Dispersion Strengthened Superalloys by

Mechanical Alloying
JOHN S. BENJAMIN

A new p r o c e s s called " m e c h a n i c a l a l l o y i n g " has b e e n developed which p r o d u c e s homogeneous

c o m p o s i t e p a r t i c l e s with an i n t i m a t e l y d i s p e r s e d , u n i f o r m i n t e r n a l s t r u c t u r e . M a t e r i a l s f o r m e d
by hot consolidation of this powder achieve the l o n g - s o u g h t c o m b i n a t i o n of d i s p e r s i o n s t r e n g t h -
e n i n g and a g e - h a r d e n i n g in a high t e m p e r a t u r e alloy. While the p r o c e s s is a m e n a b l e to m a k i n g
a v a r i e t y of alloys, its f i r s t use has been to c o m b i n e y t t r i u m oxide and g a m m a p r i m e h a r d e n i n g
in a complex n i c k e l - b a s e s u p e r a l l o y . T y p i c a l s t r e s s r u p t u r e p r o p e r t i e s a r e 40,000 psi for 100
h r at 1400~ and 15,000 p s i for 100 hr at 1900~ together with e x c e l l e n t sulfidation and
cyclic oxidation r e s i s t a n c e . F r o m a f u n d a m e n t a l standpoint, r e s u l t s show that the a g e - h a r d e n -
ing d o m i n a t e s the l o w - t e m p e r a t u r e s t r e n g t h , d i s p e r s i o n s t r e n g t h e n i n g d o m i n a t e s at high t e m -
p e r a t u r e , and the two a r e a u g m e n t a t i v e in the i n t e r m e d i a t e t e m p e r a t u r e range 1300 ~ to 1500~

T u s e of i n H e r t additions to E improve elevated temper-

a t u r e m e c h a n i c a l p r o p e r t i e s in m e t a l s was f i r s t e x -
ploited in 1910 by W. D. Coolidge 1 in t h o r i a t e d t u n g s t e n .
The fact that o t h e r m i n o r a d d i t i o n s or " d o p a n t s " could
also i n c r e a s e c r e e p r e s i s t a n c e was soon d i s c o v e r e d .
T h e s e m a t e r i a l s were m a i n l y d e s i g n e d for sag r e s i s -
t a n c e , r e q u i r i n g the s t r e n g t h to s u p p o r t t h e i r own
weight for v e r y long t i m e s at high t e m p e r a t u r e s .
The f i r s t d i s p e r s i o n s t r e n g t h e n e d m a t e r i a l d e s i g n e d
as a s t r u c t u r a l load b e a r i n g s y s t e m was SAP. 2 A d i s -
p e r s i o n of a l u m i n u m oxide flakes in a l u m i n u m c o n f e r r e d
s t r e n g t h in this s y s t e m up to the m e l t i n g point of the
a l u m i n u m m a t r i x . Studies showed s'4 that the s t r e n g t h of
this m a t e r i a l i n c r e a s e d with i n c r e a s i n g v o l u m e f r a c t i o n
of the oxide and with d e c r e a s i n g i n t e r p a r t i c l e spacing.
The r e l a t i v e l y low m e l t i n g point of a l u m i n u m , however,
r e p r e s e n t s a s e v e r e l i m i t a t i o n for u s e at elevated t e m -
p e r a t u r e s . This led to a t t e m p t s to apply d i s p e r s i o n
s t r e n g t h e n i n g to higher m e l t i n g point b a s e s such a s
copper and n i c k e l , s In these m e t a l s , the self oxides
cannot be used as they a r e not s u f f i c i e n t l y stable a g a i n s t
Ostwald r i p e n i n g growth at e l e v a t e d t e m p e r a t u r e s . Even
though the p r o b l e m s of e s t a b l i s h i n g a fine d i s p e r s i o n of
s u f f i c i e n t l y r e f r a c t o r y oxide in a high m e l t i n g m e t a l
m a t r i x , for e x a m p l e T,hO2 in n i c k e l , w e r e solved, 6 and
m e c h a n i c a l w o r k i n g t e c h n i q u e s giving v a s t l y i m p r o v e d
high t e m p e r a t u r e s t r e n g t h w e r e developed, 7 the r e s u l t -
ing d i s p e r s i o n s t r e n g t h e n e d m e t a l s w e r e still l i m i t e d
in t h e i r u s e f u l n e s s by t h e i r low s t r e n g t h at i n t e r m e d i a t e
t e m p e r a t u r e and lack of c o r r o s i o n r e s i s t a n c e .
While s o m e s u c c e s s has b e e n achieved in p r o d u c i n g
a d i s p e r s i o n s t r e n g t h e n e d c o r r o s i o n r e s i s t a n t alloy
with an 80 Ni-20 C r m a t r i x this a l l o y s t i l l s u f f e r s f r o m
r e l a t i v e l y low i n t e r m e d i a t e t e m p e r a t u r e c r e e p s t r e n g t h .
Hypothetically these s h o r t c o m i n g s could be solved by
c o m b i n i n g the c o r r o s i o n r e s i s t a n c e and i n t e r m e d i a t e
t e m p e r a t u r e s t r e n g t h of ~,' p r e c i p i t a t i o n h a r d e n e d n i c -
k e l - b a s e s u p e r a l l o y s with the high t e m p e r a t u r e s t r e n g t h
and s t a b i l i t y of oxide d i s p e r s i o n s t r e n g t h e n i n g . The p r i -
m a r y h u r d l e to be o v e r c o m e to make such a m a t e r i a l is
the p r o d u c t i o n of a d i s p e r s i o n of fine r e f r a c t o r y oxide
JOHN S. BENJAMIN is Supervisor, Composites Section, Paul D.
Merica Research Laboratory, The InternationalNickel Co., Sterling
Forest, Suffern, N. Y.
Manuscript submitted February 2, 1970.
p a r t i c l e s l e s s than 0.1 # in size upon o r within an alloy
powder p a r t i c l e in such a m a n n e r as to lead to i n t e r -
p a r t i c l e s p a c i n g s of l e s s than 0.5 ~z in a c o n s o l i d a t e d
product.
It is a well known fact that the m o s t effective p r e c i p i -
tation h a r d e n i n g e l e m e n t s in n i c k e l - b a s e a l l o y s , a l u m i -
num, t i t a n i u m , and n i o b i u m , a r e e a s i l y oxidized. T h e i r
oxidation would r e m o v e them as p r e c i p i t a t i o n h a r d e n e r s .
T h e r e f o r e , oxygen c o n t a m i n a t i o n m u s t be kept low
enough to leave s u f f i c i e n t y ' f o r m e r s in a r e d u c e d state
to give adequate age h a r d e n i n g for i n t e r m e d i a t e t e m -
p e r a t u r e s t r e n g t h . In addition the c o m b i n a t i o n of effec-
tive oxide d i s p e r s i o n s t r e n g t h e n i n g and p r e c i p i t a t i o n
h a r d e n i n g m u s t be a c c o m p l i s h e d at a r e a s o n a b l e cost.
T h e r e a r e four m a j o r t e c h n i q u e s which have been
used p r e v i o u s l y to c o m b i n e oxide d i s p e r s i o n s t r e n g t h -
ening and solid s o l u t i o n s t r e n g t h e n i n g in alloy s y s t e m s
containing relatively nonreactive elements. A brief
c o n s i d e r a t i o n of the n a t u r e and l i m i t a t i o n s of each of
t h e s e t e c h n i q u e s will show why they a r e not suited to
the t a s k of p r o d u c i n g an alloy c o n t a i n i n g ~':
Simple m e c h a n i c a l m i x i n g involves the u s e of a high
speed blenderS, 9 o r a ball m i l l 1~to coat the s u r f a c e of
a m e t a l o r alloy powder with oxide-powders. The i n t e r -
p a r t i c l e spacing in the consolidated a l l o y produced f r o m
these powders is l i m i t e d by the s t a r t i n g m e t a l powder
p a r t i c l e size. P o w d e r s i z e s of l e s s than 5 ~t a r e r e -
q u i r e d to get s u f f i c i e n t l y fine i n t e r p a r t i c l e s p a c i n g s
even with l a r g e m e c h a n i c a l r e d u c t i o n s d u r i n g c o n s o l i -
dated and s u b s e q u e n t working o p e r a t i o n s . P o w d e r s
this fine c o n t a i n i n g y ' f o r m e r s such as a l u m i n u m and
t i t a n i u m a r e v e r y r e a c t i v e b e c a u s e of t h e i r high specific
s u r f a c e a r e a and c o m p l e t e o r n e a r l y c o m p l e t e oxidation
of a l u m i n u m and t i t a n i u m can r e s u l t .
Ignition s u r f a c e coating technique 11 i n v o l v e s mixing
m a t r i x alloy p o w d e r s with a liquid s o l u t i o n of a salt of
a r e a c t i v e m e t a l . This m i x t u r e is d r i e d and p u l v e r i z e d
and the powders a r e heated in an i n e r t o r r e d u c i n g e n -
v i r o n m e n t c o n v e r t i n g the salt to a r e f r a c t o r y oxide.
This technique also p r o d u c e s oxide coated powders
which have, t h e r e f o r e , the s a m e d i s a d v a n t a g e s as pow-
d e r s produced by the s i m p l e m e c h a n i c a l m i x i n g t e c h n i -
que. In addition, t h e r e is a g r e a t e r c o n t a m i n a t i o n p r o -
b l e m b e c a u s e of the oxidizing potential of the r e a c t i o n
p r o d u c t s of the s a l t d e c o m p o s i t i o n step.
I n t e r n a l oxidation technique 12-17 i n v o l v e s exposing

