OVERVIEW

A SECOND

REPORT

11

ON SINTERING

DIAGRAMS

F. B. SWINKELS and M. E ASHBY

Cambridge

Untverslty. Engineering Department. Trumpington

Cambridge CB:! I PZ. England
(Receiwd

Street.

11 .4uyusr 1980)

Abstract-Sintering-mechanism
diagrams are diagrams with axes of neck-size or density. and temperature. which identify rhtz jrlds
qf domirmce
of each of the several mechanisms
which contribute
10
sintering. and show the rate or PY~VU~
qfsirurritly
that all the mechanisms. acting together. produce. The
present paper incorporates certain new ideas about sintering into the diagrams: the coupling of boundary diffusion and surface diffusions new criteria for the stages of sintering: and an approximate treatment
of particle rearrangement. Diagrams showing hoc\ both the neck size and the dens&\ of compacts of
wires and of spheres change with rime and temperature are developed. Their use is-illustrated b> an
analysis of a large hod! of sintering data for both wires and spheres of Ag. Cu. Ni. Fe. W. NaCl and
Stainless Steel.
Risum&-Les
diagrammes de mecanismes de frittage sent rep&en&
dans des axes taille des coliets (on
dens&+--tem+rature:
ils identifient les domaines dans lesquels prCdodomine chacun des mecanismes
contribuant au frittage. et ils montrem la vitesse ou le taux de frittage que tous ces mecanismes
produisem ensemble. Dans cet article. nous introduisons dans les diagrammes quelques idtes nouvellrs
concernant le frittage: couplage des diffusions aux joints et en surface: nouveaux c&&es pour les stades
de frittage et traitement approche du rearrangement des particules. Nous prtsentons des diagrammes
montrant a la fois les variations de la taille des coliefs et de la densite dagglom&ats de fils en fonction
du temps et de la tempirature. Nous illustrons Milisation
de ces diagrammes en analysant de nombreuses donnees sur le frittage de fils et de spheres dAg. Cu. Ni. Fe. W, NaCl et acier inoxydable.
Zusamme&sau~--Diagramme
der Sintermechanismen mit den Achsen Briickengr&e
oder Dichte
und Temperarur beschreiben die Be&he.
in denen die verschiedenen Sintermechanismen dominieren;
sie stellen die Geschwjndigkei~ oder das AusmaB des Sinterns dar. die siimtliche Mechanismen zusammen erzeugen. Die vorhegende Arbeit beriicksichtigt im Diagramm einige neue Vorstellungen zum
Sintern: die Verkoppelung von Korngrenz-und
Obertliichendiffusion. neue Kriterien fiir die verschiedenen Stadien des S$erns. eine neue Behandlung der Umlagerung
der Teilchen. Es werden Diapramme
entwickelt. die die Anderungen von BriickengriSBe und Dichte von Proben aus Driihten und Kugeln mit
der Zeit und der Temperatur beschreiben. Die Anwendung dieser Diagramme wird mit einer Anal?se
einer gro&n Datenmenge Nr das Sintern von Drfhren und Kugeln aus Ag. Cu. Ni. Fe. W. NaCl und
rostfreiem Stahl verdeutlicht.

1. INTRODUCTION

as

independent:

sharply

Six or more distinguishable mechanisms contribute to

neck growth and densification when a powder aggregate is sintered (Fig. I and Table 1). It is helpful to
have some way of displaying the range of dominance
of each of these mechanisms; that is, the range of
conditions over which a given mechanism contributes
in an important way. One way of doing this was described in an earlier paper [t J. It described the construction of sinrering mechanism di~rarn~~ diagrams
with axes of homologous temperature, T/T, (where
TMis the melting temperature), and normalised neck
radius, x/a (where Za is the particle diameter) showing
thefield cf d~inanc~ of each mechanism,and (as contours superimposed on the fields) the net sj~feri#g rote
or the sintering time.
In that paper, mechanisms of sintering were treated
*.u. 29 t-4

259

no attempt

the transition

from

to show

how

one field to the next

was made

took

Fig. 1. The mechanisms of sintering (the identifying

numbers are defined in Table I). Alf lead to neck-growth.
Only mechanisms 4. 5 and 6 cause densification.

SWINKELS AED ASWBY: SECOND REPORT ON SINTERING

260

DIAGRAMS

Table 1. Mechanisms of sintering

Transport path

Source

Surface Diffusion

Surface

Non-Densifying
Neck

Lattice Diffusion

Surface

Neck

Unchanged*

Vapour Transport

Surface

Neck

Unchanged*

Neck

Major modification of driving force

to include redistribution of matter
emerging from boundary by surface
diffusion in neck

Mechanism

Sink

Modification of equations
Modified by the redistribution
associated with mechanism 4

Densifying
4

Boundary Diffusion

Boundary

Lattice Diffusion

Boundary

Neck

Unchanged*

Lattice Diffusion

Dislocations

Neck

Unchanged*

* The physical assumptions of the sintering model are the same as those quoted or developed in the earlier paper [I],
The treatment of the driving force, however. is modified somewhat (see Section 2).

place; and the treatment of the driving force for sintering resulted in an un~tisfactory positioning of the
Stage I transition (discussed below in detail). The
present paper incorporates a necessary coupling
between certain mechanisms, illustrates the diffuseness of the transitions between mechanisms, and uses
a more satisfactory treatment of the driving force.
Many of the sintering-rate equations used here are
identical with those used earlier; the reader will be
referred to the First
Report [l]
and other
reviews [2,3,4] for their derivation. But the modifications, which have an important effect on the diagrams, are dealt with in detail below. One further
extension of the earlier paper is included here: diagrams showing the progress of densi~~tion (as well
as that of neck-growth) are developed.
1.2 Stages of sintering and the stage transitions
It is convenient to think of sintering as occurring in
four sequential stages. If loose powder particles are
brought into contact, inter-atomic forces causes small
circles-of-contact (necks) to form between them, and
may also cause some particle-rearrangement.
This
Stage 0 of spontaneous adhesion occurs instantaneously, and leads to a certain minimum initial neck
size [S, 6.71. This is followed by Stage 1, a stage of
neck-growth by diffusion during which the necks
remain small and the indi~dual particles are still distinguishable. Stage 2 is an intermediate or transitional
stage: the necks are now quite large and the pores are
often assumed to be cylindrical (a valid assumption
for wires, but not for spheres). When the pores
become isolated and spherical. the final stage (Stage 3)
of sintering has been reached.
The proper rate-equation for a mechanism depends
on the stage of sintering. In treating the sintering of
wires (Sections 2 and 3) we consider Stages 0, 1 and 2,
as distinct, each with its own rate-equations; there is
no Stage 3. In treating the sintering of spheres
(Sections 4 and 51, on the other hand, we consider
Stages 0, I and 3 as well-defined, each with its own

rate-equations; but we omit Stage 2. This is because

pores in an aggregate of sintering spheres are never
even approximately cylindrical; in the transition from
Stage 1 to Stage 3, the pores form connected channels,
but the channels vary in section and surface curvature, making the cylindrical approximation a very
poor one. Instead, we link Stage 1 to Stage 3 with a
transition region by interpolating between them (in a
manner described below) to make them continuous.
1.3 Modijkations

to the treatment of the mechanisms

The most important modification introduced in this

paper is that of Mechanism 4: sintering by boundarydiffusion. The standard treatment of this mechanism
(as used in the earlier paper) identi~es the driving
force as the neck-curvature where the boundary intersects the neck, implicitly assuming that the atoms
which flow into the neck out of the boundary are
redistributed over the entire neck surface so quickly
that the simple neck shape of Fig. 1 is maintained.
But if more atoms arrive at the neck surface than can
be redistributed by local surface-diffusion. a build-up
will occur, reducing the curvature and thus the driving force for boundary diffusion. The curvatures will
change until a baiance is reached. when the boundary
flux matches the redistribution flux (Fig. 2).
The problem has been recognised for some
time [4,8,9. lo] but there have only been two
attempts to analyse it. The first one of these (the computer-simulation of Bross and Exner [ 11-J)included
surface redistribution in calculating neck size and
shape, but this simulation-method does not readily
lead to explicit equations for the (modified) rate of
sintering. The other (an approximate analytical treatment of Swinkels and Ashby [123) coupled boundary
diffusion with surface-redistribution and partitioned
the total driving force such that the rates of the two
were matched. ft used the simplest geometry which
could include such a coupling: the circular neck profile of earlier models was replaced by an ellipse. thereby creating a driving force for surface redistribution.

\\\
\
1.l
SWINKELS

AND

ASHBY:

SECOND

REPORT

ON SINTERING

DlAGRAMS

lies in the material data (notably that for boundar!

and for surface diffusion) used to evaluate the equations.
This lack of precision is not a deficiency of the
sintering-diagram
concept: it simply reflects the
present level of understanding of the sintering process
and of material data relating to it. As better models
and more accurate data become available. they can
readily be incorporated into the diagrams. This
present paper is just such an advance over the earlier
one.

