G r a i n Refinement T h r o u g h Thermal

Cycling in an Fe-Ni-Ti Cr yogeni c A l l o y

S. JI N, J. W. MORRI S, J R. , AND V. F. ZACKAY
A t h e r ma l c y c l i n g t e c h n i q u e whi c h a l l o ws t he g r a i n r e f i n e me n t of F e - 1 2 Ni - 0 . 2 5 Ti a l l o y
f r o m 4 0 ~6 0 / z m ( ASTM #5~6) t o 0. 5 ~ 2/ z m ( ASTM #15~18) i n f our c y c l e s ha s b e e n d e -
v e l o p e d . The p r o c e s s c o n s i s t s of a l t e r n a t e a n n e a l i n g i n 9' r a n g e and ( a + 7) r a n g e wi t h
i n t e r me d i a t e a i r c ool i ng. The t r a n s f o r ma t i o n b e h a v i o r , t he c ha nge of mi c r o s t r u c t u r e s
and c r y o g e n i c me c h a n i c a l p r o p e r t i e s on e a c h c y c l i n g s t e p a r e d e s c r i b e d .
Due t o t he u l t r a f i n e g r a i n s i z e , t he d u c t i l e - b r i t t l e t r a n s i t i o n t e mp e r a t u r e of t h i s f e r r i t i c
a l l o y i n Ch a r p y i mp a c t t e s t i n g wa s s u p p r e s s e d be l ow 6 K. In f r a c t u r e t o u g h n e s s t e s t i n g
at 77 K, t he mo d e of f r a c t u r e wa s a l t e r e d f r o m b r i t t l e q u a s i - c l e a v a g e t o c o mp l e t e d u c t i l e
r u p t u r e t h r o u g h t he g r a i n r e f i n i n g .
R E C E NT r e s e a r c h i n t h i s l a b o r a t o r y 1-4 h a s shown
t h a t a l l o y s f r o m t he F e - Ni - T i s y s t e m ( e . g . , F e - 1 2 Ni -
0. 25 Ti t c a n b e p r o c e s s e d t o ha ve a p r o mi s i n g c o mb i -
na t i on of s t r e n g t h and t o u g h n e s s at c r y o g e n i c t e mp e r -
a t u r e . As e x p e c t e d , t he d u c t i l e - b r i t t l e t r a n s i t i o n t e m-
p e r a t u r e s of t h e s e a l l o y s t e nd t o d e c r e a s e i f t he e f f e c -
t i ve g r a i n s i z e i s ma d e s ma l l . He nc e a ma j o r f oc us of
o u r r e s e a r c h h a s b e e n on t he d e s i g n of p r o c e s s e s whi ch
a c c o mp l i s h s i g n i f i c a n t g r a i n r e f i n e me n t .
P r e v i o u s wo r k 5-r e s t a b l i s h e d t wo t e c h n i q u e s f o r r e -
f i n i n g t he g r a i n s i z e of F e - Ni a l l o y s of mo d e r a t e n i c k e l
c ont e nt . Fo l l o wi n g s t u d i e s b y Gr a n g e , 8 P o r t e r and
Da bkows ki s d e mo n s t r a t e d g r a i n r e f i n e me n t t h r o u g h a
t h e r ma l c y c l i n g p r o c e d u r e whi ch i n c l u d e d r e p e a t e d
c y c l e s of r a p i d a u s t e n i t i z i n g and c ool i ng. Gr a i n s i z e
a s s i nai 1 a s 3 t o 5 ~ m ( me a n i n t e r c e p t l e ngt h: ASTM
#13- 14) wa s o b t a i n e d . Saul e t a l 6 a l s o o b s e r v e d g r a i n
r e f i n e me n t i n ma r a g i n g s t e e l s on s i mp l e r e p e a t e d a u -
s t e n i t i z i n g ( f r o m ASTM #2 t o # 7 i n 4 c y c l e s ) . An a l -
t e r n a t e t e c h n i q u e wa s u s e d b y Mi l l e r , 7 who r e p o r t e d
u l t r a f i n e g r a i n s i z e (0. 3 t o 1.1 ~tm; ASTM #17 t o 19)
i n an F e - Ni a l l o y whi c h ha d b e e n s e v e r e l y c o l d - wo r k e d
and t hen a n n e a l e d i n t he t wo - p h a s e ( a + 7) r a n g e .
Va r i a n t s of bot h t h e s e p r o c e s s i n g t e c h n i q u e s we r e
us e d i n our r e s e a r c h 2 on t he a l l o y F e - 1 2 Ni - 0 . 2 5 Ti ,
and bot h l e d t o a l l o y s of e x c e p t i o n a l s t r e n g t h and d u c -
t i l i t y at c r y o g e n i c t e mp e r a t u r e . Ho we v e r , bot h p r o -
c e s s i n g t e c h n i q u e s had u n d e s i r a b l e f e a t u r e s . When
t he c y c l i c a u s t e n i t i z i n g p r o c e s s wa s us e d, t he g r a i n
s i z e s e e me d t o s t a b i l i z e at 5 t o 10 ~tm. A f u r t h e r i m-
p r o v e me n t i n l ow t e mp e r a t u r e d u c t i l i t y mi ght be o b -
t a i n a b l e wi t h f i n e r g r a i n s i z e . A mo r e r e f i n e d s t r u c -
t u r e c a n b e a c h i e v e d wi t h me c h a n i c a l wo r k i n g , but
me c h a n i c a l wo r k i n g i s of t en an i mp r a c t i c a l o r unde -
s i r a b l e s t e p i n f i na l a l l o y p r o c e s s i n g . We t h e r e f o r e
s ought an a l t e r n a t e t h e r ma l t r e a t me n t whi ch woul d
accomplish a grain refinement comparable to that ob-
tainable with mechanical work.