METALLURGICALTRANSACTIONS VOLUME l, OCTOBER 1970 2943

m e t a l powders o r thin m e t a l s t r i p c o n t a i n i n g a dilute
solid s o l u t i o n of a r e a c t i v e e l e m e n t to an oxidizing e n -
v i r o n m e n t at elevated t e m p e r a t u r e s . The r e a c t i v e e l e -
m e n t i s c o n v e r t e d to a d i s p e r s o i d by diffusing oxygen.
It has b e e n found e x o e r i m e n t a l l y 17 that the p a r t i c l e
size of the d i s p e r s o i d i n c r e a s e s with i n c r e a s i n g depth
of p e n e t r a t i o n of the i n t e r n a l oxidation front into the
m e t a l . V e r y fine, c o n t a m i n a t i o n - p r o n e powders o r e x -
p e n s i v e u l t r a - t h i n s t r i p a r e r e q u i r e d to obtain s u f f i -
c i e n t l y fine d i s p e r s o i d p a r t i c l e s i z e s . In the case w h e r e
the a l l o y also c o n t a i n s r e a c t i v e T ' f o r m i n g e l e m e n t s
such a s t i t a n i u m and a l u m i n u m , an additional p r o b l e m
would a r i s e . The oxygen p o t e n t i a l could not be r a i s e d
above the e x t r e m e l y low v a l u e s r e q u i r e d to oxidize the
7t f o r m i n g e l e m e n t s and the oxidation rate of the d e -
s i r e d d i s p e r s o i d f o r m i n g e l e m e n t s would be p r o h i b i -
tively slow.
S e l e c t i v e r e d u c t i o n p r o c e s s s has b e e n used to m a n u -
facture commercial dispersion strengthened materials.
It i n v o l v e s producing an i n t i m a t e m i x t u r e of m e t a l o x -
ides, and s e l e c t i v e l y r e d u c i n g the oxides of the m a t r i x
alloy while leaving the d i s p e r s o i d u n r e d u c e d . If a l u m i -
num and t i t a n i u m a r e to be p r e s e n t in the m a t r i x alloy,
the r e d u c t i o n step is not p o s s i b l e with g a s e s b e c a u s e of
the s t a b i l i t y of AltOs and TiO2. T h e s e oxides can be
r e d u c e d by the u s e of m o l t e n a l k a l i and a l k a l i n e e a r t h
m e t a l s . However, this i n t r o d u c e s two m a j o r new p r o b -
l e m s : e x c e s s i v e growth of the d i s p e r s o i d p a r t i c l e s , and
the n e c e s s i t y to r e m o v e the r e a c t i o n product oxides
and c a r r i e r agent, u s u a l l y a s a l t .
In this p r e s e n t i n v e s t i g a t i o n a new " m e c h a n i c a l a l l o y -
i n g " technique has b e e n developed which c i r c u m v e n t s
the p r e v i o u s s h o r t c o m i n g s and p e r m i t s the effective
c o m b i n a t i o n of oxide d i s p e r s i o n s t r e n g t h e n i n g and T'
p r e c i p i t a t i o n h a r d e n i n g in n i c k e l - b a s e s u p e r a l l o y s .
E X P E R I M E N T A L PROCEDURE
Raw M a t e r i a l s
The raw m a t e r i a l s u s e d i n this study were Type 123
c a r b o n y l nickel powder of 4 to 7 ~z p a r t i c l e size, c h r o -
m i u m powder of - 2 0 0 m e s h s i z e , d i s p e r s o i d s c o n s i s t i n g
of t h o r i u m oxide and y t t r i u m oxide of 100 to 500/~ p a r -
ticle s i z e s , and N i - A 1 - T i v a c u u m - m e l t e d m a s t e r a l l o y
c r u s h e d to powders of --200 m e s h p a r t i c l e size. The
m a s t e r a l l o y powders w e r e e m p l o y e d to reduce the r e -
a c t i v i t y of a l u m i n u m and t i t a n i u m below that of t h e i r
e l e m e n t a l powder f o r m s . T h i s technique is c o m m o n l y
used in p y r o m e t a l l u r g y for the addition of v o l a t i l e e l e -
m e n t s . The t h e r m o d y n a m i c a c t i v i t i e s (partial p r e s -
s u r e s ) of the r e a c t i v e e l e m e n t s a r e r e d u c e d by f i r s t
a l l o y i n g t h e m with one of the m a j o r c o n s t i t u e n t s o~ the
alloy. An example is the addition of n i c k e l - z i r c o n i u m
to a m o l t e n n i c k e l - b a s e alloy. The m a s t e r alloy t e c h -
nique has also b e e n p r e v i o u s l y employed in powder
m e t a l l u r g y in the p r o d u c t i o n of a l l o y s c o n t a i n i n g a r e -
active component.18
In the Ni-A1 s y s t e m , it has b e e n shown that the a c t i v -
ity c o e f f i c i e n t of a l u m i n u m is 1.8 • 10-4 on the n i c k e l -
r i c h side of the i n t e r m e t a l l i c compound NiA1 at 1800~ 19
The a c t i v i t y of a l u m i n u m in this compound is r e d u c e d
n e a r l y t e n - t h o u s a n d fold beyond a s i m p l e R a o u l t ' s law
dilution. This effect was used to p r o t e c t the a l u m i n u m
and t i t a n i u m additions to the a l l o y s in this study by u s -
ing a compound c o n s i s t i n g of 65 at. pct Ni and 35 at. pct
2944-VOLUME 1. OCTOBER 1970
of the s u m of AI and Ti. Z i r c o n i u m and b o r o n w e r e
also added as m a s t e r a l l o y s .
E q u i p m e n t and P r o c e s s i n g
The alloy p o w d e r s produced in this study w e r e p r o -
c e s s e d in Model 1-S and 10-S Szegvari A t t r i t o r G r i n d i n g
Mills *z~ d e s i g n e d for paint and ink p r o d u c t i o n . T h e s e
* RegisteredTrademarkof UnionProcess,Inc.
m a c h i n e s a r e high e n e r g y d r i v e n b a l l m i l l s i n which the
charge of b a l l s and powder is held in a s t a t i o n a r y , v e r -
tical, w a t e r cooIed tank and agitated by i m p e l l e r s r a d i -
ating f r o m a r o t a t i n g c e n t r a l shaft.
The a t t r i t o r c h a r g e c o n s i s t e d of 10 kg of powder with
175 kg of +0.6 c m nickel p e l l e t s . U n l e s s o t h e r w i s e s p e -
cified, b a t c h e s w e r e p r o c e s s e d at 132 r p m f o r 40 h r in
a sealed a i r a t m o s p h e r e . After s c r e e n i n g to r e m o v e
the c o a r s e +45 m e s h p a r t i c l e s , the r e m a i n i n g powder
was packed in s t e e l e x t r u s i o n cans, e v a c u a t e d to l e s s
than 0.01 # at 7 5 0 ~ and s e a l e d by f u s i o n welding. The
powders w e r e c o n s o l i d a t e d by hot e x t r u s i o n in a c o n -
v e n t i o n a l 750 ton e x t r u s i o n p r e s s at t e m p e r a t u r e s of
2150~ o r below with e x t r u s i o n r a t i o s of 12:1 or g r e a t e r .
U n l e s s o t h e r w i s e stated s p e c i m e n s w e r e heat t r e a t e d
a s follows: 2 h r at 2 3 2 5 ~ in argon, a i r cool; 7 h r at
1975~ in a i r , a i r cool; 16 h r at 1300~ in a i r , a i r cool.
The f i r s t t r e a t m e n t was for h o m o g e n i z a t i o n and g r a i n
growth while the l a s t two t r e a t m e n t s w e r e c o n v e n t i o n a l
n i c k e l - b a s e s u p e r a l l o y solution and aging t r e a t m e n t s .
Standard t e c h n i q u e s w e r e employed in m e t a l l o g r a p h i c
s p e c i m e n p r e p a r a t i o n . Elevated t e m p e r a t u r e t e n s i l e
and s t r e s s r u p t u r e t e s t s w e r e p e r f o r m e d i n a i r a c c o r d -
ing to ASTM s p e c i f i c a t i o n s E 2 1 - 6 6 T and E139-66T.
E X P E R I M E N T A L RESULTS AND DISCUSSION
R e s u l t s and t h e i r d i s c u s s i o n fall 5nto two i n t e r r e l a t e d
c a t e g o r i e s : e v a l u a t i o n of the m e c h a n i c a l a l l o y i n g p r o -
c e s s , and c h a r a c t e r i s t i c s of the r e s u l t i n g d i s p e r s i o n
strengthened, precipitation hardened superalloys.
M e c h a n i c a l Alloying P r o c e s s
The d i s p e r s i o n s t r e n g t h e n e d alloys for this study
w e r e made by the d r y , high e n e r g y m e c h a n i c a l alloying
technique. The key f e a t u r e s of this p r o c e s s a r e the high
e n e r g y m i l l i n g and the o m i s s i o n of any s u r f a c e active
agent other than the a i r s e a l e d into the a t t r i t o r tank
with the c h a r g e . T h i s p r a c t i c e a c t u a l l y p r o m o t e s p a r -
ticle welding in c o n t r a s t to c o n v e n t i o n a l m e t a l ball m i l -
ling p r a c t i c e s i n which welding is i n h i b i t e d by u s e of
liquids and s u r f a c t a n t s .
The n a t u r e of the m e c h a n i c a l a l l o y i n g p r o c e s s can
b e s t be u n d e r s t o o d by r e f e r e n c e to the i n t e r n a l s t r u c -
t u r e s of powder p a r t i c l e s p r o c e s s e d for v a r y i n g lengths
of time with all o t h e r p r o c e s s i n g c o n d i t i o n s held fixed.
In o r d e r to i I l u s t r a t e the r a t e of d e v e l o p m e n t of the
composite p a r t i c l e s t r u c t u r e , b a t c h e s of powder w e r e
p r o c e s s e d for six t i m e i n t e r v a l s f r o m 1.5 to 40 h r d u r a -
tion. P h o t o m i c r o g r a p h s o r i g i n a l l y taken at 250X of
s a m p l e s of powder f r o m these b a t c h e s a r e shown in
Fig. 1. Fig. l(a) shows the s t r u c t u r e of powder p r o c e s -
sed for 1.5 hr. Note that the f o r m a t i o n of c o m p o s i t e
m e t a l p a r t i c l e s h a s begun. Many of t h e s e p a r t i c l e s a r e
METALLURGICAL TRANSACTIONS
 Unprocessed Unprocessed
lklir k~al Chromium

