Materials Characterization 118 (2016) 560–569

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Materials Characterization

journal homepage: www.elsevier.com/locate/matchar

SEM and TEM characterization of microstructure of stainless steel

composites reinforced with TiB2
Iwona Sulima a,⁎, Sonia Boczkal b, Lucyna Jaworska a
a
Institute of Technology, Pedagogical University of Krakow, Podchorążych 2 st., 30-084 Krakow, Poland
b
Institute of Non-Ferrous Metals in Gliwice, Light Metals Division, Skawina, Poland

a r t i c l e i n f o a b s t r a c t

Article history: Steel-8TiB2 composites were produced by two new sintering techniques, i.e. Spark Plasma Sintering (SPS) and
Received 13 November 2015 High Pressure-High Temperature (HP-HT) sintering. This study discusses the impact of these sintering methods
Received in revised form 31 May 2016 on the microstructure of steel composites reinforced with TiB2 particles. Scanning electron microscopy (SEM),
Accepted 6 July 2016
wavelength dispersive spectroscopy (WDS), X-ray diffraction, electron backscatter diffraction (EBSD) and trans-
Available online 06 July 2016
mission electron microscopy (TEM) were used to analyze the microstructure evolution in steel matrix compos-
Keywords:
ites. The results of microscopic examinations revealed a close relationship between the composite microstructure
Microstructure and the methods and conditions of sintering. Substantial differences were observed in the grain size of materials
Complex boride sintered by HP-HT and SPS. It has been demonstrated that the composites sintered by HP-HT tend to form a chro-
Phase mium-iron-nickel phase in the steel matrix. In contrast, the microstructure of the composites sintered by SPS is
Composite characterized by the presence of complex borides and chromium-iron phase.
Spark Plasma Sintering (SPS) © 2016 Elsevier Inc. All rights reserved.
High Pressure-High Temperature (HP-HT)
sintering

1. Introduction
Powder metallurgy (PM) is considered one of the key technologies
for the fabrication of composites reinforced with ceramic particles [1,
2]. Compared with other methods, its undeniable advantage is better
control of microstructure, allowing for a uniform distribution of the re-
inforcing phase in sintered composite [3–5]. Sintering by conventional
methods takes a long time and requires high temperature, both of
which produce sinters of high density. However, the long time of
sintering causes grain growth and loss of the unique properties resulting
from the fine-grained microstructure of a composite material [6–8]. The
use of modern sintering technology allows reducing both time and tem-
perature of the sintering process with positive impact on the economic
aspect of the fabrication of composite materials. Both HP-HT and SPS
techniques are included in the group of modern advanced technologies.
Application of technologies in which different mechanisms control the
sintering process can affect the composite microstructure and, as a fur-
ther consequence, its physical, mechanical and functional properties [9].
Compared with the conventional sintering process, HP-HT offers several
quite unique advantages, to mention only energy savings, shorter time
of sintering (a few minutes only), full consolidation of the sintered
material, and suppressed grain growth [10,11]. In addition to the
⁎ Corresponding author.
E-mail address: isulima@up.krakow.pl (I. Sulima).
aforementioned benefits, the widespread use of SPS is also the matter
of the economic viability of this process, resulting partly from the
lower temperature and partly from the shorter time of sintering. In
this method, heating of the sintered powder is done with pulse current.
During flow of this current, sparks are generated in pores of the sintered
material, removing particles of adsorbed gases and oxides from the sur-
face. This facilitates active contact between particles of the sintered
powder. Consequently, this and other similar phenomena shorten the
time and reduce the temperature of the sintering process [12,13].
Recent years have witnessed a growing interest in iron alloys, main-
ly due to their potential applicability as a matrix of the composite mate-
rials. The main factors that decide about this fact include the low cost of
production, high mechanical properties of iron alloys and satisfactory
corrosion resistance. Compared with aluminium and its alloys, iron-
based alloys, austenitic steels - in particular, offer higher strength, better
stiffness and ductility [14]. The ceramic particles most commonly used
as a reinforcement of the steel matrix are oxides (Al2O3, ZrO2), nitrides
(TiN, Si3N4), carbides (TiC, Cr3C2, VC, B4C) and borides (TiB2, ZrB2) [15–
22]. Abenójar et al. [23] studied the effect of the type and content of the
reinforcing phase (AlCr2, Cr2Ti, VC and SiC) and sintering atmosphere on
the microstructure and properties of 316L stainless steel matrix com-
posites. It has been demonstrated that the use of intermetallic phases
is a good way towards the achievement of improved properties of the
composites tested. Akhtar et al. [24] analyzed the effect of MoSi2 addi-
tion on the sintering behavior and microstructure evolution of sintered
316L stainless steel. It was found that MoSi2 dissociated during sintering

