Spark plasma sintering of pure TiCN: Densification mechanism,grain growth and mechanical properties

This study aims to disclose the densification mechanism and grain growth behaviors during the spark plasma sintering (SPS) of undoped TiCN powder. The SPS experiments were performed under temperatures ranging from 1600 °C to 2200 °C and a fixed pressure of 50 MPa. The sintering mechanisms were described in different models according to two grain growth behaviors: densification without grain growth at low temperatures (1600–1700 °C) and grain growth without apparent densification at higher temperatures (1800–2200 °C). At the constant grain stage, a creep model is applied to describe the densification process. In addition, the effective stress exponents, n, are calculated, indicating that the densification can be attributed to both grain boundary sliding (n = 1.5) and dislocation climbing (n = 3.13 or n = 4.29). During the second stage of sintering, the grain growth model reveals that the grain-growth is controlled by grain boundary diffusion. In addition, the Vickers hardness varies from 4326 Hv to 6762 Hv when the density ranges from 90% to 96.3%.     

Microstructure evolution and densification kinetics of Al2O3/Ti(C,N) ceramic tool material by microwave sintering

The microstructure evolution and densification kinetics of Al₂O₃/Ti(C,N) ceramic tool material during microwave sintering were studied. The density and grain growth significantly increases at the temperatures higher than 1400 °C. The calculated kinetics parameter n indicates that volume diffusion is the main densification mechanism when the sintering temperature is below 1300 °C, while grain boundary diffusion plays a leading role in the densification process when the sintering temperature is higher than 1300 °C. The grain growth activation energy of Al₂O₃/Ti(C,N) composite is 48.82 KJ/mol, which is much lower than those of monolithic Al₂O₃ in the microwave sintering and conventional sintering. The results suggested that the Al₂O₃/Ti(C,N) ceramic tool material with nearly full densification and fine grains can be prepared by two-step microwave sintering.     

Temperature dependence of microstructure evolution during hot pressing of ZrB2–30 vol.% SiC composites

Microstructure evolutions of ZrB₂–30 vol.% SiC composites, prepared by hot pressing at different processing temperatures (1700, 1850 and 2000 °C) for 30 min under 10 MPa, were investigated by optical microscopy, scanning electron microscopy and transmission electron microscopy (TEM). The microstructures of the fabricated composites were compared with and the effects of the processing temperature on the sintering process and densification behavior during the hot pressing were found. The amount and the orientation of dislocations which were indicated by TEM analysis in the sample hot pressed at 1700 °C showed that no plastic deformation and atomic diffusion occurred. But the presence of amorphous phases and rearrangement of particles are signs of the fact that liquid phase sintering and particle fragmentation/rearrangement is the main densification mechanism. On the other hand, in the sample hot pressed at 1850 °C, aggregation of dislocations behind the grain boundaries and the presence of twinnings addressed wide plastic deformations which were introduced as the main densification mechanism at 1850 °C. Finally in the sample hot pressed at 2000 °C, lower amounts of un-oriented dislocations and also some annealing twinnings were observed in TEM micrographs together with fractographical SEM analysis and showed that the atomic diffusion is the dominant densification mechanism of hot pressed ZrB₂–30 vol.% SiC composite.     

Spark plasma sintering of a commercially available granulated zirconia powder: Comparison with hot-pressing

A commercially available granulated TZ3Y powder has been sintered by hot-pressing (HP). The “grain size/relative density” relationship, referred to here as the “sintering path”, has been established for a constant value of the heating rate (25 °C min^?1) and a constant value of the macroscopic applied pressure (100 MPa). It has then been compared to that obtained previously on the same powder but sintered by spark plasma sintering (SPS, heating rate of 50 °C min^?1, same applied macroscopic pressure). By coupling the analysis of a sintering law (derived from creep rate equations) and comparative observations of sintered samples using transmission electron microscopy, a hypothesis about the densification mechanism(s) involved in SPS and HP has been proposed. Slight differences in the densification mechanisms lead to scars in the microstructure that explain the higher total ionic conductivity measured, in the temperature range 300–550 °C, when SPS is used for sintering.     

