Field-Assisted Sintering of Nanocrystalline Titanium Nitride

Nanosized TiN powder was densified via field-assisted sintering at temperatures of 1150°–1350°C and a pressure of 66 MPa under vacuum. A maximum relative density of ∼97% and a maximum mean grain size of 150–200 nm were obtained. Densification and microstructural evolution have been discussed, in terms of superplasticity and electric-field effects.     

Novel Fabrication Route to Al2O3–TiN Nanocomposites Via Spark Plasma Sintering

A novel method for the preparation of Al₂O₃–TiN nanocomposites was developed. A mixture of TiO₂, AlN, and Ti powder was used as the starting material to synthesize the Al₂O₃–TiN nanocomposite under 60 MPa at 1400°C for 6 min using spark plasma sintering. X-ray diffractometry, scanning electron microscopy, and transmission electron microscopy were used for detailed microstructural analysis. Dense (up to 99%) nanostructured Al₂O₃–TiN composites were successfully fabricated, the average grain size being less than 400 nm. The fracture toughness ( K _{I C} ) and bending strength (σ_b) of the nanostructured Al₂O₃–TiN composites reached 4.22±0.20 MPa·m^1/2 and 746±28 MPa, respectively.     

Fine-grained transparent MgAl2O4 spinel obtained by spark plasma sintering of commercially available nanopowders

A high transmittance/small grain size combination for pure spinel ceramics from commercially available nanopowders without sintering aids can be obtained by SPS sintering. By using a low heating rate ≤10 °C/min and a sintering temperature ≤1300 °C, a transparent polycrystalline MgAl₂O₄ spinel was fabricated by SPS with an in-line transmission of 74% and 84% for 550 nm (visible) and 2000 nm (NIR) wavelengths respectively. A small average grain size of about 250 nm was obtained and the pores located at the multiple grain junctions have a mean size of about 20 nm. The high in-line transmission is linked not only to the low residual porosity but particularly to the very small size of pores.     

Synthesis and two-step sintering behavior of sol–gel derived nanocrystalline corundum abrasives

Nanocrystalline corundum abrasive with mean crystal size of less than 100 nm was synthesized by two-step sintering method using sol–gel process. A remarkable suppression of grain growth was achieved by controlling sintering temperature and taking advantage of sintering aids during the final stage of a two-step sintering process. The grain size of the high densification samples (>99% theoretical density) produced by two-step sintering method was about 10 times less than the samples made by the conventional sintering technique. The microstructure of the samples was homogeneous without abnormal grain growth and the sol–gel derived corundum abrasive with two-step sintering technique exhibited excellent mechanical properties and wear resistance compared to those sol–gel derived corundum abrasive with conventional sintering methods and fused corundum abrasive.     

Spark plasma sintering of TiN ceramics codoped with SiC and CNT

In this research, we investigated the effects of SiC and multi-walled carbon nanotube (MWCNTs) addition on the densification and microstructure of titanium nitride (TiN) ceramics. Four samples including monolithic TiN, TiN-5?wt% MWCNTs, TiN-20?vol% SiC and TiN-20?vol% SiC-5?wt% MWCNTs were prepared by spark plasma sintering at 1900?°C for 7?min under 40?MPa pressure. X-ray powder diffraction patterns and scanning electron microscope (SEM) micrographs of the prepared ceramics showed that no new phase was formed during the sintering process. The highest calculated relative density was related to the TiN ceramic doped with 20?vol% SiC, while the sample doped with 5?wt% MWCNTs presented the lowest density. In addition, the SEM investigations revealed that the addition of sintering aids e.g. SiC and MWCNTs leads to a finer microstructure ceramic. These additives generally remain within the spaces among the TiN particles and prohibit extensive grain growth in the fabricated ceramics.     

Densification and grain growth of nanocrystalline 3Y-TZP during two-step sintering

Two-step sintering (TSS) was applied on nanocrystalline yttria tetragonal stabilized zirconia (3Y-TZP) to control the grain growth during the final stage of sintering. The process involves firing at a high temperature (T1) followed by rapid cooling to a lower temperature (T2) and soaking for a prolonged time (t). It is shown that for nanocrystalline 3Y-TZP (27 nm) the optimum processing condition is T1 = 1300 °C, T2 = 1150 °C and t = 30 h. Firing at T1 for 1 min yields 0.83 fractional density and renders pores unstable, leading to further densification at the lower temperature (T2) without remarkable grain growth. Consequently, full density zirconia ceramic with an average grain size of 110 nm is obtained. XRD analysis indicated that the ceramic is fully stabilized. Single-step sintering of the ceramic compact yields grain size of 275 nm with approximately 3 wt.% monoclinic phase. This observation indicates that at a critical grain size lower than 275 nm, phase stabilization is induced by the ultrafine grain structure.     

