High-frequency induction heated sintering of High-energy ball milled TiC0.5N0.5 powders and mechanical properties of the sintered products

Commercial TiC_0.5N_0.5 powders were high-energy ball milled for various durations and consolidated without binder using the high-frequency induction heated sintering method (HFIHS). The effect of milling on the sintering behavior, crystallite size and mechanical properties of TiCN powders were evaluated. A nanostructured dense TiCN compact with a relative density of up to 98% was readily obtained within 3 min. The ball milling effectively refined the crystallite structure of TiCN powders and facilitated the subsequent densification. The sinter-onset temperature was reduced appreciably by the prior milling for 10 h from 1170 °C to 820 °C. Accordingly, the relative density of TiCN compact increased as the milling time increases. The microhardness of sintered TiCN was linearly proportional to the density while its toughness did not show any correlation with the crystalline size or density. It is clearly demonstrated that a quick densification of nano-structured TiCN bulk materials to near theoretical density could be obtained by the combination of HFIHS and the preparatory high-energy ball milling processes.     

Nano-sized Ag–BaTiO3 composite powders with various amount of Ag prepared by spray pyrolysis

The preparation of precursors of BaTiO₃ nanopowders with various amounts of Ag by spray pyrolysis is reported. The precursor powders obtained with hollow and thin-wall particles are composed of uniformly dispersed Ba, Ti, and Ag components. After post-treatment and a simple milling process, the precursor powders, irrespective of the amount of Ag, are transformed into Ag–BaTiO₃ composite nanoparticles. The mean particle size of the Ag (10 mol%)–BaTiO₃ powders is 142 nm. BaTiO₃ pellets containing Ag exhibit dense structures even at a low sintering temperature of 1000 °C. BaTiO₃ pellets with 10 mol% Ag show the highest dielectric constant of 2950, as opposed to the pure BaTiO₃ pellets (without Ag), whose dielectric constant is 1827.     

Comparison among different sintering routes for preparing alumina-YAG nanocomposites

Al₂O₃-YAG (50 vol.%) nanocomposite powders were prepared by wet-chemical synthesis and characterized by DTA-TG, XRD and TEM analyses. Amorphous powders were pre-heated at different temperatures (namely 600 °C, 800 °C, 900 °C and 1215 °C) and the influence of this thermal treatment on sintering behavior, final microstructure and density was investigated. The best performing sample was that pre-calcined at 900 °C, which yields dense bodies with a micronic/slightly sub-micronic microstructure after sintering at 1600 °C. A pre-treatment step to induce controlled crystallisation of the amorphous powder as well as a fast sintering procedure for green compacts, were also performed as a comparison.Finally, the previously stated thermal pre-treatment of the amorphous product was coupled to an extensive mechanical activation performed by wet planetary/ball milling. This procedure was highly effective in lowering the densification temperature, so that fully dense Al₂O₃-YAG composites, with a mean grain size smaller than 200 nm, were obtained by sintering in the temperature range 1370–1420 °C.     

Microwave sintering and grain growth behavior of nano-grained BaTiO3 materials

In this paper, we investigated the effect of microwave sintering parameters on the development of the microstructure of nano-grained BaTiO₃ materials co-doped with Y and Mg species. It is observed that the materials can not only be sintered densely at a lower temperature (1150 °C) and a shorter soaking time (20 min), but also the grain growth can be suppressed by 2.45 GHz microwave heating process. However, the grain growth exhibits a unique tendency in some processing conditions such as microwave sintering for longer intervals (≧60 min) or at higher temperatures (1200 °C). The grain growth behavior after densification was investigated in terms of the phenomenological kinetics, and the activation energy for grain growth using microwave sintering (59.4 kJ/mol) is considerably less than that of the conventionally sintered ones (96.0 kJ/mol), which indicates that microwave sintering process can accelerate the densification rate of the BaTiO₃ materials comparing with the conventional sintering process.     

The processing and properties of (Zr,Hf)B2–SiC nanostructured composites

(Zr, Hf)B₂–SiC nanostructured composites were fabricated by high energy ball milling and reactive spark plasma sintering (RSPS) of HfB₂, ZrSi₂, B₄C and C. Highly dense composites with homogeneously intermixed ultra-fine (Zr, Hf)B₂ and SiC grains (100–300 nm) were obtained after RSPS at 1600 °C for 10 min. The densification was promoted by high energy ball milling and ZrSi₂ additive. The additives were almost completely transformed into ZrB₂ and SiC during densification. The improvement of flexural strength and fracture toughness (641 MPa and 5.36 MPa m^1/2, respectively) was achieved. The relationships between the ultra-fine microstructure and mechanical properties were discussed.     

