Diffusion of Silicon in Aluminum

SHIN-ICHIRO FUJIKAWA, KEN-ICHI HIRANO, AND YOSHIAKI FUKUSHIMA

I n t e r d i f f u s i o n coefficients in A1-Si a l l o y s were d e t e r m i n e d by M a t a n o ' s method in the t e m -

p e r a t u r e r a n g e f r o m 753 to 893 K with the couple c o n s i s t i n g of pure a l u m i n u m and an
A1-Si alloy. T e m p e r a t u r e dependence of the i m p u r i t y diffusion coefficients of Si in A1,
obtained by e x t r a p o l a t i o n of the c o n c e n t r a t i o n dependence of the i n t e r d i f f u s i o n coeffi-
cient to z e r o mole f r a c t i o n of Si, is given by the following equation:
+0,97
DSi/A 1 = (2.02_o.06) • 10 -4 exp [- (136 + 3) kJ mol-1/RT] mZ/s.
The K i r k e n d a l l m a r k e r was found to move toward the S i - r i e h side, indicating that the
Si atom diffuses f a s t e r than the A1 atom in ANSi a l l o y s . F r o m the i n t e r d i f f u s i o n coeffi-
cient and the m a r k e r shift, the i n t r i n s i c diffusion coefficients were calculated.
The d i f f e r e n c e in the a c t i v a t i o n e n e r g i e s (AQ) between the i m p u r i t y diffusion of Si in
A1 and the s e l f - d i f f u s i o n of A1 was e s t i m a t e d by m e a n s of the a s y m p t o t i c o s c i l l a t i n g po-
t e n t i a l and the Le C l a i r e t h e o r y . The c a l c u l a t e d value of AQ is in f a i r a g r e e m e n t with
the e x p e r i m e n t a l value. The v a c a n c y - s o l u t e b i n d i n g e n e r g y for Si in A1 was a l s o d i s -
c u s s e d b a s e d on the diffusion data.

