Chuyn pha

chng 3: to mm v pht trin mm

Bin son: PGS. Nguyn Hng HI
HBK H ni
Xt mt phn th tch pha lng nhit AT thp hn T
m
vi nng lng
t do G
1
G
1
= (V
S
+ V
L
) G
V
L
Nu mt s nguyn t trong pha lng
cng sp xp li hnh thnh pha rn
c dng cu, th nng lng t do ca
h chuyn thnh G
2
:
G
2
= V
S
G
v
S
+ V
L
G
V
L
+ A
SL

SL
AG = G
2
G
1
= -V
S
AG
V
+ A
SL

SL
(3.1)
AG
V
= G
V
L
- G
V
S
Liquid
b) Solid
G
2
= G
1
+ AG
m
V
V
T
T L
G
A
= A
Nu pha rn c dng cu bn knh r
th phng trnh 3.1 s tr thnh:
SL V r
r G r G t t
2 3
4
3
4
+ A = A
Liquid
a)
G
1
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
Nh vy, s hnh thnh cc phn t rn
lun lm tng nng lng t do.
S tng nng lng t do khin cho
pha lng c th tn ti trng thi gi
n nh nhit thp hn T
m
.
Vi mt qu ngui nht nh th bn
knh ti hn r* ng vi s tng ti a
nng lng t do.
Nu r < r* h thng c th gim bt
nng lng t do ca mnh bng cch
ha tan tr li pha rn
Khi r > r* (mm) nng lng t do ca
h s gim nu pha rn pht trin.
SL V r
r G r G t t
2 3
4
3
4
+ A = A
Chuyn pha
Khi r = r* , dG = 0, mm ti hn s
trng thi cn bng khng bn vng
(unstable) vi pha lng xung quanh
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
Bng cch ly vi phn phng trnh
SL V r
r G r G t t
2 3
4
3
4
+ A = A
( )
2
3
3
16
*
V
SL
G
G
A
= A
t
Th vo cc pt trn:
m
V
V
T
T L
G
A
= A
( ) T L
T
r
v
m SL
A
|
|
.
|

\
|
=
1 2
*

( )
2 2
2 3
1
3
16
*
T
L
T
G
v
m SL
A
|
|
.
|

\
|
= A
t
V
SL
G
r
A
=
2
*
G
V
L
AT
AG
V
G
V
S
2/r*
r =
r = r*
T
T
m
G
V
Tmr* v AG* nh th no?
Chuyn pha
V nhit nng chy pha lng c th tch ln hn pha
rn 2-4% nn cc nguyn t trong pha lng c th
chuyn ng t do hn v c th to ra cc cm nguyn
t xp cht (embryos) c sp xp nguyn t ging nh
trong pha rn .
S cc cm hnh cu vi bn knh r c th c tnh theo cng thc:
|
.
|

\
|
A
=
kT
G
n n
r
r
exp
0
n
0
: tng s nguyn t trong h
AG
r
: s tng nng lng t do do s hnh thnh
cmnguyn t
k : hng s Boltzmanns.
n
r
gimtheo hm m ca AG
r
: th d trong 1 mm
3
ng nguyn cht
nhit nng chy ca n (~10
20
nguyn t ) trung bnh c
~ 10
14
cm ng knh of 0.3 nm (i.e. ~ 10 nguyn t)
~ 10 cmng knh of 0.6 nm (i.e. ~ 60 nguyn t)
Kch thc ln nht ca cml khong 100 nguyn t.
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
Khi qu ngui nh, r* s l rt ln n mc
khng c kh nng hnh thnh cc mmn nh
( )
2 2
2
1
3
2
*
T
L
T
r
v
m SL
A
|
|
.
|

\
|
=

Khi AT tng r* and AG* gim
Khi qu ngui tng n AT
N
hoc
ln hn s c c hi tt mt s
cmt gi tr r* v pht trin thnh
cc phn t rn bn vng.
Nhng trc khi tr thnh cc mm
bn vng cc cm tinh th phi vt
qua hng ro nng lng t l vi
exp (-AG*/kT).
Nh vy, s to mmch c th xy
ra khi AG* gim xung di mt gi tr
ti hn no (~ 78 kT)
Chuyn pha
r*
0 AT
N
+ AT
r
r
max
-
( )
2 2
2 3
1
3
16
*
T L
T
G
v
m SL
A
|
|
.
|

