CHAPTER 9

CASE STUDIES IN PHASE

TRANSFORMATIONS

Introduction

W e now apply the t h c r m o d y n a m i c and kinctic theory of C h a p t e r s 5 - 8 t o f o u r p r o b l e m s :

making rain; getting fine-grained castings; growing crystals for s e m i e o n d u c t o r s ; and
making a m o r p h o u s metáis.

Making rain

O í t e n , during p e r i o d s of d r o u g h t , t h e r e is e n o u g h m o i s t u r e ¡n the a t m o s p h e r e to give

clouds. bul rain d o c s not fall. T h e f r u s t r a t i o n of seeing t h e elouds but not getting any rain
has s t i m u l a t e d al) m a n n e r of black magic: successful r a i n m a k e r s h a v e b e e n highly
h o n o u r e d m e m b e r s of soeiety since soeiety existed. B u t it is only recently t h a t r a i n - m a k i n g
has aequired s o m e scientifie basis. T h e p r o b l e m is o n e of h e t e r o g e n e o u s n u c l e a t i o n .
A cloud is cloudy b e e a u s e it is a suspensión of vast n u m b e r s of m i n u t e , spherical w a t e r
droplets. T h e d r o p l e t s are t o o small and light to fall u n d e r gravity; and they are stable, that
is to say they d o not c o a r s c n and b e c o m e large e n o u g h to fall.*
Rain falls w h e n (surprisingly) the d r o p l e t s f r e e z e t o ice. If a d r o p l e t f r e e z e s it b e e o m e s a
stable ice nucleus which then grows by attracting w a t e r v a p o u r f r o m the s u r r o u n d i n g
droplets. T h e ice particle quickly grows t o a size at which gravity can pulí it d o w n , and it
falls. O n eold days it falls as hail or s n o w ; but in w a r m e r w e a t h e r it remelts in the w a r m e r
air near the g r o u n d and falls as rain. T h e difficult stage in m a k i n g rain is getting the ice t o
nueleatc in the first place. If the w a t e r d r o p l e t s are clean then they will not c o n ta in any
h e t e r o g e n e o u s nucleation catalysts. Ice can t h e n only f o r m if the cloud is cooled to the
h o m o g e n e o u s nucleation t e m p e r a t u r e , a n d t h a t is a very low t e m p e r a t u r e (—40°C; see
E x a m p l e 7.1). C l o u d s rarely get this cold. So the ice must nucleate on s o m e t h i n g ,
h e t e r o g e n e o u s l y . Industrial pollution will d o : the s m o k e of a steel w o r k s contains so much
dirt that the rainfall d o w n w i n d of it is significantly increased (Fig. 9.1). But building a
steelworks t o p r o d u c e rain is unnecessarily e x t r a v a g a n t . T h e r e are c h e a p e r ways.

4
W e s a w ¡ti C h a p t e r 5 t h a t t h e r e is a d r i v i n g f o r c c t e n d i n g l o t n a k c d i s p e r s i o n s o f p r e c i p i t a t e s in a l l o y s < ' o < v r v f « ;
a n d w e w o u l c i e x p e e t a d i s p e r s i ó n o f d r o p l e t s in w a t e r v a p o u r t o d o t h e s a m e . W a t e r d r o p l e t s in e l o u d s , h o w c v c r ,
carry elcctrostatic eharges; a n d this gives a differenl result for the driving foree.

81
82 ENGINEERING MATERIALS

K i g . 1 . R a i n f a l l s w h c n t h e w a t e r d r o p l e t s in c l o u d s t u r n t o i c e . T h i s c a n o n l y h a p p e n if t h e c l o u d s a r e b e l o w O ° C
t o b e g i n w i t h . If t h e d r o p l e t s a r e c l e a n , i c e c a n f o r m o n l y in t h e u n l i k e l y e v e n t t h a t t h e c l o u d s c o o l d o w n t o t h e
h o m o g e n e o u s n u c l e a t i o n t e m p e r a t u r e o f — 4 0 ° C . W h e n d u s t p a r t i c l e s a r e p r e s e n t t h e y c a n c a t a l y s e n u c l e a t i o n at
t e m p e r n t u r e s q u i t e c i ó s e t o ()°C. T h i s is w h y t h e r e is o f t e n h e a v y r a i n f a l l d o w n w i n d o f f a c t o r y c h i m n e y s .

