Densification and grain growth of Gd2Zr2O7 nanoceramics during pressureless sintering

Gd₂Zr₂O₇ nanoceramics were fabricated using pressureless sintering method, in which the nanopowders were synthesized via solvothermal approach. The effects of starting powders on grain growth and densification during sintering of ceramics were revealed. Two distinct pressureless sintering methods were investigated, including conventional and two-step sintering. The sample grain size increases abruptly as sintering temperature increases during conventional sintering. In contrast, in two-step sintering, abnormal or discontinuous grain growth was suppressed in the second step, leading to Gd₂Zr₂O₇ nanoceramics formation (average grain size 83 nm, relative density ∼93%). Such distinct behaviors may originate from the interplay between kinetic factors such as grain boundary migration and diffusion. Moreover, suppression of grain growth and promotion of densification in the two-step sintering are mainly due to dominant role of grain boundary diffusion during the second-step sintering process.     

Hot pressing of nanocrystalline zinc oxide compacts: Densification and grain growth during sintering

Sintering behavior of nanocrystalline zinc oxide (ZnO) powder compacts using hot pressing method was investigated. The sintering conditions (temperature and total time) and results (density and grain size) of two-step sintering (TSS), conventional sintering (CS) and hot pressing (HP) methods were compared. The HP technique versus CS was shown to be a superior method to obtain higher final density (99%), lower sintering temperature, shorter total sintering time and rather fine grain size. The maximum density achieved via HP, TSS and CS methods were 99%, 98.3% and 97%, respectively. The final grain size of samples obtained by HP was greater than that of TSS method. However, the ultra-prolonged sintering total time and the lower final density (88 ks and 98.3%) are the drawbacks of TSS in comparison with the faster HP (17 ks and 99%) method.     

Dynamic pore coalescence in nanoceramic consolidated by two-step sintering procedure

Two-step sintering (TSS) concept was adopted in the consolidation of 3 mol% yttria doped zirconia nanopowder. Partially densified bodies with 87% theoretical density (TD) were firstly prepared using high-pressure spark plasma sintering (SPS) technique and followed by second-step pressureless sintering. The samples achieved only 96% TD final density after 30 h soaking. It was found that the densification process was impeded by dynamic pore coalescence with a pore growth factor of 10. The phenomenon was explained by the coalescence of interconnected small pores generated by differential sintering of nanoceramic green compacts. Such pore coalescence was accompanied with particle movement, which resulted in sintering state deviating from the frozen state. Present results indicated that the active range for particle rearrangement was greatly extended during nanoceramic sintering and the efficiency of TSS approach was greatly dependent on the homogeneity of green bodies.     

Two-step sintering of M-type strontium ferrite with high coercivity

Two-step sintering (TSS) was applied on the M-type Sr-hexaferrite to control grain growth and form a desirable microstructure during the final stage of sintering. The process involved T₁ (temperature in the first sintering stage), t₁ (holding time at T₁), T₂ (temperature in the second sintering stage), and t₂ (holding time at T₂). The effects of each setting parameter on the density, grain growth, degree of orientation and magnetic properties were systematically investigated. The results revealed that T₁ was the main factor that primarily controlled microstructure and magnetic properties. Compared with conventional sintering (CS) process, the magnets with smaller average grain size were achieved by TSS, which suggested that two-step sintering could improve the coercivity of Sr-hexaferrites. It was shown that the high integrated magnetic properties for Sr-hexaferrites, including B_r =?440.4 mT, H_cj =?328.2?kA/m and (BH)_max =?37.6?kJ/m³, were obtained under the optimum processing condition: T₁ =?1200?°C, T₂ =?1000?°C, t₁ =?5?min, and t₂ =?2?h.     

Effect of temperature and holding time on the densification of alumina obtained by two-step sintering

The two-step sintering technique is a process of controlling the sintering curve, which provides materials with higher density and smaller grain size when compared to conventional sintering. This technique was evaluated by optical dilatometry with three commercial alumina powders of different purity (92, 96 and 99 wt% of Al₂O₃) and particle size (between 0.73 and 2.16 µm). Different sintering conditions in the first (temperature, T1) and second (temperature, T2, and holding time, t2) steps were studied in order to evaluate the effect of these variables on densification and grain growth. Considering T1 as the temperature at which a relative density (D_rel) of 83% was achieved, and for the range of conditions tested, it was found that higher D_rel values and lower grain size of alumina were obtained with higher T2 and lower t2. Alumina with 99 wt% purity sintered at T1 of 1550 °C for 5 min and T2 of 1500 °C for 4 h showed the best relationship between higher densification (~96% relative density) and reduced grain size (0.94±0.15 µm). Thus, this work demonstrated that suppression of grain growth can also be obtained for commercial alumina.     

