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.     

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 and optical properties of transparent alumina

The microstructure and optical properties are evaluated for alumina sintered by spark plasma sintering at temperatures between 1100 and 1550 °C. With increasing sintering temperature, grain growth and densification occur up to 1250 °C, and above 1300 °C, rapid grain growth and pore growth occur. Light transmission increases with the densification and decreases with the grain/pore growth. It is found that the total forward transmission and the reflection of light are related to the porosity and the pore growth, whereas the in-line transmission and the light absorption are related to the grain size and the defects, respectively. The relationships are explained by using the Mie scattering theory, model prediction and observed microstructural characteristics.     

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).     

Microstructure and mechanical properties and of pulse plasma compacted WC - Co

Tungsten carbides-based inserts have been considered as one of the dominant hard materials in the cutting industry, receiving great interest for their excellent combination of mechanical properties. Pulse plasma compaction (PPC) process has been applied to a series of WC-Co samples with varying sintering temperature, initial particle size and sintering pressure in order to study the mechanical and microstructural behaviour. The quality of the products, as well as the mechanical properties and microstructural features this process yields, are commendable and worth looking into. A high hardness of more than 2000 HV has been achieved while a maximum fracture toughness of 15.3 MPa √ m was recorded in samples that were sintered at 1100 °C and 100 MPa. Microstructural features like grain growth and other properties are discussed with respect to the varying parameters. While grain size shows an incremental pattern with increasing temperature, it was still possible to limit them to a great extent ensuring high mechanical properties. The effect of sintering pressure in the range of 60–100 MPa, while keeping sintering temperature constant, was found to be almost negligible.     

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.     

Grain growth inhibition by connected porosity in sintered niobium

Pore–boundary interaction plays an important role in densification during solid-state sintering. This paper reports the evolution of porosity and grain size in niobium sintered at 2073 and 2273 K for different sintering times. The densification curves show a decrease in porosity up to 8 and 4 vol.% after 10,800 s for the samples sintered at 2073 and 2273 K, respectively. Grain growth is observed to take place together with this decrease in porosity. A new model for grain growth inhibition during sintering is proposed for connected porosity. This model considers that the moving grain boundaries and the outer surface of cylindrical pores remain in contact during grain growth and that energy dissipation takes place owing to the fact that the grain boundary is moving relative to the porosity. Our mechanism is akin to a friction between the grain boundary and the connected porosity at their contact region. In contrast to the traditional particle–grain boundary bypassing mechanisms, the present model is not a purely geometrical relationship but is material dependent. The model gives agrees well with experimental results obtained in this paper for sintered niobium as well as for other sintered materials reported in the literature. Our model is a novel approach to treating grain growth inhibition by pores during the sintering stage in which the porosity becomes interconnected.     

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.     

Texture evolution and mechanical properties of ion-irradiated Au thin films

Microstructure control of thin films is of particular importance for improving the reliability of microdevices in terms of electromigration, fatigue damage and hillocking. High-energy ion bombardment has turned out to be an appropriate modification instrument as it leads to selective grain growth, resulting in single-crystal-like structures. The current work addresses the effect of 7 MeV Au⁺ and 1.5 MeV N⁺ irradiation at high fluences (up to 45 × 10¹⁶ ions cm^?2) on the microstructure and the mechanical properties of 500 nm Au thin films of small initial grain size (70–90 nm). The following microstructure changes were observed: selective grain growth, texture changes, sputtering, interfacial degradation, formation of geometrically necessary dislocations, and defect clusters. Hardening behavior was found to be a consequence of grain growth (Hall–Petch effect) and the formation of ion-induced defects.     

Effect of sintering temperature on the structure and magnetic properties of SmCo5/Fe nanocomposite magnets prepared by spark plasma sintering

Highly dense SmCo₅/Fe nanocomposite bulk magnets were prepared by spark plasma sintering of magnetic field-milled SmCo₅/Fe nanocrsytalline powders. The sintering experiments were conducted with varying temperatures of 973–1123 K. The resultant bulk materials had densities of 85–98% and mean grain sizes of 17–30 nm. The SEM analysis showed that the bulk samples prepared at higher sintering temperature exhibited dense and uniform microstructure. The XRD studies in complement with energy dispersive X-ray analysis revealed that the bulk magnets sintered at or above 1073 K exhibited Sm(Co,Fe)₅ as main phase, along with other secondary phases such as Sm₂(Co,Fe)₁₇ and α-Fe(Co). A single-phase behavior with high remanence ratios (0.67–0.77) for the nanocomposite magnets was demonstrated by the magnetic measurements. In the present study, the sintering temperature of 1073 K was found to be optimum in achieving relatively high coercivity (8.2 kOe), magnetization (97.5 emu/g) and energy product (278.7 kJ/m³) for the SmCo₅/Fe nanocomposite bulk magnets.     