T h e crystal structure of ice is hexagonal, with lattice constants of a = 0.452 nm and

c — 0.736 nm. T h e inorganic c o m p o u n d silver iodide also has a hexagonal structure, with
lattice constants (a = 0.458 n m , c = 0.749 n m ) that are a l m o s t i d e n t i c a l t o t h o s e o f ice. So
if you put a crystal of silver iodide into supercooled water, it is almost as good as putting in
a crystal of ice: m o r e ice can grow on it easily, at a low undercooling (Fig. 9.2).
This is an example of h e t e r o g e n e o u s nucleation. T h e good matching betwecn ice and
silver iodide means that the interface between t h e m has a low energy: the contact angle is
very small and the undercooling needed to nucleate ice decreases from 40°C to 4°C. In

F i g . y .2. T h e e x e e l l e n t c r y s t a l l o g r a p h i c m a t c h i n g b e t w e e n s i l v e r i o d i d e a n d i c e m a k e s s i l v e r i o d i d e a v e r y p o t e n t
n u c l e a t i n g a g e n t f o r ice c r y s t a l s . W h e t i c l o u d s a t s u b - z e r o t e m p e r a t u r e s a r e s e e d e d w i t h A g í d u s t . s p e c t a e u l a r
rainlall oceurs.
 CASE STUDIES IN PHASE TRANSFORMATIONS 83

artificial r a i n - m a k i n g silver iodide, in the f o r m of a very fine p o w d e r of crystals, is either

dusted into the cloud f r o m a p l a ñ e flying a b o v e it, or is shot into it with a r o c k e t f r o m below.
The p o w d e r " s e e d s " ice crystals which g r o w , a n d start to fall, taking the silver iodide with
them. But if the ice, as it grows, t a k e s o n snow-flake f o r m s , and the tips of the snow flakes
break off as they fall, then the process (once s t a r t e d ) is self-catalysing: cach oíd g e n e r a t i o n
of falling ice crystals leaves b e h i n d a new g e n e r a t i o n of tiny ice f r a g m e n t s to sced the next
lot of crystals, and so o n .
T h e r e are even b e t t e r catalysts for ice nucleation than silver iodide. T h e most c e l e b r a t e d
ice nucleating catalyst, p r o d u c e d by the m i c r o o r g a n i s m Pseudomonas syringac, is capable
of forming nuclei at u n d e t e c t a b l y small undercoolings. T h e organism is c o m m o n l y f o u n d
on plant leaves a n d , in this situation, it is a great nuisance: the slightest frost can cause the
leaves to f r e e z c and die. A m u t a n t of the organism has been p r o d u c e d which lacks the
ability to n u c l e a t e ¡ce (the so-called " i c c - m i n u s " m u t a n t ) . A m e r i c a n bio-engineers have
proposed t h a t the ice-minus o r g a n i s m should be released into the wild, in the h o p e that it
will displace the natural o r g a n i s m and solve the f r o s t - d a m a g e p r o b l e m ; but environ-
mentalists h a v e t h r e a t e n e d law suits if this goes a h e a d . Interestingly, ice nucleation in
organisms is not always a bad thing. T a k e the e x a m p l e of the alpine plant Lobelia teleki,
which grows on the slopes of M o u n t K e n y a . T h e a m b i e n t t e m p e r a t u r e fluctuates daily o v e r
the range — 10°C to + 1 0 ° C , and s u b j e e t s the plant to c o n s i d e r a b l e physiological stress. It
has d e v e l o p e d a cunning r e s p o n s e t o c o p e with these t e m p e r a t u r e changes. T h e plant
m a n u f a c t u r e s a p o t e n t biogcnic nucleating catalyst: w h e n the outside t e m p e r a t u r e falls
through 0°C s o m e of the w a t e r in the plant f r e e z e s a n d the latent h e a t evolved stops the
plant cooling any f u r t h e r . W h e n the outside t e m p e r a t u r e goes back u p t h r o u g h ()°C, of
course, s o m e ice melts back to w a t e r ; and the latent h e a t a b s o r b e d n o w helps k e e p the
plant cool. By r e m o v i n g the b a r r i e r to n u c l e a t i o n , the plant h a s d e v e l o p e d a t h e r m a l
buffering m e c h a n i s m which k e e p s it at an even t e m p e r a t u r e in spite of quite large
variations in the t e m p e r a t u r e of the e n v i r o n m e n t .