1. INTRODUCTION for 2 weeks to homogenize the s t r u c t u r e . The a v e r a g e

T HERE a r e many i n v e s t i g a t i o n s of the i n t e r d i f f u s i o n
in the A1-Si s y s t e m , but the r e s u l t s differ s i g n i f i c a n t l y
a m o n g v a r i o u s w o r k e r . ~'e M o r e o v e r , v e r y little is
known about the K i r k e n d a l l effect in the ANSi s y s t e m .
T h u s , r e l i a b l e r e s u l t s of the i n t e r d i f f u s i o n in the A1-
Si s y s t e m a r e d e s i r e d f r o m the following r e a s o n s :
1) A n a p p r o p r i a t e r a d i o i s o t o p e for the i m p u r i t y dif-
fusion e x p e r i m e n t i s not a v a i l a b l e for Si,
2) The r e a c t i o n between A1 thin f i l m s o r A[ w i r e s
and Si l a y e r s has b e e n widely studied b e c a u s e of the
i m p o r t a n c e in the i n t e g r a t e d c i r c u i t d e v i c e s . The
diffusion r e s u l t s a r e u s e f u l to u n d e r s t a n d the i n t e r -
metallic reactions,
3) Silicon is one of the m o s t i m p o r t a n t a l l o y i n g e l e -
m e n t s in the c o m m e r c i a l A1 a l l o y s . Diffusion data
a r e useful in a n a l y z i n g the f u n d a m e n t a l b e h a v i o r of Si
in A1 a l l o y s , and
4) It is f u n d a m e n t a l to c o m p a r e the e x p e r i m e n t a l
r e s u l t s with the t h e o r e t i c a l r e s u l t s on the i m p u r i t y
diffusion of Si in A1, b e c a u s e Si has positive e x c e s s
v a l e n c e in A1.
In the p r e s e n t work, the i n t e r d i f f u s i o n was i n v e s t i -
gated in the t e m p e r a t u r e r a n g e f r o m 753 to 893 K, and
the i m p u r i t y diffusion coefficients of Si in A1 were de-
t e r m i n e d by applying D a r k e n ' s r e l a t i o n 7 on the i n t e r -
diffusion r e s u l t s .
2. E X P E R I M E N T A L PROCEDURES
ANSi alloys containing 0.58, 0.87 and 1.15 at. pct
Si were p r e p a r e d f r o m 99.999 wt pct Si and 99.999
wt pct A1. T h e y w e r e m e l t e d in an a l u m i n a c r u c i b l e
u n d e r a NaC1-KCI flux and cast into an i r o n mold.
T a b l e I shows the c h e m i c a I a n a l y s e s of the a l l o y s .
The cast ingots were hot forged and armealed at 773 K
SHIN-ICHIRO FUJIKAWAand KEN-ICHIHIRANO are Instructor
and Professor, respectively, Department of Materials Science, Faculty
of Engineering,Tohoku University, Sendal 980, Japan. YOSHIAKI
FUKUSHIMA,formerly Undergraduate Student, Tohoku University,
is now with the Tyota Central Laboratory, Nagoya 468, Japan.
Manuscript submitted March 20, 1978.
ISSN 0360-2133/78/ 1211-1811500.75/0
METALLURGICALTRANSACTIONSA 9 1978AMERICANSOCIETYFOR METALSAND
THE METALLURGICALSOCIETYOF AIME
g r a i n size of the alloy a f t e r these t r e a t m e n t s was ap-
p r o x i m a t e l y 3 m m in d i a m . Rods of the 99.999 wt pct
A1 and the A1-Si alloys were m a c h i n e d to p r e p a r e
s p e c i m e n in the f o r m of a disk 12 m m in d i a m by 6 m m
thick. Both faces of each d i s k were ground with e m e r y
p a p e r and e l e c t r o p o l i s h e d in a solution of e t h y l - a l c o h o l
and p e r c h l o r i c acid to r e m o v e the A1 oxide l a y e r . The
sandwich type diffusion couple c o n s i s t e d of t h r e e d i s k s
two o u t e r A1 d i s k s and a c e n t r a l disk of the a l l o y s .
The couple was put in a s t a i n l e s s s t e e l holder, p r e s s e d
by the s c r e w s and bonded by diffusion at 773 K in p u r i -
fied hydrogen gas for 1 h. The diffusion width a c r o s s
the i n t e r f a c e a f t e r this t r e a t m e n t was about 40 p m
and n e g l i g i b l y n a r r o w , c o m p a r i n g with that obtained
by the s u b s e q u e n t a n n e a l i n g (1500 to 4000 p m ) . Dif-
fusion couples were sealed in evacuated P y r e x glass
tubes and diffusion a n n e a l e d in e l e c t r i c r e s i s t a n c e
f u r n a c e s in the t e m p e r a t u r e r a n g e f r o m 753 to 893 K,
which were c o n t r o l l e d within ~1 K. Each of A1-Si a l -
loys was diffusion a n n e a l e d in the single phase r e -
gion. The r a n g e of diffusion t i m e s was b e t w e e n 9.36
x 104 s at 893 K and 6.05 x l 0 S s at 753 K.
A f t e r the diffusion a n n e a l i n g , the couple was filled
up with r e s i n and cut p a r a l l e l to the diffusion d i r e c -
tion u s i n g a p r e c i s i o n c u t t e r . The s u r f a c e of the s p e c i -
m e n was ground with 6/0 e m e r y p a p e r and f i n a l l y
polished on a lap with only w a t e r . T u n g s t e n w i r e s
(10 ~tm in diam) were used as the K i r k e n d a l l m a r k e r .
M a r k e r shift was m e a s u r e d by r e f e r e n c e to the Matano
i n t e r f a c e with an a c c u r a c y of +10 g m u s i n g a t r a v e l -
ling m i c r o s c o p e . A n e l e c t r o n probe X - r a y m i c r o -
a n a l y z e r ( S h i m a z u - A R L - I I type) was used to d e t e r m i n e
the c o n c e n t r a t i o n - p e n e t r a t i o n c u r v e by line s c a n n i n g .
Table I. Chemical Analyses of AI-Si Alloys, Wt. Pet
Alloy Si Mg Fe Cu Ti Mn M
A 0.60 <0.001 0.004 <0.001 0.001 <0.001 balance
B 0.90 0.001 0.001 <0.001 < 0 . 0 0 i <0.001 balance
C 1.19 0.001 0.004 <0.001 0.001 <0.001 balance
VOLUME 9A,DECEMBER 1978-1811
The a n a l y s i s conditions of the m i c r o a a m l y z e r were as
follows: a c c e l e r a t i o n voltage; 20 kV, take-off angle of Table II. Impurity Diffusion Coefficients of Si in AI
radiation; 52.5 deg, s p e c i m e n c u r r e n t for pure A1; 0.03
Temperature,K D, | 0 "13 m2/s
/xA, and s c a n n i n g speed; 24 ~tm/min. The r a d i a t i o n s
of Si-K(~ were used for the m e a s u r e m e n t . The r e l a t i v e 893 20.7
i n t e n s i t i e s of the r a d i a t i o n s were converted into con- 873 12.9
c e n t r a t i o n u s i n g the c a l i b r a t i o n curve d e t e r m i n e d with 853 9.30
843 8.16
the t h r e e a l l o y s . F i g u r e 1 shows the c a l i b r a t i o n c u r v e . 833 5.96
The l i n e a r r e l a t i o n s h i p was o b s e r v e d between the 823 4,89
r e l a t i v e i n t e n s i t y of Si-K~ and the Si c o n c e n t r a t i o n by 813 3.78
chemical analysis. 808 3.66
The i n t e r d i f f u s i o n coefficients 0~) were d e t e r m i n e d 793 2.21
773 1.28
f r o m the c o n c e n t r a t i o n - p e n e t r a t i o n c u r v e s by m e a n s 753 0.636
of M a t a n o ' s method s u s i n g a NEAC 2200 Model 700
E l e c t r i c C o m p u t e r at the Computation C e n t e r in
Tohoku U n i v e r s i t y . The i n t r i n s i c diffusion coefficients,
lated to the s e l f - d i f f u s i o n coefficients, D*si and D~I by,
Dsi and DA1, were calculated on the b a s i s of the
D a r k e n a n a l y s i s , 7 u s i n g the v a l u e s of D and the velo- d In 7si
city of m a r k e r m o v e m e n t (v). : (NsiD~l + NA1D~i)(1 + - - )
d In Nsi
3. RESULTS = (NsiD~l + NA1D~i)m, [3]
F i g u r e 2 shows the ~ r e s e n t r e s u l t s on the c o n c e n -
t r a t i o n dependence of D in the A l - r i c h A1-Si solid where 7 si is the a c t i v i t y coefficient of Si in the alloy
solutions, In c o m p a r i s o n with the r e s u l t s by B/ickle 5 at of composition NSi and m is the t h e r m o d y n a m i c fac-
823 K and by Mehl 6 at 774 K. The p r e s e n t r e s u l t s t o r . If a value of unity for the factor m is a s s u m e d
show a l e s s e r c o n c e n t r a t i o n dependence of ~ than that over the r a n g e 0 to 0.01 atom f r a c t i o n of Si in A1,
o b s e r v e d by B(ickle and Mehl. then D in the i n f i n i t e s i m a l l y dilute solution c o r r e -
A c c o r d i n g to D a r k e n , 7 D and v a r e r e l a t e d to Dsi and sponds to the i m p u r i t y diffusion coefficient of Si in
DA1 for the c o m p o s i t i o n at the m a r k e r by: A1 (Dsi/A 1 ). T h e r e f o r e , in the p r e s e n t work, we r e -
garded the i n t e r d i f f u s i o n coefficient d e t e r m i n e d by
= NsiDA1 + NA1Dsi [1] e x t r a p o l a t i o n of the c o n c e n t r a t i o n dependence of D to
and z e r o Si c o n c e n t r a t i o n as DSi/A 1 . The l i n e s in F i g . 2
v = ( D s i - DA1)(dNsi/dX)m , [2] were d r a w n by e y e b a l l . The d i f f u s i v i t i e s d e t e r m i n e d
in such a way a r e l i s t e d in T a b l e II. The v a l u e s of
where Nsi and NA1 a r e the r e s p e c t i v e a t o m i c f r a c t i o n s DSiJA 1 were not dependent on the c o m p o s i t i o n of the
in the alloys, and (dNsi/dX) m is the c o n c e n t r a t i o n diffusion couple. The t e m p e r a t u r e dependence of
g r a d i e n t at the m a r k e r position. F u r t h e r m o r e b is r e - DSi/A 1 is given by:
+0.97
DSi/A 1 = (2.02-0.66) • 10 -4 exp [-(136 =E3) kJ mol-I/RT]
O.OOE I I I I I