Sintering of tungsten powder with and without tungsten carbide additive by field assisted sintering technology

Tungsten powder (0.6–0.9 μm) was sintered by field assisted sintering technology (FAST) at various processing conditions. The sample sintered with in-situ hydrogen reduction pretreatment and pulsed electric current during heating showed the lowest amount of oxygen. The maximum relative density achieved was 98.5%, which is from the sample sintered at 2000 °C, 85 MPa for 30 min. However, the corresponding sintered grain size was 22.2 μm. To minimize grain growth, nano tungsten carbide powder (0.1–0.2 μm) was used as sintering additive. By mixing 5 and 10 vol.% WC with W powder, densification was enhanced and finer grain size was obtained. Relative density above 99% with grain size around 3 μm was achieved in W–10 vol.% WC sintered at 1700 °C, 85 MPa, for 5 min.     

Two-step hot pressing of bimodal micron/nano-ZrB2 ceramic with improved mechanical properties and thermal shock resistance

The densification and grain growth behaviors for micron- and nano-sized ZrB₂ particles were investigated. The densification on-set temperature (T_d-micron) and grain growth on-set temperature (T_g-micron) for micron-sized ZrB₂ particles were about 1500 °C and 1800 °C, respectively. And the densification on-set temperature (T_d-nano) and grain growth on-set temperature (T_g-nano) for nano-sized ZrB₂ particles were about 1300 °C and 1500 °C, respectively. A bimodal micron/nano-ZrB₂ ceramic was therefore prepared using a novel two-step hot pressing. A high relative density of 99.2%, an improved flexural strength of 580.2 ± 35.8 MPa and an improved fracture toughness of 7.2 ± 0.4 MPa·m^1/2 were obtained. The measured critical thermal shock temperature difference (ΔT_c) for this bimodal micron/nano-ZrB₂ ceramic was as high as 433 °C.     

Densification and grain growth during early-stage sintering of Ce0.9Gd0.1O1.95−δ in a reducing atmosphere

The present work investigates the processes of densification and grain growth of Ce_0.9Gd_0.1O_1.95?δ (CGO10) during sintering under reduced oxygen partial pressure. Sintering variables were experimentally characterized and analyzed using defect chemistry and sintering constitutive laws. Based on the results achieved, the grain size–relative density relationship, the densification rate and the grain-growth rate were determined. The activation energies for densification and grain growth were evaluated, and the dominant densification mechanism was indicated. For comparison, the densification behavior of CGO10 sintered in air was also studied. Accelerated densification was observed in early-stage sintering of CGO10 in a reducing atmosphere. This might be attributed to the oxygen vacancies generated by the reduction of Ce⁴⁺ to Ce³⁺ in the reducing atmosphere, which facilitate the diffusion of ions through the lattice. The densification activation energy of CGO10 in the reducing atmosphere was evaluated to be 290 ± 20 kJ mol^?1 in the relative density range of 0.64–0.82, which was much smaller than that of CGO10 sintered in air (770 ± 40 kJ mol^?1). The grain-growth activation energy of CGO10 sintered in the reducing atmosphere was evaluated to be 280 ± 20 kJ mol^?1 in the grain size range of 0.34–0.70 μm. The present work describes a systematic investigation of sintering behavior of CGO10 under reduced oxygen partial pressure, which contributes to the first known determination of the fundamental parameters associated with densification and grain growth during early-stage sintering of CGO10 in a reducing atmosphere.     

Effect of ball-milling time on structural characteristics and densification behavior of W-Cu composite powder produced from WO3-CuO powder mixtures

Understanding the microstructure of W–Cu nanocomposite powder is essential for elucidating its sintering mechanism. In this study, the effect of milling time on the structural characteristics and densification behavior of W-Cu composite powders synthesized from WO₃-CuO powder mixtures was investigated. The mixture of WO₃ and CuO powders was ball-milled in a bead mill for 1 h and 10 h followed by reduction by heat-treating the mixture at 800 °C in H₂ atmosphere with a heating rate of 2 °C/min to produce W-Cu composite powder. The microstructure analysis of the reduced powder obtained by milling for 1 h revealed the formation of W–Cu powder consisting of W nanoparticle-attached Cu microparticles. However, Cu-coated W nanocomposite powder consisting of W nanoparticles coated with a Cu layer was formed when the mixture was milled for 10 h. Cu-coated W nanopowder exhibited an excellent sinterability not only in the solid-phase sintering stage (SPS) but also in the liquid-phase sintering stage (LPS). A high relative sintered density of 96.0% was obtained at 1050 °C with a full densification occurring on sintering the sample at 1100 °C. The 1 h-milled W-Cu powder exhibited a high sinterability only in the LPS stage to achieve a nearly full densification at 1200 °C.     

