured into a
tundish with a top ceramic filter and a bot-
tom nozzle which controls the shape and
size of the falling metal stream. This stream
passes through an atomizing nozzle sys-

Table 4-2. Typical atomization variables.

Parameter Liquid metal Water jet Gas jet

Flow rate 4.5-90 100-400 1-14


Powder kg/min 1/min m3/min
collection
Flow velocity, — 70-230 20-super-
m/s sonic
Pressure, MPa — 5.5-21 0.3-8.5
Figure 4-9. Inert gas atomization unit (Courtesy Superheat, °C 75-150 - -
DMRL).
4.2 Production of Powders 155

Figure 4-10. Atomized powder particles: (a) bronze, water atomized, (b) aluminum, water atomized, (c) high
speed steel, water atomized, (d) aluminum, ultrasonic gas atomized, (e) Nimonic 80 A, argon gas atomized, and
(f) Astroloy, argon gas atomized.
156 4 Powder Metallurgy

tern, in which the high velocity jets of the Table 4-3. Heat transfer coefficients for convective
atomizing medium (gas/air/water) strike cooling of liquid metal droplets by different gases.
and disintegrate the stream into fine Cooling Heat transfer coefficient, W x 10 3 /m 2 K
droplets. These droplets are carried at high gas for droplet diameter (in jim)
velocity with the atomizing gas stream in-
1 10 100 1000
side the chamber and solidify owing to
heat loss by convection. It is possible to Argon 49.0 11.8 3.3 1.02
increase the solidification rate by cooling Nitrogen 70.8 16.8 4.7 1.45
the atomizing gas, or even by pumping ad- Helium 350.0 60.0 10.0 3.00
ditional precooled gas from the bottom of
the chamber.
ited only to metals and alloys from which
The selection of the atomizing jet
the surface oxide can be easily removed by
medium is based mainly on the reactivity
mechanical or chemical methods.
of the metal and the cost of the medium.
Air and water are inexpensive, but react
4.2.4.3 Centrifugal Atomization
with many molten metals. Inert gases can
be expensive and it may be necessary to The driving force for the development of
recycle the gas when helium is used as the centrifugal atomization processes has been
atomizing medium. The heat transfer char- the cleanliness of the product. These pro-
acteristics of the gases are different as cesses avoid gas jets and atomization noz-
shown in Table 4-3 and these also deter- zles, and therefore the liquid metal con-
mine the particle size and other character- tinues to remain pure during the entire
istics; but the mechanism of atomization is process. Thus this method is eminently
independent of the medium. suited for atomizing reactive metals such
Nozzle design controls the efficiency of as titanium and zirconium. Several cen-
disintegration and thus dictates the final trifugal atomization processes have been
characteristics of the powder. The nozzle developed, as listed in Table 4*4. On the
can be an annular concentric ring around
the metal stream, or can be a set of discrete
jets (Klar and Fesco, 1984). The nozzle de- Table 4-4. Centrifugal atomization processes.
sign also incorporates the choice of a "free Mode of Mode Process References
fall" or "confined" atomization. In the free energy of
fall atomization, disintegration takes place transfer melting
some distance ahead of the tundish orifice,
Direct Arc Rotating electrode Friedman
while in confined atomization the disinte- process (REP) (1970)
gration is at the tundish orifice itself. Con- EB 'Pulverisation Decours
fined atomization with its higher efficiency sous vide' (PSV) (1976)
of energy transfer is used for gas atomiza- Rotating rod Arunachalam
tion. process (RRP) etal. (1975)
Plasma Plasma rotating Roberts
The apex angle for water atomization is rod process (PREP) (1984)
smaller than for gas and is designed for free Indirect Arc Centrifugal shot Hodkin
fall atomization. Spherical and fine pow- casting (CSC) (1973)
ders are difficult to produce in water atom- EB Electron beam Stephan
rotating disc and Fisch-
ization and particles generally tend to be
process (EBRD) hof(1976)
irregularly shaped. The process is also lim-
4.2 Production of Powders 157

basis of the mode of centrifugal energy


Rotating
transfer, the processes can be broadly di- Water
consumable
cooling
vided into direct energy transfer processes electrode
where the liquid metal pool itself is rotated,
and indirect transfer processes where the
liquid metal is poured on to a rotating sur-
face. 0
Among the processes listed, only the ro-
Stationary
tating electrode process (REP) and plasma electrode
rotating electrode process (PREP) are Inert •£ Vacuum
commercially well developed. These are di- gas (He)
rect energy transfer processes, where a rod Collection port
is rotated at high speed and simultaneously
melted at one end. The melting is carried Figure 4-11. Schematic of rotating electrode process
out with a tungsten electrode as in a vac- (Lenel and Ansell, 1982).
uum arc furnace or with another electrode
of the same material. The centrifugally at-
omized liquid droplets are cooled by con-
vection with the helium gas present in the thermal forging for the manufacture of
atomizing chamber and the powder is col- high-temperature turbine discs for gas tur-
lected at the bottom. A schematic diagram bines. On the other hand, REP and PREP
of a REP atomization chamber is shown in powders are generally large-sized and
Fig. 4-11. There are many variations to the spherical with a cooling rate of about
design shown in the figure. In one variant, (102 K/s). It is therefore not possible to
a long rod to be atomized is fed through a produce rapidly solidified powders by
vacuum seal into the chamber, with the these routes.
rotating mechanism kept outside. In an-
other variant, small electrodes are kept
4.2.4.4 Ultrasonic Gas Atomization
within the chamber itself and are substi-
tuted into the rotating spindle as and when Ultrasonic atomization is used for the
the molten electrodes are consumed. A production of powder with particle size
glove compartment is provided to effect finer than those obtained in conventional
this substitution without breaking the fur- atomization. The process is similar to con-
nace atmosphere. ventional gas atomization except for the
In an indirect energy transfer process, discrete gas jets impinging on the metal
liquid metal is poured through a tundish stream in a pulsed fashion, with frequen-
on to a fast rotating disc which acts as a cies of 40-100 kHz. The high speed gas jets
rotary atomizer. The centrifugally atom- are accelerated by a shock wave tube to
ized droplets are cooled by precooled he- speeds up to Mach 2. The shearing action
lium gas before solidification. By this, it is results in fine droplets, usually less than
possible to solidify the droplets rather 30 jim and with very high cooling rates (up
rapidly, generally with a rate higher than to 106 K/s) as well. Ultrasonic atomization
105 K/s. Rapidly solidified nickel base al- has so far been used for low-melting alloys
loy powders have been produced by this based on aluminum and is yet to be widely
process and subsequently formed by iso- applied.
158 4 Powder Metallurgy

4.2.4.5 Vacuum Atomization 4.2.4.6 Rapid Solidification

Vacuum atomization, or soluble gas at- Many techniques have been developed
omization, employs the difference in solu- employing the advantages of rapid solidifi-
bility of gas in liquid metal at different cation processing (RSP) for utilizing
pressures to fragment the liquid into fine metastable phase structures to advantage
droplets. In this process, the molten metal (see Chapter 2). Most of the conventional
is first supersaturated with a soluble gas atomization processes discussed in the ear-
under high pressure and the liquid stream lier sections lead to a normal cooling rate
is then suddenly exposed to vacuum. The of 103 K/s. With some enhanced heat
supersaturated gas almost explodes out of transfer techniques, several atomization
the liquid fragmenting it into very fine techniques have been developed to achieve
droplets. A schematic diagram of the pro- cooling rates of over 104 K/s. Such tech-
cess is shown in Fig. 4-12. Alloys of iron, niques with increased cooling produce
cobalt, nickel, copper and aluminum have rapidly solidified powders, flakes, wires
been vacuum-atomized with hydrogen as and strips (Grant, 1983; Savage and Froes,
the dissolved gas. The powders are gener- 1984). Rapid solidification techniques de-
ally fine and spherical. As this process de- veloped (Table 4-5) are based on atomiza-
pends exclusively on dissolved gases, it has tion, continuous casting, melt extraction
only limited applicability and is not being and melt extrusion (Jones, 1981, 1982). In
used extensively. rapid solidification rate centrifugal atom-
ization (Fig. 4-13), liquid metal is centrifu-
gally atomized off a disc rotating at very
high speeds (35 000 rpm) and the droplets
Vacuum cool by flight through high velocity helium
gas streams to give powders in the size
range 25-100 \im (Cox et al., 1976). An im-
pinging melt stream contacts a moving
chill surface in chill block melt spinning,
planar flow casting and free jet casting to
— Powder produce tapes with thickness 10-100 |im
collection
tank and widths 3-250 mm. In melt extraction
processes, a rotating disc is brought into
contact with a liquid metal pool for pro-
Melting ducing rapidly solidified fibers and tapes
crucible
(see Chapter 2).
While the rapidly solidified atomized
powders can be consolidated directly, in
the case of tapes and fibers, some com-
|— Powder minution or shredding is necessary for fur-
drain
Induction heater
ther PM processing. Often the RS powders
Vacuum — Container see application in the form of powder itself.
For applications that call for consolidation
Figure 4-12. Schematic of vacuum atomization unit of the RS powders, suitable consolidation
(Lawley, 1986). techniques are employed with minimum
4.3 Characterization of Powders 159

He gas input
H t

Air out Figure 4-13. Schematic of


rapid solidification rate
atomization process (Joens-
son and Hohmann, 1987).

Table 4-5. Rapid solidification techniques.

Process Technique Product Powder Cooling Application


type size, urn rate, K/s

Atomization Water atomization Irregular 75-200 10 2 -10 4 Fe, Cu, Ag


Ultrasonic gas atomization Spherical 10-50 <10 6 Fe, Cu, Ag, Al, Ni
Centrifugal Rapid spinning cup Variable <50 106 Fe, Cu, Ag, Al, Ni
Atomization Rapid solidification rate Spherical 20-100 105 Fe, Cu, Ag, Al, Ni
Splat Electron beam splat quench Splat 40-100 10 -10 7
4
Fe, Al, Ni, Ti
Extraction Twin roll atomization Flaky 200 10 5 -10 6 Fe, Al, Ni
CBMS Tape < 3 mm 10-100 105 107 Fe, Al, Ni, Ti
PFC/MD Tape, wide 20-100 10 5 -10 6 Fe, Al, Ni
CME/PDME Filament /Fiber 20-100 10 5 -10 6 Fe, Al, Ni, Ti

exposure to high temperature, to retain the 4.3 Characterization of Powders


structural advantages of rapid solidifica-
tion (Lee and Carbonara, 1985; Froes and Characterization of powders is impor-
Savage, 1986). tant because of their relevance in PM pro-
cessing. Often the choice of a particular
processing route is determined by the char-
acteristics of the available powder. Powder
160 4 Powder Metallurgy

characterization is a complex procedure Table 4-6. Characterization of powders.


(Wang, 1982) as the properties reflect not Characteristics Characteristics Characteristics
only those of individual powder particles of a powder of a powder of porosity in
but of the powder aggregates and of the particle mass a powder mass
voids in the aggregates as well. These char-
acteristics are listed in Table 4-6 (Poster, Particle size Average particle Total pore
size volume
1966). Particle shape Particle size Pore volume
Particle size is considered one of the distribution between particles
most important properties of the powder. Density Specific surface Pore volume
It is customarily represented as a diameter, within particles
although not all particles are spherical. It is Surface Apparent density Number
topography of pores
therefore usual in any measurement to Microstructure Tap density Average pore size
consider the size and the shape together. A Lattice defects Flowability Pore size
simple system of classification of particle distribution
shapes is shown in Fig. 4-14. The basic Gas content Compactability Pore shape
shapes include one-dimensional (large as- (contained
and adsorbed)
pect ratio) acicular, rod-like and fibrous Surface oxide
powders, two-dimensional (length and Reactivity
width much greater than the thickness)
dendritic and flaky powders, and three-di-
mensional spherical, rounded, irregular therefore a powder description must also
and angular powders. The majority of the include the parameters defining the parti-
powders used in PM fall in the last cate- cle size distribution. The size distribution
gory, and are represented by an equivalent can be normal (unimodal), or bimodal, or
particle diameter called simply "the parti- with a broad band, or can be even irregu-
cle size". A real powder aggregate does not lar.
have all particles of the same size, and Several techniques are used for the mea-
surement of size and its distribution. Both
One-dimensional
Acicular Irregular
direct and indirect measurement tech-
rod-like niques can be used. Direct measurement
techniques include sieving, microscopy,
Two-dimensional
elutriation and sedimentation, while indi-
Dendritic Flaky rect techniques use turbidimetry, measure-
ment of electrolytic resistivity, permeabil-
ity and surface area. Sieve analysis consists
Three-dimensional
of tapping powder through a set of stan-
Spherical dard sieves assembled in order in a me-
O Rounded
chanical sieve shaker. The quantity re-
maining on each screen is weighed to
Irregular
o obtain the particle size distribution. The
finest standard screen opening is 25 jim.
For powders finer than this, the average
Angular
O
Figure 4-14. System of particle shape characteriza-
particle size is obtained in a Fisher sub-
sieve sizer. Essentially, the sizer determines
tion. the surface area of the powder by measur-
4.4 Compaction of Metal Powders 161

ing the resistance to the flow of air through compact by shaping in a mold or a die,
a packed column of powder. This measure- usually with the application of pressure.
ment is directly correlated with the average We use the term 'compaction' to describe
particle size. For sub-micron powders, the consolidation without the application of
surface area itself is characterized directly, heat. Compaction is a necessary step in
generally by gas adsorption technique in a powder processing as loose powder cannot
BET apparatus. be shaped without consolidation. This step
Apparent and tap densities of the pow- also provides for the making of near-net-
der are also important parameters in char- shape parts which is an advantage in PM
acterization and these depend on the par- processing. Compaction is subsequently
ticle shape, size and its distribution. Ap- followed by sintering to make the final
parent density is defined as the weight of a parts. Hot consolidation where external
unit volume of powder as poured through pressure and temperature are simulta-
a standard Hall flowmeter. It varies widely neously applied is also a method of com-
from a high 50-60% of the specific gravity paction and is now becoming increasingly
of the material in atomized spherical pow- popular for fabricating load bearing high
ders, to a low 5-10% in fine flaky powders. temperature parts and ceramic compo-
Tap density is the weight per unit volume nents. Hot consolidation cannot be strictly
of powder after tapping or vibrations to defined as compaction as simultaneous sin-
obtain maximum consolidation of the tering is also involved, and is described in
loose powder and is therefore higher than a later section.
the apparent density. The frictional condi-
tions of the powder which determine the
apparent density are overcome during tap- Table 4-7. Methods for forming compacts from pow-
ping and the tap density can be much ders.
higher. Methods with Methods without
The flow rate of metal powders is a char- applied pressure application of pressure
acteristic that may contribute nothing to
the final part made from the powder, but a Unidirectional pressing Loose powder sintering
Single action pressing in mold
good flow is important for ease in com- Double action pressing
paction as it involves the movement of pre- Isostatic pressing Vibratory compacting
cise quantities of powder. This parameter Powder rolling Slip casting
is defined as the time taken for the flow of Stepwise pressing Metal injection molding
50 g of powder through a standard Hall Explosive compaction
flowmeter. The flow rate is influenced by
the particle shape, particle size and its dis-
tribution, the apparent density of the pow- There are many methods of compaction
der and its specific gravity. The powder is (Table 4-7) and the choice is dependent on
said to have no flow if the powder does not the application envisaged and the scale and
all flow out of the flowmeter. economy of operation. Most of the meth-
ods depend on the application of external
pressure on powder contained in a die or
4.4 Compaction of Metal Powders mold, while some use techniques like vi-
In conventional PM processing, the bratory compaction or slip casting where
powder is generally consolidated into a the effect of external pressure is negligible.
162 4 Powder Metallurgy

4.4.1 Pressureless Compaction Table 4-8. Packing of equal sized spheres.

In any agglomeration of powder, the Packing Coordination No. Porosity (%)


powder particles acquire one of four geo-
Cubic 47.6
metric configurations. These configura- Orthorhombic 39.5
tions are shown in Fig. 4-15 and their Tetragonal 10 30.2
packing densities given in Table 4-8 Rhombohedral 12 26.0
(James, 1972). As the size of the voids is
determined by the particle size, it is possi-
ble to introduce particles of appropriate Table 4-9. Effect of size distribution on powder pack-
diameter in these voids. With such an addi- ing.
tion the size of the voids reduces further, Order Relative Relative Porosity pet. Weight pet.
as also the total volume of the voids. The size of number in powder in final
smaller voids can also be filled with parti- spherical of powder mixture mixture for
cles and this sequence of operation can be particles particles with this optimum
carried till a high packing density of pow- addition packing
der is achieved even before consolidation 1 1 1 22.95 77.1
(Table 4-9). Though this system of extreme 2 0.414 1 20.70 5.5
dense packing is not known to have been 3 0.225 2 19.0 1.7
used in practical applications, it is a corn- 4 0.175 8 15.8 3.3
5 0.117 8 14.9 1.0
6 fines large 3.9 11.4

mon practice to use powder of appropriate


size distribution to obtain high packing
densities.

4.4.1.1 Vibratory Compaction


An effective method of increasing the
packing density of powder particles is by
vibration. Mechanical vibration helps in
settling particles in the voids present in ag-
glomerates leading to the formation of
nearly close packed powder configura-
tions. This method has also an additional
advantage of using only low pressures,
thus avoiding generation of internal
stresses within the compact.
The process generally consists of vibrat-
ing a powder mass w contained in a mold,
against a punch assembly with a mass W. A
Figure 4-15. Basic coordination in packing of spheri- small pressure is usually superimposed by
cal powder: (a) cubic, (b) and (c) orthorhombic, (d) means of a pneumatic cylinder (Brackpool
tetragonal, (e) and (f) rhombohedral (James, 1972). and Phelps, 1967). Compaction is effected
4.4 Compaction of Metal Powders 163

by both the direct force Fp and the cyclic sintering operations. Injection molding is
force / v = iv • sin (co t). The peak vibratory different from other compaction tech-
compaction force Fc is given by niques in that it uses very fine particles: a
typical particle size for injection molding is
W
(4-17) ten |im or less. The powder to be com-
(W+w) pacted is mixed with large quantities of
Generally vibratory compaction is more thermoplastic binder. The volume of
effective than static pressure compaction binder is determined by the rheological
for the less ductile powders. Such brittle properties of the mix, linear shrinkage ob-
materials as borides and carbides are served during processing and sintering and
prone to developing cracks when com- the uniformity of dispersion. Uniformity of
pacted under pressure, which can be the mix and a proper coating of all the
avoided in vibratory compaction. But the powder particles with the binder are essen-
handling strength of these compacts is low, tial prerequisites for injection molding.
as the particle bonding is only through me- Conventional plastic molding equip-
chanical interlocking. ment is adequate for this compaction. In-
jection pressures and velocities are gener-
4.4.1.2 Slip Casting ally lower for powders than for plastics
though mold temperatures tend to be high.
Slip casting is frequently used for com- The feedstock can be recycled a number of
pacting ceramic powders to complex and times in the molding machines so that the
large shapes and for limited production loss of material is avoided. An important
runs. The slip is a suspension of the powder part of the compaction is concerned with
in water, which is poured into an ab- debinding, the stage at which the thermo-
sorbent (usually plaster of Paris) mold, plastic binder is removed before sintering.
dried and sintered. The formation of ap- This is done by solvent extraction and
propriate and consistent slip is important evaporation. Many variations of this pro-
for successful slip casting and it is achieved cess are now available for injection mold-
by maintaining a proper control of particle ing and the process appears ideally suited
size and size distribution, deflocculant ad- for producing small but complex parts
dition, water content, viscosity and pH val- (Erickson and Amaya, 1984).
ues. This technique is extensively used for
ceramics but has also been extended to
metals. 4.4.2 Unidirectional Compaction
Unidirectional compaction is perhaps
4.4.1.3 Injection Molding
the most widely used consolidation process
Injection molding provides another in powder metallurgy. In this process the
method of consolidating metallic or ce- powder is shaped in a die by pressing in a
ramic powders without the application of mechanical or hydraulic press. Die com-
stress (Billiet, 1985; Pease III, 1987). This paction is so well suited for process au-
method is very similar to the molding of tomation that today most of the large scale
plastics and consists of mixing powders production of small sized PM components
and thermoplastic binders, and injection depend on this route. The only limitations
molding to required shapes. This is fol- countering still larger usage appear to be
lowed by debinding, sintering and post- the size of the press and the mechanical
164 4 Powder Metallurgy

and geometrical constraints imposed by isostatic compaction rather well (James,


the size and shape of the compact. 1983). The Kawakita equation relates the
The densification mechanisms both in reduction A Fin the initial volume Vo of the
unidirectional and isostatic (Section 4.4.3) powder mass with pressure P:
(4-18)
compaction depend on the material and
the structural characteristics of the powder (A V/Vo) = 1 - (Qapp/Qcomp) = a b P/(l + b P)
and also on geometrical factors such as the where gapp and Qcomp are the apparent den-
particle size, shape and size distribution. sity of the initial powder and the density of
The surface characteristics of the powder the compacted mass. Eq. (4-18) can be sim-
are also important in compaction. plified as
Consolidation occurs in three overlap-
ping stages: initially, under low pressures, P/(AV/V0) = (4-19)
interparticle friction is predominant and
consolidation is therefore controlled by the The constant a in the equation is related to
geometrical aspects of the powder agglom- @app, and b is a coefficient of compression
erate. At intermediate pressures, elastic related to the deformation characteristics
and plastic deformation of the powder oc- of the powder.
cur and the material properties become im- The Konopicky-Shapiro-Kolthoff equa-
portant. At these pressures there is in- tion takes the change in density to be pro-
creased mechanical interlocking and cold portional to pore fraction, leading to
welding of particles, leading to a good
(dg/dP) = A (1 - £comp) (4-20)
'green strength' of the compact. ('Green
strength' is the strength of a compact be- Two distinct regions of compaction are
fore any sintering or hot-pressing has be- seen experimentally, the slope K in the first
gun.) In ductile powders, interparticle con- region being proportional to the inverse of
tact area increases with plastic defor- yield stress. Above a critical pressure, the
mation, while in brittle powders, massive slope becomes proportional to the work-
fragmentation occurs at points of contact hardening rate of the powder (Fig. 4-16).
where the local pressures are high. Strain- The constant A in Eq. (4-20) is given by
hardening in ductile powders also changes In {1/(1 -£ a p p )}. The effect of initial parti-
the rate of densification. Finally, at higher cle rearrangement and restacking on @app
pressures, the forces transmitted within the can be obtained by extrapolation from the
compact become more isotropic and the second region.
particles tend to come into contact with In its simplest form, unidirectional com-
12 nearest neighbor spheres, forming a paction is done in a mechanical press with
dodecahedral configuration with all faces a suitable die for shaping the powder ag-
in total contact. In practice, the com- glomerate and for ejecting the compact.
paction stops when the porosity becomes Because of die wall friction and the nature
largely disconnected and when further de- of load distribution inside the die, densifi-
formation of the compact becomes merely cation of the compact is not uniform, par-
elastic. ticularly at the corners. This problem is
Many mathematical equations are avail- minimized by using lubricants and also by
able to model unidirectional compaction. using double action presses where the load
Among these, the following two have been is applied from the top and the bottom
shown to describe both unidirectional and simultaneously.
4.4 Compaction of Metal Powders 165

as 4.5 GPa, in what has been termed as


'cold sintering' (Gutamanas, 1983). Tool
steel dies and punches can be designed for
use at pressures up to 3 GPa, while still
higher pressures need cemented carbide in-
serts. Plastic deformation and fracture of
powder particles in gradients of such high
pressures lead to the bonding of freshly
formed contamination-free surfaces. It
may be possible to employ cold sintering
to advantage in compacting composite and
other multi-component materials, also
rapidly solidified powders.

