Kinetics of Phase Layer Growth During

Aluminide Coating of Nickel

A. J. HICKL AND R. W. HECKEL

The diffusion coating of n i c k e l with a l u m i n u m was studied by a t w o - s t e p a l u m i n i z i n g pack

p r o c e s s involving i n i t i a l l y an influx of a l u m i n u m at the s u r f a c e (step 1) and l a t e r a p a r t i a l
h o m o g e n i z a t i o n of the a l u m i n u m - r i c h r e g i o n u n d e r conditions of z e r o s u r f a c e flux (step 2).
The p r o c e s s was studied in the t e m p e r a t u r e r a n g e f r o m 870 to 1000~ Step 1 was c h a r a c -
t e r i z e d m a i n l y as the rapid, p a r a b o l i c growth (after an i n i t i a l t r a n s i e n t period) of the NizA13
phase (y) as a s u r f a c e l a y e r with c o n c u r r e n t growth of a t h i n n e r NiAI (5) l a y e r . Step 2 was
c h a r a c t e r i z e d m a i n l y as the r a p i d loss of the a l u m i n u m g r a d i e n t in the y l a y e r followed by
p a r a b o l i c growth of the 5 l a y e r p r i m a r i l y by the solution of the ~ phase. M a t h e m a t i c a l m o d -
els were developed, in which n u m e r i c a l methods and c o m p u t e r t e c h n i q u e s as well as c l o s e d -
f o r m solutions were utilized. The m o d e l s yielded growth r a t e p r e d i c t i o n s in a g r e e m e n t with
the e x p e r i m e n t a l data and were used to define the c r i t i c a l p a r a m e t e r s c o n t r o l l i n g growth
k i n e t i c s for the a l u m i n i d e l a y e r s f o r m e d d u r i n g this p r o c e s s .

ALUMINIZATION is a p r o c e s s b y which i n t e r m e d i a t e ing heated to the a l u m i n i z i n g t e m p e r a t u r e . The a l u m i -

a l u m i n i d e phase l a y e r s can be f o r m e d on the s u r f a c e of
high-temperature nickel-base alloys. Aluminization
p r o d u c e s a s u r f a c e with i m p r o v e d r e s i s t a n c e to oxida-
tion and hot c o r r o s i o n , thus extending the s e r v i c e life
and t e m p e r a t u r e l i m i t s for the coated alloy. 1'2's Many
n i c k e l - b a s e s u p e r a l l o y p a r t s a r e s u b j e c t e d to a l u m i n i -
zation t r e a t m e n t s p r i o r to t h e i r use in e n v i r o n m e n t s
which could produce s e v e r e s u r f a c e d e g r a d a t i o n (i.e.,
a i r c r a f t t u r b i n e hot s e c t i o n s ) .
There are many commercial aluminizing techniques
e m p l o y e d today, with the exact d e t a i l s of most p r o c e s -
s e s c o n s i d e r e d p r o p r i e t a r y . However, the m a j o r i t y of
the p r o c e s s e s r e l y on the i n t r o d u c t i o n of high a l u m i n u m
c o n c e n t r a t i o n s at the s u r f a c e of p a r t s to be coated, with
the a l u m i n u m - r i c h coating l a y e r s f o r m e d through solid
state diffusion. 4 Coating l a y e r s of 25 to 125 m i c r o n s
(0.25 • 10 -4 to 1.25 • 10 -4 m) in t h i c k n e s s a r e u s u a l l y
sufficient for s u r f a c e p r o t e c t i o n .
A t y p i c a l a l u m i n i z a t i o n p r o c e s s would r e q u i r e expo-
s u r e of the p a r t to be coated to an a t m o s p h e r e c o n t a i n -
ing a l u m i n u m (activated b y c h e m i c a l r e a c t i o n with a
halide salt) at t e m p e r a t u r e s well above the m e l t i n g
point of a l u m i n u m (700 to l l 0 0 ~ s The a c t i v a t e d a l u -
m i n u m , t r a n s p o r t e d r a p i d l y to the s u r f a c e , f o r m s i n -
t e r m e d i a t e phase l a y e r s with the b a s e alloy. The s u r -
face a l u m i n u m c o n c e n t r a t i o n and the i n t e r m e d i a t e phase
l a y e r s which f o r m a r e dependent on the s u r r o u n d i n g
a l u m i n u m activity. The growth r a t e s of the i n t e r m e d i -
ate phase l a y e r s a r e c o n t r o l l e d b y the i n t e r d i f f u s i o n
of a l u m i n u m and b a s e alloy c o m p o n e n t s through the
coating l a y e r s .
Pack a l u m i n i z a t i o n is one method of p r o v i d i n g the
n e c e s s a r y a l u m i n i z i n g a t m o s p h e r e , z'5 It is a s i m p l e ,
e a s i l y r e p r o d u c e d p r o c e s s which l e n d s itself to both
s m a l l l a b o r a t o r y and l a r g e i n d u s t r i a l s c a l e o p e r a t i o n s .
The pack employed c o n t a i n s a l u m i n u m powder, a h a l -
ide salt, and an i n e r t f i l l e r . The p a r t s to be coated a r e
placed in the c e n t e r of the pack with the e n t i r e pack b e -
A. J. HICKL is Hertz Fellow, and R. W. HECKELis Professor and
Head, Department of Metallurgyand Materials Science,Carnegie-Mel-
lon University, Pittsburgh, Pa. 15213.
Manuscript submitted May 24, 1973.
n u m s u r f a c e c o n c e n t r a t i o n is b e l i e v e d to r e m a i n con-
s t a n t throughout most of the pack t r e a t m e n t . 6
An a l u m i n i d e coating on p u r e n i c k e l , while not d i s -
playing as c o m p l e x a m i c r o s t r u c t u r e , s t i l l exhibits
m a n y of the s a m e f e a t u r e s as coatings on n i c k e l - b a s e
s u p e r a l l o y s . The i n t e r m e d i a t e - p h a s e l a y e r s produced
on s u p e r a l l o y s c o r r e s p o n d to p h a s e s found in the a l u -
m i n u m - n i c k e I b i n a r y s y s t e m . 1 At a l u m i n i z i n g t e m p e r -
a t u r e s , the b i n a r y s y s t e m c o n s i s t s of four solid p h a s e s :
V (NizA13), 5 (NiA1), e (Ni3A1), and ~ (Ni). 7 The y, 6, and
e p h a s e s m a y all be p r e s e n t in the coating of a s u p e r -
alloy. They each e x i s t as a s i n g l e continuous l a y e r or
as a p a r t of a m u l t i p h a s e l a y e r along with other m i n o r
p h a s e s due to the p r e s e n c e of additional alloy c o m p o -
n e n t s , z'a However, the g e n e r a l a p p e a r a n c e and s t r u c -
t u r e of the continuous phase l a y e r s a r e quite s i m i l a r
to those found in the a l u m i n u m - n i c k e I s y s t e m .
The m o s t oxidation r e s i s t a n t coatings have a 5 - p h a s e
l a y e r on the s u r f a c e of the alloy. S This phase can be
produced e i t h e r by u s i n g an a l u m i n u m alloy powder in
the pack to r e s t r i c t the a l u m i n u m a c t i v i t y and p r o h i b i t
phase f o r m a t i o n ( o n e - s t e p p r o c e s s ) , or, it m a y be
f o r m e d by m a i n t a i n i n g a high a l u m i n u m activity, p r o -
ducing the ~ l a y e r , and then p a r t i a l l y h o m o g e n i z i n g the
coating (solution of ~, into 6) in an i n e r t e n v i r o n m e n t at
t e m p e r a t u r e s equal to o r above the pack t r e a t m e n t t e m -
p e r a t u r e (two-step p r o c e s s ) . The t w o - s t e p p r o c e s s has
b e e n the m a j o r c o n c e r n of this study.
The l a y e r s expected to be found in an a l u m i n i z e d
n i c k e l coating (after pack t r e a t m e n t ) a r e r e p r e s e n t e d
s c h e m a t i c a l l y in Fig. 1. A c o n c e n t r a t i o n - d i s t a n c e p r o -
file is shown for n i c k e l a l u m i n i z e d with a High a l u m i -
n u m a c t i v i t y pack (first step of a t w o - s t e p p r o c e s s ) .
The p o s i t i o n s of the i n t e r f a c e s a r e given b y ~i (i = 0,
1, 2, 3) (not to s c a l e in this figure). The r a t e of i n t e r -
diffusion within the p h a s e s d e t e r m i n e s the widths of
the phase l a y e r s d u r i n g a l u m i n i z i n g . P a r t i a l h o m o g e -
n i z a t i o n (second step), with a z e r o s u r f a c e flux, r e -
s u l t s in the l o s s of a l u m i n u m f r o m the Y phase (into
the 5 phase) until the s u r f a c e l a y e r is c o m p l e t e l y
t r a n s f o r m e d to 5 as s e e n in Fig. 2.
The p u r p o s e of this s t u d y was to i n v e s t i g a t e the n a -
t u r e of the growth k i n e t i c s of coating phase l a y e r s in

