Microhardness of ceramics produced from different alumina nanopowders by different techniques

Fine-grained ceramics (with a grain size on the order of a micron) have been produced by the spark plasma sintering (SPS) of various alumina nanopowders. We have compared the microhardness of ceramic samples prepared from 11 alumina nanopowders and that of composites based on such powders. The ceramics have been prepared by both SPS and a conventional technique (sequential pressing and sintering). We examine the effect of the phase composition and average particle size of the starting nanopowder on the microhardness of the ceramics.     

Transparent ceramics prepared from ultrapure magnesium aluminate spinel nanopowders by spark plasma sintering

We have studied the properties of transparent magnesium aluminate spinel ceramics prepared by spark plasma sintering (SPS) of ultrapure nanopowders. The starting powders, of ? 99.98% purity, ranging in specific surface area from 30 to 160 m²/g, were prepared through the hydrolysis of alcoholic solutions of magnesium aluminum alkoxide complexes, followed by calcination at temperatures from 900 to 1100°C. SPS was carried out at 1450°C, with the holding time at the highest temperature not longer than 15 min. The transparent ceramic samples thus prepared have a transmission of up to 73% in the visible and IR spectral regions (λ = 2.5–5.0 µm). The crystallite size in the ceramics is 0.2–0.4 µm, and their microhardness is HV0.1 = 14.8–16.2 GPa.     

Spark plasma sintering of ductile ceramic particles: study of LiF

Densification of cuboidal micrometer-sized lithium fluoride particles as ductile ceramic by spark plasma sintering (SPS) was investigated. Specimens were fabricated at different pressures and temperature conditions, ranging from 2 to 100 MPa at 500 °C and from 200 to 700 °C under 100 MPa of applied pressure, respectively. Dense specimens of 99 % relative density were fabricated by heating to 500 °C under constant pressure of 100 MPa. The densification showed first compaction by particle rearrangement, followed by plastic deformation via dislocation glide. Hot-pressing models were used to describe the densification by considering the temperature dependences of the yield stress, the strain hardening behavior and coefficients, and the pore size and shape dependences on the applied stress. A good agreement was found between the experimental and the theoretical densification curves. At low pressure of 2 MPa, the densification occurs by particle sliding, assisted by viscous flow at their surfaces, and local plastic deformation at the particle contacts, due to the intensified local stress. Finally, the micrometer-sized structural features and the contiguity achieved by plastic deformation at the start of spark plasma sintering (SPS) nullify any field effects in this model system at higher pressures; good agreement was obtained with expected conventional hot pressing.     

Effect of spark plasma sintering on microstructure and electrical properties of ZnO-based varistors

Conditions for the elaboration of varistors by spark plasma sintering (SPS) are investigated, using 70 nm zinc oxide nano-particles. For this purpose, the system constituted of zinc oxide, bismuth oxide and other metal oxide is used. Material sintering has been performed by SPS at various temperatures and dwell times. Determination of the microstructure and chemical composition of the as-prepared ceramics are characterized by scanning electron microscopy and X-ray diffraction analysis. Micro-structural analysis revealed the presence of ZnO, spinel and bismuth rich phases. ZnO based Varistor samples sintered within climb speeds 100 and 400 °C/min are compared. The nonlinear electrical characteristics, current–voltage, are measured. The breakdown voltage of the varistors strongly depends on grain sizes. The results show that the best varistors are obtained by SPS at sintering temperatures ranging from 900 to 1200 °C.     

