Metal Science and Heat Treatment

Vol. 49, Nos. 3 4, 2007

UDC 621.762:661.66:669.14018.252.2

CHANGES IN THE PHASE COMPOSITION, STRUCTURE,

AND HARDNESS OF TITANIUM CARBIDE HIGH-CARBON STEEL
CERMETS UNDER HEAT TREATMENT
N. Frage,1 L. M. Kaputkina,2 V. G. Prokoshkina,2 D. E. Kaputkin,2 and N. R. Sverdlova3
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 4, pp. 11 15, April, 2007.

Ceramic metals obtained by pressing and sintering of briquettes from titanium carbide powders with constant
compositions (stoichiometric and with carbon deficit) followed by impregnation with steels U8, U10, and U12
are studied. The effects of the compositions of the metallic binder and of titanium carbide on the processes of
austenization, dissolution, and segregation of carbides, martensitic transformation, and on the hardness of the
cermets after subsequent heat treatment are determined.

As a rule the heat treatment mode is chosen empirically,

which is quite expensive and not always optimum. The
choice of the grade of the steel and of the content of carbon
and alloying elements can be insufficiently well substantiated. For example, in some cases it is more expedient to use
plain steels for heat hardenable composites instead of highspeed ones. At the same time, strong interaction of the components, their composition and structure, and, hence, the
structure and properties of the cermet, may change substantially during fabrication of the composite and its subsequent
treatment, which should be allowed for in the choice of the
heat treatment mode.
The aim of the present work consisted in determining the
laws governing the action of the composition of the TiCx carbide and of the carbon content in the impregnating steel
binder on the structure and hardness of the composite during
fabrication and subsequent heat treatment.

INTRODUCTION
Ceramic metals based on a titanium carbide steel
combination are promising structural materials due to the
possibility of creation of a high-density state characterized
by good cohesion between the metallic binder and the carbide. In addition, the properties of such composites can be
varied widely due to the use of various initial materials and
various regimes of heat treatment of ready parts.
One of the methods for fabricating such cermets is impregnation of pressed and sintered briquettes from titanium
carbide with molten steel.
The microhardness of titanium carbide exceeds those of
other transition metal carbides [1]. Titanium carbide has high
thermodynamic stability in metallic melts, melting temperature, and corrosion resistance, and a low density. It differs
in principle from other carbides in the fact that it has a wide
domain of homogeneity and can form wide domains of
solid solutions with other carbides of metals of groups
IVa VIa [2].
A usual binder in high-hardness titanium carbide composites is steel (high-carbon tool steels including the highspeed kind) [3].
Heat treatment (hardening and tempering) of cermets
with a steel binder can noticeably change the properties of
the binder and thus affect the properties of the cermet, in particular, increase substantially its hardness and strength [4].
1
2
3

METHODS OF STUDY
We studied ceramic metals consisting of TiCx titanium
carbide and steels U8, U10, and U12, i.e., TiC0.98 U8,
TiC0.8 U8, TiC0.98 U10, TiC0.8 U10, TiC0.98 U12, and
TiC0.8 U12. A powder of titanium carbide with stoichiometric composition (TiC0.98 ) or with carbon deficit (TiC0.8 )
was pressed into briquettes at 20C and sintered at 1500C.
Then the briquettes were impregnated at 1450C for 10 min
in 0.013-Pa vacuum with melts of plain high-carbon steels
U8, U10, and U12 that contained 0.8, 1.0, and 1.2 wt.% C,
respectively.

Ben-Gurion University of the Negev, Beer-Sheva, Israel.

Moscow Institute for Steel and Alloys (Engineering University),
Moscow, Russia.
Moscow Plant of Composite Metals, Moscow, Russia.

167
0026-0673/07/0304-0167 2007 Springer Science + Business Media, Inc.