\
|
= A
t
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
Th d: Tnh kch thc ti hn v s lng nguyn t Cu trong mt
mmni sinh, bit:
AT
(Cu)
= 236
0
C T
m
(Cu)
= 1085 + 273 = 1358 K
o
sl
(Cu)
= 177.10
-7
J/cm
2
AH
f
(Cu)
= 1628 J/cm
3
Li gii:
V
SL
G
r
A
=
2
*
m
V
V
T
T L
G
A
= A
T H
T
T L
T
r
f
m SL
V
m SL
A A
=
A
=
2 2
*
cm r
8
7
10 . 51 , 12
236 . 1628
1358 . 10 . 177 . 2
*

= =
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
Ta hy tnh s nguyn t trong mm ni trn
Cu c mng FCC vi thng s mng a
0
= 0,3615 nm = 3,615 x 10
-8
cm
Nh vy th tch ca mt c s s l: V
c s
= (3,615.10
-8
)
3
= 47,24.10
-24
cm
3
Th tch ca mm V
r0
= 4tr
3
/3 = 4.3,14.(12,51.10
-8
) /3 = 8200.10
-24
cm
3
S c s trong mt mm: 8200.10
-24
/47,24.10
-24
= 174
V trong mi c s mng FCC c 4 nguyn t, nn s nguyn t trong
mms l 4 X 174 = 696
Lu : trong cc tnh ton ni trn ta gi thit rng mm, cha khong
vi trm nguyn t, vn c cc tnh cht ca vt liu khi. iu ny khng
hon ton chnh xc v l mt im yu ca thuyt to mm kinh in
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
S lng cc cm tinh
th c th t kch thc
ti hn c tnh theo
cng thc
Tc to mm ng th
|
.
|

\
|
A
=
kT
G
n n
r
r
exp
0
|
|
.
|

\
| A
=
kT
G
C C
*
hom
0
exp *
clusters m
-3
C
0
l s nguyn t trn mt n v th tch, ~10
29
ng.t m
-3
.
|
|
.
|

\
| A
=
kT
G
C f N
*
hom
0 0 hom
exp
Tc to mmtrung bnh (1 mmcm
-3
s
-1
)
t c khi AG* ~ 78 kT
0 AT
N
AT
N
hom
qu ngui ti hn cho qu trnh to
mmng th , AT
N
, l khong ~0.2 T
m
i vi a s kim loi (i.e. ~ 200 K).
Lmth no
gim AT
N
?
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
S thm 1 nguyn t vo mi cmnh vy s
lmchng tr thnh mmn nh v, nu iu
xy ra vi tn s f
0
(~10
11
) , th tc to
mmng th c th c tnh theo cng
thc:
S ln ln ca mm sau khi hnh thnh chu nh hng ca cc yu t sau:
ng hc qu trnh lin kt nguyn t
tnh thm t
s khuch tn nhit v cht
Vai tr ca ng hc qu trnh lin kt nguyn t:
L quan trng trong trng hp vt th ng c theo kiu tinh th c b
mt r rng (in hnh cho phi kim loi hoc kim)
Nu cht c trng bi s ln ln ca mm theo kiu khng c b mt
r rng (in hnh cho kim loi), c th gi thit rng ng hc qu trnh
vn chuyn nguyn t t cht lng n tinh th nhanh ti mc chng c
th b b qua.
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
Qu trnh to mms d dng hn khi qu
ngui nh nu nng lng b mt
SL
gim.
( )
2
3
3
16
*
V
SL
G
G
A
= A
t
Cch n gin nht t c iu
mt cch c hiu qu l khi cc mm
tip xc vi thnh khun
Vi mt th tch pha rn nh th
nng lng mt phn cch ca h s
gimthiu nu nh mm c dng chm
cu vi gc thm t u c xc nh
bi cn bng ng sut ti imgp
nhau ca 3 pha (lng, rn, thnh khun):

ML
=
SM
+
SL
cosu
cosu = (
ML
-
SM
) /
SL
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.1. Tommngth
To mm ng th AG
hom
= -V
S
AG
V
+ A
SL