METALLURGICALTRANSACTIONSA VOLUME 6A, MARCH 1975-43|

 ALUMINIZING ( S T E P I) d e s c r i p t i v e m a t h e m a t i c a l models as well as p r o v i d e
some n e c e s s a r y input to the m o d e l s .
Samples to be coated in this study w e r e p r e p a r e d
f r o m a 2.5 cm (2.5 • 10-2m) r o u n d b a r of v a c u u m
m e l t e d n i c k e l . The n o m i n a l c o m p o s i t i o n was 99.95 pct
n i c k e l . The flat s u r f a c e s of d i s c s , 0.5 to 1.0 cm (0.5
c-
• 10 -2 to 1.0 • 10 -2 m) cut f r o m the b a r w e r e ground,
~
O polished, and c l e a n e d in p r e p a r a t i o n for coating. The
t w o - s t e p p r o c e s s was p e r f o r m e d f i r s t in an a l u m i n i z -
EQ; ing pack c o n s i s t i n g of 15 pct a l u m i n u m powder, 3 pct
0 NH4C1 (activator) and 82 pct A120 ~ powder ( i n e r t f i l l e r )
t-
O b y weight. A n i c k e l c o n t a i n e r , 75 c m 3 (7.5 • 10 -s m s)
c.)
was filled with the pack m i x t u r e and the n i c k e l disc.
The packs were heated in an Inconel tube f u r n a c e with
an a r g o n a t m o s p h e r e . T e m p e r a t u r e s were 870, 930,
and 1000~ for t i m e s f r o m 0.25 to 4 h (9 • 10 z s to 1.44
• 104 s).*
~0 ~', (2 Q *AluminiAagtimesweremeasuredfromthe timepacksreachedtemperature.
Pos i t ion The packs w e r e r e m o v e d f r o m the f u r n a c e , opened,
Fig. 1--Schematic representation of the aluminum concentra- and the coated d i s c s and pack f i l l e r dumped f r o m the
tion-distance profile developed during the aluminizing of nickel pack to cool. Samples to be given the second step of
(step 1 treatment). Arrows indicate the motion of the surface the t r e a t m e n t were s u b j e c t e d to diffusion a n n e a l s for
and the three interphase interfaces. (Phase-layer thicknesses
are not to scale.) 0.25 to 6.6 h (9 • 102 s to 2.25 • l0 s s) at the s a m e
t e m p e r a t u r e as the i n i t i a l a l u m i n i z i n g t r e a t m e n t . An
a r g o n a t m o s p h e r e was used with the s a m p l e s contained
PARTIAL HOMOGENIZATION (STEP 27 in a c e r a m i c c r u c i b l e along with p i e c e s of bulk Ni2AI~
to r e d u c e a l u m i n u m l o s s f r o m the s a m p l e s u r f a c e .
All s a m p l e s to be e x a m i n e d m e t a l l o g r a p h i c a l l y were
given an e l e c t r o l e s s n i c k e l p l a t i n g to p r e s e r v e the s u r -
face edge d u r i n g p r e p a r a t i o n . They were sectioned,
t

-%
ground, and p o l i s h e d and then e x a m i n e d in both the
C etched and unetched conditions. Etching was c a r r i e d
o
out with both a m i x e d c o n c e n t r a t e d acid etch (HNOs,
oI b
HzSO4, H3PO4; 1:1:1) and with a s p e c i a l solution c o n -
e-
t a i n i n g 20 g Fe(NO3)3, 100 m l HC1, 50 m l HzSO4, 50 m l
U
t- H3PO4, and 1000 m l H20. P h a s e s were identified by
O
o e i t h e r t h e i r etching c h a r a c t e r i s t i c s or b y t h e i r color
u n d e r white light in the m i c r o s c o p e . P h a s e i d e n t i f i c a -
tion was v e r i f i e d b y X - r a y d i f f r a c t i o n for p h a s e s a p -
p e a r i n g at the s u r f a c e (7 and 5). All phase l a y e r t h i c k -
n e s s e s over 10 -4 cm (10 -~ m) were m e a s u r e d with a
c a l i b r a t e d r e t i c l e at a m a g n i f i c a t i o n of 400 t i m e s . B e -
Position tween 20 and 100 m e a s u r e m e n t s for each phase l a y e r
Fig. 2--Schematic representation of the aluminum concentra- m e a s u r e d and each e x p e r i m e n t a l condition were made
tion-distance profile at the end of homogenization treatment at u n i f o r m i n c r e m e n t s along the s u r f a c e . Average v a l -
(step 2). The 3' phase has completely dissolved leaving the 5 ues and s t a n d a r d d e v i a t i o n s w e r e c a l c u l a t e d .
phase on the surface. (Phase-layer thicknesses are not to
scale.)

a t w o - s t e p a l u m i n i d e coating p r o c e s s on n i c k e l . Major E X P E R I M E N T A L RESULTS

use of m a t h e m a t i c m o d e l l i n g was made to d e t e r m i n e
the c o n t r o l l i n g s y s t e m p a r a m e t e r s in this d i f f u s i o n -
c o n t r o l l e d p r o c e s s . A s e r i e s of t w o - s t e p a l u m i n i z a t i o n
e x p e r i m e n t s was u n d e r t a k e n to provide input to the
m a t h e m a t i c a l m o d e l s as well as c h a r a c t e r i z a t i o n s of
l a y e r growth k i n e t i c s and phase m o r p h o l o g i e s of c o a t -
ings on p u r e n i c k e l .
E X P E R I M E N T A L PROCEDURE
A series of pack aluminizing treatments was under-
taken in order to characterize the aluminization of
nickel by a two-step process. Selected aluminized
samples were also given subsequent homogenization
anneals. Results were used to check the validity of
A v e r a g e m e a s u r e d v a l u e s and s t a n d a r d d e v i a t i o n s
for N and 5 l a y e r t h i c k n e s s e s after the indicated a l u -
m i n i z i n g t r e a t m e n t s a r e given in Table I. The s a m p l e s
coated at 870~ had an a l u m i n i d e coating c o n s i s t i n g of
97 pct 7. The f r a c t i o n of 7 d e c r e a s e s with i n c r e a s i n g
t r e a t m e n t t e m p e r a t u r e (~ 80 pct ~, at 1000~ but the
total l a y e r t h i c k n e s s i n c r e a s e d s u b s t a n t i a l l y for the
s a m e pack t r e a t m e n t t i m e . 7 - l a y e r growth a p p e a r s to
be p a r a b o l i c after an i n i t i a l t r a n s i e n t p e r i o d . T h i s
t r a n s i e n t p e r i o d is b e l i e v e d due to the t i m e r e q u i r e d
to b u i l d s u r f a c e a l u m i n u m content to the e q u i l i b r i u m
value. ~ - l a y e r r e s u l t s were fitted to the equation:
X3' = g T ( t - - to) ~2 [1]
with:

432-VOLUME6A, MARCH 1975 METALLURGICALTRANSACTIONSA

 X v = v-layer thickness
K T = temperature dependent growth constant
t o = "delay" time 2.C

Values for K T and t o are given in Table I also. Fig. 3

displays both the above equation and the experimental
values for the v-layer thicknesses for given aluminiz-
ing times. 1.6
The microstructure of a t y p i c a l s a m p l e a f t e r p a c k
a l u m i n i z i n g i s s h o w n i n F i g . 4 on c o l o r i n s e r t s . T h e E
%
V layer, at the surface, appears lavender gray while
x
t h e 6 l a y e r c o n s i s t s of a t h i n b l u e b a n d a l o n g w i t h a
1.2
much thinner yellow band. The e-phase layer re- bJ
Z
v-
m a i n e d e x t r e m e l y t h i n (< 10 -s m ) i n a l l b u t t h e l o n g e s t 0
high-temperature treatments.
Average measured values and standard deviations
bJ
for layer thicknesses after the indicated aluminizing o.e
p l u s h o m o g e n i z i n g t r e a t m e n t s a r e g i v e n in T a b l e 17. .J

With increasing homogenization times the 6 layer

g r e w p r i m a r i l y a t t h e e x p e n s e of t h e V l a y e r w i t h l i t t l e

0.4
~ '~two stondord
j deviotions
Table I. Layer Thicknesses for 3"and 6 Phasesafter Step 1
Treatment (Aluminizing)

Layer Thicknesses(X 10+4) 40 8O 120 160

(Values and Standard
Deviation in m) Growth Eq.* Constants (t- to) ~/2 s '/2
TempCC) Time(s) 3' 5 KT(m/s 89 to (s) Fig. 3 - P l o t of e x p e r i m e n t a l l y d e t e r m i n e d y - l a y e r growth for
step 1 t r e a t m e n t s at t h r e e t e m p e r a t u r e s . P a r a b o l i c growth
870 1800 21.7 (6.3) <1.0 a f t e r a t r a n s i e n t period is d e m o n s t r a t e d by a l i n e a r r e g r e s -
870 3900 45.8 (9.6) ~1.5 sion fit of the equation, X y = K T ( t - to) 1/2.
870 4700 47.7 (7.7) ~1.5 0.93 • 10-6 1480
870 8100 68.6 (5.4) 2.0(0.5)
870 14400 111.9(12.2) 3.3 (0.5) i n c r e a s e in a l u m i n i d e c o a t i n g t h i c k n e s s . A f t e r a n i n i -
tial transient period, characterized by little change in
930 3000 57.3 (10.7) 3.9 (0.8)
930 7200 112.8((9.9) 4.4 (0.7) 1.48 X lO"6 1570 layer thicknesses, the 5 layer begins to thicken con-
930 10800 132.2(12.5) 7.5 (0.3) s i d e r a b l y . T i m e f o r t o t a l d i s s o l u t i o n of t h e V l a y e r
930 14400 174.4(17.0) 6.6 (0.5) was dependent on both the original v-layer thickness
1000 1800 50.4 (7.8) 12.4 (1.8) a n d t h e t e m p e r a t u r e of t h e h o m o g e n i z a t i o n t r e a t m e n t .
1000 3600 71.8 (6.3) 14.8 (1.4) Higher treatment temperatures or thinner 7 layers re-
1000 7200 129.9 (5.4) 22.5 (1.0) 1.74 • 10-6 1310 s u l t e d in m o r e r a p i d c o n v e r s i o n of V t o 5. A s e r i e s of
1000 7200 207.7(11.0) 24.0 (1.0)
1000 14400 207.7 (7.3) 17.7 (2.1) micrographs displaying the homogenization sequence
i s f o u n d in F i g s . 5(a) t h r o u g h (d) ( s e e c o l o r i n s e r t ) .
*X T = KT(t-t o)89