.~r Alloy
nent
Unprocessed
Master Alloy lickel Matrix

nium
~ent

<~)L . . . _ ~ J
Composite Phrticle

Fig. 1--Structures of composite powders pro-

c e s s e d for v a r i o u s t i m e s in a 1O-S a t t r i t o r
q~) (c) o p e r a t e d at 132 rpm. Ball c h a r g e : 175 kg of
+.6 c m nickel pellets; 10 kg of powders. (a)
1.5 h r ; (b)3.5 h r ; (c)9.5 hr; (a3 20 hr; (e)30 hr;
(f) 40 hr. Magnification 163 t i m e s .

(a) (e)
within the composite particles can be identified. Ex-
amples of these features are labeled in Fig. l(a). Un-
processed nickel is identified by its small size and rela-
tively equiaxed cross section. The larger, single-phase,
light particles are unprocessed chromium. The master
alloy powders can be identified by the fact that they are
two-phased. Within the composite particles the chro-
mium fragments stand in strong relief against the light
gray nickel matrix. The darker phase of the master
alloy can also be seen.
The dispersoid which was added in the amount of 2.5
vol pct cannot be detected in these photomicrographs.
This oxide was formed by the thermal decomposition
of a less stable compound of the reactive metal. The
(2 decomposition product consisted of very fine 100 to
500]k oxide crystallites arranged in tightly agglomerated
larger than the coarsest starting materials which were pseudomorphs having the approximate size and shape
74 /~ i n s i z e . U n p r o c e s s e d p a r t i c l e s of t h e m a j o r c o n - of the compound particles prior to calcination. These
s t i t u e n t s a n d t h e p r e s e n c e of p r o c e s s e d f r a g m e n t s agglomerates, originally up to 20 # in size, have been