1.5 Definition

of symbols

The symbols used m this paper have the following

I_

x---d

curvatures (m-l)
diffusion distances for surface redistribution
and for surface diffusion (m)
diffusive currents (ms)
rate of neck growth (m/s)
rate of approach of particle centres (m s)
densification rate
rate of normal displacement of surface (m s)
surface diffusion coefficient times efiectlve
surface thickness:
d,D. = d,D,.exp - Q,,RT(m3:s)
lattice diffusion coefficient:
D,, = Dol. exp - Q, ,RT(m&)
grain-boundar!
diffusion coefficient times
effective boundary thickness:
C&D, = 6,D0,:.\p - Qb/R7(m3;s)
vapour pressure:
P, = PO exp - (QvapR T)(N fm)
surface free energy (J/m*)
grain-boundary free energy (J,m*)
atom or molecular volume (m3)
Boltzmanns constant (I.38 x 1O-3 J/K)
Gas Constant (8.3 I J ,mol)
absolute temperature (K)
melting temperature (K)
theoretical density (kg m)
initial densitv of powder compact (kg m3)
relative density
shear modulus (N/m
Burgers Vector of dislocations. or the atomic
or molecular diameter (m)
dislocation density (me2)
velocity of sound (taken as IO3 m/s)
a smoothing function used to make non-densifying mechanisms go lo zero at the end of
Stage 1

The calculation showed that redistribution could limit

the rate of boundary diffusion; but the method of
partitioning the driving force omitted an important
aspect of the problem (the redistribution length. dl.
discussed below) which severely limits its usefulness.
In this paper we develop and use a new and more
complete model which incorporates surface-redistribution into all stages of sintering. for both wires and
spheres.
This modification necessitates lesser changes in the
treatment of Mechanism 1: the flux of matter from
the surface no longer flows into the base of the neck.
but is distributed over the nearby region (d2 in Fig. 2):
and is driven by a greater curvature difference than
before.
of the diagrams

It should be clearly understood that the diagrams

are based on approximate models, and on data, some
of it uncertain, for the material properties which
appear in them. The diagrams are no better (and no
worse) than the equations and data used to construct
them. We aim here at equations which predict the
rates (and thus times) of sintering and densification to
within a factor of 2, and neglect terms whose influence
is much less than this. The chief source of error then
t Curvatures are taken to be positive when the centre-oflies within the material. negative when it lies
outside it. Note that the symbol p is used for the component of neck curvature in the plane of figure for all

mean-

particle radius (m)

modified particle radius (m)
radius of disc of contact of two particles (m)
one half of the interpenetration between two
particles (m)
radius of curvature of the neck (m)

Fig. 2. The matter which flows out of the boundary must

I redistributed over the surface. This requires that K, is
., .: negative than K , . and that the total driving force is
,;r.;!,aned so that the rates of boundar) diffusion and
surface redistribution match properly.

1.4 Precision

261

2 SINTERING

OF WIRES

When two wires are joined by sintering only Stages

0 and 1 are involved.
2.1 Rate-equationsfor

mechanisms

2. 3. 5 and 6,for

two

curvature

wires

stages of sintering. but that its definition depends on the

stage of sintering and is given in the appropriate section.

We consider first the Mechanisms 2. 3. 5 and 6

which are unaffected by the requirement of surface
redistribution. Let the mean curvature+ of the neck

SWINKELS

262

AND

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SECOND

REPORT

ON SINTERING

Table 2. Rate-equations for neck-growth

DIAGRAMS

and densitication

Stage 0 Rate-equations
Spheres

Wires

i=-

ySa

L-Cl

for

xc

[ 1%

Adhesion
1=0

for

x2

2 L3

i=E

12
1

for

X<

?.-

x = 0

for

213
1
I

10/J

x 2 [ &

Sta8e 1 rate-equations
Spheres

Wires
Non-Densfying Mechanism
1. Surface diffusion from
a surface source.

v _ 3nxD,G,;,R(K,
*d2kT

2. Lattia diffusion from a

surface source.

P _ 3D.;,Q(Ka - K,)
z2kT

3. Vapour transport
from a surface source

v,= PepY$[ & 0

Densijying Mechanism
4. Grain boundary diffusion
from a boundary source.

3 = 3nxD,y,R(K,
2

c = 6D,p@;,R(l - K,x)
5
.xkT

6. Lattice diffusion from

dislocation sources.

p = 2nx2ND,;,R
6
3kT

Redisrribution Mechunism
Surface diffusion

( -Km

- K,)

12
R1

kT

1:2

w3 - KJ

4-

_ 16nD&;,R

v, =
-- 4Px
n;,a >

_ 6D&,R(K,
- K,)(d, + 2dz)
S, kTd,(d,
+ 3d2)

(KJ - K,)

kT [ 2nA,kT
ilR
-

r, = 2nxpep,
v

P = 3D,,&7.Q(l - Krx)
4
x2kT

5. Lattice diffusion from

a boundary source.

- K1)

xkT
32npgD,;,R
xkT

v _ 8ns2p&VD,./$2
69kT

_K
(

ti = lZn.uD,d,y,R(K,
l,
kTd,(d,

_ *

- Kl)(d,
+ 3d2)

Neck 8rowth rate.

Linear shrinka8e rate.

iq
j.=

X
Densification

rate.

-=Ao

1.814f,a

A(K)
L\O

(1 - !./a)3

-=
A0

jla

(1 - )Xl)4

Rate equations
Stage 2 wires
7. Grain boundary diffusion
from a boundary source.

Pd = 3D,&.xn(l
- Kix)
x2kT

8. Lattia diffusion from

a boundary source.

Ps =

Redisrriburion Mechanism
Surface diffusion.

v,, =

ZnpD,y,R(l

CD.&Y,R(K~
;pkT

Neck growth rate.

- K,x)

xkT

- KJ

Stage

3 spheres

G = -kT(4;[D$&

u,, =

4nD&,R(K,
In (2) kT

- Kz)

2;y

+ 2d2)

SWINKELS

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SECOND REPORT ON SINTERING

DIAGRAMS

263

Table 2 continued
Rate equations
Stage 2 wires
Linear shrinkage rate.

j =

Stage 3 spheres

r; + i;

Densification rate.

_is _
A0

ri, + r3

j=

x(x2

p2)

1.814~.a
(1 - !.!a)

1. The symbol p is used for the component of curvature of the pore in a plane normal to the neck. Its definition
depends on the stage of sintering. and on whether wires or spheres are being sintered. See the text for the appropriate
definition of p.
2. The constant in a number of rate-equations differs slightly from that used in Paper 1[I] because we have used
refinements ofdiffusion geometry as introduced by Rockiand [14]. The changes make very little difference to the diagrams.
3. The rate-equation for Mechanism 4. Stage I, for spheres, differs from that of Paper 1 both because of the
coupling with surface redistribution and because of a change in boundary condition in integrating the rate-equation.
We use
I
2x
rpdr = Zx.x;.R
f0
instead of
x
2n
rpdr = 0
s0
leading to the term [i - (Ktx,!2)3. The equivalent change. applied to wires. leads to the term (1 - Krx).
4. We have made changes. based on the calculations of Eadie er al. [15] in the way in which the lattice-diffusion
mechanism (5) is related to that for boundary diffusion (4) for spheres. Stage 1. using the replacement
2nx6,DB = Znx*2%p.D,
instead of
2nxd,D, = 2nx2D,
with ICI replaced by K,. An equivalent relation is used for wires and Stage 3 for spheres.
5. The distances d, and d2 are related by:
(a) d, + d2 = p%
where
P=

x2 + y* + a2 - ai - ZaJ,
Z(a, - x)

and

2
[ X+-P 1

&Jrtan-
3

1 (I<, - K2)
3 (Ks - K2) d*
--=(I
- K2);j;
- 4 (K1 - K2)

4 (.K,

6. The curvatures K,, K2 and K, are related by

K,K2 = K;
7. The curvature difference for non-densifying mechanisms are modified by a smoothing function S, given by

where

a = f (wires)

t 5

Q 5

(spheres).