http://dx.doi.org/10.1016/j.matchar.2016.07.005
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 I. Sulima et al. / Materials Characterization 118 (2016) 560–569
Fig. 1. XRD patterns of sintered 316L steel and composites steel-8TiB2: a) HP-HT method
(1300 °C-7 GPa) and b) SPS method (1100 °C-30 min).
with the resulting segregation of Mo and Si at grain boundaries. Exces-
sive amounts of Mo and Si appeared as separate phases in the micro-
structure. The addition of MoSi2 to 316L stainless steel was observed
to increase the density, hardness and tensile strength of this steel after
sintering. On the other hand, Jain et al. [25] have proved that the addi-
tion of 5 wt% of YAG improves both density and hardness of the sintered
ferritic and austenitic steels. The effect of YAG particles on the compac-
tion process is definitely enhanced by the sintering process carried out
at 1400 °C. In turn, Akhtar et al. [26] sintered 465 steel with the addition
of Si3N4. Tests covered the stability of the Si3N4 phase in a steel matrix. It
has been shown that the increasing content of Si3N4 phase increases the
sintered density. The maximum theoretical density of 98.5% was obtain-
ed in the composite containing 5 wt% of Si3N4, but it was found that par-
ticles of Si3N4 are stable in the steel matrix only up to the content of
2 wt%. Higher content of Si3N4 dissolves the ceramic phase in the matrix.
Patankar and Tan [18] studied 316L stainless steel reinforced with SiC.
Table 1
List of phases identified in the composites sintered by SPS and HP-HT.
Ref. code Compound name
01-089-4185 Iron
04-014-0258 Iron
04-002-3697 Iron-nickel
04-015-0310 Iron-nickel
04-015-0503 Chromium-molybdenum-nickel
04-006-2019 Titanium diboride
561
They proved that adding SiC to this steel allowed obtaining higher den-
sities of the sintered material. This effect was attributed to reactions oc-
curring between the SiC phase and steel matrix at 1100 °C giving rise to
the formation of a low melting Fe-SiC phase.
The aim of this study was to investigate the effect of two sintering
methods on changes in the microstructure of steel-8TiB2 composites. Ti-
tanium diboride was selected as a steel matrix reinforcement owing to
its low density, very high hardness, high strength at elevated tempera-
tures, and good thermal stability and wettability [27]. Several authors
produced steel composites reinforced with TiB2 by the technique of
powder metallurgy using conventional sintering and hot isostatic press-
ing (HIP) [28–30]. The techniques selected in this study for the manu-
facture of steel-8TiB2 composites included two modern advanced
techniques, i.e. Spark Plasma Sintering (SPS) and High Pressure-High
Temperature (HP-HT) sintering.
2. Methods
Commercially available TiB2 powder (H.C.·Starck) and 316L steel
powder (99.9 wt.%, Hoganas) were used in these studies. The stainless
steel powder had the following chemical composition: 17.20 wt% Cr,
12.32 wt% Ni, 2.02 wt% Mo, 0.43 wt% Mn, 0.89 wt% Si, 0.03 wt% S,
0.028 wt% P, 0.03 wt% C and Fe as a balance. The average particle size
of TiB2 and AISI 316L steel powders was 2.5–3.5 μm and 25 μm, respec-
tively. The raw powders were mixed for 8 h in a TURBULA mixer. For the
sintering process, a composite mixture of powders of the 316L steel
+8 vol% TiB2 was prepared.
Composites were sintered by the HP-HT and SPS techniques. In the
case of SPS, the composite mixture was fed into a cylindrical graphite
mould with an inner diameter of 20 mm. The sintering process was car-
ried out in SPS HP5 equipment made by FCT (Germany). The following
sintering parameters were observed: temperature - 1100 °C, pressure -
35 MPa, and heating rate - 200 °C/min. The sintering time was 5 and
30 min. The sintering temperature was measured with a pyrometer
(IGA-5). The height of the sintered samples was 7 mm. In the HP-HT
process, disk-shaped samples with a diameter of 15 mm and a height
of 4 mm were used. The samples were first cold-pressed in a steel die
under a pressure of 100 MPa. Next, the process of sintering was carried
out using a toroidal Bridgman-type apparatus. The sintering tempera-
ture and time were 1300 °C and 60 s, respectively. Two sintering pres-
sures of 5 and 7 ± 0.2 GPa were applied.
Composite microstructure was examined by scanning electron mi-
croscopy (SEM) using a new concept, ultra high-resolution, Hitachi
SU-70 scanning electron microscope equipped with a field emission
gun and a set of Thermo detectors. Chemical analysis of sintered ma-
terials was made by WDS. The X-ray diffraction patterns were ob-
tained using PANalytical Empyrean diffractometer with copper
radiation. The phase identification was done with the ICDD (PDF4+
2015) files. The quantitative phase analysis of the examined composites
was performed by the Rietveld refinement using HighScore PANalytical
software.
Phase analysis and analysis of the crystallographic orientation of
grains were performed under a high-resolution INSPECT F50 FEI
Chemical formula Crystal system Space group
γ-Fe Cubic, a = 3.6468 Å Fm-3 m
α-Fe Cubic, a = 2.8700 Å Im-3 m
γ-Fe0.66Ni0.34 Cubic, a = 3,6040 Å Fm-3 m
γ-Fe0.8Ni0.2 Cubic, a = 3,5830 Å Fm-3 m
Cr0.099Mo0.172Ni0.729 Cubic, a = 3.6100 Å Fm-3 m
TiB2 Hexagonal, a = 3.0190 Å, c = 3.2180 Å P6/mmm
562 I. Sulima et al. / Materials Characterization 118 (2016) 560–569