SL
Phng trnh trn c th c vit
li vi s c mt ca gc thm t
u v bn knh chm cu r nh sau:
( ) u t t S r G r G
SL V het
)
`

+ A = A
2 3
4
3
4
( )
( )( )
4
cos 1 cos 2
2
u u
u
+
= S
Chuyn pha
AG
het
= - V
S
AG
V
+ A
SL

SL
+ A
SM

SM
- A
SM

ML
V
S
: th tch chm cu,
A
SL
v A
SM
: din tch mt phn cch
rn/lng v rn/khun.
To mm d th
Liquid
Solid
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.2. Tommd th
Bng cch ly vi phn phng trnh:
V
SL
G
r
A
=
2
*
( ) u
t
S
G
G
V
SL
2
3
3
16
*
A
= A
Ging trng
hp to mm
ng th
Chuyn pha
Lu :
1. Hng ro nng lng i vi qu trnh to mm d th,
AG*
het
, nh hn so vi trng hp to mmng th,
AG*
hom
, mt i lng bng hm hnh dng S(u):
AG*
het
= AG*
hom
S(u)
u =10
0
, S(u) ~ 10
-4
u =30
0
, S(u) = 0.02
u =90
0
, S(u) = 0.5
2. Bn knh ti hn ca mmca hai trng hp l nh
nhau v ch ph thuc vo qu ngui.
( )
( )( )
4
cos 1 cos 2
2
u u
u
+
= S
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.2. Tommd th
( ) u t t S r G r G
SL V het
)
`

+ A = A
2 3
4
3
4
Gi thit rng gi tr ti hn ca AG*
l 78 kT, c th thy rng qu trnh
to mm d th c th xy ra
qu ngui nh hn nhiu so vi
trng hp to mm ng th.
Tc to mm d th (theo th tch):
|
|
.
|

\
| A
=
kT
G
C f N
het
heter
*
1 1
exp
C
1
l s lng nguyn t tip
xc vi cc v tr to mm d th
trn mt n v th tch pha lng.
|
|
.
|