8. The coupling of mechanism 4 with surface redistribution requires that

i; = t;,,

264

AND

SWINKELS

SECOND REPORT ON SINTERING DIAGRAMS

ASHBY:

These four variables are determined

(Fig. 2) be
I(,=

(2.1)

by four equations. The first simply requires that the (geometric)

mean curvature be equal to - 1 p:

K,K,

where

= K;t,

f2.4)

The second requires that the total distance d, + d2 be

equal to pB (Fig. 2):
(2.2)

X2

p=2m
if there is no densification. Then lattice diffusion
from the boundary and from dislocations (Mechanisms
5 and 6) are driven by this curvature; and lattice
diffusion from the surface and vapour transport
(Mechanisms 2 and 3) are driven by the curvature
difference
-

K ,=!+A
a

(2.3)

ti, = I,,

modified ~ecjla}lis~s

I and lfir

Consider first the flow of matter into the neck by

boundary diffusion (Mechanism 4). It is driven by the
curvature of the neck at A (Fig. 2) where the boundaq
intersecrs if; call this K,. But this curvature will
rapidly go to zero (removing the driving force) unless
matter is redistribute
from the region A to the
regions B of more negative curvature, Kt. on either
side (Fig. 2). This redistribution is driven by the difference (ICI-K& and occurs by surface diffusion. In addition to this redistribution-flux. there is a flux of
matter into the regions B. by surface diffusion from
more distant parts of the surface (regions C), driven
by the curvature difference (1 /a-K J. This is Mechanism 1 of Table 1. modified because matter leaving C is
deposited between B and C instead of flowing to A.
This new formulation of the problem involves two
new curvatures (I< i and K 2) and two new distances
(d, and d2) over which diffusion takes place (Fig. 2).

c,

rl

Zd,=;i;

Loose random packing

Dense random packing
f.c.c. or h.cx. packing
b.c.c. packing
Simple cubic packing

Plastic spheres. squeezed to full density

Typical powder packings prior to sintering

(2.7)

The individual fluxes i;. e, and psr. calculated by

traditional methods. are listed in Table 2 under the
heading Stage I. These equations. solved by numerical methods, have been used in the construction of the
maps shown later.
It is helpful to derive approximate analytical solutions for them also. To allow this, we simplify the
equations. neglecting curvatures of order 1 a and. in
Mechanism 4 of Table 2. the term 1us.to give:

(2.8)
v,, =

-4D,6,;;R
kTdl

(Kz - Ki)

(2.9)

These equations can be solved for the curvatures K t

and K2 and the distances dl and dl. Substituting them

Table 3. Packing geometries for spheres

Geometry

(2.6)

where r,, is the total diffusion current (a volume per

set) flowing away from A by surface diffusion.
We further require that the normal growth-rate of
the neck surface between A and B. cussed by the
deposition of the material from the boundary onto it.
be equal to the normal growth-rate of the surface
beyond B caused by the deposition of the surface flux
from the surface (I,) onto it:

Matter flows into the neck region of each of these

mechanisms at rates which are calculated by standard
methods as used and referenced in the First
Report [I]. The equations are listed in Table 2.
2.2 Rure-e9uafio~s,~r
two wires

(2.5)

The remaining two are continuity equations for the

flux. We require that all the material flowing out of
the boundary (I,) be redistributed over the area d,
[times unit depth) on either side of the boundary:

becoming

K3

dl -I=d2 = p0

Density A!A,
-0.54
0.636

Coordination
-8
8-14 (mean: (11))

0.742
0.68 I
OS24

12
8(+6 = 14)
6

1.00

14
-

OS-O.8

SWINKELS

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DIAGRAMS

265

10
A:100

lo- '

0.0

I
0.2

0.1

1
O-3

NORMALISCD NECK RADIUS

I
04

0.1

0.0

0.2

NORnALlSED NECK RAOIUS

X/a

Fig. 3. The curvature difference AK required to drive redistribution during Stage 1 of the sintering of wires. Note
that, when A and the neck size are small, this difference is
slight, and the neck has a circular profile; but when A and
x/n are both large. it deviates from a circle.

04

0.3
x/a

Fig. 5. The redistribution length. d,, normalised by the

average neck radius p. For small values of A and .~:a. the
redistribution length is small; for large A and .x,ia is tends
to the value 0.5.
writing AK = KL - K, , we obtain:

into equations

(2.6) and (2.7) gives:

K2 -=-K1

K,

K2--K,
--;__
K2

3Adl

dl_y{l-l+(~Af$)

(2.14)

(2.11)

4x
3d:

d2 =

(2.12)

4 d:

where
and
(2.13)
Making the further approximation
(common to
almost all sintering models) that d, + d2 = p, and

AK
-I
KI

3Ap
-+;-;[3(!$
x

+4(F)+

(2.16)
which, with
K,K,

1000

il2

= K:

completely determines K1, K2. d, and d2.

This last equation is plotted in Fig. 3. It shows the
part of the driving force required to drive redistrihutiotl

and the way in which this varies with A and ~/a.

When A is small, redistribution is rapid. and requires
almost no driving force (so AK is small). When the
reverSe is true, most of the driving force is used to
drive the redistribution mechanisms. The individual
curvatures, K, and K, are plotted in Fig. 4, and the
redistribution length dr [equation (2.14)] is shown in
Fig. 5.
We now define the regime in which re-distribution is
dom~~ont, limiting the rate of sintering, as that for
which AK 3 K,. At the boundary of this regime the
two lengths d, and d2 [equations (2.14) and (2.15)] are
0.1
0.2
NORMALISEQ NECK RAWJS

Fig. 4. The driving forces involved in

wires, when D,&/D,6, I: 100. The full
curvature (I<,). the broken lines show
the point A and the curvature K,

03
x/a

04

the sintering of two

line shows the mean
the curvature K, at
at the point B.

almost equal:
d, = 0.45 p

I
d2 = 0.55 p ..!

(2.17)

The boundary itself is defined by setting AK = K1

in

266

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SECOND

REPORT ON SINTERlNG

DIAGRAMS

equation (2.16) to give

AP

--23

(2.18)

from which
(2.19)

HC+lOLOGOUS TEHPERATURE

This result is plotted in Fig. 6 on the axes used for

the sintering diagrams (using data for copper given
later in Table 4). To the right of the full line. Mechanism 4 is controlled by boundary diffusion (that is.
more than half of the total available driving force is
used to drive the boundary flux); to the left. Mechanism 4 is controlled by the surface redistribution mechanism. The other cbntours show where AK/K1 has
given values. When the activation energy for bound-

T/T~

Fig. 6. The full line shows the transition from control of

Mechanism 4 by boundary diffusion (right of full line) to
control by surface redistribution (left to full line). using
data for copper (Table 4). The broken lines show the curvature differences AL\KIK, used to drive the redistribution
mechanism.

arv dj~us~on is less than

that for surface

diffusion.

redistribution controls neck growth on the left hand

side of the diagram (as in Fig. 6); but when the reverse
is true, it controls on the right. The diagram is independent of a.

Table 4. Material data

Property

Silver

Copper

Nickel
1.09 x lo-
2.49 X lo-0
1730
8.90 x IO

Atomic volume R Im3

Burgers vector b (m)
Melting point T,,, (K)
Density A0 (kg,im3)

1.71 X 10-29
2.89 x IO-
1234
1.05 x lo4

1.18 x lo-=
2.56 x 10-l*
1356
8.96 x IO3

Shear modulus p (MN/m21

T-coefficient of p (K - )
Dislocation density p (m-*)
Surface energy ;s (J/m*)

2.64 x lo4
4.36 x 1O-4
104
1.12

4.21 x IO4
3.97 x 1o-4
lOI
1.72

(b)
(b)

Pre-exp. lattice diff. D,, (m.s)

Activ. energy, lattice diff. QIp(kJ/moie)
Pre-exp, boundary diff. 6 f),, (m3/s)
Activ. energy. boundary difX Qb (kJ/mole~

tg

6.20 x 10-s
207
5.12 x 1o-s
10s

(m)

Pre-exp. surface diff. b, D,, (m3/s)

Activ. energy. surface diff. Qs (kJ/mole)
Pre-exp. vaporisation PO (MN/m)
Activ. energy. Vaporisation Q,, (kJ/mole)

x 10T5

6.94 x IO-
89.8

(i)
(m)
(ml
I;
S

6..

x lO-O

1.23 x IO5
324

(i)

;
(t)
(aa)
(aa)
(gg)
(gg)

7.65 x
3.70 x
lOI
2.00
6.00 x
271
3.50 X
115

IO4
1o-4

Cc)
(C)

lo--5

ci1
(n)

1o-5

1:;
(uf

4.40 x IO-2
199
7.4s x 105

(bb)
(bb)

401

(a) Neighbours J. R. and Alers G. A., Phys. Ret;. 111, 707 (1958).
(b) Overton W. C. and Gaffney J., Phys. Reu. 98. 969 (1955).
(c) Alers G. A.. Neighbours J. R. and Sato H., J. Phys. Chem. Solids 13.40 (1960).
(d) Leese J. and Lord A. E., J. uppl. Phys. 39, 3986 (1968).
(e) Using p = 0.375 E, and data from Kiister W., Z. Mefaffk. 39, 1 (1948).
(f) Blackburn. L. D., The Ge~erur~uf~ ~~isoch~}lo~s
Stress-Sfrai~
&rues, Paper presented at ASME Winter Annual
Meeting, New York. November (1972).
(g) Lowrie R. and Gonas A. M.. J. appl. Phys. 38, 4505 (1967).
(h) Durand M. A.. Phys. Rec. 50,449 (1963).
(if Jones H.. Metal!. Sci. J. 5, 15 (1971).
(j) Roth T. A., Mater. Sci. Engng. 18. 183 (1975).
(k) Murr L. E., Wong G. 1. and Horylev R. J., Acca Metal/. 21, 595 (1973).
(1)Gutshall P. L. and Gross G. E., J. appl, Phys. 36, 2459 (1965).
(m) Peterson N. L., Solid St. Phys. 22, 429 (1968).
(n) Kniepmeier M., Griindler M. and Helfmeier H., 2. Metallk. 67, 533 (1976).
(0) Buffington F. S., Hirano K. and Cohen M., Acta Merail. 9,434 (1961).
(p) Smith A. F. and Gibbs G. B.. Metals Sci. 3, 93 (1969).
(qt Data of Anderlin R. L., Knight J. D. and Kahn M.. Trajzs. Merall. Sot. A.I.M.E. 233, 19 (1965). As modified by
Robinson S. L. and Sherby 0. D., Acra met& 17, 109 (1969).

