Al_2O_3/B_4C的致密化机制

初始晶粒尺寸为0.33μm和7.0μm的Al2O3/14%B4C粉末在不同温度烧结,并模拟计算陶瓷粉末烧结过程。通过对比实验结果和计算结果,找出影响材料致密化的机制,讨论晶粒尺寸对扩散机制的影响,并估算出致密化激活能。在实验烧结温度范围内,界面反应被认为是影响Al2O3/B4C粉末致密化过程的主要因素。Al2O3/14%B4C陶瓷的致密化激活能是1820±60KJ.mol-1,这结果很大程度上支持界面反应致密化机制。     

Fabrication of transparent mullite ceramic by spark plasma sintering from powders synthesized via sol–gel process combined with pulse current heating

Mullite nanopowders were synthesized by combining the advantages of the sol–gel process with the rapid synthesis provided by pulse current heating. The mullite ceramic with an infrared transmittance of 83–88% in the wavelength range from 2.5 to 4 μm with a fine grain size of 200 nm was obtained by spark plasma sintering at 1350 °C. Due to the high relative density and the small grain size, the hardness and toughness values of the sample reached 17.82 GPa and 3.6 MPa m^1/2, respectively. In contrast, when the mullite powders synthesized in a muffle furnace, an intermediate phase occurred so that the powder synthesis required high crystallization temperatures and resulted in agglomerated particles. Thus, the mullite ceramics required high temperatures for densification. As a result, the optical and mechanical properties of the ceramics were poor due to the low relative density and the elongated grain growth.     

Fabrication of Al2O3–ZrB2 in situ composite by SHS dynamic compaction: A novel approach

Al₂O₃–ZrB₂ in situ composites of 97% of theoretical density were successfully fabricated by a novel self-propagating high temperature synthesis (SHS) dynamic compaction, using less expensive raw materials zirconium oxide, boron oxide, and aluminium. The process is fast, energy efficient, where no furnace sintering is required. The process inhibits and controls the grain growth and microstructure. The densification behaviour and correlation with microstructure of the SHS dynamic compacts were compared with the furnace sintered composite samples where the composite powder was prepared by SHS process. The furnace sintered samples showed coarser grain growth and maximum density of 94.5% of theoretical density was achieved. The SHS dynamic compacted in situ composite had much finer grains in the range of 0.5–3 μm with density 95.5% of the theoretical value. The average grain size was found to decrease from 10 μm to 1.4 μm for alumina and from 5.4 μm to 1.0 μm for zirconium diboride from furnace sintering to SHS dynamic compaction, respectively. Addition of Al₂O₃ as a diluent during SHS reaction enhanced the density to 97%. During SHS dynamic compaction, the amount of liquid and the time interval at which the sample stays at high temperature are the controlling factor of the final microstructure and the densification of the composite.     

A comparison study of the agglomeration mechanism of nano- and micrometer aluminum particles

The agglomeration mechanism of micro- and nanosize aluminum particles with a primary mean particle diameter of 4.5 μm and 75 nm, respectively, was comparatively investigated under an incident shock wave. The morphology, particle size, and agglomeration process of micro- and nanometer alumina particles were comprehensibly compared by X-ray diffraction, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy. Images of X-ray diffraction reveal that a varied of phases of alumina (γ-, δ-, ε-, and α-Al₂O₃) were simultaneously found in the nanosize alumina products, which may give some detail information of the wide variety of reacting temperature of aluminum nanoparticles, while Al₄C₃ was detected in micrometer alumina products, which also gives some dynamic information of aluminum to alumina, i.e., aluminas have actually reacted with the free active carbon atoms to produce their intermediates. The microstructure of aluminas induced by the incident shock waves was detected and analyzed by using transmission electron microscopy combined with X-ray photoelectron spectroscopy spectrum. These results are an additive evidence to support that the initial stage sintering of the alumina nanosize powders is dominated by grain boundary diffusion, while the volume diffusion is the main character for the initial stage sintering of the micrometer alumina powders.     