Spark Plasma Sintering of Magnesia-Doped Alumina with High Hardness and Fracture Toughness

The effect of grain size of magnesia and its content as well as spark plasma sintering conditions on the density, grain size, strength, hardness, and toughness of alumina was investigated. Spark plasma sintering conditions were optimized at 1150°C/5 min/175°C/min. Addition of 100 nm magnesia gave higher density levels (99.5%), while better strength (600 MPa), hardness (25 GPa), and fracture toughness (4.5 MPa·m^1/2) were obtained with 15 nm magnesia. The good strength and hardness is attributed to the submicrometer grain size of the matrix, and the improved toughness to the presence of Mg-rich nanoparticles and nanopores at grain boundaries.     

Sintering of titania nanoceramic: Densification and grain growth

Two-step sintering (TSS) has been applied in the current study to suppress the accelerated grain growth of TiO₂ nanopowder compacts in the final sintering stage. While the grain size ranges between 1 and 2 μm in the full dense structures produced by pressureless conventional sintering (CS), application of two-step sintering has led to a remarkable grain size decline to ～250 nm. With regard to the expensive procedure of spark plasma sintering (SPS), similar density and grain size results determine the straightforward TSS method as a desirable rival for SPS.     

Design of Electroceramics for Solid Oxides Fuel Cell Applications: Playing with Ceria

Nanostructured samaria- and gadolinia-doped ceria (SDC and GDC) powders were synthesized at low temperature (400°C) using diamine-assisted direct coprecipitation method. Fast-firing (f.f.) processes, where sintering temperatures are reached in a short time to promote lattice diffusion, were compared with conventional sintering, for the formation of dense microstructures from the nanostructured powders. Highly dense SDC and GDC samples (96%) with reduced grain size (150 nm) were obtained by f.f. even at 1300°–1400°C and, unexpectedly, high electrical conductivity and low blocking effect at grain boundary was obtained. Conventionally sintered samples showed that the grain boundary resistivity decreased with increasing the grain size, in agreement with the increase in geometrical bulk volume/grain boundary area ratio. Conversely, f.f. samples showed grain boundary resistivity smaller for small grain size. The above effect was observed only for high dopant (>10% molar) contents. The combined effect of powder grain size, dopant content, and sintering temperature–time profile, can be exploited to tune ceria microstructures for specific ionic device applications.     

Pressureless low temperature sintering of nanocrystalline zirconia ceramics via dry powder processing

Pressureless sintering approaches provide a simple avenue to manufacture dense ceramic parts with minimal processing equipment, but current pressureless sintering techniques have yet to demonstrate capabilities of producing dense ceramics while maintaining sub-50 nm grain sizes. Nanocrystalline yttria stablized zirconia ceramics were process from 4 mol% yttria stablized zirconia (4YSZ) nanopowders with a crystallite size of 7.5 nm using dry cold isostatic pressing (CIP) where powders are dried immediately prior to green compact formation and CIP vacuum bagging. It is shown that CIP pressures >75 000 psi (517 MPa) effectively remove pores larger than 100 nm and that pressureless sintering occurs at reduced temperatures for green densities ≥50%. Though the sintering kinetics are shown to be similar to other zirconia nanopowder sintering studies, the small initial crystallize size and reduced sintering temperature allowed densities as high as 97.2%, while retaining a ceramic grain size at or below 40 nm. Produced nanocrystalline 4YSZ ceramics with a grain size of 30.3 nm and a density of 96.3% had Vicker's hardnesses as high as 14.2 GPa and Vicker's indentation fracture resistance of 3.43 MPa·, demonstrating that simple processing approaches can be refined to fabricate nanocrystalline ceramics while maintaining high hardness and indentation fracture resistance.     

Microstructure and electrical properties of zirconia and composite nanostructured ceramics sintered by different methods

The aim of this study is the preparation and characterization of dense cubic zirconia ceramics and zirconia nanocomposites (reinforced with 5 wt% alumina). The powders were obtained through sol–gel methods and densified using classical sintering and spark plasma sintering (SPS) methods. The obtained ceramics were characterized through X-ray diffraction, scanning electron microscopy and impedance spectroscopy at room and high temperature. The average grain size of cubic zirconia particles was found to be approximately 8 and 2.5 μm for the classical sintering and 99 nm for SPS. The alumina particles in composites have an average grain size of 0.7 μm for classical sintering and 53 nm for SPS ones. The total conductivity for nanocomposites sintered through both methods was also determined.     

