Metal Science and Heat Treatment

VoL 38, Nos. 9 - 1 0 , 1996

HARDENING FROM THE LIQUID STATE

UDC 669.14.018.253.3:621.78.08

STRUCTURAL TRANSFORMATIONS IN BORON-CONTAINING

HIGH-SPEED STEEL HARDENED FROM THE MOLTEN STATE
IL A. Oganyan, t Ya. N. Oganyan, t and A. G. Roshchupkin t
Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 9, pp. 12 - 15, September, 1996.
It is known that steels of the RtM5 type containing over 0.1% 13 become brittle due to the formation of a
coarse eutectic along grain boundaries. In previous works we have shown that methods of hardening from the
liquid state can be used to increase the boron content in this steel to 0.5 - 1% without increasing the brittleness.
A special heat treatment involving controlled transformation from an amorphous-crystalline state to a microcrystalline one made is possible to increase the ductility and curing properties of the steel. However, the
mechanism of this transformation was not considered earlier. The present article is devoted to this problem.

It has been shown in [1 - 3 ] that high-speed steels of the

R6M5 type that contain over 1% boron can be fabricated in
an amorphous state by hardening from the liquid slate. The
same steels with a lower boron concentration have an amorphous-crystalline structure after hardening. The alloys are
ductile in the amorphous initial state and are embrittled after
high-temperature annealing. On the other hand, the alloys
with an amorphous--crystalline initial state are brittle and become ductile after heat treatment by a special regime. Here
ductility is understood as the capacity of a rapidly quenched
ribbon to withstand bending to 180 without failure.
In the previous work [3] we established a relation between the carbon and boron content in steel and the temperature of its transformation to a ductile state. It has been shown
that the higher the concentration of these elements in the steel
the higher the temperature of the transformation. However,
the mechanism of the corresponding structural change in the
metal has not been considered.
In the present work we investigated structural transformations occurring upon heating in the tested steel (1.13% C,
5.8% W, 4.9% Me, 4.0% Cr, 1.7% V, 0,5% B, the remainder
Fe) hardened from the liquid state. The metal was melted in a
vacuum induction furnace in an alundum crucible in an argon
atmosphere. The ingots were cut into 30-g pieces, placed in
quartz ampoules, and melted by a high-frequency inductor.
After this the melt was squeezed out of the ampoule under an
excess argon pressure through an opening 0.5 mm in diameter, and the resulting stream was cooled on the external sur-

face of a massive copper drum 300 mm in diameter rotating

at 3000 rpm. This gave a ribbon about 20 psn thick and 1 mm
wide.
The phase composition of the specimens was studied using a DRON-2.0 diffractometer and a Siemens D-500 diffiactometer (Germany) in cobalt and copper Ka-radiation. A seleetive x-ray spectral analysis was conducted on a JXA-5 device. An electron-microscopic study was conducted using
JEM-100CX and JEM-1000 transmitting microscopes. Foils
were prepared from the ribbon by etching in an electrolyte
based on orthophosphoric acid and chromic anhydride. The
middle part of the foil cross section was investigated. The
process of crystallization of the amorphous-crystalline ribbon
was studied by the method o f scanning differential calorimetry using a DSC 111 device produced by the Setaram
firm (France).
In the initial condition (after hardening from the molten
state) the tested steel had an amorphous-crystalline structure.
In a Debye crystallogram taken from a milled ribbon a well
manifested line of bcc iron was clearly seen against the first
halo; a diffractogram of the same powder had a peak corresponding to the plane (110) of ct-Fe against a background of
the first amorphous halo.
The special features of the microstructure of rapidly hardened steel in the initial state were determined using transmission electron microscopy.
The electron diffraction pattern in Fig. la shows point reflections corresponding to an ct-Fe-base solid solution and a
diffusion halo. The halo is quite smeared and does not contain
individual reflections (except for the six 110 c~-Fe ones),

Institute of Solid-State Physics of the Russian Academy of Sciences,

Russia.

377
0026-0673/96/0910-03775 ] 5.00 O 1997 Plenum Publishing Corporation

378

R . A . Oganyan et al.

a-Fe

583.6C

loooc
,

500

550

600

650

t, C

JL

850C

Fig. 2. Thermogram of steel with 0.5% B.

which indicates the absence of crystalline particles of a second phase exceeding 10 nm in size. The smearing of distant
reflections in the electron diffraction pattern shows that individual regions are oriented at angles of at most 10.
Figure 1b presents a light-field image of a microstructure
in which we discovered individual dendrite regions 30 - 50 nm
in size under conditions of a near-Bragg orientation.
The white network in the dark-field image of the halo region in Fig. lc represents an amorphous phase. In all probability, it forms in hardening of a liquid phase of eutectic
composition that solidifies in the form of thin layers between
dendrites ofbcc iron. The width of the layers is 10 - 20 nm.

