Unit

!
4

SolmptcanloN & PHASB DiacRaH,t - i

s1

p
p

1.1

IN'|RODUCTION-SOLIDIFICATION

li
liquid
Soliditlcation is ihe proccss by s'lich a substance undcrgoes a phase fansfomatior orn
metals
Pure
ice
tums
to
water
state lo a solid state. IIlc process is nlost oftcn obse cd whcn
(steel' cast
(copper, alLrlninunl, iron.;tc-) solidil-vat a lixed (constanl) tempcrature, while alloys
iion,ir*s, brn-q e1..1 solidily over a range oftempcraturs- The change |ion liquid to solid does
the
not occu, all at oncc, instead, procceds through a series olevents- It is impor'tant to sludy
need to know
vadous changes lhat occLrr when a molten metal soliclifies A lew reasons for thc
about the soliditlcatiorl phenomenon arc discussed belorv

is a uselLll process. one ofthe eerliest and mosl widely used rpplications ofpropcr
just the right amouni ofctrbon oan
solidillcation came aboui rvhen steel rvas inverltcd. Lon with
ctc.' are
malte sicel' Whcn cliffercnt amounts ol.other elcments likc manganese, nickcl, cl-rron]iurl.
SteeljlsuilabLy
addcd and soliclified. steelcan be nade to have aliflcrcff lavourablc fropertics

solidiflcaiio

cooled. rakcs the ductile folm, but

\ther rapidly cooled, it iakes thc b ttlc fornl Thc

rate

ol

ri!'!c"rior'-r'
t rs l#',.-.
-r".'"*'"

p(

Whenanlaterialundergoesaphasctransl_onnation,theatomsormolcculesinthemalcrialare
.,:ar,,nsc,l. ln,,Lhcr'\i6iillliei;r-iTali]r]ga Glr] fr-Lrqtllre otthc material The clrange in
rt," ,,,'i,.tnrctLr,. rcr,rlts in clLaLrces rn til;propcrt-rtie. nlthe ntut"tial llke strengih, torigllrcss'
th c sc'lidiiication proiess suitablv' thcpropertiel cal l' altcred
H.e-Irc;,
J,,.1f

',;'-tc

q$9!!r9d.

!y!!l'l,l"iiing

ofsolidificatio olcasllngs and its colltrol furobnininS sound castings is themosi

inlportant problcm lor loundrlmen we know thal all metals shink duri gcl ngcofpl se liom

he mechenism

tle-I-d

rfi': illro rr n cchd n i\ m rs cssenljal in

tiquict rn .n]i]il stal". llence thc propcr unders tur.ling oI
jnvolve
nrc\,enlins shilkaqc. rvhich is a connnon delcct in cast pafts. .-\Vcldirrg proccsses also

importa|t lorone to knolN the mode ofsolidiflcation, as it oficrs

weallh ofinlbnration lcrr many

practicel applications.

At.)ni.alnrt is th. !)rocess uscrl conunctcnllt to Ptu h(e thc ldrgest to d(et)Jt '\dl Por'|?tj '1
strtantoJau orwoicr srtik.s tht,tulltn tu||nuteiat Lausi g il to lisitttqtdk d di tnl tulidil' k)
Jont' s kl! \iz.d panicles hotder paaiclcs)

