International Journal of Refractory Metals & Hard Materials 70 (2018) 101–106

Contents lists available at ScienceDirect

International Journal of Refractory Metals

& Hard Materials
journal homepage: www.elsevier.com/locate/IJRMHM

Influence of pulsed current during high pressure sintering on crystallite size MARK
and phase composition of diamond with TieB bonding phase
L. Jaworskaa,⁎, M. Karolusa, S. Cygana, J. Morgielb, J. Cyborońa, J. Laszkiewicz Łukasika,
P. Putyraa
a
Institute of Advanced Manufacturing Technology, Wroclawska 37a, PL-30011 Krakow, Poland
b
PAS, Inst Met & Mat Sci, Reymonta 25, PL-30059 Krakow, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: Diamond production by sintering and synthesis is known from the mid-fifties of the twentieth century. The
Diamond sintering technology of PCD materials has not significantly changed even to this day. Nonetheless, there are
Sintering publications providing a lot of success in the field of synthesis of diamond composite materials sintering using
High pressure SPS technology, yet these studies are limited to pressures mainly up to 140 MPa. In this work HP SPS (High
Pulsed current
Pressure Spark Plasma Sintering) device, was used to sinter diamond composite with titanium‑boron bonding
Crystalline size
Phase composition
phase. Thus obtained material was then compared with HP-HT (High Pressure High Temperature) sintered
sample, to investigate the influence of the heating by means of direct pulsed current on the crystallite size and
phase composition of diamond with 10 wt% of Ti + 2B bonding phase. Both HP SPS and HP-HT processes were
carried out at 8.0 ± 0.2 GPa and at the temperature of 1650 ± 50 °C during 20 s of holding time. The XRD
analysis carried out showed that the different type of current used for heating has significant influence on
kinetics of the sintering, which is visible in differences in phase composition and level of lattice strain, when
comparing standard HP-HT with HP SPS methods.

1. Introduction
Most sintering and synthesis processes of diamond are carried out in
special HP-HT (High Pressure High Temperature) equipment, under
static loads. Generally, the industrial production presses are used,
which achieve a pressure in the range of 5 to 8 GPa and a temperature
of 1300 to 2000 °C, while the maximum pressure obtainable in a re-
action chamber is 12 GPa [1–5]. The production technology of these
materials has not significantly changed. Spark Plasma Sintering of
diamond due to the direct heating by pulsed electric current, high
heating rates and short sintering times is interesting for diamond
synthesis and the diamond powders sintering. The biggest problem for
most SPS devices is relatively low pressure (mainly up to 140 MPa) in
comparison to the HP-HT apparatus. Diamond is an allotropic form of
the element carbon with cubic structure, which is thermodynamically
stable at pressures above 1.6 GPa at room temperature and metastable
at atmospheric pressure. In the low pressure, for diamond the allotropic
transition to graphitic or amorphous carbon occurs. Nevertheless, there
are publications providing a lot of success in the field of synthesis of
diamond and the diamond composite materials sintering using SPS
technology. One example involves obtaining of diamond crystals at the
tips of the carbon nanofibers with aid of pulsed current at low pressures
[6]. Other works concern the combination of the ultrafast heating rate
about 2000 °C/min and short holding time to successfully fabricate
diamond/cemented carbides [7]. For most of experiments the size of
diamond was over 40 μm [7,8] and the diamond participation is limited
up to 30 vol%. Several experiments show that it is possible to prevent
the diamond graphitization and improve its bonding strength with the
matrix [9]. Next way for diamond compacts obtaining using SPS is the
spark plasma reactive sintering. For example Si, Ti powders were added
to react at sintering temperature with transformed graphite phase on
diamond, to form hard carbide phases such as SiC and TiC which could
chemically bond diamond particles [8]. SPS technique was also suc-
cessfully employed for sintering of composites containing metastable
cBN (cubic Boron Nitride) for example with alumina [10] and Sialon
[11]. Also, there are new types of materials for the SPS punches/die
such as WC. In the case of WC punches the pressure can exceed
500 MPa, but for higher pressures it is difficult to extract the samples
without damaging the high pressure die and the strength of WC rapidly
decreases for temperature exceeding 1200 °C [12]. More promising are
carbon fiber composite (CFC) dies for the SPS, it is because their low
cost and possible temperature of sintering for SPS process up to 2000 °C