S. JIN, J. W. MORRIS, Jr., and V. F. ZACKAY are Assistant Re-
search Engineer, Associate Professor, and Professor, respectively,
Department of Materials Science and Engineering, University of
California and Center for the Design of Alloys, Inorganic Materials
Research Division, Lawrence Berkeley Laboratory, Berkeley,
California 94720.
Manuscript submitted January 16, 1974.
METALLURGI CAL TRANS ACTI ONS A
An i n i t i a l s o l u t i o n t o t hi s p r o b l e m wa s r e p o r t e d i n
Ref . 2, wh e r e we s howe d t ha t an F e - 1 2 Ni - 0 . 2 5 Ti a l -
l oy c oul d be p r o c e s s e d t o a g r a i n s i z e n e a r 1. 0 ~zm b y
t r e a t i n g i t wi t h a l t e r n a t e a n n e a l s i n t he a u s t e n i t e (77
and t he t wo - p h a s e (~ + 77 f i e l d s . The r e s u l t i n g a l l o y s
s howe d e x c e p t i o n a l d u c t i l i t y i n f r a c t u r e t o u g h n e s s
t e s t s at l i qui d n i t r o g e n t e mp e r a t u r e (77 K). The p r o -
c e s s i n g s e q u e n c e u s e d wa s , h o we v e r , c o mp l e x , i n v o l v -
i ng ni ne s e p a r a t e a n n e a l i n g s t e p s . We ha ve s i n c e f ound
t h a t t h i s p r o c e s s i n g s e q u e n c e c a n be s i mp l i f i e d c o n s i d -
e r a b l y wi t hout s a c r i f i c i n g t he g r a i n r e f i n e me n t o r t he
l ow t e mp e r a t u r e d u c t i l i t y of t he r e s u l t i n g a l l o y s . The
g r a i n r e f i n e me n t t e c h n i q u e s and a s s o c i a t e d c h a n g e s
i n l ow t e mp e r a t u r e me c h a n i c a l p r o p e r t i e s a r e d e -
s c r i b e d i n t he f ol l owi ng s e c t i o n s .
I. TECHNICAL APPROACH
The technical approach leading to the grain refine-
ment processes used here and in Ref. 2 may be briefly
described as follows: The Fe-12 Ni-0.25 Ti alloy is ex-
pected to show roughly the same transformation be-
havior as the Fe-12 Ni binary, given the small amount
of Ti present and its partial consumption in scavenging
interstitials. Previous research on the transformation
behavior of Fe-Ni alloys in this composition range
(summarized, for example, by Floreen 9) indicates that
when the alloys are rapidly heated or cooled between
room temperature and the ~-field both the (~~ 7 and
T ~ c~transformations occur primarily through a dif-
fusionless shear mechanism, while if the alloys are
annealed within the two phase (c~+ 7) field the trans-
formation proceeds through a diffusional nucleation
and growth process leading to an equilibrium partition-
ing of nickel between the two phases. Either transfor-
mation mechanism may be used for grain refinement.
If c~is heated to the 7-field and then cooled to room
temperature, a decrease in apparent grain size (or
martensite packet size) results, presumably to relieve
the internal strain built up during the shear transfor-
mation. 6 If c~is annealed inside the two phase region
a very fine lath-like structure results, presumably
from preferential Y nucleation in the boundaries of the
martensite plates. 7
The fine lath-like structure obtained after two-phase
anneal is, however, not a desirable structure for high
VOLUME6A, JANUARY!975-141
Fe -Ni PHASE DIAGRAM HEAT TREATING CYCLES
800 )"
. . . . . . . . . . . . . . . . . . . . . . IA . . . . 2A . . . . 73.0"C/ZHRS(7 RANGE)
~600 r~ ~ 400 . . . . . . . . . . . . . . . . . . . . . ~ 18 _ 2B _650aC/2 HRS{r + ~ RANGE)
I I I I - _ - ROO M TEMPERATU~
Fe 20 40 60 80 Ni
ATOMICPERCENTNIC;,~JEL
XI~- 739 ~1884
F i g . l - - T h e F e - N i e q u i l i b r i u m p h a s e d i a g r a m w i t h h e a t t r e a t -
i n g cycl es.
t o u g h n e s s , and ma y e ve n c a u s e a d e c r e a s e i n t o u g h n e s s
due t o e a s y c r a c k p r o p a g a t i o n p a r a l l e l t o t he l a t h s . In
Mi l l e r ' s r e s e a r c h 7 t he s t o r e d e n e r g y of p r i o r c ol d wo r k
s e e me d e f f e c t i v e i n d e s t r o y i n g t he p r e f e r e n t i a l a l i g n -
me n t of t h o s e l a t h s . It s e e ms p l a u s i b l e t ha t r e s i d u a l
s t r a i n f r o m a c y c l i c s h e a r t r a n s f o r ma t i o n ma y a c c o m-
p l i s h t he s a me e f f e c t , p a r t i c u l a r l y i f t he s t r a i n i s a l -
l owe d t o a c c u mu l a t e t h r o u g h r e p e a t e d c y c l i n g .