4.4.3 Cold Isostatic Compaction


There are many limitations to die com-
paction. The size and shape of the compact
Compacting pressure P are limited by the capacity of the press and
also by the geometry of the part. The ne-
Figure 4-16. Konopicky-Shapiro-Kolthoff relation-
ship in powder compaction. Slope Kx is related to the cessity of fabricating complex dies and
material yield stress, and slope K2, to the work-hard- provide for ejection after pressing, and die
ening behavior of the material. friction, makes unidirectional pressing
unattractive for some applications. Cold
isostatic pressing provides an alternative
An important aspect of unidirectional method for such applications. In this
compaction is the design of dies, which method, powder in a mold is subjected to
must take into account not only the shape a hydrostatic pressure, commonly referred
of the compact, but also the ease of its to as isostatic pressure, of about 200 to 500
ejection after pressing. This, in fact, limits MPa for a short time. The pressure is then
the shapes that can be achieved by this released and the compact removed from
method. Many factors are built into the the mold. Sealed molds of powder are
design of dies to achieve correct dimen- loaded in a liquid inside a high pressure
sions and surface finish of the product chamber, and hydrostatic pressure is ap-
(Goetzel, 1950; Kuhn, 1978). These include plied by pressurizing the liquid to the re-
powder characteristics such as the shrink- quired level. Hydrostatic pressure does no
age factor, lubricant characteristics, and work on a homogeneous solid. However,
also properties of the die material. The in a porous material, this pressure is re-
hardness, surface finish and dimensional solved into shear stresses which are large
tolerances that are achievable by machin- near the pores but decrease with distance.
ing determine not only the making of a die, With increasing density (decreasing poros-
but also the effectiveness of compacting. ity), these stresses become negligible and
Typical compacting pressures are in the compaction ceases.
range of 100-400 MPa. Recent develop- The effective pressure Peff can be calcu-
ments indicate the use of pressures as high lated on the basis of the applied pressure
166 4 Powder Metallurgy

Papp and the volume porosity 9 of the pre-


form and can be shown to be Vent valve

(4-21) Sealing nut


app
1-/ Cover
A detailed derivation of this equation is
given in Section 4.6.1. Initially, the resolved _ Back-up ring
shear stress densifies the compact by parti- O-Ring
cle sliding and rotation. This stage is deter- - — Pressure vessel
mined, as in unidirectional compaction, by Plug
the packing geometry and the flow proper-
Envelope
ties of the powder aggregates. In the sec-
ond stage, deformation of powder particles Powder
takes place. Experiments on particles with
different geometries have confirmed these
observations. Even though spherical parti-
cles initially have high packing densities,
they do not mechanically interlock with
Pressure relief
one another and do not easily deform;
higher pressures are therefore required for
their compaction. This is not the case for
irregularly shaped particles which inter-
lock with one another and also deform
during both the stages.
Cover plate
A cold isostatic pressing unit consists of
a thick pressure vessel with an appropriate
top closure which can either be threaded to
the vessel itself or axially loaded with ap-
Pressure
propriate seals from an external frame. The vessel
pressurizing medium in the vessel is gener-
ally a liquid. Wire wound external frames
are advocated to support the pressure ves-
sel which is subject to both radial and axial
stresses. The process can be automated so
that loading, pressurization, depressuriza-
tion and unloading are carried out in a
proper sequence to ensure almost continu-
ous production.
Two different types of isostatic equip-
ment are available, depending on the na-
ture of the mold chosen for isostatic press- Perforated Powder En\e|
(b) support
ing (Jackson, 1967). These are known as
wet-bag tooling and dry-bag tooling Figure 4-17. Schematic of cold isostatic pressing: (a)
(Fig. 4-17). In wet-bag tooling, the mold, wet bag technique, (b) dry bag technique (James,
made from natural rubber (latex) or flexi- 1971).
4.4 Compaction of Metal Powders 167

ble elastomeric material such as neoprene, explosive compacting are determined ei-
polyvinyl chloride or polyurethane, is filled ther experimentally or calculated, using the
with powder, evacuated if required and properties of the explosive and the prod-
then sealed. A number of such molds are ucts of the explosion.
loaded into the pressure vessel and pres- There are many variants of this process
surized, and after the compaction dwell of explosive compaction which can be
time has elapsed, the compacted molds are broadly divided under three headings
removed from the vessel. This method is (Fig. 4-18): contact operations, where an
versatile and appropriate for low volume explosive charge is located on the surface
production. Dry-bag tooling consists of of the container with powder aggregates
molds made from rubber rigid enough to generating normal or tangential incidence
retain shape, firmly fixed as in conven- of shock waves on explosion; remote oper-
tional type presses. The powder is filled ations, in which the high explosive charge
into the mold automatically from a hop- is placed at a distance from the powder
per, the top punch of the press closes the being compacted and the pressure trans-
mold, and isostatic pressure is applied. Af- mitted through an intermediate medium
ter pressing, the pressure is released, the like water, air or even a metallic flying
mold returns to its original size and the plate or a punch; and explosive isostatic
part is removed by ejection using the top or pressing, where a large isostatic pressure is
bottom punch. generated in a closed volume by an explo-
The size of the isostatically pressed part sive charge. In some recent developments,
is limited only by the volume capacity of dynamic compaction is achieved by using a
the press and of the mold. Depending on projectile accelerated by electromagnetic
the applications envisaged, parts are force instead of an explosive charge.
pressed as billets, forging preforms or near- In explosive isostatic pressing, the explo-
net shapes. The process parameters include sive charge is kept in a specially designed
the pressure, dwell time and depressuriza- chamber on top of a pressure vessel. The
tion rate. Isostatic pressing is widely ap- ignition of the charge generates a pressure
plied in compacting porous filters, high wave which moves the piston inside the
speed steel billets, titanium and superalloy pressure vessel pressurizing the medium
near-net shapes and large cemented car- (usually water) containing the powder
bide parts. A recent application is in the mold. The dynamic pressure P can be
compaction of metal-matrix composites. large, around 0.6 GPa, and can be calcu-
lated using the following equation (Roman
and Gorobtsov, 1989)
4.4.4 Explosive Compaction
High energy rate forming using explo- P= (4-22)
sives is also used to advantage for com- 1-5K.
pacting powder aggregates. Explosive where / is the propellant force characteriz-
compaction is made possible by the deto- ing the efficiency of the propellant under
nation wave front generated by the shock isobaric expansion, Vx9 the volume of the
wave, which can travel with a velocity as propellant gases for unit mass propellant
high as 7000 m/s, developing pressures up and S is the charge density i.e., the ratio of
to 28 GPa and raising the local tempera- the mass of the propellant to the volume of
ture up to 5000 K. Various parameters of the combustion chamber. The value of S is
168 4 Powder Metallurgy

Detonator Detonator
assembly
Card board
tube -Explosive
Wooden cone
Projectile

Steel tube
.Barrel

Explosive

. Die

Powder
. Anvil

Die holder^
assembly
Detonator
(b)

, Piston

, Pressure vessel

. Powder
Figure 4-18. Schematic of explosive compaction: (a)
contact compaction (Bhalla and Williams, 1976); (b)
remote compaction (after Raybould, 1981); (c) explo-
sive isostatic compaction (Roman and Gorobtsov,
1989).
(c)

typically equal to 0.7 kg/dm3, for which the There are also other interesting effects
pressure can be as high as 2000 MPa. associated with the interaction of shock
The microstructure of explosively com- waves with powder. For instance, the
pacted powder shows intense deformation shock wave compression of graphite pow-
of powder particles, often seen as bands. der for synthesis of diamond is well known.
Sometimes the pressure can be very high, Similar results are available for producing
leading to local melting and even rapid so- cubic boron nitride and some other refrac-
lidification. The density of the compact can tory compounds. Another effect is con-
also be high, often in excess of 95%. Duc- cerned with the shock-wave induced acti-
tile materials show intense deformation, vation of powders. Shock-wave-induced
while brittle solids fracture into fine parti- deformation produces a very high disloca-
cles which are themselves filled with cracks. tion density in powders and this in turn
4.4 Compaction of Metal Powders 169

(a) Gravity-fed (b)


powder -. Gravity-fed
powder
- Hopper

(c)
powder
force-
Hopper
Figure 4-19. Powder rolling: (a)
and (b) vertical powder feed, two-
high and four-high mills; (c) hori-
Hopper zontal powder feed; (d) inclined
angle powder feed (after Dube,
1981; Evans and Smith, 1959).

influences their subsequent sintering be- positioning using gravity feed offers a
havior. Many refractory compounds sinter good flexibility in controlling powder feed
better, often without binders, after the and also in introducing different powders
powder has been subjected to explosive simultaneously for layered rolling.
treatment. Some advantages of this kind of The important parameters in powder
activation are now only beginning to be rolling are the control of powder feed, roll
realized in sintering multi-phase materials. diameter, edge control, sintering, optional
re-sintering and rerolling. The powder feed
between the rolls from a hopper is con-
4.4.5 Powder Rolling
trolled to ensure uniform thickness and
Roll compacting, or powder rolling, is a uniform density of the rolled strip. Height
process of cold compacting metal powder of the powder bed in the hopper is kept
continuously in a rolling mill. In this pro- constant, to ensure uniform pressure on
cess, the powder is fed from a hopper to a the powder in the roll gap. In some cases,
set of rolls to produce a continuous green the powder feed to the roll gap is con-
strip or sheet (Dube, 1981, 1982, 1983; Ro trolled by means of adjustable gates, to
et al., 1982,1983). The strip is then sintered take into account variations in compacted
and re-rolled to produce the finished prod- density. Edge control is essential in powder
uct. As in conventional die compaction, the rolling to ensure that the edge is as well
starting material can be elemental, blended formed and as dense as the center of the
or prealloyed powder with good flowabil- strip. This is achieved by floating flanges
ity and adequate compactibility. attached to one of the rolls and overlap-
For powder rolling, the rolls can be posi- ping the other roll.
tioned horizontally, vertically or even at an A relatively high green density is re-
inclined angle (Fig. 4-19) (Ro and Toaz, quired for handling the powder-rolled strip
1982; Knopp et al., 1984). Horizontal roll for sintering. It is mainly the roll diameter
170 4 Powder Metallurgy

that determines the strip density and thick- creation of new grain boundaries at junc-
ness. Even though the nip angle in powder tions where powder particles meet. To
rolling is about the same as in conven- provide a larger driving force, sintering is
tional metal rolling, the arc included by the sometimes carried out with very small ad-
nip angle on the roll surface depends on the ditions of reactive elements which alter the
roll diameter. Consequently, a larger balance between the surface energy of the
amount of powder is pulled into the roll particles and the grain boundary energy
gap by larger diameter rolls and a higher favorably for sintering; or, sintering with
density strip is produced. The strip density an additional component which becomes a
is also determined by the coefficient of fric- liquid phase at the sintering temperature.
tion and the roll temperature. With higher External pressure which induces plastic
friction, larger amount of powder is pulled flow can also be applied concomitantly
into the roll gap to give a higher strip den- with sintering for a fuller densification.
sity. Higher temperature of the rolls also There are also instances where sintering is
increases the friction with the same effect. followed by mechanical processing and an-
In practice, the roll gap and the roll friction nealing to eliminate any residual porosity.
are adjusted to give a green density of 75 to Such post sintering processing is usually
90% of the theoretical density. required when load-bearing and other crit-
There are many options available in ical applications are envisaged.
handling compacted powder strips for sin-
tering. The compacted strip can either be 4.5.1 Solid State Sintering
coiled and sintered afterwards, or can pass
directly to the sintering furnace as it comes Solid state sintering can be broadly di-
out of the rolls. vided into the following stages (Thummler
Studies on products manufactured from and Thomma, 1967):
powder strips show that powder rolling (i) bonding of powder particles forming
has reached a level of technological matu- necks;
rity to meet the demands of many applica- (ii) shrinkage of the compact due to de-
tions and of the forming processes usually crease in porosity and change in pore
encountered in manufacturing operations. geometry; and
(iii) isolation of pores followed by homog-
enization of composition and grain
4.5 Sintering growth, with the elimination of resid-
ual porosity.
An important step in powder processing
These processes do not occur in discrete or
is the densification of compacted powder
serial steps, but overlap, a particular pro-
aggregates. This is carried out by heating
cess being predominant at a specific tem-
the powder compacts at temperatures be-
perature and time.
low their melting point and is known as
The driving force for mass transport that
sintering. The driving force for sintering is
leads to solid state sintering is the change
not large and is provided by the reduction
of surface energy by reduction of the sur-
in surface energy of the powder. Often, this
face area, dAs. The corresponding change
energy is clearly inadequate to eliminate all
d£ in the free energy of the system is then
the porosity present in the material. In ad-
given by
dition, there is also a slight increase in the
free energy of the compact because of the dE = y dAs (4-23)
4.5 Sintering 171

where y is the surface tension. The varia-


tion in surface curvature which occurs with
the growth of the neck that joins individual
powder particles is thus reflected in the en-
ergy change dE with respect to the change
in volume dV at the neck: /A . ..
(4-24)
dE/dV=y • d
where rx and r2 are the principal radii of
curvature. The term (d£/dF) formally cor-
responds to the stress a which is tensile on
the concave surface of the neck and com-
pressive on the convex side and is given by Figure 4-20. Mass transport mechanisms in sintering:
(A) lattice diffusion from grain boundary; (B) lattice
a = y[(l/r1) + (l/r 2 )] (4-25) diffusion from surface; (C) lattice diffusion from de-
fects; (D) boundary diffusion from grain boundary;
Similarly, we can define a change in chem- (E) surface diffusion from surface; (F) vapor phase
ical potential between the two curved sur- transport.
faces and this is seen as a gradient in vapor
pressure p and vacancy concentration c:
Table 4-10. Mass flow mechanisms in solid state sin-
(p/p0) (4-26) tering.

and Mechanism Mass Mass Contri-


flow flow bution to
(c/c0) (4-27) source sink shrinkage

These gradients lead to material transport A. Plastic flow Matrix Neck Yes
from convex to concave surfaces by plas- (viscous flow in
tic deformation, or evaporation and con- non-crystalline
densation, or by vacany diffusion (Fig. materials)
B. Vapor phase Surface Neck No
4-20). Part of the mass flow occurs merely transport
around the neck region and does not result C. Surface diffusion Surface Neck No
in shrinkage, while other parts readjust D. Lattice diffusion Surface Neck No
the entire particle surface, leading to the E. Lattice diffusion Grain Neck Yes
shrinking of pores (Table 4-10). boundary
F. Lattice diffusion Dislocation Neck Yes
A chemical driving force is also present G. Grain boundary Grain Neck Yes
in multicomponent systems due to differ- diffusion boundary
ences in diffusion rates among the compo-
nents. Initially, these differences can lead to
inhomogeneous compositions at the neck,
takes place in the entire powder compact,
and porosites at sites from where the faster
removing the initial inhomogeneities seen
diffusing species have migrated. This phe-
on the necks formed between particles.
nomenon is known as the Kirkendall shift
(see Vol. 5, Ch. 2, Sec. 2.2.2.4) and can lead
4.5.1.1 Equations of Sintering
to the creation of porosities at least during
the initial stages of sintering. However, There have been many models, reviewed
as sintering proceeds, re-homogenization exhaustively by Exner (1979), to describe
172 4 Powder Metallurgy

the growth of necks and shrinkage of anisms. Analysis of Eq. (4-28), using ideal-
pores, but a quantitative model still re- ized experiments, show that diffusional
mains to be developed because of diffi- creep (Nabarro-Herring and Coble creep),
culties associated with the modelling of involving lattice and grain boundary diffu-
spheres of different radii and with the con- sion, play a more predominant role than
stant changing of positions and particle either vapor transport or plastic flow.
contacts during sintering. It is possible, However, the problem becomes very
however, to develop an idealized two- complex when we consider sintering of real
sphere model with equal sized spheres in powder particles with different particle
contact with one another, the contact area sizes and geometries (Exner, 1980). There
becoming a neck and growing with time. A have been attempts to model densification
great deal of work has been done using this in real systems by relating the compact
approach and this helps us in identifying shrinkage to center-to-center approach of
the various mechanisms of sintering. the particles. A classical equation of this
In general, sintering of two spheres of type is given by Kingery and Berg (1955)
the same diameter can be described by an
AL h 1
equation of the type (Kuczynski, 1949) — = - =ktn (4-29)

i] =ka (4-28) Here, AL is the linear shrinkage for the


original length L0,h, half of the distance of
where x is the radius of the neck, a, the approach of the two particle centers and t
particle radius and t, the time of sintering, is the time for sintering with k and n as
while n, k and m are parameters which de- appropriate constants.
pend on the rate-controlling mechanism. Another approach to analyze sintering is
Table 4-11 gives the range of values for two by evaluating the changes in surface area of
of these parameters for the different mech- the powder system. On the basis of statisti-
cal modelling, the following relations for
changes in surface area As during sintering
Table4-ll. Equations for neck growth for different have been derived by German and Munir
mass flow mechanisms in solid state sintering. Basic (1975, 1978) as
form of equation: (xn/am) =F (T) • t

Mechanism F(T) (4-30)


dt
Viscous flow 3 y/2 r\ 2 1
Vapor phase K y ft1-5 g°-5 Vjj' ^ j
and
1
transport (RT)
Mi \ae+l
(4-31)
( 5-7 2-3 dt
V VMR Eq. (4-30) is applicable during the initial
Surface diffusion K y Q ws DJRT 1 3
stages of sintering and Eq. (4-31), for the
KyQ033VMDJRT 3-6 1-2 intermediate stage. The exponent m is
Lattice diffusion KyQD 4-5 1-2 based on the initial density and sintering
RT
mechanism, while Bs is a microstructure
Grain boundary Ky Q whDh
diffusion 6 2 based constant; As0 is the surface area at
RT
the start of the grain growth and ag, a grain
4.5 Sintering 173

growth parameter. However, these equa- Table 4-12. Rate equations used in Ashby's sintering
tions are difficult to verify experimentally mechanism maps. F = yQ/kB T; Kl9 K2, K3: surface
curvature difference of the pore.
because of constantly changing particle ar-
rangements during sintering. Mechanism Neck growth rate equation