SWINKELS

AND

ASHBY:

SECOND REPORT ON SINTERING

3. SINTERING OF AN AGGREGATE
OF WIRES
3.1 Stages 0 and 1 for an aggregate

of wires

When a close-packed array of parallel wires is sintered (Fig. 7) neck growth and densification in Stage 0
and early Stage I are described by the rate-equations
discussed in Section 2 and listed in Table 2. But as the
necks grow, the pores become rounded, and the driving force for the non-densifying
mechanisms
(Tables 1
and 2) diminishes; it must obviously go to zero at the
start of Stage II when the pore becomes cylindrical. If
no densifying mechanisms operate in Stage 1, the pores
become cylinders when the neck size, x/a, reaches
the value xc&a
= 0.35 [Fig. 7(a)]. But if only densifying mechanisms operate in Stage I, Stage II starts
when xc&a reaches the value 0.44 [Fig. 7(b)].
In the earlier report [l], the driving force for nondensifying mechanisms was made to go to zero (for
wires) by multiplying it by a smoothing function:
S=(l->

if x<xca,r

S = 0

x-Iron

if x 2 xca,r

y-Iron

1.18 x IO-r9
2.48 x IO-
1810
7.62 x IO3

S=

I.21 x lo-29
2.58 x 10-i
1680
8.00 x IO3
8.1 x IO4
5.06 x lO-4
lOI
2.15

(i)

8.10 x IO4
5.03 X lo-4
lOI
2

1.90 x lo-4
239
I.12 x lo-
174

(0)
(0)
(v)
(v)

1.80 x lO-4
270
7.50 x lo-*
I59

(0)

2.50 X lo-
232
3.67 x IO
382

(cc)
(cc)

I.10 x lo-i0
220
3.67 x IO5
382

(cc)
(cc)

(i)

i:;

I%

d SOURCE
dsovm + &miK

(3.2)

It varies from unity at the start of sintering to zero

at the end of Stage 1. as the old one (equation

I.21 X lo-29
2.58 x 10-i
1810
7.65 x 10
(d)
(d)

267

This method has two difficulties. First. by using a

fixed value of yCRIT/a (of 0.42) it assumed a constant
contribution from the densifying mechanisms. And
second, it is entirely empirical, having no physical
basis beyond the need to suppress these mechanism
when x > .yCRIT.
We have replaced this by an equivalent, but physically more acceptable scheme which incorporates
variable densification. It is illustrated by Fig. 8. The
non-densifying mechanisms draw material from the
region P of length (or area) dWuRcE, and deposit it
onto all or part of the region Q. of length (or area)
dSINK, equal to the length (d, + d,) of Fig. 2. As the
neck grows, the source-length
diminishes and
becomes zero when the pore becomes cylindrical. It is
then that the driving force for non-densifying mechanisms becomes zero. We define the new smoothing
function

Tungsten

304 L Steel

6.4 x IO4
4.48 x lO-4
1or4
2.10

I%

(3.1)

DIAGRAMS

3.70 x lo-5
280
2.00 X lo-3
167
I.10 x IO-
220
3.67 x lo5
382

NaCl

1.59 x 1o-*9
2.73 x 10-r
3683
1.93 x IO4

(k)

I.55 x IO5
I.04 X lo-4
lOI
2.65

I!1
(w)
(w)

5.60 x 1o-4
585
5.48 x lo-l3
378

(f)
(f)

(dd)
(dd)
iz

2.55 x 10-i)
326
3.23 x IO5
782

4.49 X lo-z
3.99 x 10-O
1074
2.16 x IO3
(h)
(1~)

(i)

I.51 X IO4
6.82 x IO-
lOI
0.28

I:1
(x)
(x)

2.50 x IO-
217
6.20 x IO-
155

(r)
(r)
(y)
(Y)

1.00 x 10-i
217
2.97 x IO4
182

(8)
(8)
(gg)
(gg)

(g)
(g)

(ee)
(ee)
1z

(1)

(r) Verrall R. A.. Fields R. J. and Ashby M. F.. J. Am. Ceram. Sot. 60. 211 (1977).
(s) Hoffman R. E. and Turnbull D., J. appl. Phys. 22. 634 (1957).
(t) Inferred by scaling data of materials of the same structure and of comparable melting points. The activation energy is
the same as that observed for Au in Cu grain boundaries. Austin A. E.. Richarchs M. A. and Wood E.. J. appl. Phrs. 37.
3650 (1966).
(u) Lange W., Haessner A. and Mischer G., Plrysico sratus Solidi 5, 63 (1957).
(v) James D. W. and Leak G. M., Phil. Mag. 12.491 (1965).
(w) Perkins R. A., Padgett R. A. and Tunali N. K.. MetaIl. Trans. 4. 2535 (1974).
(x) Kreider K. G. and Bruggeman G., Trans. Metal/. Sot. A.I.M.E. 239, 1222 (1967).
(y) Burke P. M., Ph.D. Thesis, Stanford University Metallurgy Dept. (1968).
(z) Hough R. R.. Scripra metal/. 14, 559 (1970).
(aa) Choi J. Y. and Shewmon P. G.. Trans. Metal/. Sot. A.I.M.E. 222. 589 (1962).
(bb) Mills B.. Douglas P. and Leak G. M.. Trans. Metal/. Sot. A.I.M.E.
245. 1291 (1969).
(cc) Blakely J. M. and Mykura H.. Acta merall. Il. 399 (1963).
(dd) Assumed to be the same as for y-iron. Ref. (cc).
(ee) Allen B. C.. Trans. Metal/. Sot. A.I.M.E. 236. 915 (1966).
(ff 1Approximated by lattice diffusivity times Burgers Vector for NaCI.
(gg) Dushman S. and Lafferty J. M. (Eds), Scientific Foundarious oj Vacuum Techology Wiley, New York (1962).

SWINKELS

268

AND

ASHBY:

SECOND REPORT ON SlNTERlNG

DIAGRAMS

In constructing the maps, x, y and p are calculated in

a step-like way, so that dsouRc, and dsfFac are known.
and properly include the effect of densifi~tion. They
are then used to calculate S (equation 3.2).
The end of Stage I is defined as the line S = 0; it
appears on subsequent diagrams for wires as a broken
line near .x/a = 0.40 or A/A, = 0.95. Its slope is
caused by the varying contribution of densi~~ation
across the diagram. The rates of the non-densifying,
Stage 1, mechanisms (Mechanisms 1,2 and 3. Table 2)
are modified by multiplying curvature difference
which drives them by the factor S [equation 3.2): that
for vapour
transport,
for example, becomes
W, - Kn)S.
3.2 Stage 2 for an aggregate of wires
Once the pore has become cylindrical, the driving
forces for Mechanisms 1, 2 and 3 disappear, leaving
only Mechanisms 4 and 5. The basic rate-equations
for these two mechanisms are unchanged. There are,
however, two modifications which enter Stage 2. The
first is an obvious one: the mean curvature (which
acts as the driving force for Mechanism 5) is now
Km=

-
P

(3.7)

tbi

where p is the mean radius of the pores, which, from

the geometry of Fig. 8 is

By approximating

the pore as a circle of radius p we

Fig. 7. The sintering of a close-packed agffregate of wires,

illustrating the calculation of the density at the start of
Stage 11, (a) when no densifying m~hani~ms operate in
Stage I, and (b) when only densifying mechanisms operate
in Stage I.

3.1) did, and is used (as before) to multiply the

curvatures driving the non-densifying mechanisms.
The geometry of Fig. 8 requires that, for closepacked wires, p is given by
P =

x2 + y2 + a2 - a: - 2ay
%a, - 4

(3.3)

where 2y is the centre-to-centre approach of the wires

due to densification and al is the current radius of
each wire, which differs from a because material has
been removed from its surface to fill the neck (a, is
calculated by applying conservation of volume to the
nondensifying mechanisms). In addition:
dsouscr = at@ - 7V3)
d SINK = pe

(3.4)
(3.5)

where
(3.6)

Fig. 8. The .pore between an aggregate of

showing
. wires,
.
the dlmenslons tnvoived m the calculatmns.