We ha ve , t h e r e f o r e , i n v e s t i g a t e d t h e r ma l c y c l i n g
t r e a t me n t s of t he t ype i l l u s t r a t e d s c h e ma t i c a l l y i n
Fi g. 1 ( t he F e - Ni e q u i l i b r i u m p h a s e d i a g r a m wa s o b -
t a i n e d f r o m Ha ns e n l~ i n whi c h a u s t e n i t e r e v e r s i o n s
a r e a l t e r n a t e d wi t h t wo - p h a s e d e c o mp o s i t i o n s . The
a n n e a l i n g t e mp e r a t u r e s we r e c h o s e n f r o m t he r e s u l t s
of d i l a t o me t r i c s t u d i e s of t he k i n e t i c s of t he p h a s e
t r a n s f o r ma t i o n s , wi t h t he gui di ng p r i n c i p a l t ha t t he
a u s t e n i t i z i n g t e mp e r a t u r e s houl d b e l ow, t o mi n i mi z e
g r a i n gr owt h, whi l e t he t wo - p h a s e d e c o mp o s i t i o n t e m-
p e r a t u r e s houl d be hi gh, t o ma x i mi z e t he r a t e of d e -
c o mp o s i t i o n . The a n n e a l i n g t i me s and t o t a l n u mb e r of
c y c l e s we r e c h o s e n f r o m me t a l l o g r a p h i c s t u d i e s of
g r a i n r e f i n e me n t and l o w- t e mp e r a t u r e me c h a n i c a l
t e s t s of t he r e s u l t i n g a l l o y s .
II. MATERI ALS AND PROCESS OF
GRAI N REF I NEMENT
a. Ma t e r i a l s P r e p a r a t i o n
A l ow c a r b o n a l l o y of n o mi n a l c o mp o s i t i o n F e - 1 2 Ni -
0. 25 Ti wa s o b t a i n e d f r o m p u r e s t a r t i n g ma t e r i a l s (99. 9
pc t p u r i t y ) b y i nduc t i on me l t i n g i n an i n e r t ga s a t mo -
s p h e r e . Two t we nt y pound i ngot s of 2. 75 i n. (7. 0 c m)
d i a me t e r we r e p r e p a r e d b y s l ow c a s t i n g i n a r o t a t i n g
c o p p e r c h i l l mol d. I ngot c o mp o s i t i o n wa s d e t e r mi n e d
t o be (in wt pot ) : 12. 07 Ni , 0. 26 Ti , 0. 001 C, 0. 014 N,
0. 003 P, 0. 004 S, wi t h t he b a l a n c e Fe . The i ngot s we r e
h o mo g e n i z e d unde r v a c u u m at 1050~ f or 120 h, c r o s s -
f o r g e d at ~ l l 0 0 ~ t o t h i c k p l a t e s 4 i n. (10. 2 c m) wi de
b y 0. 75 i n. (1. 9 c m) t hi c k, t hen a i r - c o o l e d t o r o o m t e m-
p e r a t u r e . The p l a t e s we r e t hen a n n e a l e d at 900~ f or
t wo h o u r s t o r e mo v e mo s t of t he p r i o r d e f o r ma t i o n
s t r a i n and a i r c o o l e d t o r o o m t e mp e r a t u r e . Thi s f i na l
a n n e a l wa s i n c l u d e d t o e s t a b l i s h a s t a n d a r d i n i t i a l s t a t e
f o r r e s e a r c h p u r p o s e s ; o u r p r i o r wo r k h a s s hown t ha t
t he p r o c e s s e d a l l o y s ha ve s o me wh a t b e t t e r c r y o g e n i c
me c h a n i c a l p r o p e r t i e s when g r a i n r e f i n e d d i r e c t l y f r o m
t he a s - f o r g e d c ondi t i on.
b. P h a s e T r a n s f o r ma t i o n St u d i e s
Di l a t o me t r i c s t u d i e s we r e c o n d u c t e d t o d e t e r mi n e
p h a s e t r a n s f o r ma t i o n k i n e t i c s i n t h i s a l l o y . Tu b e -
12
IC
,."I, 8
_z
4
~ 2
C
- 2
- ~
I I
As=675=C
MS=475 *C
4 0 0 8 1 0
TEMPERATURE, *C
(a)
, 2 /
IO
8
~G
g2
5C
-2
i 1
iSOTHERMALDECOMPOSITK~N
AT 650"C
f
2-
~ 20hrs _
M
i I
25 400 800
TEMPERATURE, ~
(b)
Fi g. 2- - Di l at omet r i c anal ysi s of the phase t r ans f or mat i ons in
Fe- 12 Ni-0. 25 Ti al l oy, (a) on continuous heat i ng and cooling,
(b) on i s ot her mal decomposi t i on with the (~ + 7) r ange for di f -
f er ent per i ods.