Fine-grained castíngs

M a n y e n g i n e e r i n g c o m p o n e n t s — f r o m cast-iron drain covers to a l u m i n i u m alloy cylinder

h e a d s — a r e castings, m a d e by p o u r i n g m o l t e n metal into a m o u l d of the right s h a p e , and
allowing it t o go solid. T h e casting process can be m o d c l l c d using the s e t - u p shown in Fig.
9.3. T h e m o u l d is m a d e f r o m a l u m i n i u m but has Perspex side windows to allow the
solidification b e h a v i o u r t o b e w a t c h e d . T h e casting " m a t e r i a l " used is a m m o n i u m chloride
solution, m a d e u p by h e a t i n g w a t e r to 50°C and a d d i n g a m m o n i u m chloride crystals until
the solution just b e c o m e s s a t u r a t e d . T h e solution is then w a r m e d u p to 75°C and p o u r e d
into the cold m o u l d . W h e n t h e solution t o u c h e s the cold metal it cools very rapidly and
b e c o m e s highly s u p e r s a t u r a t e d . A m m o n i u m chloride nuclei f o r m h e t e r o g e n e o u s l y on the
aluminium and a thin layer of tiny chill crystals f o r m s all o v e r the m o u l d walls. T h e ch¡11
crystals grow competitively until they give way t o the m u c h bigger columnar crystals (Figs
9.3 a n d 9.4). A f t e r a while the t o p surface of the solution cools b e l o w the saturation
t e m p e r a t u r e of 50°C and crystal nuclei f o r m h e t e r o g e n e o u s l y o n floating particles of dirt.
The nuclei grow to give equiaxed (spherical) crystals which settle d o w n into the bulk of the
solution. W h e n the casting is c o m p l e t e l y solid it will h a v e the grain s t r u c t u r e shown in Fig.
9.5. This is the elassie casting s t r u c t u r e , f o u n d in any cast-metal ingot.
84 ENGINEERING MATERIALS

E q u i a x e d crystíils tjrowing
f r o m s o l u t i o n in m o u l d c e n t r e

- A m m o n i u m chloride
solution

. -• S m a l l " c h i l l " c r y s t a l s
on m o u l d walls

.. . - Perspex
windrtws
g l u e d l<>
block

A l u m i n i u m block

B o t t o m of b l o c k
p l a c e d in d i s h of l i q u i d
nitrogen

Fig. 9.3. A simple laboratory set-up for observing the casting process direclly. T h e m o u l d v o l u m e m e n s u r e s ahout
.SO x 5 0 x ft m m . T h e w a l l s a r e c o o l e d b y p u t t i n g t h e b o t t o m o f t h e b l o c k i n t o a d i s h o!' l i q u i d n i t r o g e n . T h e
w i n d o w s a r e k e p l f r e e of f r o s t b y s q u i r t i n g t h e m w i t h a l c o h o l f r o m a w a s h b o t t l e e v e r y 5 m i n u t e s .

Liquid b e t w e e n
dendrites has now
all s o l i d i f i e d t o
give c o m p l e t e l y solid
Dendrilic columnar grains
growth front

la)
(b) —

Ib) —

¡a)

—Unfavourable
5 orientations
"wedged out"
Chill c r y s t a l s
5
Stage 1 Stage 2 Stage 3

F i g . l >.4. C h i l l c r y s t a l s n u c l e a t e w i t h r a n d o m c r y s t a l o r i e n t a t i o n s . T h e y g r o w in t h e f o r m o f dendrites. Dendrites

a l w a y s l i e a l o n g s p e c i h c c r y s t a l l o g r a p h i c d i r c c t i o n s . C r y s t a l s o r i c n t c d l i k e ( a ) w i l l g r o w f u r t h e r i n t o t h e l i q u i d in
a g i v e n t i m e t h a n c r y s t a l s o r i e n t e d l i k e ( b ) ; ( b ) - t y p c c r y s t a l s w i l l g e l " w e d g e d o u t " a n d ( a ) - t y p c c r y s t a l s will
d o m í n a t e , cvcntually bccoming columnar grains.
 CASE S T U D I E S IN P H A S E T R A N S F O R M A T I O N S 85

