Carbide Refining Heat Treatments for 52100 Bearing Steel

C. A. S T I C K E L S

The life of t h r o u g h - h a r d e n e d 52100 a n t i - f r i c t i o n b e a r i n g components is improved if the e x c e s s c a r b i d e s , undissolved during austenitization, a r e s m a l l and uniformly d i s p e r s e d . One kind of c a r b i d e - r e f i n i n g heat t r e a t m e n t c o n s i s t s of 1) dissolving a l l c a r b i d e s , 2) i s o t h e r m a l l y t r a n s f o r m i n g the austenite to p e a r l i t e or bainite, and 3) austenitizing, quenching and t e m p e r i n g in the usual manner. Each step in this sequence of t r e a t m e n t s was investigated, and the behavior of p e a r l i t i c and bainitic m i c r o s t r u c t u r e s during subsequent austenitization was c o n t r a s t e d with the b e h a v i o r of f e r r i t e / s p h e r o i d i z e d - c a r b i d e m i c r o s t r u c t u r e s . It was shown that: 1) The usual hardening t r e a t m e n t s given s p h e r o i d i z e - a n n e a l e d b e a r i n g components r e s u l t in an inhomogeneous m i c r o s t r u c t u r e , p o s s i b l y due to the f a s t e r dissolution of c a r b i d e s near austenite grain b o u n d a r i e s . 2) Austenitization of p e a r l i t e or bainite p r o d u c e s v e r y uniform d i s p e r s i o n s of u l t r a - f i n e c a r b i d e s on the o r d e r of 0.1 g m d i a m e t e r or l e s s . 3) Specimens with u l t r a - f i n e c a r b i d e s tend to have more r e t a i n e d austenite. 4) The r a t e of c o a r s e n i n g of u l t r a - f i n e c a r b i d e s at austenitizing t e m p e r a t u r e s of 840~ and below, is slow enough so that conventional furnace heat t r e a t m e n t s a r e s a t i s f a c t o r y for producing this microstructure.

has been r e c o g n i z e d for some t i m e that the r o l l i n g contact fatigue life of b e a r i n g s t e e l s such as 52100 is b e t t e r , the s m a l l e r the size of the e x c e s s c a r b i d e p a r t i c l e s p r e s e n t in the m i c r o s t r u c t u r e . However, b e cause soft s t e e l is needed for f a b r i c a b i l i t y , the m a t e r i a l c u s t o m a r i l y supplied to b e a r i n g m a n u f a c t u r e r s is s p h e r o i d i z e d to produce r a t h e r c o a r s e c a r b i d e s in a soft f e r r i t e m a t r i x . The c a r b i d e size and d i s p e r s i o n p r e s e n t a f t e r hardening heat t r e a t m e n t r e f l e c t s to a m a r k e d d e g r e e the size and d i s p e r s i o n of c a r b i d e s in the s p h e r o i d i z e d m a t e r i a l . Thus, n e a r l y all c o m m e r c i a l l y produced 52100 b e a r i n g components have c a r b i d e s which a r e too l a r g e for the b e s t fatigue life. The intent of the p r e s e n t work is to develop heat t r e a t m e n t s which could be applied to s p h e r o i d i z e d m i c r o s t r u c t u r e s to produce hardened b e a r i n g components with uniform d i s p e r s i o n s of fine c a r b i d e s .

IT

LITERATURE

REVIEW

Little has been published of a s y s t e m a t i c nature on the effect of c a r b i d e s i z e on b e a r i n g fatigue life. There a r e s c a t t e r e d r e f e r e n c e s to improved p e r f o r m a n c e with finer c a r b i d e s : Tallien 1 c l a i m s a f a c t o r of t h r e e difference in fatigue life as a function of c a r b i d e size. Faunce and Justusson 2 c l a i m an i m p r o v e m e n t of 2.8 t i m e s with c a r b i d e r e f i n e m e n t in the life at which 10 pct of a sample of b e a r i n g s fails (B10 life). I n v e s t i g a t o r s at T. L Desford Tubes Ltd. found an i m p r o v e ment in B10 life by n e a r l y a f a c t o r of 2 with finer c a r b i d e s , a In none of these r e p o r t s is it mentioned if components were c o m p a r e d with the s a m e h a r d e n ing heat t r e a t m e n t s , or c o m p a r e d at the s a m e h a r d n e s s ; it is not known if differences in amounts of r e tained austenite existed. A m o r e thorough examination of the effect of c a r b i d e
C. A. STICKELS is a Member of the Process Research Department, Scientific Research Staff, Ford Motor Co, Dearborn, Mich. 48121. Manuscript submitted September 17, 1973. METALLURGICAL TRANSACTIONS

