Control of 'Particle Size and Volume Fraction
in the High Temperature Superalloy Udimet 700
E. H. VAN DER MOLEN, J. M. OBLAK, AND O. H. KRIEGE
Experiments were conducted to determine the chemical composition, volume fraction and par-
ticle size of the 7 ' precipitate in Udimet 700 as a function of temperature and time. Growth of
the 7 ' particles was found to follow t ~/3 diffusion controlled coarsening kinetics. The composi-
tion of 7 ' varied only slightly with temperature and was independent of time. From this infor-
mation, a method was developed to estimate the volume fraction and average particle size of
the 7 ' precipitate for any given heat treatment. It is suggested that this approach could be ap-
plied to other 7 ' strengthened superalloys.
NICKEL-BASE s u p e r a l l o y s are widely used in appli-
cations requiring strength at high temperatures. Most
of these alloys are precipitation hardened by a Ni3
(Al, Ti) 7 ' phase which has an ordered fcc structure
(LI2) and precipitates coherently in a nickel-rich fcc 7
matrix. The strength of a given alloy is dependentupon
such factors as volume fraction, particle size, coars-
ening rate, and composition (antiphase boundary en-
ergy) of the 7 ' precipitate. All of these factors can be
controlled to varying degrees by heat treatment; but
since most standard heat treatments have evolved em-
pirically, little is known quantitatively about the influ-
ence of time and temperature on the ~' precipitate in
commercial alloys. Information of this type would be
valuable not only in the desigm of heat treatments for
superalloys but also for understanding the effects of
high service temperatures where coarsening and per-
haps partial solution of the ~' phase occur.
There have been several contributions of interest in
this area. Kriege and Baris ~ have determined the com-
position and volume fraction of the 7 ' precipitate in a
large number of commercial alloys following standard
heat treatment. Ardell2-~ and others 6'7 have demon-
strated that in simple binary or ternary ~ - ~ ' (low
volume fraction) systems, growth of the ~' precipitate
obeys a diffusion-controlledcoarsening model where
the average particle radius increases linearly with
time to the one-third power, r c~t ~/3. In addition,
Mitchell 8 has shown that the coarsening of 7 ' in the
relatively simple, low volume fraction superalloy Ni-
monic 80A is also diffusion-controlled. Recently, the
effect of high volume fraction and irregular distribu-
tion of second phase particles on coarsening kinetics
has been evaluated mathematically.9 It was shown
that a t ~/3 coarsening rate will be obtained for an ar-
ray of spherical particles when coarsening is con-
trolled by volume diffusion, even though the Lifshitz-
Wagner theory ~~ of diffusion-controlledcoarsening
may not accurately describe the system. It has not
yet been experimentally shown, however, that a t '/3
kinetic law holds for complex commercial alloys con-
taining large volume fractions of the 7 ' phase.
In this study Udimet 700 was chosen as being a rep-
E. H. VAN DER MOLEN, formerly Research Assistant, Pratt &
Whitney Aircraft, Middletown, Conn., is now Research Metallurgist,
General Electric Aircraft Engine Division, Evendale, Ohio. J. M.
OBLAK and O. H. KRIEGE are Senior Research Associate and Re-
search Supervisor, respectively, Pratt & Whitney Aircraft.
Manuscript submitted December 14, 1970.
METALLURGICALTRANSACTIONS
reseatative advanced high temperature nickel-base
superalloy. Characterization of the alloy included
determination of the volume fraction, particle size
and c o m p o s i t i o n of the 7 ' p r e c i p i t a t e as a function of
t i m e and t e m p e r a t u r e . P r e c i s e q u a n t i t a t i v e d e t e r m i -
nation of the v o l u m e f r a c t i o n and c o m p o s i t i o n of the
7 ' p h ase was p o s s i b l e u si n g the technique of 7 ' s e p a -
r a t i o n r e c e n t l y r e f i n e d by K r i e g e and c o w o r k e r s . 1'~2
The r e s u l t s define the e x t e n t to which the 7 ' p h ase
can be c o n t r o l l e d by heat t r e a t m e n t . F u r t h e r m o r e ,
the p a r t i c l e s i z e data d e m o n s t r a t e that the growth of
the 7 ' p r e c i p i t a t e in this high v o l u m e f r a c t i o n n i c k e l -
b a s e alloy follows t ~/s diffusion c o n t r o l l e d c o a r s e n i n g
kinetics.