34

32

30

28

26

24

22

20

Q, deg

Fig. 3. Diffractograms of steel with 0.5% B after annealing at different temperatures (the numbers at the curves): e ) M23(C , B)6; ) MrC.

Such a structure is typical for steels after eutectic crystallization at very high cooling rates. In our case the cooling rate
determined from measured distances between axes of dendrites of second order (20 - 50 nm) exceeded l 0 6 deg/sec.

Structural Transformations in Boron-Containing High-Speed Steel Hardened from the Molten State

The rigid skeleton of the eutectic component of the steel

seems to be the cause of intergrain or interparticle fracture in
the ribbon in the initial state.

379

Data obtained by the method of differential scanning calorimetry show that crystallization in the studied amorphouscrystalline steel with an atomic fraction of boron and carbon

380

R . A . Oganyan et al.

Fig. 5. Structureof steel with 0.5% B afterannealingat 1000C:a) in a light field;b) in a dark field.

equal to about 7% occurs in the 5 0 0 - 6 5 0 C temperature

range in one stage with an exothermic peak at 584C and a
thermic effect of 36.7 kJ/kg (Fig. 2). This indicates that the
amorphous component of the metal begins to crystallize at
550C and ceases to crystallize at 650C.
In order to investigate the phase composition of steel in
the temperature region we were interested in, we annealed it
in the 5 5 0 - 1000C range for 2 h. Diffractograms of the annealed specimens photographed in cobalt Ks-radiation are
presented in Fig. 3. It can be seen that the phase composition
of the metal is mainly changed at 650C. At this temperature
the diffractogram contains the principal lines of bee iron,
M23(C, B)6 carboboride, and M6C carbide. The same phases
are the main ones after annealing at a temperature up to
1000C. Some lines remained unidentified. Assumably, they
correspond to cementite Fe3C.
It should be noted that segregation of an M6C carbide
from the solid solution occurs in the amorphous-crystalline
steel at about 650C. In steel fabricated by the conventional
technology the process of secondary hardening occurs at
550C.
After annealing in the entire temperature range, the predominant phase was bcc iron; the total amount of the carbides
M23(C, B)6 and M6C was about 20% (10% each). After prolonged annealing (6 and 8 h) the proportion of the phases
changed, bcc iron still remained the base phase, but the
amount of M23(C, B)6 exceeded that of M6C by almost a factor of two.
Let us consider what changes occur in the structure of the
steel in the annealing process.
In "in situ" experiments conducted directly in the column
of a high-voltage JEM-1000 electron microscope changes in
the structure of the steel were observed after heating all the
wax up to 850C (see Fig. 4).
It has been established (Fig. 4a, b) that after heating to
750C the microstructure of the steel does not undergo any
substantial change. The eutectic network is retained along
grain boundaries, and the dendrite structure is retained inside
the grains.

The increased number of point reflections in the electron

diffraction pattern (Fig. 4c) indicates crystallization of the
amorphous component in annealing.
After the metal is heated to 800C, the amorphous phase
decomposes, forming a chain of highly disperse spherical
segregations that repeat the configuration of the initial skeleton (Fig. 4d, e). Dendritic grains disintegrate in the process of
the ct ~ y transformation.
In subsequent heating (to 850C) the grains and particles
of the excess phase grow in size. The continuous chain of
segregations breaks into separate regions (Fig. 4f). Some segregations that have been positioned along boundaries of dendrite cells are enclosed by newly formed grains (Fig. 4g). The
size of the austenite grains is about 3 lain and that of the segregations is 0.1 - 0.2 ~tm.
It follows from the analysis of the microstructure in heating that all the processes described occur intensely upon passage through the temperature of the et ~ y transformation

(- 8oooc).
As the annealing temperature is increased, the matrix
grains and the particles of the excess phase grow. The number
of particles of the excess phase decreases due presumably to
dissolution of the finest particles and the resulting growth of
the coarser ones and also coagulation of particles.
This restructuring creates favorable conditions for the development of processes of plastic deformation and provides
bending to 180 without failure.
A 2-h annealing of specimens at 1000C was conducted
in evacuated quartz ampoules in a KS-400 furnace with Silit
heaters. After thinning, the structure of the ribbons was studied under an EM-100CX electron microscope.
After annealing at 1000C the grain size in the matrix
was 5 ~tm (Fig. 5). Particles of the excess phase were positioned along grain boundaries and inside grains. The electron-microscopic examination allowed us to identify particles
of M23(C, B)6 carboboride 0.3 - 0 . 5 ~tm in size and particles
of M6C carbide 0.15 - 0 . 3 ~tm in size.

