From t4eta|]ovede~ie i Term.

Obrabotka Hetal]ov, Dec, 1959, ~12, 2-11

HB

No. 5002

EFFECT ON Prof. Dr. A. THE

OF

ALLOYING TEMPERING

ELEMENTS OF STEEL

S. Zav'yalov and Eng. M. I. Senchenko

T h e hardness of quenched steel is due to local static distortions of the iron lattice by interstitial carbon atoms [I]. In low carbon martensites, it is due basically to phase strain-hardening [2]. A partial decomposition of m a r tensile by plastic deformation during mechanical tests should also harden the martensite because of the strengthening action of precipitating, highly dispersed carbide particles [3]. U p o n quenching, phase strain-hardening results in a break-up of the m o s a i c blocks to a size of approximately 2-3 X 1 0 - 6 c m [4]. P r o c e s s e s which a c c o m p a n y the tempering of carbon-steel m a r t e n sites w e r e studied in considerable detail [5-9]. These processes are strongly affected by alloying. T h e Effect of Titanium and C o l u m b i u m on Tempering. This investigation showed that in steels containing titanium and columbium, the hardenability decreases with increasing content of these elements. T h e effect of Ti and C b during tempering is similar to the effect of reducing the carbon content. H o w e v e r , these elements do not affect the decomposition temperature of m a r tensile. T h e carbides TiC and C b C are f o r m e d w h e n the steel is still liquid. T h e y do not dissolve in solid steel even after heating to 1350~ [i0]. Hence, titanium and c o l u m b i u m as well as the carbon contained in their carbides are neutralized and can only protect the steel f r o m being overheated. C h a n g e of C a r b o n Concentration in the a - P h a s e During T e m p e r i n g of Alloy Steels. During tempering of quenched steels alloyed with carbideforming elements, the a-phase remains supersaturated with carbon to higher temperatures than in tempering of carbon steel [I i]. E v e n alloying with such a w e a k carbide f o r m e r as m a n g a n e s e strongly retards the separation of carbon f r o m the a-phase and after tempering for ten hours, the a-phase remains supersaturated with carbon to nearly 500~ Stronger carbide-forming elements naturally cause a still higher degree of supersaturation with carbon of the a-phase. It w a s s h o w n in [II] that the separation of carbon (carbides} in hardened steel is retarded both by carbide-forming elements and by those p r o m o t ing graphitization (e.'g. silicon}. Silicon increases the temperatures of m a r tensite decomposition and separation of carbides and also lowers the carbon in silicon rich zones of the alloy. T h e changes of hardness with tempering temperature for steel with variable silicon content is s h o w n in Fig. I. The tempering temperature at which the hardness begins to fall, increases with the silicon content. This process is directly dependent on the temperature of carbide formation and separation. F i g . 2 a n d T a b l e 1 g i v e t h e r e s u l t s of a n X - r a y a n a l y s i s of t h e a and carbide-phases, respectively, of t h e s t e e l s l i s t e d in T a b l e 2. T h e d a t a a l s o s h o w t h e c o n s i d e r a b l e s t a b i l i z i n g e f f e c t of s i l i c o n on m a r t e n s i t e a t a n y t e m p e r a ture. The temperature a t w h i c h c a r b i d e s b e g i n to f o r m a n d s e p a r a t e o n t e m p e r i n g of c o n s t r u c t i o n a l s t e e l s is r a i s e d v e r y l i t t l e b y a l l o y i n g w i t h n i c k e l .

450

e 35o
,g

2.~,5%.r
~ a) b)

:~ 2"50

I O.gg%S/~ ;0.2% i

O.O8

~1762.
600

I0

1003005001000 2-

,I,

10

! ~,~ 1003005001000

Tempering time, hrs=

# 200 r

Tempering Temperature',, C

Fig. i. Effect of tempering temperature on hardness of 0.30-0.36% C steels with varying silicon content.

F i g . 2. C h a n g e of c a r b o n c o n t e n t s in s o l i d s o l u t i o n of s t e e l s l i s t e d in T a b l e 2 w i t h t e m p e r i n g t e m p e r a t u r e and t i m e . D i a g r a m s a , b , c , d p e r t a i n to H e a t s 1-4, r e sp e c l i v e lye.

Table
Temperlng Tempera- 1 t u r e (Cl and TTme j Heat 1

1.
CarbTde Heat 2 Type Heat 3 Heat

350~ I000 Hrs.

Fe~C
Fe C and Weak Me~C L;nes

No Carbides

500~ 2 hrs. 500~ 1000 hrs. 650~ hrs. 650~ I00 hrs. 650~ IO00 hrs.