Effect of particle size on densification of pure magnesium during spark plasma sintering

The effect of particles size ranges (<38 μm, 75–150 μm, 270–550 μm) of atomized magnesium powders on densification mechanisms during spark plasma sintering (SPS) process was investigated. The intrinsic driving force, local pressure and current of Mg powders with different particle sizes were analyzed by theoretical calculation. The results obviously indicate that the densification of pure magnesium can be improved by the reduction of particle size, suggesting the intrinsic driving force, local pressure and current intensity are enhanced significantly by a decrease in the particle size at the same sintering conditions, which can promote shrinkage of pores, formation of the sintering neck and mass transportation in the SPS process. Not only that, rapid densification is also interpreted in term of mechanical movement of particles, Joule heating effect and plastic deformation. However, the mechanical movement of the large particles is higher than that of small particles due to high punch displacement, and plastic deformation, detected by scanning electron microscopy, plays a main role in densification for large particles in the case during the sintering. Joule heating effect is the key factor for densification of small Mg particles, and high densification degree can be obtained by sintering small particles.     

Structure and strength of aluminum with sub-micrometer/micrometer grain size prepared by spark plasma sintering

A spark plasma sintering (SPS) technique has been applied to prepare fully dense Al samples from Al powder. By applying a sintering temperature of 600 °C and a loading pressure of 50 MPa, fully recrystallized samples of nearly 100% density with average grain sizes of 5.2 μm, 1.3 μm and 0.8 μm have been successfully prepared using a sintering time of less than 30 min and without the need for a nitrogen atmosphere. A similarity between the grain size and powder particle size is found, which suggests a potential application of the SPS technique to prepare samples with a variety of grain sizes by tailoring the initial powder particle size. The SPS samples show higher strength than Al samples with an identical grain size prepared using thermo-mechanical processing, and a better strength–ductility combination, with the 1.3 μm grain size sample showing a yield strength (σ_0.2%) of 140 MPa and a uniform elongation of more than 10%. This higher strength is related to the presence of oxide particles in the grain boundaries of the samples. It is concluded that SPS is an excellent technique for the production of very fine grained Al materials with high strength, by combining both grain boundary and oxide dispersion strengthening.     

Dilatometry of attrition milled nanocrystalline titanium powders

The sintering behavior of nanosized titanium powders was investigated by dilatometry. The nanosized Ti powders (40 nm) were produced by the attrition milling of micron sized Ti powders (12 μm) in Ar atmosphere. Sintering was carried out in Ar atmosphere in the temperature range of 450–1250 °C for nanosized Ti and 650–1250 °C for micron sized Ti by heating at 10 °C/min, up to the sintering temperature followed by isothermal holding for 1 h. The nanosized Ti powders exhibited a lower sintering onset temperature, larger shrinkage, larger shrinkage rate, and lower activation energy for sintering as compared to the micron sized Ti powders. The sintered micron sized Ti specimens exhibited both intraagglomerate and interagglomerate porosity while the nanosized Ti specimens exhibited well densified agglomerates (almost no interagglomerate porosity) and large intraagglomerate porosity. In nanosized Ti grain growth was found to take place beyond 700 °C and reached a maximum of 66 nm in samples sintered at 1100 °C.     

Development of an instrumented and automated single mode cavity for ceramic microwave sintering: Application to an alpha pure alumina powder

This paper describes the development of an instrumented and automated single mode microwave cavity for sintering ceramic powders. This setup includes an optical dilatometer and a motorized plunger to control heating cycles in a wide range of heating rates (from 5 °C ∙ min^− 1 to 200 °C ∙ min^− 1) up to 1600 °C and to allow reliable comparison with conventional sintering. The cavity and the sintering cells for both hybrid and direct microwave sintering were designed using finite element simulation. For accurate temperature measurement, an optical pyrometer calibrated with a specific protocol has been used. Microwave sintering of fine grained (< 100 nm) alpha alumina compacts was thus investigated and compared to conventional sintering. This pure alumina powder has been sintered by direct microwave heating, without any susceptor nor doping element to initiate heating as often achieved in the literature. The comparison of the densification kinetics along an identical thermal cycle evidenced a significant enhancement of sintering under microwaves during the first and intermediate stages.     

Sinter-HIP of polymer-derived Al2O3–SiC composites with high SiC contents

Submicrometer Al₂O₃ composites with more than 20 vol.% of SiC particles were produced using a multiple infiltration of porous bodies with a liquid polymer SiC precursor. The fully dense composites were successfully densified using a sinter-HIP process. Parameters of sintering and HIP steps are discussed with respect to both densification and microstructure evolution of the composites. The initial pressure during the sintering step plays an important role for the preparation of fully dense composites with a submicrometer alumina matrix at 1750 °C. Optimized densification schedule of sinter-HIP represents a novel approach of densification at relatively mild conditions compared to previously reported or common densification methods of Al₂O₃–SiC composites with high SiC content, such as pressureless sintering, hot pressing and post-HIPing. The method expands the possibilities for preparation of alumina based composites with SiC volume fraction > 20 vol.%, filling the gap in available literature data.     