Fig. 2. EBSD images for 316L steel sintered by: a) HP-HT (1300 °C-7 GPa) and b) SPS (1100 °C-30 min).

scanning electron microscope with attachments for the chemical
analysis by EDS and a camera for EBSD. The EBSD analysis was per-
formed using TSL OIM software and ICCD 2011 PDF database format.
In the last stage of microscopic examinations, thin films were pre-
pared on a Leica RES101 ion thinner. Microstructural studies were
performed using a high-resolution Tecnai G2 20XT (200 kV) trans-
mission electron microscope with STEM (HAADF) and EDX attach-
ment made by FEI.
The apparent density of sintered composites was determined by a
hydrostatic method. A systematic error of the density measurements
in samples weighing more than 1 g was below 0.1%. Open porosity Po
was calculated in accordance with relevant standards [31]. Young's
modulus was determined by the measurement of longitudinal and
transverse velocity of wave propagation in the sample. The Panametrics
Epoch II flaw detector was used. The measurement error was 2%. Hard-
ness measurements were performed with Vickers hardness tester
under a load of 2.942 N. Compression tests were carried out on an
INSTRON TT-DM testing machine with the crosshead speed of
1 ∗ 10−4 mm/s. For tests, cylindrical samples of 3 mm diameter and a
height of 4.5 mm were used.

