TRANSLATION AND EVALUATION OF SOVIET PAPER ON EFFECT OF SIMULTANEOUS ADDITIONS OF VARIOUS METALS ON CRYSTALLIZATION OF STEEL

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• Publication Date: November 25, 1953
• Content Type: REPORT

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DEC 1991
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CENTRAL INTELLIGENCE AGENCY
INFORMATION REPORT
COUNTRY
SUBJECT
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Translation and Evaluation of Soviet Paper on
Effect of Simultaneous Additions of Various
Metals on Crystallization of Steel
U M C N 0 PUN-WOW-01014 TTNO TN[ RAY IONAI b[/IN NI
Or TAO YNIT[0 ITATI/. .ITNIM TMI M[ANIIIO1 O7 TITLI II. /ICTIONI 711
ANY 7t I, 0, TM[ Y.I. COD[. AS AM[NO0D. I71 THAN/M I.LION ON IIIVI.
I.ATION OF ITI CONTENTI TO OD /IC[I-T BY AN YNAYTMONIN[0 .[A10N 1.
P.O. .uT- .T u.. r....PA00..TInN or TN1. AItAAT. 1A_.RA
J.LJ1SL.
THIS Is UNEVALUATED !INFORMATION
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NO. OF PAGES 7
NO. OF ENCLS.
SUPP. TO;
REPORT NO,
Effect of Titanium and of Simultaneous Additions of Boron,
';anal um. and Ti iuni on the Crys a1 iztxtion o Sec i
by
Niemark, V. E., Peletskaya, I. A. and Entin, R. T.
Stal, Moscow, v. 8, 1948, pp=.248-254.
1. Studies, regretfully rathor few, of the modification of steels by small additions of
alloying elements ina9,cate wide possibilities of influencing primary and secondary
crystallization of a wide range of alloys (steels).
2. The work previously done (Ref a. 1 arid' 2) permitted to bring to light the influence of
boron and vanadium on crystallization and kinetics of isothermal heat treatments in
steel; the most effective were small concentrations of boron (up to .06%) and vanadium
(up to .2%). The next step in the work was the present investigation ofthe influence
of small additions of titanium and additions, simultaneously, of boron, vanadium and
titanium on the mode of primary crystallization of steel and on the kinetics d the
isothermal transformation in austenite.
The addition of small amounts of titanium is used in industry primarily to reduce the
dangers of overheating, To improve deoxidation and degasification of steel, to obtain
a dense and fine primary structure of the ingots, and to some degree to improve mechani-
cal properties.
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4. Investigation of the effects of small additions of titanium on the properties of steels
was done by other investigators. Insofar as the hardenability of the investigated
steels is concerned, the results were somewhat _,ontraaictory. This apparently can be
explained by the different. effects that titanium has when it is in solid solution or
when it '!e present as carbide or nitride.
Effect of Small Additions of Titanium on the
Structure ofu_iat Steel
The steel was made.. in a 30 kg. capacity high frequency furnace. The raw materials con-
sisted of low carbon steel containing .1% carbon, .38% manganese, .03% phosphorus, .03%
sulfur,.1%o copper, .06% nickel, and cant iron containing approximately 4% carbon, .15%
manganese and .06% silicon. The heats were deoxidized with Ferro manganese and ferro sili-
con. Just before. tapping and for complete deoxidation .02% aluminum was added to the
furnace.
6. When steel -was to be made with additions of titanium, at first the heat was made without
any additions th
T
y
8 fi
a za w a rather pronounced
rMai4l cry3tallization very much like in steel without any addition. When the concon-
tration of titanium is increased to .038%, the radial characteristics of the fracture
are somewhat loss and. with .045% titanium they disappeared, but the grain structure was
not much smaller. It is only when titanium, in increased to .1-.3% that th*adial type
of crystallization is completely gone and the fracture shows a very fine grain.
um, according to chemical analysis, varied from .08 to as high
as .31%. The ingots were forged between 3.000-1100?C into a rod of about 18 mm. in dia-
motor which were than annealed. The method of studying the austenitic grain-of primary
Crystallization and the method of.metallographic analysis have been described before
(Ref. 2).