Y
O.O
E
~ ~ _ m2/s.
The Kirkendall marker movement toward the Si-
rich side was observed, indicating that the Si atom
[4]

~ o.oo4 diffuses faster than the A1 atom in AI-Si alloys.

E Figure 3 shows the linear relationship between marker
shift and square root of diffusion time, showing that
.~ 0.002
the marker shift is controlled by diffusion. F r o m the
values of v and ~, the values of DAI and Dsi were cal-
~: 0 culated using Eqs. [I] and [2], and shown in Table HI.
00.4 0.2
0.6 0.8 1.0 1.2
Si (at.pet) It is evident from this that the Si atom diffuses faster
Fig. 1--Dependence of the relative intensity of Si-Kce on Si than the A1 atom. The intrinsic diffusion coefficients
concentration. can be expressed by the Arrhenius relationship in the
l0 -II ~- ] I I [ [
I~ A alloy/AI couple 100 , , , , [
B altoy/AI couple~ Present work

10-'z
F
~ K
7
3
8
~ 853K
6
823 0
lo ~\823K(Buckle) 823K vxe 40 808K 753 K
20

10-13["--",
0 0.1
, "---
773 .'~.> ' - . 774K(Mehl)
0.2 0.3 0.4 0.5 0.6
]
24
I
6
Time1/2(102s1/2)
8
i 1
10 II

Si (at. pet) Fig. 3--Relationship between the Kirkendall marker shift and
Fig. 2--Concentration dependence of the interdiffusion coef- square root of diffusion time for the interdiffusion on A1-Si
ficients in A1-Si alloys. alloy/A1 couple.