M A T E R I A L S AND E X P E R I M E N T A L P R O C E D U R E
C o m m e r c i a l l y a v a i l a b l e wrought U d i m e t 700* b a r
* Cr Co Mo Ti AI B C Mn Si Ni
wt pet 14.5 17.5 5.1 3.7 4.1 0 .0 t 5 0.08 - - Bal.
st o ck was u s e d in this study. The m i c r o s t r u c t u r e of
this alloy a f t e r a r e p r e s e n t a t i v e high t e m p e r a t u r e age
is p r e s e n t e d in Fig. 1. All s p e c i m e n s w e r e annealed
above the 7 ' s o l v u s t e m p e r a t u r e f o r 4 hr at 2150~F
followed by a f a s t a i r cool. The ~ ' s o l v u s t e m p e r a t u r e
was d e t e r m i n e d m e t a l l o g r a p h i c a l l y . The e q u i l i b r i u m
v o l u m e f r a c t i o n of ~,' at v a r i o u s t e m p e r a t u r e s was d e -
t e r m i n e d f o r s a m p l e s aged in the t e m p e r a t u r e r a n g e
1300 ~ to 2000~ In a l l o y s such as U d i m e t 700 addi-
tional fine y ' p a r t i c l e s u s u a l l y f o r m upon cooling a f t e r
e x p o s u r e at high aging t e m p e r a t u r e s . F o r a c c u r a t e
d e t e r m i n a t i o n of y ' v o l u m e f r a c t i o n at a given t e m -
p e r a t u r e , it is i m p e r a t i v e that t h e r e be no p r e c i p i t a -
tion of such cooling 7 ' . F o r this r e a s o n thin s p e c i m e n s
(2.5 m m thick) w e r e d r o p - q u e n c h e d in iced b r i n e d i -
r e c t l y f r o m the heat zone of a v e r t i c a l f u r n a c e a f t e r
aging. T r a n s m i s s i o n e l e c t r o n m i c r o s c o p y as shown in
Fig. 2 c o n f i r m e d that aged s p e c i m e n s q u e n c h e d f r o m
2000"F o r below w e r e f r e e of fine cooling 7 ' -
The v o l u m e f r a c t i o n of 7 ' in the aged s a m p l e s was
m e a s u r e d by an e x t r a c t i o n m e t h o d . E x t r a c t i o n of the
7 ' was p e r f o r m e d by anodic d i s s o l u t i o n of the m a t r i x
using an e l e c t r o l y t e c o m p o s e d of 1 pet a m m o n i u m s u l -
fate and 1 pct c i t r i c acid in w a t e r , z Since c a r b i d e s a r e
i n so l u b l e in this e l e c t r o l y t e , a c o r r e c t i o n f o r c a r b i d e
co n t am i n at i o n was n e c e s s a r y . T h e r e f o r e , a second
anodic d i s s o l u t i o n which s e p a r a t e d only c a r b i d e s was
VOLUME 2, JUNE 1971-1627
 Fig. l~Udimet 700 aged for 4 hr at 2000~F. Magnification
1190 times.
Fig. 2--Absence of fine coolingT' in Udimet 700 quenched
from 2000~ The coarse particles were present before
quenching.
p e r f o r m e d and the a m o u n t of Y' was obtained by weight
d i f f e r e n c e m e a s u r e m e n t s . (The c o r r e c t i o n turned out
to be m i n o r s i n c e the amount of c a r b i d e s was slight,
1 wt pct.) C o n v e r s i o n of weight f r a c t i o n 7 ' to v o l -
u m e f r a c t i o n V' was s i m p l i f i e d b e c a u s e c a l c u l a t i o n
showed that the two w e r e e s s e n t i a l l y equivalent. When
p o s s i b l e , the v o l u m e f r a c t i o n d e t e r m i n a t i o n s w e r e
c h e c k e d by r e p l i c a m i c r o s c o p y . Such r e s u l t s w e r e in
a g r e e m e n t , but the l a r g e s c a t t e r in the data obtained
f r o m r e p l i c a s indicated that the e x t r a c t i o n method was
m u c h m o r e r e l i a b l e . The c o m p o s i t i o n of the e x t r a c t e d
Y' was d e t e r m i n e d by an a t o m i c a b s o r p t i o n method. ~3
P a r t i c l e s i z e m e a s u r e m e n t s w e r e m a d e on the e x -
t r a c t e d y ' p a r t i c l e s . Since the p a r t i c l e s w e r e not in
situ, g r e a t c a r e was taken to obtain a r e p r e s e n t a t i v e
d i s t r i b u t i o n of p a r t i c l e s i z e s . A s m a l l quantity of
w e l l - m i x e d p a r t i c l e s was d e p o s i t e d on a carbon film
s u p p o r t e d by a c o p p e r grid. P h o t o g r a p h s of the p a r -
t i c l e s w e r e taken in a Hitachi HU-11A e l e c t r o n m i c r o -
s c o p e , at l e a s t fifty p a r t i c l e s p e r s p e c i m e n being pho-
tographed. The s i z e of the g e n e r a l l y cuboidal p a r t i c l e s
1628-VOLUME2, JUNE 1971
Fig. 3--Extracted y, used for particle size measurements
after heat treatment of 1900~ for 27 hr.