AND

SWINKELS

ASHBY:

SECOND

REPORT ON SINTERING

DIAGRAMS

269

For this stage (Fig. 9a) d2 has disappeared.

d, is simply
n

dl = jp
Equating
gives

(3.11)

Pk and r,, (as before} and solving for K1

Ki =
STAGE:2

and

ct - {c: + 4(1 + Crx)K:j2

(3.12)

2(I + C,x)

where

WIRES

(3.13)
and X1 is given by KIKz = I(,,!,. The results readily
simplify to

5fAGE

and

SPHERES

Fig. 9. The pore for late stage sintering, showing the

dimensions involved in the calculations during (a) Stage II
for wires. and (b) Stage III for spheres.

obtain a second relationship, based on conversion of

volume:
(a - y)(x + p)
np2
?ra2
=:--+-+.
2
6
12
Combining these two equations and solving for p
gives
p = -2.53.x -t {3.87.x*i- 0.765~7;
(3.8)
As before, Mechanism 4 can proceed only if the
material it pumps into the neck is r~ist~b~ted across
the surface of the pore, so a curvature-difference must
exist to drive the redistribution (Fig. 9a). The matter
entering the neck from the boundary does so at a rate

and the rate of redist~bution~

p _
SI

kTdl

+2

When two spheres

Stages 0 and 1 are
closely resemble those
ences arise because the

OF TWO SPHERES
are joined by sintering, only
involved. The rate-equations
for a pair of wires. The differnew geometry involves slightly

(3.10)

t During Stage I material is plated onto the void surface

as a wedge of maximum thickness at the point A (Fig. 2),
diminishing to zero thickness at a distance (d, + d2) away.
But during Stage 2, the pore remains geometrically identical, merely shrinkjng in size, so the redistributed material
must be plated uniformly over the pore surface. In the numerical calculations we accomplish the transition by re+
placing the constant 4 in equations (2.9) by
c=4

4. SINTERING

is

c~,a,Y,w* - K2)

In the subsequent calculations the rates of neck

growth and densification have been calculated from the
rate-equations V, and 9, of Table 2, using these
values of K, and K2. These resui?s are plotted in the
same way as before in Figs 1O- 13.

2P
(x + P - x,)

where x, is the neck size at the start of Stage 2.

ltf3

0.0

i
01

0,2

NORHALISCD

o-3
NECK R&MS

04

0.5
x/a

Fig. 10. The curvature difference. AK/K,, required to drive

redistribution during Stages I and II of the sintering of
wires (compare with Fig. 3).

270

SWINKELS

AND

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SECOND REPORT ON SINTERING

DIAGRAMS

0.0
fulld&y,

COPPER

-0.0

0.1

0.2

0.3

04

NORMALISEO NECK RADIUS

05

x/a

Fig. I I. The driving force for the sintering of wires during

Stages I and II when D,S,/D,& = 100. The full line shows
the mean curvature, K,. the broken lines show the curvatures K, and K, (compare with Fig. 4).

changed curvatures, and slight changes in the continuity equations. Both are discussed below.
4. I Rate-equations

for mechanisms 2, 3, 5 and 6 for

0.4

0.6

0.8

HOMOLOGOUS TEMPERATURE

;lO
T/TM

Fig. 13. The transition from control of Mechanism 4 by

boundary diffusion (right of full line) to control by surface
diffusion (left of full line) for Stages I and II of the sintering
of wires. The broken lines show the curvature differences
AK;Ki used to drive the redistribution mechanism (compare with Fig. 6).

(Mechanisms 2 and 3) are driven by the curvature

difference

spheres

Mechanisms 2, 3, 5 and 6 are unaffected by the

requirements of surface redistribution. The mean
curvature at the neck (Fig. 2) is now

K,+i

where p is given by equation 2.2. Lattice diffusion

from the boundary and from dislocations (Mechanisms
5 and 6) are driven by this curvature; and lattice
diffusion from the surface, and vapour transport

0.61

-0.0

//I

0.1

0.2

0.3

NORMALISED NECK

04

RADIUS

05

x/a
Fig. 12. The redistribution length, d,, normalised by the
length n/3p for Stages I and II of the sintering of wires
(compare with Fig. 5).

Matter flows into the each of these mechanisms at

rates which are calculated by standard methods, as
used and referenced in the First Report [I]. The equations are listed in Table 2.
4.2 Rate-equations for the modijed
for spheres

mechanisms I and 4

As with wire, boundary diffusion can deliver matter

steadily into the pore only if surface diffusion can
redistribute it over the pore surface. There must then
exist a curvature difference AK = K, - K, to drive
the surface redistribution, leaving the lesser curvature
(K,) to drive boundary diffusion (Mechanism 4). This
in turn influences the rate of surface diffusion (Mechanism 1) which is now driven by the curvature difference (2/a - K2). The need for surface redistribution
introduces two new curvatures (K, and K2) and two
new distances (d, and d2) over which diffusion takes
place. They are related (as before) by equations (2.4)
and (2.5), and by two continuity equations. As with
wires (Section 2.2) we require that the redistribution
flux be equal to the boundary flux where it enters the
pore (equation 2.6) and that the rate of normal
growth of the surface of the pore be continuous where
the redistribution flux and the surface flux meet
(equation 2.7).
If the equations for spheres given in Table 2 are
now simplified as in Section 2 and substituted into
these equations, they can be solved for K,. K,. d, and
d,. The results are identical, but for a numerical constant of magnitude 3/4, with those of Section 2. Since

SWINKELS

AND

ASHBY:

SECOND REPORT ON SINTERiNG

this approach is an approximate one. we may regard

all results and figures for wires of Section 2 as apply
ing to Stage 1 for spheres also.
In computing the maps of later sections we have
used an iterative technique to solve the problem
exactly. But from a practical point of view. the analytical results of Sectjon 2 given an adequate approximation to the true result.
5. SfNTERflVG OF Al; AGGREGATE
OF SPHERES
When spherical particles of a single size are packed
randomly [ 131.the density can vary between 0.56 and
0.64. and the coordination number (number of neighbours per particle) between 8 and 14. These results are
compared with those for ordered packings of spheres
in Table 3. If the particles are non-spherical. the
densities are generally smaller; but if two or more sizes
of particles are mixed. so that the smaller spheres fit
between the larger ones. the density can h larger. It
must be generally true that the packing geometry will
change during sintering. so that the number of contact neighbours. and thus necks. per particle increases
as sintering proceeds.
This introduces a new problem (one we did not
have with wires). Not only is the initial packing a
variable when aggregates of spheres are sintered. but
the packing geometry may change during the sintering itself. A wire in a close-packed array of wires has 6
nearest neighbours throughout sintering: a sphere in
a compact of spheres might start with 8 nearest neighbours and end up with 14. We shall first discuss sintering at fixed packing geometry and then introduce
changes of geometry with time.

* =
v4

(5.1)

tr = 16A,A,, - 2
so that n increases towards the value 14 as sintering
proceeds,)
In the calculations (described in more detail in
Section 6) the current values of s. y and al are used to
calculate the angle 8 [equation (3.6)] and p [equation
(3.3)]. The angle z is calculated from the current value
of the density. as described above. Then the new density is calculated from
_A _ tA&)iAo)
(1 - ?;aJ3
Ao
where Ai(Z)~ABis obtained from the equation of the
line on Fig. 14. In this way, densi~cation both by neck
growth and by particle rearrangement are included.

5
d
05

60

u,,= 12axD,6,~,fJ(K,

- KdW, + Id*)
kTddt(d, + 3dz)

(5.2)

These vary with the quantity A and with x,/a. in a way

71

which closely resembles the equivalent equations for

Stage 1 of wires plotted in Figs 3-6.
We assume that the packing geometry varies continuously throughout Stage 1. Figure 14 shows plane
sections through three possible geometries. The first is
simple-cubic packing (A A0 = 0.52): the second is
bee. packing (A A0 = 0.68): and the last is fee. packing (A A0 = 0.74). The figure illustrates that the angle
z can be used to characterise the structure. and that
as z decreases from 90 to 60. the density rises from
0.52 to 0.74 in a roughly linear way.
We have used this as a basis of a device to include
particle rearrangement into our calculations. The initial angle xi is chosen to match the initial densit! of
the green compact. We have then kept track of the
density throughout the computation of the maps and
caused x to decrease from this initial value towards
60. in a way which varies linearly with the density.
and would cause r to become 60 when A A0 reaches
1. This rearrangement contributes to the densification.
over and above that caused by the diffusional removal
of matter from the neck. (It incidentally causes the
number n of contact neighbours. and thus necks-perparticle, to increase; the data in Table 3 is consistent
with the approximate relationship

5.1 Stages 0 and I for a compact of spheres

When an aggregate of packed spheres of equal size
is sintered, neck growth and densification in Stage 0
and early Stage I are described by the rate-equations
discussed in Section 4 and listed in Table 2. But (as
with wires) the pores become rounded as the necks
grow and the driving force for the non-densifying
mechanisms diminishes; it must go to zero at the start
of Stage 3. when the pore becomes spherical. (Note
that pores are never even roughly cylinidrical during
the sintering of spheres, so no Stage 2 mechanisms are
listed. We bridge the gap between Stage 1 and Stage 3
with a Transition stage described below.)
Throughout Stage I, we calculate the neck curvature, p. from equation 3.3. The coupling of boundary
with surface diffusion is treated as follows. The rateequations involved (Table 2) are

DIAGRAMS

70

80

90

SMALLCST
AwClEWWEEN PARTICLES
ON A CLOSE-PACKED
RANE, deg.

Fig. 14. The variation of density with packing peometr!.

charactcrised by the angle 1.