Effect of high energy ball milling on compressibility and sintering behavior of alumina nanoparticles

The effect of high-energy ball milling on the textural evolution of alumina nanopowders (compaction response, sinter-ability, grain growth and the degree of agglomeration) during post sintering process is studied. The applied pressure required for the breakage of the agglomerates (P_y) during milling was estimated and the key elements of compressibility (i.e. critical pressure (P_cr) and compressibility (b)) were calculated. Based on the results, the fracture point of the agglomerates decreased from 150 to 75 MPa with prolonged milling time from 3 to 60 min. Furthermore, the powders were formed by different shaping methods such as cold isostatic press (CIP) and uniaxial press (UP) to better illustrate the influence of green compact uniformity and powder deagglomeration on the densification behavior of nanopowders.     

Properties of Si3N4–TiN composites fabricated by spark plasma sintering by using a mixture of Si3N4 and Ti powders

Si₃N₄–TiN composites were successfully fabricated via planetary ball milling of 70 mass% Si₃N₄ and 30 mass% Ti powders, followed by spark plasma sintering (SPS) at 1250–1350 °C. The sintering mechanism for SPS was a hybrid of dissolution–reprecipitation and viscous flow. The electrical resistivity decreased with increasing sintering temperature up to a minimum at 1250 °C and then increased with the increasing sintering temperature. The composites prepared by SPS at 1250–1350 °C could be easily machined by electrical discharge machining. Composite prepared by SPS at 1300 °C showed a high hardness (17.78 GPa) and a good machinability.     

Synthesis of nanocrystalline cerium oxide by high energy ball milling

We have synthesized pure nanocrystalline CeO₂ powders of nearly spherical shape using high-energy attritor ball mill. Milling parameters such as the milling speed of 400 rpm, ball to powder ratio (40:1), milling time (30 h) and water cooled media were determined to be suitable for synthesizing nanosize (～10 nm) powders of CeO₂. The powders after milling for various durations (up-to 50 h) were characterized by X-ray Diffraction, Scanning Electron Microscopy, Energy-dispersive X-ray Spectrometry and Transmission Electron Microscopy. An average particle size of 10 nm was obtained at 30 h milling, after which the particle agglomeration started, and a mixture of nanocrystalline and amorphous phase was observed after 50 h milling.     

Effect of preparation route on the microstructure and electrical conductivity of co-doped ceria

Dense Ce_0.8Sm_0.1Gd_0.1O_2?δ electrolytes were fabricated by sintering of CeO₂ solid solutions which were prepared from metal nitrates and NaOH using self propagating room temperature synthesis (SPRT). Three different routes were employed to obtain CeO₂ solid solution powders: (I) hand mixing of reactants, (II) ball milling of reactants and (III) ball milling of Ce_0.8Sm_0.2O_2?δ and Ce_0.8Gd_0.2O_2?δ solid solutions previously prepared by ball milling of corresponding nitrates and NaOH. Density measurements showed that ball milling, which is more convenient than hand mixing, is an effective way to obtain almost full dense samples after presureless sintering at 1550 °C for 1 h. These samples had larger grain size and consequently higher conductivity than the samples obtained by hand mixing. The highest conductivity of 2.704×10^?2 (Ω cm)^?1was measured at 700 °C in a sample prepared by route II. It was found that reduced grain size in samples obtained by hand mixing leads to a decrease in grain boundary conductivity and therefore decrease in the total conductivity. The results showed that mixing of single doped ceria solid solutions improved densification and inhibited grain growth.     

Transparent YAG obtained by spark plasma sintering of co-precipitated powder. Influence of dispersion route and sintering parameters on optical and microstructural characteristics

A fine-grained (330 nm) yttrium aluminium garnet (YAG) ceramic, presenting a non-negligible transparency (66% RIT at 600 nm), was obtained by spark plasma sintering. The YAG powder was manufactured by co-precipitation, starting from a yttrium and aluminium chlorides solution. A soft precursor was obtained, whose phase evolution was studied by X-ray diffraction. Calcined powders were dispersed by either ball milling or by ultrasonication and then subjected to spark plasma sintering at several temperatures (1200–1400 °C) and for a reduced time (15 min). It is shown that the dispersion method plays a key role in enhancing the optical characteristics of YAG ceramics, in order to obtain a material with a small grain size, transparent in both the visible and the infrared range.     