s i z e has been r e p o r t e d by Monma, e t a l . 4 These authors p r e p a r e d two s e t s of s p e c i m e n s , one with a mean e a r hide d i a m e t e r of 1.4/zm (sizes ranged up to 2.7/zm) and another with a mean s i z e of 0.56 ~tm ( s i z e s ranged up to 1.5 ~zm). Samples were heat t r e a t e d to give the s a m e h a r d n e s s , using a lower austenitizing t e m p e r a t u r e for the fine c a r b i d e s p e c i m e n s , hut the s a m e t e m p e r i n g t r e a t m e n t for both. Thus, the c o m p a r i s o n was made at about the s a m e m a t r i x carbon content. The a v e r a g e fatigue life of the fine c a r b i d e m a t e r i a l was 2.5 t i m e s that of the c o a r s e r c a r b i d e m a t e r i a l . These authors also show that e x c e s s c a r b i d e s do not make a positive contribution to fatigue strength, but up to 3 to 4 vol pet e x c e s s c a r b i d e i m p r o v e s w e a r r e s i s t a n c e . The heat t r e a t m e n t used to refine c a r b i d e s was not specified by Tallien;* Monma, e t a l 4 produced t h e i r two c a r b i d e s i z e s by modified spheroidizing heat t r e a t ments. (Total t r e a t m e n t t i m e was about 13 h and 80 h for the fine and c o a r s e c a r b i d e s , r e s p e c t i v e l y . ) D i f f e r ent s p h e r o i d i z e anneals were also used in the T. I. Desford e x p e r i m e n t s , a Faunce and ffustusson a p r o dueed fine c a r b i d e s by heating to a t e m p e r a t u r e sufficient to d i s s o l v e all c a r b i d e s , a i r cooling to room t e m p e r a t u r e (forming p e a r l i t e ) , then heating for two hours at about 760~ and a i r cooling. The l a t t e r w o r k e r s z'a'4 used conventional austenitizing, quenching and t e m p e r i n g t r e a t m e n t s following t h e i r p r e t r e a t ments. Grange 5 developed v e r y uniform d i s p e r s i o n s of v e r y fine c a r b i d e s in 52100 steel by heating to a t e m p e r a t u r e sufficient to d i s s o l v e all c a r b i d e s , oil quenching in warm oil, and t e m p e r i n g to e l i m i n a t e r e t a i n e d a u stenite and form fine t e m p e r c a r b i d e s . When such p i e c e s were r a p i d l y induction heated and a u s t e n i t i z e d for about 1 rain, quenched and t e m p e r e d , c a r b i d e s on the o r d e r of 0.1 p m d i a m e t e r were produced (like Fig. 11(a)). He also r e p o r t e d 8 that a s i m i l a r m i c r o s t r u c t u r e can be produced by heating to dissolve a l l c a r b i d e s , then quenching to a t e m p e r a t u r e at which h a i n ite f o r m s and holding until the austenite is c o m p l e t e l y
VOLUME 5, APRIL 1974-865

t r a n s f o r m e d , then hardening as before using s h o r t time a u s t e n i t i z a t i o n t r e a t m e n t s . Grange did not d e t e r m i n e the effect on fatigue life of c a r b i d e refinement. EXPERIMENTAL PROCEDURE The s a m p l e s used for heat t r e a t m e n t were taken f r o m a length of s p h e r o i d i z e - a n n e a l e d hot extruded 52100 tubing such as is used to make b e a r i n g r a c e s . The composition of the s t e e l is given in Table I. Samp l e s were cut from the i n t e r i o r of the tubing wall, avoiding the s u r f a c e s . A standard s a m p l e size of 5 8 13 mm was used. Samples heat t r e a t e d at elevated t e m p e r a t u r e s for t i m e s of 30 min and longer were enclosed in evacuated vycor c a p s u l e s . Heat t r e a t m e n t s of s h o r t e r duration were done in lead pots. If p i e c e s w e r e i s o t h e r m a l l y t r a n s f o r m e d after austenitizing, the capsules were broken and the s p e c i m e n s i m m e r s e d in molten salt, held for a fixed p e r i o d of time, then water quenched. Capsules were also broken for oil quenching a f t e r austenitizing; an oil t e m p e r a t u r e of 54~ (130~ was used and s a m p l e s were in the oil for s e v e r a l minutes p r i o r to cooling to room t e m p e r a t u r e . Allowing s p e c i m e n s to r e m a i n in the quench oil r e sults in some austenite stabilization. It was found, however, that m e a s u r e m e n t s of h a r d n e s s and r e t a i n e d austenite made a f t e r t e m p e r i n g were more consistent if s p e c i m e n s were left 2 to 5 min in the quenchant. Specimens were slightly h a r d e r ( ~ 0 . S R c at the level of R c 63) and had l e s s r e t a i n e d austenite if left in the quench oil only 15 s, but r e s u l t s were e r r a t i c . Conventional m e t a l l o g r a p h i c techniques were e m ployed. In spite of c o n s i d e r a b l e effort, no r e l i a b l e method of etching to r e v e a l austenite grain s i z e could be found, unless all the carbon was in solution b e f o r e quenching. Chromium r a d i a t i o n was used for m e a s u r i n g the amount of r e t a i n e d austenite with the spec.imen enclosed in a h e l i u m - f i l l e d c h a m b e r to reduce intensity l o s s e s due to absorption in a i r . By using only the (200) m a r t e n s i t e and (220) austenite lines, i n t e r f e r e n c e from c a r b i d e lines was avoided. An independent check ( u l t r a sonic m e a s u r e m e n t s of Young's Modulus on s a m p l e s cut p a r a l l e l to and p e r p e n d i c u l a r to the tube axis) showed no p r e f e r r e d orientation in the tubing. RESULTS The methods used h e r e for c a r b i d e refinement a r e modifications of the methods r e p o r t e d by Faunce and Justusson e and Grange. B Specimens were heated to dissolve all c a r b i d e s , quenched in s a l t for i s o t h e r m a l