1812-VOLUME9A, DECEMBER 1978 METALLURGICALTRANSACTIONSA

 r(~:)
Table III. Calculated Intrinsic Diffusion Coefficients in AI-Si AIIoy/AI Couples, 10-" ~D0 550 500 1.50
DAI and DSi , at the Marker Position I I I I

Temperature, Composition, DAb DS9

9 [)Si ~1"Present work
K Alloy At. Pet Si 10 "~3 m2/s 10 "~3 m2/s ~,~ ~ [:)SiIAI(Sergner)
873 A 0.32 14.1 16.7 10_12 ~.. " DSi~d(Seerwald)
873 A 0.31 13.9 16.1 9 ~a.x---Ds~/,~ (Fricke)
853 B 0.48 9.00 10.3
853 B 0.46 9.19 10.3
853 B 0.47 8.99 10.3
823 B 0.47 3.98 5.10
823 B 0.50 4.02 5.06 10"13 __ . 9
808 B 0.47 2.78 3.30 D~T"(Beyeler) x ~ x ~ \..
808 B 0.46 2.71 3.30
808 B 0.47 2.72 3.30
753 A 0.32 0.637 0.770 se~f ~-
753 A 0.32 0.606 0.771

I.I 1.3 1.2 1.4

K-1 103 [ T
c o n c e n t r a t i o n r an g e f r o m 0.31 to 0.50 at. pet Si:
Fig. 4--Temperature dependence of DSifA1, DSi and DAb in
Ds i = t 3 . oa*z.Ta~
. . . z.z2, x 10 "4 exp [-(140 • 3) kJ m o l - ~ / R T ] comparison with the other works on the diffusion of Si and A1
in A1.
me/s [5]

and, Th e diffusion c o e f f i c i e n t of Si in the e v a p o r a t e d A1

DA1 = (5 907-o.7s)
+o.92 • 10 -4 exp [-(143 • 1) kJ m o l - ~ / R T ]
m~/s-
Figure 4 shows the temperature dependence of DSi/AI,
Dsi and D A b compared with the results of the inter-
diffusion in AI-Si system 2"~ and the self-diffusion in
A I % I~
4. DISCUSSION
4.1. C o m p a r i s o n of P r e s e n t R e s u l t s with T h o s e of
Other Workers
T a b l e IV s u m m a r i z e s v a l u e s of the p r e - e x p o n e n t i a l
f a c t o r (D 0 ) and the a c t i v a t i o n e n e r g y (Q) f o r the dif-
fusion of Si in A1 obtained in the p r e s e n t work, along
with t h o s e of Si and A1 in A1 by p r e v i o u s w o r k e r s .
O u r v a l u e s of D O and Q f o r the diffusion of Si in A1
a r e in a g r e e m e n t with none of t h o s e by o t h e r i n v e s t i -
gators.
f i l m is m u c h g r e a t e r than in the bulk A1. T h e n the
a c t i v a t i o n e n e r g y f o r the diffusion of Si in the e v a p o -
[61 r a t e d A1 f i l m n'12 is s m a l l e r than that in the bulk A1.
T h e s e r e s u l t s m ay be e x p l a i n e d by s h o r t - c i r c u i t dif-
fusion al o n g a high d e n s i t y of d i s l o c a t i o n s and g r a i n
b o u n d a r i e s in the e v a p o r a t e d A1 f i l m . The l a r g e v a r i a -
tion of DO and Q in the bulk A1 can not be e x p l a i n e d in
t e r m s of m e t a l l u r g i c a l s t r u c t u r e o r al l o y p u r i t y and
r a t h e r m ay be a t t r i b u t e d to the d i f f e r e n c e s in the
m e t h o d s of the c o n c e n t r a t i o n a n a l y s i s and the d e t e r -
m i n a t i o n of d i f f u si o n c o e f f i c i e n t s . B e r g n e r et al 3 and
B e e r w a l d 4 i g n o r e d the c o n c e n t r a t i o n d e p e n d e n c e of dif-
fusion c o e f f i c i e n t s and a n a l y z e d the i n t e r d i f f u s i o n r e -
sult without using Matano method. T h e r e f o r e , they did
not r e p o r t the e x t r a p o l a t e d v al u e of D to z e r o Si con-
c e n t r a t i o n and the i n t r i n s i c diffusion c o e f f i c i e n t s . T he
data of D in F i g , 2 by Bfickle 6 a r e not r e l i a b l e , b e -
cau se they d e t e r m i n e d the c o n c e n t r a t i o n p r o f i l e by
m e a n s of the h a r d n e s s m e a s u r e m e n t . T h e o r i g i n of
l a r g e v al u e f o r DO and Q by F r i c k e in T a b l e IV is not
known.