168

We studied cermet specimens in an initial state (after the

impregnation) and after a heat treatment that consisted of
hardening and tempering. In order to obtain a high-temperature state, specimens at the temperature of austenization were
hardened with cooling in water after each heating in 1.3-Pa
vacuum in the following modes:
(1 ) 780C, 30 min;
(2 ) 780C, 30 min + 900C, 30 min;
(3 ) 780C, 30 min + 900C, 30 min + 900C, 60 min;
(4 ) 780C, 30 min + 900C, 30 min + 900C, 60 min +
900C, 90 min;
(5 ) 780C, 30 min + 900C, 30 min + 900C, 60 min +
900C, 90 min + 950C, 60 min;
(6 ) 780C, 30 min + 900C, 30 min + 900C, 60 min +
900C, 90 min + 950C, 60 min + 1100C, 60 min.
Tempering was performed at 100, 150, 200, 300, 400,
500, 600, and 650C for 60 min after water hardening from
1000C (60 min).
We measured the hardness of all specimens and performed metallographic analysis and x-ray study of the phase
composition and of the structure of the crystal lattices of the
phases. Microscopic x-ray spectrum analysis was used to estimate the element composition.
The volume fraction and the sizes of carbide particles
and of the binder were measured with the help of an
OLYMPUS GX51 light microscope. Photographs of microstructure were made by a Hitachi KN-1U CCD camera.
The x-ray phase analysis included determination of the
lattice periods of the phases; for hardened compositions exhibiting split lines {hhl } of martensite we evaluated the corresponding degree of tetragonality and the content of carbon.
The diffraction lines were obtained using a DRON-3 installation in cobalt Ka radiation.
The chemical composition of the cermets was determined using a K-2000 scanning microscope with a Noran

N. Frage et al.

attachment for microscopic x-ray spectrum analysis. We

evaluated the concentration of metallic elements (Fe and Fe)
in the center of a carbide particle or of a steel layer and with
a step Dx 1 mm along a line connecting centers of carbide
particles. The place to be photographed was chosen so that
the distance between the carbide particles was less than 4 mm
and the carbides themselves were at least 10 mm in size. The
diameter of the probe was 0.5 mm and the duration of analysis at one point was 60 sec.
The microhardness was measured using an automatic
LECO LM-700 AT microhardness meter at a load on the indenter P = 2 N. The Vickers hardness was determined with
the help of a TPP-2 hardness meter at P = 50 N.
The sides of each specimen of macrohomogeneous
cermet were marked in the following manner: the side contacting the melted steel plate in the impregnation process and
having a higher hardness and a larger amount of carbide
phase was marked as a top and the opposite side was
marked as a bottom.
RESULTS AND DISCUSSION

In all cases of impregnation the particles of the carbide

were well fused to the steel particles. Titanium carbide particles with spherical and polyhedral shapes had a mean size of
7.3 8.6 mm for the top and 6.8 8.1 mm for the bottom
and were distributed quite uniformly in the steel binder.
Microscopic x-ray spectrum analysis showed that when
the cermet was impregnated with carbon steel, the titanium
dissolved in the metallic binder and the iron alloyed partially
the titanium carbide (see Table 1). Titanium passed into the
binder due to the dissolution of titanium carbide and due to
the interaction between the iron of the binder and the titanium of the carbide.
The concentration of carbon in the
steel affected the kinetics of the processes and the composition of the comTABLE 1. Distribution of Metallic Elements after Impregnation and Water Hardening
ponents of the composite, specifically,
Content of elements, wt.%
the composition of the metallic binder
Cermet
Treatment
Carbide
Binder
after the impregnation. The less the
carbon in the binder and in the carbide,
Ti
Fe
Ti
Fe
the more strongly the titanium disTiC0.98 steel U8
Impregnation
96.2/99.4
3.8/0.6
3.3/2.9
96.7/97.1
solved in the binder. The very occurHardening
96.0/99.2
4.0/0.8
6.5/6.0
93.5/94.0
rence of the impregnation process deTiC0.98 steel U12 Impregnation
96.0/99.3
4.0/0.7
3.0/2.8
97.0/97.2
termined the appearance of gradient in
Hardening
95.7/99.1
4.3/0.9
3.4/3.1
96.6/96.9
the structure and properties of the
Impregnation
TiC0.8 steel U8
99.2/99.0
0.8/1.0
4.6/3.3
95.4/96.7
composites due to the interaction beHardening
96.1/95.8
3.9/4.2
7.6/5.7
92.4/94.3
tween the titanium carbide and the
Impregnation
TiC0.8 steel U12
96.2/98.9
3.8/1.1
/1.8
/98.2
steel.
Hardening
95.9/98.4
4.1/1.6
5.7/4.7
94.3/95.3
The lattice period of titanium carbide in all impregnated composites
Notes. 1. Water hardening was performed after each heating in a mode of 780C, 30 min +
was greater at the bottom (by about
900C, 30 min + 900C, 60 min + 900C, 90 min + 950C, 60 min + 1100C, 60 min.
2. The numerators present data for the top of the cermet; the denominators present data for the 0.00010 0.00015 nm) than at the
bottom of the cermet.
top (Fig. 1). The lattice period of

