!
4
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
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$9!!r9d.
!y!!l'l,l"iiing
he mechenism
tle-I-d
practicel applications.
At.)ni.alnrt is th. !)rocess uscrl conunctcnllt to Ptu h(e thc ldrgest to d(et)Jt '\dl Por'|?tj '1
strtantoJau orwoicr srtik.s tht,tulltn tu||nuteiat Lausi g il to lisitttqtdk d di tnl tulidil' k)
Jont' s kl! \iz.d panicles hotder paaiclcs)
in
st
pi
li(
b\
rh
tu^nllo tDaq ruatol 2tl1 sD tuaq sr aP$ p@s puD Pnb! dry aa\Qq Bbu)
[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
otu s.a d@splnblt ttl ttuotD zaet"q eruolslp sn ptpsJopyt uDL? -oq8n! s1 /8)aua
tolt apdy1 ptl1bl {o asDr uI l,&aua tDl4apd ul aauahlllp tuDrllil!'ls st a|t luq 'auDs aql ?q ls tu
{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
P!|os
PtD
,t1raua puuapd 4ayt s! DpaB
$.oua) swotD u.a pq D DlJ^1p
aLtt sruolo
"ry
o1 znP
ary alP.1Dt?1sIP D! )"4p a10 uo i&2u2lDauapd e^lt.D alou a' suolD puD tltuaua )ryuy.t|)qt
uottlunJD {lt!r^'\t puD , \atu .tuntn ,tlt 4)11tM
si D4&4 artuDn.tuot aqr s1.tat!3111
"lnlDtaduatltr
tu paads aq ot patopi sr [4raua ruauyEtatz touxzlod puD )1]au11 4ttrq a^Dq pualD t D ur sxalr'
'o.rnFraduel uroor qtear ol sloo. slBloLupllos eql'(olJlurod LtlorC slsleftc Bultlprlos oql
put sulBecl
*uorsluJo leerl eplJo uoqnlo^a 3q1Jo esneteq 'olnt?rodttle] luelsuoc 1e s4elduroc
^q
uoqsaurprlos'Jlrllod]ssclaldlooauoDszlielsfuctsplo,tr.Jaq]oul p{os ol peue uoc^loguo sI pnbll
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
se erntEleallllal]eFcrupd 3lV Suqooo uodn t]]eLllodns sI dn Sunr8 s els pleul prnbl oql lurod
omleredurtl suunod eql stucseldar s-^rnc eql uo V lnod aq] '(t) l t eln8g ol Suul6fox
srql
^u
sl t
e^l
'I1
lso
'ss
ule
EJ
lV
JO
.{l
ltc
ou!1
red
o".r.,e
surere Ll
oq
sso
lse
slel
pln
lsso.ord
I t eln8u ur u^\oqs se po[IEtqo eq,{Bur o^rna Sutlooc e
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\\
"
Jo e8ueqo
lv.r..qr r sund.{o
NorrvJrilrfllos
| - uier6erc aseqd
Ll I
z't
uoqe34!prros
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:
.
.
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
'ulol]q
possnasrp clE
NOIJVtr'IJn
JO SI^JHO.'l
9't
'elq?nsanlR sr q.q^\'sPtatrl ur
serUcdord .rdolosrup ol speel uoqullrplos n oJrun-uoii fqpejnpo:lehro$s{*L{e.-o-roJrun -uoLL .1lJ
'eru.r.lJ4) l".uorlrsodluo. p.ol r ur 3lr!lnaei .suolSar .rauui crp uriolpoqlreqFro$sfdtuo.-iiitaJr p c
s,rEqiouolxc rqt ulo{ polluol slulu ol puop oqf }ucurale elnlProdlu:rl SuqFlu reqftq aql]o olollr
umlaj ol sre,{ul rouelxa eql sasnur SuuoJ Joualul oqt uBqt lctsEJ ueplllq ol llruclBtu erp.+oJollalxo
eqt sasnla srql ,{lprdur loor oj p.,ro1p sr 1c1eui pclreq e uaq,r iLredduq uorlefs:Fci..r1 rpu.p
rdE-uuoJ slqsfuc ozrs {lpuls ur sllnser qo[],\\ '8urloo. ]$rJ auros pue .slslsfu. .SjEI rII slnser qcrq,\\
'6urloor,rols olrnbel sese. urct]oJ pruuoJ (suel8) slels,{l] ctltJo ezrs eqt u uorlEulr^ Sursne.
lllJaleul e lll ql,roj8 rnpri pue uoqEclJnu sa.rallgur aa!ld sclpl uoqeag{prlos LI.rqI\lu llPJ eqf
DNIdO) t'l
r,'-' trq ILrr srr. ,tr (rr-nJ lt.lo l^ttl-. ttrJ \uoJ tJ.l8 q e )q \ll,\t.rr,.q | .s:r.rcfrrrnq r rrjF
^.
\ll Duri .l;i,gr.
gl'li.
pr
o j prn6rlE;i-E
rlP.I9|ll.cl:9l
tos
f rplr:1: Lr surorc l, r .t r \ ln or.roq
lqli-u9.1.