Table IV. Diffusion Parameters for Diffusion of Si and AI in AI 4.2. A p p l i c a t i o n of the E l e c t r o s t a t i c T h e o r y to the
D i f f u si o n of Si in A1, and the V a c a n c y - S i A t o m
Diffusing D0, Q, Temp. Range,
Atom ]O-4 m2/s k J real. "J K Method Worker
Binding E n e r g y

Si 202 136 753 - 893 Interdiffusion Present We have c a l c u l a t e d the s c r e e n i n g p o t e n t i a l about a

XMA work Si solute in a dilute A1 al l o y by a s e m i - e m p i r i c a l
3.95 140 753 - 873 Intrinsic method w h e r e the p a r t i a l wave phase shifts a r e ob-
18 151 623 - 823 Interdiffusion Fricke 2 t a i n e d f r o m the r e s i d u a l r e s i s t i v i t y , and have e v a l u -
XMA
0.346 124 618 -904 Interdiflusion Bergner
3 ated the d i f f e r e n c e in a c t i v a t i o n e n e r g y (z~Q) b e t w e e n
XMA the i m p u r i t y d i f f u s i o n and s e l f - d i f f u s i o n of A1 by the
0.9 192 738 - 873 Interdiffusion Beerwald
4 Le C l a i r e t h e o r y . 13
Spectrographic Th e a s y m p t o t i c s c r e e n i n g p o t e n t i a l 14 used in the
- 82 373 - 573 Thin film Gurp~1 p r e s e n t w o r k is given by:
Precipitation
Resistivity a Oe cos (2K F 9~" + r
- 76 633 - 773 Thin film McCaldin ~2 v(r) = 4~F " r~ [7]
Interdiffusion
X/vIA w h e r e V(r) is the e l e c t r o s t a t i c p o t e n t i a l at a d i s t a n c e
AI 5.07 143 753 - 873 Intrinsic Present (r) f r o m the s o l u t e atom, K F is the F e r m i wave n u m -
work
b e r f o r the s o l v e n t , a o w h e r e o~o = 2 a is a constant
2.25 145 673 - 883 Tracer Beyeler 9
0.144 127 297-773 NMR Sun ~~ and 9 is a p h ase a n g l e . T h e y a r e co n n ect ed with the
p h ase s h i f t s by the following e q u a t i o n s ,

METALLURGICAL TRANSACTIONS A VOLUME 9A, DECEMBER 1978-1813

 a cos 9 = ~1 l~=o (_ 1) / ( 2 / + 1)sin2~? l e x c h a n g e and the e n e r g y f o r a v a c a n c y - s o l v e n t e x-
change in the p u r e s o l v e n t . Th e l a s t t e r m , C
and, [= kS l n f i / O ( 1 / T ) ] , a r i s e s due to the t e m p e r a t u r e de -
pendence of the c o r r e l a t i o n f a c t o r , f i , f o r the i m p u r i t y
a s i n 9 ~ ( - 1 ) / (2l + 1)sin2~l, [8] diffusion, and EBi = (-zk/-/f) is the v a c a n c y - s o l u t e bind-
/=o ing e n e r g y . T h e n f i is g i v en by: la,22

w h e r e ~?l is the phase shift c o r r e s p o n d i n g to the / - t h wz + (7/2)w3 [13]