Mechanochemical synthesis of MoSi2–SiC nanocomposite powder

MoSi₂–25 wt.%SiC nanocomposite powder was successfully synthesized by ball milling Mo, Si and graphite powders. The effect of milling time and annealing temperature were investigated. Changes in the crystal structure and powder morphology were monitored by XRD and SEM, respectively. The microstructure of powders was further studied by peak profile analysis and TEM. MoSi₂ and SiC were synthesized after 10 h of milling. Both high and low temperature polymorphs (LTP and HTP) of MoSi₂ were observed at the short milling times. Further milling led to the transformation of LTP to HTP. On the other hands, an inverse HTP to LTP transformation took place during annealing of 20 h milled powder at 900 °C. Results of peak profile analysis showed that the mean grain size and strain of the 20 h milled powder are 31.8 nm and 1.19% that is in consistent with TEM image.     

SPS densification and microstructure of ZrB2 composites derived from sol–gel ZrC coating

A technique for densifying ultra high temperature ceramic composites while minimising grain growth is reported. As-purchased ZrB₂ powder was treated with a zirconia-carbon sol–gel coating. Carbothermal reduction at 1450 °C produced 100–200 nm crystalline ZrC particles attached on the surface of ZrB₂ powders. The densification behaviour of the sol–gel coated powder was compared with both the as-purchased ZrB₂ and a compositionally similar ZrB₂–ZrC mixture. All three samples were densified by spark plasma sintering (SPS). The ZrB₂ reference sample was slow to densify until 1800 °C and was not fully dense even at 2000 °C, while the sol–gel modified ZrB₂ powder completed densification by 1800 °C. The process was studied by ram displacement data, gas evolution, SEM, and XRD. The sol–gel coated nanoparticles on the ZrB₂ powder played a number of important roles in sintering, facilitating superior densification by carbothermal reduction, nanoparticle coalescence and solid-state diffusion, and controlling grain growth and pore removal by Zener pinning. The sol–gel surface modification is a promising technique to develop ultra-high temperature ceramic composites with high density and minimum grain growth.     

Analysis of reactions during sintering of CuO-doped 3Y-TZP nano-powder composites

3Y-TZP (yttria-doped tetragonal zirconia) and CuO nano powders were prepared by co-precipitation and copper oxalate complexation–precipitation techniques, respectively. During sintering of powder compacts (8 mol% CuO-doped 3Y-TZP) of this two-phase system several solid-state reactions clearly influence densification behaviour. These reactions were analysed by several techniques like XPS, DSC/TGA and high-temperature XRD. A strong dissolution of CuO in the 3Y-TZP matrix occurs below 600 °C, resulting in significant enrichment of CuO in a 3Y-TZP grain-boundary layer with a thickness of several nanometres. This “transient” liquid phase strongly enhances densification. Around 860 °C a solid-state reaction between CuO and yttria as segregated to the 3Y-TZP grain boundaries occurs, forming Y₂Cu₂O₅. This solid-state reaction induces the formation of the thermodynamic stable monoclinic zirconia phase. The formation of this solid phase also retards densification. Using this knowledge of microstructural development during sintering it was possible to obtain a dense nano–nano composite with a grain size of only 120 nm after sintering at 960 °C.     

Spark plasma sintering of combustion-synthesized β-SiAlON powders

In this paper, the sintering behavior of β-Si_6−zAl_zO_zN_8−z (z=1) powder prepared by combustion synthesis (CS) was studied using spark plasma sintering (SPS). The CSed powder was ball milled for various durations from 0.5 to 20 h and was then sintered at different temperatures with heating rates varying from 30 °C/min to 200 °C/min. The effects of ball milling, sintering temperature, and heating rate on sinterability, final microstructure, and mechanical property were investigated. A long period of ball milling reduced the particle size and subsequently accelerated the sintering process. However, the fine powder was easily agglomerated to form secondary particles, which accordingly decreased the densification of the SPS product. The high sintering temperature accelerated the densification process, whereas the high heating rate reduced the grain growth and increased the relative density of the sintered product.     

High pressure FAST of nanocrystalline barium titanate

This work studies the microstructural evolution of nanocrystalline (<1 µm) barium titanate (BaTiO₃), and presents high pressure in field-assisted sintering (FAST) as a robust methodology to obtain >100 nm BaTiO₃ compacts. Using FAST, two commercial ~50 nm powders were consolidated into compacts of varying densities and grain sizes. Microstructural inhomogeneities were investigated for each case, and an interpretation is developed using a modified Monte Carlo Potts (MCP) simulation. Two recurrent microstructural inhomogeneities are highlighted, heterogeneous grain growth and low-density regions, both ubiqutously present in all samples to varying degrees. In the worst cases, HGG presents an area coverage of 52%. Because HGG is sporadic but homogenous throughout a sample, the catalyst (e.g., the local segregation of species) must be, correspondingly, distributed in a homogenous manner. MCP demonstrates that in such a case, a large distance between nucleating abnormal grains is required—otherwise abnormal grains prematurely impinge on each other, and their size is not distinguishable from that of normal grains. Compacts sintered with a pressure of 300 MPa and temperatures of 900 °C, were 99.5% dense and had a grain size of 90±24 nm. These are unprecedented results for commercial BaTiO₃ powders or any starting powder of 50 nm particle size—other authors have used 16 nm lab-produced powder to obtain similar results.     