was d e t e r m i n e d by taking the a v e r a g e of the p a r t i c l e
width and length f r o m e n l a r g e d p r i n t s such as that
shown in Fig. 3. The a c c u r a c y of this method was
c o n f i r m e d by c o m p a r i s o n to in situ p a r t i c l e s i z e s
m e a s u r e d by dark field t r a n s m i s s i o n e l e c t r o n m i c r o -
scopy, for e x a m p l e , F i g . 2.
RESULTS
Solvus T e m p e r a t u r e of u
The y ' solvus t e m p e r a t u r e is the u p p e r l i m i t for
p r e c i p i t a t i o n of the y ' phase. To d e t e r m i n e this t e m -
p e r a t u r e , s p e c i m e n s w e r e f i r s t aged at 1900~ to ob-
tain c o a r s e y ' , then h e a t e d to a t e m p e r a t u r e above
2050~F, held 1 hr, and rapidly cooled. The k i n e t i c s of
~ ' d i s s o l u t i o n at t h e s e t e m p e r a t u r e s a r e v e r y rapid and
the e q u i l i b r i u m v o l u m e f r a c t i o n is attained in a m a t t e r
of s e c o n d s . As shown in Fig. 4, 7 ' is d i s t r i b u t e d h e t -
e r o g e n e o u s l y in the s a m p l e e x p o s e d at 2055~ at
2065~F, it is seen only at grain b o u n d a r i e s ; a,ld at
2075~ it is absent. T h e s e r e s u l t s indicate that the
s o l v u s t e m p e r a t u r e is 2070 = & 5~
Volume F r a c t i o n of y '
The e q u i l i b r i u m v o l u m e f r a c t i o n of 7 ' was d e t e r -
m i n e d for t e m p e r a t u r e s f r o m 1300"F to the solvus. A
plot of this data is p r e s e n t e d in Fig. 5. Since e x p e r i -
m e n t a l r e s u l t s d i s c u s s e d below showed that t h e r e was
no m e a s u r a b l e i n c r e a s e in v o l u m e f r a c t i o n of ~ ' a f t e r
l o n g e r p e r i o d s , a s t a n d a r d aging t i m e of 16 hr was
used. The m a x i m u m amount of ~ ' p r e s e n t in the alloy
is 38 vol pct and this amount is p r e c i p i t a t e d by agiz~g
at 1650=F or l o w e r . Above 1650~F, the e q u i l i b r i u m
v o l u m e f r a c t i o n of y ' d e c r e a s e s g r a d u a l l y but at a con-
tinuously i n c r e a s i n g r a t e with t e m p e r a t u r e . H o w e v e r ,
s i g n i f i c a n t amounts of 7 ' p e r s i s t to high t e m p e r a t u r e s .
F o r e x a m p l e , 14 vol pct is p r e s e n t at 2000~ only 70"F
below the solvus.
The e f f e c t of aging t i m e on the v o l u m e f r a c t i o n of y '
p r e c i p i t a t e d is indicated in T a b l e I. Within e x p e r i m e n -
tal e r r o r , the amount of ~.' is e s s e n t i a l l y independent
of aging t i m e . T h i s r e s u l t is due to the e x t r e m e l y r a p i d
k i n e t i c s of Y' p r e c i p i t a t i o n . P r e v i o u s l y r e p o r t e d work
by K r i e g e and Sullivan ~2 on U d i m e t 700 d e m o n s t r a t e d
M E T A L L U R G I C A L TRANSACTIONS