Microstructure characterization of a cobalt-oxide-doped cerium-gadolinium-oxide by analytical and high-resolution TEM

The microstructure and chemistry of 2 mol.% and 5 mol.% cobalt-oxide-doped Ce_0.8Gd_0.2O_1.9 sintered at different temperatures were examined by a combination of electron energy-loss spectroscopy and energy-filtering and high-resolution transmission electron microscopy. Co grain boundary excess was evaluated. It is found that Co solubility in Ce_0.8Gd_0.2O_1.9 is low at temperatures between 800 and 1150 °C, resulting in a large number of Co precipitates at grain boundaries. With increasing sintering temperature, precipitates grow, influencing the Co redistribution and further altering the segregation amount in the grain boundary. The Co grain boundary concentration is shown to increase with the increase of sintering temperature from 890 to 1050 °C, which is suggested to be due to grain growth. It is found that Co grain boundary segregation induces a detectable variation in the ELNES of Ce-M_4,5 and O-K absorption edges, indicating a reduction of Ce atoms in the grain boundary region. The phase of the precipitates was identified as CoO at temperatures between 890 °C and 1150 °C. HRTEM reveals that grain boundaries are less disordered after prolonged sintering time at higher temperature. At a dopant level of 5 mol.% Co oxide in Ce_0.8Gd_0.2O_1.9, the grain boundaries become more disordered, and exhibit a high amount of Co segregation.     

Effect of initial particulate and sintering temperature on mechanical properties and microstructure of WC–ZrO2–VC ceramic composites

Owing to improving the mechanical properties of cemented carbides in high speed machining fields, a new composite tool material WC–ZrO₂–VC (WZV) is prepared from a mixture of yttria stabilized zirconia (YSZ) and micrometer VC particles by hot-press-sintering in nitrogenous atmosphere. Commercial WC, of which the initial particle sizes are 0.2 μm, 0.4 μm, 0.6 μm and 0.8 μm, is mixed with zirconia and VC powder in aqueous medium by following a ball mill process. The sintering behavior is investigated by isostatic pressing under different sintering temperature. The relative density and bending strength are measured by Archimedes methods and three-point bending mode, respectively. Hardness and fracture toughness are performed by Vickers indentation method. Microstructure of the composite is characterized by scanning electron microscopy (SEM). The correlations between initial particles, densification mechanism, sintering temperature, microstructure and mechanical properties are studied. Experimental results show that maximum densification 99.5% is achieved at 1650 °C and the initial particle size is 0.8 μm. When temperature is 1550 °C and particle size is 0.4 μm, the optimized bending strength (943 MPa) is obtained. The best hardness record is 19.2 GPa when sintering temperature is 1650 and particle size is 0.8 μm. The indention cracks propagate around the grain boundaries and the WC particles fracture, which is associated with particle and microcrack toughening mechanism.     

Spark plasma sintering of a commercially available granulated zirconia powder: I. Sintering path and hypotheses about the mechanism(s) controlling densification

Spark plasma sintering (SPS) of a commercially available granulated zirconia powder has been investigated. The “relative density/grain size” trajectory, or “sintering path”, has been established for a constant heating rate (50 °C/min) and a constant applied pressure (100 MPa). In addition, an attempt has been made to identify the mechanism(s) that could be invoked for the control of densification during the SPS experiments.     

Grain-boundary structure and microstructure development mechanism in 2–8 mol% yttria-stabilized zirconia polycrystals

Microstructural developments during sintering in 2 and 3 mol% Y₂O₃-stabilized tetragonal zirconia polycrystals (2Y- and 3Y-TZPs) and 8 mol% Y₂O₃-stabilized cubic zirconia (8Y-CSZ) were systematically investigated in the sintering temperature range of 1100–1500 °C. Above 1200 °C, grain growth in 8Y-CSZ was much faster than that in 2Y- and 3Y-TZPs. In the grain-boundary faces in these specimens, amorphous layers did not exist; however, Y³⁺ ions segregated at the grain boundaries over a width of ∼10 nm. The amount of segregated Y³⁺ ions in 8Y-CSZ was significantly less than in 2Y- and 3Y-TZPs. This indicates that an increase in segregated Y³⁺ ions retards grain growth. Therefore, grain growth behavior during sintering can be reasonably explained by the solute-drag mechanism of Y³⁺ ions segregating along the grain boundary. The segregation of Y³⁺ ions, which directly affects grain growth, is closely related to the driving force for grain-boundary segregation-induced phase transformation (GBSIPT).     