in

st

pi

li(
b\

rh

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[Braua s14J IADUa I" 1\?t D tt .r stDlo u.t]n1!.lirtlas s11ll atDts
lDi1rD1od ui nu
"41
pttosu1t qttr\t "I[!p
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{EDua rtpull ?ql1ltr1suo s! e.nuu?dtual a.uls alaD Ddtual
atob puos puD pnblt aq u! saalDa|t
lo
pnbl 2LF
an44\ 1'.t\od 3a1za.4 stt tD luaul alld o Dltluor NoN
2wDs a\r p a1D atDls
4!oq
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si D4&4 artuDn.tuot aqr s1.tat!3111
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put sulBecl
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^q
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eql rnereq.\,! 'J lurod.{q poleclpul ss poqteol sI lulodjo o}t}s e 'sessolSod orqt sV plos
sUels
pue pmbl,4luBdjo SuUslsuoc srnlxi.u aseqd o.4dl st oloql 'uoqlpuol sq:l Ln pue '(.4&ol3 o1 ^lIed
qetsb) sezlFtsftc pFb[ eq] 'spro,{\ raqlo q trprlos o] sm8eq{.Lu plnhl oqt'g lulod.{q poprpur
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3urlooc oql Suunp sle^relul au{t snou^ le popio.ar sI p}elll eqlJo ornle.rodlual or0JI lmod
uote.grprlos ro lurod Surzoo{ oq} se u.{\orrl erntDdurol pex4 e }9 sJnarc prlos ol plnbl ulo+ e]els
er! ' (Surloor ,{\ols) suorlpuoc muqTnba l9pun ,lpllos o} po,\\olp sr leFlu arnd uow\\
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NorrvJrilrfllos

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lMaterlal Science and Metallurgv

118

It is impodart to note that, when a pure metal is cooled at a laster rate (mpidly cooled), it experiences
considerable dilllculty in commencing solidification. In such oase, liquid melt ccxlls slighilybelow
its licezing ternperature, zurd actual solidification starts at B' instead ofB. Refer figure 4.1(b).
This is known as undercooling or supercooling. Thus, undercooling can be defined as the point or
tempemturc below the normal fteezjng point a materiai wi ll stay liquid and lirthei fonns nuclei and
crystallizes wln it cools-

4.3

MECHANISM OF SOLIDIFICATION

It is intcresting to examine the mctallic grain growth and fonnation durjng the solidification process.
ln genc.al, the solidification ofa metal or alloy takes place in two stages:

.
.

Nuclcation- fomationof stabte nucleiin the meli.

Grain growth - nuclei grows to fbrm crystals rcsulting in grain structure.

a) Nucleation
When a liquid cools below its Aeezing poin! it starls to soiidify, fomling very slnall sized crystals
called nuclei. Refer figurc 4.2(a). Thc moment a crystal begins to grow is known as nucleation
and the point where it occurs is the nucleationpoint.

Crystallgraln
Crysta{

growth

(c)

Figure4.2 Mechanismofsolidification

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uec uortel.nu {slu u.le u*.toJ]o olor eq} uo Surpuc.lec
leFttl uollou 5qt 0r tuosld (srllndutr)
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Material Science and Metallurgy

120

,1.5.1 tlomogeneous Nuclation

the help ofany impurities, thcn it is known
when nucleation takes p lace in the liquid metal wiilrout
piace in
selfn'rcleation Nuclcation based on this mechanism takes

;;ffi;;;;;;il;nor

pure liquid metals only

nuclei'

the atoils needcd to foon

'
Homogencous nucleatiorl occus when the metal itseifptovides
Foranucleusto be
ofundercooling
amount
consjdemble
be
a
should
,hcre
rr*ri""* ftapp"t,ni..
A crilical sized
into a crystaL, il rnust reach a critioal size or oritical radius '
i"r,r. .nrttuiir.un
tizc such that its rate olgrowth is cqual to its mte ol

*n

#;r;;ffiilup,ii'l
i"""". Ci*"^

i'Ji".i."ri"
and disappcar.

tl or"

*ftt.-ft nrLctuate

.ir.,

probably cdtinue to grow

a sizc largcr than the critical size will
to "ot

'urr,t".turt"..