p a r t i a l wave e v a l u a t e d at the F e r m i s u r f a c e . T h e
r e s i d u a l r e s i s t i v i t y x5 of Si a t o m s in a dilute A1-Si a l -
loy is g i v en by:
co
47rhc ~ l s in ~ ( ~ / _ 1 - ~t),
Ap = eZKFZA z
w h e r e ~ is the P l a n c k constant, c is c o n c e n t r a t i o n of
the solute in the a t o m i c f r a c t i o n and Z A is the v a l e n c e
of the s o l v e n t . The v a l u e of ~?l is r e q u i r e d to s a t i s f y
the s u m r u l e :
AZ = 2 ~ (2/+ 1 ) ~ l ,
7r/:0
w h e r e AZ is the v a l e n c e d i f f e r e n c e b e t w e e n the solute
and the s o l v e n t in units of l e l .
B l ai r 16 h as s u g g e s t e d that if the s o l u t e c a u s e s a
s i g n i f i c a n t l a t t i c e dilation (positive o r n e g a t i v e ) in the
m a t r i x , the F r i d e l s u m r u l e should be m o d i f i e d by
r e p l a c i n g AZ in Eq. [10] by AZeff in the following:
AZeff = A Z - ~3E ' ~ -Oa
ZA,
w h e r e TE is g i v e n in t e r m s of P o i s s o n ' s r a t i o , a, by
~E = 3(1 - or)/(1 + a), and Oa/a is the f r a c t i o n a l change
of the l a t t i c e constant p e r a t o m i c f r a c t i o n of the s o l u t e .
A s it has b e e n g e n e r a l l y shown that in the c a l c u l a t i o n
of a and 4, f o r n o n t r a n s i t i o n e l e m e n t s in a l u m i n u m
only ~70 and 7/1 a r e the m o s t s i g n i f i c a n t , we i g n o r e d
?/l (l > 1). xT'xs ~ Z e f f , /10, rh, ~ and ff a r e c a l c u l a t e d
by using the following v a l u e s and E q s . [8] to [11]; a
= 0.349 (at 297 K), ~9 ( l / a ) " (da/dc) = - 0.042 p e r a t o m i c
f r a c t i o n 2~ of Si in A1, Ap = 0.76 • 10 -8 f~ 9 c m / a t , pct
Si, 2x K F = 0.927 ( a t o m i c units-X). T h e c a l c u l a t e d v a l -
ues a r e shown in T a b l e V.
T h e d i f f e r e n c e in the a c t i v a t i o n e n e r g i e s (AQ) b e -
t ween the i m p u r i t y diffusion and s e l f - d i f f u s i o n i s
given by:
f i = wl + w2 + (7/2)w3'
w h e r e w i (i = 1,2,3) have t h e i r u su al m e a n i n g s in the
s o - c a l l e d f i v e - f r e q u e n c y m o d e l . Th e d e t a i l e d t r e a t -
m e n t for c a l c u l a t i o n of AQthe, AQexp, z~/f, zXH2,
[9] M/x, zX/-/3and C have been d e s c r i b e d e l s e w h e r e Y ''8
H e r e , AQthe and AQexp a r e the t h e o r e t i c a l and e x-
p e r i m e n t a l v a l u e s of ZxQ, r e s p e c t i v e l y . ~r/x and A/-/3
a r e the d i f f e r e n c e s b et w een the e n e r g y f o r wl o r w3
jump of a v a c a n c y and a v a c a n c y - s o l v e n t a t o m e x -
change in the p u r e solvent. T a b l e VI shows the r e s u l t s
obtained in the p r e s e n t w o r k al o n g with the t h e o r e t i -
cal and e x p e r i m e n t a l v a l u e s by o t h e r w o r k e r s . T h e r e
[10] is a c o n t r o v e r s y on the v a l u e s of D O and Q f or s e l f -
diffusion of A1 and T a b l e VI shows two e x t r e m e v a l -
u e s . Th e v a l u e s of AQth e and AQex p obtained in the
p r e s e n t w o r k f a i r l y a g r e e with e a c h o t h e r . T h e r e f o r e ,
it can b e s a i d that the s e m i - e m p i r i c a l m e t h o d u s e d in
the p r e s e n t w o r k can give a f a i r l y good ex p l a na t i on of
e x p e r i m e n t a l r e s u l t s . A l s o , it m ay be noted that b e t -
t e r a g r e e m e n t is obtained b e t w e e n the v a l u e 2~ of AQth e
c a l c u l a t e d by Ho u si n g the p s e u d o p o t e n t l a l method and
the v a l u e of LxQexo d e t e r m i n e d in the p r e s e n t work, if
[11] we use D s e l f = 1.i4 x 10 --5 m 2 / s and Qself = 127 kJ
mole-X.lo v
We d i s c u s s the v a c a n c y - s o l u t e binding e n e r g y f or
Si in A1. At high t e m p e r a t u r e , the i m p u r i t y diffusion
c o e f f i c i e n t (19i) of solute a t o m s m ay be a p p r o x i m a t e d
as:
D i : D O exp ( - Q / R T )
= C v A i exp ( E B i / R T ) exp ( - E M i / R T )
= A o A i e x p [- (El + EMi - E B i ) / R T ] [14]
w h e r e CV is the v a c a n c y c o n c e n t r a t i o n , A i the p r e -
e x p o n e n t i a l f a c t o r f o r m i g r a t i o n of a s o l u t e - v a c a n c y
p a i r , E M i the a v e r a g e m i g r a t i o n e n e r g y of a s o l u t e -
v a c a n c y p a i r , A 0 the p r e e x p o n e n t i a l f a c t o r f or f o r m a -
tion of v a c a n c y and E f the f o r m a t i o n e n e r g y of v a c a n c y