METALLURGICAL TRANSACTIONS VOLUME 1, OCTOBER 1970-2945

s u f f i c i e n t l y b r o k e n a p a r t by the m e c h a n i c a l alloying l u r e s developed in the conventional, low e n e r g y , 15.25
p r o c e s s that the r e s u l t i n g u l t r a f i n e oxide c r y s t a l l i t e s , cm d i a m ball m i l l o p e r a t i n g d r y at 80 r p m u n d e r s t a n d -
d i s t r i b u t e d along weld i n t e r f a c e s within the m a t e r i a l , ard conditions of a 3 - t o - 1 b a l l - t o - p o w d e r ratio and
cannot be r e s o l v e d by the o p t i c a l m i c r o s c o p e . with a h i g h e r 6 - t o - 1 b a l l - t o - p o w d e r r a t i o for 32 and
With i n c r e a s i n g p r o c e s s i n g t i m e the s t r u c t u r e of the 125 h r a r e shown in Fig. 3.
c o m p o s i t e p a r t i c l e s b e c o m e s m o r e u n i f o r m , its s t r i - The s t r u c t u r e of powders of the y t t r i a t e d s u p e r a l l o y
ated n a t u r e , as d e l i n e a t e d by the c h r o m i u m p l a t e t e t s composition p r o c e s s e d for 32 h r with a 3 - t o - 1 b a l i - t o -
b e c o m e s m o r e a p p a r e n t and u n p r o c e s s e d powders a r e powder r a t i o a r e shown in F i g 3(a). Most of the m a t e r i a l
l e s s plentiful. The shape of the c h r o m i u m f r a g m e n t s is unchanged f r o m i t s s t a r t i n g size. Within the few a g -
then b e c o m e s m o r e equiaxed than at s h o r t e r t i m e s and g l o m e r a t e s which o c c u r even the o r i g i n a l n i c k e l p a r t i -
both the s p a c i n g and the size of the f r a g m e n t s a r e m u c h cles c a n be i d e n t i f i e d by outlines of r e f r a c t o r y oxide
smaller. p s e u d o m o r p h f r a g m e n t s n e a r the r e v o l v i n g power of
A f t e r 20 h r of p r o c e s s i n g , s e e Fig. l(d), no l a r g e the optical m i c r o s c o p e in size, see c i r c l e d a r e a in Fig.
c h r o m i u m f r a g m e n t s a r e p r e s e n t within the c o m p o s i t e
p a r t i c l e s . The s t r u c t u r e s of both large and s m a l l c o m -
posite p a r t i c l e s a r e s i m i l a r . With f u r t h e r p r o c e s s i n g
an i n c r e a s i n g p r o p o r t i o n of the c h r o m i u m f r a g m e n t s
within t h e s e p a r t i c l e s b e c o m e r e d u c e d in size below
the r e s o l v i n g power of the optical m i c r o s c o p e , about
0.5 ~. P o w d e r s p r o c e s s e d for 40 hr, see Fig. l ( f ) , and
l o n g e r a r e , t h e r e f o r e , r e l a t i v e l y f e a t u r e l e s s . It is l i k e l y ,
h o w e v e r , that r e f i n e m e n t of the s t r u c t u r e c o n t i n u e s
with i n c r e a s i n g p r o c e s s i n g t i m e but on a level below
that of optical r e s o l u t i o n .
The m e c h a n i c a l alloying p r o c e s s involves the w e l d i n g
of the v a r i o u s powder c o n s t i t u e n t s to the g r i n d i n g c h a r g e
p e l l e t s . An i r r e g u l a r welded l a y e r is b u i l t up which
c o n s t a n t l y flaked off the b a l l s , f r a g m e n t e d and r e w e l d e d .
At each of t h e s e w e l d - f l a k i n g c y c l e s of the p r o c e s s the
d i m e n s i o n s of the c o n s t i t u e n t f r a g m e n t s a r e r e d u c e d 5
to 10 fold in t h e i r s m a l l e s t d i m e n s i o n . Fig. 2 shows a
s e c t i o n through a b a l l w i t h d r a w n at an i n t e r m e d i a t e
stage in the p r o c e s s . Note the welded composite l a y e r
and the n i c k e l ball beneath.
When the p r o c e s s i n g of a b a t c h is complete, a v a l v e
on the b o t t o m of the a t t r i t o r i s opened and the m a c h i n e
is r u n u n t i l the e n t i r e batch has b e e n dewelded and (a)
drained.
The r a p i d h o m o g e n i z a t i o n of s t r u c t u r e obtained in
the high e n e r g y a t t r i t o r can be c o n t r a s t e d with the r a t e
of p r o c e s s i n g in a c o n v e n t i o n a l b a l l m i l l . The s t r u c -

Fig. 3--Structures of composite powders processed for various

times in conventional ball mill operated at 80 rpm. Area of
nickel particles outlined by oxide pseudomorph fragments is
circled in (a). (a) 32 hr, 3-to-1 ball-to-powder ratio; (b) 125
hr, 3-to-1 baH-to-powder ratio; (c) 32 hr, 6-to-1 ball-to-
Fig. 2---Surface of sectioned nickel pellet showing welded com- powder ratio; (d) 125 hr, 6-to-1 ball-to-powder ratio. Magni-
posite layer. Magnification 260 times. fication 240 times.