Structural Transformations in Boron-Containing High-Speed Steel Hardened from the Molten State

A local x-ray analysis did not show any inhomogeneity in

the distribution of elements in the metal annealed at temperatures below 1000C, which means that the structure was homogeneous. In steel annealed at 1080C some inhomogeneity
in the distribution of tungsten, molybdenum, and chromium
was caused by growth of the grain size.
Analyzing the results obtained and comparing them with
published data we can conclude the following. It is known [4]
that the main shortcoming of cast high-speed steel is the carbide inhomogeneity caused by the coarseness of the eutectic
structure that appears in massive castings due to the low cooling rates. The presence of a eutectic network along grain
boundaries causes embrittlement in cast steel. Only with the
help of hot forging (rolling) with a high degree of deformation (up to 90,6) can the rigid eutectic skeleton be broken up
and the ductility of the steel increased.
In recent years methods of powder technology, including
gas spraying of the melt, have been tested with the purpose of
breaking up the structure of the ingot. The use of high cooling
rates gave powders with a fine-grained structure and highly
disperse carbides. However, the formation of the eutectic network along grain boundaries has not been eliminated completely. For example, in powder particles 200-315 pm in size
with austenite grains 3 - 5 ~un in size the thickness of the eutectic layer is 1 - 1.5 pm [4].
In our experiments on hardening molten steel of the
R6M5 type with 0.5% B we could attain a cooling rate exceeding 106 deg/sec and thus reduce the size of dendrite cells
to 30 - 50 um and the thickness of the eutectic layer to about
10 nm. This allowed us to transform the rigid eutectic skeleton rather easily into a set of spherical carbides by heat treatment of a rapidly hardened ribbon, which improved its ductility. The fact that heating to 750C does not cause a substantial change in the microstructure of the metal compared to the
initial state shows that high heat resistance can be obtained in
a compact specimen.
Comparing our results with data obtained in [5] in hardening molten steel R6M5 at a cooling rate of about
l0 s deg/sec, we can state the following. In [5] the matrix
grains reached 1 vm in size on the contact side of the ribbon
and 3 - 4 ~m on the free surface, whereas in our experiments
the grain size was an order of magnitude smaller. It seems

381

that the introduction of boron into the steel compositions is

one of the causes of break up of the structural components.
The method used for breaking up the structural components of the alloy, in particular, the thinning of its eutectic
and its transformation into fine spherical formations, can be
useful for other classes of metallic alloys, for example, beatresistant ones.
CONCLUSIONS
1. The brittleness of amorphous-crystalline ribbons in
the initial state is caused by the rigid skeleton of the amorphous component of the structure.
2. The increase in the ductility of amorphous-crystalline
ribbons with increase in the annealing temperature can be explained by the following successively occurring processes:
crystallization of the amorphous component of the alloy, disintegration of the rigid eutectic skeleton and formation of a
continuous chain of spherical segregations in its place, breaking of the continuous chain into separate regions due to dissolution of fine particles and growth of coarser ones, and
growth of matrix grains proceeding especially intensely
above the temperature of the (x --) y transformation. As a msuit of these processes some of the segregations formerly located on grain boundaries move inside the grains, which promotes plastic deformation of the ribbon without its failure.
REFERENCES
1. Patent 2116207 A. G. B. (Great Britain), Publ. 21.09.83.
2. O. V. Abramov, R. A. Oganyan, Ya. N. Oganyan, et al., "Special
features of the structure and properties of microcrystalline tool
steel fabricated by hardening from the liquid state," Poroshle
Metallurg., No. 10, 89-93 (1988).
3. Ya. N. Oganyan. R. A. Oganyan, and O. V. Abramov, "Effect of
the composition of microcrystalline tool steel on its ductility,"
Metalloved. Term. Obrab. Met., No. 1, 45 - 4 8 (1991).
4. Yu. A. Geller, Tool Steels [in Russian], Metallurgiya, Moscow
(1983).
5. V. N. Fedorov and V. V. Smimov, "Crystallization kinetics and
structure of high-speed steel R6M5 obtained by hardening from
the melt," Izv. Ros. Akad. Nauk, Metally, No. 6, 120-125
(I 993).