Tough yttria-stabilized zirconia ceramic by low-temperature spark plasma sintering of long-term stored nanopowders

Weakly agglomerated 1.75 and 3 mol% yttria stabilized zirconia nanopowders were used in this study after six years of storage in vacuum-processed plastic containers. The proper storage conditions of the Y-TZP nanopowders avoided the hard agglomeration. Untreated and bead-milled nanopowders were used to obtain dense ceramics by slip casting and subsequent low-temperature sintering. Fully dense nanostructured 1.75Y-TZP and 3Y-YZP ceramics with and without doping of 1 wt% Al2O3 were produced by an optimized spark plasma sintering (SPS) technique at the temperatures of 1050-1150 degrees C at a pressure of 100 MPa. The SPS has revealed the clear advantage of consolidation of the weakly agglomerated nanopowders without preliminary deagglomeration. The Vickers hardness of both the low-temperature and spark plasma sintered samples was found to lie in the range of 10.98-13.71 GPa. A maximum fracture toughness of 15.7 MPa m(1/2) (average 14.23 MPa m(1/2)) was achieved by SPS of the 1.75Y-TZP ceramic doped with 1 wt% Al2O3 whereas the toughness of the 3Y-TZP ceramics with and without alumina doping was found to vary between 3.55 and 5.5 MPa m(1/2).     

Spark plasma sintering and decomposition of the Y<Subscript>3</Subscript>NbO<Subscript>7</Subscript>:Eu phase

The spark plasma sintering (SPS) of Eu³⁺-doped Y₃NbO₇ niobate phase was investigated to obtain dense ceramics. Although SPS allowed obtaining high-density ceramics, decomposition of the niobate phase occurred at high temperature and was promoted by the SPS process, which limited its use as an optical material. The niobate phase has been prepared by two synthesis methods: a solid-state route and a sol–gel method. The purity, density and microstructure of the dense ceramics were analyzed after spark plasma sintering. Translucent ceramics were only obtained from sol–gel powders after SPS at 1600 °C during 20 min with a heating rate of 5 °C/min. The sintering study of the pure niobate phase showed that during SPS process and especially in the presence of the high electrical field the Y₃NbO₇ phase is metastable at 1600 °C. A decomposition of the niobate compound is clearly demonstrated by luminescence measurements when high heating rates were used.     

Density variation and piezoelectric properties of Ba(Ti1 − x Sn x )O3 ceramics prepared from nanocrystalline powders

Nanocrystalline powders of tin-doped barium titanate with different concentrations of tin have been synthesized by a combination of solid state reaction and high-energy ball milling. The average particle size of the milled powders as determined from TEM analysis was about 5·96 nm. Analysis of all the milled powders using X-ray diffraction method showed single phase perovskite structure. The density variation of the ceramics with sintering temperature has been studied by sintering the samples at different temperatures. Density variation results show that 1350°C is the optimum sintering temperature for tin-doped barium titanate ceramics. SEM micrographs show high density and increasing trend of grain size with increasing content of Sn. The ferroelectricity decreases with increasing concentration of Sn. The electromechanical coupling coefficient also decreases with increasing Sn content corroborating decreasing trend of ferroelectricity. The bipolar strain curves show piezoelectric properties of the prepared ceramics.     

A novel spray co-precipitation method to prepare nanocrystalline Y<Subscript>2</Subscript>O<Subscript>3</Subscript> powders for transparent ceramics

A novel spray co-precipitation method was adopted to synthesize well dispersed nanocrystalline Y₂O₃ powders for transparent ceramics. Several analytic techniques such as XRD, SEM, BET and UV–Vis–NIR spectrophotometer were used to determine the properties of coprecipitated powders, and the microstructure and optical properties of as-fabricated ceramics. The influences of the aging time on powders and ceramics were systematically investigated. Precursors were completely reached to yield the Y₂O₃ phase after being calcined at 1250 °C in air. The calcined Y₂O₃ powders exhibited an approximately spherical morphology with narrow size distribution and weak agglomeration, with mean particle size of ~140 nm. The co-precipitated nanopowders with an aging time of 12 h exhibited the best sintering activity due to the low agglomeration, and the in-line transmittance of Y₂O₃ ceramic sintered at 1800 °C for 8 h in vacuum reached to 77.2% at 1064 nm (1 mm thickness).     