Changes in the Phase Composition, Structure, and Hardness of Titanium Carbide High-Carbon Steel Cermets
ac , nm

af , nm
0.2881

0.4332

169

1
2
3

0.4330

1
0.2877

0.4328

0.2873

0.4326
0.8

1.0

0.2869

1.2

Cb , %
0.2865

ac , nm
b

0.4328

3
4
5

0.4324

0.4322

1.0

1.2 b , %

HV, kgf/mm2

HV, kgf/mm2

0.8

1.0

Fig. 2. Dependence of the lattice period of ferrite af after impregnation of the cermet on the carbon content in the steel binder Cb: empty
symbols) bottom of the cermet; filled symbols) top of the
cermet; 1, 2 ) cermet with TiC0.8; 3, 4 ) cermet with TiC0.98.

2
0.4326

0.8

1800
1.2

1700

6
5
4

1600

Cb , %
1400

Fig. 1. Dependence of the lattice period ac of TiC0.98 (a) and

TiC0.8 (b) titanium carbides in cermets on the content of carbon Cb
in the steel binder: empty symbols) bottom of the cermet; filled
symbols) top of the cermet; 1, 2 ) after impregnation; 3, 4 ) after
hardening in water from 900C (90 min) (mode 4 ); 5, 6 ) after hardening in water from 1100C (60 min) (mode 6 ).

ferrite was considerably greater at the top. In specimens

with initially nonstoichiometric titanium carbide the difference attained 0.0005 nm (Fig. 2). In composites with TiC0.8
the lattice period of titanium carbide was less and the lattice
period of ferrite was greater than in composites with TiC0.98.
Metallographic and x-ray diffraction studies showed that
the steel binder was represented by a mixture of ferrite and
cementite. The x-ray analysis showed the presence of a small
amount of a Fe2Ti phase in all the specimens.
After impregnation the hardness of the composite with
initially stoichiometric composition of titanium carbide was
higher. It increased with the growth in the carbon content in
the impregnating steel and reached 670 810 HV and
860 965 HV for the specimens with TiC0.8 and TiC0.98, respectively (Fig. 3).
When the specimens were hardened, the interaction between the binder and the carbide gave rise to processes that
changed their composition and, to a certain degree, changed
their quantitative proportion due to the dissolution and segregation of the phases. This was determinable from the
changes in the sizes of the carbide particles after the hardening. Growth of carbide particles was promoted by the in-

b
5

1300

4
1100

1200
1000
800
600

1500

0.8

1.0

900

700

1.2

Cb , %

500

3
2
1

0.8

1.0

1.2

Cb , %

Fig. 3. Dependence of the hardness HV of cements with titanium

carbides TiC0.98 (a) and TiC0.8 (b ) on the carbon content in the steel
binder Cb : empty symbols) bottom of the cermet; filled symbols)
top of the cermet; 1, 2 ) after impregnation; 3, 4 ) after hardening
in water from 900C (90 min) (mode 4 ); 5, 6 ) after hardening in
water from 1100C (60 min) (mode 6 ).

crease in the time of heating for hardening and growth in the

temperature. The sizes of the carbides increased noticeably
after hardening from 900C (60 min) (mode 3 ) and from
900C (90 min) (mode 4 ). The mean size of the carbide particles was the largest after hardening from 1100C (60 min)
(mode 6 ) in all the composites (8.6 9.4 mm for the top
and 7.9 8.7 mm for the bottom of the composite). In any
hardening mode the mean size of the carbides on the side of
the top was larger than on the side of the bottom. A typical feature of participation of TiC in the structural transformations during heat treatment was a decrease in the number
of its small particles that dissolved in the steel upon heating.