t r a n s f o r m a t i o n of the austenite, then cooled to room t e m p e r a t u r e . It was hoped that r a p i d cooling by salt quenching would minimize the f o r m a t i o n of c a r b i d e f i l m s in austenite g r a i n b o u n d a r i e s . Complete t r a n s f o r m a t i o n of the austenite to p e a r l i t e or bainite avoids the c r a c k i n g p r o b l e m s a s s o c i a t e d with high carbon m a r t e n s i t e s . P r e l i m i n a r y e x p e r i m e n t s showed that a f t e r this p r e t r e a t m e n t , conventional hardening t r e a t ments produced uniform d i s p e r s i o n s of v e r y fine c a r bides. The sections to follow d e s c r i b e in d e t a i l the e x p e r i ments done to e s t a b l i s h the f e a s i b i l i t y of each step of this p r o c e s s i n g sequence. Carbide Dissolution The m i c r o s t r u c t u r e of the a s - r e c e i v e d 52100 s t e e l is shown in Fig. 1. The volume f r a c t i o n of c a r b i d e is about 16 pct; an X - r a y powder p a t t e r n on c a r b i d e s e x t r a c t e d using a b r o m i n e - m e t h a n o l solution shows only (Fe, Cr)zC. A c h e m i c a l a n a l y s i s of the e x t r a c t e d c a r bides indicates the c a r b i d e s a r e 9 pct chromium by weight, confirming the r e s u l t s of Glowacki e t a l . 7 A s t r a i g h t f o r w a r d calculation using the composition in Table I shows that e s s e n t i a l l y a l l the c h r o m i u m in the alloy is combined as c a r b i d e in the s p h e r o i d i z e d condition. Heating 30 min at 1040~ (1900~ d i s s o l v e s a l l the c a r b i d e s . The austenite g r a i n s i z e is ASTM 5-6. This t r e a t m e n t has been s a t i s f a c t o r y for c a r b i d e dissolution in s e v e r a l heats of c o m m e r c i a l l y produced 52100 tubing and wire with carbon contents as high as 1.10 pct. Austenite T r a n s f o r m a t i o n The r a t e of i s o t h e r m a l t r a n s f o r m a t i o n of austenite is s u m m a r i z e d in Fig. 2. Dots on the d i a g r a m m a r k the heat t r e a t m e n t s used. Lines have been drawn m a r k i n g 0, 50 and 100 pct t r a n s f o r m a t i o n of austenite. At t r a n s f o r m a t i o n t e m p e r a t u r e of 480~ (900~ and above, p r o e u t e c t o i d c a r b i d e f i l m s were o b s e r v e d to f o r m in p r i o r austenite g r a i n b o u n d a r i e s b e f o r e t r a n s f o r m a t i o n of the austenite. However, no line is shown for the initiation of the p r o e u t e c t o i d c a r b i d e f o r m a -

Table I. Composition of 52100 Tubing

C Mn S P Si Cr Ni Cu Mo

1.04 0.32 0.009 0.004 0.19 1.35 0.12 0.12 0.01

V W Nb < Co A1 Ti Ca <

0.005 0.003 0.002 0.005 0.03 0.002 0.0002 Fig. 1 - - M i c r o s t r u c t u r e of a s - r e c e i v e d 52100 steel. S p h e r o i d ized c a r b i d e s in a f e r r i t e m a t r i x . Magnification 1250 t i m e s . P i c r a l etch. METALLURGICAL TRANSACTIONS

866-VOLUME 5, APRIL 1974

tion, because anneals of a few seconds could not be assumed to be " i s o t h e r m a l " with the specimen size used. Pearlite is the transformation product formed at t e m p e r a t u r e s of 620 to 700~ (1150 to 1300~ and bainite is formed from 370 to 590~ (700 to ll00~ Because it is difficult to distinguish pearlite and bainite in the light microscope when the carbide lamellae of pearlite are fine, products having relatively smooth interfaces with the austenite are called pearlite, Fig. 3, and those with jagged or acicular interfaces are called bainite, Fig. 4. This definition is consistent with the known growth habits of these products. 8'9 At temperatures of 480~ and above, the t r a n s f o r mation product forms initially at p r i o r austenite grain boundaries. Since films of proeutectoid carbide exist in these boundaries prior to transformation at these temperatures, the product is actually forming at a carbide/austenite interface. At 675 to 700~ there is a tendency for the initial pearlite colonies to be located at grain edges (triple points on a section), Fig.

5, and to grow rapidly, with only a few pearlite colonies in each austenite grain. A partially transformed specimen will consist of some austenite grains c o m pletely transformed to pearlite and others transformed not at all, Fig. 6. At somewhat lower temperatures, pearlite or bainite nucleation is more rapid relative to its growth rate, and transformation product is formed along the austenire grain boundaries before any individual grain is consumed, Fig. 6(c).

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(a)

Fig. 2 - - I s o t h e r m a l T r a n s f o r m a t i o n d i a g r a m for 52100 steel, austenitized 30 rain at 1040~ ASTM grain size 5-6. Points shown the t r a n s f o r m a t i o n t r e a t m e n t s used. Lines a r e for 0, 50 and 100 pct t r a n s f o r m a t i o n of austenite.

(b)
Fig. 3--After carbide dissolution at 1040~ salt quenched to 650~ held 30 s, then quenched to r o o m t e m p e r a t u r e . P e a r l ite colonies consuming an austenite grain. Note c a r b i d e s in grain boundaries. Magnification 1250 t i m e s . Nital etch. METALLURGICAL TRANSACTIONS Fig. 4 - - A f t e r carbide dissolution at 1040~ (a) salt quenched to 595~ held 30 s, then quenched to r o o m t e m p e r a t u r e , (b) salt quenched to 540~ held 5 min, then quenched to room t e m p e r a t u r e . Bainite consuming austenite grains. Magnification 1000 t i m e s . Nital etch. VOLUME 5, APRIL 1974-867

Fig. 5 - - A f t e r c a r b i d e d i s s o l u t i o n at 1040"C, s a l t q u e n c h e d to 705"C, held one m i n , then q u e n c h e d to r o o m t e m p e r a t u r e . Note c a r b i d e f i l m s in g r a i n b o u n d a r i e s and f o r m a t i o n of p e a r l i t e at t r i p l e p o i n t s and along g r a i n b o u n d a r i e s . M a g n i f i c a t i o n 1250 t i m e s . Nital e t c h .