272

SWINKELS

AND

ASHBY:

SECOND REPORT ON SINTERING

Stage 1 ends when the section of the pore becomes

circular. If the particles were close-packed this would
simply be the neck size at which 0 = 60. But we start
with a non-close-packed geometry, characterized by
the angle z (which decreases towards 60 as the density increases). It is readily shown that, when z is a
variable. equation 3.4 must be replaced by:

DIAGRAMS

Stage 3 sintering. is readily calculated by equating the

volume V, of the regular tetrakaidecahedron of edgelength I
v c =8 \ i213
to the volume of matter per cell
v,

&,..,.=a~(~+~--~)

za3

plus the volume of six pores

-l-hend,,,,, goes to zero, and the pore becomes

nrcular, when

VP = 6 x ; np3

This is the criterion we have used for the end of

Stage 1.
5.2 Stage 3 and rhe transition stage. for a compact oj
spheres

The start of Stage 3 is calculated in the manner

described in the next paragraph; then a transition
zone is constructed by linearly interpolating between
the values of A/A0 at the end of Stage 1 and the start
of Stage 3, and using these interpolated values of density to calculate self-consistent values of x/a and y/a.
We assume that, at the start of Stage 3, all particles
have 14 contact neighbours. packed so that the neck
surfaces are coplanar with the faces of a regular
tetrakaidecahedron (ICfaced solid, Fig. 15) and that
no further changes in packing geometry occur. There
is a pore at each corner (there are 24 comers each
shared with 3 other particles). We assume further that
the larger neck associated with each pore (Fig. 15) has
the same size as that at the end of Stage I. (The
density, of course. is larger because we have replaced
cylindrical pores by spherical holes.) The new pore
radius, p. which determined the driving force for

PI

(5.6)

and noting (Fig. 15) that I = x + p.

These considerations fix the start of Stage 3. As
explained, the gap between Stage 1 and 3 is bridged
by a transition zone, based on a linear interpolation
of A/A, between its value at the end of Stage 1 and
that at the start of Stage 3. The further progress of
Stage 3 is then calculated using the Stage 3 equations
of Table 2 at fixed packing geometry. The numerical
procedure is described briefly in Section 6.
Throughout Stage 3 the coupling of boundary and
surface diffusion is included. The rate of this coupled
process is calculated as follows. The pore, although
almost spherical, cannot be a perfect sphere if there is
to be any driving force for surface redistribution. If we
think of a pore sitting on a planar grain boundary
(the neck), then by symmetry, its shape is that of a
surface of revolution about an axis normal to the
plane of the neck. For such a surface, the rate of
normal displacement of the surface due to a surface
flux is

-.-

(5.7)

where y is the perpendicular distance from the axis

of the surface of revolution (Fig. 9b) and s is the
distance along the pore surface from the grain
boundary. Assuming that the pore remains nearly
spherical, y and s are related by Y = p cos s/p where
p is the mean pore radius. For uniform distribution,
roughly preserving the pore shape, we require that

1
- Y

ds

= constant

(5.8)

The solution to the equation is

.(Isec$II

K - CIpln

+C,ln

sec?+tanz
P

(I

P I>

using the boundary conditions

Fig. 15. A particle at the start of Stage III. The spherical
holes are located at the 24 coreners
of the
tetrakaidecahedron.

J, = 0

at

SE-

It
2p

+C,

(5.9)

SWINKELS

AND

ASHBY:

K=K,at

s=O

K=K,at

s=:p

SECOND

we obtain, by in~egratjon. the flux of material

leaving the boundary and flowing over the pore
surface by surface diffusion. Expressed as a volume
rate, the result is:
V = 4~D,&$(K1
- Kz)
SR
In (2)kT

(5.10)

This we equate to the grain boundary flux, which is

calculated by standard methods. To a sufficjent
approximation, the boundary rate is
Vd =

2nD&@K
kT lnX?__
!
P

1
3

(5.11)

Equating the two rates we obtain

Using K,K2 = Ki we can solve explicitly for both

K, and K2, and hence (by substitution in equation
5.11) obtain the rate df sintering by mechanism 4
when it is coupled to surface redistribution.
Once again, the way in which K, and K, vary with
x/a and A are so similar to the results which we
obtained for wires (Section 3 and Figs 10, 11 and 12)
that the reader is referred to these for a description of
the characteristics of the distribution mechanisms.

REPORT ON SINTERING

DIAGRAMS

273

heavy broken line marks the transition from Stage I

to Stage II or III: the mechanism does not change
here, but the equation used to describe it does (see
Table 2). On either side of some of the field boundaries is a shaded band. Within the non-shaded
regions. a single mechanism contributes more than
5504 of the total neck-growth rate. Within the shaded
regions, two or more mechanisms contribute in an
important way to sintering, though none contributes
more than 55%: the shading gives some idea of the
width of the field boundaries. FinaIly, the heavy
dash-dot line shows where redistribution begins to
control Mechanism 4 (boundary diffusion): on the
side of this line Iabelled SL, surface-redistribution
limits the rate; on the other side labelied BL, boundary diffusion does so. (Its construction was described
in earlier sections and illustrated by Figs 6 and 13. It
is the line along which the driving force is partitioned
equally between the boundary flux r, and the redistribution flux ri,a.) The part of the diagram labelled
BL is aimost uninffuenced by the need for redistribution; the part labelled SL. however. reflects its presence.
Superimposed on the fields are contours of constant
time. The neck growth-rate is the sum of the contributions of the mechanisms listed in Table 2. according
to the stage of sintering. The contours of constant
time are computed by integrating this sum of the rateequations with respect to time.
6.2 Density diagrams
The second type of diagram is new. The axes are
relative density A/A, and homologous temperature
T/TM (Figs. 16 and 17, lower diagrams). At first sight

it would seem logical to show it on the fields of

dominance of each densification mechanism, of which
only two are ever important (M~hani~s
4 and 5).
But where these dominate densi~cation they also
We construct two types of sintering diagrams, one
dominate neck growth (so the field boundaries for
showing neck-size the other density, as a function of
both coincide); and where non-densifying mechanisms
temperature and time. Such diagrams for wires of two
operate in Stage I. they influence densification (by
different radii are shown in Fig. 16, and for aggregates
changing the neck shape, and so the driving forces)
of spheres of two different radii in Fig. 17.
even though they do not contribute directly to it. So
more information is contained in the diagram if, as on
6. I Neck-size diagrams
the first type of diagram, we plot fields of d~inant
neck-growrh mechanism, remem~ring that throughout
The first type of diagram is the same as that shown
Stages II and III, they are identical with those of
in the earlier paper [ 11. The axes are normafised neck
size .uJa and homologous temperature T/T,, where TM dominant densification mechanisms. As before, heavy
is the melting temperature of the material (Figs 16 full lines show field boundaries; heavy broken lines
and 17, upper diagrams). It shows the jelds over show stage transitions; and the dash-dot line separates the region of control of Mechanism 4 by redistriwhich each mechanism of neck-growth is dominantbution (SL) from its control by boundary diffusion
that is, the range of neck size and temperature over
which each mechanism contributes more to neck(BL).
Superimposed on the fields are co~rours of constant
growth than any other mechanism does. The boundaries of these fields can be found by equating pairs of time. The densifi~tion rate is the sum, appropriate to
the rate-equations (listed in Table 2) and solving for the stage of sintering, of the contributions of Mechanneck-size as a function of temperature. At a field isms 4, 5 and 6, listed in Table 2. The contours of
boundary (shown as heavy lines on the Figures) two constant time are computed by integrating this sum of
mechanisms contribute equally to the sintering rate. A the rate-equations.
4 CONSTRUCIION
OF SINTERlNG
DIAGRAMS

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DIAGRAMS

Fig. 16. A set of sintering diagrams for a close-packed array of silver wires of two different radii: 10and
100 pm. The upper diagrams show the neck growth, the lower show the density as a function of time and

temperature.

6.3 method of construction

The diagrams were constructed by numerical

methods, using the data listed in Table 4. A practical
method is as follows. Pick a starting value for T/TM
(we generally used 0.4) and for neck size, x/a (the
adhesive neck-size, see Table Z), and evaluate the rate
equations for the volume flux ri of the mechanisms of
a given stage of sintering. Sort and record the dominant mechanism. Form the sums given in Table 2 to
give the net growth-rate J/a, linear shrinkage-rate j/u
and densification-rate &Ao. Then increase x/a and
T/TM in steps, evaluating these quantities at each step
and calculating also the time interval At between
steps in x/a, and sum the results to give the time t, the
total shrinkage y/a and total density change A/A,.
Finally, plot on axes of x/a or A/A, and T/TM the
locus of points at which the dominant mechanism
changes (the field boundaries), the locus of points at

which t has chosen values (the time contours) and the

locus of points at which AK = K, (the boundary
between boundary diffusion and surface redistribution-control of Mechanism 4). The 55% contours are
added by the obvious modification of the same procedure.