MATHEMATICAL ANALYSIS OF
DIFFUSION DURING ALUMINIZATION

Table II. Layer Thicknessesfor 3' and ~ Phasesafter Step 2 A numerical model was used employing finite differ-
Treatment (Homogenization) e n c e m e t h o d s to d e v e l o p s o l u t i o n s t o t h e d i f f u s i o n
e q u a t i o n s i n o r d e r to e v a l u a t e t h e k i n e t i c s of l a y e r
Layer Thicknesses(X 10+~)
growth during aluminization. Similar approaches have
(Values and Standard
p r o v e n s u c c e s s f u l in p r e v i o u s s t u d i e s of d i f f u s i o n -
Deviation in m) Prior Treatment
c o n t r o l l e d l a y e r g r o w t h . 9 - n B o t h s t e p s of t h e a l u m i -
Temp (~ Time(s) 3, 8 (Step 1)
nization process were simulated. The model yielded
870 900 101.9(14.1) 5.1 (0.5) interphase-interface positions and concentration pro-
870 3600 103.2 (9.8) 9.0 (1.0) Aluminizedat 870~ f i l e s a s f u n c t i o n s of t i m e f o r p a r t i c u l a r a l u m i n i z a t i o n
870 8100 96.8 (11.8) 16.8 (2.4 14400 s conditions. The model also allowed for the determina-
870 14400 71.7 (12.9) 30.0 (6.0)
870 22500 68.2 (11.1) 40.3 (8.7) t i o n of t h e s y s t e m p a r a m e t e r s t h a t h a v e m a j o r i n f l u -
930 900 123.3(10.1) il.2 (1.1) e n c e s d u r i n g e a c h of t h e t w o s t e p s of t h e p r o c e s s . T h e
930 3600 114.2(10.0) 26.0 (2.9) Aluminizedat 930~ numerical model results were used in the development
930 7200 85.6 (11.2) 50.2 (5.0) 10800 s of s i m p l i f y i n g a s s u m p t i o n s t h a t e n a b l e d " c l o s e d - f o r m "
930 14400 53.6 (10.8) 78.5 (4.6) a n a l y t i c a l s o l u t i o n s to b e f o u n d .
1000 90o 118.2 (8.0) 38.2(3.0) The aluminization process may be characterized as
1000 1800 102.6 (8.9) 59.7 (5.0) Aluminizedat 1000~ semi-infinite, multi-phase, volume diffusion. Both the
1000 4500 40.9 (13.6) 114.4(5.8) 7200 s
concentration-distance profiles and the interface posi-
1000 10800 10.5 (4.1) 162.1(7.1)
tions change with time as the phase layers grow. Par-

METALLURGICAL TRANSACTIONS A VOLUME 6A, MARCH 1975-433

t i a l d i f f e r e n t i a l e q u a t i o n s d e s c r i b e t h e c h a n g e in c o n - d) z e r o f l u x a t t h e s u r f a c e d u r i n g h o m o g e n i z a t i o n
c e n t r a t i o n w i t h e a c h p h a s e a n d t h e v e l o c i t y of t h e i n t e r - e) c o n s t a n t p a r t i a l m o l a r v o l u m e f o r a l u m i n u m a n d
f a c e s , x~ T h e e q u a t i o n f o r t h e y - p h a s e c o n c e n t r a t i o n nickel.
change with time due to volume diffusion is:
MATHEMATICAL MODE LLING~RESULTS
OC ~ \~{~7 0C
Ot
- Ox
-g-) [21 AND D I S C U S S I O N
T h e m a t h e m a t i c a l m o d e l l i n g of t h i s s t u d y w a s d e -
with
v e l o p e d to a n a l y z e t h e e x p e r i m e n t a l r e s u l t s of t h e
C = aluminum concentration c o a t i n g p r o c e s s . It w a s t h o u g h t t h a t t h e n u m e r i c a l
t = time model, using reported values for phase solubility lim-
x = displacement its and interdiffusion coefficients, would accurately
D7 = y-phase interdiffusion coefficient. predict the coating kinetics and allow for a descrip-
t i o n of t h e r a t e - c o n t r o l l i n g p a r a m e t e r s i n e a c h p r o -
SimiIar equations hold for the other three phases.
cess step. Solubility limits for the phases present
A s u r f a c e v e l o c i t y (O~o/Ot), d u e t o t h e n e t i n p u t of
during coating were taken from Hansen 7 and converted
mass into the solid system from the aluminizing at-
t o n o r m a l i z e d m a s s c o n c e n t r a t i o n s a s g i v e n in T a b l e
m o s p h e r e i s f o u n d d u r i n g s t e p 1 ( p a c k a l u m i n i z i n g ) . It
Ill. V a l u e s f o r / ~ 5 , /~e, a n d D ~ h a v e b e e n r e p o r t e d ~4
has been determined that, under aluminizing condi-
f o r t h e t e m p e r a t u r e r a n g e of t h i s s t u d y , h o w e v e r , v a l -
tions, aluminum atoms enter the system from the at-
ues for D7 were extrapolated from lower temperature
m o s p h e r e w i t h o u t a c o n c u r r e n t e x i t of n i c k e l a t o m s
(< 610~ s t u d i e s . 14'15
from the solid to the gas. 6 This results in a simple
The numerical model predictions did not correspond
a c c u m u l a t i o n e q u a t i o n f o r t h e m o t i o n of t h e s u r f a c e : ~
well with the experimental results. Growth rates for
~o -J-y were predicted much higher than step 1 experimental
- - - [3] results while growth rates for 5 were predicted much
at (1- Cs) x=~0
lower than step 2 experimental results. The percent-
with: a g e ( b y v o l u m e ) of 5 i n t h e a l u m i n i d e c o a t i n g w a s a l s o
p r e d i c t e d l o w e r t h a n t h e r e s u l t s of s t e p ~ l e x p e r i m e n t s .
~o = s u r f a c e p o s i t i o n
A c l o s e r l o o k a t t h e v a l u e s u s e d f o r D 7 a n d D 6 in t h e
3C
J7 = flux in y phase = -Dy mathematical model revealed the probable cause for
Ox
t h e d i s c r e p a n c i e s in t h e p r e d i c t i o n s . T h e l a r g e t e m -
D u r i n g t h e s e c o n d s t e p ( h o m o g e n i z a t i o n ) it w a s a s - p e r a t u r e r a n g e i n v o l v e d in t h e e x t r a p o l a t i o n of D 7 v a l -
s u m e d t h a t no m a s s t r a n s f e r a c r o s s t h e e x t e r n a l s u r - ues could magnify experimental errors in lower tem-
f a c e o c c u r r e d . T h e r e f o r e , 3 ~ o / O t = 0 ( s i n c e J y = 0) if
volume changes resulting from phase growth and dis-
solution are excluded.
Table III. Concentrations and Interdiffusion Coefficients Used in
I n t e r p h a s e i n t e r f a c e s m o v e d u r i n g b o t h s t e p s of t h e Mathematical Models
p r o c e s s d u e to d i f f e r e n c e s in f l u x e s o n b o t h s i d e s of
the interfaces. Interface velocities may be expressed Interface Concentration* D (deter-
i n t h e f o r m of E q . 4, w r i t t e n f o r t h e 7 - 5 i n t e r f a c e p o s i - Tetnp (Normalized M a s s D(Reported) minedin this
(~ Phase Concentration) (m2/s) study) (m2/s)
t i o n (~1).
870 7(Ni2Ala) Cs 0.728 C76 0.687 7,1 X 10"~2~ 2.1 X 10q2
O~l _ (Jy - Js) I [4] 3.2 • 1 0 "11 ~
Ot (C76 - C67) ~x=~t 870 5(NiAI) C87 0.653 Cse 0.482 4.6 X 10"ts 82 1.5 • 10q4
870 e(NiaAl) Ce~ 0.362 Cef 0.321 1.5 X 10"ls~
with 870 {(Ni) Cfe 0.175 CO 0 1.2 X 10"1682
C76 = a l u m i n u m c o n c e n t r a t i o n in y in e q u i l i b r i u m 930 T(Ni~Ala) Cs 0.726 C7~ 0.687 1.4 X 10n ? 6.0 X 10t2
with 5 7.9 X 10 "ll :[:
C57 = aluminum concentration in 6 in equilibrium 930 5(NiAI) C6,r 0.655 Cae 0,474 1.6 X 10 "1482 6.3 X 10 "14
w i t h ~. 930 e(NiaAl) Ce8 0.362 Cef 0.321 2.2 X 10"Is82
930 ~-(Ni) C~.e 0.183 CO 0 4.3 X 10"1682
S o l u t i o n s to t h i s s e t of e i g h t m a j o r p a r t i a l d i f f e r e n t i a l
1000 7(NizAIa) Cs 0.719 C7~, 0.687 3.2X 10-H? 1.1 X 1 0 "11
equations, employing the necessary boundary and initial
2.2 X 10q~
conditions for the aluminizing or homogenizing treat- 1000 6(NiAI) C~,,.r 0.659 C~e 0.469 6.3 X 10"1482 3.5 X 10qt
ments, were developed by numerical techniques (see 1000 e(NiaAl) Ce6 0.362 Ce~.0.320 3.5 X 10qs82
A p p e n d i x A). A s s u m p t i o n s m a d e i n d e t e r m i n i n g t h e 1000 f(Ni) C~.e 0.195 CO 0 2.0X 10qs82
solutions included:
a) 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 * i n d e p e n d e n t of c o m p o - *Normalized mass concentration = (mass of Al/volumeof solution)/density of
sition within each phase pure A1 (XAI.MAI)/(V.PAI); where XAI = mole fraction of A1,MAI = molar
weight of AI, V = molar volume of solution, and PAl = density of pure AI. Solu-
b) e q u i l i b r i u m i n t e r f a c e c o n c e n t r a t i o n s * a s d e r i v e d
tion molar volumesare calculated assumingno change in partial molar volumes of
from the literature 7 AI (VAI)or Ni (VNi). VAIand VNiare assumedto be those of the pure materials.
c) s u r f a c e c o n c e n t r a t i o n * d u r i n g s t e p 1 e q u a l t o t h e V = X•IVAI + XNi VNi.
+Castleman & Seigle, 1958.14 Extrapolated from data determined at 600~
*The first five columns of Table III contain specificvalues for these terms as CJannsen & Rieck, 1967) s Extrapolated from data determined at 428 to 610~
reported or derived from published sources. The sixth column contains valuesof Jannsen & Rieck, 1967) s Interpolated frmn data determined at 655 to
eventually used in the mathematical models (to be discussedin a later section). l O00~
maximum a l u m i n u m s o l u b i l i t y in