AQ = Qimp - Qself

= zXHf+ zkH2- k s i n f i Table VI. Comparison of Theoretical and Experimental Values of • H f ,

o(Z/T) A H i (i = 1, 2, 3) and AQ for Diffusion of Si in AI
(All Values are Given in kJ tool "* )
= - - E B i + zXH2- C, [12]
AH~xp AH}he AH~ AH, AHav C AQthe AQexp Worker
w h e r e M-/f is the d i f f e r e n c e b e t w e e n the e n e r g y to
+12 -49 9.2 -7.6 _31 a, b _18 a,b _9 b Present Work
f o r m a v a c a n c y next to a solute and the e n e r g y to _45a, c _3.1a,c +9c PresentWork
f o r m a v a c a n c y in the p u r e s o l v e n t , and M-/2 is the -6.8 d Takamura21
d i f f e r e n c e b e t w e e n the e n e r g y f o r a v a c a n c y - s o l u t e +1.8 +4.9 +3.1 Ho23
- 16d Peck24
-0.96e Kim2s
- 19f Burke26
Table V. Calculated Values of AZeff, T/O, 7/1 9 and <~ (a) calculatedat 773 K, (b) usingD~ If =2.25 • 10-4 m2/sandQ,olr = 145 kJ
Ap, mol.-I 9 (c) usingDself=
O 1 44 • 10-5 m2/s and Qsetf= 127 kJ m~7"1 l~ obtained
(I/a) 9 (da/dc) AZef
f 10"8 ~2 9m/at. pct r}O ~l ~O r rad from quenchingexperiment,(e) obtained frompositron annihilationmethod, (f)
obtained fromequilibriummethodcombininglength and lattice parameter ex-
-0.042 1.3 0.76 3.4 -0.46 2.6 -0.42 pansion.