Equiaxed grains

Columnar grains

Chill c r y s t a l s

Fig. 9.5. T h e grain s i r u c t u r e of the solid casting

This structure is far f r o m ideal. T h e first problem is one of segregation: as the long
columnar grains grow they push impuritiesahead of t h e m . * If, asisusually the case, we are
casting alloys, this segregation can give big differenccs in composition—and therefore in
properties—between the outside and the inside of the casting. T h e second problem is o n e
of grain size. As wc mentioned in C h a p t e r 8, fine-grained materials are harder than
coarsc-grained ones. Indeed, the yield strength of steel can be doubled by a ten-times
dccrease in grain size. Obviously, the big columnar grains in a typical casting are a source
of weakness. But how do we get rid of t h e m ?
O n e cure is to cast at the equilibrium t e m p e r a t u r e . If, instead of using undersaturated
ammonium chloride solution, we pour saturated solution into the mould, we get what is
called "big-bang" nucleation. A s the freshly poured solution swirls past the cold walls,
heterogeneous nuclei f o r m in large n u m b e r s . These nuclei are then swept back into the
bulk of the solution wherc they act as growth centres for equiaxed grains. T h e final
structure is then almost entirely equiaxed, with only a small columnar región. For some
alloys this technique (or a modification of it called "rheocasting") works well. But for most
it is found that, if the molten metal is not s u p e r h e a t e d to begin with, then parts of the
casting will freeze p r e m a t u r e l y , and this may prevent metal reaching all parts of the mould.
The traditional cure is to use inoculants. Small catalyst particles are added to the melt
just before pouring (or even p o u r e d into the mould with the melt) in order to nucleate as
many crystals as possible. This gets rid of the columnar región altogcther and produces a
fine-grained equiaxed structure throughout the casting. This important application of
heterogeneous nucleation sounds straightforward, but a great deal of trial and error is
needed to íind effective catalysts. T h e choice of A g í for seeding ice crystals was an
unusually simple one; finding successful inoculants for metáis is still nearer black magic
than science. Factors other than straightforward crystallographic matching are important:
surface defeets, for instance, can be crucial in attracting atoms to the catalyst; and even the

k
T h i s i s . o f e o u r s c , j u s t w h a t h a p p c n s i n z o n c r e f i n i n g ( C h a p t e r 4 ) . B u t s e g r e g a t i o n i n z o n e r e h n i n g is n i u c h
m o r e c o m p l e t e t h a n it is i n c a s t i n g . I n c a s t i n g . s o m e o f t h e r e j e e t e d i m p u r i t i e s a r e i r a p p e d b e t w e e n t h e d e n d r i t e s
so t h a t o n l y a p r o p o n i o n of t h e i m p u r i t i e s a r e p u s h e d i n t o t h e l i q u i d a h e a d o f t h e g r o w t h f r o n t . Z o n e r e f i n i n g , o n
t h e o t h e r I n m d . is d o n e u n d e r s u c h c a r e f u l l y c o n t r o l l c d c o n d i t i o n s t h a l d e n d r i t e s d o n o t f o r m . T h e s o i i d liquid
i n t e r f a c e is t h e n t o t a l l y H a t , a n d i m p u r i t y t r a p p i n g c a n n o t o c c u r .
86 ENGINFERING MATERIALS

smallest q u a n t i t i e s of impurity can be a d s o r b e d on the surface t o give m o n o l a y e r s which

may poison the catalyst. A n o t o r i o u s e x a m p l e of e r r a t i c s u r f a c e nucleation is in the fieldof
e l e c t r o p l a t i n g : electroplatcrs o f t e n have difliculty in getting their platings to " t a k e "
p r o p e r l y . It is well k n o w n ( a m o n g e x p e r i e n c e d electroplatcrs) t h a t p o u r i n g c o n d e n s e d
milk into the plating bath can help.