Finally, at still lower temperatures (370 to 480~ transformation to bainite occurs in bands, following the pattern of alloy segregation in the material, Fig. 6(d). Banded structures are apparently due to differences in nucleation rate rather than growth rate, because the banding is evident as soon as any t r a n s f o r mation is visible. Microprobe analyses show that transformation occurs first in bands low in alloy content. It is not clear whether or not transformation begins at austenite grain boundaries within the bands. An unusual feature in Fig. 2 is the sluggish t r a n s formation occurring at 480~ (900~ Bainite forms both above and below this temperature, so the sluggish transformation is unrelated to the transition from pearlite to bainite. There is a correlation, however, with the initial distribution of the bainite; above 480~ transformation begins generally at all austenite grain boundaries, Fig. 6(c), while at 480~ and below, banded m i c r o s t r u c t u r e s occur, Fig. 6(d). Networks of carbide in prior austenite grain boundaries are undesirable. Films of proeutectoid grain boundary carbide do not form at transformation t e m peratures of 425~ and below. However, if a carbide boundary film is present, it may dissolve and/or spheroidize during subsequent austenitization. It will be shown in the next section that no difficulty was experienced in eliminating carbide networks during austenitization in this material. However, one heat of commercially produced 52100 steel* has been encoun*This heat had 1.10 pct carbon and was high in residual impurities such as Ni, Cu and Mo.

treatment of one hour at 175~ (350~ was used in the experiments described in this section. Fig. 7 shows that for specimens in condition A (spheroidized carbides) increasing austenitizing time at 840~ (1550~ results in increasing hardness and fraction of retained austenite and decreasing volume fraction of excess carbides. From the volume fraction of carbide remaining after 8 h, one calculates that the carbon content of the austenite is 0.55 pct. Carbides were extracted from samples austenitized from 8 min to 32 h at 840~ and analyzed for chromium, Table III. Since no change in carbide composition is observed for times through 30 min, the principal reaction is simply dissolution of existing carbides. The slight decrease in chromium content at longer times may be due to growth of lower chromium M3C carbides at the expense of higher chromium MaC carbides. The m i c r o s t r u c t u r a l appearance of the specimens austenitized at 840~ indicates that the p r o c e s s of c a r bide dissolution is more complex than the regular behavior shown in Fig. 7 would suggest. Specimens austenitized from 8 min to two h have a mottled appearance, most noticeable at magnification of about 200 diam, Fig. 8(a). An examination at higher magnification shows that the undissolved carbides are no longer uniformly distributed. The light-etching material is in a pattern which suggests that it is adjacent to prior austenite grain boundaries, although no grain boundaries can be revealed by etching. If carbides are dissolving first near grain boundaries, then the austenite in these regions should be enriched in chromium and carbon. This enriched austenite should have a lower martensite start temperature (Ms) than the austenite immediately adjacent to the remaining carbides. To test this, specimens* were austenitized
*For this experiment, the specimen size was 8 5 3 mm.

for 30 rain at 870~ quenched in salt at temperatures from 163 to 218~ held 15 s, tempered two rain at
Table II. Pretreatments for Microstructural Control

Condition A B

Treatment As received 30min 1040~ salt quench to 650~ hold 30 min, then air cool 30 min 1040~ salt quench to 425~ hold one h, then air cool

Microstructure Spheroidized Carbides in Ferrite Matrix Peadite with a thin carbide fdm in Prior Austenite Grain Boundaries Bainite. No continuous grain boundary carbide

Table III. Chromium Content of Extracted Carbides

tered in which the carbide films could not be broken up during subsequent heat treatments of the kind customarily used to harden 52100 steel. In this material, the only way to avoid a carbide network in the final product was to t r a n s f o r m at 425~ or below. Austenittzation for Hardening In order to compare the effect of initial m i c r o s t r u c ture on hardening response, specimens were prepared with the pretreatments shown in Table II. A tempering
868-VOLUME 5, APRIL 1974

Initial Condition* A A A A A A A B B *See Table II.

Austenitization Treatment None 840~ 840~ 840~ 840~ 840~ 900~ 840~ 840~

Wt Pct Cr in Extracted Carbides 9 9 9 8 8 7 7 7 5.5

h h h h

METALLURGICAL TRANSACTIONS

(a)

(b)

(c) (d) Fig. 6-(a) After 30 min at 1040"C, quenehed to 735~C to allow carbide precipitation on austenite grain boundaries, then
quenched to room temperature. (b) Same heat treatment as Fig. 5. (c) Transformed two min at 540"C. (d) Transformed four min at 480"C. Magnification 200 times. The austenite grain size is the same in all four treatments. 218~ then quenched to r o o m t e m p e r a t u r e . Fig. 9 shows that m a r t e n s i t e does indeed f o r m f i r s t in the a u s t e n i t e which is a d j a c e n t to the u n d i s s o l v e d c l u s tered carbides. F i g . 10 shows the effect of a u s t e n i t i z i n g t i m e at 840~ on the h a r d n e s s and f r a c t i o n of r e t a i n e d a u s t e n ire of s p e c i m e n s in c o n d i t i o n s B and C. Peak h a r d n e s s in t h e s e s p e c i m e n s is a c h i e v e d a f t e r fifteen s e c onds a u s t e n i t i z i n g t i m e . T h e r e is a v e r y slight d e c r e a s e in h a r d n e s s at l o n g e r t i m e s . The f r a c t i o n of r e t a i n e d a u s t e n i t e a l s o a c h i e v e s its m a x i m u m v a l u e in a few s e c o n d s , and r e m a i n s at e s s e n t i a l l y the s a m e v a l u e for a u s t e n i t i z i n g t i m e s up to 32 h. METALLURGICALTRANSACTIONS