434-VOLUME 6A, MARCH 1975 METALLURGICAL TRANSACTIONS A

perature results. Also, the inclusion of low tempera-
ture effects (i.e., grain boundary diffusion) at higher
temperatures could contribute to the error. While the
values for D5 were reported over the required temper-
ature range, there appears to be some error in the
evaluation of D5 due to improper identification of the
layer in the experimental diffusion couples of that
study. ~4 Using the D5 values from that source in the
numerical models of this work yielded accurate pre-
dictions for the growth rate of the low aluminum r e -
gion of the 5 layer (yellow band) and not the entire 5
layer. More recent data '6 for D6 have been determined
for a specific aluminum concentration in 5 but cannot
be directly applied in the model calculations which r e -
quire an effective D6 for the entirecomposition range.
Therefore, effective values for DT and D5 were de-
termined from experimental layer growth kinetics of
this study in order to present an accurate description
of the a2uminization process. The numerical model
was used to analyze the experimental layer growth
data from both processsteps to develop values for Dy
and/~6- The values of Dy and D6 determined from step
1 data were those that gave the best fit of the model
predictions to the experimentally determined growth
rates for both the y and 5 phases. Fig. 6 is a plot of
calculated y-layer thickness as a function of aluminiz-
ing time for the three temperatures of the experimen-
tal work. The experimentally determined layer thick-
nesses are also plotted. The same values of D~ a n d / ~
determined from step I yielded a very good fit to the
step 2 experimental results when used in the numeri-
I I
2.C
%
E 1.5
u)
bJ
Z
I"
I.O
O~
W
>-
0.5
( •two}devstondord
lotions
model predicted
curve
II I I I
0 0.5 1.0 1.5
ALUMINIZING TIME x lO-4s
Fig. 6--Plot of y-layer thickness as a functionof aluminizing
time (step 1) as calculatedby the numerical model utilizing
the values of D~/andD6 determinedin this experiment. Ex-
perimental values for average y-layer thicknesses and stan-
dard deviations are also plotted for the three experimental
temperatures and the various experimentaltreatment times.
METALLURGICALTRANSACTIONSA
ca2 model. Fig. 7 shows the 5 - l a y e r growth as a f u n c -
tion of t i m e as c a l c u l a t e d for step 2 conditions along
with the e x p e r i m e n t a l v a l u e s .
With the aid of the model, the e x p e r i m e n t a l a l u m i n i -
zation e v e n t s were c h a r a c t e r i z e d for the two p r o c e s s
s t e p s . During step 1 the total a l u m i n i d e coating grows
parabolica21y, after an i n i t i a l t r a n s i e n t period, with
r a t e s that i n c r e a s e with i n c r e a s i n g t e m p e r a t u r e . The
coating is p r e d o m i n a n t l y y phase but the v o l u m e p e r -
centage of y in the coating d e c r e a s e s with i n c r e a s i n g
t e m p e r a t u r e (96 pct ), at 870~ 93.5 pct y at 930~
and ~ 80 pct y at 1000~ ~ l a y e r s n e v e r exceed 1 pct
of the total coating t h i c k n e s s in e i t h e r the c a l c u l a t i o n s
o r the e x p e r i m e n t a l e v a l u a t i o n s . The step 2 t r e a t m e n t
r e s u l t s in the growth of the 5 l a y e r with only a slight
i n c r e a s e in total coating t h i c k n e s s (~ 10 pct i n c r e a s e
d u r i n g the l o n g e s t h o m o g e n i z a t i o n t r e a t m e n t s ) . The
c o n c e n t r a t i o n g r a d i e n t developed in y d u r i n g step 1
p e r s i s t s in the e a r l y s t a g e s of step 2 t r e a t m e n t r e s u l t -
ing in s o m e slight growth of the y l a y e r in the model
c a l c u l a t i o n s . As this g r a d i e n t d i m i n i s h e s , 6 - l a y e r
growth i n c r e a s e s , with r a t e s much h i g h e r than in step
1. The 5 - l a y e r growth r a t e is c a l c u l a t e d to be p a r a -
b o l i c once the y - l a y e r g r a d i e n t r e d u c e s to a n e g l i g i b l e
value. The e x p e r i m e n t a l 5 - l a y e r growth exhibits this
p a r a b o l i c b e h a v i o r a f t e r an i n i t i a l t r a n s i e n t period.
The s e q u e n c e of events d u r i n g step 2 is p r e s e n t e d in
Fig. 8 as a s e r i e s of c a l c u l a t e d c o n c e n t r a t i o n d i s t a n c e
p r o f i l e s at i n c r e a s i n g t i m e s , tr, used in the figure, is
the t i m e at which the y-5 i n t e r f a c e r e v e r s e s d i r e c t i o n
"l_o
)<
1.0
/
de,iotio.,
model predicted
curve
I
//f -
v
_o
I
nr
"i
,
oO 0.5
/ B-ro-C>
1
'J~'~ L s~ L L I L
0 1.0 2.0
HOMOGENIZATION TIME x l O - 4 s
Fig. 7--Plot of 5-1ayer thickness as a functionof homogenizing
time (step 2) as calculated by the numerical model utilizing
the values of Dy and D6 determinedin this experiment. Ex-
perimental values and standard deviationsare also included.
Values of y-6 interface turnaround time (tr) and the time at
which parabolic growth begins (5tr) are indicated for each of
the three homogenizing conditions.
VOLUME 6A, MARCH 1975-435