Fe~C Fe~C

Found

No Carbides Found
Fe~C Fe=C

F~3c
FeBC Fe~C

Fe3C Fe~C MerCs

Fe~C

7 3MeTC 3 MeTC~

Me~3

MeTC~ MeTC~

The processes during tempering of alloy steels w e r e further studied on four different heats (Table 2) melted in an induction furTable 2. nace. T h e compositions w e r e selected on the following premises: Heat 1 Composition, 1o had a high content of carbide-forming o t s I P Is, tMnlo t.ol elements, including m o l y b d e n u m . AcI cording to [I0] and [12], in this steel 1 0.16 0,02110.0190,220.28 1,940.730,19 2 10.15 0.0200,0191.420.462,81 - - q - the process of carbon separation f r o m 0,15 [0,022 0.017 2 44 0.43 2.2810.71t0,20 the solid solution should be relatively 4 3 01 10 o,9;o ,o ]o 2,1o 31122,1o 671o,9 slow as c o m p a r e d with carbon steel and the redistribution of carbon with its subsequent migration to the grain b o u n d a r i e s is o b s t r u c t e d . In s t e e l s 2 a n d 3 w i t h l a r g e a m o u n t s of s i l i c o n , s u c h r e d i s t r i b u t i o n of c a r b o n and i t s s e g r e g a t i o n at g r a i n b o u n d a r i e s [13] as w e l l as c a r b i d e f o r m a t i o n s h o u l d p r o c e e d at h i g h e r t e m p e r a t u r e s . In v i e w of the h i g h p h o s p h o r u s c o n t e n t in t h e s t e e l f r o m H e a t 4, t e m p e r i n g s h o u l d c a u s e t h e g r a i n b o u n d a r i e s to b e c o m e g r a d u a l l y e n r i c h e d in p h o s p h o r u s and, t h e r e f o r e , d e p l e t e d in c a r b o n [12, 13].

W e studied the processes which occur during tempering at 350, 500, and 650~ At 350~ the martensite in a carbon steel transforms into equilib r i u m ferrite and separated carbides; at 500~ the m o s t pronounced embrittlem e n t usually occurs; 650~ is about the upper limit of high-temperature tempering of steels. T h e changes of carbon concentration in the a-phase w e r e determined by X-rays. Specimens 1.4mm in dia. and 1 0 - 1 5 r a m long w e r e etched in 6 % nitric acid solution to r e m o v e the surface layer distorted by machining. X - r a y photographs w e r e taken with cobalt radiation in the s a m e D e b y e c a m e r a with a one m m dia. diaphragm. T h e photographs w e r e scanned on a M F - 4 microphotometer. To determine the effect of carbon content on the half-width of the (211) line on the X - r a y photograph, it w a s arbitrarily a s s u m e d in constructing the d i a g r a m that in hardened steel the entire carbon is in the martensite and that after quenching followed by two successive tempering treatments - at 650~ i000 hrs. and at 680~ hrs. - the ferrite contains no carbon. T e m p e r i n g at 350~ for up to I000 hours of all steels and especially of Heat 3, had little effect on the carbon concentration in martensite {see Fig. 2) and after tempering at 5 0 0 ~ hrs. the a-phase r e m a i n e d for a long time slightly supersaturated with carbon. In Heat 4, this w a s the case even after i000 hours of tempering. This definitely proves that in steels alloyed with carbide-forming elements, a is not an equilibrium phase. Carbide F o r m a t i o n in Alloy Steels. F o r m e d i u m - c a r b o n constructional and temper-resistant steels, it w a s established [i0] that in compositions based on m a n g a n e s e , only cementite-type carbides are f o r m e d at all tempering temperatures [I0]. In c h r o m i u m steels only cementite-type carbides separate on tempering up to 400-450~ w h e r e a s at higher temperatures the m o r e c o m p l e x carbides (Cr, F e ) 7 C 3 appear. A s the tempering temperature and the c h r o m i u m content of the steel increase, the a m o u n t of the c o m p l e x carbide increases at the expense of cementite but carbides of both types increase their c h r o m i u m content. In steels w~th up to 2 % tungsten, tempering produces only cementire and a cubic carbide (W,Fe)23C6; the latter appears on tempering near 500~ In steels with less than 0 . 4 ~ m o l y b d e n u m , only cementite-type carbides are formed. With higher m o l y b d e n u m content, a hexagonal carbide M o z C appears at 5 0 0 - 5 5 0 ~ in addition to cementite. W h e n m o l y b d e n u m exceeds 0.8%~ high tempering temperatures result also in the formation of the cubic carbide ( M o , Fe)z3C6. In steels with less than 0 . 6 % v a n a d i u m , there is a preferential formation of (Fe, V ) 3 C type carbides. With higher v a n a d i u m contents and at 550~ and above, large a m o u n t s of cubic v a n a d i u m carbide are f o r m e d in addition to eementite; the latter type m a y vanish eventually. In steels alloyed with titanium or c o l u m b i u m only, both cementite and cubic carbides TiC and C b C appear and they do not dissolve in the steel below the melting point. In c o m p l e x C r - W - M o steels, on tempering up to 4 0 0 ~ only cementire-type carbides form; at higher temperatures, trigonal and cubic carbides containing all the elements specified, appear. Steels with Cr, W, M o , V, and T~ contain, after quenching and t e m pering at 690~ carbides of the M e 7 C 3 and M e 6 C type. It is probable that with a high titanium content, a TiC carbide m a y also exist. W h e n replacing titanium by c o l u m b i u m , carbides M e 7 C 3 and C b C w e r e found after quenching and t e m p e r ing at 690~ Carbide M e 6 C w a s not detected; at a lower c o l u m b i u m content, carbide C b C might have, perhaps, vanished to be replaced by carbide M e 6 C . X - r a y (Table I) and chemical analyses of the residues after an electrolytic dissolution of alloy s p e c i m e n s (see Table 2) enabled the process