Fig. 3. The results of EBSD analysis of the steel-8TiB2 composite sintered by HP-HT (1300 °C-7 GPa): a) the crystallographic orientation of grains, and b) phase analysis (Chi-Scan).
 I. Sulima et al. / Materials Characterization 118 (2016) 560–569
Fig. 4. The results of EBSD analysis of the steel-8TiB2 composite sintered by SPS (1100 °C-30 min): a) the crystallographic orientation of grains, and b) phase analysis (Chi-Scan).
3. Results and discussion
Fig. 1 and Table 1 show the X-ray diffraction patterns obtained for
316L steel and steel-8TiB2 composites. The results of tests (Fig. 1a) car-
ried out on the 316L austenitic stainless steel sintered by HP-HT re-
vealed the presence of γ-Fe phase (cubic crystal system; a = 3.6468 Å
1). In steel-8TiB2 composites, the following phases were identified: γ-
Fe (cubic crystal system; a = 3.6468 Å), α-Fe (cubic crystal system;
a = 2.8700 Å), Fe0.8Ni0.2 (cubic crystal system; a = 3.5830 Å) and TiB2
(hexagonal crystal system; =3.0190 Å, c = 3.2180 Å). In 316L austen-
itic steel (Fig. 1b), the SPS process has contributed to the formation of
two phases, namely γ-Fe (cubic crystal system; a = 3.6468 Å) and
Cr0.099Mo0.172Ni0.7 (cubic crystal system, a = 3.6100 Å). The steel-
8TiB2 composite contained the following phases: α-Fe (cubic crystal
system; a = 2.8700 Å), Fe0.66Ni0.34 (cubic crystal system; a =
3.6040 Å) and TiB2 (hexagonal crystal system; a = 3.0190 Å, c =
3.2180 Å). The main components of 316L austenitic stainless steel
were Fe, Cr and Ni, i.e. the elements grouped together in the periodic
table. They have similar properties and their lattice parameters are sim-
ilar. Hence result the differences in the identified phases (Fig. 1). In this
situation, using the results of X-ray diffraction analysis, it is practically
impossible to determine in a sufficiently accurate way the phase com-
position of the sintered steel-8%TiB2 composites, since all that the re-
sults of this analysis can prove is the presence of the solid solution of
iron Fe(Cr, Ni). Chromium and nickel atoms are embedded in the crystal
structure of iron changing its lattice parameters. For γ-iron from the pe-
riodic table crystallizing in a cubic system, the lattice constant a is
563
3.6468 Å [32], and it is similar to an Fe(Cr, Ni) system with the lattice
constant a equal to 3.5830 Å [33]. Atoms embedded in the structure of
γ-iron either reduce or increase its crystallographic parameters, de-
pending on the size of the atoms of impurities.
The EBSD technique was applied in the next stage of studies and
allowed for accurate identification of phases observed in the micro-
structure of sintered materials. Figs. 2–4 show the results of EBSD anal-
ysis depicted in the form of maps of the crystallographic orientation of
individual grains and maps representing the phase analysis of the mi-
crostructure. The conducted analysis (Fig. 2) has indicated a relation-
ship between the size of grains in the steel material and the applied
method of sintering. In the 316L steel sintered by HP-HT, the grains
were very fine, i.e. ranging from 1 to 4 μm. The SPS method produced
coarser grains, i.e. from 5 to 12 μm (Fig. 2b). In spite of this, no new
phases were detected in the microstructure of the sintered 316L steel
in either case.
The EBSD results (Fig. 3) obtained for the steel-8TiB2 composites
sintered by HP-HT confirmed the presence in the structure of the fol-
lowing phases: γ-Fe, TiB2 and Cr0.18Fe0.09Ni0.73 (numbers in the
ICCD2011 - PDF database: 001126, 0783430 and 0330946, respective-
ly). The identified γ-Fe phase had a cubic structure (a = 3.5537 Å)
[36], contrary to the TiB2 ceramic phase crystallizing in a hexagonal con-
figuration (a = 3.024 Å, c = 3.154 Å) [37]. The Cr0.18Fe0.09Ni0.73 phase
was also characterized by a cubic structure (a = 3.5537 Å) [38]. The
EBSD results (Fig. 4) obtained for the composite sintered by SPS showed
the presence in the microstructure of the following phases: γ-Fe, TiB2,
Cr0.18Fe0.09Ni0.73 (numbers in the ICCD2011 - PDF database: 0011262,
564 I. Sulima et al. / Materials Characterization 118 (2016) 560–569