2946-VOLUME 1,OCTOBER 1970 METALLURGICALTRANSACTIONS


(c)
Fig. 3 - C o n t i n u e d (d)
3(a). T h e s e nickel p a r t i c l e s a r e r e l a t i v e l y equiaxed in
shape. The ball m i l l e d a g g l o m e r a t e s a r e e a s i l y b r o k e n
a p a r t by a V i c k e r s ' m i c r o h a r d n e s s i n d e n t o r with a 100
g load while c o m p o s i t e p a r t i c l e s p r o c e s s e d 40 h r in
the a t t r i t o r withstood at l e a s t a 500 g load. T h e s e o b s e r -
v a t i o n s s u g g e s t that the a g g l o m e r a t e s f r o m the c o n v e n -
tional b a l l m i l l a r e held t o g e t h e r by weak m e c h a n i c a l
i n t e r l o c k i n g r a t h e r than by cold welding typical of high
energy milling.
Powder processed for 125 hr in a 15.25 cm ball mill
with a 3-to-I ball-to-powder ratio, see Fig. 3(b), does
show evidence of welding and has an appearance simi-
lar to powder processed for 1.5 hr in the attritor, see
Fig. l(a).
Batches of yttriated superalloy powder were also
processed in a 15.25 cm ball mill with a higher 6-to-1,
ball-to-powder ratio. The structure of powders pro-
cessed for 32 hr is shown in Fig. 3(c). While a few
welded composite particles are present, the majority
METALLURGICAL TRANSACTIONS
of the powder i s u n p r o c e s s e d and the s t r u c t u r e is l e s s
homogeneous than that of powder p r o c e s s e d for 1.5 hr
in the a t t r i t o r . A f t e r 125 h r of p r o c e s s i n g in a b a l l m i l l
with a 6 - t o - 1 b a l l - t o - p o w d e r ratio, see Fig. 3(d), the
s t r u c t u r e is a p p r o x i m a t e l y e q u i v a l e n t to that of powders
p r o c e s s e d for 3.5 h r in the a t t r i t o r , see Fig. l(b). It i s
c l e a r that an e x t r e m e l y long t i m e would be r e q u i r e d to
obtain the d e s i r e d h o m o g e n e i t y with c o n v e n t i o n a l ball
m i l l i n g if, in fact, such m i l l i n g would e v e r r e s u l t in
s u i t a b l e powders.
T h e s e d i f f e r e n c e s in p r o c e s s i n g r a t e s in an a t t r i t o r
and a c o n v e n t i o n a l b a l l m i l l a r e d i r e c t l y r e l a t e d to the
r e l a t i v e efficiency of the m i l l s and the e n e r g y input
rate achieved in the two m i l l s . The m a x i m u m o p e r a t i n g
speed of a c o n v e n t i o n a l b a l l m i l l is a f u n c t i o n of the
d i a m e t e r of the m i l l . C e n t r i f u g a l p i n n i n g of b a l l s and
powders o c c u r s at higher r o t a t i o n s p e e d s , e2 The a t t r i -
tor, in which the e n e r g y is i m p a r t e d to the b a l l s by the
p a s s a g e of r o t a t i n g i m p e l l e r s through the b a l l charge
and not by r o t a t i n g the e n t i r e m a c h i n e , can be r u n at
e s p e c i a l l y high s p e e d s . F o r example, the c r i t i c a l speed
for a 40.6 cm d i a m b a l l m i l l is about 63 r p m and such
a m i l l would n o r m a l l y be r u n at 43 r p m . A 40.6 cm
d i a m a t t r i t o r is t y p i c a l l y o p e r a t e d at s p e e d s b e t w e e n
125 and 185 r p m .
In the foregoing, the m e c h a n i c a l a l l o y i n g p r o c e s s
has b e e n r e l a t e d to the phenomenon of cold welding, a
p r o c e s s long used to join m e t a l s on the m a c r o s c o p i c
scale, z~ It is known that a t r u e m e t a l l u r g i c a l bond is
f o r m e d when two p i e c e s of m e t a l sheet which have been
cleaned of g r e a s e and g r o s s oxides a r e placed together
and c o m p r e s s i v e l y d e f o r m e d to true s t r a i n s i n e x c e s s
of 1.0. This is d e m o n s t r a t e d by the fact that f a i l u r e of
the welded p i e c e s o c c u r s by t e a r i n g of the p a r e n t m e t a l
r a t h e r than s e p a r a t i o n at the weld i n t e r f a c e . It is also
known that a m i l d coating o r welding a c t i o n can o c c u r
in conventional b a l l m i l l i n g and this fact is employed
in the production of t u n g s t e n c a r b i d e - c o b a l t m a t e r i a l s . 24
However, the d e g r e e to which the p h e n o m e n o c c u r s in
t u n g s t e n - c a r b i d e - c o b a l t production i s slight and the
p r o c e s s i n g t i m e s r e q u i r e d a r e very long.
The r e l a t i v e e a s e of welding an alloy in b a l l m i l l i n g
can be e s t i m a t e d by the e a s e of cold w e l d i n g sheet of
the s a m e m a t e r i a l . This in t u r n is a function of the
r a t i o of the m i l l i n g t e m p e r a t u r e to the m e l t i n g point
of the m a t e r i a l . It can be shown that low m e l t i n g m e t a l s
such as lead and a l u m i n u m can be cold welded v e r y
e a s i l y at room t e m p e r a t u r e and that they also d e m o n -
s t r a t e a g r e a t t e n d e n c y to weld d u r i n g c o n v e n t i o n a l
m i l l i n g . However, h i g h e r m e l t i n g point m e t a l s such as
copper, i r o n , and n i c k e l a r e much m o r e difficult to cold
weld in m a c r o s c o p i c f o r m , r e q u i r i n g 5 to 20 t i m e s as
much e n e r g y i n p u t p e r weld as a l u m i n u m and lead.
S i m i l a r l y , they cannot be welded at r e a s o n a b l e r a t e s
in a c o n v e n t i o n a l b a l l m i l l , but can be r e a d i l y welded
in a high e n e r g y m i l l .
A u n i f o r m fine d i s p e r s i o n of r e f r a c t o r y oxide p a r t i -
cles can be e s t a b l i s h e d by the m e c h a n i c a l a l l o y i n g p r o -
c e s s within r e l a t i v e l y c o a r s e composite powder p a r t i -
cles containing r e a c t i v e e l e m e n t s such as a l u m i n u m
and t i t a n i u m while l i m i t i n g oxygen c o n t a m i n a t i o n to
a c c e p t a b l e l e v e l s . C o a r s e e l e m e n t a l and p a r t i a l l y p r e -
alloyed powders, which a r e stable and r e l a t i v e l y i n e x -
p e n s i v e , can be e m p l o y e d to produce m e c h a n i c a l l y
alloyed p a r t i c l e s , c h e m i c a l l y h o m o g e n e o u s on a s u b -
m i c r o n s c a l e . The s p a c i n g s of c o m p o s i t i o n a l v a r i a t i o n s
VOLUME 1, OCTOBER 1970-2947
 d o m i n a n t l y ThO2 and Alg)~. The m a j o r i t y of these p a r -
Table I. Compositions of Experimental Dispersion Strengthened t i c l e s a r e f i n e r than 1000A and a r e well within the
Nickel-Base Superalloys r a n g e r e q u i r e d for d i s p e r s i o n s t r e n g t h e n i n g .
Alloy C AI Ti Cr Mo Nb Zr B ThO2 Y203 A1203
Properties
A 0.061 0.92 2.46 20.4 0.029 0.005 - 1.22 0.37
B 0.049 0.96 2.77 18.7 0.09 0.003 - 1.33 0.99 The s t r e s s r u p t u r e p r o p e r t i e s of t y p i c a l y~triated
C 0.056 0.90 2.33 20.6 0.065 0.005 - 1.22 0.83 s u p e r a l l o y s A and B at t e m p e r ~ u r e s of 1200 ~ 1400 ~
D 0.055 0,74 2.10 19.0 0.025 0.002 2.71 - 1,30 1500 ~ 1700 ~ and 1900~ a r e shown in Fig. 6. The
E 0.069 4.19 0.82 10.4 3.0 1.6 0.03 0.007 3.00 - 1,38
s t r e s s r u p t u r e p r o p e r t i e s of t h o r i a t e d s u p e r a l l o y D at
t e m p e r a t u r e s of 1200 ~ 1500 ~ 1700 ~ 1850 ~ and 2000~
a r e a c t u a l l y l e s s than those found in m a n y c a s t i n g s . a r e shown in Fig. 7. It is i n t e r e s t i n g to note that the
The d i s p e r s i o n of all the oxides p r e s e n t i n c l u d i n g any slopes of the s t r e s s r u p t u r e plots at h i g h e r t e m p e r a -
p o s s i b l e c o n t a m i n a n t s , is v e r y fine and is achieved in t u r e s , 1900 ~ and 2 0 0 0 ~ a r e l e s s than at lower t e m -
a r e l a t i v e l y short t i m e . p e r a t u r e s , 1200 ~ and 1400~ This i s in d i r e c t c o n t r a s t
to the case for c o n v e n t i o n a l n i c k e l - b a s e s u p e r a l l o y s

D i s p e r s i o n S t r e n g t h e n e d Superalloys
Nothing in the p r e c e d i n g c o n s i d e r a t i o n of the m e c h a n -
ical a l l o y i n g m e c h a n i s m s u g g e s t s that it is r e s t r i c t e d
to any p a r t i c u l a r alloy b a s e . While a wide v a r i e t y of
p r o d u c t s can be made with this p r o c e s s , we shall c o n -
c e n t r a t e h e r e on t h o r i a t e d and y t t r i a t e d n i c k e l - b a s e
s u p e r a l l o y s . The c o m p o s i t i o n s of some of the s u p e r -
a l l o y s which have been produced by the m e c h a n i c a l
alloying p r o c e s s a r e given in T a b l e I.