1814-VOLUME 9A, DECEMBER 1978 METALLURGICALTRANSACTIONS A

in t h e s o l v e n t . F r o m E q . [14], t h e f o l l o w i n g r e l a t i o n
is obtained:
V = E f + EMi - E B i . [15]
T o e x p l a i n t h e p o s i t i v e a n d l a r g e v a l u e s 24,26 of E B i
= ( - AHf) f o r Si i n A1 s h o w n in T a b l e VI, t h e v a l u e of
EMi m u s t b e l a r g e r t h a n 69 k J m o l e -x , w h e n 136 a n d
68 k J m o l e -1 a r e s u b s t i t u t e d 27 i n t o Q a n d E f of E q . [15],
respectively. However, this possibility may be ruled
out, j u d g i n g f r o m t h e t h e o r e t i c a l m i g r a t i o n e n e r g y of
a v a c a n c y i n p u r e A1 (59 k J m o l e - l ) , 2s t h e v a l u e s of
AH2 i n T a b l e VI a n d t h e K i r k e n d a l l m o v e m e n t t o w a r d
t h e S i - r i c h s i d e o b s e r v e d in t h e p r e s e n t w o r k . T h e r e -
f o r e , it m a y b e m o r e p r o b a b l e t h a t t h e v a l u e of EBi
f o r Si in A1 i s n e a r l y z e r o in s u c h a h i g h t e m p e r a t u r e
range where the diffusion experiment is usually
c a r r i e d out.
5. CONCLUSIONS
I n t e r d i f f u s i o n c o e f f i c i e n t s (3) i n A 1 - S i a l l o y s w e r e
d e t e r m i n e d b y M a t a n o ' s m e t h o d in t h e t e m p e r a t u r e
r a n g e f r o m 753 to 893 K . T h e p r e s e n t r e s u l t s h o w s a
l e s s e r c o n c e n t r a t i o n d e p e n d e n c e of ~ t h a n t h a t o b -
s e r v e d b y B / i c k l e 5 a n d M e h l e t a l . 6 T h e l o g a r i t h m of
d e c r e a s e d w i t h a n i n c r e a s e in Si c o n c e n t r a t i o n . T h e
i m p u r i t y d i f f u s i o n c o e f f i c i e n t s of Si in A1 w e r e d e -
t e r m i n e d b y e x t r a p o l a t i o n of t h e c o n c e n t r a t i o n d e p e n d -
e n c e of ~5 t o p u r e A1. T h e t e m p e r a t u r e d e p e n d e n c e
is e x p r e s s e d by the following equation:
966) X 10 -4 e x p [--(136 :~ 3) k J m o l - 1 / R T ]
DSi/A 1 = ( 2 . 0 2 ~ "9~
m2/s.
The Kirkendall marker moves toward the Si-rich
s i d e , s h o w i n g t h a t t h e Si a t o m d i f f u s e s f a s t e r t h a n
t h e A1 a t o m i n A 1 - S i a l l o y s ( i . e . DSi > DA1). F r o m t h e
interdiffusion coefficient and the observed Kirkendall
e f f e c t , t h e i n t r i n s i c d i f f u s i o n c o e f f i c i e n t s , DAI a n d
DSi , w e r e c a l c u l a t e d .
C a l c u l a t i o n s h a v e b e e n c a r r i e d out t o e v a l u a t e t h e
d i f f e r e n c e i n t h e a c t i v a t i o n e n e r g i e s (AQ) b e t w e e n t h e
i m p u r i t y d i f f u s i o n of Si i n A1 a n d t h e s e l f - d i f f u s i o n
METALLURGICAL TRANSACTIONS A
of A1 by m e a n s of t h e a s y m p t o t i c o s c i l l a t i n g p o t e n t i a l
and the Le Claire theory. The result shows that the
t h e o r e t i c a l v a l u e i s in f a i r a g r e e m e n t w i t h t h e e x -
perimental value.
ACKNOWLEDGMENT
T h i s w o r k was s u p p o r t e d p a r t l y by the Light M e t a l s
Educational Foundation.
REFERENCES
1. M. Bishopand K. E. Fletcher:Int. Met. Rev., 1972, vol. 17, pp. 203~25.
2. W. G. Fircke, Jr.: Scr. Met., 1972, vol. 6, pp. 1139-44.
3. D. Bergnerand E. Cyrener:NeueHfitte, 1973, vol. 18, pp. 356-61.
4. A. Beerwald:Z. Elektrocherrt, 1939, vol. 45, pp. 789-95.
5. H. Buckle: Z. Elektroehe~, 1943, vol. 49, pp. 238-42.
6. R. F. Meld, F. N. Rhines,and K. A. yon den Stein: Metals Alloys, 1941,
vol. 13, pp. 41-44.
7. L. S. Darken: Tranz A1ME, 1948, vol. 175, pp. 184--201.
8. C. Matano: Jap. J. Phyz, 1933, vol. 8, pp. 109-13.
9. M. Beylerand Y. Adda: 3:. Phyx, 1968, vol. 29, pp. 345-52.
10. C. Y. Sun: Ph.D. Thesis, Universityof Illinoisat Urbana-Champaign,1L,
1971.
11. G. J. Van Gurp: J. AppL Phy~, 1973, vol. 44, pp. 2040-50.
12. J. O. McCaldinand H. Sankur: AppL Phyx Lett., 1971, vol. 19, pp. 524-27.
13. A. D. Le Claire:Phil Mag., 1962, vol. 7, pp. 141-67.
14. A. P. Blandinand J. L. Ddplant&J. Phyz Solids, 1965, vol. 26, pp. 381-89.
15. C. P. Flynn:Point Defects and Diffusion, p. 729, ClarendonPress, Oxford,
1972.
16. F. J. Blatt: Phy~ Rev., 1957, vol. 108, pp. 285-90.
17. S. Fujikawa and K. Hirano: Tranz Jap. Inst. Metals, 1976, vol. 17, pp. 809-18.
18. S. Fujikawa and K. Hirano: Mater. Sei Eng., 1977, vol. 27, pp. 25-33.
19. R. P. Reed: Cryogenics, 1972, voi. 12, pp. 259-91.
20. W. B. Pearson:A Handbook of Lattice Spacings and Smwture of Metals and
Alloys, p. 382, PergamonPress, New York City, 1958.
21. J. Takamura, M. Koike, and D. Furukawa: J. NucL Mater., 1978, vol. 69 and
70, in press.
22. P. G. Shew'mon:Diffusion in Solids, p. 106, McGraw-Hill,New York City,
1963.
23. P. S. Ho and R. Benedek: Report No. RC 4705, IBM ThomasJ. Watson
Research Center, NYc, January, 1974.
24. R. L. Peck and K. H. Westmacott:Metals Sci J.., 1971, vol. 5, pp. 155-59.
25. S. M. Kim, W. J. L Buyers,P. Martel, and G. M. Hood: J. Phyx F: Metal
Phyx, 1974, vol. 4, pp. 343-50.
26. J. Burke and A. D. King:PhiL Mag., 1970, vol. 21, pp. 7-22.
27. K. Furukawa, J. Takamura, N. Kuwana, R. Tahara, and M. Abe:J. Phy~
Soc. Japan, 1976, vol. 41, pp. 1584-92.
28. L. Kornblit and J. Pelleg:Phy~ Rev. B, 1977, vol. 16, pp. 1164-67.
VOLUME 9A, DECEMBER 1978-1815