of carbide formation to be followed during extended tempering treatments. N o carbides w e r e found in the residues of Heats 2 and 3 t e m p e r e d at 3 5 0 ~ hrs. and 5 0 0 ~ hrs., although the heats contained 0 . 7 1 - 1 . 6 0 % of various carbide-forming elements (of this up to 8 5 % Fe). T h e X - r a y analysis of the residue showed only highly alloyed austenite w h i c h disappeared during i000 hours at 500~ It is possible that carbides w e r e not detected by X - r a y s in the residues of Heats 2 and 3 because the carbide nuclei which appeared in the first carbide-forming stage dissolved during the electrolytic dis solution of the specimens. T h e remaining carbide particles w e r e evidently not discovered because of their high degree of dispersion. In Heats 2 and 3, carbides w e r e found by X - r a y s only after t e m p e r ~ ing for i000 hours at 500~ Hence, while in Heats 1 and 4 a separation of cementite (in v e r y small amounts) w a s observed already at 350 ~ such separation could be noticed in steels with higher silicon (Heats Z and 3) only at 500~ T h e changes in the carbide phase on tempering at 650~ are noteworthy. After two hours, carbides of the cementite type w e r e precipitated in all four heats; only on the X - r a y photograph of Heat 1 w e r e found also very w e a k lines of the M e 7 C 3 type. Extension of the tempering time at 650~ caused the cementite-type carbides to vanish and the M e 7 C 3 to appear instead. Cubic M e 6 C carbides found in multi-alloy steels [i0], w e r e not detected in these heats; this might have been due to different carbon contents and a too low tempering temperature. Such change of the carbide type supports the results contained in [i0, II, 14] suggesting two simultaneous processes during tempering. First, the formation of n e w carbides or the growth of n e w layers on certain carbide particles which precipitated earlier; the n e w carbide phase f o r m e d at the proper temperatures is a special-type carbide. T h e second process is a solution of carbides already formed. T h e first to dissolve are those carbides which had the least heat of formation. T h e reaction of forming free cementite in alloys other than iron is, in contrast with the reaction of the formation of other carbides quoted above, not exothermic but endothermic. Thus, cementite is the least stable of all the carbides discussed. This is why, as w a s s h o w n in [i0] and also in Table I, cementite-type carbides and certain particles of special carbides which have a m a x i m u m of free energy, are dissolved first. F r o m Figs. i and 2 and Table 2 it can be concluded that carbideforming elements and those non-carbide-forming elements which cause a drastic depletion in carbon of the alloy zones rich in such elemer~ts, increase the temperature level of all three stages of carbide formation and slow d o w n the separation of carbon f r o m the solid solution. T h e reason for such action of the carbide-formers [s p r e s u m a b l y as follows: A t o m s of carbide-forming elements distributed relatively uniformly within a grain attract to their surroundings carbon a t o m s thereby counteracting the concentration in these or other grain zones of sufficient carbon a t o m s to f o r m carbide nuclei. T h e diffusion rate of alloy elements increases with t e m p e r a t u r e and a redistribution of alloy and carbon followed by an appearance of zones with carbon concentration n e c e s s a r y to f o r m carbide nuclei b e c o m e s a possibility. B e l o w the formation temperature of such special carbides, only alloy cementite can be formed; limited n u m b e r s of carbon atoms, such as are m o s t feebly held by the carbide-forming elements participate in this process. T h e less the content of carbide f o r m e r s in the steel and the higher its carbon content, the m o r e readily will cementite-type carbides appear. T h e reason for the increased temperature of nucleation and separation of carbides by elements such as silicon, is as follows: In the solid solution carbon atoms can accumulate only at a certain distance f r o m the Si, P,