⁎
Corresponding author.
E-mail address: lucyna.jaworska@ios.krakow.pl (L. Jaworska).

http://dx.doi.org/10.1016/j.ijrmhm.2017.09.011
Received 30 May 2017; Received in revised form 15 September 2017; Accepted 21 September 2017
Available online 22 September 2017
0263-4368/ © 2017 Elsevier Ltd. All rights reserved.
L. Jaworska et al. International Journal of Refractory Metals & Hard Materials 70 (2018) 101–106

[12,13]. The CFC die can work at pressure up to 400 MPa. current with max. current of 15,000 A (HP SPS). Installed inverter al-
In this work investigations carried out were aimed at analysis of the lows to program the time of the current pulse and the pause between
influence of pulsed current under ultra-high pressure HP SPS (High pulses in the range of 1 to 500 ms. This design of high pressure appa-
Pressure Spark Plasma Sintering) on the phase composition of diamond ratus allows for sintering with 50 Hz alternating current or 1 kHz
composites with 10 wt% of the stoichiometric (Ti + 2B) mixture of ti- pulsed direct pulsed current (Fig. 1b).
tanium with boron. The main idea of the HP SPS is to join the appli- For this method of sintering there is no possible way of direct
cation of high pressure with the SPS technique. Namely, during SPS temperature measurement during the process. To gain insight into the
process pulse current discharges among particles removing the gases heat generated during sintering, a special gasket assembly was prepared
which are adsorbed on surface of the powder. Therefore, the formation with thermocouple, shown on Fig. 1. With thus prepared gasket tem-
of active contacts is promoted. The HP SPS technique was already perature calibration was carried out, where the dependency of tem-
successfully applied for sintering of not only superhard PCD materials perature on current power and pulse degree of filing for 50 Hz alter-
but also of ZrC based composites [14] and Ti–Al–Si Alloys [15]. nating current and 1 kHz direct current respectively was determined.
To designate the sintering temperature the HP-HT sintering processes
within the range from 1500 up to 1800 °C were carried out. For all
2. Experimental
experiments, the sintering was carried out at 8.0 ± 0.2 GPa and the
holding time at sintering temperature was equal to 20 s. For all cases,
For the sintering experiments, as a bonding phase for diamond, the
the heating and cooling rates were at about 150 °C/s [21]. For HP SPS,
mixture of titanium with boron with stoichiometric ratio of titanium to
pulse characteristics were 40 ms of current pulse time and 20 ms of
boron being 1:2, was selected. The use of such a material was aimed at
pause between pulses.
comprehensive analysis of resulting phases within the material after
After grinding and ionic precision etching (equipment model 682
sintering, whereas targeted bonding phase to be obtained was TiB2.
PECS Gatan firm) the surface of the sintering compacts was analysed by
This type of material designated for cutting tools was previously in-
X-ray diffraction method (XRD). The X-ray diffraction patterns were
vestigated after High Pressure High Temperature sintering [16–19].
obtained by using the PANalytical Empyrean diffractometer with the
Diamond with titanium diboride shows good properties and high
copper radiation (λCu Kα = 1.5418 Å).
thermal resistance, moreover the lack of solvent/catalyst additions
The phase analysis was conducted using ICDD (PDF-4 + 2015) files.
make this material a good candidate to show the potential differences
The crystallite sizes and lattice strains of identified phases were ana-
between HP-HT and HP SPS methods. Even though the pressure con-
lysed on the basis of Williamson-Hall method [22].The quantitative
ditions of both processes (8 GPa) accordingly to Berman-Simon line
phase analysis and the refinement of the unit cell parameters for the
[20] are well above value required for the stability of diamond the
studied materials were performed using the High Score Plus PANaly-
conditions on diamond surfaces in void areas, which in this case are not
tical software basing on the Rietveld refinement [23,24]. The Rietveld
filled with solvent/catalyst phase, are subjected to conditions allowing
refinement is a well-known and useful tool for structure determination.
for graphite formation [4].
It allows the determination of lattice parameters, atom positions and
As a starting powders, commercially available synthetic diamond
occupation parameters. It also could be used in quantitative phase
(Element 6, Micron + MDA M36), Ti (Alfa Aesar, < 20 μm) and B (Us
analysis.
Research Nanomaterials, 2–5 μm) were used. To prepare the mixture of
Density was investigated using hydrostatic method, hardness was
diamond with 10 wt% (Ti + 2B) addition the planetary mill
measured using Vickers method at 9.8 N and Young's modulus was
PULVERISETTE 6 with WC vessel and millers (φ 5 mm) was employed.
calculated using ultrasonic method by measuring the transmission ve-
Acetone was used as a lubrication medium, mixture was homogenized
locity of longitudinal and transversal ultrasonic waves through the
during 1 h at 200 rpm.
sample. The microstructures were observed using Scanning Electron
After drying, mixtures were pre pressed at 100 MPa into discs
Microscope JEOL JSM-6460LV and TECNAI SuperTWIN FEG trans-
~ 15 mm in diameter and ~5 mm high. Green bodies were then put in
mission (TEM) electron microscopes. The thin foils for the last one were
the graphite heater which subsequently was inserted into remaining
cut using Quanta 3D FIB.
ceramic elements of the special high pressure gasket assembly (Fig. 1a).
Sintering was carried out using a Bridgman-type (toroidal) high-
pressure apparatus equipped with not only high-power transformer
(standard HP-HT) but also inverter providing 1 kHz, 8.3 V direct pulsed

