Chuyn pha trng thi rn

4.1 Gii thiu

- Rt nhiu qu trnh chuyn pha xy ra trong vt liu m khng dn n cc cu
trc cn bng
- Cc qu trnh chuyn pha ny rt quan trng v i khi chng sinh ra cc sn
phm khng mong mun hoc chng to ra nhiu tnh cht p dng quan trng.
- Gin pha cn bng s khng cung cp kin thc v cc cu trc khng cn
bng. Tuy nhin chng l nhng tham kho c gi tr khi x l bt u t cn
bng cn phi thm mt ta thi gian nhn c cc gin ng hc
c s dng nhiu trong x l nhit.

4.2 Khuch tn
- Nhiu phn ng v qu trnh quan trng trong x l vt liu da vo vic truyn
khi trong lng mt cht rn hoc t mt pha lng, kh, hoc rn n mt pha
khc.
- Qu trnh truyn khi ny c thc hin bng khuch tn, mt hin tng vn
chuyn vt liu do s chuyn ng ca cc nguyn t.
- Hin tng khuch tn c th c minh ha bng cch s dng mt cp
khuch tn, to thnh bng cch ghp st vo nhau b mt ca hai ming kim loi
khc nhau (v d Cu v Ni).

 Qu trnh m cc nguyn t ca kim loi ny khuch tn vo kim loi kia

c gi l ni khuch tn (interdiffusion) hoc khuch tn tp cht
(impurity diffusion).
Khuch tn cng xy ra trong kim loi nguyn cht, khi cc nguyn
t cng loi trao i v tr cho nhau gi l t khuch tn (self-diffusion).

4.2.1 C ch khuch tn
Cc nguyn t trong cht rn thng xuyn chuyn ng v v tr ca
chng thay i nhanh chng.
nguyn t c th chuyn ng nh vy, cn phi c hai iu kin:
phi c v tr trng ln cn
nguyn t phi c nng lng b gy lin kt vi cc nguyn t
xung quanh v gy ra bin dng mng tinh th trong qu trnh di chuyn.
Nng lng ny nng lng dao ng ca cc nguyn t.
mt nhit xc nh ch c mt phn trong tng s nguyn t c
nng lng di chuyn,
Nhit cng cao, phn nguyn t c kh nng di chuyn cng ln.

 C nhiu c ch khuch tn c ngh, nhng c hai c ch khuch tn

trong kim loi c tha nhn l khuch tn theo c ch nt trng v nguyn t
xen k.

4.2.1.1 C ch khuch tn theo nt trng

Nguyn t t nt mng s di chuyn n nt trng ln cn theo c ch khuch
tn nt trng i hi s c mt ca cc nt trng ln cn.
Mc khuch tn theo c ch nt trng l mt hm ca s nt trng c mt
trong mng nhit cao mt nt trng c th rt ln nn khuch tn
theo c ch nt trng rt d xy ra.

 Do nt trng v nguyn t trao i v tr cho nhau s khuch tn ca nguyn

t theo mt hng ng vi s khuch tn ca nt trng theo hng ngc li.
Hin tng ni khuch tn v t khuch tn xy ra theo c ch ny.

4.2.1.2 C ch khuch tn theo nguyn t xen k

Nguyn t t v tr xen k ny s di chuyn n v tr xen k ln cn khc cn
trng theo c ch khuch tn nguyn t xen k.
C ch ny thng gp trong hin tng ni khuch tn ca cc tp cht nh
hydr, cabon, nit v oxy nhng nguyn t c kch thc nh nm
trong cc v tr xen k.

 Cc nguyn t gc ca mng (host atoms) hoc nguyn t tp cht v tr thay

th t khi nm v tr xen k nn thng khng khuch tn theo c ch ny.
Trong a s hp kim, khuch tn theo c ch nguyn t xen k xy ra nhanh
hn rt nhiu so vi c ch khuch tn theo nt trng v cc nguyn t xen k c
kch thc nh hn, linh ng hn.
Hn na, s v tr xen k cn trng nhiu hn s nt trng nn xc sut di
chuyn theo c ch xen k ln hn xc sut di chuyn theo c ch nt trng.