Stage 0
4.5.1.2 Pore Closure and the Development
Adhesion x( 0 = ca2/x for x<(a2/10fis)033
of Microstructure
Stage I
A green compact consists of particles Surface diffusion
from surface x1=2wsDsFK3l
and pores. With the beginning of sintering,
Lattice diffusion
grain boundaries form in the contact area from surface x2 = 2DyFK\
between particles. The growth of necks Vapor phase
leaves a continuous network of pores transport :i3=PF(Q/2 n Q0 kB T) 0 5 Kx
which has a well defined relationship with Boundary diffusion
from grain boundary x4 = 4whDhFK2/x
the grain size of particles surrounding
Lattice diffusion from
them (Zener relationship) (Exner and Arzt, grain boundary x5=4DvFK2
1983). With further sintering, the continu- Lattice diffusion x6 = (4/9) K2Nx2 D V F-
ity of the pore network breaks down and from dislocations • {K2-(3 fisx/2ya)}
the pores get isolated at grain boundaries. Stages II and III
Boundary diffusion (l/16)whDhFK33
Both densification and coarsening of pores
from grain boundary Xl {\n(xfK3/2)-0J5)}
as well as grains occur simultaneously dur-
ing the final stage of sintering. The pores Lattice diffusion {1/16) DyFK33
can coarsen by either diffusional mass flow from grain boundary *8 {\n(x{K3/2)-0J5)}
between the pores, or by coalescence of the
pores due to grain growth (Kaysser, 1988).
With grain growth, it is also possible that temperature. The regimes where a particu-
pores get "trapped" inside grains. Such lar sintering mechanism predominates are
pores are not easily removed as they can be marked on this map, as exemplified in Fig.
closed only by volume diffusion, which is a 4-21. Although these maps have been gen-
slow process. The relative values of surface erated for ideal conditions, they povide a
and grain boundary diffusion determine convenient framework for appreciating the
the extent of such trapping of pores within specific requirements for sintering.
grains. The choice of sintering tempera-
tures and other parameters that determine 4.5.2 Liquid Phase Sintering
the diffusion behavior is therefore critical
in controlling the excessive grain growth While sintering multicomponent sys-
and in minimizing the residual porosity. tems, it is possible to choose a component
which will be in the liquid state at the sin-
tering temperature, thereby accelerating
4.5.1.3 Sintering Mechanism Maps
the sintering. This has a strong practical
On the basis of the equations of sintering interest as many products based on tung-
(Table 4-12), Ashby (1974) has developed a sten, tungsten carbides, ceramics and rare
system of graphs which are known as sin- earth materials are commercially sintered
tering mechanisms maps. These maps are this way.
drawn for the normalized neck size (x: a), Liquid phase sintering takes place in
linear shrinkage or relative density against three stages (Kingery, 1959; Kaysser and
174 4 Powder Metallurgy

Temperature (°C)
600 700 800
I Full I density
boundary diff. from boundary 2 / A Volume diff. from

Volume diffusion
from boundary

Surface diffusion
from surface
Boundary diffusion
from boundary
I I
0.6 0.7 0.8 0.9
Homologous temperature T /Tm

(b) Temperature (°C)


400 500 600 700 800 900
10-3
I T I Full I density I
Boundary diff^fromj>6undary 2 /3 ^ '\^ol.diff.f.boundary

Boundary diffusion Surface Figure 4-21. Sintering


from boundary diffusion mechanism maps for (a)
from silver spheres of radius
surface a = 100 urn, and (b) silver
spheres of radius a = 10 um,
both with an initial relative
Adhesion
density of 0.8 (Ashby,
-2.0 I I J_ 10"5 1974).
0.5 0.6 0.7 0.8 0.9 1.0
Homologous temperature T /Tm
4.5 Sintering 175

Solution-reprecipitation can be rate con-


trolled by either one of the two steps, dis-
solution and diffusion (Huppmann, 1979;
Huppmann and Petzow, 1979). Diffusion
controlled shrinkage in this stage follows:
zlL\3_
(4-34)

For interface reaction control the shrink-


age follows
Time
Figure 4-22. Mechanisms of liquid phase sintering: fALY = k4 (4-35)
Stage 1 - rearrangement; Stage II - solution-reprecip-
itation; and Stage III - final solid solution sintering
(German, 1985). The constants k± and k2 are related to dif-
fusivity and reaction rate respectively of
the solid in the liquid.
Petzow, 1985). The effect of the three stages The solution-reprecipitation sequence
on densification is shown in Fig. 4-22. Ini- leaves a skeleton of solid phase with liquid
tially, the liquid phase (for example, Co squeezed out to larger voids in the solid
with WC or Cu with W) wets the particles and on to the surface. The microstructure
leading to rearrangement of the particles of a liquid-phase-sintered heavy alloy sys-
and densification. With the capillary pore tem is shown in Fig. 4-23 and indicates the
size decreasing with sintering, the stress liquid phase component solidified in such a
from the surface tension of the liquid phase network. In the third stage of sintering, the
increases. Hence the shrinkage from the solid skeleton sinters just as does a normal
viscous flow in this stage is not directly powder compact.
proportional to sintering time t, and the The three stages are sequential, and the
relative linear shrinkage is given by kinetics of liquid phase sintering is more
sensitive to temperature than to sintering
AL
(4-32)

where x is a small fraction.


In the second stage, the solid phases dis-
solve in the liquid and reprecipitate else-
where due to differences in solubility be-
tween small and large particles. This
difference in solubility is given by the
Gibbs-Thomson equation:
2ys0Q
S Sr\ — (4-33)
RT
where s and s0 are the solubility of a parti- Figure 4-23. Microstructure of a liquid-phase-sin-
cle with radius r and that of a flat surface, tered tungsten heavy alloy, showing the two phases
respectively, and Q is the atomic volume. (Courtesy: DMRL).
176 4 Powder Metallurgy

time. The initial volume fraction of the liq- lower melting point than the base metal,
uid phase can be as high as 35%. The use with a high solubility in the base metal and
of fine particle size and large volume of a low solubility for the base metal. The
liquid enhances sintering. Coarse particle amount of activator addition is also impor-
sizes and high green densities sinter poorly tant: excessive activator can lead to local
as the compact swells instead of densifying. clusters retarding grain boundary move-
There is a particular case of liquid phase ment.
sintering where the liquid phase is tran- Activation of sintering is also produced
sient (German, 1990). With the dissolution by other methods. These include con-
of the solid phase, the liquid composition trolling the sintering atmosphere, increas-
changes, raising the melting point. Some ing defect structure by shock, and con-
instances of fragmentation of particles dur- trolling the microstructure by stabilizing a
ing the initial stage of sintering are also higher diffusivity phase.
seen when alloy powders are sintered at Although the activated sintering of re-
supersolidus temperatures. This arises due fractory metals has been studied exten-
to the formation of liquid phase in each sively, it has not found industrial applica-
particle which leads to fragmentation. The tion. This is because the accompanying
subsequent re-arrangement step would brittleness problems have not been over-
then be the rearrangement of fragments come yet. However, activated sintering has
rather than that of particles. found industrial application in the case of
steels and superalloys in a process called
consolidation by atmospheric pressure
4.5.3 Activated Sintering (CAP) (Dax, 1983). In this process, boric
Uniform and monatomic layers of cer- acid in a methanol carrier is used as the
tain transition metals coated on powder activating agent, and the powders are
particles lower the activation energy of sin- sealed in evacuated glass molds. Sintering
tering and this is known as activated sinter- is activated by the boric acid and is aided
ing (Reshamwala and Tendulkar, 1970). by the atmospheric pressure acting on the
Because of its potential in lowering sinter- mold, to achieve over 95% density.
ing temperatures, this phenomenon has
been studied extensively both in refractory
metals and in ceramics. An analysis of ex-
perimental results shows that activators, 4.6 Deformation Processing
by their presence on the grain boundaries, at High Temperatures
enhance the grain-boundary diffusion rate
significantly, leading to better sintering Fully dense compacts of metal powder
(German and Munir, 1982). For instance, with controlled microstructure can be pro-
the presence of nickel, an activator, on the duced by hot consolidation, in which pres-
grain boundaries of tungsten increases the sure and heat are applied simultaneously.
grain boundary self diffusion coefficient by Various techniques have been developed
a factor of 500 to 5000 at 1675 K (Kaysser, for the application of pressure: static or
1988). dynamic, uniaxial or isostatic pressures
The choice of an activator for sintering is have all been used for one application or
dependent on its meeting some specific re- another. The available major techniques
quirements. For instance, it must have a include (uniaxial) hot pressing, hot iso-
4.6 Deformation Processing at High Temperatures 177

static pressing, powder forging and powder


extrusion.

4.6.1 Principles of Pressure Sintering


When a powder aggregate is subject to
high pressure and temperature, densifica-
tion occurs in three stages. In the first
stage, the aggregate is almost instanta-
neously consolidated to high density by
plastic deformation. No further closure of
pores is possible by plastic collapse as the
external pressure reaches equilibrium with
the internally developed stresses. The ex- Figure4-24. Effective stress on particle contacts in
isostatic pressing (Courtesy: DMRL).
tent of densification is of course dependent
on the applied pressure: with sufficiently
high pressures it is possible instanta-
neously to attain densities as high as 95%. fective stress varies, depending on the par-
In the second stage of densification, vari- ticle size and the contact characteristics
ous creep mechanisms become operative. (Fig. 4-24).
At higher stresses, dislocation creep is Many expressions have been derived to
prominent. But with increasing pore clo- describe the first stage when the plastic col-
sure the stresses become low and diffu- lapse takes place. A closed form solution
sional creep becomes more prominent. In derived by Carrol and Kim (1984) for the
the final stage, with the increased curvature applied pressure P using a hollow sphere
of pore surfaces, diffusion as in the case of model has the form
normal sintering becomes the dominant
P = § <r0 ln0 - |(<70-<7y) lne (4-37)
mechnism of densification.
Thus densification is seen as the net ef- where
fect of local strains which combine to give
overall contractions; these strains arise be- 8 =
cause of an effective stress present in the
material due to the externally applied pres- Here <r0 is the overall stress, oy, the yield
sure. An expression for the effective pres- stress of the material; 9 is the porosity and
sure has been proposed by a number of 0o, its initial value. At the yield point, this
workers and can be derived from an analy- equation reduces to
sis of the stress pattern when a hollow
sphere is subject to an external pressure P. P = f<7yln0 (4-38)
Results of this analysis show that the effec- which was derived by Torre. The plastic
tive pressure Peff, or the average effective collapse stops once the pressure reduces
stress <7eff, is below the critical value of P in Eq.(4-37).
The second stage of densification is char-
acterized by a time dependent deformation
where P is the applied pressure and 0, the which is driven by the effective stress <reff
porosity. Within the compact itself, the ef- and temperature T. Specifically, for the
178 4 Powder Metallurgy

power law creep processes, the net creep based on experimental results on iron and
rate can be approximated to the sum of steel powders which is found to be valid for
individual creep rates: copper, aluminum and alumina powders
as well. In this equation the pore-closure
^Z^eff)1" (4" 39 ) rate is given by
i

where s is the total creep rate, A{ and nt are


the creep constants for a particular mecha- APn (4-41)
nism i. At this stage of densification, it can
be easily shown that the overall densifica- where A and n are material constants.
tion rate 9 is related to the porosity as well As with sintering (see Section 4.5.1.3),
as the overall strain rate due to creep and densification mechanism maps have been
is given by, evolved by Arzt et al. (1983) for pressure
sintering also. A typical mechanisms map
9 = (s +£ +s )(l—0) (4-40)
is shown in Fig. 4-25. Such maps are useful
where ex0, £y0 and sz0 are the strain rates in in visualizing regimes of various mecha-
three perpendicular directions over the nisms operative during the pressure sinter-
compact as a whole. ing cycle, and design the cycle parameters
The rate of densification during diffusion for maximum densification.
creep was derived by Coble (1970) and for An equation for pressure sintering using
the entire sequence of pressure sintering by finite element analysis has been given by
Wilkinson and Ashby (1975). Wilkinson Bhatt etal. (1981). This equation was
and Ashby (1975) have derived separate derived by computer simulation of a pow-
sets of equations to describe pressure sin- der aggregate under isostatic pressure and
tering at the initial, intermediate and the temperature. By measuring individual dis-
final stages of sintering. placements at various points in the ag-
Caligiuri (1980) has derived a semi- gregate and by imposing the necessary
empirical equation for pressure sintering boundary conditions, the strain rates can

(a) lbl
Temperature, °C Pressure, Mn/m 2

w7 f
800 1000 1200 10 100 1000
1.0

Ah >^
^ 0.9
c
0) /creep^/ law /
T3 / N-H/C 1 Power-/
a> 0.8 creep /
Power-law / Yield
creep 5
£ 0.7

_J 0.6 i 1
0.7 0.8 0.9 -2 -1 0 1
Homologous temperature, T/Tm Normalized pressure, log(P/o y )
Figure 4-25. Pressure sintering mechanism maps for tool steel: (a) density-temperature map for particles of radius
a = 25 jum and mean grain size 50 um at pressure P = 100 MN/m 2 ; (b) density-pressure map for particles of radius
a = 50 urn and mean grain size 10 \xm at temperature T=1475 K (Helle et al., 1985).
4.6 Deformation Processing at High Temperatures 179

be calculated using Eq. (4-41). The corre- 4.6.2 Hot Isostatic Pressing
sponding effective pressure Peff for these
boundary conditions is seen to be the same Hot isostatic pressing (HIP) was origi-
as that derived from Eq. (4-40). Using this nally developed for cladding nuclear fuel
effective pressure, the pore closure rate 6 is elements, but is now widely adapted for
given by powder consolidation to complex shapes
in many areas of technology. The advan-
tages of HIP include its capability for
forming complex shapes, for consolidation
where A and n are dense material creep at a lower temperature and for handling
parameters appropriate to the operating radioactive and toxic materials. In its sim-
pressure. Fig. 4-26 shows a comparison of plest form, HIP of powders is a process
this "effective stress" model with the other where the pressure is applied isostatically
two models described in this section. on a hermetically sealed powder can inside
The above analysis is broadly valid for an autoclave. The powder to be compacted
uniaxial pressing as well except for some is tap filled in a shaped container, degassed
differences: the effective pressure is mar- under vacuum at elevated temperature and
ginally lower and varies exponentially with sealed. The canned components are loaded
the coefficient of friction and with distance into the HIP pressure vessel, and processed
from the surface of the plunger. through the pressure/temperature/time
cycle for consolidation and sintering. After
1CT3 i i |
HIP, the can material is stripped off the
Commercial purity component by acid leaching or machining.
Fe powder A schematic layout of the HIP system is
shown in Fig. 4-27. Argon is the most com-
mon pressurizing gas. Gas pressures of
Wilkinson-Ashby eqn. ^ \
over 200 MPa are possible, which is higher
than the pressure normally used for uniax-
#v Caligiuri eqn. ial hot pressing. Complex sealing arrange-
"5 ments are employed for the pressure vessel.
Temperatures of up to 1450 K are routine
I/) with Kanthal resistance heating and higher
Average stress '
temperatures up to 2300 K are also attain-
1 0 " b -- model
able either with graphite or molybdenum
heating elements.
• Experimental data The various sequences in the process of
by Caligiuri hot isostatic pressing are shown in Fig. 4-28.
r=700°C There are modifications to this sequence
when special processing steps are consid-
I 1 1 1 ered. An important commercial applica-
0.20 0.16 0.12 0.08 tion of HIP is in the manufacture of ce-
Porosity 9
mented carbide parts. For this, the equip-
Figure 4-26. Comparison of the average stress model,
Caligiuri model and Wilkinson-Ashby model for pore ment is designed to combine both the de-
closure in pressure sintering of commercially pure waxing and sintering operations with HIP.
iron (Bhatt et al., 1989). In other instances, HIP is the primary con-
180 4 Powder Metallurgy

Pressure vessel Heat


Exchanger

Mantle

Furnace
Tooling
Thermo couple —

Controls
Figure 4-27. Schematic of a hot
isostatic press (Price, 1984).
Pump

(2) (3) (5)

i
m
P Ik
t
Figure 4-28. Processing steps in hot isostatic pressing for powder consolidation: (1) fabricate can to fit formed
part; (2) fill powder in can, evacuate, degas and seal; (3) HIP; (4) strip can to give (5) consolidated part (Meiner
and McCall, 1981).

solidation step, followed by secondary 4.6.3 Uniaxial Hot Pressing


metalworking operations. The economics
Uniaxial hot pressing is a relatively old
of HIP for powder consolidation is a cru-
route and was first developed to consoli-
cial concern in the choice of the technol-
date refractory metals and alloys. In this
ogy. The high capital costs involved in the
technique, as in cold compaction, pressure
setting up HIP facilities can be justified
is applied on the powder in a die either in
only when there is a large output or when
a single acting or in a double acting press.
special processing conditions are envis-
In addition, the press has facilities for heat-
aged as in the manufacture of nuclear fuels,
ing the die in controlled atmosphere or in
jet engine turbine components of high tem-
vacuum. Depending on the application en-
perature composite materials. There are
visaged, hot pressing tools are made from
also developments in automating the pro-
TZM molybdenum, tungsten, stellites, hot
cess and in reducing the cycle time to im-
die steels, cemented carbides, ceramics or
prove the production efficiency.
graphite. Metallic dies and punches used
have to be water cooled to avoid plastic
deformation. The alternate materials graph-
ite and ceramics are strong, but are prone
to failure by brittle fracture.
4.6 Deformation Processing at High Temperatures 181

Hot pressing consists of charging the 4.6.4 Powder Forging


powder in the cold die, heating the die as-
sembly to the pressing temperature and ap- Forging a sintered preform to the re-
plying pressure. Sometimes preformed pel- quired shape and density is yet another
lets are preferred to avoid cooling the die useful technique of deformation processing
each time for charging powder. A con- in PM. This has become a popular process
trolled atmosphere is essential in hot press- for forging steels and aluminium alloys for
ing to protect the die and the charge mate- automobile applications. In this method,
rial, and is provided either by vacuum or the powder is first compacted to a preform
by bleeding an inert gas like argon into the shape, sintered and then press-forged to
furnace chamber. The die is heated either the final shape and full density. The pro-
by resistance heating or by induction. There cessing steps are shown schematically
are also instances where high electric cur- (Brown, 1981) in Fig. 4-29. In powder forg-
rents are passed directly through powders ing, there are some conflicting process re-
in ceramic dies. In some instances, the filled quirements with regard to the desired den-
die assembly is heated separately in a fur- sity and shape of the preform. For instance,
nace before transferring it to the press. a high preform density gives a better
Until recently this process was not con- strength and oxidation resistance, but
sidered economically viable because of the leads to greater wear on the compaction
costs of the die, the complex furnace setup tooling. Accordingly, the preform density
with protective atmospheres and the long is maintained around 75-80% of the theo-
process cycle. Currently the increased retical value. The preform shape is dictated
availability of ceramic and graphite dies, both by the shape of the final part, and by
coupled with an awareness of the benefits the extent of the material flow desired.
of hot pressing, has brought a resurgent Good flow enhances the mechanical prop-
interest from PM manufacturers in this erties of the forged component, but in-
technology, which promises good growth creases die wear. In optimal preform de-
in the coming decade. signs, the shapes are so chosen that the

(2)

i m
m
i I (3)
i
m
U)
Ii Figure 4-29. Steps in the
powder forging process:
(1) fill compacting die with
powder and (2) compact to
required density for pre-
form; eject compact and
sinter in controlled atmo-

m sphere in (3) preheat fur-


.'ii',7':.*.'
8 —
* nace; transfer preform
rapidly to (4) forge press

Q and press forge to full den-


sity part.
182 4 Powder Metallurgy

maximum material flow occurs in areas of


the component that require maximum
strength.
In the absence of friction, the change in
density Q during unconfined forging is
given by (James, 1982):

= dsr + dez (4-43)


(b)

where sr, se and ez are the radial, circumfer-


ential and axial strain increments respec-
tively. The strains are interrelated as
dsr = dse = v dsz.
If the Poisson's ratio v is also incorporated,
the densification equation becomes
An
(c)
-Q°J2) = zz (4-44)
£rel

where grel is the relative density. For closed Figure 4-30. Schematic of powder extrusion process:
die forging (repressing), the densification (a) powder is canned, evacuated and sealed for the
expression simplifies to extrusion billet; (b) with loosely packed powder on
extrusion the can may fold; (c) penetrator technique
used to avoid folding of can.
— = dez (4-45)
Q

Finite element methods (FEM) are also


available for designing the forging pre- as a container not only for degassing, dehy-
forms and for calculating the stresses and driding or annealing of powders before ex-
density distributions in various parts of the trusion, but also to protect the powder
forging (Kobayashi et al., 1989). from contamination from the atmosphere,
extrusion lubricants and the tooling. The
4.6.5 Powder Extrusion can material is selected on the basis of its
hot plasticity, its reactivity and cost.
Powder extrusion differs from its con-
Typical extrusion pressure and displace-
ventional counterpart only in the need to
ment curves (Fig. 4-31) show four regions
have the extrusion preform canned first
(Hughes and Sellars, 1972): barrelling of
and dejacketed after extrusion. The pro-
the can to make contact with the container
cess offers the advantages of shaped extru-
walls, hot upsetting of the billet to full den-
sions and complete densification in a single
sity, stable extrusion at constant velocity
consolidation step. The process (Fig. 4-30)
consists of canning the powder, evacuation and constant pressure and finally extrusion
and sealing, followed by extrusion (Gard- under unstable flow conditions at the end
ner et al., 1967). Often some degree of cold of the billet. The stable extrusion pressure
or hot compaction on the powders is em- PR is approximated by
ployed prior to extrusion. The can serves PR = AKlnR (4-46)
4.6 Deformation Processing at High Temperatures 183

Ram displacement i where R is the extrusion ratio, A and K are


Extrusion pressure constants related to the system and to the
deformation resistance of the material, re-
spectively. A more rigorous analysis (Shep-
pard and McShane, 1976) takes into ac-
count the local temperature increase at the
die exit due to pressure dissipation. This
suggests

Time PR=AK(l-CAT)lnR (4-47)

Figure 4-31. Stem displacement and extrusion pres- where C( = dX/dT) is the slope of the de-
sure developed during powder extrusion. formation resistance against temperature
curve, and A T is the temperature rise dur-
ing extrusion which is itself related to PR.
The above equations, as also the extrusion
I I I i i i i limit diagrams (Causton and Dunkley,
Product
1987) which show the permissible extru-
50 Pressure limit: over- sion ratios against temperature (Fig. 4-32),
o no extrusion V heating provide the necessary guidelines for de-
o 30 signing optimum extrusion conditions.
I20
•D
Sound
extrusion
\ - Powder extrusion is widely used in the
production of high speed steels, com-
X
jj posites, beryllium and oxide dispersion
10 z strengthened nickel base superalloys. This
Low ratio: unsound product
~~i i T* i i i route has a special attraction for beryllium
1050 1100 1150 1200 processing as it produces fine grained
Preheat temperature, °C structure with good ductility. In oxide-dis-
Figure 4-32. Typical extrusion limit diagram for a tool persion-strengthened alloys, powder extru-
steel powder. sion results in elongated grain structure
which can be further enhanced by anneal-
ing to produce zone aligned polycrystals.
This microstructure (Fig. 4-33) is resistant
to creep and can therefore be used for high
temperature applications as in gas tur-
bines. As there is minimum thermal expo-
sure during processing, this route is being
evaluated for producing components from
rapidly solidified powders.