Microstructure and strength of pure Cu with large grains processed by equal channel angular pressing

The pure Cu rods with an initial grain size of 410 μm were treated by using equal channel angular pressing (ECAP). The deformed microstructure and mechanical properties of ECAPed Cu samples were investigated. Special attention was paid on the refinement of grain size and local micromechanics of ECAPed Cu samples. The original coarse grains were refined to 320 μm after 4 passes. The final grains were composed of dislocation cells with a size of 500 nm–3 μm after 5–8 passes. The yield strength reached a saturation value of 368 MPa after 5 passes. The maps of microhardness distribution illustrated the inhomogeneity of local mechanical properties. The dislocation subdivision was the main deformation mode to refine the grain size, while twin fragmentation was restrained by dislocation slips for the reason of large initial grain size. Furthermore, the strengthening of ECAPed Cu was discussed.     

Mechanically induced self-propagating reaction and consequent consolidation for the production of fully dense nanocrystalline Ti55C45 bulk material

We employed a high-energy ball mill for the synthesis of nanograined Ti₅₅C₄₅ powders starting from elemental Ti and C powders. The mechanically induced self-propagating reaction that occurred between the reactant materials was monitored via a gas atmosphere gas-temperature-monitoring system. A single phase of NaCl-type TiC was obtained after 5 h of ball milling. To decrease the powder and grain sizes, the material was subjected to further ball milling time. The powders obtained after 200 h of milling possessed spherical-like morphology with average particle and grain sizes of 45 μm and 4.2 nm, respectively. The end-products obtained after 200 h of ball milling time, were then consolidated into full dense compacts, using hot pressing and spark plasma sintering at 1500 and 34.5 MPa, with heating rates of 20 °C/min and 500 °C/min, respectively. Whereas hot pressing of the powders led to severe grain growth (~ 436 nm in diameter), the as-spark plasma sintered powders maintained their nanograined characteristics (~ 28 nm in diameter). The as-synthesized and as-consolidated powders were characterized, using X-ray diffraction, high-resolution electron microscopy, and scanning electron microscopy. The mechanical properties of the consolidated samples obtained via the hot pressing and spark plasma sintering techniques were characterized, using Vickers microhardness and non-destructive testing techniques. The Vickers hardness, Young's modulus, shear modulus and fracture toughness of as-spark plasma sintered samples were 32 GPa, 358 GPa, 151 GPa and 6.4 MPa·m^1/2, respectively. The effects of the consolidation approach on the grain size and mechanical properties were investigated and are discussed.     

Comparative dielectric studies of nanostructured BaTiO3, CaCu3Ti4O12 and 0.5BaTiO3⋅ 0.5CaCu3Ti4O12 nano-composites synthesized by modified sol–gel and solid state methods

BaTiO₃ (BTO), CaCu₃Ti₄O₁₂ (CCTO) and 0.5BaTiO₃·0.5CaCu₃Ti₄O₁₂ (BTO–CCTO), as a new nano-composite ceramic, were successfully designed and fabricated by a semi-wet gel route and a modified solid state method. The dielectric properties of the BTO–CCTO ceramic were compared to those of the BTO and CCTO ceramics at lower sintering temperatures and durations. The X-ray diffraction analysis revealed that the BTO and CCTO ceramics form a single crystalline phase and the average crystalline sizes calculated from X-ray diffraction data were in the range of 40–65 nm. The particle sizes of the BTO, CCTO, and BTO–CCTO ceramics obtained from transmission electron microscopy images were in the ranges of 40–65 nm, 80–110 nm, and 70–95 nm, respectively. The phase composition and microstructure were studied by X-ray diffraction and scanning electron microscopy. The energy dispersive X-ray results demonstrated the purity and stoichiometry of the BTO–CCTO nano-composite. The grain sizes of the BTO, CCTO and BTO–CCTO ceramics were found to be in the ranges of 500 nm–1 μm, 4–24 μm, and 250 nm–4 μm, respectively. The AC conductivity as a function of frequency confirmed the semiconducting nature of all of the ceramics and obeyed the Jonscher's power law. The impedance spectrum measurement result showed that the CCTO ceramic possessed an exceptional grain boundary resistance, which supports the internal barrier layer capacitance (IBLC) mechanism present in this ceramic and is responsible for the high ε_r values.     