4.2.2 Khuch tn trng thi n nh

Tc khuch tn thng c biu din bi dng khuch tn J
J chnh l khi lng cht M hoc s nguyn t M khuch tn ngang qua v
vung gc vi mt n v tit din cht rn trong mt n v thi gian.
n v ca J l [kg/m2s] hoc [s nguyn t/m2s].
Nu dng khuch tn khng thay i theo thi gian th gi l khuch tn trng
thi n nh (steady-state diffusion).

 Mt v d v khuch tn n nh ph bin l s khuch tn ca cc

nguyn t kh ngang qua mt bn kim loi m nng (hoc p sut) ca
cc ht khuch tn b mt hai bn c gi khng i

 Khi biu din nng theo v tr x bn trong cht rn, th th thu c gi l

profile nng
dc ti mt im trn ng cong gi l gradient nng (dC/dx).
Gi s profile nng l ng thng, khi gradient nng s l

C C A C B

x x A x B
Trong cc bi ton v khuch tn, nng thng tnh theo [kg/m 3] hoc [g/cm3]
nh lut Fick I: Dng khuch tn s t l vi gradient nng theo phng trnh

dC
J D
dx

D: h s khuch tn [m2/s]
Du tr ch ra hng khuch tn theo
hng gim nng , t ni nng
cao n ni c nng thp.

Trong thc t, bi ton khuch tn n nh tm thy trong tinh ch kh hydr

mt bn ca mt bn mng bng Pd tip xc vi hn hp kh tp cha hydr
v cc tp cht khc nh nit, oxy, hi nc, cn mt bn cha kh hydr c p
sut thp v c gi khng i. Hydr s khuch tn c chn lc qua bn.

4.2.3. Khuch tn trng thi khng n nh

Hu ht cc trng hp khuch tn trong thc t u l khuch tn
khng n nh (nonsteady-state diffusion) dng khuch tn v gradient
nng ti mt s im trong cht rn thay i theo thi gian tch t
hoc thiu ht cc ht khuch tn.
nh lut Fick II:

C
2C
D 2
t
x

 Li gii ca bi ton s thu c khi c iu kin bin xc nh.

Mt li gii quan trng ca bi ton l cho trng hp mt vt rn bn v hn
(semi-infinite) trong nng b mt (Cs) c gi khng i.
Mt thanh rn c xem l bn v hn khi khng c nguyn t no khuch tn
n c u cui ca thanh trong thi gian khuch tn.
Thanh c chiu di l c xem l bn v hn khi l > 10

Dt

Thng thng, ngun ca cc ht khuch tn l pha kh m p sut ring phn

ca n c gi khng i.
Mt s gi thit c t ra:
Trc khi khuch tn cc nguyn t cht tan trong cht rn c phn b u
vi nng C0.
Gi tr x b mt bng 0 v tng theo khong cch t b mt vo trong cht
rn.
Thi gian c tnh bng 0 thi im bt u qu trnh khuch tn.

 Khi cc iu kin bin c xc nh nh sau:

t = 0,

C = C0 ti 0 x

t > 0,

C = Cs (nng khng i b mt) ti x = 0

C = C0 ti x = (khuch tn khng n c u cui)

Li gii ca phng trnh Fick II c dng

C x C0
1 erf ( z )
CS C 0

vi

x
z
2 Dt

Cx l nng su x sau thi gian t

erf(z) l hm sai s nh ngha theo
z

2
y2
erf ( z )
e dy

0
Gi s cn t n mt nng C1 xc nh trong hp kim, khi

C x C0
const
CS C 0

x
const
2 Dt

x2
const
Dt

4.2.4. Cc yu t nh hng n s khuch tn

4.2.4.1 Dng khuch tn
ln ca h s khuch tn tng trng cho tc khuch tn.
Bng sau cho thy ln ca h s khuch tn v nh hng ca dng
khuch tn cng nh ca vt liu nn n h s khuch tn.