Fig. 1. High pressure gasket assembly cross-section (a) and high pressure sintering process schematic, where: 1 – ceramic gasket (outer part); 2 – ceramic gasket (inner part); 3 – ceramic
disc; 4 – sample; 5 – graphite disc; 6 – graphite tube; 7 – thermocouple (only for T-calibration). Quasi-isostatic compression of the preliminary consolidated powders is achieved as a result
of plastic deformation of the gasket material (1) between anvils (2); electrical heating during HP-HT process is provided by transformer (10), for HP SPS process the transformer works
together with inverter (11), thus providing 1 kHz direct pulsed current.

102
L. Jaworska et al.
Fig. 2. Densities and Young's modulus of samples sintered with the use of HP-HT method
at temperature range from 1500 up to 1800 °C.
3. Results and discussion
Do designate the sintering temperature for investigated material, an
optimization process for HP-HT sintering was carried out. Fig. 2 shows
the Young modulus and densities of samples sintered with the use of
HP-HT technique within the temperature range from 1500 up to
1800 °C.
The properties of samples rise with the increase of the sintering
temperature up to 1650 °C, above that temperature there is slight de-
crease of both density and Young's modulus. Measurements on sample
sintered at 1800 °C were not possible due to it being severely cracked
and broken. Bothe the decrease in properties of the sample sintered at
1700 °C and decomposition of sample sintered at 1800 °C were caused
by extensive graphitization of diamond particles. This is confirmed by
increase of the peak corresponding to graphite for these temperatures
(Fig. 3).
As shown on Fig. 2 sample sintered at 1650 ± 50 °C was char-
acterized by highest value of Young's modulus and density. This sin-
tering temperature was subsequently applied for HP SPS sintering
method, all remaining parameters were as for HP-HT sintering, the only
difference is the type of current used for heating. Thus obtained
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International Journal of Refractory Metals & Hard Materials 70 (2018) 101–106
materials (sintered at 1650 ± 50 °C for both HP-HT and HP SPS pro-
cesses) where then subjected for further investigations.
Microstructures of diamond with 10 wt% (Ti + 2B) compacts ob-
tained using HP-HT and HP SPS methods are presented in the Fig. 4.
Microstructure images of investigated materials, presented in
Fig. 4a and b, show that despite different current type used for heating
there are no visible differences in materials homogeneity. Both HP-HT
and HP SPS sintered samples are consisting of diamond matrix and
inclusions which are products of the reaction between titanium, boron
and carbon, which is confirmed by the phase compositions determined
by X-ray diffraction, presented in subsequent part of this paper. Some
selected properties of these compacts are shown in the Table 1.
For these materials a slight difference in hardness and density oc-
curs. The main reason is the graphite participation in the samples from
HP HT method. During the solid state sintering of diamond there are
voids present. Additionally at contact points between diamond grains
there are compressive stresses, at diamond surface near the voids there
are tension stresses. Because of that in voids the conditions present are
in thermodynamic range for the stability of graphite carbon form. It is
typical that for solid state sintering of diamond there is about 3 wt%
participation of graphite. This is not the case during sintering of dia-
mond with the presence of liquid phase of Co [4,25]. The crystallite
sizes and values of unit cells of identified phases were analysed to de-
termine the influence of type of current used during sintering on ki-
nematics of reactions between Ti, B and C.
In the Fig. 5, the X-ray diffractions are presented. Differences in the
phase compositions and lattice parameters for the same initial mixtures
sintered by HP SPS and HP-HT methods were compared in the Table 2.
Table 3 shows differences in lattice strain and crystallite sizes.
The differences are observed for graphite content, lattice parameters
and in grain size of diamond composites. For the HP-HT method ma-
terials are characterized more complex phase composition.
In both materials there is a small amount (< 1 wt%) of WC, which
is a contamination from the milling process. The influence of WC pre-
sence in this type of materials was well described in [26]. Furthermore,
Fig. 6 shows the phase composition of both the milling bowl and
grinding balls used for mixtures preparation process.
It can be seen that the materials of milling bowl and balls consists
only from tungsten carbide, therefore no other additions/contamina-
tions could possibly be present in prepared mixtures.
Beside of the diamond phase (~ 88 wt%), there is observed presence
of graphite (4 wt%), TiB2 (1 wt%) and TiBxCy (6 wt%) phases. While
after HP SPS process there are observed only diamond, TiB2 (8 wt%),
TiBxCy (1 wt%) and small amount of WC contamination (below 1 wt%)
with no evidence of graphite phase. TiBxCy phase is formed by a solid
Fig. 3. XRD analysis of samples sintered in the temperature
range from 1550 °C up to 1800 °C.
L. Jaworska et al. International Journal of Refractory Metals & Hard Materials 70 (2018) 101–106