Processing and characterization of sintered reaction bonded Si3N4 ceramics

The present contribution reports the influence of nitridation and sintering conditions on the densification, microstructure, mechanical and thermal conductivity properties of sintered reaction bonded Si₃N₄ (SRBSN) mixed with 3.5% Y₂O₃-1.5% MgO. The nitridation of samples was carried out at 1450 and 1500 °C for different time schedules (2.5, 8 and 16 h) in order to increase β Si₃N₄ phase and subsequently sintering was performed at various temperatures (1850, 1900 and 1950 °C) for 10 h to enhance densification and properties of SRBSN ceramics. It was observed that the density of the samples slightly decreased and β Si₃N₄ phase significantly increased to 87% with increasing nitridation temperature and time. The density of gas pressure sintered (GPS) samples increased with increasing sintering temperature, almost full density was measured for all the samples at the respective sintering temperature (except those samples which were given nitridation at 1500 °C for 16 h). The microstructure of SRBSN samples were characterized by bimodal microstructure with equiaxed and rod like elongated grains and average grain size of SRBSN samples varied between 1.62 and 2.43 μm and aspect ratio of grains varied from 3.78 to 6.88 with varying the sintering temperature. Depending on the sintering density and microstructure, the SRBSN samples exhibited hardness (16.69 to 19.47 GPa), fracture toughness (7.02 to 9.20 MPa·m^1/2) and thermal conductivity (77.32 to 98.52 W/m·K). The coarsening of grain size and aspect ratio negatively affected hardness and fracture toughness, on the contrary the thermal conductivity increased. Among all samples, the SRBSN (which was subjected to nitridation at 1500 °C for 16 h; GPS at 1950 °C for 10 h) measured with good combination of hardness: 17.32 GPa, fracture toughness: 8.36 MPa·m^1/2and thermal conductivity: 98.52 W/m·K.     

Nano-sized zirconium carbide powder: Synthesis and densification using a spark plasma sintering apparatus

Nano-sized zirconium carbide powder was synthesized at 1600 °C by the carbothermal reduction of ZrO₂ using a modified spark plasma sintering (SPS) apparatus. The synthesized ZrC powder had a fine particle size of approximately 189 nm and a low oxygen content of 0.88 wt%. The metal basis purity of the synthesized powder was 99.87%. The low synthesis temperature, fast heating/cooling rate and the effect of current during the modified SPS process effectively suppressed the particle growth. Using the synthesized powder, monolithic ZrC ceramics with high relative density (97.14%) were obtained after the densification at 2100 °C for 30 min at a pressure of 80 MPa by SPS. The average grain size of the densified ZrC ceramics was approximately 9.12 μm.     

Pressure effects and grain growth kinetics in the consolidation of nanostructured fully stabilized zirconia by pulsed electric current sintering

The effect of applied uniaxial pressure on the densification and grain size of nanocrystalline cubic zirconia (c-YSZ) was investigated during sintering by the pulsed electric current sintering (PECS) method. The role of the pressure depended on temperature, being highly significant at lower temperatures and of little significance at higher temperatures. The kinetics of grain growth were determined under PECS conditions. Analysis of the results indicated a grain growth process that is retarded, probably due to the effect of the current on grain boundary energy or dopant segregation. The activation energy for grain growth of c-YSZ was determined as 252 ± 34 kJ mol^?1, a value that is slightly smaller than reported values for microcrystalline samples.     

Self-compacting high density tungsten–bronze composites

Green compacts of W–bronze were encapsulated in shells of bronze powder, placed in a ceramic mold and sintered in alumina tube furnace at 1150 °C. Throughout the sintering cooling stage the differential coefficient of thermal expansion ΔCTE of W–bronze was employed to induce an external compressive densification action. The process included simultaneous sintering, hot isostatic pressing (HIP) and infiltration act to enhance densification. By this technique, pilot sintered compacts of different W50–80 wt.%–pre-mix bronze of 97–99% theoretical density were produced. This process resulted in compacts of higher hardness, higher sintered density and better structure homogeneity as opposed to similar compacts densified by the conventional sintering process. The results showed a gain in hardness by 10–20% and in density by 5–15%. The impact of different cooling rates of 3, 4, 8 and 30 °C min^?1 on sintered density, microstructure and densification mechanisms was examined and evaluated. Low cooling rates of 3 and 4 °C min^?1 gave the best results.     