4.6.6 Special PM Processes


In addition to the above processes in
PM, there are also a few others which have
Figure 4-33. Elongated coarse-grained structure of
powder-extruded Ni - 20 Cr - 2 ThO 2 (Courtesy: been developed with some specific applica-
DMRL). tions in mind. We shall enumerate some of
184 4 Powder Metallurgy

these in this section, as also the processes Spray forming is an integral manufac-
which are used after sintering to tailor the turing process which employs atomization
PM products for specific applications. as the primary step (Singer, 1970; Leatham
Ceracon process and rapid omnidirec- et al., 1984). The spray of the atomized liq-
tional compaction are pseudo-isostatic hot uid metal in an inert atmosphere is directed
consolidation processes that do not use on to a mold. The particles flatten on im-
complex and expensive gas pressurizing pact, coalesce and solidify to produce a
systems as in hot isostatic pressing. The preform which can be further hot worked
Ceracon process (Ferguson et al., 1984) by forging or rolling to full density (Singer,
uses ceramic granules as a pressure trans- 1970; Singer and Evans, 1983; Williams,
mitting medium. In this process a hot po- 1987). Processing of rapidly solidified
rous preform is inserted into the ceramic powders are possible by this route without
medium in a hot die and an axial load a need to handle or store these powders
applied on the ceramic grains in a conven- (Singer et al., 1985).
tional forge press. The ceramic grains The Osprey process (Fig. 4-34) is a
transmit the pressure to the preform nearly specific spray processing route which uses
isostatically. Very short cycle times under manipulators to move the mold inside the
pressure are employed and the processing atomization chamber so that the powder is
is completely automated, using robotic deposited uniformly to high densities. Fur-
handling in all steps. After consolidation, ther processing is done by forging to re-
the fully dense part is ejected and the hot quired shapes. Currently, Osprey process is
granular medium recycled. Because of the used in the manufacture of rolls, disks,
soft tooling and unrestricted metal flow, tubes and other shapes from high alloy
the process calls for a complete characteri- steels, superalloys and high strength alu-
zation of the ceramic grains, preform de- minum alloys. Other methods of atomiza-
sign and strict control of operating pres- tion are also being used for spray forming.
sures and temperatures. Among these, low pressure plasma deposi-
Rapid omnidirectional compaction tion uses as feedstock prealloyed powders
(ROC) uses a thick-walled powder con- which are melted in a low pressure plasma
tainer as a fluid die (Kelto, 1984). The pow- and sprayed into a mold (Apelian, 1986).
der is sealed in a die made of soft steel With a high temperature plasma, it is pos-
which is heated and placed in a pot die. sible to spray-form refractory metals, car-
Uniaxial pressure is transmitted by the bides, borides, oxides and intermetallics.
fluid die to the powder as a pseudoisto-
static pressure, enabling complete consoli-
4.6.7 Post-Consolidation Operations
dation with very short pressure dwells. Un-
like the Ceracon process, this process is There are some post-sintering process-
amenable for consolidation to complex ing steps for realizing the requirements of
shapes. The preheat temperatures can be the envisaged product which are unique to
considerably lower than the HIP tempera- PM. These are secondary cold pressing
tures and thermal exposure times can also (coining / sizing / repressing) and infiltra-
be very short. This offers a special advan- tion, in addition to the standard metal fin-
tage for processing metastable microstruc- ishing operations such as machining, heat
tures with their attendant property advan- treatment, hot working and surface treat-
tages. ment.
4.7 Applications 185

Molten metal Crucible

Atomizing gas

Spray of Spray deposited shape


particles shape

-Transfer mechanism

Discharge chamber
Collector
Figure 4-34. Schematic of Osprey
Spray chamber process (Mathur et al., 1989).

Secondary cold pressing of the sintered first infiltering tin in sintered niobium com-
parts is carried out to improve the dimen- pact which is then heat treated to produce
sional accuracy (sizing), or to increase the Nb 3 Sn intermetallic compound.
density (repressing), or to change the top
and bottom surface configurations (coin-
ing). 4.7 Applications
Infiltration is a process by which a liquid
metal is introduced into the pores of a sin- Metal powders even in their elemental
tered compact and is used to reach full form find many industrial applications and
density without secondary mechanical also as feedstock for the manufacture of
processing. It may also be used to form PM components. Metallic flakes of alu-
multilayer composite structure, or to ob- minum, copper, gold and bronze are used
tain a surface layer compatible for welding in pigments. Aluminum powder is exten-
or brazing. For subsequent infiltration, the sively used in rocket propellants, pyrotech-
sintering conditions are adjusted to pro- nics and explosives. Fine iron powder is
duce compacts with the required intercon- used as a nutrient, food additive, and in
nected porosity. The infiltrant, which has a magnetic particle inspection. Fillers and
lower melting point, is then injected into coatings on welding electrodes, plasma
the pores by a variety of techniques which guns and laser equipment also use elemen-
include capillary dip, contact infiltration, tal or prealloyed powder for coating or
gravity feed and pressure or vacuum infil- hardfacing. Electrostatic imaging systems
tration. like xerox use powders for image transfer.
Infiltration is widely used in refractory In this application, the powder is used as a
metal based and carbide based systems. carrier core material for carrying electric
Major infiltrated components include elec- charge and dry ink.
trical contacts and electrodes (W/Mo/ Interconnected porosity that can be re-
WC-Cu/Ag), rocket nozzles (W-Ag), ex- tained in a PM part has many industrial
perimental cermet turbine blades (TiC- applications. Porous parts are used vari-
superalloy), tools (TiC-steels), mechanical ously for filtering, damping and metering
parts (iron/steel-copper alloy), and bear- in fluid flow devices. Porosity in a self-lu-
ings (steel-babbitt alloy). Superconducting bricating bearing serves as a storage reser-
Nb 3 Sn tapes and wires are prepared by voir for the lubricant. Interconnected
186 4 Powder Metallurgy

porosity in a battery element increases the these alloys ensures a fully dense product.
surface area, thus enhancing its chemical To improve the wear resistance, tungsten
reactivity. Parts made from bronze, stain- carbide inserts are surface coated with tita-
less steel, nickel-based alloys, titanium and nium carbide, titanium nitride and alu-
aluminum are used in such applications. mina. Friction materials are the other com-
The compaction technique is chosen de- mon cermet products which are used as
pending on the desired level of porosity aircraft brake pads and as clutch plates.
and the shape of the component, with cold These are sintered iron-based or copper-
compaction and sintering being the most based alloys with silica and alumina addi-
popular. Pressureless compacting is used tions. Recent experiments by L. McCan-
for the manufacture of filters where poros- dlish and B. H. Kear at Rutgers University
ity levels as high as 50% are required; for have shown that tungsten carbide/cobalt
filters with large length-to-diameter ratios, cermets made from nanocrystalline com-
however, isostatic compaction or even ex- ponents (see Chap. 13 of this volume) are
plosive compaction are used. Because of considerably harder and more wear resis-
the shape of electrodes, batteries use pow- tant than conventional cermets.
der-rolled sheets. Self-lubricating bearings Powder metallurgy products are also
with their extensive applications are pro- widely used in electrical and magnetic ap-
duced in large numbers by die compaction. plications. Electrical contacts of silver or
Bronze and iron-based journal bearings copper with tungsten, molybdenum, tung-
are compacted from elemental powder sten carbide or cadmium oxide are made
blends and sintered to retain about 15% by PM techniques. Liquid phase sintering
interconnected porosity. Lubricating oil or liquid infiltration are some of the tech-
infiltrated into the pores provides life-time niques used in the manufacture of these
lubrication for the bearing by a unique contacts. A wide variety of magnetic mate-
mechanism. The oil is drawn out to the rials with different BH values are produced
bearing surface by thermal and centrifugal by PM. These include the widely used hard
effects when the shaft within the bearing ferrites such as barium and strontium fer-
rotates, and is drawn back into the pores rites, the cobalt-rare earth permanent mag-
by capillarity when the rotation stops. nets with high BH value, and the new
Cermets, or ceramic-metal composites, compositions based on neodymium, iron
are another class of materials where PM and boron. This last type is capable of pro-
processing appears to be the only optimal ducing an energy product as high as
route. A classic example is cemented car- 40 MG Oe, and this is made possible by
bides which have been used for machining compacting in a magnetic field which ori-
and wear applications for over sixty years. ents the magnetic domains favorably. A
They are used mainly in the form of small typical process chart for producing rare
throwaway inserts made from tungsten earth permanent magnets is given in Fig.
carbide with titanium and tantalum car- 4-35. Multifilamentary tapes of supercon-
bide additions and with cobalt as binder. ducting Nb 3 Sn are produced by powder
The carbides are made by high tempera- rolling niobium to tapes followed by liquid
ture carburizing of mixtures of tungsten tin infiltration. Among the many processes
and carbon black. These carbides are then considered for producing high temperature
milled together with cobalt, compacted superconductor tapes and wires, PM offers
and sintered. Liquid phase sintering in some attractive routes. The YBa 2 Cu 3 O 7 _ ;c
4.7 Applications 187

composition for such superconductors is tance heating using the compact itself as
obtained from precursor oxide and car- the resistor. Further processing is carried
bonate powders by suitable reactions and out by rolling, swaging and wire drawing.
consolidation. Hot isostatic and explosive The bubbles formed by doping anchor the
compaction have been used with some suc- grain boundaries and prevent any large
cess in the consolidation. scale grain boundary migration and grain
Powder processing is a convenient coarsening. The elongated grains formed
method for manufacturing components of by processing ensures that the microstruc-
refractory metals and alloys. Practically all ture remains stable even at high tempera-
tungsten lamp filaments are drawn from tures. (For further details, see Welsch and
sintered tungsten rods doped with alkali Walter, 1990.)
metals which prevent the degradation of The above applications are some exam-
microstructure by creep. The process in- ples where the special attributes of PM
volves the doping of tungsten oxide pow- have been used with advantage. But there
der with aluminum, potassium and silicon are also areas where PM is attractive be-
prior to reduction. It is then pressed and cause of the ease it provides for large scale
sintered at very high temperatures by resis- economic production. The automobile in-
dustry is such an example and has been a
large consumer of PM products manufac-
Alloy Preparation by tured mainly from iron based alloys (Mo-
Vacuum Melting or Co-reduction carski et al., 1989). These components are
necessarily small and add a maximum
weight of only 16 kg per car. Various types
Premilling <500/xm of gears, pressure plates and small but
complex parts of automatic transmission,
Fine Milling <10 /xm power steering and power brake systems
make up these parts. Several powder forged
parts are also used in automobiles, includ-
Composition Control and Adjustments ing the carbon steel connecting rods. Pow-
der forging is economically more attractive
for this component than ingot forging be-
Compaction in Magnetic Field
for Particle Alignment
cause of the higher production rate and
reduced machining.
The automotive applications have been
Sintering and Heat Treatment dictated by three main attributes of the
PM process, viz., economy, large scale pro-
duction and capacity to manufacture com-
Machining
plex parts. PM is also used with advantage
in manufacturing many ordnance items
Coating such as mortar bodies, complex machine
gun and rifle parts and sintered iron driv-
ing bands infiltrated with lead. In addition,
Magnetizing some major components are also produced
Figure 4-35. Production of cobalt-samarium perma- only by the PM route. One such example is
nent magnets (Ormerod, 1985). the manufacture of heavy alloy ( W - C u -
188 4 Powder Metallurgy

placed in zircaloy or stainless steel tubes to


make fuel bundles. Strict dimensional con-
trol is necessary to ensure efficient opera-
tion and good burn-out. There are also
plate type fuel elements which are used in
special reactors as in nuclear submarines.
For these applications, the U235-enriched
nuclear fuel is dispersed in a metallic ma-
trix, sintered and diffusion bonded in hot
isostatic presses. With a large surface area,
these fuels ensure efficient heat transfer
Figure 4-36. Composite carbon-carbon nosecone of a enabling a rapid rise to peak power on
rocket.
demand. Control rods and shielding mate-
rials are also manufactured by PM tech-
Ni/Fe) anti-tank penetrators used in ki- niques using neutron-absorbing materials
netic energy ammunition. Because of their such as Eu 2 O 3 and B4C dispersed in
high density and good ductility, these have metallic matrix. Radioactive wastes are
replaced other materials. Another applica- also contained by PM techniques. In this
tion is in the development of carbon-car- process, highly active wastes are encapsu-
bon composites for the reentry nose-cones lated in glass or ceramic materials and then
of rockets and missiles (Fig. 4-36) and for hot isostatically pressed to seal the con-
high performance aircraft brakes. These tents effectively and provide the container
are produced by first impregnating carbon with adequate mechanical strength. This
filament-wound structures with pyrolytic process appears to be promising though it
carbon and hot isostatically pressing them is not used extensively today (see also
at elevated temperatures to high densities. Vol. 10).
Even though the starting material for this Powder metallurgy processing has been
application is not powder, the use of pow- developed for manufacturing highly al-
der processing techniques has enabled the loyed tool steels which are prone to segre-
realization of high strength and high densi- gation. In the commonly used commercial
ties. Similar developments are also taking processes, atomized tool steel composi-
place for manufacturing metal matrix com- tions are canned and either hot extruded,
posites with good strength and adequate or cold isostatically compacted and then
ductility. hot isostatically pressed. The mechanical
Nuclear fuel elements and control rods and wear properties of powder processed
of power reactors are manufactured solely tool steels are shown in many cases to be
by powder metallurgy. The fuel is generally superior to their conventionally produced
UO 2 which is produced either from natural counterparts.
uranium or enriched with U 2 3 5 . These fuel In recent times, powder metallurgy has
pellets are compacted from granulated made inroads into the processing of
uranium dioxide powder blended with ap- aerospace components. An integral rotor
propriate binders, and sintered in reducing component of a rocket engine produced by
atmosphere at about 1900 K, in a slow cy- PM processing is shown in Fig. 4-37.
cle which incorporates dewaxing. After sin- Many of the high temperature alloys are
tering and inspection, these pellets are based either on nickel or on cobalt and are
4.8 References 189

heavily alloyed. They have poor ductility


and the workability of these compositions
is poor. In some cases, the alloy composi-
tions have become so complex that casting
appears to be the only option. Atomized
powder eliminates segregation and thus
provides an option for processing powder
to required shapes and properties. There
are some conditions though: the powder
has to be very pure and free from ceramic
and gas inclusions and must be sintered to
almost theoretical densities. Even a small
amount of residual porosity, acceptable in
many other applications, cannot be toler-
ated in jet engine components. Such com-
ponents are now produced from argon-at-
omized powder of nickel base superalloys Figure 4-37. PM integral rotor component for an im-
pulse turbine.
which are freed from ceramic and inert gas
inclusions, canned, evacuated and hot iso-
statically pressed to near-net shapes. The components. The fabrication can also in-
purity of the powder and its characteristics clude drilling complex cooling channels
are important, as otherwise the sintered required in turbine blades and vanes. As
components show the particle boundaries discussed in an earlier Section, for these
decorated by oxides and nitrides. Though applications, oxide dispersion strength-
the economics of this process is shown to ened materials are zone aligned to produce
be very attractive, the industry still uses elongated grains.
some supplementary hot forging to ensure In addition to the above aerospace ap-
total densification. Another limitation of plications, PM components from alu-
the near net-shape process is imposed by minium, titanium and beryllium alloys are
the current non-destructive techniques. being used in aircraft and rocket struc-
These techniques can examine the product tures. Beryllium is specially used for manu-
only when it has some extra thickness for facturing some critical components in the
the shape of the 'sonic envelope'. In spite of inertial navigation system, heat shields and
this limitation, it is expected that the use aircraft brakes. Some new compositions of
of near-net shape powder processing will beryllium alloys are now being investi-
grow in the coming years. gated for their suitability as skin materials
Oxide dispersion strengthened alloys de- for aeorspace vehicles.
scribed in an earlier Section (4.2.1.2) have
been used for some years to fabricate com-
bustor chambers. They are now entering 4.8 References
service as materials for high temperature Apelian, D. (1986), in: Progess in Powder Metallurgy,
turbine blades and vanes in jet engines. Vol. 42: Carlson, E. A., Gaines, G. (Eds.). Prince-
Sheets of these materials are formed by hot ton, NJ: MPIF/APMI, p. 17.
Arunachalam, V. S., Gopinathan, K.G., Krishnan,
extrusion followed by rolling and are then R.V., Raghuram, A.C., Sundaresan, R. (1975),
diffusion bonded to fabricate the required Trans. PMA12, 1.
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Ashby, M.R (1974), Ada Metall 22, 275. dam: North-Holland Physics Publishing, pp.
Benjamin, J. S. (1976), Scientific American 234 (5), 40. 1885-1912.
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Huppmann, W. J. (1979), Z. Metallkde. 70, 792-797.
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192 4 Powder Metallurgy

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Federation. Powder Industries Federation.
5 Mechanical Milling and Alloying

Carl C. Koch

Materials Science and Engineering Department, North Carolina


State University, Raleigh, NC, U.S.A.

List of Symbols and Abbreviations 194


5.1 Introduction 195
5.2 High Energy Ball Milling: Equipment and Process Variables 196
5.3 The Mechanics/Physics of Mechanical Milling and Alloying 198
5.3.1 Ductile/Ductile Components 198
5.3.2 Ductile/Brittle Components 199
5.3.3 Brittle/Brittle Components 200
5.3.4 Modeling the Kinetics of Mechanical Alloying in a SPEX Shaker Mill . . . . 201
5.3.5 Modeling the Mechanics of Mechanical Alloying in a Planetary Mill 204
5.3.6 Temperature Effects During Milling 206
5.3.7 Relationships to Wear and Erosion Processes 209
5.4 ODS Alloys by Mechanical Alloying 210
5.4.1 ODS Ni-Base Superalloys and Fe-Base High Temperature Alloys Produced
by Mechanical Alloying 211
5.4.2 ODS Aluminium-Base Alloys Produced by Mechanical Alloying 213
5.4.3 Other ODS Alloys Produced by Mechanical Alloying 214
5.4.3.1 Ti-Base Alloys 214
5.4.3.2 ODS Intermetallics by Mechanical Alloying 215
5.4.3.3 ODS Refractory Metal Alloys 216
5.5 Synthesis of "Equilibrium" Phases by Mechanical Alloying 216
5.5.1 Solid Solutions 216
5.5.2 Intermediate Phases 217
5.5.3 Immiscible Alloy Systems 220
5.5.4 Synthesis of Materials for Special Applications 223
5.6 Mechanical Milling/Alloying as a Nonequilibrium Processing Tool 224
5.6.1 Extended Solid Solutions 224
5.6.2 Disordering by Mechanical Milling 226
5.6.3 Amorphization by Mechanical Alloying/Milling 228
5.6.4 Crystallization of Amorphous Alloys by Mechanical Milling 237
5.6.5 Demixing Reactions by Mechanical Milling 238
5.6.6 Nanocrystalline Materials by Mechanical Alloying/Milling 239
5.6.7 Quasicrystalline Materials by Mechanical Alloying 240
5.7 Chemical Reactions Induced by Mechanical Alloying 240
5.8 Summary 241
5.9 Acknowledgements 241
5.10 References 241

Materials Science and Technology


Copyright © WILEY-VCH Verlag GmbH & Co KGaA. All rights reserved.
194 5 Mechanical Milling and Alloying

List of Symbols and Abbreviations


a0 lattice parameter
C% critical concentration
cP specific heat
D diffusion constant
E total strain
A£ b total energy released by a ball
F dissipated energy flux
F observed physical quantity (e.g. resistivity, volume change, enthalpy)
k0 thermal conductivity
P probability of ball impacting
P* normalized power
R radius of a disk
atomic radii
r ratio of atomic radii RA/RB
r radius of a container
S LRO parameter
T temperature
T. glass transition temperature
t time
time between impact events
processing time
total powder volume
Vr relative velocity
QP powder particle density
°n normal stress
Q,co rotation speed of the disk and container relative to the disk
DSC differential scanning calorimetrie
EXAFS extended X-ray absorption fine structure
GAR grain aspect ratio
INCO International Nickel Company
LRO long range order
MA mechanical alloying
MG mechanical grinding
MM mechanical milling
ODS oxide dispersion-strengthened
PPD parameter phase diagram
SAP sintered aluminum powder
SEM scanning electron microscopy
SRO short range order
SSAR solid state amorphization reaction
TD thoria dispersion
TEM transmission electron microscopy
YAG yttrium-aluminum garnet
5.1 Introduction 195