Structure
T y p i c a l longitudinal and t r a n s v e r s e m i c r o s t r u c t u r e s
of the y t t r i a t e d s u p e r a l l o y , Alloy A, Table I, a f t e r e x -
t r u s i o n and heat t r e a t m e n t a r e shown in Fig. 4. The
heat t r e a t m e n t c o n s i s t e d of a g r a i n c o a r s e n i n g a n n e a l ,
2 h r at 2 3 2 5 ~ solution t r e a t m e n t , 7 hr at 1975~ and
aging, 16 h r at 1300~ The g r a i n s t r u c t u r e of the d i s -
p e r s i o n s t r e n g t h e n e d s u p e r a l l o y s in the p a r t i a l l y and
fully heat t r e a t e d conditions c o n s i s t s of elongated
c y l i n d r i c a l g r a i n s of v e r y i r r e g u l a r c r o s s section. The
long a x e s of the g r a i n s a r e p a r a l l e l to the e x t r u s i o n a x i s (a)
of the b a r . Such elongated s t r u c t u r e s have p r e v i o u s l y
been shown to give s u p e r i o r e l e v a t e d t e m p e r a t u r e p r o -
p e r t i e s in d i s p e r s i o n s t r e n g t h e n e d m a t e r i a l s f l ~ T h i s
has also been found to be t r u e of the d i s p e r s i o n s t r e n g t h -
ened s u p e r a l l o y s c o n s i d e r e d in this i n v e s t i g a t i o n .
V e r y l i t t l e else of the s t r u c t u r e of the heat t r e a t e d
alloy is r e v e a l e d by optical m i c r o s c o p y . The y ' and
YaOa a r e too fine to be r e s o l v e d and only the c a r b i d e s
o r o c c a s i o n a l c o a r s e c o n t a m i n a n t oxides a r e v i s i b l e .
E l e c t r o n m i c r o g r a p h s r e v e a l the c o p r e s e n c e of oxide
and ~ ' c l e a r l y . Fig. 5 shows the s t r u c t u r e at 4950X of
a l o n g i t u d i n a l s e c t i o n of d i s p e r s i o n s t r e n g t h e n e d s u p e r -
alloy E, heat t r e a t e d by a n n e a l i n g 4 h r at 2250~ f o l -
lowed by a f u r n a c e cool. E x a m p l e s of the m i c r o s t r u c -
t u r a l f e a t u r e s a r e labeled. Note the g r a i n b o u n d a r y
A - A ' r u n n i n g diagonally a c r o s s the photograph. T h e r e
a p p e a r s to be both c a r b i d e and ~ ' p r e c i p i t a t e d at this
b o u n d a r y . B e c a u s e of the h i g h e r a l u m i n u m content of
this alloy, see T a b l e I, and the f u r n a c e cooling t r e a t -
m e n t , the ~ ' is p r e s e n t a s c o a r s e i r r e g u l a r p a r t i c l e s
as well a s a fine s e c o n d a r y p r e c i p i t a t e . The r e m a i n i n g
d i s p e r s i o n composed of ThO2, AlaO3, and c a r b i d e p a r t i -
c l e s i s m o s t e a s i l y d i s t i n g u i s h e d within the c o a r s e y' ~)
p a r t i c l e s . The l a r g e r of t h e s e d i s p e r s o i d p a r t i c l e s a r e
Fig. 4-Extruded yttriated superalloy (alloy A, Table I). Heat
p r o b a b l y MC c a r b i d e s and have s i z e s up to 3000/~. T h e treated: 2325~ hr/AC, 1975~ hr/AC, 1300~ hr/AC.
f i n e r p a r t i c l e s with s i z e s down to at l e a s t 100.~, the (a) Longitudinal section; (b) transverse section. Magnifica-
l i m i t of r e s o l u t i o n of the r e p l i c a t i o n technique, a r e p r e - tion 104 times.

2948 VOLUME 1, OCTOBER 1970 METALLURGICALTRANSACTIONS

 100,000
80,000
60,000 "~--~h'--ll~.__ 12000F
40,00~
~ I400~
-~ 20,000
@ "Z ~ ~. /900oF
I0,000
8000
6000
40O0 9 ALLOY A
9 ALLOY 8
ZOO0

1000 I
,!o ,~ ,~o ,o~ ,o,ooo
LIFE ( HOURS)
Fig. 6-Results of stress rupture tests performed on yttriated
superalloys A and B.

100,000
80,000
60,000 ----------_ - . . . . . __ lgOOOF

40,000
• ISO0~
~ 20,000
9 -- 9 9 9 I700"F
I0,000 " - %o%~
8000
6~0

200(

100
,'o ,'o ,~,o ,ooo' ,0,000
LIFE (HOURS)
Fig. 5--Electron photomicrograph of surface replica of com-
plex thoriated superalloy (alloy E, Table I). Extruded and Fig. 7--Results of stress rupture tests performed on thoriated
heat treated 4 hr at 2250~ followed by a furnace cool. Mag- superalloy D.
nification 4950 times.
I00,000
where the slopes of the s t r e s s r u p t u r e plots i n c r e a s e 80,000 9
with i n c r e a s i n g t e m p e r a t u r e . T h i s u n u s u a l b e h a v i o r 60,000
i m m e d i a t e l y s u g g e s t s that m o r e than one s t r e n g t h e n i n g t~
a. 4 0 , 0 0 0 YTTRIATED SUPERALLOYS
m e c h a n i s m i s o p e r a t i n g . The e l o n g a t i o n s at r u p t u r e \\ A ( ~ J AND B ( e )

for both y t t r i a t e d and t h o r i a t e d s u p e r a l l o y s r a n g e d

f r o m 1 to 10 pct, the m a j o r i t y of the v a l u e s b e i n g b e -
tween 2.5 and 7.5 pct.
I0,00s
In o r d e r to c o m p a r e the p r o p e r t i e s of these a l l o y s 800C NIMONIC 80A \'~
with c o n v e n t i o n a l l y produced m a t e r i a l s , the 100-hr 6000~ \ %.
r u p t u r e s t r e s s e s of y t t r i a t e d and t h o r i a t e d s u p e r a l l o y s
o 4 0 0 0 ll- \ %. \ %.
a r e plotted as a function of t e m p e r a t u r e in F i g s . 8 and
9. The 1 0 0 0 - h r r u p t u r e s t r e s s e s of y t t r i a t e d s u p e r -
alloys a r e plotted as a function of t e m p e r a t u r e in Fig. 2ooof x\
10. Also included 2e a r e t y p i c a l v a l u e s for TD Nickel,*
I000 ~ I I I /
*RegisteredTrademarkof Fansteel,MetalsDivision. 1200 1400 1600 1800 2000
TEMPERATURE, ~

a c o m r r l e r c i a l d i s p e r s i o n s t r e n g t h e n e d m a t e r i a l , and Fig. 8--Stress for 100 hr life in yttriated superalloys as a

function of temperature.
NIMONIC *80A, a c o m m e r c i a l n i c k e l - b a s e s u p e r a l l o y

*RegisteredTrademarkof The InternationalNickelCo.,Inc.

with a c o m p o s i t i o n s i m i l a r to the m a t r i x c o m p o s i t i o n
of the e x p e r i m e n t a l d i s p e r s i o n s t r e n g t h e n e d s u p e r a l l o y s .
The p r e s e n c e of the two s t r e n g t h e n i n g r e g i m e s in
d i s p e r s i o n s t r e n g t h e n e d n i c k e l - b a s e s u p e r a l l o y s is
s t r i k i n g l y d e m o n s t r a t e d in F i g s . 8 and 9. At t e m p e r a -
t u r e s below 1500~ both the y t t r i a t e d and t h o r i a t e d
s u p e r a l l o y s a r e s t r o n g e r than t h o r i a t e d nickel and f o l -
low the c u r v e f o r 7 ' s t r e n g t h e n e d NIMONIC 80A v e r y
c l o s e l y . At t e m p e r a t u r e s above 1500~ the 100-hr
r u p t u r e s t r e s s c u r v e s of the y t t r i a t e d and t h o r i a t e d
s u p e r a l l o y s a r e p a r a l l e l to that of t h o r i a t e d (TD) n i c k e l .
The a p p a r e n t s u p e r i o r i t y of the y t t r i a t e d s u p e r a l l o y
o v e r the t h o r i a t e d s u p e r a l l o y at t e m p e r a t u r e s above
1500~ i s p r o b a b l y due to d i f f e r e n c e s in p r o c e s s i n g
r a t h e r than to d i f f e r e n c e s in d i s p e r s o i d identity. T h e s e
r e s u l t s also show that y t t r i u m oxide, a n o n r a d i o a c t i v e
oxide, i s as s u i t a b l e a d i s p e r s o i d in a complex alloy
b a s e as t h o r i u m oxide.
An additional f e a t u r e of the d i s p e r s i o n s t r e n g t h e n e d
s u p e r a l l o y is s e e n in Fig. 10. B e c a u s e the s t r e s s r u p -
t u r e c u r v e s of the d i s p e r s i o n s t r e n g t h e n e d s u p e r a l l o y
a r e f l a t t e r than those of c o n v e n t i o n a l s u p e r a l l o y s at
i n t e r m e d i a t e t e m p e r a t u r e s such a s 1400~ it follows
that the d i s p e r s i o n s t r e n g t h e n e d s u p e r a l l o y is s i g n i f i -
cantly s t r o n g e r than e i t h e r TD Nickel o r NIMONIC 80A
at l o n g e r t i m e s , s u c h as 1000 hr. The effects of d i s p e r -
sion s t r e n g t h e n i n g and p r e c i p i t a t i o n h a r d e n i n g a p p e a r
to a u g m e n t each o t h e r at long t i m e s in this t e m p e r a -
ture range.
T e n s i l e p r o p e r t i e s of y t t r i a t e d alloys at r o o m and
elevated t e m p e r a t u r e a r e plotted as a f u n c t i o n of t e m -
p e r a t u r e in Fig. 11 and l i s t e d in Table II. Also included
in Fig. 11 a r e t y p i c a l t e n s i l e s t r e n g t h s of TD Nickel
and NIMONIC 80A. ~ C o m p a r i s o n of t h e s e c u r v e s again
shows the t e m p e r a t u r e r e g i o n s in which the 7 ' and oxide
d i s p e r s i o n s t r e n g t h e n i n g r e g i m e s p r e d o m i n a t e in the
y t t r i a t e d s u p e r a l l o y s . The t e n s i l e s t r e n g t h of the y t t r i -