and other non-carbide forming atoms [IZ, 13]. Z o n e s rich in carbon are then depleted in these elements and vice versa. After quenching, silicon is distributed relatively uniformly in the solid solution within each particular grain (not in the overall volume). With m u c h silicon uniformly distributed in the solid solution, conditions for a concentration of carbon a t o m s in quantities needed to f o r m stable carbide nuclei do not exist. In hlgh-silicon steels, carbide formation is possible only at temperatures at which a diffusional redistribution of carbon and silicon b e c o m e s possible. This results in the formation of microscopic and submicroscopic zones of which s o m e are rich in silicon but low in carbon and while with others the situation is reversed. Carbide nuclei of critical size are f o r m e d in the latter type zones. Redistribution of C a r b o n During T e m p e r i n g of Q u e n c h e d Alloy Steel. T h e distribution of carbon in steels similar to those in Table 2 w a s investigated hy autoradiography. Irrespective of the heat treating conditions, no preferential redistribution of carbon along grain boundaries w a s found in Heat i. N o r w a s an enrichment of the grain boundaries with carbon discovered in Heat 4 with high phosphorus content [I 2]. A n intense migration of carbon towards the grain boundaries w a s found in Heats Z and 3 upon tempering at 350 and 500~ Fig. 3 shows autoradiographs of Heats Z and 3 after quenching and tempering for 300 hours at 350~ T h e concentration of carbon in the grain boundaries is plainly visible, T h e effect w a s v e r y w e a k after 3 5 0 ~ hrs. H o w e v e r , I00 hours at 500~ w a s sufficient to cause a substantial redistribution of carbon in these heats, Fig. 4.

Fig. 3.

Autoradiographs of alloys. a) Heat Z; b) Heat 3.

Magn.

XI05,

Fig. 4. Autoradiograph of alloy 3 t e m p e r e d at 5 0 0 ~ hrs. after quenching.

Fig. 4.

Magn.

105

T e m p e r i n g of Heat g at 6 5 0 ~ hrs. caused only a slight redistribution of carbon which did not increase after I000 hours. In Heat 3, a redistribution of carbon could not be detected at all at 650~ Apparently, m o s t of the carbon in Heat 3 is tied up in the carbides m u c h faster than in Heat 2, these carbides being rather stable at 650~