s h a p e d d i l a t o me t r y s p e c i me n s 1. 5 i n. (3. 8 c m) l ong
and 0. 25 i n. (0. 64 cm) i n d i a m wi t h 0. 04 i n. (0. 1 c m)
wa l l t h i c k n e s s we r e ma c h i n e d f r o m t he a n n e a l e d s t a r t -
i ng ma t e r i a l . T e mp e r a t u r e s we r e mo n i t o r e d wi t h a
c h r o me l - a l u me l t h e r mo c o u p l e , s pot we l d e d at t he mi d -
poi nt of t he s p e c i me n l engt h. The e x p e r i me n t s we r e
c a r r i e d out wi t h h e a t i n g and c o o l i n g r a t e s of a p p r o x i -
ma t e l y 15~ r o u g h l y d u p l i c a t i n g t he r a t e s us e d
i n h e a t t r e a t me n t of t he a l l o y .
Sa mp l e d i l a t o me t r i c c u r v e s a r e gi ve n i n Fi g. 2. Fi g.
2(a) i l l u s t r a t e s t r a n s f o r ma t i o n b e h a v i o r when an
( ma r t e n s i t e ) i s c o n t i n u o u s l y h e a t e d i nt o t he ~ r e g i o n ,
t hen c o o l e d t o r o o m t e mp e r a t u r e . Re v e r s i o n t o a u s t e n -
i r e b e g i n s at a t e mp e r a t u r e s l i g h t l y b e l o w t he ma x i mu m
i n t he d i l a t i o n c u r v e at 673~ ( whi ch we ha ve t a k e n a s
a me a s u r e of t he a u s t e n i t e s t a r t t e mp e r a t u r e , A s) and
i s c o mp l e t e d at a t e mp e r a t u r e s l i g h t l y a bove t he mi n i -
mu m i n t he c u r v e at 715~ ( whi ch me a s u r e s t he a u s t e n -
i t e f i n i s h t e mp e r a t u r e , Af ) . On c ool i ng, t he ma r t e n s i t e
t r a n s f o r ma t i o n b e g i n s n e a r 473~ (M s) and i s l a r g e l y
c o mp l e t e b y 412~ (Mr). On c y c l i n g , t he s a mp l e u n d e r -
goe s a s ma l l p e r ma n e n t s e t , me a s u r e d b y t he o f f s e t i n
t he c o o l i n g c u r v e a t l o w- t e mp e r a t u r e . Thi s o f f s e t r e -
s u l t s f r o m t r a n s f o r ma t i o n s t r a i n of t he s a mp l e and d o e s
not s i g n i f y t he p r e s e n c e of r e t a i n e d a u s t e n i t e ; no a u s t e n -
i t e i s d e t e c t e d i n X- r a y s t u d i e s of s a mp l e s c y c l e d b a c k
t o r o o m t e mp e r a t u r e . Fi g . 2(a) s u g g e s t s an a u s t e n i t i z -
142-VOLUME 6A, JANUARY 1975 METALLURGICAL TRANSACTIONS A
~ ~~ -o ~
T I M E , P ~ U R 5
Fig. 3--Estimated isothermal transformation rate at 650~
I I
673~C
I ~ 5 ~ 1 6 2
,r ,
1 I
25 400 8 0 0
TEMPERATURE,~
Fig. 4--(a) Dilatometry for an initially homogeneous speci-
men (same as Fig. 2(a)), (b) dilatometry for a specimen i ni -
tially decomposed at 650~ for 2 h. After the transformation
of the duplex structure to ? is finished, the specimen was
held at 730~ for two hours for partial homogenization and
then cooled to room temperature, (c) same as (b) except t hat
the homogenization was minimized by holding at 730~ for
just a few seconds. (d) The homogenization cycle (b) was fol-
lowed by another continuous heating to the 7 range to see the
change in A s, Af temperatures from those of (a) and (b).
i ng t emper at ur e of about 730~ to i ns ur e t hat the t r a ns -
f or mat i on i s compl et ed, and a maxi mum t wo- phase de-
composi t i on t emper at ur e of about 650~ to i ns ur e t hat
shear r e ve r s i on has not become si gni f i cant .
Di l at omet r i c cur ves moni t or i ng i s ot her mal decompo-
si t i on at 650~ ar e shown i n Fi g. 2(b). The M s t e m-
per at ur e i s es s ent i al l y i ndependent of t r ans f or mat i on
t i me (t___ 30 mi n. ) i ndi cat i ng t hat the ni ckel cont ent of
the 7 f or med i s es s ent i al l y i ndependent of the 7 vol ume
f r act i on. Thi s 7 appar ent l y t r a ns f or ms compl et el y to
a on cool i ng; no r et ai ned aust eni t e i s det ect ed i n X-
r ay di ffract i on anal yses of s ampl es cool ed to r oom
t emper at ur e. (We do, however, fi nd r et ai ned aust eni t e
aft er decomposi t i on at t emper at ur es < 6000C).