5.1 Introduction ternational conferences devoted to mate-


rials synthesis by MA ("New Materials by
The synthesis of materials by high ener- Mechanical Alloying Techniques", 1989;
gy ball milling of powders was first devel- "Solid State Powder Processing", 1990;
oped by John Benjamin and his coworkers and "Structural Applications of Mechani-
at the International Nickel Company in cal Alloying", 1990). The subject of amor-
the late 1960's (Benjamin, 1970). The goal phization by MA has also played a promi-
of this work was the production of com- nent role in conferences devoted to solid
plex oxide dispersion-strengthened (ODS) state amorphization ("International Con-
alloys for high temperature structural ap- ference on Solid State Amorphizing Trans-
plications. It was found that this method, formations", 1988; "International Sympo-
termed mechanical alloying, could success- sium on Amorphization by Solid-State Re-
fully produce fine, uniform dispersions of action", 1990).
oxide particles (A12O3, Y 2 O 3 , ThO 2 ) in A number of general reviews of MA
nickel-base superalloys which could not be have appeared (Benjamin, 1976; Gilman
made by more conventional powder metal- and Benjamin, 1983; Benn et al., 1984;
lurgy methods. In addition, reactive alloy- Sundaresan and Froes, 1987; Koch, 1989),
ing components such as Ti, could be incor- as well as reviews of specific topics (e.g.,
porated from master alloy powders such amorphization) or materials (e.g., refrac-
that it was clear that "alloying" could oc- tory metal alloys). This chapter will cover
cur on the atomic level during the ball much of the material presented in previous
milling process. Benjamin and his cowork- reviews but will emphasize the more recent
ers at INCO also explored the synthesis of work, in particular, the use of high energy
other kinds of materials, e.g. solid solution ball milling as a nonequilibrium processing
alloys and immiscible systems, and pointed method which can be analogous to rapid
out (Benjamin, 1976) that mechanical solidification. The paper will first describe
alloying (MA), in addition to synthesis the equipment and some of the process
of dispersion-strengthened alloys, could variables used for high energy ball milling.
make metal composites, compounds, and/ Next, the physics of the milling processes
or new materials with unique properties. will be described to the extent that it is
However, the major application of MA so presently understood, and models of the
far has been the production of oxide-dis- mechanics of several mills will be reviewed.
persion-strengthened (ODS) alloys. An important parameter - the temperature
Fundamental research on MA also was of the powder during milling - will be dis-
concentrated on ODS alloys for some cussed. The remainder of the chapter will
years. In the early 1980's, however, an in- be devoted to a description and analysis of
crease of interest in MA as a nonequilib- the results of mechanical milling and/or
rium processing method occurred, partly alloying of specific classes of materials in-
due to the discovery that amorphous al- cluding ODS alloys, difficult-to-make al-
loys could be made by MA (Koch et al., loys or compounds, immiscible alloy sys-
1983), and to the renewed interest in inter- tems, and many metastable materials such
metallic compounds and other materials as amorphous alloys, nanocrystalline ma-
which were difficult to synthesize by con- terials, and quasicrystals.
ventional processing techniques. During
the last several years there have been in-
196 5 Mechanical Milling and Alloying

5,2 High Energy Ball Milling:


Equipment and Process Variables balls
material-
The milling of materials has been a ma-
drive
jor component of the mineral, ceramic rollers
processing, and powder metallurgy indus-
tries. The objectives of milling include par-
Figure 5-1. Schematic cross-section of a tumbler ball
ticle size reduction, mixing or blending,
mill.
and particle shape changes. The typical
mill used for these purposes has been the
tumbler ball mill (or for small charges the drive shaft
jar mill) which is a cylindrical container
rotated about its axis in which balls impact
upon the powder charge. The balls may
roll down the surface of the chamber in a .rotating
impeller
series of parallel layers or they may fall stationary
freely and impact the powder and balls be- tank — attritioning
neath them. The tumbler ball mill is illus- balls
trated in Fig. 5-1. Figure 5-2. Schematic of an attrition mill.
While a number of ingenious milling
devices were developed early in the centu-
ry, the one high energy ball mill that has loys, attrition mills have been largely re-
been adopted by industry was invented by placed by the large tumbler ball mills.
A. Szigvari in 1922, in order to quickly Another type of mill that has been used
attain a fine sulfur dispersion for use in for pilot-size production is the vibratory
vulcanization of rubber. This mill is called tube mill. The motion of the balls and par-
an attritor or attrition mill and is illustrated ticles in a vibratory mill is complicated.
in Fig. 5-2. Milling occurs by the stirring The cylindrical container is vibrated and
action of an agitator that has a vertical the impact forces acting on the powders
rotating shaft with horizontal arms. The are function of the rate of milling, ampli-
motion causes a differential movement be- tude of vibration, and mass of the milling
tween the balls and the powder thus medium. High-energy milling forces can be
providing a much higher degree of surface obtained by using high vibrational fre-
contact than is achieved in tumbler ball quencies and small amplitudes of vibra-
mills. The kinetic energy imparted to the tion. The details of the tumbler ball mill,
milling media in either of these kinds of the attrition mill, and the vibratory mill
mills also depends on the speed of rotation construction and operation are given in the
of the tumbler mill cylinder or the attritor review by Kuhn et al. (1985).
shaft. Tumbler mills may also be consid- Several different kinds of laboratory-
ered high energy mills if of sufficiently scale high energy mills have been used
large diameter (of the order of meters) and for research purposes. The SPEX model
operated just short of the critical rotation- 8000 shaker mill has been used extensively
al speed at which centrifugal force "pins" for research on small batches of powder
the balls to the mill chamber wall. For (^10cc), especially in the U.S.A. This
large scale production of commercial al- high energy ball mill agitates the charge
5.2 High Energy Ball Milling: Equipment and Process Variables 197

of powder and balls in three mutually per- may experience, a good deal of experimen-
pendicular directions at approximately tal, albeit indirect, evidence as well as mod-
1200 rpm. It is highly energetic compared el calculations suggest modest temperature
to the attrition and vibratory mills. A giv- rises - ^ 100 to 200 °C - are likely under
en reaction can typically take place an-or- most conditions. This question will be ad-
der-of-magnitude faster in the SPEX mill dressed in more detail in the next section.
than in the typical attritor or vibratory One serious problem with the milling of
mill. Planetary ball mills have also often fine powders is the potential for significant
been used for research studies, particular- contamination from the milling media or
ly by European investigators (see Fig. 5-8, atmosphere. If steel balls and containers
below). The commercially available Fritsch, are used, iron contamination can be a
Pulverisette 5 has typically been used (e.g. problem. It is most serious for the highly
Hellstern und Schultz, 1986), or modifica- energetic mills, e.g., the SPEX shaker mill,
tions there of (e.g. Gaffet, 1990). Several and depends on the mechanical behavior
researchers have designed their own high of the powder being milled as well as its
energy milling devices, for example, the chemical affinity for the milling media. Ex-
single large steel ball (6 cm) in a tungsten tended milling times in a high energy shak-
carbide bottom steel vial (6.5 cm diameter) er mill can result in iron contamination of
attached to a vibrating frame used by >10 atomic percent in some refractory
Bakker and coworkers (Weeber et al., metal powders. In order to minimize such
1987). contamination, less energetic mills - such
The energy of the milling media depends as the vibratory mill - may be used, or
on the internal mechanics of the specific other more inert milling media can be used
mill, the power supplied to drive the such as tungsten carbide. In extreme cases,
milling chamber, and the composition, balls and container lining can be made of
size, and size distribution of the balls. the same or similar alloys as the composi-
Since the kinetic energy of the balls is a tion of the powders being processed.
function of their mass and velocity, dense The other potential source for contami-
materials (steel or tungsten carbide) are nation of the powders is the milling atmo-
preferable to ceramic balls, and the size sphere. If milling is carried out in air, sig-
and size distribution should be optimized nificant contamination with oxygen, or in
for the given mill. Too dense packing of some cases with nitrogen, can occur. Oxy-
balls reduces the mean free path of the ball gen contamination is, of course, most
motion, while a dilute distribution mini- severe in reactive metals such as Al, Ti, Zr,
mizes the collision frequency. Empirically, etc. Oxide concentrations can be more
ball mass-to-powder-mass ratios of 5 to 10 than tripled in aluminum powders after 3 h
are typically used and are effective. of milling (Gilman and Nix, 1981) and
One important process variable is the doubled in Ni3Al powders after 6 h of
temperature of the mill and that induced in milling in a SPEX mill in an impure argon
the powders by the kinetic energy of the atmosphere (Jang and Koch, 1988). Oxy-
milling media. This temperature may be gen concentrations of «10 atomic percent
critical for the reactions or transforma- are not unusual for milling of reactive
tions in the powders during milling. While powders such as Zr- or Ti-base alloys.
there is still some doubt as to the precise While the usual concern for atmospheric
temperatures that the powder surfaces contamination is for oxygen, the possibili-
198 5 Mechanical Milling and Alloying

ty of nitrogen contamination should not Co. trade name for ethylenebisdistear-


be ignored in certain cases. Fu et al. (1990), amide, C 2 H 2 _ 2 (C 18 H 36 ON)). They mini-
have recently shown that nitrogen gas in mize excessive cold welding and allow me-
the milling vial reacted with the powder in chanical alloying to occur in very ductile
a mixture of Fe and Er powders to form an systems. This occurs even though the sur-
ErN phase. It was suggested that the steel factant often disappears after short milling
vial did not remain hermetically sealed times ( < l h ) . Ovesoglu and Nix (1986)
during the milling process and the nitride used differential scanning calorimetry to
phase was formed due to the catalytic ac- monitor the melting point of Nopcowax-
tion of the Fe in dissociation of the N 2 22DSP. They found that after 25 minutes
molecules. of milling, the melting peak for the surfac-
Atmospheric contamination can be min- tant disappeared. It is assumed that the
imized or eliminated by milling in an inert surfactant is incorporated into the metal
atmosphere or vacuum. One approach is powder or volatilizes by forming gaseous
to load the ball/powder charge in an inert species. It can, therefore be a serious
gas (argon) glove box and seal the vial with source of contamination of the metallic
an "O" ring seal. It must then be assumed powders.
that the seal is maintained during milling.
A more certain method, which is applica-
ble to small experimental mills, is to en- 5.3 The Mechanics/Physics of
close the mill in an inert gas glove box. Mechanical Milling and Alloying
Less contamination is also often observed
with the less energetic mills which may be The central event in mechanical milling
a consequence of the lower powder tem- or alloying is the ball-powder-ball colli-
peratures and/or the better maintenance of sion. Powder particles are trapped between
the vial seal. While most attention of ex- the colliding balls during milling and un-
perimentalists has focused on minimizing dergo deformation and/or fracture pro-
atmospheric contamination during milling, cesses which define the ultimate structure
the handling of the powder after milling is of the powder. The nature of these process-
also important. In many cases the final es depends upon the mechanical behavior
milled particle size is a few micrometers in of the powder components, their phase
diameter, presenting a large powder sur- equilibria, and the stress state during mill-
face area for atmospheric contamination ing. It is convenient to classify the powder
of reactive alloys. components into 1) ductile/ductile, 2) duc-
tile/brittle, and 3) brittle/brittle systems.
While mechanical milling/alloying is de-
fined as a dry milling process, certain very
5.3.1 Ductile/Ductile Components
ductile metals such as Al (Benjamin and
Volin, 1974; Benjamin and Bomford, 1977; The phenomenological description of
Gilman and Nix, 1981) and Sn (White and the mechanical alloying of ductile compo-
Nix, 1979), require the addition of a sur- nents (and ductile/brittle components) was
factant, process control agent, to obtain first presented by Benjamin and Volin
the proper balance between cold-welding (1974). They discuss the mechanical alloy-
and fracture. The process control agents ing of ductile components in terms of a
are typically organic compounds such as competition between cold-welding and
Nopcowax-22DSP, (Diamond Shamrock fracture. They divided the mechanical al-
5.3 The Mechanics/Physics of Mechanical Milling and Alloying 199

loying process into five sequences as delin- strated that true atomic level alloying oc-
eated by observations with optical micros- curred by mechanical alloying of Ni-Cr al-
copy of the powders at various stages of loys by showing that the magnetic-behav-
milling. Initially, micro-forging flattens ior of the mechanically alloyed Ni-Cr pow-
ductile powders into plates and fragments der was identical to Ni-Cr alloys of the
more brittle components into finer parti- same composition prepared by conven-
cles. A schematic drawing of a ball-pow- tional ingot metallurgy.
der-ball collision of a powder mixture is
given in Fig. 5-3. Extensive cold-welding
5.3.2 Ductile/Brittle Components
follows the first stage with a composite
lamellar structure of the ductile compo- The evolution of microstructure during
nents in the form of plates. At longer mechanical alloying of ductile/brittle sys-
milling times, the composite powder parti- tems has also been described phenomeno-
cles are further refined, the lamellar spac- logically (Benjamin, 1970; Benjamin and
ings decrease, and lamellae become convo- Volin, 1974; Benjamin, 1976). The hard
luted. At this stage, alloying begins, aided brittle powders are fragmented during
by any heating that may be introduced by milling, and the fragments are trapped at
milling, the enhanced diffusion paths of the boundaries between the ductile pow-
the lattice defects created by the deforma- ders. As milling proceeds and the welds
tion, and the shortened diffusion paths as between ductile particles come closer to-
the lamellae become finer and more convo- gether - and finally blend - a fine disper-
luted. Eventually, the lamellar spacing be- sion of the brittle phase results if it is in-
comes too fine to be resolved by optical soluble in the ductile matrix, as inert ox-
microscopy. With continued milling, com- ides in ODS alloys. However, brittle inter-
ponents which exhibit complete solid solu- metallics are also incorporated into, for
bility mix to the atomic level, i.e. a true instance, Ni-base ODS superalloys by me-
alloy is formed. Benjamin (1976) demon- chanical alloying. The brittle intermetallics
are fragmented but apparently alloy with
the Ni-base matrix so that they are not
resolvable by optical microscopy when me-
chanical alloying is complete.
Another example of the alloying of duc-
tile/brittle components by milling wherein
a homogeneous alloy is formed is the mix-
ture of Zr (ductile) with NiZr 2 (brittle)
powder to form an amorphous Ni-24 at.%
Zr alloy (Lee and Koch, 1988). Schultz
et al. (1988) did not observe the alloying of
brittle amorphous boron particles into Fe,
Fe-Si, or Fe-Zr powders by ball milling. In
all cases the boron particles were dispersed
in the metal matrix. In Fe-Zr-B, the boron
did alloy after annealing the dispersion be-
Figure 5-3. Ball-powder collision of powder mixture low the crystallization temperature of the
during mechanical alloying. amorphous Fe-Zr alloy. Brittle Si did form
200 5 Mechanical Milling and Alloying

an alloy with Fe during mechanical alloy- pound MnBi), (Davis et al., 1988) and var-
ing. These observations presumably reflect ious mixtures of intermetallic compounds
the differences in the mutual solid solubili- such as NiZr 2 /Ni 11 Zr 9 (which forms
ties of the components. Boron has negligi- amorphous alloys) (Lee et al., 1988a).
ble solubility in Fe, while Si exhibits signif- Davis and Koch (1987) observed the for-
icant solid solubility in Fe. Likewise, the mation of a Si-Ge solid solution on me-
stable oxide dispersoids, such as A12O3, chanical alloying of the pure components
Y 2 O 3 , ThO 2 , are essentially insoluble in which are both nominally brittle at ambi-
the metal matrices of ODS alloys in which ent temperature. The solid solution forma-
they are incorporated by mechanical alloy- tion was detected by measurement of pre-
ing. cise lattice parameters for Si and Ge as a
Thus, alloying of ductile/brittle compo- function of milling time. As illustrated in
nents during milling requires not only that Fig. 5-4, the lattice parameters of Si and
the brittle particles become fragmented so Ge move towards each other with increas-
that short-range diffusion can occur, but ing milling time until they merge to a single
the brittle component must also have some value, which is identical to that for the
solubility - as indicated by either the stable solid solution of this composition (Si-28
or metastable phase equilibria - in the duc- at. % Ge) prepared by conventional metal-
tile matrix component. lurgical methods. Thus, it is possible to
attain atomic level alloying by milling brit-
tle components together.
5.3.3 Brittle/Brittle Components The mechanism for mechanical alloying
It might be expected that mechanical al- of brittle components is not well under-
loying of brittle/brittle powder systems stood as yet. The microstructural evolu-
would not occur and that milling would tion during milling differs markedly from
simply reduce the brittle powder compo- the lamellar morphology of ductile compo-
nents' size down to what is called the limit nents. A granular morphology is observed
of comminution. The grinding of brittle during mechanical alloying as illustrated in
mineral powders to achieve fine particles Fig. 5-5 for Ge and Si powder milled for
for subsequent processing reaches a limit
on particle size below which further frac-
turing stops - the limit of comminution
(Harris, 1967). It has been suggested that 0.57- D
a Ge
^ Si
this limit may be due to extremely small c D D
D
• ALLOY
particles deforming plastically rather than
meter

fracturing, the increased cohesion between 0.56-

fine particles leading to aggregation, or 2


(0
phase changes in surface layers. £L
O
••
O 0.55- •
It has been shown, however, that milling •

of certain nominally brittle components i


can lead to homogeneous alloys. The brit- 0 54 •

tle/brittle systems which have been studied 2 4 6 8 10

in this regard include Si/Ge (which form milling time (h)


solid solutions) (Davis and Koch, 1987), Figure 5-4. Lattice parameter vs. milling time for Si
Mn/Bi (which forms the intermetallic com- and Ge powder for the composition Ge-72 at.% Si.
5.3 The Mechanics/Physics of Mechanical Milling and Alloying 201

formation which is made possible by (a)


local temperature rises, (b) microdeforma-
tion in defect free volumes, (c) surface de-
formation, and/or (d) hydrostatic stress
state in the powders during milling. A fric-
tional wear mechanism, to be discussed in
more detail later, may also be operable.
The material transfer in the brittle powder
agglomerates during milling may be relat-
ed to the conditions that control the "limit
of comminution", as described above.
When the limit of comminution is reached
Figure 5-5. SEM micrograph of Ge (dark) and Si in multicomponent brittle powders, the
(light) powder milled 2 h in a SPEX mill. conditions may be favorable for the cold
welding or other material transfer mecha-
nisms that result in mechanical alloying.
two hours in a SPEX mill. It would appear
that the harder Si particles are embedded
5.3.4 Modelling the Kinetics of Mechanical
in the softer Ge. It was also noted in the
Alloying in a SPEX Shaker Mill
Si-Ge system that mechanical alloying was
suppressed by milling in a vial cooled by McDermott (1988) and Davis et al.
liquid nitrogen. In this brittle/brittle sys- (1988) examined the mechanics of the
tem, thermal activation - diffusion - is SPEX shaker mill. The following questions
apparently a critical requirement for me- related to the kinetics of mechanical alloy-
chanical alloying. In contrast to this ob- ing in the SPEX mill were considered.
servation, mechanical alloying has been What velocities do the milling media
achieved at sub-ambient temperatures in (balls) attain? How much energy is trans-
ductile/ductile systems, e.g. at -40°C in ferred to the environment (powders) dur-
Ni-Ti alloys (Schwarz et al., 1985), and ing an impact? How much energy is trans-
ductile/brittle systems, e.g. Nb-Ge at - ferred to the powders as heat? To help an-
15 °C (Koch and Kim, 1985). This differ- swer these questions, a computer simula-
ence may reflect the longer diffusion dis- tion of the interior of the SPEX mill during
tances required in the brittle/brittle granu- operation was constructed to gain insight
lar vs. ductile/ductile lamellar geometry, into the collision process as related to me-
and/or the enhanced diffusion paths pro- chanical alloying.
vided by severe plastic deformation in duc- The model consists of a simplified ver-
tile/ductile systems. sion of the movements of the vial, com-
While the mechanism for mechanical al- bined with the inferred ball movements
loying of brittle/brittle systems is not yet based on classical mechanics and analytic
well understood, it is clear that material geometry. The vial motion was recorded
transfer can occur between certain brittle on videotape after slowing its apparent ve-
components. Possible mechanisms which locity by use of a high precision strobo-
may contribute to material transfer during scope. This videotape was then analyzed
mechanical alloying of brittle components by a "Motion Analysis" computer transla-
(Davis et al., 1988) may include plastic de- tion system. This converted the analog mo-
202 5 Mechanical Milling and Alloying

tion of the vial into digital coordinate dis- induced by the kinetic energy of the balls.
placements and velocities, based on appro- An expression for temperature increases
priate time constants of length calibra- from localized shear of powder particles
tions. The ball motion and velocity within trapped between two colliding balls is giv-
the vial was monitored continuously by the en by Schwarz and Koch (1986) as
program. The ball motion was studied by 1/2
F At
observation through a transparent lucite AT= (5-1)
i (-1
vial. If any two balls were within 1 diame-
2 Vt£o£p
ter of their loci, or any one ball was within where F= dissipated energy flux = crni;r,
1 radius of the vial interior surface, then an where an = normal stress due to a head-on
impact was recorded, the ball impact dissi- collision and vr = relative velocity of the
pated kinetic energy and mean free paths balls before impact. At = stress state life-
were recorded, and the ball's direction and time, gp = powder particle density,
velocity adjusted based on geometry of k0 = thermal conductivity of the powder,
collision, vial impulse, and gravitational and Cp = specific heat of the powder. With
effects. The geometric and kinetic energy the appropriate constants put into this ex-
values were adjusted based on the restitu- pression for Ge (Davis and Koch, 1987;
tion of the stainless steel powder-coated Davis et al., 1988) temperature rises of
balls, as determined by separate experi- A r - 1 0 K and A r = 9 5 K are calculated
mentation. for vT = 2 m s" 1 and t;r = 18.7 m s" 1 respec-
Table 5-1 shows the number of impacts tively. The value of i;r = 18.7 m s~ * was the
occurring for 0.5 and 1.0 seconds of mill maximum value determined by the com-
operation at several different ball loads. As puter model. Further discussion of the
can be seen, the vast majority of impacts temperature induced in the powders by the
occurred in the 1 x 104 to 105 ergs (10" 3 to kinetic energy of the balls will follow de-
10 ~2 J) range of energy dissipated during scriptions of other models of the ball
the collision. milling process.
This information can be used to estimate Courtney and Maurice (1990) have con-
the temperature increases in the powder structed a model for the mechanical alloy-
ing of ductile powders which they have ap-
Table 5-1. Number of impacts for various ball and plied to both the SPEX shaker mill and the
kinetic energy values.
attritor mill. They treat the impaction of a
Number Kinetic energy of impact (J) porous powder cylinder, composed of
of balls many individual powder particles, between
used 10" 7 10~4 10~3 10~2 10" 1 two flat surfaces. The surfaces are assumed
(2geach) tol0~ tol0~ 3 tol0~ 2 tolO" 1 to 1.0
4
flat since the powder cylinder radius is
much smaller than the ball surface radius.
Mill operation for 0.50 s
5 0 0
The geometry for this model is given in
43 297 3
10 0 78 505 13 1 Fig. 5-6. The authors developed an expres-
15 4 124 928 24 0 sion for the time for mechanical alloying
Mill operation for 1.00 s
based on this model. This processing time,
5 0 78 612 3 0
tp9 is given by:
10 0 148 1201 13 2 V Ft
15 4 229 1873 24 0
r (5-2)
5.3 The Mechanics/Physics of Mechanical Milling and Alloying 203