Microstructure characterization,mechanical properties,compressibility and sintering behavior of Al-B4C nanocomposite powders

In the present work, Al-xB₄C nanocomposite (x = 0, 1, 2, 3, 4 and 5 in wt%, having the average B₄C size of 50 nm) were prepared using a high-energy ball mill. The milling times up to 16 h were applied. Then, the microstructural evolutions, mechanical properties, compressibility and sintering behavior of nanocomposites were investigated. The changes in powders morphology and microstructure during the milling process were characterized by laser diffraction particle size analyzer (LDA), SEM, XRD, EDS and TEM techniques. Compressibility and sintering behavior of milled powders compacted under different pressures (100–900 MPa) and at different sintering temperatures (500, 550 and 600 °C) were also studied. The pressing behavior of the nanocomposites was analyzed using linear compaction equations developed by Heckel, Panelli-Filho and Ge. The results showed the significant effects of B₄C amounts and sintering temperatures on the compressibility and sintering behavior of nanocomposites. The increase in the B₄C amount led to a decrease in both the compressibility rate and the sinterability of specimens. The maximum compression strength of 265 MPa and Vickers hardness of 165 VHN were obtained for Al-5 wt.% B₄C nanocomposite milled for 16 h followed by sintering at 600 °C.     

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.     

Size effect on piezoelectric properties of barium stannate titanate ceramics prepared from nanoparticles

Piezoelectric properties of Ba(Ti_1?x Sn _x )O₃ ceramics with x = 0.025, 0.045 and 0.065, prepared from 16 nm powders, were compared with those of the corresponding ceramics obtained from 86 nm powders to see the effect of tin content and particle size of the starting powders. Ba(Ti_1?x Sn _x )O₃ powders were synthesized by solid state reaction of BaCO₃, TiO₂ and SnO₂ at 1,050 °C. The powders were high energy ball milled to produce nanocrystalline powders having average particle size of 16 nm. The milled powders were sintered at 1,350 °C for 4 h to yield ceramics. For these ceramics, increasing Sn content from x = 0.025–0.065 produces a decrease in (1) unipolar strain level s from 0.084 to 0.027 %, and (2) electromechanical coupling factor k _p from 33.6 to 19.3 %. However, the bulk density, room temperature dielectric constant and piezoelectric charge constant d ₃₃ exhibit an increase from 5.03–5.84 g/cm³, 1,342–2,156 and 7–110 pC/N, respectively, with increasing Sn content. The increasing trend of density and d ₃₃ presently observed is in sharp contrast to the result of corresponding ceramics prepared from 86 nm nanopowders. The present study reveals a cooperative mechanism involving both the nanoscale size of the starting particles and optimum tin content which results in the enhancement of d ₃₃ with tin content.     

Sintering Behavior and Microwave Dielectric Properties of MgTiO3 Ceramics Doped with B2O3 by Sol-Gel Method

The B2O3-doped MgTiO3 powders and ceramics have been prepared by sol-gel method using Mg(NO3)2·6H2O, Ti(C4H9O)4 and H3BO3 as the starting materials. The sintering behavior and microwave dielectric properties of ceramics prepared from powders with different particle sizes were investigated. The gels were calcined at 650, 700, 750, 800, 850 and 900 C and the derived particle sizes of powders were 20-30 nm, 30-40 nm, 40-60 nm, 60-90 nm, 90-120 nm and 120-150 nm, respectively. The nanoparticles with the size of 30-60 nm benefited the sintering process with high surface energy whereas nanoparticles with the size of 20-30 nm damaged the microwave dielectric properties due to the pores in the ceramics. The addition of B2O3 used as a liquid sintering aid reduced the sintering temperature of MgTiO3 ceramic, which was supposed to enter the MgTiO3 lattice and resulted in the formation of (MgTi)2(BO3)O phase. The B2O3-doped MgTiO3 ceramic sintered at 1100 C and prepared from the nanoparticles of 40-60 nm had compact structure and exhibited good microwave dielectric properties: εr=17.63, Q × f=33,768 GHz and τ f= 48×10 6 C 1.     