I'rr.n.\.tt rurfl)nrt\{ctL'qcLJuurpi:rrllcl'\r\.uo'tr|('p'
eot\.'ealc..ll ,uJ!ed ucr.i '1!Jr)rLI. r \\orl. tu l
op qtrll,a\ 'serlmdlur s q.ns'ertt:tcJ e.loUud lou el? teql sluclDlu,{q pauroJ el]l scuEpunoqrq.L
'qr}?tusru.lo uorter ! st 'Flupunoq urprF eqt s0 u^\ou)l15etrl sFls,{lc qrrq,r Suole roft iqJ ,trrrv
'aues oql ulP'rxal arnlcnlls arurolP neql la
:uollplue o pu cz s lu3J3+lrl
^,\\oq
srq urBr3 ro Jt$,fu qcea (a)Z telnSrj ur rr,roqs s! prltlro.I sr ,ir?p[noa] ur8li e ,.Ilpuop Bur,\\olt
luarelpD eq]Ilocln sc8rndufi e puop ouo urq,&,{ euq pue 1L]s,tla qaeo ur suortmnpltora-llrp ,{\or8
rtrjpuap st u,\\oul si put .oiuplpodde o)rl oerl .rlsuJl.plrqa e ol cs s:^r8 slll-L
sclBpu.p
oql
'Isls,{J. flluo scx! .r 6uol!,{llBnsn 'suoq)alp p:raIr rd urCUJJ ut sr^l)sur:qt ButqJet}e surole
aqt 'suorsucuflp oarql ur scnuquoo q1,nol3 F1s {lJ lq )Z t :fiiu LI u \\uqs sc tlrl.L pLn!]!] rlt nro{
\.u^ruJouJrrprll?Jrl,(q.rorF.nr1'nrqrr:lurror.aqrl.rJ,Jnut.rulrn3rJ'lrnu?rrr."r,;
()1
qtuoJi luts,&J (q
uortc, r{(lrr)rlurtrot irrrr:.'.nrre:p, g'qi..
e^!q qrq,r 'lolcnu eseq.l. .ril.nu str u.roll)l ere pur piiu u.1pur e4 ur ser-jd
F.ra,res 1u peuuql
.rp sruoie t-Z punore ,(ll nsn 'sutot Jo lalsnla litttsV -tlleiJt rcc,\lags?noq aallrott8LrrqsrtqEts.
:curqlolpDi oiiisdla BuiLuor suole ur slln.se.r sri1y,{--rsu-rollt csol .sruata.ucrl p-u*.s".;Jp
.suoqrsod pax4
' elnirjcdmotSjaqnoc
rcqt ulo{,{l.erl c our o} su;tr; cqt tmsnpc
ietaru-.--prnb11-eq1s\'
uelolq eqlf,^\ sruolp orJt uoa,,!\trq puoq cqt pue ,,{15!nspar.ur aluqI^
prnbll oql uI sluo}t all}
tlrlu
01 iultsorollrr,lla sr tl
'sernlerrdtuet roLISq
tV
leFLLr uctlolrl
oln
6Lt
^\ou)
120
;;ffi;;;;;;il;nor
nuclei'
*n
#;r;;ffiilup,ii'l
i"""". Ci*"^
i'Ji".i."ri"
and disappcar.
tl or"
*ftt.-ft nrLctuate
.ir.,
'urr,t".turt"..
,,rr"tt"itt,-
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
-----(r)
6 - II nr AC.
where r : sphcrical radius olnuclei fonned
Volune 6 cc (ncr:ly
L, ' lnt't
where T
----(2)
r is givenby
Thus thc net energy change loranuclei of mdius
LG = G,+ G.
aG:
4
l,u-r46,,
'--
+4Dr1
-(3)
r-"ii..,, ,.ff"*at*.trrhlunherirtrc,'cinthennniclcrJJiu'
Lhc ncL
irceenc'g1 dccrec'esand
.lcvt
Il.-l!'
t^?l
!-("cv)s :
llrqt
I'rvl
tVl
lx
-.\^z)n
,{q poqlelqo
{I)V}
=DV
eqJ
'Jedd?sslp lo lultqs ,4llsour I IL{{ '3sie ',{3]oue e3{ sI StnsEoJaaP dq .44016 01 anuquo' Pue
eql 'Cl) sruper itquc aqt ueql loleer8 $ (-r) snelsnu oqlJo oLl s eql ueq.\\ snqJ
eq r ,! snelrmr
ralcnuio snrper
s/,^ e8uEqc
"9V:J:t.
"
Lz
bv
:J
LZ
g
=A.ug +^ggr.nttr =
('r,'ur+
c \r,
^wfl:-)v:
tzl
tDv)v
|
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
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
(/)
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,'$f l_.rn llrccloLd..