METALLURGICALTRANSACTIONS VOLUME 1, OCTOBER 1970-2949

 I00,00r 200,000
80,00C I
tso,ood
60,00C
i IOO,OOO
~. 40,00C
~ THOR/ATED $UPERALLOY D 80,000
60,000 ,~ NIMONIC8 0 A

20,00C 40,000
30,00C T D NICKEL.v ~ ~ ~ ~. -.
uJ
IO,OOC % uJ 20,000
800C 15,ooe
600C N/MON/C 80.4 "x~'~~' \
\ IO, OOq - - ~ ,ooo ' ' , \ I
,% ,2oo ,4oo ,~oo ,800 2000
400C % TEMPERATURE *F

%
Fig. 11-Ultimate tensile strength of yttriated superalloys as
200C \ a function of temperature.
%

I I I I
lOOC
1200 1400 1600 1800 2000
TEMPERATURE, *F Table II. Tensile Properties of Yttriated N ickeI-Base Superalloys
Fig. 9-Stress for 100 hr life in thoriated superalloy as a func-
0.2 Pet Offset
tion of temperature. Yield Stress, UltimateTensile Elongation, Red.of
Alloy Test Temp. psi Strength, psi Pet Area, Pet
I00,0001_
80.00 O~ C RoomTemp 129,000 175,000 9.0 13.5
60,000~
A 1000~ 106,800 141,000 10.0 10.5
A 1400~ 81,200 84,400 25.0 32.5
.~ ~ L ~ YTTRIATED SUPERALLOYS
o. . . . . . . [ ~ A (4KI AND B ( 0 ) A 1600~ 31,400 33,200 25.0 42.0
A 1900~ 20,900 22,800 9.0 19.0

-- I0,00( \ TO NICKEL ~
8ooc ~,.\
8ooc NI~,ONIC aoA \
TTRIATED SUPERALLOY
o 400c N
o \
o \ a.
2oo0 \

x
IO0~=O0 14~)O 16100 '
1800 2000 2c
TEMPERATURE *F
Fig. 10---Stress for 1000 hr life in yttriated superalloys as a o
function of temperature.

ated s u p e r a l l o y is s o m e w h a t l o w e r than that of NIMONIC
80A at 1600~ While this f o l l o w s f r o m the f l a t t e r s l o p e
o f the s t r e s s r u p t u r e plot of t h e y t t r i a t e d s u p e r a l l o y at
this t e m p e r a t u r e , the l o w e r l e v e l of the s t r e n g t h m a y
be a t t r i b u t e d to the f a c t that the soluble a l u m i n u m c o n -
tent in the y t t r i a t e d s u p e r a l l o y , 0.92 wt pct, is l o w e r
than the 1.3 pct p r e s e n t in NIMONIC 80A.
Notched-unnotched combination s t r e s s rupture tests
w e r e p e r f o r m e d on d i s p e r s i o n s t r e n g t h e n e d s u p e r a l l o y
A at 1400 ~ and 1900~ Notch s t r e n g t h e n i n g o c c u r r e d
at 1 4 0 0 ~ as is c o m m o n in the ~ ' s t r e n g t h e n i n g r e g i o n
of n i c k e l - b a s e s u p e r a l l o y s . T h e r e was no a p p a r e n t
e f f e c t of the n o t ch e s at 1 9 0 0 ~ f a i l u r e s o c c u r r e d in
e i t h e r the s m o o t h o r notched p o r t i o n s of the c o m b i n a -
tion t e s t b a r s depending on w h i c h s e c t i o n had the s m a l -
ler c r o s s section.
The d y n a m i c e l a s t i c m o d u l u s , E , of the y t t r i a t e d
s u p e r a l l o y is plotted as a function of t e m p e r a t u r e in
Fig. 12. Also g i v e n a r e v a l u e s f o r NIMONIC 80A 28 and
TD N i c k e l . 2E The m o d u l u s of the y t t r i a t e d s u p e r a l l o y is
s l i g h t l y h i g h e r than v a l u e s g i v e n f o r NIMONIC 80A and
shows an i d e n t i c a l v a r i a t i o n with t e m p e r a t u r e . It i s
i n t e r e s t i n g that the m o d u l u s of the y t t r i a t e d s u p e r a l l o y
is about 50 pct h i g h e r than that of TD N i c k e l , e v e n at
2 0 0 0 ~ w h e r e the m e c h a n i c a l b e h a v i o r of the two a l l o y s
is o t h e r w i s e v e r y s i m i l a r . T h i s t e s t w a s p e r f o r m e d
t~ IC
TEST TEMPERATURE (*F)
Fig. 12-Dynamic elastic modulus of yttriated superalloy as a
function of temperature.
u s i n g a p r e c i s i o n ground rod of 0.5 in. d i a m and 6 in.
length. The d e n s i t y of the y t t r i a t e d s u p e r a l l o y c a l c u -
lated f r o m t h e s e d i m e n s i o n s and the w e i g h t of the rod
is 8.09 g p e r cc.
Hot c o r r o s i o n r e s i s t a n c e of the d i s p e r s i o n s t r e n g t h -
ened s u p e r a l l o y w a s e v a l u a t e d by s u l f i d a t i o n c r u c i b l e
t e s t s and by c y c l i c oxidation t e s t s . R e s u l t s of t h e s e
t e s t s z7 a r e g i v en in Tab l e III along with data f or Udimet*
*RegisteredTrademark of SpecialMetals,Inc.
500 and NIMONIC 80A. The sulfidation t e s t s i n v o l v e d
i m m e r s i o n at 1700~ in 90 pct NazSO4-10 pct NaC1 f o r
100 and 300 h r . Oxidation t e s t s i n v o l v e d r a p i d l y c y c l i n g
f r o m 2000~ t o r o o m t e m p e r a t u r e and b a c k to 2000~
once a day with a total e x p o s u r e t i m e of 400 hr .