Fig. 5. The SEM micrograph of 316L steel sintered by (a) HP-HT method (1300 °C-7 GPa)
and SPS method (1100 °C-30 min).
0783430, 0330946, respectively) and two complex borides: BCr0.2Fe1.8
and (Cr,Fe,Mo,Ni,Ti)3B2 (numbers in the ICCD2011 - PDF database:
0570490 and 0180387, respectively). In the composite sintered by
SPS, the volume fraction of the Cr 0.18Fe0.09 Ni 0.73 phase decreased
quite considerably compared with the microstructure of the com-
posite sintered by HP-HT. The identified complex borides were
characterized by a tetragonal structure of BCr0.2Fe1.8 (a = 5.098 Å,
c = 4.226 Å) and (Cr,Fe,Mo,Ni,Ti)3B 2 (a = 5.783 Å, c = 3.134 Å),
respectively [39,40].
Figs. 5–7 compare the microstructures of 316L steel and steel-8TiB2
composites sintered by SPS and HP-HT. In 316L stainless steel, the HP-
HT sintering produced a fine-grain microstructure with the size of
grains reaching maximum several μm (Fig. 5a). The microstructure of
SPS sintered steel was characterized by coarser grains, i.e. ranging
from 10 to 25 μm (Fig. 5b). A similar grain size dependency was valid
for the matrix of sintered steel-8TiB2 composites. The reinforcing TiB2
phase was distributed in a uniform way in the steel matrix (Figs. 6, 7).
Occasionally only, some scarce, small, locally formed TiB2 agglomerates
were observed.
Chemical analysis by WDS indicated the presence of titanium
diboride in the form of black precipitates at the grain boundaries in
the matrix (Figs. 8, 9). Additionally, microstructural examinations
showed that the sintered composites were nearly totally free from po-
rosity. SEM examinations revealed some differences in the microstruc-
ture of the examined composites. In the steel-8TiB2 composites
sintered by HP-HT, local clusters of the precipitates containing large
Fig. 6. The SEM micrograph of steel-8TiB2 composites sintered by HP-HT at: (a) 1300 °C-
5 GPa, (b) 1300 °C-7 GPa.
amounts of nickel were observed (Fig. 8). Most probably they corre-
spond to the Cr0.18Fe0.09Ni0.73 phase (Fig. 3) identified by EBSD. In the
case of HP-HT method, the consolidation of powder was stimulated by
the high pressure and temperature. The created conditions gave rise
to the formation of the Cr0.18Fe0.09Ni0.73 phase in all the tested compos-
ites. In contrast, the SPS sintered composites (Figs. 7, 9) showed the
presence of numerous fine precipitates distributed in the matrix and,
as proved by the WDS analysis (Fig. 9), containing chromium. These
phases correspond to the complex borides (Fig. 4) identified by EBSD.
The different sintering times applied in the SPS method affected mainly
the number and the size of complex borides. With the sintering time
prolonged to 30 min, the number and the size of chromium phases in-
creased in the entire volume of the composite (Fig. 7b). In composites
sintered at 1100 °C for 30 min, large precipitates with a characteristic
band substructure appeared around the particles of TiB2 (Fig. 9).
Figs. 10 and 11 show the results of TEM examinations of the micro-
structure of the steel-8TiB2 composite sintered by HP-HT. The structure
of the grains in the steel matrix is characterized by numerous disloca-
tions and slip lines. The examinations also confirm the presence of chro-
mium-iron-nickel phase in the form of characteristic irregular
precipitates with numerous stacking faults (Fig. 10b,c). The precipitates
are located in the vicinity of grain boundaries in the matrix of austenitic
steel (Fig. 11, gray precipitates). The TiB2 particles-steel matrix interface
is smooth and regular. Its characteristic feature is the presence of small
precipitates surrounding TiB2 particles. Chemical analysis identifies this
phase as Cr0.18Fe0.09Ni0.73 (Fig. 11, points 2, 4).
 I. Sulima et al. / Materials Characterization 118 (2016) 560–569
Fig. 7. The SEM micrograph of steel-8TiB2 composites sintered by SPS at: (a) 1100 °C-
5 min, (b) 1100 °C-30 min.
Figs. 12–14 show the results of TEM examinations of the microstruc-
ture of the steel-8TiB2 composite sintered by SPS. The results confirm