Up to two min austenitizing time at 840~ B and C specimens have fine, uniformly dispersed carbides, Fig. 11(a). With increasing annealing time, carbide growth occurs, Figs. 11(b) through 11(d). The microstructures of B and C specimens are similar, except for a faint banding in the C specimens related to banding of the bainite prior to austenitization. No grain boundary carbide films, or orderly sheets of spheroidized carbides left over from such films can be seen in B specimens even for austenitizing times as low as 15
s at 840~ The c h r o m i u m c o n t e n t of c a r b i d e s e x t r a c t e d f r o m B s p e c i m e n s held 8 and 32 h at 840~ is given in T a b l e VOLUME 5, APRIL 1974-869

III. Most of the c a r b i d e s e x t r a c t e d a r e p r o b a b l y the c o a r s e r c a r b i d e s shown in F i g s . l l ( c ) and l l ( d ) . Xr a y p o w d e r p a t t e r n s i n d i c a t e that only MsC c a r b i d e s

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AUSTENITIZING TIME A T 8 4 0 = r

,MINUTES

Fig. 7--Hardness (H) pot retained austenite (RA) and vol pet undissolved carbide (C) as a function of time at 840~ for specimens in condition A (spheroidal carbides). Temper: one h at 175~

a r e p r e s e n t . While the r e p r o d u c i b i l i t y of c a r b i d e a n a l y s e s f r o m B s p e c i m e n s was not a s s a t i s f a c t o r y a s the a n a l y s e s of A s p e c i m e n s , s t i l l it a p p e a r s that the c o a r s e c a r b i d e s which g r o w at the e x p e n s e of the u l t r a - f i n e c a r b i d e s a r e l o w e r in c h r o m i u m than e i t h e r the u l t r a - f i n e c a r b i d e s , o r the s p h e r o i d a l c a r b i d e s in A specimens. The r e s u l t s m a y be c o m p a r e d with t h o s e of Glowacki e t a l . 7 T h e s e a u t h o r s c o n c l u d e d that c a r b i d e s in 52100 which f o r m in a f e r r i t i c m a t r i x c o n t a i n m o r e c h r o m i um. than t h o s e which f o r m in an a u s t e n i t i c m a t r i x . T h e y found that 1) s p h e r o i d a l c a r b i d e s contain 9 pct C r , 2) the c a r b i d e s in p e a r l i t e contain 7 pct C r (a r e sult obtained i n d i r e c t l y ) , and 3) c a r b i d e s which f o r m in a u s t e n i t e at 840~ f r o m a s u p e r s a t u r a t e d s o l i d s o l u tion contain 2 pct C r . Such l a r g e d i f f e r e n c e s in c a r b i d e c h r o m i u m content w e r e not o b s e r v e d in the c u r r e n t work, but t h e r e is q u a l i t a t i v e a g r e e m e n t that the MsC c a r b i d e in e q u i l i b r i u m with a u s t e n i t e at 840~ has a l o w e r c h r o m i u m content than the MsC c a r b i d e s p r o duced by a s p h e r o i d i z e a n n e a l .

(a)

Fig. 9--Specimen with spheroidal carbides (condition A) austenitized for 30 min at 870~ quenched in salt at 190~ and held 15 s, then tempered in salt for 2 rain at 218~ and quenched to room temperature. Nita] etch. Magnification 1250 times. ' ' ...... [
65

........ I
S

........ I

........ 1

........

.u 64

63 RA 62 Lt~ e | 9 9 9

20~

15 Z

61

O~ LU Z

59 O. I

I II1111

I
I

[ Illlll

I
I0

I i i Iiii I00

I IIIIII

I
I000

I Illl

0 IO,O00

AUSTENITIZlNG TIME AT S40~

MINUTES

(b)
Fig. 8--Condition A, austenitized 30 min at 840~ quenched, tempered at 175~ Nital etch. Magnification (a) 190 times, (b) 1250 times. 870-VOLUME 5, APRIL 1974

Fig. 10--Hardness (H) and pct retained austenite (RA) as a function of austenitizing time at 840~ for specimens in conditions B and C (pearlite or bainite). There is no systematic difference in the behavior of B and C specimens. Temper: One h at 175~ METALLURGICAL TRANSACTIONS

(a)

(b)

(c)

(d)
oil quenched and tem-

Fig. ll--Specimens with a pearlitie microstrueture (eonditionB) austenitized for various times at 840~ pered at 205~ Pieral etch. Magnification 1500 times (a) 2 rain, (b) 8 min, (c) 30 min, (d) 2 h. The effect of a u s t e n i t i z i n g t e m p e r a t u r e on h a r d n e s s , f r a c t i o n of r e t a i n e d a u s t e n i t e , and v o l u m e f r a c t i o n of c a r b i d e is shown in F i g . 12 f o r s p e c i m e n s in condition A a u s t e n i t t z e d f o r 30 min. The p e a k h a r d n e s s is a c h i e v e d at a u s t e n i t i z i n g t e m p e r a t u r e s of 870 to 900~ The a m o u n t of r e t a i n e d a u s t e n t t e i n c r e a s e s with i n c r e a s i n g t e m p e r a t u r e . The r e l a t i o n b e t w e e n t e m p e r a t u r e and amount of r e t a i n e d a u s t e n i t e is a p p r o x i m a t e l y l i n e a r f r o m 840~ to 980~ Microstructural examinat i o n shows p r o g r e s s i v e d i s s o l u t i o n of c a r b i d e s with i n c r e a s i n g t e m p e r a t u r e . Only a few s c a t t e r e d u n d i s s o l v e d c a r b i d e s a r e s e e n a f t e r 30 m i n at 980~ Carbides ext r a c t e d a f t e r 30 min at 900~ w e r e found to contain 7 p c t c h r o m i u m . A p p a r e n t l y s o m e n u c l e a t i o n and growth METALLURGICAL TRANSACTIONS