Nitrate fusion synthesis and two-step sintering of nanocrystalline yttria stabilized hafnia powders

Bulk quantities of nanocrystalline yttria stabilized hafnia (YSH) powders with crystallite size ranging from 8 to 15 nm were successfully prepared for the first time through nitrate fusion synthesis at a temperature as low as 673 K. The yttrium content was varied from 6 to 30 mol%. The dependence of the properties of the final product on the quantity of the dopant was investigated. Microstructural investigations were carried out with scanning electron microscopy and transmission electron microscopy. A maximum relative sintered density of 98.2 ± 0.3% T.D (theoretical density) was obtained for YSH containing 10 mol% yttrium by using “two-step sintering” at a final temperature of 1773 K. Anisotropic shrinkage factor (0.70–0.95) was found to vary linearly with the compaction pressure. SEM investigations reaffirmed that the sintered pellets comprised uniform distribution of faceted grains and elemental mapping revealed that yttrium is distributed uniformly in these sintered YSH monoliths.     

Densification mechanism and microstructure characteristics of nano- and micro- crystalline alumina by high-pressure and low temperature sintering

Fully dense ceramics with retarded grain growth can be attained effectively at relatively low temperatures using a high-pressure sintering method. However, there is a paucity of in-depth research on the densification mechanism, grain growth process, grain boundary characterization, and residual stress. Using a strong, reliable die made from a carbon-fiber-reinforced carbon (C_f/C) composite for spark plasma sintering, two kinds of commercially pure α-Al₂O₃ powders, with average particle sizes of 220 nm and 3 μm, were sintered at relatively low temperatures and under high pressures of up to 200 MPa. The sintering densification temperature and the starting threshold temperature of grain growth (T_sg) were determined by the applied pressure and the surface energy relative to grain size, as they were both observed to increase with grain size and to decrease with applied pressure. Densification with limited grain coarsening occurred under an applied pressure of 200 MPa at 1050 °C for the 220 nm Al₂O₃ powder and 1400 °C for the 3 μm Al₂O₃ powder. The grain boundary energy, residual stress, and dislocation density of the ceramics sintered under high pressure and low temperature were higher than those of the samples sintered without additional pressure. Plastic deformation occurring at the contact area of the adjacent particles was proved to be the dominant mechanism for sintering under high pressure, and a mathematical model based on the plasticity mechanics and close packing of equal spheres was established. Based on the mathematical model, the predicted relative density of an Al₂O₃ compact can reach ～80 % via the plastic deformation mechanism, which fits well with experimental observations. The densification kinetics were investigated from the sintering parameters, i.e., the holding temperature, dwell time, and applied pressure. Diffusion, grain boundary sliding, and dislocation motion were assistant mechanisms in the final stage of sintering, as indicated by the stress exponent and the microstructural evolution. During the sintering of the 220 nm alumina at 1125 °C and 100 MPa, the deformation tends to increase defects and vacancies generation, both of which accelerate lattice diffusion and thus enhance grain growth.     

Effect of two-step sintering on the hydrothermal ageing resistance of tetragonal zirconia polycrystals

The effects of two-step sintering (TSS) on the mechanical properties and hydrothermal ageing resistance of yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) were investigated. In TSS, the first step involved heating the samples up to 1400 °C at a heating rate of 10 °C/min and holding the samples at this temperature for 1 min. The second step involved sintering by cooling the samples down to 1200 °C and holding the samples at this temperature for various holding times (t) ranging from 0 to 30 h before cooling to room temperature. Moreover, TSS promoted densification with increasing holding time without sacrificing the mechanical properties of the sintered body and causing abnormal grain growth. The average grain size was found not to be affected by the long holding times, and the final microstructure composed of a uniformly distributed tetragonal grain having sizes ranging from 0.24 to 0.26 µm. The beneficial effect of TSS in suppressing the hydrothermal ageing of Y-TZP has been revealed in the present work. In particular, samples sintered at t=20 and 30 h exhibited excellent resistance to low-temperature degradation when exposed to superheated steam at 180 °C, attributed mainly to the enhance densification of the sintered bodies.     

Densification and grain growth during solid state sintering of LaPO4

This work is devoted to the kinetic study of densification and grain growth of LaPO₄ ceramics. By sintering at a temperature close to 1500 °C, densification rate can reach up to 98% of the theoretical density and grain growth can be controlled in the range 0.6–4 μm. Isothermal shrinkage measurements carried out by dilatometry revealed that densification occurs by lattice diffusion from the grain boundary to the neck. The activation energy for densification (E_D) is evaluated as 480 ± 4 kJ mol⁻¹. Grain growth is governed by lattice diffusion controlled pore drag and the activation energy (E_G) is found to be 603 ± 2 kJ mol⁻¹. The pore mobility is so low that grain growth only occurs for almost fully dense materials.     