~ C
~o ~ Jk
~o ~, ~s
~o ~, position ~2 ~3
Fig. 8--Sequence of calculated concentration-distance profiles
for a homogenization treatment at 930~ showing the growth of
the 5 layer. F i r s t profile, t = tr; second, t = 6tr; third, t = 9t r.
from inward (resulting from residual step 1 gradients)
to o u t w a r d (the s o l u t i o n of 7 into 6) a s c a l c u l a t e d in the
numerical model.
C H A R A C T E R I Z A T I O N O F CONTROLLING
PARAMETERS
Step 1 ( a l u m i n i z i n g ) : The n u m e r i c a l m o d e l was v a l u -
able in d e t e r m i n i n g the r a t e c o n t r o l l i n g e v e n t s d u r i n g
the a l u m i n i z a t i o n p r o c e s s . The f o u r - p h a s e n u m e r i c a l
m o d e l ( 7 - 6 - E - [ ) p r e d i c t e d p a r a b o l i c growth of a l l p h a s e
l a y e r s . The E l a y e r , b e i n g e x t r e m e l y thin in the c a l c u -
l a t i o n s , was d r o p p e d f r o m the n u m e r i c a l m o d e l (in
s o m e c a s e s ) with no n o t i c e a b l e change in growth r a t e s
f o r the r e m a i n i n g c o a t i n g p h a s e s (7 and 6). The s o l u -
b i l i t y l i m i t s for the r e m a i n i n g p h a s e s w e r e not a l t e r e d .
The r e m o v a l of E - l a y e r c a l c u l a t i o n s f r o m the m o d e l
without changing the p r e d i c t i o n s f o r 7 and 5 l a y e r t h i c k -
n e s s e s i n d i c a t e s that no s i g n i f i c a n t c o n t r o l of c o a t i n g
growth is c o n t r i b u t e d b y the ~ - p h a s e diffusion. The
t h r e e - p h a s e diffusion m o d e l (7-6-~) was a l s o s o l v e d
b y an a n a l y t i c a l , " c l o s e d - f o r m " m e t h o d a s d e s c r i b e d
in Appendix B. The n u m e r i c a l m o d e l and the c l o s e d -
f o r m m o d e l gave n e a r l y i d e n t i c a l v a l u e s f o r 7 and 5
l a y e r t h i c k n e s s e s o v e r a l l input c o n d i t i o n s . A n a l y s i s
with the use of the c l o s e d - f o r m s o l u t i o n d e v e l o p e d a d -
d i t i o n a l i n f o r m a t i o n on r a t e c o n t r o l l i n g p a r a m e t e r s
d u r i n g s t e p 1.
The n u m e r i c a l m o d e l shows growth to t a k e p l a c e
both i n w a r d l y (motion of the 5 - [ i n t e r f a c e ) and o u t -
w a r d l y (motion of the o u t e r 7 s u r f a c e ) r e l a t i v e to a
r e f e r e n c e point in the s u b s t r a t e f a r r e m o v e d f r o m the
diffusion zone. The a l u m i n i d e c o a t i n g growth is g e n -
e r a l l y d e p e n d e n t on the d i f f u s i o n a l f l u x e s within the 7
and 6 l a y e r s a s well a s t h o s e in the ~ s u b s t r a t e .
With the a l u m i n u m - n i c k e l s y s t e m in the t e m p e r a t u r e
r a n g e of this study, l a r g e i n e q u a l i t i e s b e t w e e n the 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 r e s u l t in s p e c i f i c s o l u t i o n s to
the diffusion equations in which not a l l the f l u x e s a r e
influential. The p a r a b o l i c m o t i o n of the 5-~ i n t e r f a c e
is represented by
~2 = 2 K 2 (/~6/) V2
with the c o n s t a n t K S g e n e r a l l y d e p e n d e n t on f l u x e s and
i n t e r f a c e p o s i t i o n s throughout the s y s t e m ~ H o w e v e ~
due to the n a t u r e of the i n e q u a l i t y of the D v a l u e s (D 7
436-VOLUME 6A, MARCH 1975
>> D 5 >> D c ) , K z b e c o m e s a v e r y s t r o n g function of J 7
and Js, while JC h a s v i r t u a l l y no effect. T h i s is a p p a r -
ent b y e x a m i n i n g the c l o s e d - f o r m s o l u t i o n in Appendix
B. Ks is given i m p l i c i t l y in Eq. [9c] of the appendix
( r e p e a t e d below).
K 2 = - (S 2 exp ( - g ~ ) - t~sIR"~2/"-1/2exp ( - g ~ ~b2)})/
(~/2(c6~- c~)) [6]
with B 2 and B 3 b e i n g s y s t e m c o n s t a n t s defined in A p -
pendix B, C s e and C~e the e q u i l i b r i u m i n t e r f a c e c o n -
c e n t r a t i o n s for 5 and ~, and 4)2 the r a t i o D 6/Dc. The
b r a c k e t s ({ }) contain the p o r t i o n of K 2 d e p e n d e n t on
the diffusion in ~. I n t r o d u c i n g the definition f o r Bs,
this p o r t i o n of K S ( l a b e l l e d Z) b e c o m e s :
exp ( - g ~ q52)
Z = (C O - C~e) qS~1/2 1 - e r f ( K S ~ 2 1/z.)
" [7]
C O is the s u b s t r a t e a l u m i n u m c o n c e n t r a t i o n . F o r
(K S r > 10 (the s i t u a t i o n for a l l a l u m i n i z i n g c o n d i -
tions in this study) the r a t i o of the e x p o n e n t i a l to the
c o m p l e m e n t a r y e r r o r function c o n v e r g e s to K 2 q~/2 ~1/2
and Z b e c o m e s :
Z : (C o - C ~ e ) g 2 ~ 1/2 [8]
R e i n t r o d u c i n g Z and the definition of B2, Eq. [6] b e -
c o m e s , on r e a r r a n g e m e n t :
g 2 exp ( g ~ ) ( e r r ( g 2) - e r f (K 1 c,b~/2))
= ~'/~(c6~- c 6 ~ ) / ( c 6 ~ - Co) [9]
K 2 is no l o n g e r a function of the d i f f u s i o n a l f l u x e s in ~.
Eq. [9] is the s o l u t i o n that would d e v e l o p f o r the c a s e
of no g r a d i e n t in ~. Since K o and K~ a r e r e l a t e d to the
JC t h r o u g h K2, t h e y a l s o a r e independent of ~ - p h a s e
diffusion. The a l u m i n i d e c o a t i n g growth r a t e is n e a r l y
c o m p l e t e l y c o n t r o l l e d b y diffusion in the 7 and 6 p h a s e s
alone.
F o r / ~ v > D6 the c o a t i n g growth t a k e s p l a c e p r e d o m i -
n a n t l y within the 7 p h a s e . By v a r y i n g the r a t i o D T / D 6
= ~bI in the m a t h e m a t i c a l model, the r a t i o of 7 to 6
l a y e r t h i c k n e s s e s can be c o m p u t e d along with the d e -
g r e e to which 3/and 6 f l u x e s c o n t r o l a l u m i n i d e c o a t i n g
growth. F o r v a l u e s of 051 > 30, the a l u m i n i d e c o a t i n g
t h i c k n e s s a p p r o a c h e s the t h i c k n e s s p r e d i c t e d b y c o n s i d -
e r i n g 7 f l u x e s alone ( i . e . , a twoLphase, 7-~ model), qS~
r a t i o s ( c a l c u l a t e d f r o m D~ and D 5 d e t e r m i n e d f r o m the
e x p e r i m e n t a l l a y e r growth k i n e t i c s ) d e c r e a s e with i n -
c r e a s i n g t e m p e r a t u r e (from 140 at 870~ to 31 at
1000~ but a r e s t i l l within the r a n g e for p r e d o m i n a n t
c o n t r o l of a l u m i n i d e growth b y y - l a y e r f l u x e s . Fig. 9
is helpful in d e m o n s t r a t i n g this point. The i n t e r f a c e
p o s i t i o n s d u r i n g s t e p 1 t r e a t m e n t s (as defined in F i g .
B - l ) a r e n o r m a l i z e d b y the c h a r a c t e r i s t i c diffusion
length, (4DTt) ~/2. When t h e s e v a l u e s a r e p l o t t e d a g a i n s t
~ , the b a n d s in F i g . 9 r e s u l t . The s p r e a d within t h e s e
b a n d s is due to the change in s o l u b i l i t i e s of the p h a s e s
with t e m p e r a t u r e . The ~b~ r a t i o s for e a c h of the t h r e e
e x p e r i m e n t a l t e m p e r a t u r e s a r e denoted b y the v e r t i c a l
l i n e s . The points w h e r e t h e y i n t e r s e c t the c a l c u l a t e d
v a l u e s f o r ~ i / ( 4 D T t ) ~/z a r e a l s o noted. The d e c r e a s e
in ~ with i n c r e a s i n g t e m p e r a t u r e a c c o u n t s f o r the
[5]
g r e a t e r p e r c e n t a g e of 6 in the c o a t i n g a f t e r s t e p 1 e x -
p e r i m e n t a l t r e a t m e n t s at 1000~ H o w e v e r , the t o t a l
coating t h i c k n e s s f o r a l l t h r e e t e m p e r a t u r e s r e m a i n s
a s t r o n g function of/~3' alone with l i t t l e effect due to
METALLURGICAL TRANSACTIONS A
 .2
dX = 89 -t [11]
dt
h-'.2~_ IOOO= 930= 870= with
i=2