,,rr"tt"itt,-

tlle cr;tical size cal1ed emD4yo rvill mostly shrink

Significance of critical radius

kinds ofenergy chalgcs must be

two
toih" ho-og"n"ou, nucleation ofa solidirying purc metal'
consrdered: -\ ! \q6r:{ \:N
Innsri-nnarron &
trr.Hrrea'ollu'iun/releJ\e'ldurins lhe liqurd ro-(^lid
,;';.;.?f.';:"-,
sulrd surlacc ofthe crystal'
b) rhe.ud.ce encrg) reqrrrred ro lorm the npw
rra sformat;on takes place due to the
the liquid metal is unalercooled, the liqlricl-to-solid
When

givcn by the cquationl

release ofthc volume liee cnergy, which is

-----(r)

6 - II nr AC.
where r : sphcrical radius olnuclei fonned

Volune 6 cc (ncr:ly

AG" = latent heat energyrcleascd per unit voLume'

(Negatiie sign in equation (I ) indicates heal is relcased)
by thc equation:
is
The surlace energy req uired to form new crystal Siven

L, ' lnt't

where T

----(2)

Surlace cnergy / unit arca

r is givenby
Thus thc net energy change loranuclei of mdius

LG = G,+ G.

aG:

4
l,u-r46,,

'--

+4Dr1

-(3)

lrom the plot thrt' a,s the particle

A plot ofAG vcrsus radi,rs r is shc'wn in-figutc 4 _l It is clea
;Jil i'G***., the net lree energy iC also rnureases till t|e rluclcus rerchss a critical

r-"ii..,, ,.ff"*at*.trrhlunherirtrc,'cinthennniclcrJJiu'

Lhc ncL

irceenc'g1 dccrec'esand

t,".oaa, nan.r,ita. lnesL./eolthecrilicalraJluscanbeooldineLlbldife_cnlidr'rgquJ{ron

","n
(3) withr'espect to r and equatingto zlrro'

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eq r ,! snelrmr

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s/,^ e8uEqc

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Material Science and Metallurgy

12)

4.5.2

Heterogcneous Nuclcation

\\rhcn nucleation takes plece h Liquid mctal with the belp of impurities, it is known as heierogencous
purities can bcinthe fonn ofsand pafticles, alloy additions, oxides, or even the
nucleation.
surface ol_lhc mould wall (in case of castings). Such impurities lowcr the odtical liee energy
requircd to lotm a stablcnucleus and thcrebyrcduces thc amounl ol underLooling (supercooling)
needed to acluate Duclealion. The req uirement for helercgcneous nLlcleationto takcplace arc:

(a) the substrate (impurig sulface m ust be \vetted* by the liquid m cte1. Ir other words, the sudace
jt'
ofthe impurity should hold the liquid metal as il comcs ir contact widl and
(b) the liquid metalrnust solidjry casily onthe substrale.
view ofthe above requiremcnts, the anglc ofcontact () bet\\'een the substralc and the solid
metal as shown in ligu.e 4-4 is an impoilanl thcoritical conccpi in nuclcation, even though the
thcorycannot be widely used ir practice.

Figure

,1.4

Angle 0 lor hcterogenous nccleation

solidllying nucleus js considered as a sphericalcap, on a flat substrateWhen the contact angle (0) is small, mclting is high and nucieation will ocourwith srnallalnount ol'
undercooling. Tlis also mcans lhat, lhc total liee_energy change in lhc lormalion ol stable nucleus
Relerring to figure

4.,1, the

is lowel, and hcnce the criticalsize

(/)

o{ thc nucleus is smallcr

In practice, most mctals (al1oys) which conlain impurities, solidif, by heterogencous nucleation
10"C. Whcn the contactangle(e) is iarge, g.cater amountol
rvith srnall undcrcooling ofaboui

undercooling is necessary.

Nble Sonre examplcs ofpluses that may foml via hctcrogeneous n uclcation in liquids arcgaseous
bubbles, crystals orglassyrcgions- Crcationofliquid dropicts in saturalcd vapor is also chamctcrized
by nuclcation. A successlill utilization in this regerd is nin making or cloud secding, a form of
wealhcr rnodificatron using sih'er iodidc (dry ice) whioh is rclcased into the rain bcaring cloud
Siher iodide parricles sene as nucleation sites lbr thc liquid droplets to condense on them, grow
r(.\) c ^Lgn ufLrur d,'$f l_.rn llrccloLd..
Another conmon cxample ofhelcrogeneous nuclealion is ihe tbrnation ol Co, bubbles ir1 cold
drinks on insefing ar stra*', or an addition ola prncholsaltto the cold drink.