4.2.4.2 Nhit
S ph thuc ca h s khuch tn vo nhit tun theo phng trnh

Qd
D D0 exp

RT
D0 l hng s khng ph thuc nhit [m2/s]
Qd l nng lng hot ha cho khuch tn [J/mol, cal/mol hoc eV/nguyn t]
R: hng s kh = 8,31 J/mol.K; 1,987 cal/mol.K; 8,62.10-5 eV/nguyn t.K
T: nhit tuyt i [K].
Ly log hai v

Qd 1
ln D ln D0

R T

Qd 1
hoc lg D lg D 0

2, 3 R T

V lgD theo T s c phng trnh ng thng c dc l Q d/2,3R v tung

gc l lgD0. y l cch xc nh Qd v D0 bng thc nghim.

4.2.5 Khuch tn th tch trong cc cht rn ion hoc cng ha tr

- Trong phn ln cc cht rn ion, khuch tn xy ra theo c ch nt trng cation,
anion, ion xen k.
- Cc khuyt tt c nh hng n khuch tn l:
+ Cc khuyt tt ni ti: khuyt tt Schottky, Frenkel m s khuyt tt s ph
thuc vo nhit , khi lng v th tch cc pha ...
+ Cc khuyt tt do s c mt ca tp cht
- Cc cu trc cng ha tr thng khng st cht (do tnh nh hng ca cc
lin kt) nn s khuch tn trong chng kh hn trong kim loi:
Ge c nhit nng chy 1211 K, trong khi nng lng hot ha t khuch tn
(290 kJ/mol) ln hn so vi Ag (180 kJ/mol), c nhit nng chy l 1235 K.

4.2.6 Khuch tn trong cc cht rn khng kt tinh

- Cc polyme c lin kt cng ha tr mnh dc theo mch v lin kt th cp yu
gia cc mch t khuch tn chm, nht l khi kt tinh cng cao
- Tuy nhin, chng c tnh thm cc phn t nh hp thu nh phn t nc lm
polyme b trng phng v thay i cc tnh cht c, l

- Khuch tn thng xy ra u tin trong cc vng khng kt tinh

- Cc khe h ln trong thy tinh to thun li cho s khuch tn ca hydro, heli.
Cc ion Na, K cng c th di chuyn trong thy tinh nhng s di chuyn ca
chng b nh hng bi lc ht tnh in vi mng li Si-O

4.2.6 Khuch tn ngn mch (Short circuit diffusion)

- Ngoi cc khuch tn th tch k trn, qu trnh
chuyn cht cn c th i theo cc vng c cu
trc m: lch, bin gii ht, b mt
- Trong mt s rt t trng hp, ngi ta xc
nh c
Db mt >> Dbin gii ht >> Dth tch
Hnh biu din lgD = f (1/T) ca Ag

4.2.7 Khuch tn ngc (inverse diffusion )

- Th nghim ca Darken

- S dng hai loi thp khc nhau: mt cha 3,8 % Si, mt cha 0 % Si
- C khuch tn t thp c cha 3,8 % Si sang thp 0 %Si trong khi Si
khng khuch tn
S c mt ca Si lm tng hot tnh ca cacbon trong thp loi
cacbon trong thp giu Si.
Khuch tn lm tng gradient nng ca cacbon

4.3 To mm
S sinh ra mt pha mi i hi mt lch khi cn bng ln to ra mt
s chuyn ha trong phn ln thi gian hai giai on lin tip nhau: xut hin
mt th tch nh ca vt cht chuyn ha (to mm) v pht trin mm

4.3.1 To mm ng th (c ch t sinh)
- Xt th tch mt pha , bn nhit ln hn nhit chuyn ha T o v c
t trong nhit T < To pha mi phi xut hin