Fig. 4. Microstructures at 3000 × magnification of the diamond composite with 10 wt% (Ti + 2B) samples sintered with the use of HP-HT (a) HP-SPS (b) techniques at temperature of
1650 °C.

Table 1 Table 3
Selected properties for diamond/Ti + 2B composites obtained by HP-HT and HP SPS Lattice strain and crystallite size comparison for diamond composite with 10 wt% of Ti
methods at temperature of 1650 °C. + 2B, after sintering using HP-HT and HP SPS at temperature of 1650 °C.

Composition wt%/type of Density, g/cm3 Hardness, GPa Young's Phase Dhkl [Å] ε [%]
sintering modulus, GPa
HP SPS HP-HT HP SPS HP-HT
90 wt% diamond + 10 wt 3.39 ± 0.01 43.2 ± 4.5 535 ± 12
% (Ti + 2B)/HPHT Diamond > 1000 367 0.151 0.406
90 wt% diamond + 10 wt 3.42 ± 0.01 39.7 ± 3.6 539 ± 17 F d-3m
% (Ti + 2B)/HP SPS Graphite – 98 – 0.333
P 63/mmc
TiB2 622 461 0.182 0.365
P 6/mmm
TiBxCy 729 372 0.045 0.313
F m-3m
WC 187 150 0.334 0.51
P-6m2

Fig. 5. Diamond composite with 10 wt% of Ti + 2B, phase composition comparison after
sintering using HP-HT and HP SPS at temperature of 1650 °C.
solution of C into the TiB2 phase [27]. The different method of sintering
also leads to differences in values of crystallite size and values of unit
cell parameters. For example, the TiB2 crystallite size obtained by the
HP SPS sintering process is 62 nm and for the HP-HT the size is com-
pacted to value of 46 nm. The crystallite size of diamond obtained by
the HP SPS sintering process is 0.1 μm (as crystallite size of starting
powder) in comparison to the HP-HT process, which compacts the
crystallite size of diamond to 0.036 μm. Lattice parameters analysis
carried out using X-ray diffraction methods confirmed the defected
structure for the HP-HT process. The volume of the TiB2 unit cell after
both sintering processes is almost the same but there are differences in
values of (c/a) ratio. After the HP SPS sintering process, (c/a)exp is
1.064 and for the HP-HT process, (c/a) ratio is smaller than theoretical
value, (c/a)exp = 1.062 in comparison to theoretical ratio (c/a)
theor = 1.65. It might be an effect of the tendency to atom

Table 2
Phase composition and lattice parameters obtained by Rietveld refinement for diamond composite with 10 wt% of Ti + 2B, after sintering using HP-HT and HP SPS at temperature of
1650 °C.