the presence of chromium-iron-nickel phases (Cr0.18Fe0.09Ni0.73) in the
form of irregular precipitates with numerous stacking faults in the
form of bands (Fig. 12). The precipitates of Cr0.18Fe0.09Ni0.73 phase
tend to occupy the sites in the steel matrix scattered along the grain
boundaries. Their size is comprised in the range between 500 nm and
1 μm. The presence of numerous small precipitates (less than 500 nm)
was also observed at the matrix - TiB2 interface and in areas close to
Fig. 8. The microstructure (SEM) of steel-8TiB2 composite (HP-HT, 1300 °C-7 GPa) with corresponding area analysis (WDS).
565
this compound (Figs. 13 and 14). The analysis of chemical composition
suggests the presence of two complex borides in the vicinity of the TiB2
reinforcing phase. Their composition may be consistent with the com-
position of borides identified by EBSD (BCr0.2Fe1.8 and
(Cr,Fe,Mo,Ni,Ti)3B2). In contrast, the phase analysis of precipitates at
the steel matrix - TiB2 interface (Fig. 13) carried out by point diffraction
(SAD) showed the presence of very small precipitates of the CrFe
(Cr0.99 Fe1.01) phase with a tetragonal structure (a = 8.7966 Å, c =
4.5582 Å) [41]. The size of this phase was in the range of 200–300 nm.
The phase structure of the steel-TiB2 composite sintered by SPS was
very complex (Figs. 12–14). Several new phases of different sizes and
morphologies were identified. Their occurrence is due to complex
mechanisms accompanying the SPS process. The phenomena that
occur during the SPS sintering definitely accelerate the composite con-
solidation and exert an impact on changes in its microstructure. The
austenitic matrix is a solid solution of Cr, Ni, Mo in iron. The applied con-
ditions of SPS favor the diffusion of boron from the TiB2 phase to the
steel matrix, where complex borides are formed. Sulima [42] was inves-
tigated the effect of boron addition on the properties and microstructure
of austenitic steel-based composites produced by SPS. The occurrence of
complex borides in the microstructure of these materials was reported.
With the increasing time and temperature of sintering, the number and
size of the new phases was also increasing in the entire volume of the
composite. Analysis of literature indicates that numerous research
works were devoted to the problem of sintering the austenitic stainless
steel by the pressure-free technique [8,43–46]. It has been found that
boron in small amounts activates the sintering process due to the ap-
pearance of a liquid wetting the surfaces of the powder particles, and
thus contributing to an increase in the sintered compact density.
Boron segregates at grain boundaries, thereby reducing energy. Addi-
tionally, boron forms in these steels complex borides of iron, nickel
and chromium. As proved by the tests and studies, appropriate amount
of boron added to the mixture of iron powders effectively activates the
sintering process. At the sintering temperature higher than the temper-
ature of eutectic transformation, a liquid phase appears and an obvious
consequence of this fact is the sinter densification and changes in its
structure. For example, Skalon and Kazior [8] have demonstrated the
formation of complex borides (Cr, Mo, Fe) in the process of pressure-
free sintering of austenitic stainless steel. In those studies, a small
amount of boron was used as a sintering activator. In that case, sintering
took place in the liquid phase, which was formed by a eutectic reaction
between the matrix and the boride phase (Fe, Cr, Mo)2B [46,47].
In summary, the results of microstructural examinations have
proved that both sintering methods significantly affect the microstruc-
ture of the steel-8TiB2 composites. These materials vary in terms of
the phase composition. Attention deserves the fact that both sintering
processes, i.e. SPS and HP-HT, are conducted under non-equilibrium
conditions. The SPS process uses pulsed current for heating of the
sintered materials. The current flow through the particles of powder is
566 I. Sulima et al. / Materials Characterization 118 (2016) 560–569