T h u s , it w a s s h o w n t h a t at t e m p e r a t u r e s up to 500~ a n d p o s s i b l y e v e n h i g h e r , the t e m p e r i n g p r o c e s s e s a r e n o t c o m p l e t e d a n d e v e n a f t e r 1000 h o u r s , the a - p h a s e i s s t i l l c o n s i d e r a b l y s u p e r s a t u r a t e d w i t h c a r b o n . T h e p r e s e n c e of c a r b i d e s in e l e c t r o l y t i c a l l y e x t r a c t e d r e s i d u e s w a s d e t e r m i n e d b y X - r a y s a f t e r 1000 h o u r s of t e m p e r i n g at 350~ ( H e a t s 1 and 4) and a t 5 0 0 ~ ( H e a t s 2 a n d 3). No c a r b i d e s w e r e f o u n d i n the r e s i d u e s a f t e r a s h o r t t e m p e r i n g at t h e s e t e m p e r a t u r e s . A t a l l t e m p e r a t u r e s up to 6 5 0 ~ cementite-type carbides are formed i n i t i a l l y ; a f t e r l o n g h o l d i n g at 6 5 0 ~ t h e y d i s a p p e a r and a r e r e p l a c e d b y c a r b i d e s of the M e 7 C 3 t y p e . In H e a t s 2 and 3 c o n t a i n i n g s i l i c o n , a v i g o r o u s r e d i s t r i b u t i o n of c a r b o n and its m i g r a t i o n t o w a r d s the g r a i n b o u n d a r i e s o c c u r at 350 a n d 5 0 0 ~ E f f e c t of T e m p e r i n g on M e c h a n i c a l P r o p e r t i e s of the S t e e l s I n v e s t i g a t e d . T e m p e r i n g r e s u l t s i n r a d i c a l c h a n g e s of a l l m e c h a n i c a l p r o p e r t i e s . In c a r b o n s t e e l , i n the t e m p e r a t u r e r a n g e w h e r e the s i z e of the m o s a i c b l o c k s c h a n g e s c o n s i d e r a b l y , the m e c h a n i c a l p r o p e r t i e s a r e s t r o n g l y a f f e c t e d [15]. F i g . 5 s h o w s the c h a n g e s i n m e c h a n i c a l p r o p e r t i e s of the i n v e s t i g a t e d a l l o y s d u r i n g t e m p e r i n g . It is s e e n t h a t at 350~ and e s p e c i a l l y at 5 0 0 ~ l o n g t e m p e r i n g p e r i o d s c a u s e the h a r d n e s s a n d the t e n s i l e s t r e n g t h to r e m a i n c o n s t a n t o r e v e n to i n c r e a s e s o m e w h a t , H e a t 2 a t 500 ~ C b e i n g a n e x c e p t i o n . T h i s is a s s o c i a t e d w i t h d e c o m p o s i t i o n of r e t a i n e d a u s t e n i t e a n d p o s s i b l y w i t h precipitation hardening. T h e t i m e of t e m p e r i n g at 350 and 500 ~ C did n o t s i g n i f i c a n t l y a f f e c t the i m p a c t t o u g h n e s s of H e a t s 1 and 4. T e m p e r i n g of H e a t 2 at 350 and 5 0 0 ~ and of H e a t 3 ( t e m p e r i n g at 500~ f o r o v e r 300 h o u r s r e s u l t e d i n a s i g n i f i c a n t l o s s of t o u g h n e s s . T h i s i s c o n n e c t e d w i t h the v i g o r o u s m i g r a t i o n of c a r b o n t o w a r d the p e r i p h e r a l z o n e s of g r a i n s [1Z]. T h e m e c h a n i c a l p r o p e r t i e s a r e s t r o n g l y a f f e c t e d b y t e m p e r i n g a t 650 ~ C. H e n c e , the me c h a n i c a l p r o p e r t i e s of o u r g r o u p of a l l o y s w e r e d e c i s i v e l y a f f e c t e d b y (1) p r o c e s s e s of n u c l e a t i o n a n d p r e c i p i t a t i o n of c a r b i d e s , (Z) c h a n g e of c a r b o n c o n c e n t r a t i o n i n the a - p h a s e , (3) d e g r e e of c a r b o n c o n c e n t r a t i o n i n the g r a i n b o u n d a r i e s , a n d (4) the d e g r e e of d e c o m p o s i t i o n of the r e t a i n e d a u s t e n i t e . T h e e f f e c t of o t h e r f a c t o r s i n c l u d i n g t h e f i n e s t r u c t u r e (this t e r m r e f e r s o n l y to the m o s a i c b l o c k s - the r e g i o n s of c o h e r e n t s c a t t e r ing of X - r a y s ) had a p p a r e n t l y n o e f f e c t o n the m e c h a n i c a l p r o p e r t i e s of the t e m p e r e d s t e e l s . In t h i s s t u d y no d e f i n i t e e f f e c t of t e m p e r i n g o n t h e s i z e of the m o s a i c b l o c k s c o u l d be e s t a b l i s h e d . T h e s u p e r s a t u r a t e d a - p h a s e of p a r t i a l l y t e m p e r e d c a r b o n s t e e l r e p r e s e n t e d a m i x t u r e of m o s a i c b l o c k s of s i z e s 1 0 - 5 - 1 0 - 6 c m . A n i n c r e a s e of the t e m p e r i n g t e m p e r a t u r e to 300 ~ C c a u s e d l i t t l e c h a n g e w h e r e a s a b o v e 300 ~ C the b l o c k s g r e w and r e a c h e d t h e i r m a x i m u m s i z e s a t 3 5 0 ~ the h e a t i n g t i m e b e i n g one h o u r i n e a c h c a s e . S t i l l h i g h e r t e m p e r a t u r e s c a u s e d t h e s e b l o c k s to b r e a k up b u t t h e y a g a i n g r e w f r o m 4 5 0 ~ o n w a r d s [16, 17]. C a r b i d e p r e c i p i t a t i o n r e f i n e d t h e m o s a i c s t r u c t u r e of the a - p h a s e . It a p p e a r s , t h e r e f o r e , t h a t t h e g r o w t h of the m o s a i c b l o c k s b e c a m e p o s s i b l e o n l y a f t e r a n e q u i l i b r i u m b e t w e e n c o m p e t i n g p r e c i p i t a t i o n and s o l u t i o n of c a r b i d e s w a s e s t a b l i s h e d . Such e q u i l i b r i u m c a n o c c u r o n l y a f t e r a t r a n s f o r m a t i o n , d u r i n g t e m p e r i n g , of t h e s u p e r s a t u r a t e d a - p h a s e i n t o e q u i l i b r i u m f e r t i l e and c a r b i d e s . C o n c e i v a b l y , had the t e m p e r i n g t i m e i n r e f e r e n c e s [16, 17] b e e n n o t one h o u r b u t l o n g e r , t h e i n d i c a t e d t e m p e r a t u r e s c o r r e s p o n d i n g to t h e g r o w t h o r r e f i n e m e n t of t h e b l o c k s w o u l d h a v e b e e n l o w e r . W h i l e i n c a r b o n s t e e l s a n e q u i l i b r i u m b e t w e e n the p r o c e s s e s of p r e c i p i t a t i o n and dissolution of carbides could be reached below 450 ~ in alloy steels the a-phase remained supersaturated w~th carbon to very high temperatures. For this reason the equilibrium between the two processes occurred

here at higher tempering temperatures and in m a n y cases (for instance in steels alloyed with large amounts of m o l y b d e n u m , tungsten, and especially vanadium) it could not be reached inside the practically employed tempering range. Hence, in s o m e alloy steels the m o s a i c blocks did not g r o w at all during tempering while in others such growth began at higher temperatures than in carbon steel.

gmlcm

IT,
2

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kglm

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LU,
?