Phase composition wt% Unit cell parameters Experimental unit cell parameters
ICCD [Å] [Å]

HP SPS HP-HT HP SPS HP-HT

Diamond 90 88 a = 3.5668 a = 3.5675 a = 3.5666

F d-3m
Graphite – 4 a = 2.4690 – a = 2.5997
P 63/mmc c = 6.7670 c = 6.9202
TiB2 8 1 a = 3.0303 a = 3.0341 a = 3,0297
P 6/mmm c = 3.2295 c = 3.2297 c = 3.2184
TiBxCy 1 6 a = 4.3200 a = 4.3181 a = 4.3205
F m-3m
WC <1 <1 a = 2.9060 a = 2.9407 a = 2.9342
P-6m2 c = 2.8370 c = 2.8278 c = 2.8259

104
L. Jaworska et al.
reorganization which leads to the TiB2 formation. The size of TiBxCy
unit cell is not changing but there is a significant change visible of the
phase amount in final products. Moreover, the crystallite size of TiBxCy
is also changing, after the HP SPS process is 0.072 μm and after the HP-
HT process the size is compacted to 0.0372 μm.
The TEM observation of microstructure of the samples with 90 wt%
diamond + 10 wt% (Ti + 2B) are shown on Fig. 7.
It can be seen that for the sample sintered with the use of HP-HT
method (Fig.7a) there is a significant amount of graphite that foment in
triple-joint areas, whereas for sample sintered with HP SPS (Fig.7c) in
corresponding areas graphite formation is barely visible. The higher
amount of graphite formed in HP-HT sintered sample is confirmed by
the results of XRD phase analysis (Fig. 5). The dark areas visible within
diamond grains for both HP-HT and HP SPS sintered samples (Fig. 7a, c)
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International Journal of Refractory Metals & Hard Materials 70 (2018) 101–106
Fig. 6. Phase composition ow milling bowl and grinding balls
used for powder mixtures preparation process.
are defects which include nano twins and stacking faults, this may
contribute to improvement of the hardness, fracture toughness and
thermal resistance of produced material [28]. The HREM images of the
diamond grain boundary, shown on Fig. 7b and d for HP-HT and HP
SPS sintered samples respectively, visualize that also in this region the
graphitization process during HP-HT sintering is much more extensive.
The graphite layer observed at the diamond grain boundary region is
almost 6 times thicker for sintering process where alternating current
was employed (HP-HT) than for sintering with heating via 1 kHz direct
pulsed current (HP SPS).
4. Conclusions
Both HP-HT and HP SPS methods allowed to obtain diamond
Fig. 7. Images of the samples with 90 wt% diamond
+ 10 wt% (Ti + 2B), where: TEM image of sample sintered
with HP-HT technique (a), HREM image of the sample
sintered with HP-HT technique (b), TEM image of sample
sintered with HP SPS technique (c), HREM image of the
sample sintered with HP SPS technique (d).
L. Jaworska et al.
composites with similar physical and mechanical properties and mi-
crostructure. After sintering of the diamond with Ti + 2B mixtures by
the HP SPS method, smaller amount of sintering products is observed in
comparison to HP-HT method and greater amount of non-defected TiB2
phase was formed.
graphitization process of diamond, for the HP SPS more graphite is
formed in the same sintering conditions. The use of pulsed current leads
to lower level of lattice strain, what indicates on lower disorder of the
crystalline structure of HP SPS obtained materials. Graphitization pro-
cess, which is a very important factor during sintering of diamond
powders, as indicated by density, XRD phase analysis and TEM in-
vestigations, is much more extensive during sintering with alternating
current (HP-HT). Taking into account that the only HP-HT and HP SPS
processes conditions, the aforementioned differences can be attributed
to different current type used for heating during sintering. The kinetics
of the HP SPS, on the basis of presented results, provide a promising
perspective for obtaining of diamond based materials with improved
properties.
Acknowledgments
This work was supported by the European Commission under the
FP7 Specific Programme ‘Capacities’ within the framework of the
SINTERCER project “Development of a sintering centre and know-how
exchange for non-equilibrium sintering methods of advanced ceramic
composite materials” (REGPOT-2012-2013-1 EU FP7 Research
Potential, project no. 316232).
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