Gi ven the cur ves in Fi g. 2(b) we can phr ase a rough
es t i mat e of t he r at e of decomposi t i on which i s useful
i n sel ect i ng an anneal i ng t i me. If we as s ume t hat the
di l at i on i s a l i near f unct i on of the f r act i on t r ans f or med
and est i mat e the di l at i on on compl et e t r ans f or mat i on
f r om the t ot al offset i n the cur ves of Fi g. 2(a), we ob-
t ai n the es t i mat ed i s ot her mal t r ans f or mat i on cur ve
shown i n Fi g. 3. Thi s cur ve has an asympt ot e i ndi cat -
i ng equi l i br i um with sl i ght l y mor e t han 80 pct 7, which
agr ees r oughl y with an est i mat e based on the Fe- Ni
bi nar y phase di agr am. We i nf er f r om Fi g. 3 t hat an
anneal i ng t i me of 2 h at 650~ wi l l yi el d a pr oduct
which is r oughl y 60 pct 7, pr ovi di ng an over al l gr ai n
r ef i nement near the opt i mum. Thi s es t i mat e i s sup-
port ed by the met al l ogr aphi c r es ul t s gi ven bel ow.
If the 730~176 cycl e i s r epeat ed aft er decom-
posi t i on at 650~ the ki net i cs of t r ans f or mat i on ar e
compl i cat ed by the i nhomogeneous di s t r i but i on of
ni ckel t hrough t he mi c r os t r uc t ur e . A sampl e anneal ed
for two hour s at 650~ wi l l cons i s t of r oughl y 60 pct 7
of composi t i on ~ 13 pct Ni ( est i mat ed f r om the Fe- Ni
bi nar y phase di agr am) t oget her with ~40 pot r es i dual
a of mean ni ckel concent r at i on near 10 pct (well above
the equi l i br i um at ~ 4 pct Ni) which may be het er oge-
neousl y di st r i but ed. If the mat er i al i s ai r cool ed to
r oom t emper at ur e and t hen r eheat ed to 730~ r egi ons
of di f f er ent Ni concent r at i on wi l l t r a ns f or m at di fferent
t e mpe r a t ur e s (and per haps by di f f er ent mechani s ms )
l eadi ng to the mor e compl ex t r ans f or mat i on behavi or
i l l us t r at ed by the di l at omet er t r ace shown in Fi g. 4.
It nonet hel ess appear s t hat the pr onounced shear r e -
ver s i on i s es s ent i al l y compl et e at 730~
Tr ans f or mat i on behavi or on subsequent cool i ng de-
pends on the ext ent of homogeni zat i on at 730~ and
hence on the t i me of anneal , as i l l us t r at ed by cur ves
(b) and (c) of Fi g. 4. An anneal of 2 h at 730~ i s not
suf f i ci ent to homogeni ze the al l oy. The cont i nued pr e s -
ence of r egi ons of r el at i vel y high Ni concent r at i on i s
i ndi cat ed by t he s uppr es s i on of the A s t emper at ur e on
r eheat i ng (curve (d) of Fi g. 4). However, aft er the s ec-
ond 2 h anneal at 730~ the A s t emper at ur e i n the next
heat i ng l i es above 650~ i ndi cat i ng t hat s hear r e ve r -
si on to 7 does not become pr onounced unt i l the t e mpe r -
at ur e i s r ai s ed above 650~
c. Mi cr os t r uct ur al Changes on Cycl i ng
On the bas i s of di l at omet r i c and mi c r os t r uc t ur a l
st udi es we sel ect ed a gr ai n r ef i ni ng pr oces s consi st i ng
of al t er nat e t wo- hour anneal s at 730~ and 650~ A
f our - cycl e pr oces s is shown s chemat i cal l y in Fig. i ,
where the s ucces s i ve st eps ar e l abel l ed 1A (730~
I B (650~ 2A (730~ and 2B (650~ The evol ut i on
of the mi c r os t r uc t ur e dur i ng t hi s cycl i ng i s i l l us t r at ed
by the opt i cal mi cr ogr aphs gi ven i n Fi g. 5 and by the
scanni ng el ect r on mi cr ogr aphs i n Fi g. 6. Aft er f i nal
cycl e 2B the bul k of the mi c r os t r uc t ur e consi st s of a
fi ne mi xt ur e of pl at el et gr ai ns appr oxi mat el y 1 to 4
mi cr ons l ong and a f r act i on of a mi cr on in the shor t
di mensi on. The pr ef er ent i al or i ent at i on of t hese gr ai ns
has been l ar gel y el i mi nat ed.