ELU,

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Tempering Time, hrs

/0

/OO 3OO#OOlOOO

a)

Tempering

Time, hrs

c)
kgm/cm /8 15 I# 12 6 2
#

fT~ 2

DPN 7 ~
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Tempering Time, hrs

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z Io /ogmOmu I#~o Tempering Time, hrs

b)

d)

Fig. 5. Effect of tempering temperature and time on mechanical properties of Heats I (a), 2 (b), 3 (c), and 4 (d). T e m p e r e d at 350~ (broken lines), 5 0 0 ~ (dash-dot) and 600~ (s01id lines). H V [DPN] hardness; TS (O~b) tensile strength; IT (ak) impact toughness; R A (~) reduction of area; E I U (~/p) uniform elongation. [See also page 12 for list of symbols.] A determination of m o s a i c block size during tempering of three of the steels listed in Table 3 shows that upon holding for one hour the growth of a-phase blocks of steel 5 K h V S began above 650~ w h e r e a s in the two other steels the block size did not change at all between 500 and 700~ (at 400-500~ s o m e decrease of block size w a s observed) [18, 19].

No i n c r e a s e of a b l o c k s i z e w a s o b s e r v e d i n the v a n a d i u m steel which remained strongly superComposition, Steel saturated at the t e m p e r a t u r e s in I C i Cr W V question [I0] and, consequently, an 5KhV$ 0.48 1.35 2.70 0.15 equilibrium b e t w e e n the p r o c e s s e s of El 160 0.41 8.23 2 . 2 5 0.15 separation and dissolution of carbides Vanadium 0,82 --- 1,07 w a s not attained. Hence, in alloy steels in which, under the given t e m p e r i n g cond i t i o n s , the a - p h a s e r e m a i n e d s u p e r s a t u r a t e d w i t h c a r b o n , the c h a n g e in m e c h a n i c a l p r o p e r t i e s d u r i n g t e m p e r i n g w a s c o n t r o l l e d n o t b y c h a n g e s of t h e f i n e s t r u c t u r e b u t p r i m a r i l y b y a d e c r e a s e of c a r b o n and a l l o y e l e m e n t c o n c e n t r a t i o n i n the a - p h a s e ; a l s o , b y n u c l e a t i o n , s e p a r a t i o n a n d c o a l e s c e n c e of c a r b i d e s , a r e d i s t r i b u t i o n of c a r b o n w i t h i n the f o r m e r . a u s t e n i t e g r a i n s and the e f f e c t of r e t a i n e d a u s t e n i t e d e c o m p o s i t i o n . T h e e f f e c t of t e m p e r i n g on i m p a c t t o u g h n e s s a n d t r a n s i t i o n t e m p e r a t u r e i s s h o w n i n F i g . 6. It is s e e n t h a t S t e e l 1 w a s n o t d a m a g e d b y t e m p e r b r i t t l e n e s s w h i l e H e a t s 2 - 4 s u f f e r e d s t r o n g l y . T h e s e d a t a s u p p o r t the c o n c l u s i o n s i n [1Z] o n the n a t u r e of t e m p e r e m b r i t t l e m e n t . T h e m a i n a r g u m e n t a g a i n s t the i d e n t i t y of t e m p e r b r i t t l e n e s s and ' t h e r m a l e m b r i t t l e m e n t ' is the a s s u m p t i o n t h a t w h i l e the e m b r i t t l e m e n t of s t e e l a f t e r a r e l a t i v e l y s h o r t t i m e i n the 6 0 0 - 4 0 0 ~ r a n g e c a n be r e m o v e d b y s u b s e q u e n t h e a t i n g to 6 5 0 ~ o r a b o v e , the e m b r i t t l e m e n t c a u s e d b y a long s t a y i n the s a m e t e m p e r a t u r e i n t e r v a l is n o t r e m o v e d b y a f o l l o w i n g h e a t i n g to h i g h e r t e m p e r ature s.
Table

3.