\
| A
=
kT
G
C f N
*
hom
0 0 hom
exp
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.2. Tommd th
Thnh khun c th
cung cp nhiu v tr to
mmd th tt
Qu trnh to mmd th ti
cc vt nt trn thnh
khun c th xy ra
qu ngui rt nh, tuy nhin
cc vt nt ch c th c
hiu qu to mmnu
m ca n bng hoc ln
hn r*.
CHNG 3. TO MM V PHT TRIN MM
3.1. TO MM NG TH V D TH
3.1.2. Tommd th
Nh bit c hai dng mt phn cch
rn-lng chnh:
b mt m nhp nh mc nguyn t
hay cn gi l mt khuch tn thng i
lin vi kim loi
v mt nt nhn phng mc nguyn t
thng xy ra vi cc h phi kim.
Do s khc nhau v cu trc nguyn t
nn hai b mt ny thng pht trin theo
nhng cch khc nhau:
B mt m pht trin theo cch lin tc
(continuous growth)
B mt nt pht trin cnh (lateral growth)
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
S pht trin (dch chuyn) ca mt phn cch rn - lng c th
c xem xt mt cch tng t s dch chuyn ca bin gii
ht gc rng ngu nhin, song mt trong hai ht c thay th
bi pha lng .
Nng lng t do ca mi
nguyn t khi i qua mt phn
cch S/L thay i nh ch ra
hnh bn
Hng ro nng lng kch hot (activation energy barrier)
AG* (AG
a
) cng tng t nh trng hp
khuch tn trong pha lng
Lc iu khin qu trnh ng c, AG, c tnh theo cng thc
i
m
T
T
L
G A = A
( )
2
3
3
16
*
V
SL
G
G
A
= A
t
Chuyn pha
AG
a
AG
o
Solid Liquid
0
Free
energy
G
Distance
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.1. Pht trinlintc
Tc ng c c th c xc nh
theo cng thc:
v = k
1
AT
i
k
1
l i lng c trng cho linh
ng ca bin v c gi tr kh cao: tc
ng c bnh thng c th t
c vi qu ngui ca mt phn
cch, AT
i
, ch l vi phn .
Bi vy trong mt s trng hp AT
i
c th
c b qua v mt phn cch S/L c coi
l c nhit nng chy cn bng.
Ni cch khc qu trnh ng c ca kim loi thng l mt qu trnh c kim
sot bi khuch tn (khuch tn nhit i vi kim loi nguyn cht v khuch tn
cht i vi hp kim).
Nh vy c th cho rng nguyn t c th c lin kt bt c v tr no trn pha
rn v qu trnh c gi l pht trin lin tc (continuous growth).
Chuyn pha
AT
i
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.1. Pht trinlintc
Cc loi vt liu c entropy nng chy cao thng to ra b mt nhn
phng mc nguyn t v xt cht.
o = AS
f
/ R
o ~ 0,3 o ~ 2 o >> 2
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.2. Pht trincnh
Xc sut mt nguyn t bm c
vo g, cnh ln hn nhiu so vi
nguyn t bm trn mt phng .
Do cc bc v g cnh l cc khu vc
khng cn bng (non-equilibrium) ca
mt phn cch, nn qu trnh pht trin
s rt ph thuc vo vic cc bc v g
cnh xut hin tn ti nh th no.
V c bn c 3 cch khc nhau to ra
cc bc v g cnh:
i) To mm trn b mt
ii) Pht trin kiu xon c
iii) Bin gii song tinh
Mt nguyn t bm
vo bc (L) ch to
thm2 mi lin kt b
ph v .
Ti gc g (J) khng
to thm mi lin kt
b ph v no
Chuyn pha
Mt nguyn t bm trn mt phng
to thm 4 mi lin kt b ph v
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.2. Pht trincnh
To mm trn b mt
Mt khi hnh thnh a c th nhanh chng pht trin trn b mt v tc
pht trin theo hng vung gc vi b mt s chu nh hng quyt nh bi
tc to mm trn b mt v:
v exp (- k
2
/ AT
i
) k
2
l h s xt ti nhp nh b mt.
C ch ny khng c hiu qu khi qu ngui nh v r* rt ln.
Chuyn pha
Mt nguyn t n bm trn mt b mt
pha rn phng s khng n nh v c
xu hng quay tr li pha lng.
Tuy nhin nu mt s lng ln
cc nguyn t c th cng lin kt
vi pha rn di dng a th chng
c xu hng t n nh v c th
pht trin.
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.2. Pht trincnh
Nu pha rn cha cc lch c ct vi mt phn
cch S/L th vn to ra cc bc hoc g cnh
mi s c gim nh.
Xt lch xon trn b mt mt tinh th hon ho.
Pht trin kiu xon c
Vic b sung cc nguyn t vo g cnh s
lmn quay xung quanh imm lch hin ra,
tc l g cnh khng bao gi thot khi mt
phn cch.
Kt qu l khi tinh th pht trin g cnh s tr
thnh xon c.
Trng thi n nh t c khi vng xon quay vi mt vn tc gc khng i.
Trong trng hp pht trin kiu xon c tc pht trin trung bnh v v qu
ngui ca mt phn cch AT
i
quan h vi nhau theo biu thc:
V = k
3
( AT
i
)
2
k
3
l h s xt ti tnh cht ca vt liu.
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.2. Pht trincnh
Pht trin trn bin gii song tinh Mt
ngun cung cp g bc thng xuyn khc
l trng hp hai ht c nh hng khc
nhau tip xc vi nhau.
Tc pht trin trong cc
trng hp pht trin lin tc v
pht trin cnh.
Vi mt tc pht trin nh
ca pha rn th qu ngui cn
thit ca mt phn cch l nh
nht trong trng hp pht trin
lin tc vi b mt g gh.
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.2. Pht trincnh
Trong kim loi nguyn cht qu trnh ng c c kim sot bi tc
truyn n nhit kt tinh ra ngoi t mt phn cch S/L bng dn nhit.
S dn nhit c th c thc hin qua pha rn hoc pha lng ty thuc
vo gradient nhit mt phn cch;
Cn bng nhit nh sau:

S
G
S
=
L
G
L
+ vL
V
(Fourier low: q = - G)
: h s dn nhit,
G: gradient nhit (dT/dx),
v : tc pht trin ca mt mt phn cch S/L phng v pha pha lng qu
nhit,
L
V
: n nhit kt tinh trn mt n v th tch.
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
Trng hp 1: pha rn pht trin v pha pha lng qu
nhit (gradient nhit dng) a)
Mt phn cch S/L phng c th c hnh thnh v n
nh b)
Gi s rng mt s pht trin nhanh cc b no s to
ra mt imli trn mt phn cch c)
Gradient nhit trong pha lng ngay trc phn li ra
s tng trong khi gradient nhit trong pha rn gim
Kt qu l nhiu nhit hn s c truyn n phn li
v t nhit hn c truyn i t n
H qu l tc pht trin ca phn li b chmli
chmhn so vi tc pht trin ca phn phng v
phn li s bin mt.
Mt phn cc S/L s lun phng v n nh.
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
Trng hp 2: pha rn pht trin v phi pha lng
b qu ngui (gradient nhit m trong pha lng)
Nhit c truyn i t phn li d dng hn so
vi cc phn phng xung quanh.
iu cho php phn li pht trin nhanh hn
Mt phn cch pht trin v phi pha lng qu
ngui nh vy v bn cht l khng n nh.
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
Mt phn t rn hnh cu ban u
nh vy s pht trin cc nhnh
theo nhiu hng. Hnh dng
ca pha rn c gi l nhnh
cy (dendrite).
Nhnh cy trong kim loi nguyn
cht gl nhnh cy nhit phn
bit chng vi nhnh cy trong
hp kim (nhnh cy nng ).
Chuyn pha
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
M hnh chp ca mt nhnh cy u trc ang pht trin v pha kim loi
lng b qu ngui.
Gi s pha rn l ng nhit (G
S
= 0) v G
L
gn bng AT
C
/ r
AT
C
l qu ngui trng thi, tc l
lch gia nhit mt phn cch (T
i
) v
nhit ca pha lng b qu ngui xa
nhnh cy (T

)
r
T
L L
G
v
C
V
L
V
L L
A
~

= .

Chuyn pha

S
G
S
=
L
G
L
+ vL
V
AT*
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
AT* = AT
C
+ AT
r
AT* cn ph thuc vo r v lin quan
ti qu ngui to cong AT
r
thp hn T
m
do hiu ng Gibbs-
Thomson .
r L
T
T
V
m
r
2
= A
AT
r
= K I
AT
r
gl qu ngui Gibbs-Thomson
K cong ca mt phn cch S/L
K= dA/dV = 1/r
1
+ 1/ r
2
If r
1
= r
2
, K = 2 / r
I - H s Gibbs-Thomson
I = : A s
f
A s
f
entropy nng chy theo th tch
A s
f
= L /T
m
Chuyn pha
r
T
L L
G
v
C
V
L
V
L L
A
~

= .

CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
cong nh nht ca chp nhnh cy t
c khi AT
r
bng vi qu ngui tng
mt phn cch: AT
r
(max)
= AT
*
= T
m
- T

.
Vi
th AT
r
nhn chung c th c tnh theo
Cui cng, v AT
*
= AT
c
+ AT
r
nn pt
|
.
|

\
|
~
r
r
r L
v
V
L
*
1
1
.

Chuyn pha
r L
T
T
V
m
r
2
= A
AT*
( ) *
1 2
*
T L
T
r
v
m SL
A
|
|
.
|

\
|
=

r
r
T T
r
*
* A = A
r
T
L
v
C
V
L
A
= .

CHNG 3. TO MM V PHT TRIN MM

3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
Chuyn pha
Tc pht trin ca chp tin ti 0 khi:
1. r r* do hiu ng Gibbs-Thomson v
2. r do qu trnh dn nhit b chm.
Tc cc i t c khi r = 2r*.
|
.
|

\
|
~
r
r
r L
v
V
L
*
1
1
.

r L
v
V
L
2
1
.
max

~
CHNG 3. TO MM V PHT TRIN MM
3.2. S PHT TRIN CA MM TRONG KIM LOI NGUYN CHT
3.2.3. Dngnhit v snnhcamt phncch
v
*
2
1
T T T
c r
A = A = A