Analysis of abnormal grain growth behavior during hot-press sintering of boron carbide

Dense boron carbide bearings with a central through hole were fabricated by hot-press sintering. When the sintering temperature was above the critical grain growth temperature, an increase in the applied pressure at 2100 °C caused a distinct abnormal grain size region. Two grain growth mechanisms were explored; normal grain growth (NGG) is controlled by a grain boundary diffusion mechanism whereas the abnormal grain growth (AGG) pattern abides by the ‘Bose–Einstein’ grain growth law.     

Densification of nanocrystalline MgO ceramics by hot-pressing

Densification of pure nanocrystalline MgO powder with 10 nm particle size by hot-pressing was investigated in the temperature range 700–800 °C, applied pressure range 100–200 MPa, and for durations of up to 240 min. It was shown that significant densification under the pressure begins above 440 °C. Densities higher than 99.5% with grain size of 73 nm were achieved at 790 °C and 150 MPa for a 30 min duration. Remarkable densification from 90 to 99.5% was observed by temperature change from 700 to 790 °C, for which the grain size was doubled only. The final grain size decreased with increasing the applied pressure. Higher shrinkage rates and cumulative shrinkages were recorded by the application of pressure at 550 °C rather than from room temperature. The temperature at which the pressure was applied is crucial in determining the maximum shrinkage rate in the nanocrystalline compacts. This effect was related to the morphological changes of the particles caused by plastic deformation at lower temperatures. Analysis of the densification rate and its comparison to the literature data was in agreement with Coble creep, where self-diffusion of Mg²⁺ cations along the grain boundaries acts as a main densification mechanism.     

Densification and grain growth behaviour of high-purity MgO ceramics by hot-pressing

High-purity MgO ceramics with a relative density higher than 99.60% and a mean grain size of 8.1 µm were prepared by hot-pressing at 1450 °C and 35 MPa for 120 min. The MgO ceramic was 130 mm in diameter and 10 mm in height. The densification mechanism and grain growth of MgO powder during the sintering process were investigated based on the principles of general deformation and classical phenomenological kinetic theory. The threshold pressure of plastic deformation at the initial sintering stage was also analysed. The results suggest that plastic deformation is the dominant densification mechanism during the initial period and that an applied pressure of 20 MPa is sufficient for the deformation. During the final period, Mg²⁺ diffusion along the grain boundaries controls the densification process, and the grain growth activation energy at the final stage is estimated as 336.38±2.35 kJ mol⁻¹.     

Densification and grain growth kinetics of Ce0.9Gd0.1O1.95 in tape cast layers: The influence of porosity

The sintering behavior of Ce_0.9Gd_0.1O_1.95 (CGO) tape cast layers with different porosity was investigated by an extensive characterization of densification, microstructural evolution, and applying the constitutive laws of sintering. The densification of CGO tapes associates with grain coarsening process at the initial sintering stage at T < 1150 °C, which is mainly influenced by small pores and intrinsic characteristics of the starting powders. At the intermediate sintering stage, densification is remarkably influenced by large porosity. Moreover, the sintering constitutive laws indicate that increasing the initial porosity from 0.38 to 0.60, the densification at the late stage is thermally activated with typical activation energy values increasing from 367 to 578 kJ mol⁻¹. Similar effect of the porosity is observed for the thermally activated phenomena leading to grain growth in the CGO tapes. The analysis of sintering mechanisms reveals that the grain growth behavior at different porosity can be described using an identical master curve.     

Pure-phase BiFeO3 ceramics with enhanced electrical properties prepared by two-step sintering

A two-step sintering method was employed to fabricate BiFeO₃ ceramics and the influences of sintering conditions on the structural, dielectric, ferroelectric, and piezoelectric properties were investigated. It was found that high-density and pure-phase BiFeO₃ ceramics could be successfully achieved through the two-step sintering method by optimizing the sintering conditions. Furthermore, ferroelectricity and piezoelectricity were also improved by the two-step sintering method. The pure-phase BiFeO₃ ceramics obtained at T₁=850 °C and T₂=750 °C exhibited high resistivity (1.57×10⁶ Ω.m), large remanent polarization (P_r=0.80μC/cm²) and strong piezoelectric activity (d₃₃=42pC/N). All these results indicated that the two-step sintering method was an effective way to improve the properties of the BiFeO₃ ceramics.     

Sintering dense nanocrystalline 3YSZ ceramics without grain growth by plastic deformation as dominating mechanism

It is difficult to obtain nanocrystalline ceramic bulks due to its high surface activity at high temperatures. In the study, in order to achieve both high density and ultrafine morphology, the plastic deformation was induced by an ultrahigh pressure at a deliberately selected temperature, which was much lower than the threshold temperature for rapid grain growth. According to the ultra-high pressure route, nanocrystalline 3YSZ ceramics without grain growth were fully densified at 900?°C under 1.5?GPa. Both direct microstructural observations and calculation results proved that the plastic deformation including high temperature yield and sliding played a dominant role in densification during the sintering process.     