Evolution of microstructure,mechanical, and optical properties of Y2O3-MgO nanocomposites fabricated by high pressure spark plasma sintering

A high-pressure spark plasma sintering (SPS) process was applied for consolidating Y₂O₃–MgO nanocomposites. This approach enabled to fabricate a fully dense infrared (IR) transparent nanocomposites, which possess an average grain size of ∼70 nm and high hardness, at a relatively low sintering temperature of 1130 °C under a high pressure of 300 MPa. The light transmittance was improved with increasing pressure and reached to the maximum transmittance of 64.5% at a wavelength of 0.2–1.6 μm owing to the fine-grained microstructure. The Vickers hardness exhibited 16.6 ± 0.7 GPa for the grain size of 74 nm, which is significantly higher than that of the sub-micro grains obtained at a conventional sintering pressure of 70 MPa (11.9 ± 0.8 GPa). The hardness rigorously followed the Hall–Petch relationship, that is, it is enhanced with a reduction of the grain size. Successful fabrication of the high-performance Y₂O₃–MgO nanocomposites indicates that the nanopowder processing followed by the high-pressure sintering process can be applied for fabricating fully dense fine-grained nanocomposites with excellent optical and mechanical properties.     

Effect of the CoFe2O4 initial particle size when sintered by microwave on the microstructural,dielectric, and magnetic properties

The particle size of CoFe₂O₄ powders (average particle size of 350 nm) was reduced to 50 nm by high-energy milling. In this paper, special attention was given for analyzing the densification and grain growth of both particle sizes (350 and 50 nm) subject to ultrafast sintering assays using microwave sintering and their effect on the magnetic and electric properties. The results indicated that the grain growth was 10 times higher for the nanoparticle system, reaching similar sizes of ~1 μm in both cases after sintering. The relative density values were higher (95%) in the nanoparticle system due to the wide distribution of particle sizes generated in the grinding process. Qualitatively inferred microscopy analysis showed high sinterability of fine particles with a narrow distribution of grain size when subjected to ultrafast firing processes. Magnetization measurements at room temperature clearly show the reduction of Hc with increasing grain size. Electric resistivity, dielectric constant (ε′), and dielectric loss tangent (tan δ) were measured as a function of frequency at room temperature. The low values of dielectric constant (ε′) and dielectric loss (tan δ) in the low frequency range, shown for all samples sintered by microwave, prove the excellent uniformity in the microstructure.     

Preparation of a Highly Conductive Al2O3/TiN Interlayer Nanocomposite through Selective Matrix Grain Growth

An electroconductive TiN/Al₂O₃ nanocomposite was prepared by a selective matrix grain growth method, using a powder mixture of submicrosized α-Al₂O₃, nanosized γ-Al₂O₃, and TiN nanoparticles synthesized through an in situ nitridation process. During sintering, a self-concentration of TiN nanoparticles at the matrix grain boundary occurred, as a result of the selective growth of large α-Al₂O₃ matrix grains. Under suitable sintering conditions, a typical interlayer nanostructure with a continuous nanosized TiN interlayer was formed along the Al₂O₃ matrix grain boundary, and the electroconducting behavior of the material was significantly improved. Twelve volume percent TiN/Al₂O₃ nanocomposite with such an interlayer nanostructure showed an unprecedentedly low resistivity of 8 × 10⁻³Ω·cm, which was more than two orders lower than the TiN/Al₂O₃ nanocomposite without such an interlayer nanostructure.     

Preparation and Properties of Fine-Grain (1−x)BiScO3−xPbTiO3 Ceramics by Two-Step Sintering

(1− x )BiScO₃− x PbTiO₃ (BSPT) nanopowder with an average grain size of 10 nm with the composition of x =0.64, which has been reported to be close to the MPB in the bulk BSPT ceramics, was successfully synthesized. Subsequently, the techniques of preparation of high-performance fine-grain MPB–BSPT ceramics by two-step sintering were investigated, providing a feasible approach to produce a high-density fine-grain MPB–BSPT ceramic using pressureless means without any sintering aids at a low temperature of 800°C. The results have shown that the fine-grain ceramic possesses a higher piezoelectric constant and electromechanical coupling factor than the coarse-grain ceramic. The influences of the grain size on the piezoelectric and dielectric properties were also discussed. Within the scale of the grain sizes of our specimens, the piezoelectric constant increases up to 520 pC/N at the finest grain size of 200 nm, indicating a promising path for the improvement of the piezoelectric coefficient.     