wrtinl. is the spo,kux'at.: rpt"adnry DIone phase over Lhe nL{fucc ol anatltet

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uoDEalrnN snoeuoSorrtrH

Jo dleq eql lnoqtr^\ ptetu prnbrl sqt ur

aceJd so)pl uorleelanu snoiucSotlloll

uolll:llnu

aaeld scr{q

's.rlundlur Jo cllorleqt

snoaueforalclJ

'oN

'ts

'uoqecpnu snoauaSo.Flaq pue s noeu38oruoq.lo uosuldllroa Jellq ? s^\oqs

I t alqel

NOr.rvs'rlnNsitorN!30tr3JgHs/^snosNs3OI,{OH 9't
I Lrrerberc eseLld r9 uo4ec4rprtos

ezl

Material Sclence and N,4etallurgy

124

a) Chill zone
Chill zone is the region irnmcdiately next to the mould wall. lt consists oIsmallequiaxed grains
which usually have random orientation and tbe grain size is much finer than that ofthe ccniral
equiaxcd zonc because ofthe comparati\'ely cooler surf_acc ofthe mould wall. Hcterogeneous
nucleatiorl occurs at manysites simultancously dueto the chilling effect, and grain gro$th takes
placc equally in all clirections. Ilowcver the growth is limited as the graiis impingc on d1e adjaccnt
neighbouring gr-ains, and thus thenext zone takes over.

b)

Columnarzone

The region immcdiately next to thc chilizone consists oflong, tlin, coarse grains calledcolumnar
grains. The columnar gmins grow perpcnd icular to the nrould wal1, since lare thcnnal gradients
werepresent in these direotions. Columnargrains ar nonnallydendritjc in nature

c)

Equiaxial zone

Thc last metal lo solidify is the central zone, consisting ofequiirxed grains, and hence is called
equiaxal zone. This zone being last to solidiry is a result ofrandom oientation ofnew crystals.
'[ he cf]'ects ofconstiiulionali cooling rcsult in the crystallization at the ceDtral zone wiih nucleation
ofncw crystals tllatprcvcnlthe growing ofcolunxur grains- The number ofeq uiaxed grains at the
central zone increascs as the decreasing ofthe pourjng tempcrature and iicreasing ofthe solute
comPosition.
Eou axed

)0$J*'**_

;}\

",r
n\9 i

.i.

_-N* "J4"*
.J-\r
_,*d

**

Fine equiaxed grains

\,
Figure

4.5

Cast metal structure

tr\\"*.-

Coh\iihttinal vqcrc.oliry that otcu^ tl ting salidiJicdtinn, isdue too postlianal.lnnget, ahtj
r<\rltt h t:o.lihg d Liq il be!ott lhe.li?ezinspaint ah.a.l ol e salidliqt!id, e,1dcc.

'irL'..\nlrunJ.J.1. l.))lr s_ Du'ti .r loL Jrr (r)\)1\L'q

'qt;urlls rolaaB rl1l.{\ tnq 'q?lsrx uncl ol soqladold l]]lrlrrls a^Dq s,{olltl tloilnlos prlos dltuopuu srls
al|ei 3rli,{dnrco sl?13ur :ql qloqJo stuolP cql osfl puE {olF pegrprlos aql uI rliq^ldla^r rlltr?s
aq] sr esrull llr]s,(l.5q1 splo.{\ laqlo q cdoisorrllll D$punur^c pclialsp 5qlouuuo1nq lucs'ld
ad'(l3uo uI sllns.r (,{ollu faL+Ipllos) {olfl ool]nlos prlos e 'snql
rre sletoulqloq qcrqaur
IelsIroJo
'pcLLLroJ 3^eq ol ptls sI ?toqltlos pllos
? 'sesEc r{lns Lll elEls ptlos aql o1 plnbrl aq} rulol uo4lllrlro.}suerl n.ql l.url uo^a ,{:}Illqnlos llcq}
lraqt tnptor (.{olle) slE}iul iql 'spro,{ laq}o q oslD eltis pJlos eq1
,{Ducn bes uo. pup
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ur reqto qala ul.lqnlos
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pcxrLU pue pcll6rLI slP slsloLu lusraglp o^^l ['q/d