Small additions of titanium, up to .03%, have little effect on the character of the
fraet>re of the ingot. one fracture remains. lc
x a Mn ii -f 4.1.
x'
, en some
erre titanium was added to the furnace trying to get s' steel
with approximately 01% titanium. Then the next ingot was cast with increased titanium,
etc. In such a,wanner from one original heat were cast from 6 to 9 ingots with different
concentrations of titanium. Two kinds of steel were prepared. One containing .45-.55%
carbon and the other with .8-1.0% carbon.
The silicon was about .30-.4096, manganese from .50-.88g , titanium from .01-.30%, accord-
ing to caloulatlone, and from .003 to a maximum of .058% according to analysis. In
i stool of lower carbon content, i.e. 0.45-0.55%, silicon was about the same, manganese
about the same but tit i
Samples were taken from the above ingots for metallographic investigation and after
proper preparation etched with persulfate of ammonia. The etched-out microstructures
were not in agreement with the observed fractures.
Next, metallQgicaphic.,satnpleq were etched-with-the reagent of '0berhofer. Small concentra-
tions of titanium, up to .03%, have no influence on the?dendritia.structure, With.
additions of .04%, titanium dendrites become quite thin and a different structure makes
its appearance in the form of "ghost -like"grains. With .1% titanium the elongated
dendrites disappeared.
The same samples were used to study the austenitic grain size Of the primary crystalli-
zation and separation of ferrite during cooling. Additions of titanium obviously have
a significant influence on the size of the austenitic grains of primary crystallization.
In castings of 45 mm. diameter, containing .10% titanium, instead of long, large grains
extending from the periphery to the center (usually found in.steels without titanium)
the grains appeared to be equiaxed and much smaller.
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12. the concentration of titanium is increased, grains about the same size as in steel
without titanium are found in the periphery of the casting. In the central part of
the casting a considerable separation of ferrite is noted which somewhat interferes
with the determination of the grain boundaries.
13? With additions from .018 to .04% titanium, the grain size is much smaller than in
steel without titanium; increasing the titanium content to .08%, the gain size becomes
even smaller.
14. The effect of additions of titanium on separation of ferrite during cooling 1is also
quite pronounced. Even with .01% titanium, the amount of ferrite in the casting is con-
siderably increased in comparison with the steel without titanium. At the some time,
and in addition to the small grains of ferrite in steel with titanium, one also Finds
rather large areas of ferrite. As the concentration of titanium is increased; (.038 to
.046) large segregationo of ferrite are visible throughout the whole field. With a
titanium content of .087%, the amount of grains of ferrite is greatly increased and
they are equally distributed throughout the cross section.
Influx e nac of Small Additions of Titanium on Kinetics of the
15? Investigations were carried out on outectold and medium carbon steels at temppiraturea.
of 360, 450, 560 and 620?C. In the first heat, series h, we had stools with poneentrateo
of titanium no more than .06%. The second heat, series V (riussian "V") contained up to
.22% titanium, and the third hoot, aeries 0, the titanium contained was from .04 up to
.?31%. The kinetics of the isothermal transformation of austenit? were followed by mothodo
of measurinS hardness and studying the microstructuro. The ?amploo were heated in malt
bath at 92&0 and held at temperature for throe minutes. Thus envy were rapidly trans-
ferred to a load bath, were hold for di22eront times, and quenched in water. lTho U=
of holding in the lead bath was changed depending upon the rapidity of the transformation
of auatenite at a given tgmperaturu. Samples from different series were heat treated'at
the same time followed by microstructure study and hardness determination in IIookwell C
using a 150 kg. load. During holding in the lead bath, austenite changes, upon cooling
in water, into marteneite. In such a manner the microstructure and the changeis in the
hardness of the steel indicate the rate of isothermal transformation of auatenite. Study
of the curves showing the dependence of hardness of steel B upon concentrations of
titanium at different temperatures of isothermal decomposition (Fig. 6) show that titanium
.in amounts of .003-.006 somewhat lowers the stability of auatenite. As the titanium
concentration reaches .02-.06%, the stability of austenite is considerably increased in
comparison with the same steel without titanium. At all temperatures of trans ormation,
the most noticeable effect takes place with .05-.066 titanium. The studies of the micro
structure fully support the results which were observed by measuring the hardness (Fig.7).