ZrB2–SiC composites prepared by reactive pulsed electric current sintering

Fully densified ZrB₂–20 vol% SiC composites were produced by reactive pulsed electric current sintering (PECS) of a powder mixture containing ZrH₂, B, SiC and B₄C within a total thermal cycle time of only 50 min. During the combined synthesis and sintering process, the ZrH₂ powder decomposed gradually from ZrH₂ into ZrH_m and finally metal Zr that reacted with elemental B to form the ZrB₂ matrix. Reducing the ZrH₂ particle size by attritor milling significantly enhanced densification and allowed initiation of self-propagating high temperature synthesis (SHS) during PECS. The PECS grades exhibited a slightly textured structure, with ≤17% of the ZrB₂ grains oriented with their (0 0 1) planes perpendicular to the direction of pressure and DC current. Because of the ZrB₂ grain orientation, anisotropic mechanical properties were observed. Ceramics prepared from attritor milled powders and PECS with a pressure applied after 5 min upon reaching 1900 °C achieved excellent flexural strengths of 901–937 MPa. The hardness and fracture toughness were respectively 19.7–19.8 GPa and 4.0–4.7 MPa m^1/2 in the direction parallel and 20.2–21.3 GPa and 3.8–3.9 MPa m^1/2 in the direction perpendicular to the applied pressure.     

Grain size effect on electromechanical properties and non-linear response of dense nano and microstructured PIN–PT ceramics

Nanopowders of 0.63Pb(In_1/2Nb_1/2)O₃–0.37PbTiO₃ were synthesized by solid state reaction using the continuous attrition milling followed by high-energy ball milling techniques in air at room temperature. After milling for 8 h nanopowders of 20–30 nm grain size are obtained. Sintering by hot pressing of PIN–37PT green pellets leads to dense ceramics with average grain size varying from 100 nm to 1 μm. The dielectric and piezoelectric properties of PIN–37PT nanostructured ceramics with grain size bigger than about 160 nm remain roughly unchanged and comparable to those of microstructured ceramics. In addition, the stability of the permittivity and dielectric losses under high ac electric field grows when the grain size decreases. The material becomes less non-linear with decreasing grain size. This result is attractive for acoustic transducer applications.     

Microstructural evolution of nanocrystalline Al2O3 sintered at a high heating rate

Experimental sintering studies on Al₂O₃ powder (200 nm and 600 nm) were done at a heating rate of 1600 °C/min. The microstructural changes of specimens were examined and corresponding detailed data on the densification and grain size as a function of sintering time were presented. The grain-growth transition behavior during sintering was discussed. The results showed that the neck growth caused principally by surface diffusion could be negligible within 2 min. With subsequent increases of sintering time, grain growth promoted by grain boundary and lattice diffusion occurred.     

Consolidation of binderless nanostructured titanium carbide by high-frequency induction heated sintering

The rapid sintering of nanostructured TiC hard materials in a short time was investigated with High-Frequency Induction Heating Sintering process. The advantage of this process is that it allows very quick densification to near theoretical density and prohibition of grain growth in nanostructured materials. A dense nanostructured TiC hard material with a relative density of up to 99% was produced with simultaneous application of 80 MPa pressure and induced current of output of total power capacity (15 kW) within 4 min. The effect of the ball milling times on the sintering behavior, grain size and mechanical properties of binderless TiC was investigated.     

Spark plasma sintering and pressureless sintering of SiC using aluminum borocarbide additives

Aluminum borocarbide powders (Al₃BC₃ and Al₈B₄C₇) were synthesized, and the ternary powders were used as a sintering additive of SiC. The densification of SiC was nearly completed at 1670 °C using spark plasma sintering (SPS) and pressureless sintering was possible at 1950 °C. The sintering behavior of SiC using the new additive systems was nearly identical with that using the conventional Al–B–C system, but grain growth was suppressed when adding the borocarbides. In addition, oxidation of the fine additive powders did not intensively occur in air, which has been a problem in the case of the Al–B–C system for industrial application. The hardness, Young's modulus and fracture toughness of a sintered SiC specimen were 21.6 GPa, 439 GPa and 4.6 MPa m^1/2, respectively. The ternary borocarbide powders are efficient sintering additives of SiC.