Effect of high-temperature aging on the thermal conductivity of nanocrystalline tetragonal yttria-stabilized zirconia

The thermal conductivity of yttria-stabilized zirconia (YSZ) thermal barrier coatings increases with high-temperature aging. This common observation has been attributed to the densification of the coatings as porosity sinters out and pores and cracks spheroidize to minimize their surface energy. We show that the thermal conductivity of fully-dense 3 mol.% Y₂O₃ stabilized zirconia (3YSZ) also increases with high-temperature aging, indicating that densification and pore shape changes alone are not responsible for all the observed increase in thermal conductivity of coatings. Instead, there are also increases due to a combination of phase separation and grain growth. The increase in thermal conductivity can be described by a Larson–Miller parameter. It is also found that the increase in thermal conductivity with aging is greatest when measured at room temperature and decreases with increasing measurement temperature. Measured at 1000 °C, the thermal conductivity of zirconia is almost temperature independent and the changes in thermal conductivity with aging are less than 15%, even after aging for 50 h at 1400 °C.     

Fabrication and characterization of pure tungsten using the hot-shock consolidation

Crack-free pure W bulks have been fabricated by SHS assisted hot-shock consolidation (HSC). The tungsten powders were preheated by the heat released through a SHS (self-propagating high-temperature synthesis) reaction before shock wave loading. The duration of preheating was less than 3 min and the preheating temperature was controlled in the range of 700 ~ 1300 °C by adjusting the mass of the SHS mixture. The highest relative density of compacted samples can reach 96.7% T.D. (theoretical density) at 1300 °C under the shock pressure of 3.14GPa. The grain sizes of all compacted samples are nearly the same as the initial powder size of 2 μm. The hardness and modulus of the consolidated pure W bulks were measured using nanoindentation test; and the microstructure was investigated using light microscopy (LM) and scanning electron microscopy (SEM). It is found that the shock pressure plays a more important role than preheating temperature, after the pressure exceeding the crush strength of tungsten powder during the sintering process. At the preheating temperature of 1300 °C, the increase in shock pressure leads to obvious surface melting. For HSC of pure tungsten, the void collapse and surface melting are the main sintering mechanisms. The former one contributes to the densification behavior of powders, and the later one is responsible for the inter-particle bonding; and both of which are dominated by the shock pressure. The advantage of preheating for eliminating the cracks is also demonstrated by the experimental results.     

Sinterability studies of monolithic chromium diboride (CrB2) by spark plasma sintering

Spark plasma sintering (SPS) experiments were conducted to investigate the effect of the processing parameters such as temperature, mechanical pressure and dwell time on densification behavior of monolithic chromium diboride. The sintering experiments were performed at different temperatures ranging from 1100 °C to 1900 °C under the mechanical pressure of 30 MPa–70 MPa for 1 min–15 min duration. The onset temperature for the densification of CrB₂ is observed to be 1300 °C at 50 MPa. High dense chromium diboride (98.4%ρ_th) compact was obtained when processed at 1900 °C under a mechanical pressure of 70 MPa for 15 min duration. Hardness and fracture toughness of high density monolithic CrB₂ (98.4%ρ_th) sample were measured to be 15.89 ± 1.3 GPa and 1.8 ± 0.14 MPa·m^1/2 respectively.     

Processing,phase evaluation and mechanical properties of MoSi2 doped 4TaC–HfC based UHTCs consolidated by spark plasma sintering

In this research, binary 4TaC–HfC based composites were consolidated using carbide materials and addition of 0–15 vol.% MoSi₂ by means of spark plasma sintering at 2000 °C. The nearly full dense and monophase specimens were fabricated with a relative density value higher than 99%. Mechanical tests revealed values of 18–19 GPa and 4–4.3 MPa·m^1/2, for average Vickers hardness and fracture toughness of the composites, respectively. Analysis of linear shrinkage during densification revealed that MoSi₂ addition increased densification rate and decreased the time required to reach full density at 2000 °C. It is proposed that at the intermediate stage of sintering, mass transfer can be accelerated by formation of a silicide based liquid phase and viscous flow mechanisms. The formation of binary 4TaC–HfC solid solution phase enhanced the densification process at the final stage of sintering.