Two-step sintering of 0.93Bi0.5Na0.5TiO3-0.07BaTiO3 lead-free piezoelectric material

Two-step sintering (TSS) as an efficient sintering method for obtaining dense microstructure while preventing excess grain growth was used for sintering 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ composition which is located near the morphotropic phase boundary of this binary system. In order to compare the obtained microstructure and piezoelectric properties, conventional single step sintering (SSS) was also examined. Microstructure evolution during sintering at different temperatures was investigated to find the optimum sintering temperature. Ferroelectric hysteresis loop as well as unipolar strain behavior of optimally sintered ceramics was studied. According to density measurement and microstructure studies of the prepared ceramics, TSS resulted in finer and more dense and uniform microstructure compared to SSS method. As a result remnant polarization of TSSed ceramic was increased by 35% and its coercive field was decreased by 16%. The inverse piezoelectric coefficient of the SSSed and TSSed was obtained 220 and 300 p.m./V, respectively. These values are high enough for practical applications such as actuators. The obtained results clearly showed that TSS is capable of sintering 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ at temperatures lower than which is required for SSS method. Therefore the composition stoichiometry is maintained after sintering and denser microstructure without abnormal grain growth is obtained which is responsible for improved electrical properties of the piezoceramics.     

Micro-hydrothermal reactions mediated grain growth during spark plasma sintering of a carbonate-containing hydroxyapatite nanopowder

A carbonate-containing hydroxyapatite nanopowder was consolidated by spark plasma sintering at the temperatures ranging from 650 to 1100 °C. It was found that the water released by dehydroxylation was trapped inside the nanopores in the densified HAp bodies over 900 °C. Based on the analysis by the X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscope, the water-nanopore system was evaluated and its effect on the grain growth was also investigated. It was revealed that the water existed inside the closed nanopores most probably resulted in the formation of local micro-hydrothermal environments inside bulk HAp ceramics during SPS. Therefore, the grain growth was enhanced by the local micro-hydrothermal reactions activated above 900 °C. In addition, abnormal grain growth was also observed when a higher temperature or higher heating rate was employed, which may be attributed to the local highly active hydrothermal reactions.     

Grain growth stagnation in the dense nanocrystalline yttria prepared by combustion reaction and quick pressing with an ultra-high heating rate

Combustion reaction plus quick pressing was a developing technique that used the Joule heating effect of combustion reaction to sinter ceramics, and allows very high heating rate, short soaking duration and high pressure for densification of ceramics. By taking advantages of the particular conditions of this method, pure yttria ceramics with a relative density of 98.5% and an average grain size of 50 nm were obtained at 1620 K and 170 MPa. Moreover, the investigation on the grain growth of sintered yttria was carried out by analyzing the microstructure evolutions and responsible mechanisms. The combined effect of the ultra-high heating rate and the high pressure applied on compact at the peak temperature was effective in suppressing particle coarsening and enhancing densification. Besides, under the decreased sintering temperature and soaking duration, the retained nanostructure assisted to inhibit final-stage grain growth while without impeding the further densification of nanocrystalline ceramics.     

Sintering highly dense ultra-high temperature ceramics with suppressed grain growth

Grain coarsening normally occurs at the final stage of sintering, resulting in trapped pores within grains, which deteriorates the density and the performance of ceramics, especially for ultra-high temperature ceramics (UHTCs). Here, we propose to sinter this class of ceramics in a specific temperature range and coupled with a relatively high pressure. The retarded grain boundary migration and pressure-enhanced diffusion ensure the proceeding of densification even at final stage. A highly dense TaC ceramic (98.6 %) with the average grain size of 1.48 μm was prepared under 250 MPa via high pressure spark plasma sintering using a C_f/C die at 1850 °C. It was suggested that the final-stage densification is mainly attributed to grain boundary plastic deformation-involved mechanisms. Compared to the usual sintering route using a high temperature (>2000 °C) and normal pressure (<100 MPa), this work provides a useful strategy to acquire highly dense and fine-grained UHTCs.     

Two-step sintering of nanocrystalline 8Y2O3 stabilized ZrO2 synthesized by glycine nitrate process

Two-step sintering was employed to consolidate nanocrystalline 8 mol% yittria stabilized zirconia processed by glycine-nitrate method. Results verified the applicability of this method to suppress the final stage of grain growth in the system. The grain size of the high density compacts (>97%) produced by two-step sintering method was seven times less than the pieces made by the conventional sintering technique. Up to ∼96% increase in the fracture toughness was observed (i.e. from 1.61 to 3.16 MPa m^1/2) with decreasing of the grain size from ∼2.15 to ∼295 nm. A better densification behavior was also observed at higher compacting pressures.