C~
2
, ,,c-,~:;~,
8? O ~ 1 7 6 C l
....
i=2
X = layer thickness
c = temperature-dependent constant.
I n t e g r a t i o n of the above e q u a t i o n b e t w e e n the s t a r t of
E p a r a b o l i c g r o w t h (tl) and any o t h e r t i m e w i l l y i e l d an
N_
-.I
F[ e x p r e s s i o n f o r the 6 - l a y e r t h i c k n e s s (X 5) a s a function
of h o m o g e n i z a t i o n t i m e (t) m e a s u r e d f r o m the s t a r t of
the s t e p 2 t r e a t m e n t .
/ / v,IOOO=C i=O 2(5 c2 t
'~-/~1//2112~/////////// r--/-/7 f XdX = -~- /dr [J2a]
~+~"~ 47o.c
x6 t tl
-.3 or~
3 PHASE M O D E L - - / 2 PHASE
MODEL X 5 = c { t - ti + (Xsi,/c)'-}t/2 [12b]
with X61 = 6 - l a y e r t h i c k n e s s at Q.
Fig: 9--Normalized interface positions as a function of R e w r i t i n g Eq. [12b],
d)1(Dy/Ds) showing the change in the relative amount of y and
6 phases present during aluminizing (step 1). The bands are X 6 = c (te) 1/2 [13]
generated by a three-phase (y-6-~) "closed f o r m " model for
diffusion. }0 = surface position, ~I = y-5 interface position, with
~2 = 6-~ interface position. (~I ratios as determined from the
experimental growth kinetics for three temperatures are indi- te = t - tl + (X5l/c)'-
cated.
Eq. [13] is v a l i d f o r p r e d i c t i n g X 6 for v a l u e s of t _> t~
(te >>- (x6~/c)2).
i n c r e a s i n g / ~ 5 ( d e c r e a s i n g Or) until the ~b1 r a t i o b e - The c o n s t a n t c can b e d e t e r m i n e d f r o m an a n a l y t i c a l
c o m e s l e s s than 30. s o l u t i o n for m u l t i l a y e r diffusion s i m i l a r to that u s e d in
Step 2 ( h o m o g e n i z a t i o n ) : The p r e d o m i n a n t f e a t u r e of Appendix B. The V-6 i n t e r f a c e v e l o c i t y is due to a flux
t h i s s t e p i s the growth of the 5 l a y e r , p r i m a r i l y b y the in 5 alone,
d i s s o l u t i o n of the V l a y e r . T h r e e s t a g e s of 5 - l a y e r
growth a r e s u g g e s t e d b y the n u m e r i c a l m o d e l . F i r s t 8~1 J___5 x=~l [14]
Ot Cy6 - CSy
is a s h o r t p e r i o d of slow 6 growth due to the r e s i d u a l
g r a d i e n t s f r o m s t e p 1 t r e a t m e n t . Second is a t r a n s i - while the v e l o c i t y of the 5-e i n t e r f a c e is due to the d i f -
tion p e r i o d d u r i n g which the V l a y e r c h a n g e s f r o m f e r e n c e in f l u x e s b e t w e e n 5 and e,
growth to d i s s o l u t i o n while the 5 - l a y e r growth r a t e i n -
c r e a s e s . F i n a l l y , a p e r i o d of p a r a b o l i c 5 - l a y e r growth, aG _ J~-J~ [ [15]
d u r i n g which the V l a y e r i s c o n s u m e d to f o r m 5, is o b - 3t C6e- C e 6 [ x=~2
s e r v e d . C o n t r o l is n e a r l y t o t a l l y due to f l u x e s within Solving for ~ and ~2 a s in Appendix B y i e l d s :
the 5 l a y e r .
With the l a c k of an a l u m i n u m s u r f a c e input, the c o n - ~t = 2K~' ( D s t ) ~/e [16]
c e n t r a t i o n g r a d i e n t in V is r e d u c e d . The d r i v i n g f o r c e ~2 = 2K2' ( f i 6 t ) l/z [17]
f o r v - l a y e r growth is r e d u c e d and e v e n t u a l d i s s o l u t i o n
t a k e s p l a c e . The V-5 i n t e r f a c e no l o n g e r p e n e t r a t e s i n - Since X6 = G - ~t
w a r d l y but r e v e r s e s i t s d i r e c t i o n and m o v e s b a c k t o - X 5 = 2(K2' - Ki) (/~5 t) '/2 [18]
w a r d the s u r f a c e . The t i m e (tr) at which the 7-5 i n t e r -
f a c e t u r n s a r o u n d can be d e t e r m i n e d f r o m the n u m e r i - and
c a l m o d e l , t r is v e r y s t r o n g l y d e p e n d e n t on the t h i c k - C = 2(Kz' -- K i) (D6) 1/2 [19]
n e s s of the V l a y e r (X~/) and the d i f f u s i v i t y in that l a y e r
K 't and K~ both c o m e f r o m the a n a l y t i c s o l u t i o n using
(Dy). The r e s u l t s of m a n y n u m e r i c a l p r e d i c t i o n s have
the a p p r o p r i a t e i n t e r f a c e c o n c e n t r a t i o n s and i n t e r d i f -
y i e l d e d the following a p p r o x i m a t i o n f o r t r ( m e a s u r e d
f u s i o n c o e f f i c i e n t s f o r the t e m p e r a t u r e of c o n c e r n . The
f r o m the s t a r t of s t e p 2) c o n c e n t r a t i o n t h r o u g h o u t the V l a y e r was s e t at the m i n -
t~ ~ ~ x ~ / G [101 i m u m a l u m i n u m c o n c e n t r a t i o n (Cy6). G r a d i e n t s in 5,
E, and ~ w e r e c o n s i d e r e d in the c l o s e d - f o r m s o l u t i o n
with although l i t t l e effect on 6 - l a y e r g r o w t h was d e m o n -
s t r a t e d b y the s m a l l flux v a l u e s in the E and ~ p h a s e s .
I
0.23 at 870~
a r = ~ 0.19 at 930~
V a l u e s f o r c f o r the t h r e e t e m p e r a t u r e s of c o n c e r n
were determined.
( 0 . 1 1 at 1000~
1 . 4 6 x 10 -1 m / s V2 at T = 870~
In the f i n a l s t a g e of 6 - l a y e r growth the v - l a y e r g r a d i - c = 3.07 x 10 -~ m / s t/" at T = 930~ [20]
ent h a s v i r t u a l l y d i s a p p e a r e d so t h a t the 6 - l a y e r growth 7 . 6 0 x 10 -~ m / s ~/2 at T = 1000~
into the 7 l a y e r is u n d e r the influence of 6 - l a y e r f l u x e s
alone. The growth r a t e of the 6 l a y e r is then i n v e r s e l y In o r d e r to d e t e r m i n e te, v a l u e s f o r t~ and X~t w e r e
p r o p o r t i o n a l to its t h i c k n e s s , i . e . , o b t a i n e d f r o m the n u m e r i c a l solution. H o w e v e r , a good