of low C r c a r b i d e s a c c o m p a n i e s the g e n e r a l p r o c e s s of c a r b i d e d i s s o l u t i o n a t h i g h e r a u s t e n i t i z i n g t e m p e r a tures. F i g . 13 shows the effect of a u s t e n i t i z i n g t e m p e r a t u r e on h a r d n e s s and f r a c t i o n of r e t a i n e d a u s t e n i t e f o r B and C s p e c i m e n s . Note that the h a r d n e s s is l e s s d e pendent on a u s t e n i t i z i n g t e m p e r a t u r e than f o r A s p e c i m e n s . The f r a c t i o n of r e t a i n e d a u s t e n i t e v a r i e s l i n e a r l y with the a u s t e n l t i z i n g t e m p e r a t u r e to about 950~ The s l o p e of the l a t t e r c u r v e i s the s a m e a s the l i n e a r p o r t i o n of the a n a l o g o u s c u r v e in F i g . 12. M i c r o s t r u c r u r a l e x a m i n a t i o n shows m a i n l y u l t r a - f i n e c a r b i d e s at t e m p e r a t u r e s of 790 to 840~ m i x t u r e s of c o a r s e and fine c a r b i d e s at 870 to 900~ VOLUME 5, APRIL 1974-871

TEMPERATURE, ~ 1400 I 1500 I 1600 I 1700 I 1800 I

DEGREES
4O
hJ r~

200
651-

400
i I

FAHRENHEIT 600 800

i I I I

I000
I

66r .J ,J
0

30 z
>,
o

64v U n,(/3 o~ t~J 0

20 z
62-

60
a.

60-r

-10

.J
tJ

,., 55 -=2o
z

58

850 900 950 I000 TEMPERATURE,~ Fig. 12--Hardness (H), pct r e t a i n e d austenite (RA) and vol pct undissolved carbide (C) as a function of austenitizing t e m p e r ature for s p e c i m e n s in condition A. Austenitizing time is 30 min; one h at 175~ t e m p e r ,
TE M PE RATURE, ~ 1500 1600 1700 I I 1

I 750

1~

800

I o

< ~-~

<0 Q
Z

45-,.,

1400 I

1800 I

4O 4
I00

0
0
200
TEMPERING

~
300 400
TEMPERATURE

U .J _1 tO

66

500
,=C

600

3o

64 o m 62
i.al z r~
rr

20 ~ Z

Fig. 14--Hardness and pet r e t a i n e d austenite as a function of t e m p e r i n g t e m p e r a t u r e for one h t e m p e r i n g time. A, B and C r e f e r to initial conditions d e s c r i b e d in Table II; t h e s e s p e c i m e n s w e r e austenitized for 30 rain at 840~ A1 is m a t e r i a l in condition A austenitized 8 h at 840~

IO ~

58

I 750

I l I I 800 850 900 950 TE MPERATURE,~

I 0 1000

Fig. 13--Hardness (H) and pct r e t a i n e d aastenite (RA) as a function of austenitizing t e m p e r a t u r e for s p e c i m e n s in condition B and C. 30 rain austenitizing time; 175~ t e m p e r for one h.

temperature. The same behavior holds for all t e m pers in the range 150 to 230~ Thus, for B and C specimens, within the limits of austenitizing t e m p e r a ture cited above, the hardness is for all practical p u r poses a function only of the tempering treatment. This is not true for A specimens; in these specimens both the austenitizing treatment and the tempering t r e a t ment influence the final hardness, Fig. 15. DISCUSSION The kinetics of austenite transformation in 52100 steel, as summarized by Fig. 2 and similar diagrams in the literature, 1~ is well known without being well understood. When the austenitizing t e m p e r a t u r e is high enough to dissolve all carbides, the initial reaction for t e m p e r a t u r e s of 480~ and above, is formation of p r o eutectoid carbide in austenite grain boundaries. At transformation temperatures of 540~ and above, the carbide films are continuous in grain boundaries; at 425~ and below, no proeutectoid carbides can be seen. Pearlite and bainite clearly form initially at carbide/ austenite interfaces at 540~ and above. Pearlite is found at 620~ and above, and bainite f o r m s at lower temperatures. At transformation t e m p e r a t u r e s of 480~ and below, the kinetics of transformation is dominated by the influence of alloy content on nucleation, and banded m i c r o s t r u c t u r e s appear, due to alloy segregation. The size of the bainite laths within the bands s e e m s to be limited by the austenite grain boundaries, but the details of the initial reaction are not
METALLURGICAL TRANSACTIONS

Tempering The tempering response of samples in the A, B, and C condition, austenitized 30 min at 840~ quenched in oil and tempered for one h, is shown in Fig. 14. Also shown is data for A specimens (designated A1) austenitized for 8 h at 840~ The data for the B and C specimens is essentially the same. Although A1 specimens have the same h a r d ness at low tempering temperatures as B and C specimens, they a r e significantly softer for tempers above 205~ (400~ For any pretreatment and austenitizing treatment, the amount of retained austenite is about the same with t e m p e r s of 150~ and 175~ decreases p r o g r e s s i v e l y with tempers of 200 and 230~ and is close to zero at t e m p e r s of 260~ and higher. Fig. 13 shows that for B and C with a 175~ temper, the hardness is nearly constant for austenitizing t e m p e r a t u r e s f r o m 815 to 900~ although the amount of retained austenite increases with the austenitizing
872-VOLUME 5, APRIL 1974

TEMPERING TEMPERATURE ,*F 300 350 400 450 67 66 u 65 ,..I

,,-I I i I I I

"' 64 u 63 o ~: 62 cn c~ o: 60 <t "" 59 58 57 ~ B,C 815-900"C 900"C 870"C 840"C A 815"C 790"C