2950-VOLUME 1, OCTOBER 1970 METALLURGICALTRANSACTIONS


Table III. Hot Corrosion Results
1700~ SulfidationTests (Crucible
tests in 90 pet Na2SO4-10 pet NaCI)
100 hr 300 hr
Metal Sulfide Metal Sulfide 2000~ CyclicOxidation
Loss, Subscale, Loss, Subscale, 400 hr DescaledWeight
Alloy mils mils mils mils Loss, mg/crn2
Nimonic 80A 3 5 5 18 82
Udimet 500 - - 23 14 69.3
Yttriated 3 0.7 3 1 44.3
superalloy
The sulfidatiOn r e s i s t a n c e of the d i s p e r s i o n
s t r e n g t h e n e d s u p e r a l l o y i s s u p e r i o r to b o t h NIMONIC
80A a n d U d i m e t 500. T h i s i s e s p e c i a l l y a p p a r e n t i n t h e
300 h r t e s t s w h e r e t h e y t t r i a t e d s u p e r a l l o y s h o w s a
sulfide s u b s c a l e p e n e t r a t i o n of only 1 rail as o p p o s e d
to 14 r a i l f o r U d i m e t 500 a n d 18 r a i l f o r NIMONIC 80A.
In c y c l i c o x i d a t i o n a t 2 0 0 0 ~ t h e d e s e a l e d w e i g h t l o s s
a f t e r 400 h r e x p o s u r e s h o w s t h e y t t r i a t e d s u p e r a l l o y
to b e s u p e r i o r to U d i m e t 500 a n d NIMONIC 80A. It
should b e noted that the s c a l e on the y t t r i a t e d s u p e r -
alloy was adherent throughout the test while the scales
on t h e o t h e r two a l l o y s s p a l l e d c o n t i n u o u s l y a f t e r 24 to
48 h r o f e x p o s u r e . T h i s i n d i c a t e s t h a t t h e s u p e r i o r i t y
of t h e y t t r i a t e d s u p e r a l l o y w o u l d b e e v e n g r e a t e r w i t h
i n c r e a s i n g e x p o s u r e t i m e in c y c l i c oxidation.
CONCLUSIONS
I) M e c h a n i c a l a l l o y i n g b y d r y h i g h e n e r g y b a l l m i l l i n g
w i t h o u t a s u r f a c e a c t i v e a d d i t i o n h a s b e e n u s e d to p r o -
duce homogeneous composite powder particles which
a r e r e l a t i v e l y c o a r s e and f r e e f r o m d e t r i m e n t a l c o n -
t a m i n a t i o n . The p r o c e s s i n v o l v e s r e c u r r e n t cold w e l d -
i n g of c o n s t i t u e n t s to t h e b a l l s u r f a c e s a n d f l a k i n g off
of t h e c o m p o s i t e a g g r e g a t e s u n t i l a l l of the c o n s t i t u e n t s
a r e f i n e l y divided and u n i f o r m l y d i s t r i b u t e d t h r o u g h the
i n t e r i o r of e a c h p o w d e r p a r t i c l e .
2) M e c h a n i c a l a l l o y i n g p r o c e s s i n g t i m e s o f 40 h r o r
l e s s a r e a d e q u a t e to o b t a i n s u i t a b l y h o m o g e n e o u s
powders.
3) M e c h a n i c a l a l l o y i n g c a n b e u s e d to c o m b i n e f i n e
particle dispersion strengthening with age hardening
in a n i c k e l - b a s e s u p e r a l l o y . A f t e r c a n n i n g , e x t r u s i o n ,
and h e a t t r e a t m e n t , the p r o d u c t p o s s e s s e s the s t r e n g t h
METALLURGICAL TRANSACTIONS
a n d s t a b i l i t y of t h o r i a t e d n i c k e l a t 1 9 0 0 ~ a n d t h e v e r y
h i g h r u p t u r e s t r e n g t h of a y ' h a r d e n e d s u p e r a l l o y a t
1400~ At the s a m e t i m e the p r o d u c t h a s sulf idation
and cyclic oxidation r e s i s t a n c e as good as o r s u p e r i o r
to c o n v e n t i o n a l s u p e r a l l o y s o f s i m i l a r c o m p o s i t i o n .
4) It h a s b e e n f o u n d t h a t y t t r i a i s a s e f f e c t i v e a s
t h o r i a in d i s p e r s i o n s t r e n g t h e n i n g c o m p l e x n i c k e l - b a s e
a l l o y s , U s e of y t t r i a a v o i d s a n y r a d i o a c t i v i t y p r o b l e m s
associated with handling thoria.
5) In t h e t e m p e r a t u r e r a n g e 1300 ~ t o 1 5 0 0 ~ t h e d i s -
p e r s i o n and p r e c i p i t a t i o n h a r d e n i n g m e c h a n i s m s aug-
m e n t e a c h o t h e r in the n i c k e l - b a s e alloy. At l o w e r t e m -
p e r a t u r e s and h i g h e r s t r a i n r a t e s ( l o w e r r u p t u r e lives)
p r e c i p i t a t i o n h a r d e n i n g by 7 ' d o m i n a t e s , and at the
higher temperatures and/or lower strain rates (higher
rupture lives) dispersion strengthening is dominant.
REFERENCES
1. W. D. Coolidge:Proc. Am. lnst. Elec. Eng., 1910, p. 961.
2. R. Irrnann:Metallurgia, 1952, vol. 49, p. 125.
3. E. Gregoryand N. J. Grant: AIME l~tans., 1954,vol. 200, p. 247.
4. F. V. Lend, A. B. Backensto,Jr., and M. V. Rose:AIME Trans., 1957, vol.
209, p. 124.
5. C. J. Leadbeaterand discussionby E. Gregory: Symposiumon PowderMetal-
lurgy, 1954, Iron Steel Inst. Spec. Rept. No. 58, pp. 149-59, 357.
6. G. B. Alexanderet al.: U.S. Patent No. 2,972,529, Feb. 21, 1961.
7. F. J. Anders,Jr.: U.S. Patent No. 3,159,908, Dec. 8, 1964.
8. E. Gregory and C. G. Goetzeh Trans. TMS-AIblE, 1958, vol. 212, p. 868.
9. K. M. Zwilskyand N. J. Grant: Trans. TMS-AIME, 1961, vol. 221, p. 371.
10. V. A. Tracey and D. K. Worn:Powder Met., 1962, no. 10, p. 34.
11. R. Murphyand N. J. Grant: Powder Met., 1962, no. 10, p. 1.
12. C. J. SmitheUs:U.S. Patent No. 2,406,172, Aug. 20, 1946.
13. Dutch Patent No. 64030, Sept. 15, 1949.
14. J. C. Chaston:J. Inst. Metals, 1945, vol. 71, pp. 23-35.
15. L. J. Bonisand N. J. Grant: Trans. TMS-AIME, 1962, vol. 224, p. 308.
16. H. Spengler:Metall., 1964, vol. 18, p. 727.
17. M. Adachi and N. J. Grant: Trans. TMS-AIME, 1960, vol. 218, p. 881.
18. G. H. Howe:Powder Metallurgy, J. Wulff,ed., p. 530, ASM, 1942.
19. A. Steiner and K. L. Komarek: Trans. TMS-AIME, 1964, vol. 230, p. 786.
20. H. Wadham:J. Oil Colour Chemists Assoc., 1964, p. 728.
21. A. Szegvari:U.S. Patent No. 2,764,359, Sept. 25, 1956.
22. A. M. Gaudin: PHnciples o f Mineral Dressing, p. 106, McGrawHill Book Co.,
New York, 1939.
23. F. C. Kelly: Weld. J. N. Y., 1951, vol. 30, p. 728.
24. S. L. Hoyt: AIME Trans., 1930, vol. 89, p. 9, see esp. p. 25.
25. G. S. Anselland J. Weertman: Trans. TMS-AIME, 1959, vol. 215, p. 838.
26. HighTemperature,High StrengthNickel-BaseAlloys,The InternationalNickel
Co., Inc., New York, 1964. Note: The valuesfor the propertiesof TD Nickel
are givenonly for referenceand representan averageof the numbersreported
in the open literature and in manufacturers'pamphletsfor varyingbar sizesof
this alloy.
27. J. W. Schultz: The InternationalNickel Co., Inc., Paul D. MericaResearch
Laboratory, SterlingForest, Suffern,N. Y., private communication, 1969.
VOLUME 1, OCTOBER 1970-2951