- So snh hai trng thi: trng thi 1 ch c pha v trng thi 2 c mt mm hnh
cu ca pha xut hin trong pha
- chnh lch nng lng Gibbs G = G2 G1 bao gm
+ Gim nng lng th tch Gv = G G < 0 (xut hin th tch mi nng
lng t do s thay i theo chiu lm gim nng lng t do ca h)
+ Tng nng lng do vic to thnh mt b mt tip xc pha c nng lng ,
vi r l bn knh ca mm

4 3
r Gv 4r 2
3

- Qu trnh chuyn pha ch xy ra khi nng lng t do ca h gim

G
0
r

- Khi o hm ca G theo r bng 0, s tnh c kch thc mm ti hn r* v

bin thin nng lng cc i G*

r*

2
G v

3
16

G *
3 G v 2

- Nu r > r* nng lng t do gim (o hm m) mm sinh ra v ln ln

- Khi 0 < r < r* nng lng t do gim (o hm dng) khng th to mm.
- Trong thc t khng phi tt c cc mm u c nng lng G * (xt chung cho
c h) m s dao ng xung quanh G* (ba ng nng lng energy fluctuation).
- nhng vng c nng lng thp c th s to mm t kch thc ti hn r*,
cn nhng vng to mm c kch thc nh hn r* s b tan i.

- T hnh mc 4.3.1, Gv gim gn nh tuyn tnh theo nhit , cng thay i

theo T nhng t nhy hn. Do G* s tng nhanh theo T v s khi T To
(do Gv = 0) v r r* khng th to mm nhit cn bng
- S mm to thnh trong mt n v thi gian s bng s mm c kh nng t
kch thc r* v theo phn b Maxwell Boltzmann, n s t l vi -G*/kT
- Tc to mm tnh theo cng thc

n G A exp( G * / kT)
vi

G* B /( T To )2
Hnh biu din s thay i tc
to mm theo nhit

4.3.2 To mm d th (c ch k sinh)
- C ch to mm t sinh cho thy pha mi sinh ra trong lng pha c s tr
khi bt u chuyn pha v t gp trong thc t
- C ch to mm k sinh thng xy ra trong t nhin, khi c mt ca cc pha
rn khc hoc do cc bin gii ht (trong c thnh khun, tp cht khkim
loi to hp cht ha hc) lm gim nng lng t do ca h

4.3.3 Pht trin pha mi

- Xt s thay i nng lng t do ca mt nguyn t ln cn b mt . trong

khong nhit < To.
- Cc nguyn t trong c nng lng cao hn cc nguyn t trong l -Gv
- chuyn t , cn phi vt qua hng ro nng lng hot ha GA
- Dng nguyn t chu s chuyn ha t s t l vi exp(-GA/kT) v dng
chuyn ha ngc li s t l vi exp(-GA + Gv)
Tc pht trin mm s tnh theo

G A
n C Co exp

RT

G v
. 1 exp

RT

- Trn cng th, ngi ta biu din tc to mm, tc pht trin mm v

tc chung ca qu trnh chuyn ha.
- V tr tng i gia cc tc ny cho php d on kch thc ca ht to
thnh trong qu trnh chuyn ha.

 th biu din tc cc qu trnh to mm, pht trin

mm v tc chung theo nhit

4.4 Ti kt tinh
- Bin dng do cc kim loi s lm thay i tnh cht ca chng: tng gii hn
n hi, tng cng
- Mt kim loi khi b bin dng th s khng trng thi nhit ng bn nht. Khi
un nng n c th tr v trng thi c mt khuyt tt thp nht, c cc ht
khng b bin dng v phc hi li cc tnh cht ti kt tinh