170

N. Frage et al.
Ti; Fe, wt.%
100
Ti
80
60

Particle
of titanium
carbide

Binder

Particle
of titanium
carbide

40
20
Fe
0

12

16

20

24

h, mm
Fig. 4. Distribution of titanium and iron in two neighbor particles of
titanium carbide in TiC0.98 steel U8 cermet after hardening in
water from 1100C (60 min) (h is the distance from the center of the
particle).

The heating for hardening was accompanied by redistribution of carbon; the redistribution of titanium and iron between the components of the composite went on, especially
at a high heating temperature. Growth in the temperature and
in the time of heating for hardening caused progressive reduction of the lattice period of titanium carbide, which was
the most noticeable in hardening from 1100C (60 min)
(Fig. 1).
The results of the evaluation of lattice periods of ferrite
from the data of x-ray diffraction and spectrum analyses are
close. At least these methods give qualitatively similar results in a comparison of the effect of the compositions of the
carbide and of the steel, and of the tops and of the bottoms of the specimens. Estimates of diffusion paths of titanium confirm the probability of the observed processes of redistribution of elements between the components of composites during impregnation and heating for hardening. The
width of the transition zones (zones with variable concentration) is about 2.0 3.0 mm (Fig. 4).
In specimens with initially stoichiometric titanium carbide, martensite and austenite appeared after hardening from
780C, whereas in specimens with TiC0.8 they appeared after
hardening from 900C, which was connected with different
degrees of carbon diffusion from the metallic binder into the
titanium carbide. The carbon content in the martensite of the
steel binder after hardening from 780C attained 0.9 1.0%
for all the three variants of composites with stoichiometric
carbide. As the temperature of heating for hardening increased to 1100C, it grew to a value close to or even exceeding the carbon content in the steel.
The lattice period of retained austenite also increased; in
the composites with nonstoichiometric carbide the carbon
content in the martensite after hardening from 900 1100C
amounted to 0.3 0.4%. Homogenization of austenite due to
heating of titanium carbide steel composites requires
much more time than usual due to the transition of titanium
from the carbide into the steel. For this reason we observed

inhomogeneity of the composition of austenite and martensite, which appeared during hardening.
In any state (after impregnation and after hardening) the
composites contained a low amount of a Fe2Ti phase and of a
cementite-type carbide (Fe3C). The amount of this carbide
was noticeably higher in the specimens with initially
stoichiometric titanium carbide and in the TiC0.8 steel
U12 composite.
In the composites with stoichiometric titanium carbide
the hardness increased noticeably already after hardening
from 780C due to the appearance of martensite. In the composites with nonstoichiometric titanium carbide the hardness
after such hardening remained at the level of the state after
impregnation. With time, when the temperature of repeated
hardening treatment was increased, the hardness grew for the
composites of all variants (the growth was higher in the composites with initially stoichiometric carbide).The hardness of
the top side was higher than that of the bottom side in all
the specimens. After hardening from 1100C (60 min) the
hardness of the TiC0.98 steel composites increased to
1565 1710 HV; that of the TiC0.8 steel composites increased to 1120 1565 HV (Fig. 3). The hardness of the
TiC0.8 steel U12 composite hardened in mode 6 attained
the level of hardness of the specimen with stoichiometric titanium carbide after hardening in mode 4. In all the composites the hardness increased with growth in the carbon content
in the steel. The efficiency of hardening of the composites increased with growth in the carbon content in the steel
nonmonotonically upon growth in the hardening temperature, because the interaction between the cermet components
changed the chemical composition of the phases and the
structural states of the carbide and of the binder. Specifically,
hardening of TiC0.98 steel composites was accompanied
by the formation of retained austenite the amount of which
was the higher the more carbon was contained in the steel
and the less titanium was dissolved in latter.
When measuring the microhardness of the binder and of
the carbide particles in impregnated specimens we established the formation of cracks in the carbides. After the hardening, cracks did not appear when we measured the hardness, possibly due to the more stressed state of the surrounding binder. Consequently, the strengthening of the binder
produced a favorable effect on the fracture resistance. The
microhardness of the carbides after the hardening did not
change and amounted to 2870 2900 HV and 2580
2620 HV for composites with TiC0.98 and TiC0.8, respectively. The microhardness of the metallic binder after impregnation was virtually the same for all the specimens
(650 690 HV ); after hardening it differed considerably
(820 1060 HV ), which was connected with the differences
in the structure and in the composition of the components of
the composite. The microhardness of the binder increased
with growth in the carbon content in the martensite formed
due to the hardening.
The results of the evaluation of the effect of the tempering temperature on the hardness of the composites are pre-