Single crystals for semiconductors

M a t e r i a l s for s e m i c o n d u c t o r s h a v e to satisfy f o r m i d a b l e s t a n d a r d s . T h e i r electrical

p r o p e r t i e s are badly a f f e c t e d by the scattering of carriers which occurs at impurity a t o m s ,
or at dislocations, grain b o u n d a r i e s and f r e e surfaces. W e have a l r e a d y seen (in C h a p t e r 4)
h o w z o n e refining is used to p r o d u c e the u l t r a - p u r e starting materials. T h e next stage in
s e m i c o n d u c t o r processing is to grow large single crystals u n d e r carefully controlled
conditions: grain b o u n d a r i e s are climinated and a very low dislocation density is achieved.
Figure 9.6 shows p a r t of a typical i n t e g r a t e d circuit. It isbuilt on a single-crystal w a f e r of
silicon, usually a b o u t 300 ¡xm thick. T h e w a f e r is d o p e d with an impurity such as b o r o n ,
which t u r n s it into a p-type s e m i c o n d u c t o r (bulk d o p i n g i s usually d o n e a f t e r the initial zone
refining stage in a process k n o w n as z o n e levelling). T h e localized n-type regions are
f o r m e d by firing p e n t a v a l e n t impurities (e.g. p h o s p h o r u s ) into the surface using an ion
g u n . T h e circuit is c o m p l e í c d by the vapour-pha.se deposition of silica insulators and
aluminium interconnections.
G r o w i n g single crystals is the very o p p o s i t e of p o u r i n g fine-grained castings. In castings
we want to u n d e r c o o l as m u c h of the liquid as possible so that nuclei can f o r m e v e r y w h e r e .
In crystal growing we n e e d to start with a single sced crystal of t h e right o r i e n t a t i o n and the
last thing t h a l we w a n t is for stray nuclei to f o r m . Single crystals are grown using the
a r r a n g e m e n t shown in Fig. 9.7. T h e seed crystal fits into the b o t t o m of a crucible containing
the m o l t e n silicon. T h e crucible is l o w e r e d slowly out of the f u r n a c e and the crystal grows
into the liquid. T h e only región w h e r e the liquid silicon is u n d e r c o o l e d is right next t o the
i n t e r f a c e , a n d even t h e r e the u n d e r c o o l i n g is very small. So t h e r e is little c h a n c e of stray
nuclei f o r m i n g and nearly all runs p r o d u c e single crystals.

Transistor 1 Trjnsisior ?

Aluminium
intercoiinectron

Gato ! Gate

Fig. 9.6. A t y p i c a l i n t e g r a t e d c i r c u i t . T ' l i c s i l i c o n w a í c r is c u t ('rom a h r g e single crystal using a chcmical

saw—mechanical sawing would introduce too man y dislocations.
 CASE SIÜDIES IN P H A S E T R A N S P O R M A T I O N S 87

Turnace
windiny;;

Walnr cooled
chill block

Mould
slowly lowered
o u t of f u r n a c e

l'ig. 4.7. tirowing single crystals for semiconductoi devuxs.

Convetilional integrated circuits like Ihat shown in Fig. have two niajor drawbacks.
First, the dcvicc densiiy is limited: silicon is not a very good insulator. so leakage oecurs it'
deviccs are placed too cióse together. And seeond. deviee speed is liniiled: stray capaci-
tance exists between the devices and the substrate which imposes a lime eonstani on
swilehing. These problems would be removed if a very tliin film of single-crystal silicon
could be deposited on a highly insulating oxide sueh as silica (Fig. 9.8).
Single-crystal teehnology has recently been adapted lo do this, and has opened up the
possibility oí' a new generation of ultra-compact high-speed devices. Figure 9.9 .shows the
melhod. A single-crystal wafer of silicon is first coated with a thin insulating layer of S i O :
with a slot, or "gate". to expose the underlying silicon. T h e n , polycrystalline silicon
("polysilicon") is vapour deposited onto the oxide, to give a film a lew microns ihick.
Finally, a capping layer of oxide is deposited on the polysilicon to proleet it and acl as a
mould.
The sandwich is then heated to 1I0()°C by scanning it from below with an electrón beam
(this temperature is only 3 1 2 ° ( b e l o w the melting point of silicon). The polysilicon at the
gale can then be melted by line scanning an electrón beam aeross the top of the sandwich.
Once this is done the sandwich is moved slowly to the left under the line sean: the moltcn
silicon at the gate undereools, is secded by the silicon below, and grows to the right as an

( n+ P nt
) . 1 n4 (' ~írn

x
S i O . . i n s u l a t i n g layor C
) 300
\ l'Hl
Substrnte ( I
88 IiNGINHERlNG MATERIALS