Fig. 9. The microstructure (SEM) of steel-8TiB2 composites (SPS, 1100 °C-30 min) with corresponding area analysis (WDS).

Fig. 10. (a–c) TEM observations of steel-8TiB2 composite sintered by HP-HT method (1300 °C-7 GPa).

Fig. 11. The microstructure (TEM) of steel-8TiB2 composite sintered by HP-HT with corresponding point analysis (EDS).
 I. Sulima et al. / Materials Characterization 118 (2016) 560–569 567

Fig. 12. TEM microstructure of the steel-8TiB2 composite sintered by SPS (1100 °C-30 min) with corresponding point analysis (EDS) and electron diffraction pattern from the marked area.

followed by sparks formed at the contact points of grains and in voids
between them. When spark discharges appear in the gap or at the con-
tact points between particles, a local high-temperature state of several
up to ten thousands of degrees centigrade is momentarily generated.
This causes evaporation and melting on the surface of powder particles
and necks are formed around the area of contact between particles. Ad-
ditionally, the applied pressure enhances the plastic flow of material
[48–50]. Microstructural examinations have indicated that the
privileged places for the formation of complex borides are grain
boundaries and the TiB2/matrix interface (Figs. 13, 14). It should be
noted that during the SPS process, non-equilibrium conditions are
formed in the material, which has a significant impact on the diffusion
of boron and the reactions taking place during sintering. The formation
of complex borides and of the CrFe phase in the studied composites is
the result of the composite chemical composition and of the intense
phenomena taking place during SPS (surface activation, diffusion, sur-
face melting, necking between the particles of sintered powder, and
plastic flow [48,51]). In the steel-8TiB2 composites sintered by HP-HT,

Fig. 13. TEM images of the interface in steel-8TiB2 composite sintered by SPS and electron diffraction pattern from the marked area.
568 I. Sulima et al. / Materials Characterization 118 (2016) 560–569

Fig. 14. TEM microstructure of steel-8TiB2 composite sintered by SPS with corresponding point analysis (EDS).