Continuous production of hydroxyapatite powder by drip pyrolysis in a fluidized bed

Hydroxyapatite (HAp) powder was produced by drip pyrolysis in a fluidized bed (DPFB) at 913–1113 K with dry air. In this study, HAp powders derived using different concentrations of a solution-type precursor material were compared with those derived using slurry-type precursor materials. From a solution-type precursor containing calcium nitrate and ammonium phosphate dibasic, fine HAp powders with mean particle sizes of approximately 8–40 μm were produced, depending on the solution concentration and reaction temperature. In these cases, bimodal particle size distribution was observed. Spherical alumina of 250 μm was found to be superior to silica sand of 270 μm as the coarse medium particles in reducing contamination of the product powder. The thermal stability of HAp derived from a slurry-type precursor after 1-day aging was improved by DPFB. HAp powders derived from the solution-type precursor material were Ca-deficient, and their Ca/P molar ratio increased with bed temperature. In contrast, the Ca/P molar ratio of HAp powders from the slurry-type precursor material was nearly stoichiometric. Morphology strongly depended on the starting precursor material. The solid collection ratio was closely related to the population of product particle sizes larger than 25 μm.     

Pressureless sintering curve and sintering activation energy of Fe–Co–Cu pre-alloyed powders

The kinetic characteristics of Fe–Co–Cu pre-alloyed powders in the pressureless sintering process have been investigated. The expansion ratio, linear shrinkage, densification rate and effect of heating rate on the sintering have been analyzed. Based on the classical Arrhenius curve, the sintering activation energy has been calculated. Results show that the samples have a smaller expansion ratio before contracting when the Fe content is higher, and the final linear shrinkage ratio is larger too. The sintering carries out more efficiently and the final linear shrinkage ratio is larger when the samples at a lower heating rate. In the initial and final stage of sintering, the Arrhenius curve is suitable for the Fe–Co–Cu pre-alloyed powders and diffusion is the main transport mechanism. At the initial stage of sintering the sintering activation energy of Fe25%–Co15%–Cu60% powder is 453.11 kJ/mol, Fe45%–Co15%–Cu40% powder is 638.28 kJ/mol and Fe65%–Co15%–Cu20% powder is 504.6 kJ/mol, respectively. At the final stage of sintering the sintering activation energy of Fe25%–Co15%–Cu60% powder is 31.17 kJ/mol, Fe45%–Co15%–Cu40% powder is 20.09 kJ/mol and Fe65%–Co15%–Cu20% powder is 35.13 kJ/mol, respectively. The sintering activation energy in the middle stage is dominated by not only one diffusion mechanism so it is not suitable for the Arrhenius curve.     

Martensitic transformation behaviors of rapidly solidified Ti–Ni–Mo powders

For the fabrication of bulk near-net-shape shape memory alloys and porous metallic biomaterials, consolidation of Ti–Ni–Mo alloy powders is more useful than that of elemental powders of Ti, Ni and Mo. Ti₅₀Ni_49.9Mo_0.1 shape memory alloy powders were prepared by gas atomization, and transformation temperatures and microstructures of those powders were investigated as a function of powder size. XRD analysis showed that the B2–R–B19 martensitic transformation occurred in powders smaller than 150 μm. According to DSC analysis of the as-atomized powders, the B2–R transformation temperature (T_R) of the 25–50 μm powders was 18.4 °C. The T_R decreased with increasing powder size, however, the difference in T_R between 25–50 μm powders and 100–150 μm powders is only 1 °C. Evaluation of powder microstructures was based on SEM examination of the surface and the polished and etched powder cross sections and the typical images of the rapidly solidified powders showed cellular morphology. Porous cylindrical foams of 10 mm diameter and 1.5 mm length were fabricated by spark plasma sintering (SPS) at 800 °C and 5 MPa. Finally these porous TiNi alloy samples are heat-treated for 1 h at 850 °C, and then quenched in ice water. The bulk samples have 23% porosity and 4.6 g/cm³ density and their T_R is 17.8 °C.     