7. APPLICATIONS
We conclude by illustrating the use of the maps in
the interpretation of experiment and the design of intering procedures. The maps are constructed from the
data listed in Table 4. Measurements (discussed
below) are plotted onto each as bars or boxes, showing the observed values of neck size .x/a and temperature T, or of relative density A/A0 and T. The
numbers on the bars or boxes are the observed times,
in hours, to reach that neck size or density. They

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T/TM

-~*

DIAGRAMS

~~~~~~~

T/T,

1.0

(2)

Fig. 17.A set of sintering diagrams for an aggregate of spherical particles of silver of two different radii :
10 pm and 100 pm, The upper diagrams show the neck size, the lower show the density as a function of
time and tem~rature.

allow a direct comparison

mental data.

of the maps with experi-

7. I E.~peri~e~fs using wires

7.1.1 Alexander and Ballet [ 163. Sintered copper
wires (a = 64~)
wound in a close-packed array,
onto a copper spindle. Their experiments compassed
the range
T = 900-1075C (0.86-0.99 TM)
t-0-6OOh
x/a = 02-0.4
A/A, = 0.92-0.97
i

copper

The range of their experiments is shown as a box on

Figs 18 and 19. Throughout these experiments, two
mechanisms contribute in an important way to neck
growth. Up to 10 h, neck growth is mainly by surface
diffusion. Between about IO and 50 h, surface and lat-

tice diffusion contribute almost equally. Beyond that,

lattice diffusion from the boundary (a densifyinp
mechanism) becomes dominant. The predicted necksizes agree well with those measured on necks containing a grain boundary (typical discrepancy less
than 12%). When boundaries migrated away from the
pores, the necks ceased to grow. This can be incorporated into the diagram by suppressing the boundary
dependent Mechanisms 4 and 5 when migration
starts [I].
Alexander and Balluffi also measured the densificdtion of their arrays of wires. Their observations are
plotted onto Fig. 19, which is the density map corresponding to Fig. 18. The ex~rimenta~ data is not
entirely self-consistent (due to presumably to the difficulty of measuring densification); the map agrees with
it to within the experimental error.
7.1.2 Pranatis and Seigle [ 171. Studied neck growth
between close packed wires of copper (a = 51 pm)

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TfIlPCRATURf
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TEMPERATURE

OC
750

DIAGRAMS

900

1050

300

WJ

OC
750

600

900

1050

0.0

10-6

8
HOtiOLOGUiJS TEMPERATURE

T/TM

Fig. 18. A neck-size diagram for close-packed

Copper
wires: (n = 64 pm). Data of Alexander and BaIlu% [ 16) are
shown.
TEMPERATURE

HOMOlOGOUS TEHPtRAlURf

Fig. 20. A neck-size diagram for close packed Copper

wires: a = 51 pm. Data of Pranatis and Seigien [ 171 are
shown.
TfMPfRATURf

*C

T/TM

0.6
HONOlOGOUS

'C

0.8
TEMPERATURE

T/TM

Fig. 21. A neck size diagram for close-packed Nickel wires:

LI= 64 pm. Data of Pranatis and Seigle [ 171 are shown.
HOMOLOGOUS
TEMPfRAlURETM

Fig. 19. A density diagram for the wires of Fig. 18, again
showing the data of Alexander and Ballufi [ 163.
and nickel (a = 64 p),
ditions:

under the following con-

T= 106O"C(O.98
TM)
t= l-1OOh
Copper
x/a = 0.2-0.43

T = 1400C (0.97 TM)

t=3-4OOh
0.21-0.43

x/a =

Nickel
1

Their data are shown on Figs 20 and 21. The agreement between measured and predicted neck-sizes is
good (the maximum discrepancy in x/a for nickel is
5%; for copper it is 9%). In both cases surface diffusion (1) and lattice diffusion (5) contribute almost
equally to neck growth and (as observed) there should
be considerable shrinkage.

The same authors sintered close-packed iron wires

(a = 38 pm). The conditions were:
T = 875C (0.63 TM)
t=3-1OOOh
Iron
I
XJU= 0.13-0.34
Figure 22 shows their results plotted onto an appropriate diagram for pure iron. Surface diffusion is the
dominant mechanism for times up to 1 hour; beyond
that, lattice diffusion and surface diffusion contribute
about equally. The data given in Table 4 give a fair fit
to Prantis and Seigles measurements, though (in this
instance) the fit depends strongly on the choice of the
surface diffusion coefficient. We favour the present
choice because it gives a fair match also with the data
of Matsumura [ 1S] discussed below.
7.1.3 Matsumura [is]. Studied the sintering of iron,
wound in close packed arrays. His experiments extend

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over both the x and the y-range:

T = 700-1350c (0.X-0.9 TM)
r = I-2000h
x:a = 0.075-0.24

Iron

The data are plotted on Fig 23. Sintering is predominantly by surface diffusion. with a major contribution
( : 40~ from lattice diffusion. The sudden decrease in
sintering-rate at the x to ; phase boundary appears
both on the map and in Matsumuras data. But the
map consistently predicts neck sizes which are too
large (by a factor of about 2) or times to give a certain
neck size which are too small (by a factor of about 5)
implying that the surface diffusion coefficient used to
construct the map is too rapid.
0.6
HOnOLDtOUS

14

04
TEMPfRATURf

T/T6

Fig. 17. A neck size diagram for close packed Iron wires:
P = 38 pm. Data of Pranatis and Seigle [ 171 are shown.

TfWERAflJRf
SW
9.0,

*C

1000

150

1250

1500

7.2.1 Kitt(tery und Berg [19]. Measured neck growth

between two spheres of copper (N = 57 pm). Their
measurements were made at very short times. covering the range:

T = 9% 105OC(0.9-5.97 7-M)
t = 0.02-S h

Copper
I

x;a = 0.124.26

. 10-6
0.6

O-8

HOtiOLOGOUS TLHPERATURE

1.0
l/T,

A neck size diagram for close packed Iron wires:

a = 75 Itm. Data of Matsumura 1187 are shown.

Fig. 23.

TfWfRATURf
300

650

600

Y
750

900

1050

Figure 24 shows that surface diffusion was the dominant neck-growth mechanism, with a major contribution from lattice diffusion (giving densification). The
predicted neck sizes are in good agreement with the
measurements {maximum discrepancy 4x1 except at
the highest tem~ratur~ (where it jumps to 25,). We
have frequently noted that, very close to the melting
point. theory underestimates neck-growth rates by
surface diffusion; Kingery and Bergs measurements
are an example. We think that this is because surface
diffusion (unlike most other diffusion processes) is
rarely characterised by a single activation energy: and
near TMits rate is faster than that expected by extrapolation from lower tem~ratures.
The reader is
referred to Mills PI al. [20] for diffusion data showing
this effect.
7.2.2 Wilsm artd Shcwmar~ [3]. Measured neck
growth in a row of copper spheres (a = 7.5pm) under
the following conditions
7 = 750-95OC (0.75-0.90 T,)
r = I-240h
x/a = 0.1 l-0.32

HOHa_OtOU5

TEHPERATURE

l/Tpj

Fig. 24. A ?-sphere neck-size diagram for Copper:

a = 57 pm, Data of Kingery and Berg [ 191 are shown.

Copper

Their data are plotted onto Fig. 25. The diagram supports their conclusion that surface diffusion is generally dominant. though it also indicates a large contribution from lattice diffusion. The agreement between
predicted and measured neck sizes (or times) in this
instance is extremely good: within the experimental
error of the data ( 2 49;).
7.2.3 Kucz~~rski [21]. Measured the neck growthrate of copper spheres (a = 40~) on a copper plate.
The ranges of temperature and time he used. and the

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resulting

DIAGRAMS

range of neck size, was

T = 70&9OOC (0.72-0.86 TM)

t = 0.5-41 h
x/a = 0.1-0.33

10-6
HOMOLOGOUS

TEMPERATURE

T/T"

Fig. 25. A ?-sphere neck-size diagram for Copper:

a = 72 pm. Data of Wilson and Shewmon [3] is shown.

TEfiPtRATURE
300

600

450

'C
750

900

3.10-s

kz
E

-1.0

3x10-6 2
z
Y
-1.5
10-6

0.6
HOHOLOGOUS

0.8
TEMPERATURE

1.0
T/T,,

Fig. 26. A 2-sphere neck-size diagram for Copper:

a = 40 pm. Data of Kuczynski [Zl] is shown.
TCMPERATURE
__

300

450
I

HOKILCGOUS

'C

600

TIIlFfRATURE

750

Figure 26 shows these data, plotted onto the appropriate diagram. Agreement is fair: the maximum discrepancy in x/a is 359/,,although for most data points.
the agreement is much closer: typically c lo,/, discrepancy. The measurements all lie in the field for
which surface diffusion from a surface source is
dominant; but at the low temperature end, boundary
diffusion contributes nearly half of the total. and at
high temperatures lattice diffusion contributes in a
major way ( - 40%).
The same author made similar measurements using
silver spheres (a = 180 pm). They are reanalysed in
Fig. 27. The data spans the ranges
T = 5OS8OOC (0.63-0.87 TM)
t=l-90h
x/a = 0.033-O. 162

Silver
I

1050

0.0

-2.0
0.4

Copper

900

T/T,,,

Fig. 27. A 2-sphere neck-growth diagram for Silver:

(I = 180 pm. Data of Kuczynski [Zl] are shown.

Agreement between theory and experiment in this

case is very good over an exceptional range of temperature: the maximum error in predicting s/a is less
than 12%. The data overlaps two fields (surface diffusion and boundary diffusion) with a major contribution from a third (lattice diffusion from the surface).
The boundary mechanism is limited by boundary diffusion at the higher temperatures, but by surface
redistribution at lower temperatures. The map (which
of course includes the effects of redistribution) agrees