the presence of complex borides was not detected. Only the occurrence
of the Cr0.18Fe0.09Ni0.73 phase was observed in all the steel-
8TiB2composites. The high pressure applied in the case of the HP-HT
method had a significant influence on the phase formation during
sintering. The consolidation of composite powders has occurred under
the conditions of high pressure (5 GPa and 7 GPa), very short time
(60 s) and high temperature (1300 °C).
The selected physical and mechanical properties of the sintered 316L
steel and steel-8TiB2 composites are compared in Tables 2 and 3. In spite
of differences in the sintering conditions, a very high degree of consoli-
dation was achieved in all the examined materials. The density pro-
duced by HP-HT and SPS approached the theoretical density in 100%
and 97–98%, respectively. Regardless of the sintering conditions, all
composites were characterized by a very low porosity, i.e. in the range
of 0.004–0.005% and 0.006–1.12% for HP-HT (Table 2) and SPS (Table
3), respectively. The results of the measurements of Young's modulus
did not show any substantial relationship between changes in this pa-
rameter and the applied method and conditions of sintering. In the
case of HP-HT, the values of Young's modulus were comprised in the
range of 201–205 GPa and 216–221 GPa for the 316L steel and steel-8
TiB2 composite, respectively. In contrast, the SPS method gave the
values of this parameter at a level of 196–207 GPa and 214–215 GPa
for the 316L steel and steel-8TiB2 composite, respectively. The results
of mechanical tests showed that the steel-8TiB2 composites sintered
by HP-HT are characterized by higher compressive strength and lower
hardness than their counterparts sintered by SPS. The mechanical prop-
erties also depended on the sintering conditions currently applied. The
increase in pressure (HP-HT) and time (SPS) raised the hardness and
compressive strength of the manufactured materials.
4. Conclusions
1. Two different techniques, i.e. HP-HT and SPS, were applied to sinter
316L steel and the corresponding steel-8TiB2 composite. In both
cases, materials with high degree of consolidation were obtained.
2. A homogeneous distribution of TiB2 in the steel matrix was confirmed.
3. Comprehensive microstructural studies proved that the use of two
different sintering techniques has a substantial effect on changes
in the microstructure of the tested composites. Differences in the

Table 2
The properties of 316L steel and steel-8TiB2 composites sintered by HP-HT method.
ρ0
Materials HP-HT method Density [g/cm2] ρteor [%] Porosity [%] Young's modulus E [GPa] E0
[%] HV0.3 Rc [MPa]
Eteor

T [°C] Pressure [GPa] Time [sec]

316L steel 1300 5 60 7.91 ± 0.01 100 0.004 205 ± 4 94 213 715 [35]
7 7.52 ± 0.01 100 0.005 201 ± 4 93 223 810 [35]
Steel-8TiB2 5 7.77 ± 0.01 100 0.004 216 ± 4 93 282 [34] 1270 [35]
7 7.59 ± 0.01 100 0.005 221 ± 4 94 346 [34] 1375 [35]

Table 3
The properties of 316L steel and steel-8TiB2 composites sintered by SPS method.
ρ0
Materials SPS method Density [g/cm2] ρteor [%] Porosity [%] Young's modulus E [GPa] E0
[%] HV0.3 Rc [MPa]
Eteor

T [°C] Pressure [MPa] Time [min]

316L steel 1100 35 5 7.75 ± 0.01 97 1.12 196 ± 4 91 191 [22] 685 [22]
30 7,82 ± 0.01 98 0.89 207 ± 4 99 225 [22] 730 [22]
Steel-8TiB2 5 7.53 ± 0.02 98 0.034 215 ± 4 93 365 [22] 980 [22]
30 7.52 ± 0.01 98 0.006 214 ± 4 93 410 [22] 1110 [22]
 I. Sulima et al. / Materials Characterization 118 (2016) 560–569
grain size were observed between 316L steel and steel-8TiB2 com-
posites sintered by the HP-HT and SPS methods.
4. Microstructure examinations revealed some differences in the phase
composition of sintered steel-8TiB2 composites. New phases with
different sizes and morphologies were identified. Composites
sintered by HP-HT showed the presence of Cr0.18Fe0.09Ni0.73 phase,
while composites sintered by SPS contained two complex borides,
i.e. BCr0.2Fe1.8 and (Cr,Fe,Mo,Ni,Ti)3B2, and two phases, i.e.
Cr0.18Fe0.09Ni0.73 and CrFe. The amount of borides was increasing
with the increasing time and temperature of sintering.
Acknowledgements
The study was performed statutory funds of Faculty of Mathematics,
Physics and Technical Science, Pedagogical University (BS-087/M/2015)
in Krakow. Authors would like to thank Ph.D. Tomasz Tokarski (AGH
University of Science and Technology Krakow) for help with the SEM
investigations.
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