17
8

Heatl
''~3

20

Heat

2 z/

"~ _ ~ [ /.~

4,6
~u
"8 =
cr
E

I ,,.?
-r
'

,,'

Heat 3

A w ~ , .o< "'1
~--i< 2

F i g . 6. I m p a c t b e n d t e s t r e s u l t s of H e a t s 1-4 ( T a b l e 2): 1)Heated 1050~ rain.+ Q +T650~ hours + Q. 2) as (I) + T 5 0 0 ~ hrs., Q; 3) as (i) + T 5 0 0 ~ hrs., Q; 4) as (3) + T 6 5 0 ~ hrs., Q. Note: T = t e m p e r e d ; Q = q u e n c h e d (in water)

Heat

0"" Y ~ "
I00 O 100 200

Test Temperature, C

S u c h a s s u m p t i o n is c o n t r o v e r t e d b y t h e r e s u l t s i n F i g . 6. It is s e e n t h a t ' t h e r m a l l y e m b r t t t l e d t s t e e l (the t h i r d h e a t t r e a t m e n t ) r e g a i n e d i t s t o u g h n e s s a f t e r t e m p e r i n g at 650~ ( f o u r t h h e a t t r e a t m e n t ) . H e n c e , t h e r m a l e m b r i t t l e m e n t w a s e l i m i n a t e d b y s u b s e q u e n t h i g h t e m p e r i n g and f a s t c o o l i n g j u s t as t e m p e r b r i t t l e n e s s i s . T h i s s h o w s t h a t b o t h t y p e s of e m b r i t t l e m e n t h a v e the same origin. CONC LUSIONS 1. A l l o y i n g of s t e e l w i t h n o n - c a r b i d e f o r m i n g e l e m e n t s ( s i l i c o n , a l u m i n u m , etc.) which d i sp l ace c a r b o n f r o m the zones in which they a r e abundant, 10

increases the temperature of decomposition of martensite during tempering. T h e s e e l e m e n t s c a u s e , d u r i n g t e m p e r i n g , a v i g o r o u s r e d i s t r i b u t i o n of c a r b o n d i s p l a c i n g it t o w a r d s the g r a i n b o u n d a r i e s t h e r e b y i n c r e a s i n g the s u s c e p t i b i l i t y to t e m p e r ( t h e r m a l ) e m b r i t t l e m e n t . 2. I n s t e e l s a l l o y e d w i t h c a r b i d e - f o r m i n g e l e m e n t s , n u c l e a t i o n and p r e c i p i t a t i o n of c e m e n t i t e - t y p e c a r b i d e s c a n b e g i n a t the s a m e t e m p e r a t u r e s as i n c a r b o n s t e e l . H o w e v e r , a t t h e s e t e m p e r a t u r e s o n l y the p a r t of the c a r b o n c o n t a i n e d i n t h e m a r t e n s i t e w h i c h is l e a s t f i r m l y held b y c a r b i d e - f o r m i n g e l e m e n t s is a b l e to p a r t i c i p a t e i n the c a r b i d e - f o r m i n g p r o c e s s e s . The m o r e c a r b i d e f o r m i n g e l e m e n t s a r e p r e s e n t i n t h e a l l o y , the l a r g e r w i l l be the p o r t i o n of c a r b o n to p r e c i p i t a t e i n the s e c o n d s t a g e of t e m p e r i n g , i . e . , as s p e c i a l c a r b i d e s . 3. In s t e e l s a l l o y e d w i t h c a r b i d e - f o r m i n g e l e m e n t s , the a - p h a s e r e m a i n s s u p e r s a t u r a t e d w i t h c a r b o n e v e n a f t e r p r o l o n g e d high t e m p e r i n g . Such c o m p o s i t i o n s u s u a l l y c o n t a i n a n a - p h a s e s u p e r s a t u r a t e d w i t h c a r b o n i n s t e a d of e q u i l i brium ferrite. 4. At t e m p e r i n g t e m p e r a t u r e s at w h i c h a s e p a r a t i o n and c o a l e s c e n c e of c a r b i d e s is p o s s i b l e , s u c h p r o c e s s e s a r e p a r a l l e l e d b y d i s s o l u t i o n of c a r b i d e s . C e m e n t i t e - t y p e c a r b i d e s and p a r t i c l e s of s p e c i a l c a r b i d e s w i t h a m a x i m u m s u r f a c e - t o - v o l u m e r a t i o , p a s s into s o l u t i o n f i r s t . 5. T h e c h a n g e s of m e c h a n i c a l p r o p e r t i e s of q u e n c h e d a l l o y s t e e l s d u r i n g t e m p e r i n g a r e b a s i c a l l y c o n t r o l l e d b y the c h a n g i n g c o m p o s i t i o n of the a - p h a s e , b y r e d i s t r i b u t i o n of c a r b o n and c a r b i d e f o r m a t i o n , and a l s o b y the t r a n s f o r m a t i o n of r e t a i n e d a u s t e n i t e . B e y o n d the t e m p e r a t u r e of i n c i p i e n t c a r b i d e s e p a r a t i o n , the f i n e s t r u c t u r e c a n p l a y a n o t i c e a b l e r ~ l e i n c h a n g i n g the m e c h a n i c a l p r o p e r t i e s o n l y w h e n the t e m p e r i n g c o n d i t i o n s c a u s e the s u p e r s a t u r a t e d a - p h a s e to t r a n s f o r m into e q u i l i b r i u m f e r r i t e . In t h i s r e s p e c t a l l o y s t e e l s d i f f e r s t r o n g l y f r o m a n a l o g o u s c o m p o s i t i o n s w i t h v e r y low c a r b o n . 6. A d d i t i o n a l p r o o f has b e e n o b t a i n e d t h a t the t h e o r y of t e m p e r e m b r i t t l e m e n t a d v a n c e d i n [12] is c o r r e c t and a l s o t h a t t e m p e r b r i t t l e n e s s and ' t h e r m a l b r i t t l e n e s s ' r e p r e s e n t the s a m e p h e n o m e n o n . REFERENCES I. G. V. K u r d y u m o v , Zhurn. Tekhn. Fiziki, vol. 24, 1954, (7), 1254-64.

