Definition

Sintering is a heat treatment process in which a large quantity of loose aggregate material is
subjected to a sufficiently high temperature and pressure to cause the loose material to
become a compact solid piece. The amount of heat and pressure administered during the
sintering process is slightly less than the material's melting point.

Properties sintering

TiN-TiB2 composites were prepared by pressureless, Spark Plasma Sintering (SPS) and High
Pressure-High Temperature (HP-HT) sintering techniques. Powder mixtures, in wt%, 70 TiN-
30 TiB2 and 50 TiN-50 TiB2, were based on commercial TiN and TiB2 micropowders.
Parameters of sintering processes were optimized for density, hardness and Young’s
modulus. Young’s moduli were in the range 422-460 GPafor the 70-30 composite and for the
50-50 composite they were in the range 416-482 GPa. Vickers hardnesses were ~ 15GPa for
the 70-30 composite and in the range 16.4-17.5 GPa for the 50-50. Relative density ranged
from 95.7% (HP-HT, 50-50 composite) to 99.0% (SPS, 70-30 composite). HP-HT
composites had lower densities and Young’s moduli, because of microcrack’s. Nitrogen
contents, lattice constants and analyzed microstructures depended on the method of sintering.
The smallest grain growth, of TiN particles, from 1.2 μm to 2.5 μm, without the size
changing for theTiB2 particles, was observed for the HP-HT TiN-TiB2 composite, when there
was crushing of TiB2 particles. In pressureless sintered composites the growth of TiN grains
was from about 1.2 μm to 4.9 μm. Materials prepared using the pressureless sintering method
were characterized by the highest fracture toughness: 6.38 and 6.89 MPa•m1/2 for the 70
TiN-30 TiB2 and 50 TiN-50 TiB2 composites, respectively. The pressureless sintered.

The mechanism of sintering of TiB

The starting micropowders were H.C.Starck TiN (average particles size FSSS= 0.8-1.2μm, by
Fisher subsieve sizer) and H.C.Starck TiB2 (average median particles size D50= 2.5-3.5μm).
The required amounts of TiN and TiB2 (70 wt% TiN, 30 wt% TiB2 and 50 wt% TiN, 50 wt%
TiB2) were mixed in isopropyl alcohol in a centrifugal ball mill (Model Pulverisette 6,
Fritsch) for 1h. The powder mixtures were dried at 100°C for 5 h. For the pressureless
sintering process, a plasticizer (5% solution of glycol in isopropyl alcohol) was added to the
mixtures. The powders were uniaxially dry pressed in a steel die at 110 MPa into square
shapes of 16.7 mm x 16.7 mm, followed by isostatic pressing at 250 MPa. Samples were
dried at 250°C. The pressed specimens were placed in a coarse-grained TiN powder and
sintered in GERO HTK 8 (Germany) furnace in an argon atmosphere.

70 TiN-30 TiB2 and 50 TiN-50 TiB2 powders were sintered in the SPS equipment (FCT
system, Germany) as well. The powder (without a plasticizer) was placed in a graphite die
(inner diameter of 20mm) and a uniaxially pressed at 35 MPa for 10 minutes. A pyrometer
(IGA-5) was used to measure the sintering temperature, which ranged between 1400°C and
2100°C. The thickness of the sintered specimens was about 5 mm. The main criteria for
optimization of SPS sintering conditions (temperature, duration) were density, Young’s
modulus and Vickers’ hardness

For the HP-HT sintering the samples were shaped into discs (Φ = 15.3 mm, h = 4.2 mm) by
cold pressing in a steel die at 110 MPa. The green samples were consolidated by HP-HT
sintering using a toroidal Bridgmann-type apparatus with an internal graphite heater. The
sintering temperature ranged between 1200°C and 2000°C. Processing time was 20 to 60s
and the optimized duration of the sintering cycle was 40s for 70 wt% TiN, 30 wt% TiB2, and
30s for 50 wt% TiN, 50 wt% TiB2 composite, Table 1. Scheme of the optimization procedure
for HP-HT sintering. Optimal parameters for pressureless, SPS and HP-HT techniques of
sintering 70 wt% TiN, 30 wt% TiB2 and 50 wt% TiN, 50 wt% TiB2 powder mixtures.

The kinetic behaviour

Several deformed TiB2 particles with flat polygon faces can be recognizes. The presence of
dislocations was detected in pressureless sintered TiB2–SiC composite.Hence, it seems that
such linear defects can lead to the plastic deformation of TiB2 particles, assisted by the
applied pressure in this work. Based on the relative density of sample 7 and according to the
literature [8,24,26], adding nano-sized SiC particles and the in-situ formation of interfacial
TiC phases in the TiB2 matrix composites facilitate the densification of material.

Densification

For the densification of TiB2 powder the high temperature–high pressure (HT–HP) Bridgman
type apparatus was used. Compacts were obtained at pressure of 7.2 ± 0.2 GPa and at
temperatures of 1500 C, 2000 C, 2200 C and 2300 C " 50 C. Samples were the HT-HP
sintered for 60 seconds. The high temperature–high pressure (HT–HP) Bridgman type
apparatus is characterized by the ability of the sintering of compacts having relatively high
volume (usually 0,3-1 cm3). Depending on the volume of the chamber it generated the
pressure up to about 9-12 GPa, thus the smaller the chamber the bigger the pressure can be
obtained. This method assured the optimal distribution of the pressure and obtaining the high
temperatures of the sintering.

Type of sintering

Sintering; TiB2 Ceramics; HT–HP technique

Coarse

The formation of coarse TiB by Ostwald ripening or the coalescence of fine TiB. There was
no crystallographic relationship between TiB reinforcement and the matrix. There were voids
at the interface between the TiB reinforcement and the Ti matrix due to the preferential
growth of coarse TiB without a particular crystallographic relationship with pure Ti matrix
and the surface energy between the Ti matrix and TiB reinforcements