Electron
Single-crystal beam
film s e e d e d by
substrate

Polysilicon

Sinyle-crystal
silicon s u b s t r a t e

— - 1412

TiX 1100

l-'ig. y . y . I l o w s i n g l c - c r y s t a l l i l m s a r e g r o w n f r o m p o l y s i l i c o n . I l i e e l e c t r ó n h e a m is l i n e - s c a n n e d in a d i r e c t i o n a t
right a n g l c s to t h e p l a ñ e of t h e d r a w i n g .

o r i e n t e d single crystal. W h e n ihe single-crystal film is c o m p l e t e the overlay of siliea is

dissolved away to e x p u s e o r i e n t e d silicon that can be elehed and ion implanled to p r o d u c e
eompletcly isolated c o m p o n e n t s .

Amorphous metáis

In C h a p t e r 8 we saw that, when carbón steels were q u e n c h e d Irom the austenite región
lo r o o m t e m p e r a t u r e , the austenite could not t r a n s f o r m to the equilibrium l o w - t e m p e r a -
ture phases of lerrite and iron c a r h i d e . T h e r e was no time for diffusioti, and the austenite
could only t r a n s f o r m by a diffusionless ( s h e a r ) t r a n s f o r m a t i o n to give the m e t a s t a b l e
martensitc p h a s e . The m a r t e n s i t e t r a n s f o r m a t i o n can give e n o r m o u s l y altered meehanical
p r o p e r t i e s and is largely responsible for the great versalility of c a r b ó n and low-allov steels.
U n f o r t u n a l e l y , few alloys u n d e r g o such useful shear t r a n s l b r m a t i o n s . But are there o t h e r
ways in which we could change the p r o p e r t i e s of alloys by q u e n e h i n g ?
A n idea of the possibilities is given by the oíd high-sehool chemistry e x p e r i m e n t with
sulphur crystals ("llowers of s u l p h u r " ) . A 10 mi b e a k e r is w a r m e d up on a hot piale and
s o m e sulphur is a d d e d to it. A s soon as the sulphur has melted the b e a k e r is r e m o v e d from
the h e a t e r and allowcd to cool slowly on the bench. I'he sulphur will solidify to give a disc
of polycrystalline sulphur which b r e a k s easily if pressed or bent. Polyeiystalline sulphur is
obviously very briltle.
Now t a k e a n o t h e r batch of sulphur flowers. but this time heat it well past its melting
point. T h e liquid sulphur gets d a r k e r in colour and b e c o m e s m o r e and m o r e viscous. Just
b e f o r e the liquid becomes eompletcly u n p o u r a b l e it is d e c a n t e d into a dish of cold w a t e r ,
q u c n c h i n g it. W h e n we test the p r o p e r t i e s of this quenched sulphur we lind that we have
 CASE S T U D I E S IN P H A S E T R A N S F O R M A T I O N S 89

time

Fig. 9.1(1. S u l p h u r , g l a s s c s a n d p o l y m c r s t u m i n t o v i s c o u s l i q u i d s a t h i g h t e m p e r a t u r e . I h e a t o m s m t h e l i q u i d a r e
a r r a n g e d in l o n g p o l y m e r i s e d c h a i n s . T h e l i q u i d s a r e v i s c o u s b e c a u s e ii i s d i f í i c u l l l o get t h e s e h u l k y c h a i n s t o s l i d e
o v e r o n e a n o t h e r . Ii is a l s o h a r d t o g e l t h e a t o m s t o r e g r o u p t h e m s e l v e s i n t o c r y s t a l s , a n d t h e k i u c t i c s o í
c r y s t a l l i s a t i o n a r e v e r y sk>w. T h e l i q u i d c a n e a s i l y b e e o o l e d p a s t t h e n o s e of t h e C - c u r v e t o give a m e t a s i a h l e
supercooled liquid which can survive for long times at r o o m t e m p e r a t u r e .