A pr eci s e char act er i zat i on of t he mi c r os t r uc t ur e s
devel oped dur i ng t hi s t her mal cycl i ng depends on the
r es ul t s of t r a ns mi s s i on el ect r on mi cr os copy st udi es
now in pr ogr es s . The gener al f eat ur es of the gr ai n
r ef i nement pr oces s are, however, appar ent in Fig. 5
and Fi g. 6. Fi g. 5(a) shows the mi c r os t r uc t ur e of the
anneal ed st ar t i ng mat er i al . The appar ent gr ai n si ze
i s 40 to 60~m (ASTM #5 and 6). Aft er cycl e l At he
appar ent gr ai n si ze (Fig. 5(b)) has r educed to ~15 ~m
(ASTM #9). These gr ai ns cons i s t of bl ocky l at hs of
di sl ocat ed mar t ens i t e. Dur i ng cycl e 1B the mar t ens i t e
i s i s ot her mal l y decomposed to give the mi c r os t r uc -
t ur e shown in Fi g. 5(c) and i n Fi g. 6(a). The mi c r o-
METALLURGICAL TRANSACTIONS A VOLUME 6A, JANUARY 1975-143
(a) (c)
(b) (d)
Fig. 5--Change of optical microstructures on thermal cyclings. (a) starting microstructure (900~ 2 h annealed), (b) after cycle
1A, (c) after cycle 1B, (d) after cycle 2A, (e, page 145) after cycle 2B (final microstructure).
s t r uct ur e aft er cycl e 1B i s not a des i r abl e one for low
t emper at ur e t oughness. The st r ong pr ef er ent i al or i en-
t at i on of the mi c r os t r uc t ur a l f eat ur es pr ovi des pot en-
t i al pat hs for eas y cr ack pr opagat i on. The pr ef er ent i al
or i ent at i on i s l ar gel y r emoved dur i ng t he second 730~
650~ cycl i c t r eat ment .
The mi c r os t r uc t ur e aft er cycl e 2A i s shown i n Fi g.
5(d) and Fi g. 6 (b). The evi dent mi c r os t r uc t ur a l
changes ar e two. Fi r s t , a r eact i on which we as s ume
to be an homogeni zat i on r eact i on i ni t i at es al ong lath
packet boundar i es in t he mi c r os t r uc t ur e 1B, gi vi ng
r i s e to the net wor k of the white r egi ons in Fi g. 5(d).
Second, t her e i s some decomposi t i on of the al i gned
l at hs of the 1B s t r uct ur e.
The or i ent ed s ubs t r uct ur e of the al l oy is br oken up
dur i ng the next t wo- phase decomposi t i on, cycl e 2B.
144-VOLUME 6A, JANUARY 1975 METALLURGICAL TRANSACTIONS A
ost at . Subsi ze s peci mens of 0.5 in. (1.27 cm) gauge
l engt h and 0.125 in. (0.32 cm) di am wer e t es t ed at a
c r os s he a d s peed of 0.02 i n. / mi n. (0.05 c m/ mi n. ) . Two
s peci mens wer e t es t ed at each st age of t he cycl i ng
t r e a t me nt . The devi at i on in yi el d s t r engt h bet ween
t es t s was ~ 5 ksi (35 newt on/ m2).
(e)
The r es ul t i ng mi c r os t r uc t ur e i s shown in Fi g. 5(e) and
and in Fi g. 6(c). The r es ul t i ng gr ai n s i ze (0.5 to
2.0 m; ASTM #15 to #18) i s c ons i de r a bl y bel ow t he
be s t we have been abl e to obt ai n with s i mpl e cycl i c
aus t eni t i zi ng t r e a t me nt s and i s c ompa r a bl e to t hat
Mi l l er 7 obt ai ned af t er s e ve r e col d wor ki ng.
The gr a i n- r e f i ne d al l oy i s appar ent l y compl et el y
f e r r i t i c . No r e t a i ne d aus t eni t e was det ect ed usi ng con-
vent i onal X- r a y t echni ques. R. L. Mi l l er n conf i r med
t hi s r e s ul t usi ng a modi f i cat i on of hi s r e por t e d t ech-
ni ques 12'~s whi ch pe r mi t s det ect i on of as l i t t l e as 0.1
pct r et ai ned aust eni t e.
We have expl or ed t he ef f ect of addi ng addi t i onal
730~176 cycl es . Thes e do gi ve an appar ent addi -
t i onal r ef i nement of t he l a r ge r gr ai ns r emai ni ng in t he
mi c r os t r uc t ur e , but t he ef f ect i s s ma l l and has no obvi -
ous i nf l uence on cr yogeni c mechani cal pr ope r t i e s .
III. MECHANICAL PROPERTIES AT
CRYOGENIC TEMPERATURES
The mechanical test specimens were taken from the
material prepared as described in section II(a). The
annealed 0.75 in. (1.9 cm) thick plates were cut into
pieces 2.75 in. (7.0 cm) long. These pieces were then
given selected thermal processing. After processing,
one fracture toughness specimen and two Charpy im-
pact specimens were machined from each piece along
the longitudinal direction of forging, ensuring the same
heat treatment for both tests. Tensile specimens
(transverse direction) were obtained from the far end
of the broken fracture toughness specimens.
(a) Cr yogeni c Tens i l e Pr ope r t i e s
Tens i l e t e s t s wer e conduct ed at l i qui d ni t r ogen t e m-
pe r a t ur e usi ng an I nst r on machi ne equi pped with a c r y-
(a)
(b)
Fig. 6--Scanning electron mi crost ruct ures. (a) specimen 1B,
(0) specimen 2A, (c) specimens 2B, on following page.
METALLURGICAL TRANSACTIONS A VOLUME 6A,JANUARY 1975 145
Fire 6(c}
The r e s ul t s of t he t e ns i l e t e s t s a r e s hown i n Ta bl e I.