Another conmon cxample ofhelcrogeneous nuclealion is ihe tbrnation ol Co, bubbles ir1 cold
drinks on insefing ar stra*', or an addition ola prncholsaltto the cold drink.
wrtinl. is the spo,kux'at.: rpt"adnry DIone phase over Lhe nL{fucc ol anatltet
aflDtnsralr
o]
'r!.r
111\t
e.i
r9
rlll
(lln
EUL-i
otdlatro!.bl
sn tDualtna,rl
JoEu!ub
-(Sulllrts 'uorlio^uo. 3 .) suol]lpuoa Suqsm pue '(peq cllbods ',{I^q.ngroa letuaql eldruuxo)
ploul '(,dlrlrcllr uorteolarnu 'arnlPledurr] Suunocl 'uo4lsoduro. rldlutxo) sPlrePur oL0 uo spurdcp
sernl.Iuls loSur ur solloz.seqtJo tuclxo pu! eau.serd eqJ pixernb3.,{ lU sl rlnlcnrls eql's{olle
LunurLullf] auros uI -rPulunloa {llnJ ue$o sr crnlcruls oql'eldru?xc lol 'loois sseiurcls ul luasqe
sr s3uo7 oqlJorsrllolru ro cuo:ra^o^\oq 'ueuo clot\'leols,{o P .'!\ol lo uoqJto urcld ul{lltlaedse
'sleuapu lerJo slo8lrts8urlslcrn uees srlllqoLllos a.D seuoz pcuolllrolu.^oqr lql.Jo 00.q1IJV aloN
SurlooJradns lEuoltntllsuo. -ouoz Flrcrnba .
rl]^\of crlup[3p euoz reu1un]o] .
illqJ .
ql.^\orS puE uollDrlinu - euoz
:orp seuoz cerql
eqf
scdrlqs
pue sazs Ilr}sf,$Jo ]llatoeSucJlr ansualaejEqa n Sutdolo,\sp euoz qaea qll{\ '9 t crn;I u ll{\oqs se
crntanls eqtur reeddlr siuoz a]?rEdes 3arql'/glpllos 01pc,,\\ollP $ (3uUs!a) 1o,3rrl ulr ucqlA sloiur
esrqljo,{t!Fnb rqt uo pucdap l.npold ltul} ot}Jo srucdold eqf sllelu plnbll tuoll is?. 5lE
qaq,r '*stoSur Luo! p..npord r! suole.Jldde EuuoeulSuo ro.J PcrnpoJd sFelqo llloul eqUo lsol l
gunJlm ,s'IvJsl'{Jsv)
uotleclcnu snoeuafrol.l.q puc sno3UsSor.uoqlo
uosucdruoJ
l't
L'n
JJqaI
'
fo lunorllu
poqtour srrlt
{q.!rprlos s.{olll]/sltrst\l
't
a
'srlllndun,{ul]
qlra
uogralrnN snocurSouroH
uoDEalrnN snoeuoSorrtrH
uolll:llnu
aaeld scr{q
's.rlundlur Jo cllorleqt
snoaueforalclJ
'oN
'ts
I t alqel
NOr.rvs'rlnNsitorN!30tr3JgHs/^snosNs3OI,{OH 9't
I Lrrerberc eseLld r9 uo4ec4rprtos
ezl
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
**
\,
Figure
4.5
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.
^l6ioldruo.
sNolrn'ros
cl-Ios
8't
9Zl
ureroe
asettd E uo4m[rprlos
126
4.9
as:
Based on the tlpe of impuriry point defects lound in solid solutions, they are classified
a)
b)
a)
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.
solidsolution
I
Figure4.7
uourulloj aql
:err,{eqf
-uoqnlos
lEuollntltsqnsJo
ur stuoluslc 8uL{olie]o eJroqi aqt Lu3^o3 1Dql solm lror.rdluo P.uLroJ s.q ,t5q}o}J
eurnll
'uoDnlospqoseLLUoJllr^\leqts.{n.Ia8tll{oll9cql]ouoruodordpue3d,{]aqllna.roqrrrdoldr
olulu ol Frlrlcssc
sr
I'siluadod !q]o
3'rnu s,,\dsHJou
sr'{ntl
0I
'(q) l i srntg.reJ.U uol]nlos prlos lrl]I}s]rctur Lruol LroI pue uog?c alrq,\\ 'uor]qos pilos
LLUoJ uorr puE 5$uBSuEur'(&/?r
lI0
0
= sn rpE-r arllrol!) lroqm prltr (&/, zl i 0 = s psr
rol
tZl -
lp.uotnttsqns
(q)
(e)
(rLallrotl 6u
uu zt t'o
lotV
snrpeu
uorlnlos pllos
lBpBsrotq z t't
LZL
luerOero eseq,l
uoDe3urprtos
Solidificati
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'
^,,","lr.l.oi"..,u.,,d,r/conbinc.with
lormmo,?el.Howe\,er,whcnthesizerliflereneeLsnloruthanl5o,.onl}hmitct]sotuhrlitywiLlbe
obtaincd.
't1i:ffi.;;;;;;'";ja
"i.,"."* "..
ilu
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
'[
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g'
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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
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clement should bc the scrne;
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