of 0°. This probability is given by


P(<9) = l-cos9 and is plotted as curve
"a" in Fig. 5-7, which represents a random
distribution. Curve " b " represents a distri-
Porous
powder bution biased toward glancing angles. The
cylinder curve labeled "c" represents the expected
distribution in a SPEX mill containing a
few balls, while curve "d" is from the mod-
P
Figure 5-6. Schematic model of Courtney and Table 5-2. Estimated milling times for MA devices
Maurice (1990) for impaction of a porous powder (after Courtney and Maurice, 1990).
cylinder.
Device Material Time Time
(min)a (min)b
where Vp = total powder volume, E=total
Attritor Al 120-210 500-830
strain needed for alloying, rc = time be- (ball radius = Cu 3 8 - 64 120-210
tween impact events (which is determined = 2.4xlO~ 3 m) Fe 4 4 - 73 150-250
by the "unit cell" of the mill). In the SPEX SPEX Mill Al 2.4-4.0 8.1-14.0
mill the unit cell is defined as the mill vol- (ball radius = Cu 0.7-1.1 2.4- 4.0
ume divided by the number of balls within = 2.4xlO~ 3 m) Fe 0.8-1.3 2.7- 4.6
it. In an attritor the unit cell is defined as SPEX Mill Al 1.8-3.1 6.7-11.0
the volume belonging to each ball, e.g. for (ball radius = Cu 0.3-0.5 1.8- 3.1
a packing density of 0.5 the unit cell is = 6.4xlO~ 3 m) Fe 0.4-0.7 2.1- 3.6
« twice the volume of a ball. The authors b
Ball/powder ratio = 10 Ball/powder ratio = 3
describe how each of the parameters in the
expression for tp are estimated. They then
0.3
calculate the estimated milling times for A Davis, Me D e r m o t t & K o c h
mechanical alloying for the SPEX and an a Solid angle
b Biased glancing angle
attritor mill. Their results are shown in c Spex mill
0.2
Table 5-2. Qualitatively the results agree CD
with experiment in that the attritor mill Q_
requires longer milling times than the 0.1
SPEX mill. The magnitude of the milling
times are too short compared to experi-
ment, however, since the transient times 0
for the development of a steady state parti- 0 20 40 60 80
G (deg.)
cle distribution are not included, and,
Figure 5-7. Impact angle distribution functions. (Af-
more significantly only "head on" colli- ter Courtney and Maurice, 1990). The triangles repre-
sions were treated. Courtney and Maurice sent observed/simulated distributions in a SPEX mill
(1990) describe how the impact angles for containing a large number of balls (Davis et al., 1988).
the collisions may be included in the mod- Curve (a) represents a random (solid angle) distribu-
el. The simplest approach is to consider the tion. Curve (b) represents a distribution biased to-
ward glancing angles. Curve (c) represents an ex-
probability of a ball impacting a flat sur- pected distribution in a SPEX mill containing
face at an angle less than 0. A head-on relatively few balls. Curve (d = ±) refers to a SPEX
collision corresponds to an impact angle mill with many balls.
204 5 Mechanical Milling and Alloying

el of McDermott (1988) and Davis et al. scales with m Q2, and the frequency of the
(1988) for the SPEX mill with 15 balls. As occurrence of the impacts scales with co.
the number of balls in the mill increases, The power induced to the powder there-
the relative number of direct impacts de- fore scales as P oc m I2 Q2 co where I2 is a
creases. The consideration of the impact characteristic area of the order R2 or rR
angle distributions would result in decreas- for the rolling or impact regime respective-
ing the average velocities, and therefore ly. Gaffet (1990) has designed an experi-
kinetic energy of the balls, thus increasing mental planetary mill so that the parame-
the processing times listed in Table 5-2. ters Q and co can be independently varied.
He also incorporated a heater so that the
vials can be heated to a temperature of up
5.3.5 Modeling the Mechanics to 200 °C. Using 5 steel balls, he milled the
of Mechanical Alloying in a Planetary Mill intermetallic compound Ni 10 Zr 7 to milling
A schematic drawing of a planetary mill times where a previous study (Gaffet,
is given in Fig. 5-8. The mechanics of this 1989) had indicated that a steady state
mill are characterized by the rotation structure was attained (about 40 h). The
speed of the disk, Q, that of the container parameters Q and co were then indepen-
relative to the disk, co, the mass, ra, size, dently varied and a "parameter phase dia-
and number of balls, the radius of the disk, gram" (PPD) was then established as illus-
R, and the radius of the container, r. Mar- trated in Fig. 5-9. The final milled struc-
tin and Gaffet (1990) have shown that de- tures depend on the Q and co values and a
pending on the relative values of co/Q and domain in the Q — co plot for the amor-
r/R, two extreme regimes may be achieved: phous phase is delineated. At low energies
1) the ball rolls on the inner surface of the (Q) a partially amorphous phase forms, at
container or 2) it escapes and impacts an intermediate energies a completely amor-
opposite portion of the surface. For both phous structure is seen, and again at high
cases the energy transferred per unit area energies a mixed amorphous and crys-

E
£800-1
CT700- H
jj 600-
1 500-] mm $m
4
€€ C
300-
G
200.
0 240 480 720 960 1200
Co,Rotation speed (frequency)(r.p.m.)
Figure 5-9. Ball-milling parameter phase diagram for
Ni 10 Zr 7 (large circles) and Ni^Zrg (small circles).
(After Gaffet, 1990). Filled circle: homogeneous amor-
Figure 5-8. Schematic drawing of a planetary ball phous end product structure; semi-filled circle: mix-
mill. Q and co are the angular velocities of the ball mill ture of amorphous and crystalline structures; open
plate and of the vials, respectively. circle: crystalline structure.
5.3 The Mechanics/Physics of Mechanical Milling and Alloying 205

0.03
AE!
A
PW30 ® ® ® ®
Figure 5-10. Energy, A£J
PW60 vs. input power, P* for a
planetary ball mill. The
map indicates zones where
I (A) only line broadening is
-o—o—o—I—® ®—<&j W5 observed; (B) amorphous
phase formation, and (C)
amorphous + intermetallic
phase are formed for the
—n—o U ® <*>-U PW90 Fe2Zr composition of ele-
mental Fe and Zr powders
0.003 (after Burgio et al, 1991).

P* in Wh' 1

talline structure exists. These results will be put is also defined as P*, which is a func-
discussed later in the chapter. If the weight tion of the energy released by the ball
of the milling balls was decreased by a fac- (A2?b), the angular velocities of the disk
tor of a, Q is decreased by a factor oc1/2Q and vial, and their dimensions, the weight
such that the PPD diagram boundaries are of the powder, and the milling time. They
shifted. Changing the temperature of the plot AEh vs. P* as shown in Fig. 5-10 for
mill over the range from 30 °C to 200 °C milled Fe and Zr powders at an average
did not alter the PPD diagram for composition of Fe 2 Zr.
Ni 10 Zr 7 . The end products depend on the milling
Burgio et al. (1990) have also modeled conditions and a correlation between the
the energy transfer in a planetary mill. energy input and the structures observed is
They derived kinetic equations which de- evident. The AE% — P* map separates the
scribe the velocity and acceleration of a observed structure into domains where 1)
ball in a vial of a planetary mill. They only line broadening is seen, 2) only an
derive an expression for the total energy amorphous phase is observed, 3) the crys-
released by the ball during a series of colli- talline Fe 2 Zr compound is observed, or 4)
sion events, AEh. A normalized power in- demixing is noted. The temperature of the
206 5 Mechanical Milling and Alloying

powders is not considered in this model. peratures of the milling vials are thus
This model assumed that the energy trans- specific to the mill design as well as the
fer is derived from collisions of the balls, kinetic energy of the milling media. In the
the chamber walls, and the powder, al- SPEX mill, apparently about 2A of the
though the energy of interest is that im- temperature rise comes from the motor,
parted to the powder by the balls which is bearings, etc.; not from the kinetic energy
only a fraction of the total calculated ener- of the balls.
gy. The authors recognize this restriction Very large macroscopic temperature in-
but find that the parameters derived give a creases have been observed by Kimura
useful separation of the powder structures and Kimura (1990) in a high speed attritor
under various milling conditions. mill. At the fastest rotation speed used,
450 rpm, a maximum steady-state temper-
ature of 172°C was measured. Substantial
5.3.6 Temperature Effects During Milling macroscopic temperature rises, to 120 °C,
The temperature that the powders attain were also noted in a vibratory mill by
during milling is a critical parameter which Kuhn et al. (1985).
may control the final structure. If milling is However, the Invicta Vibrator Mill
carried out under ambient conditions the (Model BX 920/2, Grantham Electrical
mill and/or the powders typically absorb Engineering Co) exhibits little or no mea-
heat from the mill motor, friction in the surable macroscopic heating above ambi-
mill bearings etc., and the kinetic energy of ent. Thus, the macroscopic heating, i.e.
the milling media. The macroscopic tem- that heating which can be measured by
perature of mill and powder has been mea- thermocouples or other temperature sen-
sured by several investigators. Davis sors, is a strong function of the milling
(1987) and McDermott (1988) measured device. The maximum working tempera-
the exterior of a SPEX mill vial as a func- tures measured for most common mills,
tion of milling time with thermocouples. under ambient conditions, are modest,
The temperature increased with initial <100°C. It is also possible, of course, to
milling time and reached an equilibrium cool the mills. Attritor mills are typically
value, i.e. saturated, after about 1 hr of run with water cooling of the mill cham-
milling. The saturation value was a func- ber. Several researchers have cooled exper-
tion of the number of balls in the vial. With imental mills with liquid nitrogen (e.g.,
no balls in the mill, the vial temperature Davis and Koch, 1987; Schwarz et al. 1985,
increased to an equilibrium value of about Koch and Kim, 1985).
40 to 42 °C. The maximum temperature The powder surfaces however, might
rise observed by McDermott was up to exhibit significantly higher temperatures
about 50 °C (with 13 balls). Thus, in a during milling than can be measured
SPEX mill, much of the heat comes from macroscopically, i.e. "microscopic" heat-
the motor and bearings. It is possible to ing may be large. It has even been suggest-
significantly lower the macroscopic mill ed that melting could occur during milling
temperature in this case using forced air due to the severe localized plastic deforma-
convection, i.e. a fan, and saturation tem- tion of the powders (Ermakov et al., 1981).
peratures of 35 to 40°C can be obtained Clear evidence exists for melting of powder
even with the maximum kinetic energy of surfaces in shock-wave consolidation of
the balls operative. The macroscopic tem- powders (Cline and Hopper, 1977). How-
5.3 The Mechanics/Physics of Mechanical Milling and Alloying 207

ever, in typical shock-wave experiments, model depends critically on the volume in-
the velocities of the "flyers" are of the or- volved. All the models developed to date
der of 500 to 1000 m s " 1 compared to the for estimating AT are reasonable, but not
velocities of balls in typical ball mills; definitive. There are too many unknown
1 to 2 0 m s " 1 . variables, for example the size of the vol-
It is of course very difficult to measure ume element which is heated during a col-
the transient temperature of the powder lision, as above, to prove by calculation
surfaces during milling because of the the magnitude of the temperature rise in a
microscopic and dynamic nature of the given powder system. However, mi-
milling process. Two different approaches crostructural evidence from the final pow-
have been used to estimate the tempera- der product tends to support the modest
tures which may be attained in the milled temperature rises predicted by the approx-
powders. One method is to calculate the imate calculations for the usual mill en-
temperature from appropriate models, an- ergetics. Mechanically alloyed ductile lay-
other is to infer the temperature from the ered materials, for example, exhibit defor-
structure/microstructure of the final pow- mation bands, slip lines as revealed by op-
der product. One approximate calculation tical microscopy (Benjamin, 1976) or high
for A Tin a SPEX shaker mill was present- dislocation densities and deformation
ed in Sec. 5.3.4 as given by Schwarz bands as seen in transmission electron mi-
and Koch (1986). Temperature rises of croscopy (e.g. Schlump and Grewe, 1989).
<100°C were predicted for, e.g. Ge. An- These observations indicate recrystal-
other approach is to consider microscopic lization has not taken place during the
heating due to sliding friction (Carslaw milling process so that the powder temper-
and Jaeger, 1959). This analysis considers ature must be below the recrystallization
a system in which a body is making contact temperature of the given material. That
with another over a limited area while is, a cold-worked microstructure not a
moving over the surface at a constant ve- hot worked microstructure is observed in
locity. If the contact area is assumed milled powder. Similarly, mechanically al-
square, the microscopic temperature in- loyed amorphous alloys do not, in general,
crease is given by: exhibit in-situ crystallization, suggesting
the powder temperatures remain below the
fwvr
AT = (5-3) crystallization temperature of the amor-
phous alloy. There are several counter-
where / = coefficient of friction, w = nor- examples to this general observation, in
mal load, / = side half-length of the con- which crystalline phases are observed un-
tact area, / = mechanical equivalent of der highly energetic conditions (Schultz,
heat, kl9 k2 = thermal conductivities of 1988; Kimura and Kimura, 1990) and were
components 1 and 2. For the material con- presumed to originate from in situ crystal-
stants for given components and a speci- lization because of the temperatures at-
fied ball mass, the expression AT cc 1//. tained during milling. Some doubt has re-
Thus the magnitude of AT depends on the cently been cast on this interpretation
contact area. For the smallest contact ar- (Trudeau et al., 1990; Gaffet, 1990) and
eas, e.g. 1=1 nm, AT values for Ge-Si, Si- this topic of ball-milling induced crystal-
Si, or Ge-Ge combinations can be on the lization of amorphous alloys will be dis-
order of 500 °K. Clearly, A r i n the above cussed later in this chapter.
208 5 Mechanical Milling and Alloying

In an effort to obtain an upper limit on in that plastic deformation can be intro-


the temperatures attained in the powders duced in nominally brittle materials like
during milling, Davis et al. (1988) studied Fe-1.2 wt. % C martensite which fracture
the tempering response of as-quenched te- in the elastic regime under uniaxial defor-
tragonal ("fresh") martensite in an Fe- mation. The upper limit to the AT during
1.2 wt. % C alloy. Differential scanning milling of Fe-1.2 wt.% C martensite ex-
calorimetry (DSC) was used to follow the perimentally determined is consistent with
decomposition of the martensite as s-car- the model for the mechanics of the SPEX
bide and then Fe 3 C precipitates from the mill presented above and the approximate
martensite matrix at about 418 K and AT calculations (Davis et al., 1988).
575 K respectively. A DSC trace for the Another experiment which suggests only
unmilled Fe-1.2wt. % C martensite pow- modest (100 to 200 °C) increases in temper-
der is shown in Fig. 5-11. The percent of ature occur during milling was conducted
Fe 3 C converted from the martensite was on Bi powder (Davis et al., 1988). Bismuth
calibrated by separate annealing experi- is a low melting (271 °C) but brittle materi-
ments and in this way DSC could monitor al. It was assumed that if local powder
the amount of martensite decomposition temperatures rose above the melting point,
occurring during milling. This gave an up- microscopic examination would reveal this
per bound to the temperature the powders by the presence of smooth, glassy surface
reached during milling. It was determined morphologies indicative of surface melt-
to be 265 to 280 °C. The defects, disloca- ing. No such morphology was observed,
tions and point defects, which are pre- suggesting that milling did not result in
sumably introduced during milling, may temperature increases >271°C in Bi.
accelerate the Fe 3 C precipitation reaction In contrast to these results, larger AT
such that it could occur at lower tempera- values were measured by Miller et al.
tures. High-energy ball milling is unusual (1986) in impact experiments. Infrared
emission was measured from several insu-
lating material single crystals at impact
sample:MARTENSITE DSC from 0.5 kg loads dropped with various
size: 25.30 mg
velocities. Examples of their results are
given in Table 5-3.
If all the kinetic energy of the impact
was uniformly distributed over the sam-
ples, an overall AT of only about 0.2°C
would be expected. The observed infrared

Table 5-3. Maximum temperatures for impacted ma-


terials from Miller et al., 1986.

-2 Material Impact velocity Tm


350 400 450 500 550 600 650 700
Temperature in K

Figure 5-11. DSC analysis of martensite decomposi- NaCl 18.5 380


tion for an Fe-1.2wt.% C martensite powder. The Ammonium perchlorate 5.5 400
peaks represent decomposition of the martensite to e Cyclotrimethylene trinitranine 5.5 200
carbide (418 K) and cementite (575 K).
5.3 The Mechanics/Physics of Mechanical Milling and Alloying 209

emission suggests very small localized vol- components are further deformed and
umes, e.g. protrusions, must be the source mixed. A very fine-grained microstructure
of the observed heating. is formed with nanocrystalline grain sizes.
The above experiments and calculations Heilmann et al. (1983) observed debris
all suggest some heating of the powders particles in the wear of Cu blocks with
occurs during mechanical milling in "con- 440 C stainless steel rings which had grain
ventional" high energy ball mills such as diameters of 3 to 30 nm. Such nanocrys-
the SPEX shaker mill. However, the mag- talline grain structures are also observed in
nitude of the temperature rise is believed to ball-milled powder, as will be discussed
be modest, <100 to 200 °C. This subject later. The fine grain structure of this trans-
will be considered further in the discus- fer material in wear is believed to be stabi-
sions of crystallization of amorphous al- lized by the mixing in - i.e. mechanical
loys. alloying - of a second phase. The relative
All the above discussion pertained to hardness of the transfer material and the
heat input from the mechanical energy of adjacent substrate material affects the sur-
the milling media. It ignored any addi- face morphology and the nature of the
tional heat which may be generated by wear debris. Loose debris is often derived
exothermic reactions of the powder com- from the transfer material. Adhesion is ap-
ponents. In Sees. 5.5.2 and 5.7, very large parently an important influence at several
temperature rises during mechanical alloy- stages of the sliding wear process. Sliding
ing will be discussed which result from ei- wear also is similar to mechanical alloying/
ther large exothermic heats of formation of milling in that they both involve cyclic de-
certain intermetallic compounds, or the re- formation. Each powder or wear surface
duction of metal oxides. In these special area may be deformed many times.
cases temperature rises can even exceed the Solid-particle erosion also exhibits cer-
melting temperature of the component tain common features with mechanical al-
powders. loying/milling. In particular, single-parti-
cle impact experiments may shed light on
two aspects of mechanical alloying/
5.3.7 Relationships to Wear and Erosion
milling; that is 1) thermal effects, and (2)
Processes
deformation of brittle materials. Impact
Wear processes in sliding systems have velocities in single-particle impact experi-
some features in common with mechanical ments have been typically an order-of-
alloying and milling which may help to magnitude or more greater than in ball-
elucidate the complex mechanisms of both milling (Sundararajan and Shewmon,
phenomena. Rigney et al. (1984) have re- 1983). Even so, the calculated AT values
viewed the phenomenology of the wear for various target materials at impact ve-
processes in sliding systems. The develop- locities of about 150 m s ~ l ranged from
ment of the sliding wear process first in- only 58 K for copper to 210 K for 301
volves local contacts causing large plastic stainless steel. Single particle impact exper-
strains in either or both solid components. iments also provide information on the
The plastic deformation modifies the near- fundamental scaling relationship between
surface microstructure making it unstable fracture energy and plastic work for local-
to local shear. Material transfer can then ized deformation conditions. The critical
occur, as in mechanical alloying, and the penetration depth of the particle-into-
210 5 Mechanical Milling and Alloying