16. In Fig. 8 is shown the dependence of hardness of steel of Series V upon amounts of
titanium. Additions of .04% titanium results in increased stability of ._u3tenite which
reaches a maximum in steel with .1% titanium. However, further increase in addition
of titanium, up to .17-.22%, results in a considerable lowering of the stability of
austenite. Apparently in the above concentrations titanium combines partly with the
carbon and restricts the growth of secondary austenitic grains. Curves showing the
-relation between hardness of steel or series G end suuounts of titanium at different tem-
peratures of isothermal transformation (Fig. 9) permit the conclusion that in Steels with
medium carbon content additions of .07-.]. titanium result in a noticeable increase in.
the stability of auatenite. Increasing the titanium content to .16-.21% speeds up de-
composition of auatenite. In order to study the influence of the temperature of reheat-
ing for hardening on kinetics of isothermal transformation of austenite in steels with
small additions of titanium, measurements were made with the temperature of reheating
(begone lead. bath) :t 920-1020?C, and with isothermal transformation at' 450-
620 C (Figs. .L .:,.4 I 1,. :,fter isothermal transformation at 4500C and quenching from
920?C, the maximum stability of austenite was observed in steel with .095% titanium;
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in s tc?ci.s with .16-.21% titan:i.
i. .. ride). :Uly lover. How-
ever, with the hardening terl......1..::?? .~ .i.l; ?;'; ?
transformation, steel with .16;; ti ~c:;,:Lwr. does not ciwe loworint! of`tihexstabilityiofthermal
euw tenite . Analogous results were ri:ce:i.ved after isothermal tran::for1 mat._on at 6200C. In
fact, a steel with .16;; titanium uh,. ecd :tvuic:rlu t t;rer.tex otabil L Ly of austenite.
17. Al. jarently as the ten;,)eraturc (,i? rluuuelli:lt, i.c ; xVQUi Cl' a ion:rtc cf tlta:nium
go into solid solution. On the basis of a. ;lumber of obcervatio;lo it I.c possible to ex-
plain the increase in the stab:Li;?ty of austen.!.tc by Liu: inflllellC0 of that part of the goes steeliin -thecforrm oofintolssolveu.otoopounds acts~ltorurd lowering the dtability remains
of sauin the
stenite.
18. The above described data su(,i;esti; the advisability of nddl.:1L to ut.ul. between
titanium in order to improve the structure of primary Cryctatll:ization and achieve treater
stability of austenite.
Combined Influence of Small Additions of Boron,
Vanadium an T tan um
19? Small additions of boron, vanadium and titanium considerably improved the hardenability
of steel in comparison with the same amounts of such elements as chromium or manganese.
20. The maximum or "absolute" effect of such additions is limited by their very small (optimum)
ccncentrations, namely, for boron .003~, for vanadium 05 el
A.dding to steel amounts in excess of the just mentioned optimum dand for oes notifurther.i9 .o
hardenenability, but in fact is definitely detrimental. During the studies of therve
influence of small additions, such as above, on kinetics of isothermal transformation of
austenite, it was established that additions of boron, vanadium and titanium are different
at different temperatures. For this reason it was thought advisable to study the in-
fluence of small additions of boron, vanadium and titanium on the structure of primary
crystallization, on the kinetics of Isothermal transformation of austenite, and harden-
ability. The steels for these series of experiments were made from the same raw materials
as the above described steel with additions of titanium. After the first heat without
any additions, some ferro boron was added and the second ingot made. Just before casting
of the third heat, some Ferro vanadium was added, while the concentration of boron was
held the same. Finally, just before the fourth heat was made, titanium was added, main-
taining boron and vanadium in the same amounts as before. The experimental results show
that simultaneous additions of boron and vanadium do not further increase their effect
of refining grain size of primary crystallization, when such effect is compared with that
of the mentioned elements added, separately (Y); the separation of ferrite with simultane-
ous addition of .06% vanadium and .003% boron appears to be intensified.
The influence of simultaneous additions of boron, varAa_um and titanium on the properties
of the steel were Investigated by methods of measuring, nardnens, study of the microstruc-
ture and magnetic properties.
- -- -v ell oI .uuj~6 and vanadium of .05-.06+'(,j were first studied and then
it was found that addition to the above of .1% titanium proved to be ineffective. In
Figure 13-A is shown the relation between hardness of steel J and various additions when
isothermal decomposition of austenite was done at 450?C. In Fig. 14 the magnetic studies
are shown after the some treatment. Addition of .003% boron considerably reduces the
rate or decomposition at 450?C. After further additions of less than .056% vanadium are
made, quite opposite results were u~lexpectedly observed, that is to say, the rate of de-
composition has been increased; finally, still further addition of .035; titanium again
considerab], lowered the rate of transformation. When decomposition of austenite is
done at 570 C its stability is gradually increased from steel J-1 to st.iel J-4 (Fig.