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cl-Ios

8't

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snocuoSorsl:rl ctnpll o] (srqundul)
lJoru aq]lnoq8nonp,4lLlltoJlun slnaao uoqrclcnN uollBclanu
sluiSc 8u[?rl.nu.+o L]ouppp qSnorq]ro torEal.nu snooueSotlroqloasr. ul Slfiloo
'dnsJo]unoluD
) cql s^\oqs (q)9 t orntlJ
:3:u1e urog 8uqlnse] surur8 pal'rnbrtl!
!ll\qlllll1:l!91
clJrns plnou ploc.lollnsare 5l sLIleJS pexernbr
afll nirl erlt ul uaoqs s? ]leul oqljo rslurc aq] ]e puc}a sulr3lDuulnlor cqJ ouoz pllu'c
cqt t? uor}?rlauujo aaursqe ue sI clcr{l uaq^\ slncao 'slslclu arnd uI puno] '{lpctcl{l enlcruls
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9Zl

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asettd E uo4m[rprlos

Material Science and Metallurgy

126

4.9

TYPES OI.'SOLID SOLUTIONS

as:
Based on the tlpe of impuriry point defects lound in solid solutions, they are classified

a)

Substitutional solid solution

- Dis-ordelcd substitutional solid solution

- Ordercd substitutional solid solution

b)

Interstitial solid solution

,1.9.1 Substitutional Solid Solution

(solvent) are replaced or
substiiutional solid solution fomls when the atoms ofthc base metal
ofthetwo metals in
substituted by the atoms ofthe alloying metal (soLute)' In this case, the atoms
radius o I coPPer ]s 0 128 nm and
ttre uttuy a.. upp.o*i-ately of equal size- For exarnple, the atomic
in each another Thus'both
ttrat otnrc*ptis O.tzs nm. These hvo elements are completely solublc
(alloy)
solution
'
olthem combine to fonn motel - a substitutional solid
the order in thc suhstitution
Substitutional solid solulions are further divided into two |tpes based on

olthe two metalelencnts. TheY are:

a)

Dis-ordercd substitutional solid solulion

positioq bul arc disributed

When thc atoms ofthe alloying elcmenl (solute) do not occupy any specilic
(a), tlrc resulting
,r fandom in the lattice structure ofthe base metel (solvent) as shown in figure 4.7

randon
solid solution is callcd r-andom o( dis or(l.red subslitutiondl solid solution' This
duc to
arrangcment ofthe solute atoms (alloying elcment) takes place at higher tcmperatures
grcater thcrmal agitation.

(a) Dis-ordered substitutional

(b) Ordered substitutional solid solution

solidsolution

I
Figure4.7

Substitutional solid solution

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eurnll

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uognlos pllos leuollntlsqns peroprO (q

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uoDe3urprtos

Solidificati

Materia{ Science and Metallurgy

124

the lorverr

a) Crystal structure

llllete solubi]ity;
have the sxme crystal structtrre fL'r !o
Two or more elernents (metaLs) should
and nickel both
mto eauh othci For er.ample. loppcr
otherwise the two solutions will not mcrgc
hrve FCC structure, and combine to form norel'

aluminum

dissolves 5

Table 4.2 s

completes

b) Atomic size
Iorcomnietcsolubilityoftwoclemenis,theyshouldhaVcJpploximatcl)thcsmrcatomicradius'
copocr hd\in,'.