The behavior of pearlitic or bainitic m i c r o s t r u c t u r e s during reaustenitization is quite different from the behavior of spheroidized m i c r o s t r u c t u r e s . In the latter, at temperatures near 840~ the spheroidal carbides, rich in chromium, gradually dissolve. They do not dissolve uniformly. It appears that those carbides near austenite grain boundaries tend to dissolve first,* en*The observed approach to equilibrium at 840~ for spheroidal carbide specimens is too slow to be accounted for by carbon diffusion-limited dissolution of individual carbides, and too fast to be accounted for .by chromium-diffusion limited dissolution. (Diffusion constants were used from Ref. 12). Since the carbides are rich in Chromium, partial dissolution must cause a steep Chromium gradient to be established near each carbide, acting to inhibit carbon transport and further dissolution. Austenite grain boundaries, by providing more rapid chromium and carbon transport, may help destroy gradients at adjacent particles. Since the boundaries themselves are mobile, they may play an important role in the dissolution of all carbides.

1 150

I 175

I 200

I 225

1 250

TEMPERING TEMPERATURE , *C

F i g . 1 5 - - H a r d n e s s a s a f u n c t i o n of t e m p e r i n g t e m p e r a t u r e f o r v a r i o u s a u s t e n i t i z i n g t e m p e r a t u r e s and s p e c i m e n s in i n i t i a l c o n d i t i o n s A, B a n d C ( T a b l e II). 30 m i n a u s t e n i t i z i n g t i m e ; o n e h at t h e t e m p e r i n g t e m p e r a t u r e .

clear. It is not known ff the bainite reaction begins at an austenite grain boundary. If the temperature and time of austenitization are not sufficient to dissolve all carbides, then the structures produced by isothermal transformation of austenite will be different. Specimens austenltized at 840~ for 16 h (a time sufficient to remove local carbon g r a dients) and transformed at 700~ have no apparent p r o eutectoid reaction. Austenite grain boundaries are not decorated by any precipitate and pearlite f o r m s in a manner similar to Fig. 6(b). Specimens austenitized only 30 min at 840~ on the other hand, t r a n s f o r m to a v e r y complex structure which includes pearlite and proeutectoid ferrite. Bearing components can be produced with dispersions of ultra-fine carbides beginning with either pearlite or bainite. Austenite t r a n s f o r m s most rapidly to pearlite, but transformation is preceded by the f o r mation of continuous films of proeutectoid carbide in austenite grain boundaries. In this heat, these films redissolved during subsequent austenitization and posed no problem. In other c o m m e r c i a l l y produced heats, this is not the case; if the carbon content is at the high side of the specification and the level of residual carbideforming elements such as Mo is high, grain boundary carbide films can persist through subsequent austenitization. A bainitic m i c r o s t r u c t u r e formed at about 425~ will not have carbide films in p r i o r austenite grain boundar i e s . A disadvantage to using bainite is its sluggish rate of formation. A transformation treatment of one h at 425~ was commonly used in these experiments to form bainite. A few small regions were encountered (in over 100 samples given this treatment) in which the austenite had not completely t r a n s f o r m e d and m a r t e n site formed on cooling from 425~ Several of these untransformed regions cracked. This could not be tolerated in a commercial application. More prolonged heating at 425~ or a temper after cooling to room temperature would be n e c e s s a r y to avoid any danger of cracking.
M E T A L L U R G I C A L TRANSACTIONS

riching the regions about grain boundaries in carbon and chromium, and locally depressing the Ms t e m p e r ature. After prolonged heating at constant temperature the gradients of dissolved carbon in the microstructure diminish and the etched m i c r o s t r u c t u r e appears uniform. The mottled appearing microstructure, which is the result of local variations in composition (and Ms) occurs commonly in commercially produced bearing components. When specimens with pearlitic or bainitic m i c r o structures are austenitized, the sequence of events is different. No inhomogeneities associated with austenite grain boundaries are evident. Judging from m e a surements of hardness and fraction of retained austenite, the austenite becomes saturated in carbon in less than 15 s at 840~ Beginning at about 8 min, carbide growth becomes evident. The original ultra-flne c a r bides derived from the pearlite or bainite do not coarsen uniformly. New carbides, lower in chromium, may nucleate and grow at the expense of the small c a r bides. Thus, the shorter the austenitizing time, the more homogeneous is the m i c r o s t r u c t u r e . Hardened specimens with ultra-fine carbides tend to be harder and to have more retained austenite than hardened specimens with coarse carbides (compare Figs. 7 and 10). Most of the difference can be attributed to more rapid carbon saturation of the austenite with fine carbides. However, the amount of retained austenite in B and C specimens austenitized for 8 to 30 min at 840~ was greater than that found in A specimens after 32 h at the same temperature. It is known that the Ms temperature is depressed (thus the amount of retained austenite is increased) as the strength of the austenite increases. 11 It may be that the ultra-fine carbides strengthen the austenite sufficiently to inc r e a s e further the volume fraction of retained austenite. It is clear from the decrease in hardness with long austenitizing times in Fig. 10, that the fine c a r bides do contribute to the strength, even at hardness levels of Rc 63 and above. At tempering temperatures above 200~ the samples with fine carbides are significantly harder than samples with coarse carbides. This is undoubtedly due to enhanced dispersion strengthening of the tempered m a r tensite by the ultra-fine carbides. Thus, a bearing component with a hardness of more than 61 Rc and no retained austenite can be produced by tempering an ultra-flne carbide m i c r o s t r u c t u r e at 260~ Finally, it has been shown that when pearlitic or
VOLUME 5, APRIL 1 9 7 4 - 8 7 3