13-B). Thus, it is observed that auddition, one by one, to carbon steel of small amounts
of boron (.003%), of vanadium (. 05 - ? 0(,~,) and titanium (.03-.04) has proved to be a very
effective method to improve the stability of austenite at different temperatures of
Isothermal decomposition.
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23. Additions of the above elements in certain combinations also materially increase the
hardenability of the steel (Figs. 16 and 17).
24. CONCLUSIONS :
a. Additions to carbon steel of small amounts of titanium, about .03-.0495 and up to
.196, changes the structure of primary crystallization,of the steel, namely, elimina-
tion of strung out crystallization and causes refinement of the austenitic grains
of primary crystallization. Somewhat greater additions of titanium, up to .3%,
act in the same direction but with less effectiveness.
(1)
Additions of titanium within limits of .02-.1% considerably improve the
stability of austenite at various temperatures of decomposition. Greater,,
amounts of titanium result in rapid lowering of the stability of the
austenite.
(2) Maximum hardenability of the steel is achieved by adding .09-.1% titanium.
In the manner above described, verysnall additions of titanium improve the
structure of the cast ingot and Improve hardenability of the carbon steels.
b. Simultaneous additions to carbon steels of small amounts of boron (.003%), vanadium
(.05-.o6%) cad titanium (.03-.0496) result in :'.mprovement of the structure resulting
from primary crystallization of the ingot and in considerable improvement in the
stability of the auetenite and in its hardenability. The addition of the above
mentioned combination of three elements increases approximately two times the
hardenability that is observed with addition of .003% boron, only.
CODOE TS AND EVALUATION
1. A reasonably good paper for 1948 but not very comprehensive.
a. The effect of titanium additions up to 0.4% on?a eutectoid-carbon steel and up to
0.596 on a medium-carbon steel was studied in respect to structure, grain size,
isothermal transformation and hardenability. Small additions of tttanium refined
the structure and increased hardenability. Maximum effectiveness was found in
the range up to about 0.1% Ti in the steel.
b. Four small ingot of a medium-carbon steel were studied to determine the effect on
structure, isothermal transformation and hardenability of small additions of boron
alone, boron plus vanadiumt, and boron plus vanadium plus titanium. The combination
of the three elements gave about twice the hardenability that was obtained with
boron alone.
'.? The results obtained with small titanium additions are more or less in line with investi-
gations eleehwere. As pointed out in the introduction, the effect of titanium on
hardenability varies considerably as a function of the amount of titanium in solid
solution and the amount, present as undissolved particles (mainly carbides and nitrides).
Neymark, Piletakaya and Entin have done nothing to evaluate the actual effect of titanium
as an alloying element since they have not determined the nitrogen content of the steels
or the form in which the titanium was present. Moreover, the end-quench hardenability
curves do not include a titanium-free steel for comparison so there is no way of calculat-
ing the quantitative increase in hardenability resulting from thr titanium. The results,
however, appear to be more similar to those of Crafts and Lamont than to those of other
US investigators and to Grossman's proposed curves based on all these US results.
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G. F. Comstock, S. F. Urban and M. Cohen: Titanium in Steel, Pitman
Publishing Corp. (1949)
W. Crafts and J. L. Lamont: Effect of Some Elements on Hardenability.
TAIME 158 (1944) pp. 1571167,; disc. 1487156.
M. A. Grossmann: Elements of Hardenability. ASM (1952)
3. Boron additions in the US have, been made either with ferroboron or with
f
th
one
o
e
"complex" alloys. In addition to boron, titanium in amounts from about 10 to 20% is
present in all the complex alloys except two (Borosil and Bortam), and these two are
sometimes considered as more in a class with ferroboron than-with the other complex
alloys. TWO of the complex alloys also contain vanadium (GrainaT No. 1 and No. 6);
Electro-metallurgical Corp's Silvaz, which likewise contained titanium and vanadium,
has apparently been discontinued. The complex alloys have usually bean.-,preferroid~ ?for
boron additions to low-carbon Steels (under about 0.3% C) and for electric-furnace
steels. Almost since the time when the effectiveness of boron in increasing harden-
ability was discovered, there has been much discussion and rlany papers on the relative
virtues of the various. types of addition agents. Perhaps this controversy can be
summed up comewnat as follows:' ?
a. In medium-carbon steels, such as the one tested in the present investigation,
little difference has been,found among the various types of non-vanadium contain-
ing boron-addition agents in commercial heats prolided a satisfactory preliminary
deoxidation treatment was used. One of the'many references that might be cited in.