两步烧结法制备纳米氧化钇稳定的四方氧化锆陶瓷

采用共沉淀法制备纳米氧化钇稳定的四方氧化锆（yttria stabilized tetragonal zirconia,3Y-TZP）粉体。利用X射线衍射、N2吸附–脱附等温线,透射电子显微镜对3Y-TZP粉体的物理性能和化学性能进行表征。研究了纳米3Y-TZP粉体的烧结曲线,分析了3Y-TZP素坯在烧结过程中的致密化行为和显微结构,探讨了两步烧结工艺对3Y-TZP纳米陶瓷微观结构的影响。结果表明：采用共沉淀法,在600℃煅烧2h后,可获得晶粒尺寸为13nm、晶型发育良好、团聚较少的纳米3Y-TZP粉体;采用两步烧结法,将素坯升温至1200℃保温1min后,再降温到1050℃保温35h,可获得相对密度大于98%,晶粒尺寸约为100nm的3Y-TZP陶瓷。两步烧结法通过控制煅烧温度和保温时间,利用晶界扩散及其迁移动力学之间的差异,使晶粒生长受到抑制,样品烧结致密化得以维持,实现在晶粒无显著生长前提下完成致密化。     

Refinement of Nanoscale Grain Structure in Bulk Titania via a Transformation-Assisted Consolidation (TAC) Method

Bulk nanocrystalline TiO₂ samples (100% rutile) with a relative density as high as 97% and a grain size of <20 nm have been produced via high-pressure (up to 8 GPa)/low-temperature (∼0.3 T _m, where T _m is the melting temperature) sintering, using a toroidal-type high-pressure apparatus. Nanophase TiO₂ powder with a metastable anatase structure and an initial grain size of ∼38 nm was used as the starting material. During sintering, the anatase phase transformed to either the rutile or srilankite phase, depending on the pressure–temperature ( P – T ) combination. The starting temperature of the anatase-to-rutile phase transformation decreased from ∼550°C at ambient pressure to ∼150°C at 2.5 GPa. Grain growth was limited by the low sintering temperature and the multiple nucleation events in the parent phase. The grain size of the transformed rutile decreased as the sintering pressure increased, which can be explained by the combined effect of increasing the nucleation rate and decreasing the growth rate with high pressure. We have demonstrated that it is possible to produce a dense sintered compact with a grain size even smaller than that of the starting powder. The high-pressure srilankite phase was observed at P – T conditions as low as 4.75 GPa and 250°C, respectively; however, unlike the anatase-to-rutile phase transformation, the rutile-to-srilankite phase-transformation temperature increased as the pressure increased. Also, in contrast to the irreversible anatase-to-rutile phase transformation, the srilankite will reversibly transform to rutile under the appropriate circumstances. This observation provides an opportunity to further refine the TiO₂ grain structure by switching the sintering conditions (temperature and pressure) between the regions in which the rutile or srilankite phase are stable.     

Compressive mechanical properties of partially sintered porous alumina of bimodal particle size system

This paper examined theoretically and experimentally packing behavior, sintering behavior and compressive mechanical properties of sintered bodies of the bimodal particle size system of 80 vol% large particles (351 nm diameter)–20 vol% small particles (156 nm diameter). The increased packing density as compared with the mono size system was explained by the packing of small particles in 6-coordinated pore spaces among large particles owing to the similar size relation between 6-coordinated spherical pore and small particle. The sintering between adjacent large particles dominated the whole shrinkage of the powder compact of the bimodal particle size system. However, the bimodal particle size system has a high grain growth rate because of the different curvatures of adjacent small and large particles. The derived theoretical equations for the compressive strengths of both mono size system and bimodal particle size system suggest that the increase in the grain boundary area and relative density by sintering dominate the compressive strength of a sintered porous alumina. The experimental compressive strengths were well explained by the proposed theoretical models. The strength of the bimodal particle size system was high at low sintering temperatures but was low at high sintering temperatures as compared with that of mono size system of large particles. This was explained by mainly the change of grain boundary area with grain growth. The stress–strain relationship of the bimodal particle size system showed an unique pseudo-ductile property. This was well explained by the curved inside stress distribution along the sample height. The inside stress decreases toward the bottom layer. The fracture of one layer of sintered grains over the top surface proceeds continuously with compressive time along the sample height when an applied stress reaches the critical fracture strength.     

Effect of segregation on particle size stability and SPS sintering of Li2O-Doped magnesium aluminate spinel

Magnesium aluminate spinel (MAS) was prepared using the simultaneous precipitation method by varying the concentration of Li₂O from 0 to 5 mol%. No residual chlorine from the LiCl precursor was detected in the final powders while Li achieved the target concentration in all samples and contributed to stabilizing nanoparticles smaller than 10 nm. Li segregation to both interfaces (surfaces and grain boundaries) occurred and tended to be more pronounced at the grain boundaries stabilizing this type of interface during processing rather than surfaces. Spark plasma sintering (SPS) was used to consolidate the nanopowders into fully dense nanostructured pellets. The increase in Li content facilitated the sintering process and pore elimination occurred at 850–900 °C, a much lower temperature range as compared to conventional sintering (1650 °C). Samples containing 5 mol% Li sintered at 850 °C exhibited a medium grain size of ?25 nm, microhardness of ?24 GPa and ?50% in-line optical transmission at the 800 nm.