target to initiate lateral cracks in the target material thoriated nickel (ThO 2 in a Ni ma-
depends on the geometry of the indentor trix, Anders, 1964).
and material or defect properties of the It was desired to develop ODS alloys
target material (Lawn and Evans, 1977). with more complex matrices, such as the
This implies that in small volumes, plastic superalloys. However, the synthesis of
deformation may occur instead of frac- fine, homogeneous oxide dispersions in the
ture. Therefore, in the milling of brittle Ni-base superalloys which contain reactive
materials, small asperities, sharp edges etc. metals such as Al and Ti by techniques
of brittle irregularly shaped particles may such as internal oxidation, ignition surface
indent other particles and cause plastic coating, selective reduction, or powder
flow-cold-welding-instead of fracture, and mixing was not feasible (Benjamin, 1970).
thus allow mechanical alloying to take Thus the INCO effort involving high en-
place. ergy ball milling - mechanical alloying -
was required. This process involves high-
energy ball milling of the starting powders
5.4 ODS Alloys by Mechanical together with the dispersoid particles, fol-
Alloying lowed by consolidation and thermome-
chanical processing. In a similar process,
As pointed out in the Introduction, the termed "reaction milling", Jangg et al.,
driving force for the development of me- 1975, succeeded in forming well-distribut-
chanical alloying by the International ed dispersoid particles by chemical reac-
Nickel Co. was the goal of combining in a tion of milling additions with the powder.
nickel-base superalloy the intermediate The advantage of dispersion-strength-
temperature strength of a precipitation ened alloys lies in their ability to retain
hardened (gamma-prime, Ni3Al) material useful strength up to a high fraction of
with the high temperature strength of their melting temperatures (>0.9 Tm)
an oxide dispersion strengthened (ODS) where other strengthening mechanisms
nickel (thoria dispersion (TD) strength- such as strain-hardening, precipitation
ened Ni). The goal of dispersed-phase al- hardening, or solid solution strengthening
loys is to strengthen the alloy matrix by rapidly lose their effectiveness.
impeding the motion of dislocations. The Most of the development of ODS alloys
matrix remains the major load-bearing by mechanical alloying has been devoted
constituent. The metallic matrix will be to the Ni-base superalloys and Fe-base
strengthened in proportion to the effec- high temperature alloys. Much attention
tiveness of the dispersion as a barrier to the has also been given to Al-base ODS alloys.
motion of dislocations. While thoriated More recently, other ODS materials, such
tungsten was developed early in the cen- as Ti-base alloys and intermetallic com-
tury (e.g. Coolidge, 1910), the first struc- pounds, have been explored. A number of
tural ODS alloy was sintered aluminum review articles have described the synthe-
powder, SAP, developed by Irmann (Ir- sis, structure, and properties of specific
mann, 1952). ODS alloys prepared by mechanical alloy-
This material, Al containing A12O3 ing. These include the reviews of Gilman
flakes, exhibited strength up to the melting and Benjamin (1983), Benn et al. (1984),
point of the Al matrix. The success of SAP Sundaresan and Froes (1987), and a num-
led to development of the higher melting ber of papers in the books "New Materials
5.4 ODS Alloys by Mechanical Alloying 211

by Mechanical Alloying Techniques", edit- inert oxide pinning. After the directional
ed by Arzt and Schultz (1989) and "Solid crystallization the grains have typical di-
State Powder Processing", edited by mensions of «500 to 700 |im parallel to
Clauer and de Barbadillo (1990). The sev- the working direction and «15 jam per-
eral classes of mechanically alloyed ODS pendicular to this direction (Stephens and
alloys will be briefly described in turn. Nix, 1985). The oxide dispersoid distribu-
tion is shown in Fig. 5-12. The fine par-
ticles are a uniform dispersion of stable
5.4.1 ODS Ni-Base Superalloys
yttrium aluminates formed by the reaction
and Fe-Base High Temperature Alloys
between the added Y 2 O 3 , excess oxygen in
Produced by Mechanical Alloying
the powder, and aluminum added to getter
The major commercial dispersion oxygen (Benjamin et al., 1974). The larger
strengthened Ni-base superalloys pro- particles are titanium carbonitrides. The
duced to date by mechanical alloying are dispersoids are typically 14 nm in diameter
INCONEL alloys MA 754, MA 758 and with an average spacing of 0.2 jim. The
MA 6000. A new, but similar, ODS Ni- 1093 °C stress rupture properties of IN-
base superalloy via mechanical alloying, CONEL MA 754 are compared to those of
TMO-2, is being developed in Japan (Ya-
mazaki et al., 1990). The compositions of
these alloys are given in Table 5-4.
INCONEL MA 754 was the first
mechanically alloyed ODS superalloy to -4-
be produced in large quantity (Weber,
1980). It is essentially a Ni-20%Cr alloy
•*> ^ , -i>
strengthened by about 1 vol.% Y 2 O 3 . The
Ni, Cr, and Y 2 O 3 powders are milled until
a homogeneous Ni-20 % Cr alloy is formed
in which the Y 2 O 3 particles are uniformly
distributed. Hot extrusion, often followed
by hot rolling, is the typical consolidation Er- ^- ' ^ - i**#' -A * *F-^'
process for mechanically alloyed ODS al-
loys. The powder is sealed in a steel can for
these operations. A recrystallization step, Figure 5-12. TEM micrograph of INCONEL
MA 754 showing uniform distribution of fine primary
often directional, follows consolidation dispersion, the presence of coarser carbonitrides, and
that results in elongated, high-aspect-ratio microtwins (Courtesy of John H. Weber, INCO Al-
grains that are very stable owing to the loys International).

Table 5-4. Composition of Ni-base ODS superalloy by mechanical alloying (in wt.%).

Alloy Ni Cr Co W Mo Ta Al Ti Y2O3

INCONEL MA 754 Bal. 20 _ _ _ _ 0.3 0.5 0.6


INCONEL MA 758 Bal. 30 - - - 0.3 0.5 0.6
INCONEL MA 758 Bal. 15 4 2 2 4.5 2.5 1.1
TMO-2 Bal. 6 9.7 12.4 2 4.7 4.2 0.8 1.1
212 5 Mechanical Milling and Alloying

50 300
30 Inconel alloy MA 754 bar 200
20
TDNiCr bar 100 a
£ 10 a.
Thoriated nickel bar s
•£ 6 50 £
40
Alloy 80 A {/)
in
MAR-M 509 CD
20 .fc Figure 5-13. Stress rupture
10 properties of INCONEL
MA 754 at 1093 °C com-
6 pared to other bar materi-
als (after Weber, 1980).
10 100 1000
Rupture life in hours

other alloys in Fig. 5-13. MA 754, like oth- tures of 950 to 980 °C at rupture lives be-
er ODS materials, has a very flat log stress- yond 104 hours. These changes cause no
log rupture life slope compared to conven- serious loss in the loadbearing capability
tional alloys. The strength of MA 754, of the alloy for practical applications
about 100 MPa for 100 hours life, is some- (Benn et al., 1984). The 1000-hour creep
what higher than both of the other ODS rupture strength for MA 6000 is illustrated
alloys and several times greater than the in Fig. 5-14 along with several other MA
conventional materials MAR-M alloy 509 ODS alloys and cast and wrought superal-
and alloy 80 A. Thus, while MA 754 is loys (Sundaresan and Froes, 1987). It is
comparable to TD NiCr it has a non-ra- clear that MA 6000 has superior rupture
dioactive dispersoid and high strength, so strength at the highest temperatures
it is suitable for applications such as gas
turbine vanes. 600
INCONEL MA 6000 combines precipi-
tation strengthening (gamma prime, y',
precipitates) from its Al, Ti, and Ta con-
tent for intermediate temperature strength
with oxide dispersion strengthening from
the Y 2 O 3 addition for strength and stabili-
ty at very high temperatures. It typically
contains about 52% of y' precipitates. The
dispersoid dimensions are 30 nm average
diameter and 0.1 ^im average spacing. As 800 900 1000
in MA 754, the Y 2 O 3 reacts with oxygen Temperature in °C
and aluminum to form uniform disper- Figure 5-14. 1000 h creep rupture strength for MA
sions of yttrium aluminates, e.g. yttrium- ODS alloys compared with cast and wrought superal-
aluminum garnet 5 A12O3 • 3 Y 2 O 3 loys: (1) MA 956, (2) MA 764, (3) MA 753, (4)
(YAG). The YAG dispersoid appears to be MA 6000, (5) MAR-M 200, and (6) Ni80A (after Sun-
daresan and Froes, 1987), reprinted with permission
very stable. Negligible coarsening is ob-
from JOM (formerly Journal of Metals, Vol. 39, No. 8,
served for stress rupture tests at ^750°C p. 24, a publication of The Minerals, Metals & Mate-
and only small coarsening for tempera- rials Society, Warrendale, Pennsylvania 15086).
5.4 ODS Alloys by Mechanical Alloying 213

(>900°C) and comparable strength to ( ^ 1 0 n m to 1 jim). In order to maximize


MAR-M 200 at intermediate tempera- the strength of A1-A12O3 ODS alloys it was
tures. MA 6000 has been used to a small desired to obtain a finer and more uniform
extent so far in gas turbine engine blades. distribution of the A12O3 dispersion in Al.
The iron-base INCOLOY alloy MA 956 For a given vol.% of dispersoid,
contains about 20 % Cr, 4.5 % Al, 0.5 % Ti mechanically alloyed A1-A12O3 exhibited
and about 0.5% Y 2 O 3 . It can be used at much higher yield and tensile strength than
operating temperatures of over 1300°C in SAP. This is illustrated for tensile strength
corrosive atmospheres (Sundaresan and in Fig. 5-15. It was found necessary to use
Froes, 1987). MA 956 also has excellent a process control agent such as stearic acid
fabricability. It can be cold-worked and or methanol to prevent excessive welding.
can be joined by several welding tech- The decomposition of the process control
niques. MA 956 sheet can be bent more agent during mechanical alloying and sub-
than 150° around a diameter equal to twice sequent powder compaction by hot press-
the sheet thickness (Weber, 1980). ing and extrusion resulted in significant
The high temperature mechanical prop- contamination by carbon. The carbon was
erties of ODS alloys produced by mechan- believed present as A14C3 dispersoids.
ical alloying have been reviewed by Arzt Gilman and Nix, 1981, used Nopcowax-22
(1989). In particular the effects of disper- DSP (C 2 H 2 -2(C 18 H 36 OH)) as a process
soid particles and grain structure on creep control agent. They found that during vac-
were described. It was concluded that uum hot pressing at 773 K the Nopcowax-
grain boundaries can be very vulnerable in 22 DSP was reduced by the Al, yielding
ODS materials. In order to minimize the A1 4 C 3 ,N 2 ,O 2 and H 2 . The O 2 presum-
detrimental influence of grain boundaries, ably recombined with Al to form addi-
a high grain aspect ratio (GAR) in the tional A12O3 while the N 2 and H 2 were
loading direction must be achieved. Single removed during the vacuum hot pressing.
crystals are most desirable. Thus, dispersion strengthening in these
materials comes from both A12O3 and
5.4.2 ODS Aluminum-Base Alloys
Produced by Mechanical Alloying
The first ODS material designed as a mechanically
alloyed
structural system was SAP (sintered Al 400 £
aluminum en
c
powder) as developed by Irmann (1952). <u

SAP displayed a greater strength than pure 350 "£


Al and no changes were observed after ex-
SAP
tended heating near the melting point. 300 £
Lenel et al., 1957, among others, devel- a
oped SAP further and verified Orowan's 250 i
model for dispersion hardening (Orowan,
30,- 200
1948) in this material (see Vol. 6, Chap. 7).
2 U 6 8 10 12 U
Bars of SAP were made by extrusion of a Total volume % dispersoid
mixture of 1 to 10 vol. % of A12O3 powder Figure 5-15. Room temperature tensile strength vs.
in pure Al powder. The A12O3 particles in dispersoid content for SAP and MA Al (after Ben-
SAP exhibit a wide distribution of sizes jamin and Bomford, 1977).
214 5 Mechanical Milling and Alloying

A14C3 dispersoids. The effects of a variety tain A12O3 and A14C3 dispersions and are
of processing additives on the processing, processed without a process control agent
structure, and properties of mechanically but with carbon black and controlled addi-
alloyed Al has been presented recently by tions of oxygen from the milling atmo-
Weber, 1990. sphere. The properties and applications of
Mechanical alloying was extended to Al these DISPAL aluminum alloys have been
alloys such as Al-4% Mg (Benjamin and reviewed by Arnhold and Hummert, 1989.
Schelling, 1981). This material, with uni- The AL 9052 and AL 9021 alloys are
form, equiaxed O, C based dispersoids and also under development as matrices for
Mg solid solution strengthening, gave ten- SiC and BN particulate reinforced metal
sile strengths of 520 to 585 MPa along with matrix composites (Jatkar et al., 1985).
excellent resistance to corrosion and stress
corrosion cracking. Some Al-base me- 5.4.3 Other ODS Alloys by Mechanical
chanically alloyed materials developed by Alloying
INCO are listed in Table 5-5. Al-9052 is
5.4.3.1 Ti-Base Alloys
Table 5-5. Some aluminum-base ODS alloys pro- The possibility of dispersion strengthen-
duced by mechanical alloying (in wt.%). ing Ti by mechanical alloying was first ex-
plored by Wright and Wilcox (1974). The
Alloy Mg Cu Li C O
first attempt was not successful in that a
Inco MAP Al-9052 4 - - 1.1 0.8 homogeneous alloy with a uniform disper-
Inco MAP-A1-9021 1.5 4 - 1.1 0.8 sion of Y 2 O 3 in Ti (3 vol. % Y 2 O 3 ) was not
Inco MAP AL-905XL 4 - 1.5 1.2 0.4 attained. Considerable agglomeration of
Y 2 O 3 occurred in part of the alloy along
with bands relatively denuded in Y 2 O 3 . As
currently being considered for application a result of this inhomogeneous microstruc-
as torpedo hulls and other marine applica- ture very little dispersion strengthening
tions. Alloy A1-905XL is an Al-Mg-Li al- was realized. More recently, Sundaresan
loy for airframe applications (Schelleng et and Froes (1988) have studied mechanical
al., 1988). Quist et al., 1985, have com- alloying of several classes of Ti-base alloys
pared Al-Li alloys processed by mechani- including dispersion strengthened beta-Ti
cal alloying with those made by either ro- alloys. The alloy T i - 1 % A l - 8 % V - 5 %
tary atomization or pulverized melt-spun Fe with 1 % Er was milled in order to try
ribbon. With superior mechanical proper- to produce finer, more uniform dispersions
ties and corrosion resistance the mechani- of Er than exist in the starting atomized
cally alloyed Al-Li appears to have advan- powder. The Er internally oxidizes to form
tages over the alloys made by the other Er 2 O 3 dispersoids during consolidation.
processing methods. Milling times up to 48 hours were not suf-
The reaction milling of aluminum, de- ficient to give a homogeneous structure.
veloped by Jangg and coworkers (Jangg et The structure on consolidation was not
al., 1975), is now used to produce commer- uniform, exhibiting sub-micron grains
cial alloys under the tradename DISPAL. with 30 to 50 nm dispersions along with
The materials have been jointly developed regions of course grains of about 10 jim
by Krebsoge, Erbsloh-Aluminum and diameter. Similar non-homogeneous mi-
Eckart-Werke. The DISPAL alloys con- crostructures were observed for Ti-24%
5.4 ODS Alloys by Mechanical Alloying 215

V - 1 0 % C r - 5 % Er alloys also milled 48 ders by mechanical alloying. Mechanical


hours. However, in the fine-grained re- properties were measured on samples con-
gions of this alloy a very fine (^10nm) solidated by hot isostatic pressing. The dis-
homogeneous dispersion of Er 2 O 3 was ob- persoid additions refined the grain size and
served. It was concluded that fine disper- increased the yield strength but decreased
sions are possible in these Ti-base alloys the ductility at room temperature. All sam-
but that optimization of the processing ples failed in a brittle manner at 513 °C
parameters is needed to obtain a uniform owing to dynamic oxygen embrittlement.
structure. Jang and Koch (1988) found that the
Suryanarayana et al. (1990) studied the major strengthening effect of the oxide dis-
microstructure of Er 2 O 3 dispersoids in a persoids on Ni3Al (Hf, B) is in their con-
Ti-25% Al-10% N b - 3 % V - 1 % Mo trol of the grain size during powder consol-
alloy with 2 wt. % Er. This alloy is essen- idation by hot isostatic pressing. A Hall-
tially the Ti3Al oc2 ordered h.c.p. (DO 19 ) Petch relationship was observed such that
phase. The powder, received as rapidly so- the yield strength of the fine-grained sam-
lidified powder, was milled for times of 18 ples (1 to 2 jam) was more than twice that
to 72 hours in a SPEX shaker mill. It was for the larger grained samples (35 jam)
found that significant differences in grain without dispersoids. The dispersoids them-
size and dispersoid distribution occur be- selves provided a small (^13%) addi-
tween small and large powder particles. As tional strengthening effect via the Orowan
in the above Ti-base alloys optimization of mechanism.
the process variables are needed to achieve Benn et al. (1990) studied mechanically
desirable mechanical properties for this alloyed Ni3Al-base intermetallics with 0 to
dispersion-containing Ti3Al ordered inter- 1 % Y 2 O 3 additions. They prepared « 7 kg
metallic. charges in attritor mills and ^35 kg
charges in larger conventional ball mills.
Consolidation of the canned powder was
5.4.3.2 ODS Intermetallics by Mechanical
by extrusion at temperatures in the range
Alloying 1065 to 1150°C. The as-extruded grain
There has been renewed interest in inter- sizes were in the range of 0.5 to 1 jam with
metallic compounds in recent years as pos- a fairly uniform distribution of fine oxide
sible elevated temperature structural mate- particles. Gradient annealing heat treat-
rials. While improving ductility and fabri- ments provided some grain growth but on-
cability have been major research thrusts, ly slight directional secondary recrystal-
improvement in strength and creep resis- lization even after additional thermome-
tance at high temperature has also been chanical processing by rolling. It was not
addressed. Preliminary work on dispersion clear why directional grain growth was in-
strengthening of intermetallics has been re- hibited in these materials. Primary recrys-
viewed by Koch (1987) and Benn et al. tallization did increase the average grain
(1990). The Ni-, Fe-, and Ti-aluminides size to about 5 to 10 |im diameter. A com-
have been the intermetallics most studied. parison of the yield strength at different
Jang et al. (1988) studied the influence of test temperatures for these ODS Ni3Al al-
oxide additions (0.5 to 2.5 vol.% of either loys was made against Ni3Al alloys pro-
A12O3, Y 2 O 3 , or ThO2) to Ni 3 Al (Ni-23.5 duced by other methods. It was shown that
at.% Al-0.5 at.% Hf-0.2 at.% B) pow- the mechanically alloyed samples, with
216 5 Mechanical Milling and Alloying

fine grain sizes, have superior strength at formation of oxides or carbides if the
temperatures up to about 600 °C. Above milling environment allows for such con-
this temperature the strength drops off tamination. The reports of planned addi-
rapidly, presumably because of the stable tions of dispersoids to refractory metals
fine grain structure and the onset of grain for alloys are limited. Oxide dispersion
boundary sliding etc. There was also evi- hardening has been used in Nb to increase
dence of dynamic oxygen embrittlement in its strength for application as an implant
the 600 to 800 °C temperature range as material (Schider, 1986). A mixture of pure
shown by ductility decreases. If ODS Nb and oxide powder was mechanically
Ni3Al alloys are to be considered for ele- alloyed in an attritor mill, cold isostatically
vated temperature applications, processing pressed, sintered, and extruded. It was
to provide large, elongated grains (as in shown that the ODS Nb is biocompatible,
ODS superalloys such as MA 6000) must strong, and ductile.
be developed.
Vedula and Strothers (1990) have stud-
ied the B2 FeAl intermetallic (40 at. % Al) 5.5 Synthesis of "Equilibrium"
with and without 1 vol. % Y 2 O 3 . The pow- Phases by Mechanical Alloying
der (prealloyed Fe-40 at.% Al-0.1 at.%
Zr-0.2 at.% B + l vol.% Y 2 O 3 ) was me- In this section examples are given of ma-
chanically alloyed in a high energy vibra- terial synthesis by mechanical alloying of
tory mill for 32 h. The room temperature elemental component powders which pro-
ductility of this ODS FeAl intermetallic duce the phase predicted by the equilibri-
was as high as 9 % - the highest ductility um phase diagram. The word "equilibri-
observed in B2 FeAl compounds. The um" is put in quotation marks in the sec-
ODS alloys were also much stronger than tion heading to indicate that there may be
the non-ODS alloys at room temperature. some non-equilibrium features associated
Mechanical tests were also carried out at with the equilibrium phase product of me-
827 °C. These included tensile tests and chanical alloying.
compressive creep measurements. In con-
trast to the observations on ODS Ni 3 Al, 5.5.1 Solid Solutions
the yield stress of the ODS Fe-Al alloy was There are several examples of the forma-
higher than that of the alloy without oxide tion of solid solutions by mechanically al-
dispersions and the compressive creep loying the elemental component powders
rates were lower. These results were most in alloy systems that exhibit complete solid
pronounced for the finest grain size (4 jim) solubility. Benjamin (1976), first showed
ODS alloys. Thus, in the ODS FeAl alloys that true atomic level alloying occurred by
grain boundary strengthening was main- mechanical alloying in Ni-Cr solid solu-
tained at temperatures up to at least tion alloys. He reported that the magnetic
827 °C. The strengthening effects of the ox- behavior of the Ni-Cr alloys prepared by
ide dispersions are attributed mainly to mechanical alloying was identical to that
their role as grain refiners. of Ni-Cr alloys of the same composition
prepared by conventional ingot metallurgy.
5.4.3.3 ODS Refractory Metal Alloys Ge and Si exhibit complete solid solubil-
Because of their reactivity, the milling of ity, which would be expected since they are
refractory metal alloys can result in the isoelectronic, have the same crystal struc-
5.5 Synthesis of "Equilibrium" Phases by Mechanical Alloying 217

ture (diamond cubic), and their lattice argon was 0.529 + 0.001 nm, in excellent
parameters differ by only about 4.0%. Ge agreement with literature values for bulk
and Si are, however, both nominally brittle A15 Nb 3 Sn. The powder milled with steel
at room temperature and they were taken media, however, exhibited expanded lat-
as components in a study of the MA of tice parameters. The oxygen levels in both
brittle materials (Davis et al., 1988). Davis sets of samples were similar, but the sam-
and Koch (1987) had demonstrated that ples milled with the steel balls and vial con-
ball milling Ge and Si powder together re- tained significant quantities of iron impu-
sulted in material transfer and alloying. rities incorporated from the milling media.
The lattice parameters of Ge and Si move The apparent expansion of the Nb 3 Sn lat-
together with milling time and after about tice by Fe impurities is in contrast to the
4 h to 5 h merge into the single lattice pa- results of Caton (1985) who measured a
rameter for the Ge-Si solid solution. This small contraction of the A15 Nb 3 Sn lattice
change in lattice parameter is illustrated in with iron additions in sintered material.
Fig. 5-4 for a Ge-72 at.% Si alloy. The latter result is consistent with the
It was found that in Si-rich composi- smaller atomic radius at Fe (0.127 nm)
tions (> 50 at. % Si) the lattice parameters compared to Nb (0.147 nm) and Sn
fell on the linear extrapolation between (0.155 nm) (Pearson, 1972). Since it ap-
the lattice parameters for pure Ge and Si pears that the lattice expansion in MA
(Vegard's "law"). However, in Ge-rich al- Nb 3 Sn is due to incorporation of Fe, it is
loys (>50 at.% Si) the lattice parameters concluded that Fe must be present in the
of the as-milled powders were larger than Nb 3 Sn lattice in a non-equilibrium, per-
predicted for Vegard's law. Annealing the haps partly interstitial, arrangement.
alloys with the expanded lattice parame-
ters serve to decrease them in the direction
5.5.2 Intermediate Phases
of the Vegard's law line - i.e. partial "re-
covery" was observed. Impurities are ap- Intermediate phases and intermetallic
parently not responsible for the expanded compounds have been synthesized from
lattice parameters in Ge-rich MA Ge-Si the pure components by MA in several al-
alloys. loy systems. The equilibrium Hume-Roth-
The possibility of nonequilibrium (e.g., ery electron compounds, p'-brass (McDer-
partially interstitial) solid solutions is be- mott and Koch, 1986), y-brass, and e-brass
ing explored with further study of the re- (McDermott, 1988), were synthesized by
covery of the lattice parameters by anneal- MA of pure Cu and pure Zn powders
ing (Leonard and Koch, NCSU, work in mixed in the proper proportions. Thus the
progress). Another example of an appar- equilibrium intermediate phases were syn-
ent nonequilibrium solid solution due to thesized by MA of the elemental compo-
MA was noted during MA of pure Nb and nents. In the case of P'-brass, evidence for
Sn powders to form initially the A15 inter- f.c.c. deformation-induced martensite was
metallic compound, Nb 3 Sn, which then observed by X-ray diffraction as a minor
was found to transform to the amorphous phase in the p'-brass matrix. A nonequi-
structure on further milling (Kim and librium phase was therefore also present as
Koch, 1987). The lattice parameter mea- a result of the plastic deformation which is
sured for the A15 phase which was MA an integral part of MA. Lee et al. (1990)
with tungsten carbide milling media under have shown that the y-brass (Cu5Au8)
218 5 Mechanical Milling and Alloying

phase is very stable to milling. Milling for composition Al 75 Ni 25 MA produced the