with the data at low temperatures much more closely
than a map in which redistribution is omitted [l].
This is the only data we have been able to find which
permits a test of the redistribution model.
The diagram itself is interesting in showing both
mechanisms 2 and 5: lattice diffusion around the pore
and lattice diffusion from the boundary. Note, too,
the steepened slope of the time contours in the surface-limited boundary diffusion regime: the redistributed mechanism is slowing down the sintering very
considerably in this field.
Over the central shaded region, no one mechanisms
is responsible for even half of the total neck growthrate. Instead, four mechanisms all contribute about
equally. This illustrates just how complicated the
interpretation of sintering data can be, even in model
experiments like this, and is a good example of how
these diagrams can help in understanding what is
going on.
7.2.4 Kingery and Berg [ 193. Also studied the sintering of sodium chloride spheres (a = 60 pm). The conditions were
T = 700-75OC (0.91LO.96TM)
I = 0.025-0.25 h
x/a = 0.074.22

NaCl
1

In constructing a map (Fig. 28) we have had to guess

parameters for surface diffusion (Table 4) for which

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no date are available. With this guess. the map shows

two fields only: those of vapour transport and of
boundary diffusion. The data. which lies entirely in
the vapour transport field. agree well with the predictions of the map. Our conclusion supports that of
Kingery and Coble: vapour transport is dominant,

700

7.3 Esperinrerrts usirtg uggregates qfsplreres

7.3.1 Eadie et al. [22] and Lee et al. [23]. Sintered
aggregates of spherical silver particles (a = Z&22 pm)
in air and in argon. and measured both neck growth
and densifications. Their conditions covered the
ranges
__

I- = 700-800-C (0.794.87 T,)

t = 2.6-4.7 h
xia = 0.18-0.37
A/A0 = 0.62ZO.75

-7.0

0.6
0.8
HOtlOLOGOUS TEMPERATURE
T/T,,

04

1.0

Fig. 28. A 2-sphere neck-growth diagram for Sodium

Chloride: a = 60 pm. Data of Kingery and Berg [19] are
shown.
TEMPERATURE
0.0 I

300
'

450

600

754

900

IOHESIPI

-2.0
04

0%
HOMOLOGOUS

1.0

04
TftlPfRATURf

TEMPERATURE
300
'

L50

Some of the measurements of the neck growth in

air [23] are shown in Fig. 29. Agreement is good. and
the map confirms the authors conclusion that boundary diffusion is the dominant mechanism. with contributions from lattice diffusion and surface diffusion.
A more exacting comparison is shown in Figs 30
and 3 1. The first shows neck growth and the second
shows the density of the same set of sintering silver
spheres [22]. Both the neck sire and the density are
less than that predicted by the diagrams-though
a
small increase in the rate of lattice diffusion (the
dominant mechanism) would correct this. But we
think the discrepancy may be real,(not merely a result
of inaccurate diffusion data) and exist because the
scheme of particle-rearrangement
we have adopted
(Section 5) may lead to rates of densification which
are too rapid.
7.3.2 Germatr [24]. Measured the densification of
particles of a 304 L stainless steel (a = 2.5-20 pm: we

T/T"

Fig. 29. A neck-size diagram for a compact of Silver

spheres: a = 20 pm. Data of Lee er al. [23] are shown.

o-or

Silver

TEMPERATURE OC
450
600
150

300

900

'C

600

193

900
I

XT5

z
zl
r

---_---s&V4

!z
>
F
*
a
%

04
i+UMWJGCUS

TEMPERATURf

T/TM

Fig. 30. A neck-size diagram for a compact of Silver

spheres: a = 22 pm. Data of Eadie er al. [22] are shown.

06
0%
HOHOLOGOUS
TEnPERATURET/T,,,

10

Fig. 31. A density diagram for the same silver spheres as

Fig. 30. again showing the data of Eadie et al. [22].

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1000

750

SECOND

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TEMPERATURE
1250

1.0

1500

2000

OC
2500

3000

0.9
2
vr
t
0
i 0.8
;I
4
L
0.7

O-6
HOMOLOGOUS

04
TEMPERATURE

1.0
T/T,,

Fig. 32. A density diagram for a compact of 304 L Stainless Steel spheres: a = 15pm. Data of German [24] are
shown.

took a = 15 pm). The sintering conditions were

T = 99&l 153C (0.7NI.85 TM)
r=4h
304 L Steel
I
AlA0 = 0 66-0.75
Agreement between theory and experiment is remarkably good (Fig. 32). Densification is by boundary diffusion, with major contributions from lattice diffusion. But it should be noted that surface diffusion
has an important influence on neck growth and
(because the neck size determines the driving force for
all sintering mechanisms) surface diffusion influences
the rate of densification even though it does not. by
TfMPfRATURf

'C

1.0

0.6
04

0.6
HOMOLOGOUS

04
TEMPERATURE

T/TM

1.0

Fig. 34. A density diagram for a compact of tungsten

spheres: 0 = 2 pm. Data of Kothari [27] are shown.

itself, cause densification. We think that this is the

reason for the activation energy observed by German.
which is close to that for surface and for volume diffusion.
7.3.3 Rhirles et al. [ZS]. Measured densification of
spherical copper particles (a = 3744 pm: we used
a = 40~m) which had been densely packed but not
compressed. The conditions were
T = 915-104OC (0.884.97 Thl)
t=85h
AlA0 = 0.660.75

Copper
I

The results are plotted on the appropriate map,

shown as Fig. 33. The agreement is within the
expected error in the models and data.
7.3.4 Kothari [26.27]. We have encountered one set
of data, that of Kothari [26.27] describing the sintering of tungsten. which is inconsistent with the models
described here: Data for particles of size a = 2 pm,
corresponding to the conditions
T = 110&15OOC (0.37-0.48 Th()
t = 8.3 h
Tungsten
I
A/A0 = 0.68-0.74

06
HOMOLOCOUS

04
TEMPERATURE

1.0
T/TM

Fig. 33. A density diagram for a compact of Copper

spheres: a = 40 pm. Data of Rhines et al. [25] are shown.

is shown on Fig. 34. The observed times (and thus

rates) differ by a factor of more than 100 from those
predicted by the models. Kothari studied other particle sizes also (a = 0.25 pm and a = 7.5 m): there is
only a very weak dependence of densification on particle size (for the same T and t); according to the
models, there should be a very strong one.
Two explanations are possible. One is that sintering
is not diffusion-controlled.
but controlled
(for
example) by an interface reaction. This seems unlikely-an interface reaction should slow down the rate of
sintering, yet in Kotharis experiments the tungsten
sintered far faster than the models predict. The other

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is that the particles. being irregular in shape. sinter at

a rate determined b! the radius of the average irregularity. or surface-bump. not at a rate determined b!
the mean particle radius. Then the models should fit
the data if evaluated for an apparent particle radius
equal to that of the bumps. It is hard to test this idea
with precision: but as far as we can tell. it IS capable
of explaining the observations.
8. SLMMAR\ AND COSCLCSlOSS
(a) The paper describes two ways of assembling
models for sintering into useful diagrams. one showing tterk size and the other showing drttsiry as a function of time and temperature. These diagrams are a
development
and extension of those reported
earlier [ I]. The new diagrams include an important
coupling between grain boundary and surface diffusion. and modifications to the treatment of particle
arrangement and of the stages of sintering.
(b) The diagrams can be used to display the sintering behaviour of a specific material: as an aid to the
design and interpretation of experiment; and as a way
of visualizing commercial sintering schedules and the
effects of changes in schedule.
(c) We tested the diagrams against I7 sets of experimental data for wires. pairs of spheres and aggregates
of spheres of Cu. Ag. Ni. Fe. W. Stainless Steel and
NaCl. The tests provide a check of almost all the
equations which are used to construct the maps. We
find that. for wires and pairs of spheres of Cu. Ni. Ag
and Natl. agreement is excellent, and that the maps
provide a way of identifying the mechanisms of sintering in each experiment. with no a priori assumptions.
even when several mechanisms operate at once. For
aggregates of particles of silver. copper and stainless
steel the agreement is less good (probably because of
the difficulty of describing geometry properly in the
models), but the method still provides a practical tool
for analysing both experiments and commercial sintering procedures. For iron wires the agreement is
poor. almost certainly because the rate of surface diffusion differs from the values we have used. For tung
sten aggregates the agreement is again poor. perhaps
because of the irregular particle shape.
The coupling between surface and boundary diffusion, included here for the first time, generally slows
the rate of sintering at low temperatures. Only one set

ON SINTERING

DIAGRAMS

281

of data allows a real test of this inhibition and sup

ports it.
The computational scheme used to construct such
diagrams is a flexible one which readily allows of
further extension: the inclusion of grain growth. pore
dragging. and externally applied pressure or stressonce their effect on the individual mechanisms is
known.
Ac~rlor~/rdgPnlPrlr-This
work
Science Research Council.

was

supported

by

the

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