METALLURGICAL TRANSACTIONS A VOLUME 6A, MARCH 1975-437

a p p r o x i m a t i o n f o r t e h a s b e e n found f r o m the r e s u l t s of c) t h i r d , as the V g r a d i e n t a p p r o a c h e s z e r o , the c o n -
many numerical solutions. tinued 5 - l a y e r growth has p a r a b o l i c k i n e t i c s dependent
on the diffusional f l u x e s in the 5 p h a s e ; m a j o r p a r a m -
te ~ t - 3t r [21]
e t e r s c o n t r o l l i n g t h i s s t a g e of 6 - l a y e r growth include
Eq. [13] can b e u s e d to give a v e r y a c c u r a t e d e s c r i p t i o n the s o l u b i l i t i e s at the y - 5 i n t e r f a c e (C75 , C57), the
of 5 - l a y e r growth f o r h o m o g e n i z a t i o n t i m e s g r e a t e r m i n i m u m a l u m i n u m s o l u b i l i t y in 5 (C 5 e), the a l u m i -
than 5 t r (t e > 2 t r ) using the a p p r o x i m a t i o n for t e and the num content in the b a s e n i c k e l (Co) , and the i n t e r d i f -
c o n s t a n t c. 5 growth r e m a i n s p a r a b o l i c until the e n t i r e f u s i o n c o e f f i c i e n t in 5 (/~5)"
V l a y e r is c o n s u m e d . Using Eq. [13] f o r 5 - l a y e r growth
r e s u l t s in n e a r l y i d e n t i c a l p r e d i c t i o n s to t h o s e d e v e l -
APPENDIX A
oped in the n u m e r i c a l m o d e l . V a l u e s of m u l t i p l e s of t r
a r e noted on the 6 - l a y e r growth c u r v e s in F i g . 7. The A n a l y t i c s o l u t i o n s to the s e t of p a r t i a l d i f f e r e n t i a l
m a j o r p o r t i o n of the 6 - l a y e r growth (for t > 5 t r ) can equations d e s c r i b i n g m u l t i p h a s e , moving i n t e r f a c e d i f -
b e p r e d i c t e d b y u s i n g Eq. [13]. f u s i o n s i t u a t i o n s a r e often t e d i o u s , s e n s i t i v e to c a l c u -
l a t e d o r t a b u l a t e d function v a l u e s , o r i m p o s s i b l e f o r
given b o u n d a r y c o n d i t i o n s . However, n u m e r i c a l a p -
SUMMARY AND CONCLUSIONS p r o x i m a t i o n s can be u s e d to g e n e r a t e v a l u e s of the s o -
lution functions f o r any s e t of b o u n d a r y and i n i t i a l c o n -
A n a l y s i s of the t w o - s t e p a l u m i n i d e c o a t i n g p r o c e s s
f o r the b i n a r y n i c k e l - a l u m i n u m s y s t e m was c a r r i e d d i t l o n s d e s i r e d . The n u m e r i c a l a p p r o x i m a t i o n in this
out b y m a t h e m a t i c a l m o d e l l i n g using n u m e r i c a l and w o r k c o n s i s t e d of finite d i f f e r e n c e e q u a t i o n s which
w e r e a n a l o g o u s to and c o m p a t i b l e with the d i f f e r e n t i a l
s i m p l i f i e d a n a l y t i c a l m e t h o d s . The p r i n c i p a l a s s u m p -
t i o n s of the m o d e l included l o c a l e q u i l i b r i u m at the e q u a t i o n s along with s u i t a b l y a p p r o x i m a t e d b o u n d a r y
p h a s e l a y e r i n t e r f a c e s , c o n c e n t r a t i o n independent i n - c o n d i t i o n s . The s o l u t i o n function ( a l u m i n u m c o n c e n t r a -
t e r d i f f u s i o n c o e f f i c i e n t s , and c o n s t a n t p a r t i a l m o l a r tion a s a function of t i m e and d i s t a n c e ) is not found e x -
p l i c i t l y in this t y p e of a p p r o x i m a t i o n , but s p e c i f i c v a l -
v o l u m e s for a l u m i n u m and n i c k e l . The n e c e s s a r y s o l -
ues of the s o l u t i o n function a r e g e n e r a t e d at d i s c r e e t
u b i l i t y d a t a and 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 f o r the e
and ~ p h a s e s w e r e o b t a i n e d f r o m the l i t e r a t u r e . The t i m e i n t e r v a l s and p o s i t i o n s ( c a l c u l a t i o n nodes). The
V and 6 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 w e r e d e t e r m i n e d p a r t i a l d i f f e r e n t i a l e q u a t i o n s , the e q u i v a l e n t finite d i f -
f r o m e x p e r i m e n t a l r e s u l t s allowing for a b e t t e r fit of f e r e n c e e q u a t i o n s , and the b o u n d a r y and i n i t i a l c o n d i -
tions u s e d to d e s c r i b e diffusion in the n i c k e l - a l u m i n u m
the m a t h e m a t i c a l m o d e l and e x p e r i m e n t a l l a y e r growth
c o a t i n g s y s t e m a r e p r e s e n t e d in T a b l e IV. The d i f f e r -
k i n e t i c s . A good d e s c r i p t i o n of e x p e r i m e n t a l d a t a b y
the m o d e l was o b t a i n e d f o r both the a l u m i n i z i n g s t e p e n c e e q u a t i o n s w e r e i n d e x e d a c c o r d i n g to the t i m e and
( p r i m a r i l y growth of the ~, p h a s e (NizAI3)) and the h o - p o s i t i o n c a l c u l a t i o n node.
m o g e n i z i n g s t e p ( p r i m a r i l y growth of the 6 p h a s e
(NiAI) b y s o l u t i o n of the V p h a s e ) .
The e x p e r i m e n t a l d a t a on l a y e r growth k i n e t i c s and I Enter constants I
the m o d e l w e r e u s e d to define and a n a l y z e the r a t e - I
Approximate
c o n t r o l l i n g p a r a m e t e r s in the growth of a l u m i n i d e c o a t -
ing l a y e r s for the b i n a r y n i c k e l - a l u m i n u m s y s t e m . F o r
the a l u m i n i z i n g s t e p :
initial conditions
l
z~xi &
I
a) the c o a t i n g p r o c e s s c o n s i s t s p r i m a r i l y of the p a r a -
b o l i c growth of the V l a y e r a f t e r an i n i t i a l " t r a n s i e n t "
Calcutate z~t I
p e r i o d . The o v e r a l l r a t e of coating is high b e c a u s e of
the l a r g e f l u x e s o b t a i n a b l e at the s u r f a c e of the V l a y e r
I Set boundary conditions
I
(due to the l a r g e DT).
b) the growth of the V p h a s e is p r i m a r i l y c o n t r o l l e d I C tcut t -'i & d~i/dt I
1
b y i t s own d i f f u s i o n a l f l u x e s which p r e c l u d e any s i g n i f -
i c a n t growth of the ~ p h a s e and r e s u l t s in a 5 l a y e r that
i s only ~ 5 to 20 pct of the t o t a l c o a t i n g t h i c k n e s s . I
c) m a j o r c o n t r o l of c o a t i n g l a y e r growth is due (in [Reset Ci,j,k due to
a d d i t i o n to D 7) to the s u r f a c e and i n t e r f a c e c o n c e n t r a - ... varying grid
t i o n s in V, ( C s , C76), and the i n i t i a l c o n c e n t r a t i o n of I
a l u m i n u m in the b a s e n i c k e l (Co). A d d i t i o n a l e f f e c t s
with l e s s e r influence a r e due to the d i f f u s i o n a l f l u x e s
[ Catcutate Ci,j,k+1 I
I
in the 6 p h a s e , which b e c o m e s o m e w h a t g r e a t e r as Reset time accumulation
temperature increases.
F o r the h o m o g e n i z i n g s t e p , the 6 - l a y e r growth, p r i -
and update k
I
m a r i l y by the d i s s o l u t i o n o f V, e x h i b i t s t h r e e s t a g e s :
a) f i r s t , at e a r l y h o m o g e n i z a t i o n t i m e s , the 5 l a y e r
growth is c o m p a r a b l e to s t e p 1 as the s y s t e m is s t i l l
under the influence of the y - p h a s e f l u x e s .
b) s e c o n d , 5 - l a y e r growth r a t e s i n c r e a s e a s the g r a -
L Test for disptay or
end conditions
IE dl
|

dient in V d i m i n i s h e s and a t u r n a r o u n d of the V-6 i n t e r - Fig. A-I--Flow diagram of the calculation sequence used in
f a c e t a k e s p l a c e at a t i m e r e l a t e d to y - l a y e r t h i c k n e s s the numerical solutions for both aluminizing (step 1) and ho-
and diffusivity. mogenization (step 2) simulations.

438-VOLUME 6A, MARCH 1975 METALLURGICAL TRANSACTIONS A

 in r e s u l t s w a s o b t a i n e d . T h e t i m e s p a c i n g of t h e n o d e s
Table IV. Continuous and Discreet Equations Describing Diffusion (At) m u s t b e s m a l l e n o u g h f o r t h e s o l u t i o n v a l u e s to
Controlled Layer Growth
converge to the actual solution. Also the interpolation
Partial Differential Finite DifferenceEquations s c h e m e m u s t not b e e x c e e d e d in a n y t i m e s t e p b y t a k -
ing t o o l a r g e a s t e p . T h e f i r s t c o n d i t i o n w a s m a i n -
~c~ ~c tained by incorporating the inequality given as number
3t c'i 8x~ (Ci,/, k + 1 - Ci, L k ) / A t = Dai(Ci,] +i, k - 2 Ci, L k
+c~,/ 1,k)/A~ 9 in T a b l e IV. S i n c e a l l p h a s e l a y e r s i n t e r a c t , t h e y
1
i=i,2,3,4 for calculation in the ith phase at the node indexed m u s t all b e s t e p p e d s i m u l t a n e o u s l y in t i m e . T h e m i n -
at- = ~, ~, e, ~ at the] positionand the k + 1 time step i m u m c o n v e r g e n c e condition m u s t , t h e r e f o r e , apply to
t h e At of a l l p h a s e l a y e r c a l c u l a t i o n s .
(Cai + l, a i - Cai, ai + 1) (Ci+l,],k-Ci,],k)(~i,k+ 1 - ~i,k)/[k~ =/3ai + I T h e s e q u e n c e of c a l c u l a t i o n s p r e d i c t i n g c o n c e n t r a -
~i ~ bC (-Ci+l,]+2,k + 4 C i + l , ] + l , k - 3Ci+l,t,k) t i o n s a n d b o u n d a r y p o s i t i o n s w a s p e r f o r m e d on a d i g i t a l
ot=D~i+l~-xlX=e~ 2 /2 AXi+ 1 -Dai(Ci,]-2,k- 4Ci,/-1,k + 3Ci,/, k) computer. The major calculation sequence is outlined
/2Ax~ in F i g . A - 1 . T h e r e s u l t i n g s o l u t i o n v a l u e s w e r e m o n i -
-b~ia--cl for calculation of ~i at the position step ] contain-
~x x = ~i t o r e d b y m e a n s of o v e r a l l m a s s b a l a n c e c a l c u l a t i o n s
ing tire interfaceat the k + 1 time step
or by comparison with analytical solutions to the set
Boundary Conditions-Aluminization of e q u a t i o n s a n d b o u n d a r y c o n d i t i o n s w h e n p o s s i b l e .
C=C~atx=O C l , t , k =C$
t >~O
APPENDIX B
C=Co a t x = ~ C4, m,k = Co m = last position step in ~-phase,
t~>0 Analytical solution for a three-phase, semi-infinite,
node is movedby AX4/2 wheneverC4,m, k
~<0.999 Co at which time the boundary condi- p l a n a r d i f f u s i o n p r o b l e m : Fig. B-1 is a s c h e m a t i c c o n -
tion is reset. centration distance profile for this diffusion problem
a t t i m e (t) > 0. T h e p o s i t i o n of e a c h i n t e r f a c e , ~i, i = 0,
C = equilibriumcon- Ci, ], k = equilibriumvaluesat ] correspondingto
centration valuesat 1, 2) i s a s s u m e d t o b e p r o p o r t i o n a l t o t 1/~ a n d of t h e
position of ~i
X=~ i form:
Boundary Conditions-Homogenization ~o = 2Ko (g~, t) ~/2 [la]
0c
-- = 0 a t x = 0 el, 0,k = CI, 2,k with surface located at/= l ~1 = 2 K 1 ( D v t ) ' / z [lb]
~x 6
t~>0 node ~2 = 2 K , ( ~ , t ? / 2 [lc]
4 and 5 as in alumini- 4 and 5 as in aluminization
zation
7 The velocity of each interface is then:
Variable Grid-Calculation a~o/at = K o ( D v / t ) ~/z [2a]
8 Axi =(~/' k -~i-l,k)/ni - 1) O( 1 / O t = K 1 ( D r / t ) ~/a [2b]
n i = number of nodes in the ith phase/> 11
8~2/~t = K 2 ( / ~ 6 / t ) I/z [2c]
9 At ~<minimumof 1/4 (D~i/Ax])
w i t h K~ b e i n g t h e p r o p o r t i o n a l i t y c o n s t a n t a n d /~ t h e
Concentration AdjustmentDue to Variable Grid
interdiffusion constant for the subscripted phase.
lO qlj, k =c~,/,k + [(C~,:.l,k- q,/+~,k)/:~3 Mass balance equations at each interface take into
[(I - /i/ni)(~i,k - el,k-I) + (/i/ni)(~it,k a c c o u n t t h e m a s s f l u x to a n d f r o m e a c h i n t e r f a c e a s
-~i-~,k-01 well as the interface motion.
]i = node indexedfrom ~i-1
O ~ o / ~ t : - Jo+/(1 - Cs) [3a]
8},/at = (J1- - J,+)/(CT5 - CsT) [35]