R. A. Grange, W. B. Scene, W. S. Holt and T. M. Garvey: Effect of Boron and
Kind of Boron Addition Upon the Properties of Steel. TAS-MTM950pp.
77b. When vanadium-oontaining addition agento are 'used, the over-all increase in harden
ability 4.s greater because of the contribution of the vanadium.
a. An influencing factor in determining the offootiveness of boron is the nitrogen
content of the steel. 'Whonjthe nitrogen exceeds the small amount normally found
in open-hearth steels, it can neutralize the boron. Digger and Reinhart, for
exam].e, found that nitrogen interfered with the boron hardonability effect, or
nullified it altogether, iflthe nitrogan exceeded about 0.007%. The boron effect
was restored by the addition of titanium (zirconium has a similar affect) to
neutralize the exoias nitrogen. Therefore, the role of titanium in complex boron-
addition agents in usually considered in the U6 to be primarily a denitrogenizing
agent (as well as a deoxidizing agent if preliminary deoxidation was not complete).
T. 0. Digger and F. M. Reinhart: influence of Boron on Some Pr ortieo
o
f erimental'and Commorcia Stao e. RP 1 . J. ooesre B of
a 39--k-L947) Pp.
T. G. Diggee azd F. M. Reinhart: Influence of Nitrogen on the Hardenabillt
and Notch Toughness of Boron-Treated Steels. TASM 40 (1940) pp. 1124/1146.
4. The results obtained by Neymark,',Piletakaya and Entin for boron and vanadium appear reason-
able. On the other hand, the observed effect of titanium is probably the resv.lt of its
denitrogenizing action rather than of its Influence as an alloying element. The fact
that nitrogen contents in small induction heats (as used by them) are generally significantly
higher than would be found in large open-hearth heats, would tend to support this idea.
5. There seem to be some errors in the translation. For example, paragraph number 9 on page
2 of the translation corresponds to the paragraph starting at the bottom of the second
column on page 248 of the paper. The translation reads:
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"Samples were taken from the above ingots for metallographic investigation
and after proper preparation etched with persulfate of ammonia. .The etched
25X1 out microstructures were not in agreement with the obeerved fractures."
translated this paragraph as follows:
From these specimens were prepared metallographic sections, which were
etched with ammonium persulfate, The macrostructure developed agreed
with the fracture characteristics.
The differences between "microstructure" and "macrostructure" and "not in agreement"
and "agreed" would appear significant.
Figures 15 through 17 do not confirm the authors' conclusion that the simultaneous
addition of boron, vanadium and titanium is twice as effective in increasing harden-
ability as the addition of boron alone. A rough calculation of hardenability factors
(with a D1 based on the Rockwell C 50 used in Figure 17, which would, correspond
approximately to 90% martensite in these steels) shows the hardenabiljty factor for
the boron addition-alone to be about 2; for the triple addition, about 2.4. A boron ,-'
herdanability factor of 2 would be about normal for this steel on the basis of Ratnr*r
and Armetron 's relation between boron.herdanability factor and carbon content. The
factor of 2.Z. is somewhat higher than would normally be expected from boron alone,
This may be the result of a normal statistical variation, or of a denitrogenising effect
of the titanium as disouswod in D3 above. The effectiveness of the triple addition,
hotmver,, becomes greater when the hardenability factor is based on a lower hardness
(lower percentage of mwrtensits), but even here it is not twice no groat e./ that of
boron. For sraapte, on the basis of Rockwell a 45, or about SC%, mcwtencite, the
factor would, be 1.8 for boron alone, and about 2.4 for the triple addition. At least
part of this difference can be accounted for by vanadium as discussed in D2-
0- D. Rohrer and C. D. Armstrong: The Dffect of Carbon 0onont on the
Hardenabilityof Boron Steele. TASPI 40 (19M) pp. 1099 s sc.
iii2~'a.z23 ,
615.4 N
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