Changes in the Phase Composition, Structure, and Hardness of Titanium Carbide High-Carbon Steel Cermets
HV, kgf/mm2

CONCLUSIONS

1600
1400
1200

1
1000

800
0

200

400

600 ttemp , C

400

600 ttemp , C

HV, kgf/mm2
1400

1300
1200

2
1

1100
1000
900

b
800

200

171

Fig. 5. Dependence of the hardness HV of a cermet on the tempering temperature after water hardening from 1100C (60 min):
a) cermet with titanium carbide TiC0.98; b ) cermet with titanium
carbide TiC0.8; 1, 2, 3 ) impregnation with steel U8, U10, and U12,
respectively.

sented in Fig. 5. The hardness of the composites hardened

from 1100C (60 min) began to decrease after tempering at
200C. The most marked change in the level of the hardness
was observed for the TiC0.8 steel U12 composite after
tempering at 300C.
Tempering at 650C did not lower the hardness of the
composites to the initial level (after impregnation); the differences in the hardness of different variants of composites
were preserved too, i.e., the hardness was higher in the cases
of higher content of carbon in the steel and in the titanium
carbide.
As expected, the tempering resistance of hardened titanium carbide carbon steel composites was lower than that
of the hardened TiC steel R6M5 composites described in
[5]. However, the hardness of the hardened TiC0.98 steel
U12 composite after tempering at 650C was about equal to
that of the titanium carbide high-speed steel composite
after impregnation (1080 1100 HV ) [4, 5].

1. The method of fabrication of titanium carbide

steel ceramic metals by impregnation of carbide briquettes
with molten steel ensures good fusion of carbide particles
with steel, which is accompanied by redistribution of the alloying elements, iron, and titanium between the metallic
binder and the titanium carbide. If the carbide has carbon
deficit, the carbon of the steel diffuses into the former, depleting the metallic binder, and the depletion is the more intense the higher the carbon deficit in the TiCx carbide. For
the carbide with stoichiometric composition, fusion is more
likely to be accompanied by partial dissolution of the carbide
and enrichment of the steel with carbon. According to the
data of x-ray diffraction analysis all the specimens contain a
low amount of a Fe2Ti phase.
2. The changes in the compositions of the metallic binder
and of the carbide cause changes in the processes of
austenization, dissolution and segregation of the carbide, and
martensitic transformation in the heat treatment of the
cermet. Enrichment of the metallic binder with titanium
raises the stability of the austenite and makes it possible to
use softer cooling media for the hardening.
3. The redistribution of the elements, carbon in particular, during heating is especially noticeable in the TiC0.8
steel U12 cermet, where the titanium carbide has carbon
deficit and hence tends to acquire a stoichiometric composition and the steel contains the highest amount of carbon.
4. The maximum hardness both after impregnation and
after hardening is attained in the cermet with titanium carbide having an initially stoichiometric composition.
5. In the case of moderate requirements to the red-hardness it is possible to use a heat-treated titanium carbide
unalloyed high-carbon steel cermet as a high-hardness
material.
REFERENCES
1. R. A. Andrievskii and Ya. S. Umanskii, Interstitial Phases
[in Russian], Nauka, Moscow (1977).
2. Ya. P. Kyubarsepp, Hard Alloys with Steel Binder [in Russian],
Valgus TTU, Tallinn (1991).
3. A. Kiffer and F. Benezovskii, Hard Alloys [Russian translation],
Metallurgiya, Moscow (1971).
4. Yu. V. Levinskii, A. P. Petrov, and S. S. Kiparisov, Titanium Carbide: Fabrication, Properties, Applications [in Russian], Metallurgiya, Moscow (1987).
5. N. P. Frage, M. P. Dariel, L. M. Kaputkina, et al., Strength and
structure of titanium carbide steel ceramic metals and their
variation due to heat treatment, Probl. Mashinostr. Nadezh.
Mashin, No. 4, 65 73 (2003).