Sintering behavior and non-linear properties of ZnO varistors processed in microwave electric and magnetic fields at 2.45 GHz

A study of the densification behavior and grain growth mechanisms of ZnO-based varistors composed of 98 mol.% ZnO–2 mol.% (Bi₂O₃, Sb₂O₃, Co₃O₄, MnO₂) has been carried out. The pressed samples were sintered in microwave electric (E) and magnetic (H) fields using a single-mode cavity of 2.45 GHz. The effect of the sintering temperature (900–1200 °C), holding time (5–120 min) and sintering mode (E, H) on the microstructure and electrical properties of the sintered varistor samples were investigated. The grain growth kinetics was studied using the simplified phenomenological equation Gⁿ = kte^(?Q/RT). The grain growth exponent (n) and apparent activation energy (Q) values were estimated for both electric and magnetic heating modes and were found to be n = 3.06–3.27, Q = 206–214 kJ mol^?1, respectively. The lower value of n estimated in the E field was attributed to a volume diffusion mechanism, whereas the higher n value in the H field sintering was correlated mainly to a combined effect of volume and surface diffusion processes. Samples sintered in the H and E fields showed high final densities. Moreover, the ones sintered in the H field presented slightly higher density values and bigger grains for all sintering temperatures than E field heated ones. The optimal sintering conditions were achieved at 1100 °C for a 5 min soaking time for both H and E field processed samples, where respectively densities of 99.2 ± 0.5% theoretical density (TD) and 98.3 ± 0.5% TD along with grain size values of G = 7.2 ± 0.36 μm and G = 6.6 ± 0.33 μm were obtained. Regarding the electrical properties, breakdown voltage values as high as 500–570 V mm^?1 were obtained, together with high non-linear coefficients α = 29–39 and low leakage currents (J_l ≈ 5 × 10^?3 mA cm^?2), respectively, for E and H field sintered varistor samples. Moreover, samples sintered in an H field systematically exhibited higher breakdown voltage values compared to the ones sintered in the E field. This was attributed to an improved coupling between the H field and the present dopants within the ZnO matrix, this latter being mostly semiconductive, thus leading to an enhanced reactivity and improved properties of the electrostatic barrier.     

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.     

The role of the activator rich-W interboundary layer on liquid phase sintering of W–pre-alloy bronze composites of Fe and Co additions

In this study, the effects of 1–3 wt.% Fe and Co additions on the sintering of W 40–80wt.%–pre-alloy bronze Sn 10 wt.%–Cu compacts were examined. The isothermal part of the sintering process was conducted at temperatures ranging from 920 °C to 1300 °C for 3 h. Relative sintered densities in the range of 70–90% were achieved. The gain in the sintered densities due to activator addition was 5–15%. The sintering activation effects started at temperatures as low as 600 °C below the bulk eutectic temperature. SEM, XRD and EDX tests proved that Fe and Co-rich crystalline interboundary layers completely wet the tungsten grain boundaries in the solid state and act as a short-circuit diffusion path for mass transportation. These outcomes seem to follow the classical activated sintering model and contrast with some other recently proposed models, whereby a detected nanometer-thick, activator-enriched disordered film at W grain boundary is considered fully responsible for the solid-state activated sintering.     

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.     

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.     

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.     

Effect of Al2O3 ceramic binder on mechanical and microstructure properties of spark plasma sintered WC-Co cermets

This study investigates how the partial replacement of Co with Al₂O₃ ceramic binder has an effect on the sintering behaviour, microstructure, and final mechanical properties of WC-Co cermets via spark plasma sintering. To examine this, three batches (WC-6 wt%Co, WC-3 wt%Co-3 wt%Al₂O_3, and WC-6 wt%Al₂O₃) were mixed through high energy ball mill, and sintering was carried out at temperatures of 1350 °C and 1600 °C. The results showed nearly full dense WC-Co cermets at different temperatures. It was shown that WC-6 wt%Al₂O₃, in comparison to reference WC-6 wt%Co cermet, not only led to the rise in sintering temperature from 1350 °C to 1600 °C, but also reduced its strength and toughness. But replacing some part of Co with alumina (WC-3 wt%Co-3 wt%Al₂O₃) exhibited the combination of high strength (1095 MPa), hardness (17.62 GPa), and fracture toughness (19.46 MPa·m^1/2).     

Taguchi analysis on the effect of process parameters on densification during spark plasma sintering of HfB2-20SiC

Field assisted sintering (FAST) has emerged as a useful technique to densify ultra high temperature ceramics like HfB₂-20SiC to a high density at relatively low temperatures and shorter times. The effect of various process variables on the densification during spark plasma sintering of HfB₂-20SiC was studied using Taguchi analysis. The statistical analysis identified sintering temperature as the most significant parameter affecting the densification of HfB₂-20SiC material. A density of 99% was achieved on sintering at 2373 K for 8 min at 30 kN pressure and heating rate of 100 K/min.     

Microstructural development and mechanical properties of reactive hot pressed nickel-aided TiB2-SiC ceramics

TiB₂-SiC composites with different amounts of Ni (0, 2 and 5 wt.%) added as sintering aid were fabricated by reactive hot pressing (RHP). The mechanical properties were assessed under ambient conditions and the flexural strength was further tested in the temperature range of 700–1000 °C. The microstructures of the composites were characterized by a scanning electron microscope (SEM), transmission electron microscope (TEM) and energy-dispersive spectrometer (EDS). The flexural strength degradation mechanism occurring at elevated temperatures was studied. Addition of a moderate amount of Ni led to an improvement of the mechanical properties at room temperature. For the investigated ceramic composites, TiB₂-SiC-5 wt.% Ni sample showed significantly enhanced mechanical properties, i.e., a flexural strength of 1121 ± 31 MPa, a fracture toughness of 7.9 ± 0.58 MPa·m^1/2, a hardness of 21.3 ± 0.62 GPa, and a relative density of 98.6 ± 1.2%. Ni distributed along grain boundaries improved the interface strength. The improved fracture toughness was ascribed to crack deflection, grain rupture and crack shielding effect of Ni. A substantial strength degradation occurred at elevated temperatures, which was attributed to softening of the grain boundaries, surface oxidation and sliding of grain boundaries. The elastic modulus was found to decrease with increasing temperature.