The yi el d s t r e ngt h at 77 K i s i n t he r a nge 140 t o 150 ks i
(9. 66 t o 10. 35 x 108 ne wt on/ m 2) and i s r a t he r i ns e ns i t i ve
t o mi c r os t r uc t ur e . The s a mpl e s t r e a t e d t o s t a ge s 1B
and 2B have s l i ght l y hi ghe r yi el d s t r e ngt h and l owe r
t e ns i l e duct i l i t y t han t hos e at s t a t e s 1A and 2A. The s e
mi nor ef f ect s a ppe a r t o be due t o t he pr e c i pi t a t i on of
Ni zTi i n t he a phas e at 650~ El e c t r on mi c r os c opi c
s t udi es i ndi cat e t hat t he ext ent of t hi s pr e c i pi t a t i on i s
s ma l l .
(b) Cr yoge ni c I mpa c t Pr ope r t i e s
Cha r py V- not c h i mpa c t t e s t s we r e conduct ed at l i qui d
ni t r oge n t e mpe r a t ur e (77 K) us i ng ASTM s t a nda r d t e c h-
ni ques , 14 and ne a r l i qui d he l i um t e mpe r a t ur e (5 t o 6 K),
us i ng a me t hod r e c e nt l y de ve l ope d i n t hi s l a bor a t or y, ts
Table I. Results of the Tensile Tests at 77 K
Yield Strength Tensile Strength Elong,
Specimen ksi (newton/m 2) ksi (newton/m 2) pet R.A., pet
1A 134 (9.25X 10 a) 142 (9.80X 10 a) 31.1 73.8
IB 145 (10.09 X 10 a) 151 (10.42 X l0 s) 24.8 70.5
2A 141 (9.73 X I0*) 150 (10.35 108) 29.3 72.9
2B 149(10.28 1o a) 154(10.63 lO s) 26.8 72.1
Fig. 7--Photographs of the broken Charpy bars after testing at 77 K and 6 K.
146-VOLUME 6A, JANUARY 1975 METALLURGICAL TRANSACTIONS A
Two s pe c i me ns wer e t es t ed at each condi t i on. The r e -
s ul t s of t hes e t es t s a r e pr e s e nt e d in Tabl e II. The
br oke n s pe c i me ns a r e shown in Fi g. 7.
At 77 K al l f our s t r uc t ur e s showed hi gh t oughness.
However , at 6 K s peci mens 1A and 1B wer e br i t t l e.
Fr a c t ogr a phs t aken at t he cent er of t he f r a c t ur e s ur -
f ace in t hes e s pe c i me ns r e ve a l e d a qua s i - c l e a va ge
f r a c t ur e mode. Speci mens 2A and 2B r e ma i ne d t ough
at 6 K; t he t r ans i t i on t e mpe r a t ur e s in Char py t es t i ng
f or t he bcc s t r uc t ur e s 2A and 2B a r e bel ow t hi s t e m-
pe r a t ur e .
FRACTURE TOUGHNESS TESTING AT 77"K
27,00( (07" thick Compocf YenshmSpeci men)
~4,00(
88, 48
z= z~c_ _
o 15,00( IA~ ZA~
HEATTRF~,~ CYCLES
S 9c(x
6(3(3O
3OOO
L_ l I I 1 I
Ol O2 03
IN CH0~4 ~ 05 06
DISPLACEMENT,
XBL739- 1854
Fig. 8--Load-crack opening displacement curves in fracture
t oughne s s t e s t i ng at 77 K.
(c) Cr yogeni c Fr a c t ur e Toughness
Fr a c t ur e t oughness t e s t s wer e conduct ed at 77 K on
an MTS machi ne equi pped with a l i qui d ni t r ogen c r yo-
st at . Compact t ensi on (WOL) s peci mens of 0.70 in.
(1.78 cm) t hi cknes s wer e pr e pa r e d and f at i gue pr e -
cr acked accor di ng to ASTM s peci f i cat i ons . TM Two s pe c -
i mens wer e t es t ed at each s t age of t he t he r ma l cycl i ng
t r eat ment .
The r e s ul t s of t hes e t es t s a r e shown in Fi g. 8. Wi t h
t he pos s i bl e except i on of s ampl e 1B, t hes e s peci mens
wer e wel l away f r om pl ane s t r a i n condi t i ons; a val ue
of KQ ~ 140 KSI. ~ was comput ed f r om t he l oad-
c r a c k openi ng di s pl acement (COD) cur ves . 16 At s t ages
1A, 1B, and 2A t he al l oy exhi bi t ed unst abl e c r a c k pr op-
agat i on as ma r ke d by t he dot t ed l i nes in t he l oad- COD
cur ves . However t he f i ne - gr a i ne d al l oy 2B s e e me d
Table II. Charpy Impact Energy at 77 and 6 K
Impact Energy at 77 K, Impact Energy at 6 K
Specimen ft-lb (newton-meter) ft-lb (newton-meter)
1A 154 (209) 55 (75)
1B 116(158) 43 (59)
2A 131 (178) 116 (158)
2B 115 (156) 99 (134)
Fi g. 9- - Pos t - t e s t f r a c t ur e t oughne s s s pe c i me ns .