R : bn c
b : gii hn n
hi
A : gin di
: in tr sut

Ti kt tinh do to mm v pht trin mm s to ra cc ht mi chim cc v tr

trong mng li ca cu trc rn ngui.
- Nhit ti kt tinh thng ln hn 0,4 ln nhit nng chy ca kim loi
- qu trnh ti kt tinh xy ra phi cc bin dng thun li c tn ti bin
dng ti hn crit. Nu hi nh hn crit., cu trc mi s to thnh rt to

a) Sau khi bin dng ngui

b) Ti kt tinh mt phn
c) Ti kt tinh hon ton
d) sau khi cc ht ln ln

4.5 X l nhit cho thp

- Vic x l nhit cho thp da trn nn tng l pha (austenite- Fe Fcc) c th
ha tan nhiu cacbon hn (ti a 2 % khi lng 1146 oC), pha (ferrite Fe
Bcc) l pha bn nhit thng (cha ti a 0,022 % khi lng C 727 oC).
- l do cc l hng trong Fcc ln hn trong Bcc: K 8 mt dl/dntu l 0,414
(Fcc) so vi 0,155 (Bcc).
- Do nu lm ngui chm hp kim cha 0,77 % kim loi C sau khi nung n 800
C th s xy ra phn ng cng tch

(Fcc) (Bcc) + Fe3C (orthorhombic t phng)

- Khi cacbon s thot ra khi dung dch v kt ta di dng cementite Fe 3C
c thnh phn l 6,67 % kl C.
- T chc cng tch + Fe3C c cu trc lp. Cc lp ny rt mng, c hnh dng
ging nh x c khi nhn trn knh hin vi vi phng i thp c tn l
pearlite
S xut hin ca pearlite l do c ch to mm v pht trin mm

- Nu v gin thi gian nhit trong nhit l duy tr hp

kim cn thi gian l thi gian bt u v kt thc chuyn ha austenite
gin ng nhit (thang logarit)

- Qu trnh chuyn ha trn l mt qu trnh lm ngui chm v c dng ch C

- Vic tch cacbon di dng Fe3C s khng thi gian thc hin
- Qu trnh lm ngui nhanh c th c vit
(Fcc) (cu trc t phng tm khi body-centered tetragonal)
- c t tn l martensite l mt cu trc gn ging ferrite. Martensite bo
ha cacbon nn c tnh cng cao ti

- Pearlite c v c cng thnh phn nhng kch thc ht ca pearlite nh

hn nhiu nn c c tnh tt hn
- Martensite rt cng, nhng rt gin nn sau khi thu c martensite nung
(ram) t pearlite ram.

1. Mt bn thp c thm cacbon bng cch cho tip xc mt mt vi mi trng

giu cacbon v mt kia vi mi trng ngho cacbon 700oC. Gi s khuch tn l
n nh, hy tnh dng khuch tn cabon ngang qua bn thp nu nng cacbon
cc v tr 5 v 10 mm di b mt thm cacbon l 1,2 v 0,8 kg/m3 tng ng. Bit
h s khuch tn l 3.10-11 m2/s.
2. thm cacbon tng cng b mt cho thp, ngi ta t thp nhit cao trong
mi trng giu kh hydrocacbon nh metan (CH4). Xt hp kim c thnh phn ng
nht l 0,25 % kl cacbon v c x l nhit 950oC. Nu nng cacbon b mt
c h t ngt v gi khng i 1,20 % kl cacbon, tnh thi gian t nng
0,8 % kl cacbon su 0,5 mm di b mt. H s khuch tn ca cacbon nhit
ny l 1,6.10-11 m2/s v gi s thanh thp l bn v hn.
3. H s khuch tn ca Cu trong Al 500oC v 600oC tng ng l 4,8.10-14 v
5,3.10-13 m2/s. c lng thi gian 500oC to ra cng kt qu khuch tn (v
nng ca Cu ti mt im A) nh khi nung 600oC trong 10 h.
4. ) 909K v 1250K, h s khuch tn ca ng trong vng tng ng l 10-15,45
v 10-12,40 (m2/s). Hy xc nh nng lng hot ha cho khuch tn Qd v D0, bit
R = 8,31 J/mol.K.

Bi gii
1.
2.

CA CB
(1,2 0,8) kg / m 3
11
2
9
2
J D
(3.10 m / s)

2
,
4
.
10
kg/m
.s
3
2
xA xB
(5.10 10 ) m

3.

4.