An e x p l i c i t c a l c u l a t i o n s c h e m e was used to develop O~z/3t = (J2- - J z § - C6e) [3c]

the solution v a l u e s at each finite t i m e step. 17 B e c a u s e
the i n t e r f a c e s have changing p o s i t i o n s with t i m e it was 1.O
n e c e s s a r y to shift the c a l c u l a t i n g nodes a c c o r d i n g l y . A
fixed n u m b e r of e q u a l l y s p a c e d nodes w e r e a s s i g n e d to
each phase through the e n t i r e t i m e range. The shift in
node p o s i t i o n with each t i m e step r e q u i r e d an adjust-
ment in the indexed concentration v a l u e c o r r e s p o n d i n g
to the new node position. This was a c h i e v e d by use of C~
an interpolating equation as s u g g e s t e d b y Murray and
Landis ~s and g i v e n in Table IV.
E x p l i c i t c a l c u l a t i o n s c h e m e s r e q u i r e the t i m e - s p a c e
grid of c a l c u l a t i o n nodes to be of n e c e s s a r i l y s m a l l
d i m e n s i o n s . The s p a c i n g of the nodes (AX) in each of co~J
the p h a s e s m u s t be s m a l l enough to a c c u r a t e l y r e p r e - ~o 0 ~, ~z
sent the slope and c u r v a t u r e of the c o n c e n t r a t i o n d i s - PosHion
Fig. B - l - - C o n c e n t r a t i o n - d i s t a n c e profile for a 3-phase (y-6-~)
tance p r o f i l e s . A value of &X l e s s than 10 pct of the
approximation for a 4 - p h a s e s y s t e m (T-6-r when the E layer
phase l a y e r width was shown to be s a t i s f a c t o r y in ap- is v e r y thin. Interface positions and concentrations are Iabeltec
p r o x i m a t i n g t h e s e c u r v e s . This was done by continu- as they a r e used in the " c l o s e d - f o r m " solution. Arrows i n d i -
a l l y r e d u c i n g the AX v a l u e until no s i g n i f i c a n t change cate interface motion.

METALLURGICAL TRANSACTIONS A VOLUME 6A, MARCH 1975-439

with Ji- b e i n g the flux at ~i c o m p u t e d f r o m the n e g a -
t i v e s i d e and Ji§ the flux f r o m the p o s i t i v e s i d e .
Ji- : - D ' ~ z 8 C / 8 x x - - ~i [4a]
Ji+ =-Dai+I OC/Sx x--~i [4b]
with ~i being the i-th phase (i = 0, I, 2; ~i = ~, 6, ~).
The concentration within each phase is a function of
both time and position. The relationship is:
C (x, t) = A i + B i e r f (x//4Dai t) 1/~"
within e a c h of the t h r e e p h a s e s . A i and B i a r e c o n -
s t a n t s a s s o c i a t e d with e a c h p h a s e and a r e the r e s u l t of
the s u r f a c e , i n t e r f a c e , and infinite b o u n d a r y c o n d i t i o n s
(i.e., C = C76 at x = ~1_). T h e s e c o n s t a n t s a r e given in
E q s . [Ta] t h r o u g h [7c] f o r the t h r e e p h a s e s .
B 1 = (C76 - C s ) / ( e r f (K~) - e r f (Ko))
B 2 = (C 6 9 - C~./)/(erf (g~) - e r r (g~b~/~))
S s = (C O - C ~ 9 e r f (K2~5~/2))
A , = 89 s + C76) - B , (erf ( g 1) + e r f (go))
A~_ = 8 9 1 4 9 C61, ) - S 2 ( e r f (K2) + e r f (KlqS[/2))
As = ~t ( C o + CC 9 - Bs(1 + e r f (K2~5~/2))
with ~ = D T / D ~ , ~ = D 6 / D ~ .
T a k i n g the p a r t i a l d i f f e r e n t i a l s , a s i n d i c a t e d in Eq.
[4], f l u x e s at the i n t e r f a c e s a r e d e t e r m i n e d . T h e s e
f l u x e s , when s u b s t i t u t e d into Eqs. [3a] to [3c], y i e l d
on r e a r r a n g i n g :
~o/Ot = -~7/ ~ n~ ' e x p ( - K ~ o ) / ( n ' / = t ' / = ( 1 - Cs))
9e x p ( - g ~ d ) ~ ) ) / / ~ ' / ~ t ~ / = ( C 6 7 - C3, 6)
8~/8t = - (D~/=Bz e x p ( - g~) - D}/~-B s
9exp(-g~q~=))/(~r~/2t~/=(C~ 9 C 6 9
T h e s e t h r e e e q u a t i o n s , when c o m b i n e d with Eqs. [2a]
t h r o u g h [2c] give t h e f l o l l o w i n g e x p r e s s i o n s for Ki:
g o = B , e x p (-KZo)/(Tr ~/~ (1 - Cs) )
440-VOLUME 6 A , M A R C H 1975
K 1 = - ( B I e x p ( - K ~ ) - Bzd)-~~/2
9exp (-K~qS~))l(n ~/2 (C63, - C3,6)) [9b]
K~ = - (B2 exp ( - g ~ ) - --s-~2rt
~_,/2
9e x p ( - K~2))/(Tr ~/2 (C~ 9 - C 6 9 [9c]
Solving for K i with the a i d of a c o m p u t e r w i l l allow
for the c h a r a c t e r i z a t i o n of e i t h e r the i n t e r f a c e p o s i -
t i o n s o r the c o n c e n t r a t i o n - d i s t a n c e p r o f i l e s for any
given t i m e 9
[5]
ACKNOWLEDGMENTS
The a u t h o r s g r e a t l y a p p r e c i a t e the f i n a n c i a l s u p p o r t
and e n c o u r a g e m e n t of the M e t a l l u r g y B r a n c h of the
Office of N a v a l R e s e a r c h . In addition, the a u t h o r s a p -
p r e c i a t e the f e l l o w s h i p s u p p o r t of the F a n n i e and John
[6a] H e r t z Foundation. The a u t h o r s a l s o a c k n o w l e d g e s e v -
e r a l useful d i s c u s s i o n s with G. W. Coward, P r a t t and
[6b] Whitney D i v i s i o n of United A i r c r a f t .
[6c]
[Ta] RE F E R E N C E S
1. G. W. Goward: Y. Metals, 1970, vol. 22, no. 10, p. 31.
[75] 2. G. W. Goward, D. H. Boone, and C. S. Giggins: Trans. ASM, 1967, vol. 60,
[7c] no. 2, p. 228.
3. T. K. Redden: Trans. TMS-AIME, 1958, vol. 242, p. 1695.
4. G. Llewelyn: ASTM-STP421, 1967, p. 3.
5. Committee on Coatings, Nat. Mat. Adv. Bd., Nat. Res. Council: High-Tempera-
ture Oxidation Resistant Coatings, Nat. Acad. Sci./Nat. Acad. Eng., Wash., D.C.,
1970.
6. R. Sivakumar, N. B. Menon, and L. L. Seigle: Met. Trans., 1973, vol. 4, p. 396.
7. M. Hansen: Constitution of Binary Alloys, McGraw-Hill, New York, 1958.
8. M. J. Pleetwood: Y. Inst. Metals, 1970, vol. 98, p. 1.
[8a] 9. R. A. Tanzilli and R. W. Heckel: Trans. TMS-AIME, 1968, vol. 242, p. 2313.
l 0. R. D. Lanam and R. W. Heckel: Met. Trans., 197 l, vol. 2, p. 2255.
I 1. R. W. Heckel, A. J. Hickl, R. J. Zaehring, and R. A. Tanzilfi: Met. Trans.,
1972, vol. 3, p. 2555.
[85] 12. W. Jost: Diffusion in Solids, Liquids, and Gases, Academic Press, New York,
1960.
13. H. Hara and R. W. Balluffi: J. AppL Phy~, 1955, vol. 27, p. 954.
[8c] 14. M. M. P. Janssen and G. D. Rieck: Trans. TMS-AIME, 1967, vol. 239, p. 1372.
15. L. S. Castleman and L. L. Seigle: Trans. TMS-AIME, 1958, vol. 212, p. 589.
16. M. M. P. Janssen: Met. Trans., 1973, vol. 4, p. 1623.
17. W. E. Milne: Numerical Solution of Differential Equations, Dover Pub., New
York, 1970.
[9a] 18. D. Murray and F. Landis: Trans. ASMESer. D, 1959, vol. 81, p. 106.
METALLURGICAL TRANSACTIONS A