produced a tough and rubbery substance. We have, in fact, produced an amorphous form
of sulphur with radically altered properties.
This principie has been used for thousands of years to make glasses. W h e n silicates are
cooled from the molten state they often end up being amorphous, and many polymers are
amorphous too. W h a t makes ¡t easy to produce a m o r p h o u s sulphur, glasses and polymers
is that their high viscosity stops crystallisation taking place. Liquid sulphur becomes
unpourable at 180°C because the sulphur polymerises into long cross-linked chains of
sulphur atoms. When this polymerised liquid is cooled below the solidification temperature
it is very difficult to get the atoms to regroup thcmsclvcs into crystals. The C-curve for the
liquid-to-crystal transformation (Fig. 9.10) lies wcll to the right, and it is easy to cool the
melt past the nose of the C-curve to give a supercooled liquid at room temperature.
There are formidable problems in applying these techniques to metáis. Liquid metáis do
not polymerise and it is very hard to stop them crystallising when they are undcrcooled. In
fact, cooling rates in excess of 10 1()o C s _ 1 are needed to make puré metáis amorphous. But
current rapid-quenching technology has made it possible to make amorphous alloys,
though their compositions are a bit daunting(Fc4oNÍ4oP| 4 B 6 for instance). This is so heavily
alloyed that it crystallises to give compounds; and in order for these compounds to grow
the atoms must add on from the liquid in a particular sequence. This slows down the
crystallisation process, and it is possible to make amorphous Fe40Ni4(|Pi.tBft using cooling
rates of only 10 5o C s" 1 .
A m o r p h o u s alloys have been made commercially for the past 10 years by the process
known as melt spinning (Fig. 9.11). Al though we can only produce thin ribbons or wires of
amorphous metal these have some remarkable and attractive properties. Many of the
iron-based alloys are ferromagnctic. Because they are amorphous, and literally without
structure, they are excellent soft magnets: there is nothing to pin the magnetic domain
walls, which move easily at low fields and give a very small cocrcive forcé. These alloys are
now being used for the cores of small transformers and relays, and for the pickups of
90 ENÜINEERING MATERIALS

M o l t e i i a l l o y f e d ¡n
under pressure

Amorphous
alloy r i b b o n
- 20^mthic;k

- lOOmm
m á x i m u m width

W a t e r c o o l e d i:op[>er
w h e e l - 1 5 0 m m in d i a m e t e r
— Wheel profile
for spinning
wire

l i g . " ' . I I . R i b h o n s n i w i r e s n i a m o r p h o u s m e t a l c a n b e m a d e b y m e l t s p i n n i n g . T h e r e is a n u p p e i l i m i t 011 t h e

t h i c k n e s s o l t h e r i b b o n : it it is t o o t h i e k il w i l l n o t e o o l q u i c k l y e n o u g h a n d t h e l i q u i d w i l l e r y s t a l l i s e .

H o b b y í s t ' s e l e c t r i c drill
m o u n t e d ir? drill stand

S h a r p e d g e d c o p p e r disc
-- 1 0 0 m m in d i a m e t e r

b l o b of
molten solder

Collect wire
in p l á s t i c b e a k e r

l'ig. 9 . 1 2 . A s i m p l e lee t u r e d e m o n s t r a t i o n of m e l t s p i n n i n g .
 CASF. S T U D I F . S IN P H A S F . T R A N S F O R M A T J O N S 91

high-fidelity record players. A m o r p h o u s alloys have no dislocations (you can only have
dislocations in crystals) and they are t h e r e f o r e very h a r d . B u t , exceptionally, they are
duclile too; duetile e n o u g h lo he cut using a pair of scissors. Finally, making wire direct
from molten metal is much c h e a p e r than m a k i n g it in the conventional way (which involves
casting the m o l t e n m e t a l into ingots, rolling the ingots into rod and then drawing the rod
into wire). For this r e a s o n , melt spinning is n o w being used to m a k e crystullinc wires of
ordinary alloys (like mild stcel) for r e i n f o r c i n g c c m e n t , c o n c r c t c and polymers. In fact the
melt spinning of crystallinc wire is so s t r a i g h t f o r w a r d t h a t it can be d e m o n s t r a t e d in the
lecture t h e a t r e (Fig. 9.12).

Further reading

F. F r a n k s , Hiophysti \ and Hiot hcmislry at Low Temperatures, C a m b r i d g e U n i v e r s i l y P r e s s , I <)X.S

G . J. D a v i e s . Solidifieution and Casting, A p p l i e d S c i e n c e P u b l i s h e r s , 1973.
D . A . P o n e r a n d K . H. H a s t c r l i n g , Phasc Transfunnalians in Metals and Alloys. V a n N o s l r a n d R c i n l i n k l . I9K1
M. C. l ' l c m i n g s , Solidijication l'rocessing, M c G r a w - H i l l , 1974.