';."

l''l

:; t #,,"i"'.,.aiu"r"''ro

no'

l ''r'- bv rr'rrc th rn l5'" lorc\dmn'(

ickel.*hirhhr,onatomicradru-nlol)<ttryto

^,,","lr.l.oi"..,u.,,d,r/conbinc.with
lormmo,?el.Howe\,er,whcnthesizerliflereneeLsnloruthanl5o,.onl}hmitct]sotuhrlitywiLlbe
obtaincd.

c) Chemicnl affinity factor

lhc)lerdtofunnrnirrtenncdratcpla'<+lor
Whenrh<cheniealIlllniryol \\o'ne'J15 l'gred'
sub'riLuliorrdlsnLid su'LliL'n lo lonn'
ut'.t.*f),"...0"*O 'tittt' '*n 'nra '"'"'i'"t Hcrcc ihraotll.rrGenerallv' the faflher apart the

't1i:ffi.;;;;;;'";ja
"i.,"."* "..

ilu

aff'nirv fnr each

1o*
"hen'ical
allldty'
i"ift" o".iodic ublc, thc grcalcris their chenical

d) Eltclro-ncgalivil )

galn an
lt describes the tendency of an atom to
Electro-negativityl is the affinity lor electrons
negativity- For
ntost haue approximately the samc electro
'[
electron. he atoms (}1 tn" too "t"nr.ns
g'
(copper and
ani imt otni"let is t and thc two
example, the clectro-nguduit) nt topp"t ';1t
great dili'erences in lectro_negativiry ofthe
nickel) form subshtutlonal soLrcl solutrorr. However'
phase rather than a solid sohriion
ags the lornration oIinten'iiiate
il::i#;. -i;;r

c) valcncc factor
clement should bc the scrne;
The valencyl ofbase metal and the alloying

othc

rqc,lhc valence

4.tt

PU

Before getti

term phasc.
example, ar
phase (wate

oi intemedietc pLlase rather ihan solid solution

electron differcnce encuu.ug". tlt" ln.tnuti,n
oflower valcnce metal' whereas'
uatJnc" can dit"'lu" o"ly a small amount

donotfonr
a2 phasesy

on tlrc
ow14'pe of ctvsul LdttLe fiichrdilfLts li

the liquid wi

il"""'i, " -"i"i"r;*rt

*

t
a'*-i"""""U"a
onP"''r

J 1ld|nry nei
Cij'stals Jonle(l b) vatrcu\ elenent''
itxeiietliite phases ot intenrcdxnc &npound
c^"\tal latn:es of t|rc
e
trn"t a btixLe a hence ate tes'\ pt"JerLd lot siuen"'l
hi qenen! intetntetliat co"po"a' oa o t'
't
prekftdfin
d?
conpaututs
',:,"iii'iil",'i"
il"vwe| intenne'liate
i'",t1"

ii"'i"

,.i,-i",a

'I- rldrAt'Ihl

"'t;a
,n"'""'''ri"',"t';'

. ,,-,, "0,' ,,"i',",,^

:,!':f:^i.::i'"'a
tr"alotuttar
i1; u r'"'' "t - tta"'a"tat'"a:h L'ttt'
"
'o,
dn eletttun Atoi6 r'ith,alnbst to Pk'teb'
gdit
ofan at''n ta
Etcctro ,cCatiri4, l.scribcs nP knllencv

llti:;;;,;;;:;;;;;;'t"""t'

sr:t'zaschto'li'lte'ures,onetietectro^esativean(treulliha'cePtetc'chons
und have low

H{glfer. ulonls iilh ]P||br

electro-negatiriry'

".0,r,',,,",

i";"i",

',,;;"

sotlum

rc;lily

gile up elactrons

+vollnreklhenthefofel!.lftnsinlhealerslr}dpenewlewl'E'atnPte,|ofn]aglnlhnlls:2s)
rtua ' 't" t
',":';. ,,';,.:
, .",'"'*'- ,' i''o ; j1' "t n'' t th' 'l' "''"'''
-,,, , ,"h\,4t rt'ohbt rttanAithoth ' 'frt11\
i",t,, ,,t.,,,,.,, t
".".,,

phascs, becz

Consider a

ft
diillrcnt t

solution is
in

read ily in

air

general, a

distinctive c
composition.

Procccding l
phases prese

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