bainitic m i c r o s t r u c t u r e s a r e austenitized, quenched and tempered, the resulting hardness is quite insensitive to austenitizing treatment. While the amount of retained austenite varies with the austenitizing t e m perature (but not austenitizing time) and tempering temperature, it can be controlled within limits independent of the hardness. For example, referring to Fig. 13, samples can be prepared with a hardness of 63.5 to 64 Rc and retained austenite contents of 10 or 25 pct. The results of these experiments show that there is sufficient flexibility in the p r o c e s s to make carbide r e fining heat treatments practical. A pearlitic m i c r o structure formed isothermally at about 650~ is the p r e f e r r e d intermediate structure. To avoid problems with heavy intergranular carbide films forming prior to pearlite, the material used should be from a supplier capable of maintaining low levels of residual alloying elements in his steel. Since there is no benefit to prolonged austenitization for hardening, induction heating may be used. On the other hand, the coarsening rate of ultra-fine carbides is slow enough so that conventional austenitizing f u r naces can also be used. In furnaces, the austenitizing time can be shortened to allow just enough time for the parts to reach the maximum desired temperature. It is evident from the present work that the m i c r o structure which is developed by conventional heat t r e a t ments of c o m m e r c i a l l y produced steel is complex, quite variable (depending strongly on the result of the spheroidizing anneal), and is usually quite inhomogeneous. In contrast, if carbide refining heat treatments are e m ployed p r i o r to hardening, the final m i c r o s t r u c t u r e is independent of the spheroidized structure, and is v e r y homogeneous. The more homogeneous microstructure is expected to have better fatigue properties; the magnitude of the improvement has yet to be determined. The prime advantage to carbide refinement, however, may lie in the much superior m i c r o s t r u c t u r a l control it is possible to achieve in heat treatment, and the greater resulting uniformity of the bearing components produced. SUMMARY 1) A study has been made of the heat treatment needed to produce hardened bearing components of 52100 steel with uniform dispersions of ultra-fine carbides. Such m i c r o s t r u c t u r e s are produced by first converting a microstructure of spheroidal carbides in f e r r i t e to pearlite or bainite, then austenitizing, quenching and tempering in a conventional hardening heat treatment. 2) After dissolution of all carbides, pearlite f o r m s rapidly by isothermal transformation at 625 to 650~ while thin proeutectoid carbide films are present in austenite grain boundaries, these redissolve during subsequent austenitization.

3) If the 52100 steel used has comparatively high levels of residual carbide-forming elements, difficulty may be experienced in redissolving carbide films. Then it is preferable to begin with bainite because isothermal transformation to bainite at 425~ suppresses f o r m a tion of carbide films. The transformation is more sluggish, however, than the pearlite transformation. 4) Austenitizing pearlite or bainite produces carbon saturation of the austenite in a few seconds. Thus, the amount of austenite retained on quenching is more controllable, since it is not, for practical purposes, a function of austenitizing time. 5) As the austenitizing time is extended, ultra-fine carbides coarsen. While there is no benefit to austenitizing times longer than 15 s at 840~ times up to 30 min produce little carbide coarsening so little degradation in properties is expected. 6) Ultra-fine carbides increase the hardness for most combinations of austenitizing and tempering temperature. 7) For a given hardening treat treatment, the level of retained austenite is higher in specimens with ultrafine carbides. Most of this effect is due to rapid c a r bon saturation of austenite. 8) When a m i c r o s t r u c t u r e of spheroidal carbides in ferrite is austenitized, carbides do not dissolve uniformly. Heat treatments typical of c o m m e r c i a l p r a c tice result in mottled m i c r o s t r u c t u r e s , with clusters of undissolved carbides in a relatively low carbon matrix surrounded by material with a higher carbon content and fewer undissolved carbides. ACKNOWLEDGMENTS Retained austenite measurements were made by Carol J. Kelley, carbide extractions and analyses were done by J. L. Bell, and metallography and heat treatment were done by E. Quick and R. L. Martin, respectively, all of the Ford Scientific Research Staff. RE FERENCES
1. T. E. Tallian: J. Lubrfc Technol. (Trans. ASME), 1967, vol. 89, pp. 73-74. 2. R. L. Faunce and W. M. Justusson: U.S. Patent No. 3,595,711, July 27, 1971. 3. J. H. N. Wheeler: Private Communication, T. I. Steel Tubes (U.S.A.) Inc., Larchmont, N. Y. 4. K. Moama, R. Maruta, T. Yamamoto, and Y. Wakikado: Jap. Inst. Metals J., 1968, vol. 32, pp. 1198-204. 5. R. A. Grange: Met. Trans., 1971,vol. 2, pp. 65-78. 6. R. A. Grange: U.S. Patent No. 3,337,376, August 22, 1967. 7. Z. Glowacki and A. Barbacki: J. Iron SteelInst., 1972, vol. 210, p. 724. 8. R. F. Hehemann: Phase Transformations, pp. 397-432, American Society for Metals, Metals Park, Ohio, 1970. 9. D. Tumbull and K. N. Tu: Phase 7~ans[ormations, pp. 487-95, American Society for Metals, Metals Park, Ohio, 1970. 10. Atlas of Isothermal Transformation Diagrams, pp. 65,133, U.S. Steel Corp., 1951. 1I. E. M. Breinan and G. S. Ansell: Met. Trans., 1970, vol. 1, pp. 1513-20. 12. J. F. Elliott, M. Gleiser, and V. Ramakrishna: Thermoehemistry ,for Steelmaking, vol. II, pp. 689-96, Addison.Wesley Publ. Co., Inc. Reading, Mass., 1963.

8 7 4 - V O L U M E 5, APRIL 1974

M E T A L L U R G I C A L TRANSACTIONS