Synthesis of bulk nanocrystalline HfB<Subscript>2</Subscript> from HfCl<Subscript>4</Subscript>–NaBH<Subscript>4</Subscript>–Mg ternary system

This study reports on the synthesis and consolidation of pure HfB₂ powders starting from HfCl₄–NaBH₄–Mg blends via autoclave processing, annealing and purification followed by pressureless sintering (PS, with 2 wt% Co aid) or spark plasma sintering (SPS). During autoclave reactions conducted at 500 °C for 12 h under autogenic pressure, excess amounts of NaBH₄ were utilized to investigate its effects on the reaction products and mechanism. A subsequent washing (with distilled water), annealing (at 750, 1000 and 1700 °C) and acid leaching (HCl) were applied on the as-synthesized products. Pure HfB₂ powders with an average particle size of 145 nm were obtained after autoclave synthesis in the presence of 200 wt% excess NaBH₄, washing, annealing at 1000 °C for 3 h and 6 M HCl leaching. SPS sample has higher relative density and microhardness values (94.18% and 20.99 GPa, respectively) than those of PS sample (90.14% and 14.85 GPa). Relative wear resistance was improved considerably (8.2 times) by employing SPS technique.     

Spark plasma sintering of BiFeO3

Dense BiFeO₃ ceramics were prepared by a novel spark plasma sintering (SPS) technique. The sintering was conducted at temperatures ranging from 675 to 750 °C under 70 MPa pressure. A bulk density value up to 96% of theoretical density was achieved in the process. This contrast to around 90% of the theoretical density achieved by conventional sintering at around 830 °C. It was found that the tendency to form unwanted Bi₂Fe₄O₉ phase is higher at a high sintering temperature for SPS. The dielectric and ferroelectric properties also improved (with respect to conventionally sintered sample) for spark plasma-sintered samples.     

The Effect of Variable Binder Content and Sintering Temperature on the Mechanical Properties of WC–Co–VC/Cr3C2 Nanocomposites

WC powders with an average crystallite size of 10 nm were successfully prepared by ball milling of micron-sized tungsten carbide powders. Grain growth inhibitors (VC and Cr₃C₂) with concentrations of 0.6 wt% each were added to nanocomposites of WC–9Co and WC–12Co, in both as-received and milled WC. Powder mixtures were then consolidated using spark plasma sintering technique at 1200 and 1300 °C for 10 min under high vacuum and pressure of 50 MPa. The influence of WC crystallite size, Co content, and sintering temperature over microstructure and mechanical properties of the resulting composites were studied through XRD and FESEM. Densification and attained grain sizes of the sintered products were measured by Archimedes principle and Scherrer procedure, respectively. Moreover, microhardness (H_v30) and fracture toughness were measured and compared for each composition to comparatively assess the individual effect. It was observed that the addition of VC and Cr₃C₂ resulted in decreased densification of the synthesized composites. These grain growth inhibitors were found to limit grain sizes to 131 nm with an average hardness of 1592 H_v30 and fracture toughness of 9.23 Mpam^1/2.     

Dielectric Ba(Ti1?xSnx)O3 (x?=?0.13) ceramics, sintered by spark plasma and conventional methods

A two-step sintering approach composed of spark-plasma-sintering (SPS) technique at 1000 °C for 1 min and under a uniaxial pressure of 63 MPa followed by conventional sintering at 1400 °C for 3 h is proposed for synthesis of dense Ba(Ti_0.87Sn_0.13)O₃ ceramics. Starting powders had grain size of about 90 nm and were obtained by co-precipitation. The SPS pellets consist of submicron (300–500 nm) grains. X-ray diffraction analysis of as-prepared Ba(Ti_0.87Sn_0.13)O₃ ceramic shows the occurrence of cubic and tetragonal phase coexistence for the pellets obtained after SPS processing and the presence of only tetragonal phase in the samples after the second (conventional) sintering. Grain uniformity in the final product is high, with average size of ~2 μm. The apparent densities of the sintered pellets at temperature of 1400 °C were ~92% of the theoretical value of Ba(Ti_0.87Sn_0.13)O₃. The ceramics exhibit a high relative dielectric constant of 6,550 and a dielectric loss (tan δ) = 0.078 at Curie temperature of 63 °C and 10 Hz.     