Z. L. S. Moroz, Fine Structure and Strength of Steel (Tonkaya Struktura i Prochn. Stall), [Book] Metallurgizdat Press, 1957. 3. S. T. Kishkin, Izvestiya Akad. N a u k SSSR. O T N . 1946 (12), 1799-1808.

4. M. P. Arbuzov, L. I. L y s a k and E. G. Nesterenko, Doklady Akad. Nauk. SSS___ R, vol. 90, 1953, (3), 375-7. 5. G. V. K u r d y u m o v , Z___hurn. Fiz{cheskol Khimil, vol. 4, 1930, (i).
6. V. A. Ivensen and Go V. K u r d y u m o v ,

Zhurn. Fizicheskoi Khimii, vol. 4,

1930, (i). 7. G. V. K u r d y u m o v 1891- 1909. 8. G. V. K u r d y u m o v and N. L. Oslon, Zhurn. Tekhn. Fiziki, vol. 9, 1939,

and L. I. Lysak, Zhurn. Tekhn. Fiziki, vol. 16, 1946. (Voprosy

9. G. V. K u r d y u m o v , P r o b l e m s of Metal Physics and Metallography, Fiziki Met. i Metallov.) Akad. N a u k Ukr. SSR Press, 1950, No. 2.
11

I0. A. S. Zav'yalov and E. F. Palei, Metallovedenie [Metal, Science], Collection of Papers, Sudpromgiz Press, 1957. ii. A. S. Zav'yalov, T h e o r y on Alloying and Heat Treatment of Steel, (K Teorii Legirovaniya i T e r m . Obrab. Stall) T s N I I K T P Press, 1943. 12. A. S. Z a v ' y a l o v , L . Ya. G o l ' d s h t e i n and M. I. S e n c h e n k o , C o l l e c t i o n of P a p e r s , S u d p r o m g i z P r e s s , 1957. Metallovedenie,

13. A. S. Zav'yalov and B. I. Bruk, Metallovedenie, Collection of Papers, Sudpromgiz, 1957. 14. A. S. Zav'yalov, Phase Transformations in Iron-CarbonAlloys, Prevrashch. v Zhel.-Ugler, SpI.) Sudpromgiz Press, 1948. 15. K. F. Starodubov, D o k l a d y Akad. N a u k SSSR, vol. 3, 1946, (3). (Fazov.

16. L. I. Lysak, P r o b l e m s of Metal Physics and Metal Science, (Voprosy Fiziki Met. i Metallov.)Akad. N a u k Ukr. SSR Press, 1952, No. 3, 17. G. V. K u r d y u m o v 993-1002. and L. I. Lysak, Zhurn. Tekhn. Fiz., vol. 17, 1947,

18. L. I. Lysak and L. G. Khandros, P r o b l e m s of Metal Physics and Metal Science (VoprosyFizikiMet. i Metallov.) Akad. N a u k Ukr. SSR Press, 1953, No. 4. 19. L. I. Lysak and E. G. Nesterenko, P r o b l e m s of Metal Physics and Metal Science (Voprosy Fiziki Met. i Metallov.) Akad. N a u k Ukr. SSI~, 1953, No. 4.

MECHANICAL 0B o" S

PROPERTIES,

Some

Common

Russian Symbols:

= tensile strength, k g / s q r a m . = yield stress (strength); proof stress in a general way. ~Y0.01'~.1" O~0.2'etc. = proof stress at 0.01, 0. i, 0. 2%, ete. offset, O~p = proportional limit, k g / s q ram. 5 elongation, % 610 = elongation in i0 diams., %. = reduction of area, % .

H B = Brinell hardness, B H N . R C = R o c k w e l l C hardness, HV Vickers hardness, DPN, S k = true fracture strength (in tension). a k = i m p a c t toughness, k g m / sq era,

12