The Cu matrix cermets remarkably strengthened by TiB2 “in situ” synthesized via self-propagating high temperature synthesis

The TiB₂–Cu cermets with predominant concentration of superhard TiB₂ (from 45 to 90 vol.%) were fabricated using elemental powders by means of SHS (self-propagating high-temperature synthesis) process and simultaneously densified by p-HIP (pseudo-isostatic pressing technique). The heat released during highly exothermic SHS reaction was “in situ” utilized for sintering. The combustion occurred even for 50 vol.% Cu dilution. According to XRD metallic copper binder was formed in those cermets in whole range of investigated compositions. The TiB₂ volume fraction significantly influenced the properties of fabricated materials, especially grain size and hardness. Both the average grain size and hardness significantly increased with TiB₂ content, so the maximum value of 18 GPa was measured for TiB₂–5 vol.%Cu composite. Coarse grains of 6.4 μm in size were observed for this composite while TiB₂-based submicro-composites were formed for 40–50% of Cu where the average grain size did not exceed 0.6 μm. The Vickers hardness of 16–18 GPa obtained for cermets containing from 85 to 90 vol.% of TiB₂ and no radial cracks in Vickers hardness test proved that in term of hardness and fracture toughness the composites might be competitive to WC–Co cermets.     

Powder synthesis and properties of LiTaO3 ceramics

The LiTaO₃ powders with sub micrometer grade grain size have been synthesized successfully using a molten salt method. Lithium tantalate began to form at 400 °C reaction temperature and transformed to pure phase without residual reactants when it was processed at 500 °C for 4 h in static air. The undoped LiTaO₃ ceramics with a Curie temperature about 663 °C were obtained by pressureless sintering at 1300 °C for 3 h. The relative dielectric constant (ɛ_r) increases from 50 to 375 at temperature ranging from 30 to 663 °C and then decreases quickly as the temperature increases above 663 °C. The ceramics shows a relative dielectric constant of 49.4, a dielectric loss factor (tan δ) of 0.007, a coercive field (Ec) of 28.66 kV/cm and a remnant polarization (Pr) of 32.48 μC/cm² at room temperature.     

Enhanced properties of alumina–aluminium titanate composites obtained by spark plasma reaction-sintering of slip cast green bodies

Full dense alumina + 40 vol.% aluminium titanate composites were obtained by colloidal filtration and fast reaction-sintering of alumina/titania green bodies by spark plasma sintering at low temperatures (1250–1400 °C). The composites obtained had near-to-theoretical density (>99%) with a bimodal grain size distribution. Phase development analysis demonstrated that aluminium titanate has already formed at 1300 °C. The mechanical properties such as Vickers hardness, flexural strength and fracture toughness of bulk composites are significantly higher than those reported elsewhere, e.g. the composite sintered at 1350 °C show values of about 24 GPa, 424 MPa and 5.4 MPa m^1/2, respectively. The improved mechanical properties of these composites are attributed to the enhanced densification and the finer and more uniform nanostructure achieved by non-conventional fast sintering of slip-cast dense green compacts.     

Effect of grain size on mechanical,surface and biological properties of microwave sintered hydroxyapatite

Hydroxyapatite (HA) compacts having average grain sizes of 168 ± 0.086 nm, 1.48 ± 0.627 μm and 5.01 ± 1.02 μm are processed from synthesized HA powder by microwave sintering at varying sintering temperature for different times. Superior mechanical and biological properties are shown by nano-grain HA compacts as compared to their micron grained counterparts. Compressive strength, indentation hardness, and indentation fracture toughness are increased with the decrease in HA grain size. The highest surface energy and maximum wettability are exhibited by nano-grain HA. HA compacts are assessed for cell–material interaction by SEM, MTT and immunochemistry assays using human osteoblast cell line for 1, 5 and 11 days. MTT assays showed higher number of living cells and faster proliferation on nano-grain HA surface. Osteoblast cells on nano-grain HA surface expressed significantly higher amount of vinculin and alkaline phosphatase (ALP) protein markers for cell adhesion and differentiation respectively. This study shows the effect of grain size on physical, mechanical and in vitro biological properties of microwave sintered HA compacts.     

Preparation of YAG gel coated ZrB2–SiC composite prepared by gelcasting and pressureless sintering

In this paper, gelcasting and pressureless sintering of YAG gel coated ZrB₂–SiC (YZS) composite were conducted. YAG gel coated ZrB₂–SiC (YZS) suspension was firstly prepared through sol–gel route. Poly (acrylic acid) was used as dispersant. YZS suspension had the lowest viscosity when using 0.6 wt.% PAA as dispersant. Gelcasting was conducted based on AM–MBAM system. The gelcast YZS sample was then pressureless sintered to about 97% density. During sintering, YAG promoted the densification process from solid state sintering to liquid phase sintering. The average grain sizes of ZrB₂ and SiC in the YZS composite were 3.8 and 1.3 μm, respectively. The flexural strength, fracture toughness and microhardness were 375 ± 37 MPa, 4.13 ± 0.45 MPa m^1/2 and 14.1 ± 0.5 GPa, respectively.