Nanoceramic Toys

This paper reviews several potential applications of nanocrystalline ceramics, both frivolous and functional, and discusses the processing challenges in making 3D and 2D shapes from nanoscale powders. Structural applications, usually 3D in nature, can benefit from nanocrystalline ceramics’ superplasticity, diffusion bonding ability, and/or high fracture toughness. A major limitation in making such structures is the small scale of the parts which can be produced, which in turn is a function of the difficulty in compacting the original nanopowders to the high densities needed for subsequent pressureless sintering. Nanopowders are also used in 2D coatings or films, either for purposes of lowering the sintering temperatures or achieving finer scale structures than are possible with coarser powders. However, the tendency of nanopowders to react extensively with water or other liquid media, and the large drying stresses engendered by small pore sizes in the wet body, have meant that many of the wet‐processed coatings are made from powders that actually have a submicrometer particle size, though the grain (primary crystallite) size may be nanometer scale.     

Oleic acid assisted synthesis of CaCu3Ti4O12 powders and ceramics by sol–gel process

The CaCu₃Ti₄O₁₂ (CCTO) powders were prepared via a sol–gel method using oleic acid (OA) as surfactant. The obtained samples were characterized by thermogravimetric/differential scanning calorimeter Fourier transform-infrared spectroscopy, X-ray diffraction (XRD) and scanning electron microscope, the relative density and the dielectric properties of the ceramics were also investigated. The XRD patterns confirm the formation of CCTO crystal phase and no new peaks appeared whether the dispersant was added or not. The dispersibility of the CCTO powders is improved by adding OA as surfactant. The CCTO prepared without surfactant contains particles of various sizes ranging from 200 to 250 nm whereas the CCTO prepared with OA shows uniform particle size about 120–150 nm. The CCTO ceramics prepared with OA has higher dielectric constant (199484) and lower dielectric loss (0.0977) at 25 °C (10 kHz).     

Optimization of spark plasma sintering parameters for NiTiCu shape memory alloys

Nanostructured nickel titanium copper-shape memory alloys (NiTiCu-SMAs) were fabricated using spark plasma sintering (SPS) by varying the significant process parameters. The NiTiCu elements with different particle size were consolidated in a temperature range of 700–900°C and pressure from 20 to 40 MPa with 5 min of soaking time. The sintered products were subjected to mechanical analysis such as density and microhardness. Genetic algorithm (GA) and particle swarm optimization (PSO) techniques were used with integrated artificial neural network (ANN) to optimize the SPS process parameters to obtain better mechanical characteristics. The results indicate that the density and microhardness can be enhanced by the reduction of particle size and increase in pressure and temperature. A maximum density of 6.21 g/cc and Vickers hardness of 766 Hv were obtained the optimal for process parameters of temperature, pressure, and particle size of ~ 800°C, ~ 26 MPa and ~ 6 µm, respectively, in case of NiTiCu nanostructured SMAs.     

Mesoporous binder-free monoliths of few-walled carbon nanotubes by spark plasma sintering

Carbon nanotubes with few walls (FWCNTs) are prepared by catalytic chemical vapor deposition. Transmission electron microscopy investigations for each sample show the average number of walls (3, 4 and 8) as well as the internal and external diameter distributions. Binder-free FWCNT monoliths are prepared by spark plasma sintering (SPS) at temperatures in the range 1000–1600 °C. A combination of techniques including Raman spectroscopy, scanning- and transmission electron microscopy, electron microdiffraction is used to characterize the samples. Compared to the FWCNT powders, the high temperatures used for SPS favor the elimination of surface defects in CNT walls but also some limited amorphization, without dramatic damage to the CNTs. Increasing the SPS temperatures produces an increase in densification. N₂ adsorption–desorption cycles revealed that the powders and monoliths show microporosity and, mostly, mesoporosity. Some monoliths show a specific surface area equal to about 500 m²/g. The 4WCNTs when consolidated into monoliths by SPS at 1000 or 1100 °C are able to retain a high amount of mesoporosity that contributes to a high porous volume of the order of 0.8 cm³/g.