60 h in a planetary mill only served to Al3Ni compound in a gradual manner
broaden the X-ray diffraction lines but did consistent with layer diffusion. The reac-
not alter their positions. Similar milling tion at 60 °C (ambient conditions) was
conditions easily lead to amorphization in faster than at 35 °C (cooling with a fan)
other compounds such as NiZr 2 . The sta- presumably because of the higher interdif-
bility of Cu 5 Zn 8 was attributed to the fusion coefficient. The formation of the
modest value of stored energy of cold work NiAl compound was found to depend on
obtained by milling (2 kJ mol" 1 ) com- the vial temperature, the atmosphere in the
pared to the free energy difference between vial, and whether milling was interrupted
the Cu 5 Zn 8 compound and its supercooled or continuous. Gradual transformations
liquid at 300 K (9 kJ mol" l ). Kim (1987) to NiAl occurred for continuous milling
and Koch and Kim (1985) synthesized the (2.5 h) in pure argon at 35 °C and at 60°C
intermetallic compounds Nb 3 Ge, Nb 5 Ge 3 , in argon (2 h). Transformation to NiAl
and NbGe 2 by MA of elemental Nb and was seen at somewhat shorter milling times
Ge powders. In the cases of Nb 3 Ge and at 35 °C in a mixture of air and argon.
Nb 3 Sn, continued milling eventually re- The fascinating observation occurred
sulted in the formation of an amorphous after milling in pure argon at 35 °C for
phase. The topic of amorphization will be 1.7 to 2 h. Milling was then stopped for
discussed in more detail in Sec. 5.6. periods of 1 to 12 h, allowing the vial to
Ivanov et al., 1988, studied the synthesis cool to room temperature. Separate exper-
of Ni and Co aluminides and amorphous iments showed that the powder at this
alloys by MA of the elemental powders. stage was still elemental Al and Ni mixed
They showed the formation of the inter- lamellae. Shortly (30 to 60 sec later) after
metallic compound Ni 2 Al 3 from mixtures resumption of milling after such a pause, an
of Ni and Al powders at a composition exothermic reaction occurred. A thermo-
of Ni 40 Al 60 . Continued milling produced couple mounted in the vial bottom indicat-
a metastable P'-NiAl phase which revert- ed temperature rises of 27 °C within about
ed to the rhombohedral Ni 2 Al 3 phase 1 sec while a thermocouple in the side wall
after annealing. Powder of composition showed a rise of 20 °C in 7 sec. Atzmon
Ni 30 Al 70 formed a metastable Ni 2 Al 3 in- estimated that under adiabatic conditions
termetallic on MA that decomposed to this exothermic heat released from the
two-phase Ni 2 Al 3 and Al3Ni by annealing. sample as 49 kJ mol" 1 which is compara-
Ni 75 Al 25 powder composition formed an ble to the heat of formation of NiAl (59 kJ
f.c.c. solid solution which ordered to the mol" 1 ) given the approximate nature of
Ll 2 , Ni3Al compound on annealing. The the measurement. In fact, again assuming
formation of an amorphous alloy was ob- adiabatic conditions, it was estimated that
served in a narrow range of composition the heat of formation of NiAl was suffi-
(27 to 35 at.% Al). cient to bring solid NiAl from 25 °C to
Atzmon (1990) has made very interest- 1738 °C (100 °C higher than its melting
ing observations relevant to the mecha- point). Atzmon speculated that the inter-
nism for MA during the synthesis of Al3Ni ruption and subsequent cooling (and pos-
and NiAl intermetallic compounds by sibly oxidation?) result in lower ductility
MA of elemental Ni and Al powder in a and therefore resumed milling leads to en-
SPEX shaker mill. In a powder mixture of ergy concentration in smaller volumes, re-
5.5 Synthesis of "Equilibrium" Phases by Mechanical Alloying 219

suiting in higher local temperature upon Morris and Morris (1990) used mechan-
impact. This explanation seems unlikely ical alloying in a Fritsch Mini-Planetary
since Al and Ni do not normally exhibit ball mill to synthesize the Cr 2 Nb inter-
ductility losses at low temperatures, and the metallic compound from elemental Cr and
average temperature difference (35 °C to Nb powders. After about 15 h of milling
25 °C) is so small. More research is needed X-ray diffraction lines of the hexagonal
to understand this important experiment. Laves phase, Cr 2 Nb, were observed. This
Kumar and Mannan (1989) observed a is the stable phase at high temperatures but
similar rapid phase formation during MA it undergoes an allotropic transformation
of a mixture of pure Nb and Si powders at to the cubic Laves phase at about 1600°C
an average composition corresponding to which is the room temperature equilibrium
Nb 5 Si 3 . After milling for 73 min in a phase. Further milling to 20 and 25 h re-
SPEX mill the powders remained elemen- sulted in the disappearance of the hexago-
tal Nb and Si as determined by X-ray dif- nal Cr 2 Nb Laves phase and the reappear-
fraction. Only two more minutes of mill- ance of b.c.c. lines of Cr and Nb. Such
ing (perhaps less), i.e. X-ray examination "demixing" reactions due to milling will be
at a total milling time of 75 min, resulted discussed further in Sec. 5.6. However,
in complete transformation to crystal- Kumar (1990) did not observe the forma-
line Nb 5 Si 3 in three tetragonal allotropic tion of the Cr 2 Nb intermetallic compound
forms: oc-Nb5Si3, the stable room tempera- on milling elemental Cr and Nb powder at
ture form; p-Nb 5 Si 3 , the high temperature compositions from 49 to 52 wt. % Cr
form; and y-Nb 5 Si 3 , believed to be stabi- (within the Cr 2 Nb phase field). He ob-
lized by the presence of impurities. Further served the evolution from the elemental
milling increased the amount of P-Nb5Si3 components to an amorphous structure
at the expense of ot-Nb5Si3 and y-Nb 5 Si 3 . during milling in a SPEX shaker mill. The
No temperature measurements were made, differences in these results can not be as-
but since Nb 5 Si 3 is a high-melting point sessed without more information. Kumar
intermetallic with an estimated heat of for- carried out his milling in an argon atmo-
mation o f - 5 4 kJ mol" 1 (de Boer et al., sphere in the milling vial while the milling
1988) an exothermic reaction as in the case atmosphere in the work of Morris and
of NiAl is likely. A much larger exothermic Morris was not reported. Vial tempera-
heat effect has been observed during the tures were not reported for either experi-
reduction of CuO by Ca by mechanical ment. These very different results on
alloying (Schaffer and McCormick, 1990). milling the same components point out
This will be discussed later in the Chapter. how critical the milling variables such as
Therefore, it appears that in the case of atmosphere, vial temperature, and mill en-
compound formation or chemical reac- ergetics must be with regard to the end
tions with large exothermic heats of reac- products of the solid state transformations
tion, significant heat input leading to high induced during milling.
temperatures and even explosive reactions A number of intermetallic compounds
can occur by mechanical alloying. This is have been produced with MA as the first
in contrast to the very modest ( < 1 0 0 - step in a synthesis procedure. Benn et al.
200 °C) temperature rises usually attribut- (1988) have reviewed several intermetallic
ed to the heat generated from the kinetic compound systems where an intimate mix-
energy of the milling media. ture of the elemental components was at-
220 5 Mechanical Milling and Alloying

tained by MA, as well as partial compound Green et al. (1984) have developed a
formation in some cases. The intermetallic novel electrical contact material by MA of
synthesis was then completed during the Cu-15 vol.%Ru mixtures. Copper and
thermomechanical treatments carried out ruthenium are mutually insoluble. A Cu-
for compaction of the powders. Larson et Ru composite was produced by MA the
al. (1977) have produced the A15 structure elemental powders, annealing the MA
intermetallic Nb 3 Al by MA of stoichio- powders, cold-pressing, and warm rolling
metric mixtures of Nb and Al powders fol- the composite. Cold-rolling and annealing
lowed by heat treatment. Similarly, (Benn were used to obtain the final strip dimen-
et al., 1988), Ti3Al and TiAl have been sions. Scanning electron microscopy
synthesized by milling in the presence of a (SEM) revealed the final size of the Ru
process control agent under inert atmo- particles to be about 1 to 2 jim in diameter.
sphere. Subsequent heat treatment at Removal of surface copper by etching pro-
540 °C (Ti3Al) or 600 °C (TiAl) produced duced a structure in which the hard, refrac-
the given intermetallics. The compound tory, and conductive Ru particles protrude
Al3Ti is difficult to prepare by convention- from the surface and serve as the electrical
al ingot metallurgy because of the high Al contacts, supported by the Cu matrix that
vapor pressures, the large differences in provides electrical continuity.
melting points between Al and Al3Ti, and Iron and magnesium are immiscible in
the peritectic solidification behavior. It the solid state and form a large miscibility
has, however, been synthesized by MA fol- gap in the liquid state (Kubaschewski,
lowed by annealing (Benn et al., 1988). 1982). Konstanchuk et al. (1987) studied
the hydriding properties of a Mg-25 wt. %
5.5.3 Immiscible Alloy Systems Fe composite produced by MA. The mi-
Mechanical alloying offers one of the crostructure after MA consisted of a lami-
few methods for producing a homoge- nated mixture with iron dispersed in a
neous mixture of two or more immiscible magnesium matrix. Clean metallic contact
phases. This is the case for the ODS alloys was achieved at the Mg/Fe interfacial
where the oxides are essentially insoluble boundary; surface oxides of iron being re-
in the metallic matrices. More generally, duced by magnesium to form a clean
MA may be applied to binary alloy sys- metallic surface. A separate experiment
tems that exhibit solid, or even liquid, im- was conducted to show that the magne-
miscibility. Benjamin (1976) described the sium did indeed reduce Fe 2 O 3 to Fe during
synthesis by MA of homogeneous mix- the MA process. The Mg-25 wt. % Fe
tures of Fe-50 wt. % Cu, a system that ex- composite exhibited a large hydrogen stor-
hibits limited solid solubility, as well as age capacity (5.1 to 5.8 wt. %) and the rate
Cu-Pb alloys for which there is a liquid of hydriding was considerably higher than
miscibility gap. that for pure magnesium. At hydriding
Patel and Diamond (1988), have used temperatures above 625 K, a ternary hy-
MA, sometimes in conjunction with rapid dride, Mg 2 FeH x , formed which inhibited
solidification methods, to synthesize fine dehydriding reaction rates. Thus, a tem-
homogeneous phase distributions in im- perature of about 615 K was deemed to be
miscible alloys such as Cu-Cr, Al-In, Cu- optimum for the hydriding reaction.
W and in immiscible Cu-base bearing al- A question regarding the phase distribu-
loys such as Cu-Pb-Sn. tion in mechanically alloyed immiscible
5.5 Synthesis of "Equilibrium" Phases by Mechanical Alloying 221

systems is: what is the lower size distribu- of the system, i.e., large positive heat of
tion limit to which immiscible particles can mixing. With sufficient mobility, the like
be milled? Since in solid solution alloys, atoms will segregate together. An order of
MA can result in alloying at the atomic magnitude estimate for this segregation,
level, very fine particle distributions might using *jDt as the characteristic diffusion
be attainable by MA immiscible compo- distance, and ambient temperature diffu-
nents. Mechanical alloying has recently sion coefficients, was consistent with the
been applied to the immiscible systems microstructural observations.
Ge-Sn, Al-Ge, and Ge-Pb with the goal of A particularly interesting observation
determining the limits of phase refinement from the study of MM immiscible Ge-Sn
(Gross, 1988). Mechanical alloying was and Ge-Pb systems was the depression of
carried out for milling times up to 60 h the melting point of Sn or Pb with milling
under an air or argon atmosphere in a time and Ge concentration. The first ob-
SPEX mixer/mill. Some tests were con- servation of the melting point depression
ducted with the milling vial cooled with a was noted in DSC scans for a Sn-45 vol. %
stream of liquid nitrogen. X-ray diffrac- Ge mixture as a function of milling time
tion of powder taken at various milling (Koch et al., 1989). The magnitude of the
times showed the systems remained as two- melting point depression, ATm, increased
phase pure components and their precise with milling time, that is, with refinement
lattice parameters remained constant with of the dispersion. Melting point depres-
milling time, which indicated no alloying sions were defined from the DSC endo-
or contamination to the accuracy of the therms as A7^ eak and A7^ail as illustrated
lattice parameter measurements. Optical in Fig. 5-16. The magnitudes of the AT^'s
microscopy, SEM, and transmission elec- were found to reach constant values after
tron microscopy (TEM) were used to fol- 32 h of milling. After 32 h of milling the
low the progress of the microstructural re- average diameters of the hard Ge particles
finement with milling time. embedded in the Sn (or Pb) matrix were
The average center-to-center nearest
neighbor distance between dispersed Ge
particles was measured by the above
-rtail T peak
metallographic techniques. The logarithm 1 M 1
M

of Ge interparticle distance exhibits an in- (f) T


uni

verse linear dependence on milling time.


^ \ /
t

After 32 h of milling, the average Ge inter- -


flow larbit

particle distance was about 20 nm. Stereol-


ogy techniques determined that the Ge V
particles had a random Poisson distribu-
tion throughout the Sn matrix. Further
milling did not appear to significantly X
change the particle sizes or distributions so
the limit of refinement was attained for the
180 200 220 240
given milling conditions in this system. Temperature in °C
The mixing of these insoluble components Figure 5-16. DSC scan for the melting of Sn in Sn-
by mechanical attrition is balanced by the 45.5 vol.% Ge powder milled 32 h. 7geak and T£il are
demixing driven by the thermodynamics defined as shown (Jang and Koch, 1990 a).
222 5 Mechanical Milling and Alloying

50
approximately 10 nm. As Ge concentra-
tion was increased in each system, for a m
40 •
constant milling time of 32 h, the melting • • A
point of Sn (or Pb) decreased (Jang and 30
O

Koch, 1990a). ATm for Sn is plotted •


o 9
against vol. % Ge in Fig. 5-17. The melting :20 • A
point depression increases with vol. % Ge. • o
No ATm data are shown for Ge con- 10
o o
centrations > 80 vol. % because no endo- • A
thermic peak could be seen for the melting
20 40 60 80 100
of Sn for samples containing > 80 vol. % vol.% Ge
Ge. This is not a problem of resolution. Figure 5-17. Melting point depressions, A7^ eak and
Unmilled powder of 88 and 95 vol. % Ge AT^ail for Sn as a function of vol.% Ge after milling
clearly showed a well-defined endothermic 32 h. ATNJeak is also shown for samples milled 32 h and
melting peak in the DSC at the Tm of pure then cycled once to a temperature >505 K. • Ar,Jail:
o ATfPeak: A A7^eak after heating cycle to >505 K
Sn, and with the enthalpy of fusion for
(Jang and Koch, 1990 a).
pure Sn, 60 J g" 1 . The enthalpy of fusion
for Sn, determined from the area of the
melting endotherms, is plotted against 70.0
vol. % in Fig. 5-18. The enthalpy of fusion,
A// m , decreases with Ge concentration and
finally disappears for the Ge-rich mixtures
(88 and 95 vol. % Ge). Only minor changes
in Tm and AHm were observed after heating
the samples in the DSC through the melt-
ing point, cooling to room temperature,
and re-heating.
These experimental results suggest that
the premature melting is nucleated at the 40 60 80 100
Ge/Sn interfaces. As the fraction of Sn
vol.% Ge
atoms adjacent to the Ge particle surfaces
Figure 5-18. Enthalpy of fusion of Sn as a function of
increases, the melting point and enthalpy vol.% Ge after milling 32 h. Data for samples cycled
of fusion decreases. When the density of once to above 505 K are also shown, o as-milled:
Ge particles becomes so large that all the A after heating in DSC to > 505 K: A unmilled Sn-
Sn atoms are within a few atomic layers of 88 vol.% Ge (Jang and Koch, 1990a).
the interface, the Sn may assume a dis-
ordered or amorphous structure. Selected
area electron diffraction patterns were ob- position where the (101) Sn line should ap-
tained on samples of 76.5 vol.% Ge and pear. The electron diffraction data suggest
88 vol. % Ge. The electron diffraction pat- that an amorphous structure has been in-
tern for the 76.5 vol. % Ge sample shows a duced in the Sn layers trapped between the
ring and discrete spots for the (101) reflec- Ge particles by milling for the 88 vol. % Ge
tion of crystalline Sn. This reflection is not sample.
seen for the 88 vol. % Ge sample but a ring That mechanical milling of powder of
of diffuse intensity is observed near the immiscible components can result in a very
5.5 Synthesis of "Equilibrium" Phases by Mechanical Alloying 223

fine dispersion at the level of nanocrys- main wall pinning behavior and have excel-
talline dimensions has been demonstrated lent hard magnetic properties such as Hc
by Schlump and Grewe (1989) in systems up to 13 kOe and BHmax up to 12.8 MGOe.
such as Fe-W, Cu-Ta, TiNi-C, and W-Ni- Ivanov and coworkers (Ivanov et al.,
C. Similarly, Shingu et al. (1989) found a 1987; Song et al., 1987; Stepanov et al.,
fine grain structure in immiscible Ag-Fe 1987; Konstanchuk et al., 1987) have de-
powders at the nanometer level. Nanocrys- veloped Mg-base alloys for hydrogen stor-
talline structures prepared by ball milling age by mechanical alloying. Mechanical al-
will be discussed in more detail in Sec. loying of Mg with either Ni, Fe, Co, or Ce
5.6.6. was carried out in a planetary mill under
Fukunaga et al. (1990) give evidence for an inert or hydrogen atmosphere for short
at least the partial amorphization of the times (3 to 15 min). X-ray diffraction of
immiscible system Cu-Ta. Iron impurities the powders after MA showed only Mg
from steel milling media accelerated the and the given metal. Hydrogen absorption
amorphization reaction, but amorphiza- and desorption experiments were then car-
tion was still observed when milling was ried out on the MA powders. All the sam-
carried out with Cu-Be balls and vial. This ples demonstrated relatively high reactivi-
experiment will also be discussed further in ty with hydrogen. The elements added to
the Section 5.6.3 on amorphization by Mg could be classified with regard to their
milling. hydrogenation behavior as follows (a)
those, e.g. Ni, forming an intermetallic
compound (Mg2Ni) capable of absorbing
5.5.4 Synthesis of Materials for Special and desorbing hydrogen, (b) those, e.g. Ce,
Applications forming hydrides that can function as hy-
Mechanical alloying/milling has been drogen pumps due to stoichiometric varia-
used to prepare unique materials for a va- tions, and (c) those systems (Mg-Co, Mg-
riety of special applications. Fe) that do not form hydrides. The inter-
The excellent permanent magnet mate- metallic compound Mg2Ni was formed
rial, Nd 1 5 Fe 7 7 B 8 (see Vol. 3