METALLURGI CAL TRANSACTIONS A
VOLUME 6A, JANUARY 1975- 147
Fig. 10--Scanning electron microscope fractographs of the specimens shown in Fig. 9.
i mmune to unst abl e cr ack propagat i on. The speci men
was ful l y pl ast i c, and the pr e- i nduced cr ack grew
sl owl y i n a st abl e manner unt i l the t est was stopped.
The pos t - t es t f r act ur e t oughness s peci mens ar e com-
par ed to one anot her in Fi g. 9. The br i t t l enes s of s pec-
i mens 1A and 1B, the r epeat ed cr ack a r r e s t i n speci -
men 2A, and the duct i l i t y of speci men 2B ar e vi sual l y
appar ent .
The f r act ur e sur f aces wer e exami ned by scanni ng
el ect r on mi cr oscopy. Fi g. 10 shows scanni ng el ect r on
f r act ogr aphs t aken sl i ght l y ahead of the pr e- i nduced
fat i gue cr ack al ong the cent er l i ne of the sampl e. Spec-
i mens pr oces s ed to st ages 1A and 1B propagat ed f r a c -
t ur e i n a quas i - cl eavage mode. At st age 2A, the f r ac-
ture mode was a mixture of quasi-cleavage and ductile
rupture. Fully grain refined specimens (2B) showed
ductile dimple rupture over the whole fracture surface.
C ONC LUS IONS
I) By alternate phase transformation in y and (or + y)
range, the grain size of an Fe-12 Ni-0.25 Ti alloy was
refined from 40~60/ira to 0.5~2/im in 4 cycles.
2) With this ultrafine grain size, the ductile brittle
transition temperature of this ferritic alloy in Charpy
impact testing was suppressed below liquid helium
temperature.
3) The ductile-brittle transition temperature in a
148-VOLUME 6A, JANUARY 1975 METALLURGICAL TRANSACTIONS A
f r a c t ur e t oughne s s t e s t i ng wi t h a s ha r p c r a c k wa s s up-
pr e s s e d be l ow l i qui d ni t r oge n t e mpe r a t ur e and t he f r a c -
t ur e mode wa s c ha nge d f r om br i t t l e qua s i - c l e a va ge t o
c ompl e t e l y duc t i l e di mpl e r upt ur e .
ACKNOWLEDGMENTS
The a ut hor s wi s h to t hank Dr . R. L. Mi l l e r of t he
U. S. St eel Cor por a t i on f or a s s i s t a nc e i n r e t a i ne d au-
s t e ni t e a na l ys i s . The y a r e a l s o gr a t e f ul t o Pr of e s s or
R. M. Ful r a t h f or a s s i s t a nc e wi t h t he di l a t ome t r i c and
X- r a y a na l ys e s , and t o Pr of e s s or G. Thoma s f or he l p-
f ul di s c us s i ons .
The wor k r e por t e d he r e wa s s uppor t e d by t he Of f i ce
of Naval Re s e a r c h unde r c ont r a c t N00014- 69- A- 1062,
NR031- 762, and by t he At omi c Ene r gy Commi s s i on
t hr ough t he I nor ga ni c Ma t e r i a l s Re s e a r c h Di vi s i on of
t he La wr e nc e Be r ke l e y La bor a t or y.
R E F E R E N C E S
1. W. A. Horwood: M.S. Thesis, University of California Berkeley, 1972.
2. S. Jin, J. W. Morris, Jr., and V. F. Zackay: Aduan. Cryog. Eng., vol. 19, 1974,
p. 379.
3. G. Sasaki: Ph.D Thesis, University of California, Berkeley, 1973.
4. V. F. Zackay: Proceedings of the Thud International Conference on the
Strength of Metals and Alloys, vol. 1, August 1973, p. 591.
5. L. F. Porter and D. S. Dabkowski: Ultrafine Grain Metals, p. 113, Syracuse
University Press, 1972.
6. G. Saul, J. A. Robertson, and A. M. Adair: Met. Trans., 1970, vol. 1, p. 383.
7. R. L. Miller: Met. Trans., 1972, vol. 2, p. 905.
8. R. A. Grange: Trans. ASM, 1966, vol. 59, p. 26.
9. S. Floreen: Met. Rev., 1968, p. 115.
10. M. Hansen: Constitution of Binary Alloys, 2nd Ed., p. 677, McGraw-Hill,
New York, 1958.
11. R.L. Miller: Research Lab. of U.S. Steel Corp,, Monroevine, Pennsylvania,
Private Communication.
12. R. L. Miller: Trans. ASM, 1964, vok 57, p. 892.
13. R. L. Miller: Trans. ASM, I968, vol. 61, p. 592.
14. 1973 Book of ASTMStandards, part 31, E 23-72, p. 277.
15, S. Jin, W. A. Horwood, J. W. Morris, Jr., and V. F. Zackay: Advan. Cryog.
Eng., vol. 19, 1974, p. 373.
16. 1973Book of ASTMStandards, part 31, E 399-72, p. 960.
METALLURGICAL TRANSACTIONS A VOLUME 6A, JANUARY 1975-149