Densification,microstructure and mechanical properties of Ta4HfC5-based ceramics obtained from synthesized nanoscale powder

Solvothermal treatment was used to synthesize nanoscale 4TaC-HfC (Ta₄HfC₅) powder at a relatively low calcination temperature and in a short period (1400 °C, 2 h). The obtained powder had uniform size distribution and dispersion. Ta₄HfC₅ ceramics were then consolidated via spark plasma sintering at 2100 °C. Ceramics had a better densification and smaller mean grain size at a shorter sintering time compared with that of materials sintered using mechanical ball milling method. The densification behavior of ceramics deriving from synthesized or ball milled powders was analyzed and the mechanical properties of different samples were investigated. To further increase the mechanical properties, a nearly fully dense Ta₄HfC₅-MoSi₂ ceramic was sintered using the synthesized powder. The mechanical properties of the ceramic composite doubled the strength values. This processing route demonstrated to be a viable approach to synthesize nanoscale Ta₄HfC₅ powder with high purity and uniformity, and obtain higher performances ceramics once sintered.     

Effect of ZrB2 powders on densification,microstructure, mechanical properties and thermal conductivity of ZrB2-SiC ceramics

With the view to improve the densification behaviour and mechanical properties of ZrB₂-SiC ceramics, three synthesis routes were investigated for the production of ZrB₂, prior to the fabrication of ZrB₂-20 vol. % SiC via spark plasma sintering (SPS). Two borothermal reduction routes, modified with a water-washing stage (BRW) and partial solid solution of Ti (BRS), were utilised, alongside a boro/carbothermal mechanism (BRCR) were utilised to synthesise ZrB₂, as a precursor material for the production of ZrB₂-SiC. It was determined that reduction in the primary ZrB₂ particle size, alongside a diminished oxygen content, was capable of improving densification. ZrB₂-SiC ceramics, with ZrB₂ derived from BRW synthesis, exhibited a favorable combination of high relative density (98.6%), promoting a marked increase in Vickers hardness (21.4 ± 1.7 GPa) and improved thermal conductivity (68.7 W·m^-1K^-1).     

High-strength thermal insulating porous mullite fiber-based ceramics

How to improve the strength of fibrous porous ceramics dramatically under the premise of no sacrificing its low density and thermal conductivity has remained a challenge in the high-temperature thermal insulation field. In this paper, a new kind of high-strength mullite fiber-based ceramics composed of interlocked porous mullite fibers was prepared by nanoemulsion electrospinning and dry pressing method. Results show that as to the porous ceramics with the same density (～ 0.8 g/cm³), the three-dimensional skeleton structure composed of porous mullite fibers was much denser than that composed of solid mullite fibers. Therefore, porous mullite fiber-based ceramics exhibited a higher compressive strength (5.53 MPa) than that of solid mullite fiber-based ceramics (3.21 MPa). In addition, porous mullite fiber-based ceramics exhibited a superior high-temperature heat insulation property because the porous structure in fibers could reduce the radiant heat conduction. This work provides new insight into the development of high-temperature thermal insulators.     

High-strength thermal insulating mullite nanofibrous porous ceramics

Mullite fibrous porous ceramics is one of the most commonly used high temperature insulation materials. However, how to improve the strength of the mullite fibrous porous ceramics dramatically under the premise of no sacrificing the low sample density has always been a difficult scientific problem. In this study, the strategy of using mullite nanofibers to replace the mullite micron-fibers was proposed to fabricate the mullite nanofibrous porous ceramics by the gel-casting method. Results show that mullite nanofibrous porous ceramics present a much higher compressive strength (0.837 MPa) than that of mullite micron-fibrous porous ceramics (0.515 MPa) even when the density of the mullite nanofibrous porous ceramics (0.202 g/cm³) is only around three quarters of that of the mullite micron-fibrous porous ceramics (0.266 g/cm³). The obtained materials that present the best combination of mechanical and thermal properties can be regarded as potential high-temperature thermal insulators in various thermal protection systems.     

Synthesis routes for enhanced piezoelectric properties in spark plasma sintered Ta-doped KNN ceramics

Ta substitution in K_0.5Na_0.5NbO₃ lead free piezoelectrics helps to prevent grain growth and has been shown to improve the piezoelectric properties but always leads to hetereogeneous microstructures. Two synthesis routes have been studied to prepare K_0.5Na_0.5Nb_0.8Ta_0.2O₃ (KNNTa) substituted powders. Then highly densified KNNTa ceramics have been obtained by spark plasma sintering (SPS). The use of a synthesized oxide precursor Nb_1.6Ta_0.4O₅ during the ceramic elaboration process clearly shows through accurate Rietveld study a successful Ta substitution with 92% of Amm2 K_0.485(8)Na_0.515(8)Nb_0.819(6)Ta_0.181(6)O₃ phase, confirmed by SEM-EDS analysis and a more homogeneous chemical composition. This leads to enhanced electromechanical coupling coefficients with an improvement of 50% of k_t, 15% for k_p and low electrical losses, compared to the conventional synthesis method with a simple mixing of commercial precursors.     

Porous mullite ceramics with enhanced compressive strength from fly ash-based ceramic microspheres: Facile synthesis,structure, and performance

Porous mullite ceramics are widely used in heat insulation owing to their high temperature and corrosion resistant properties. Reducing the thermal conductivity by increasing porosity, while ensuring a high compressive strength, is vital for the synthesis of high-strength and lightweight porous mullite ceramics. In this study, ceramic microspheres are initially prepared from pre-treated high-alumina fly ash by spray drying, and then used to successfully prepare porous mullite ceramics with enhanced compressive strength via a simple direct stacking and sintering approach. The influence of sintering temperature and time on the microstructure and properties of porous mullite ceramics was evaluated, and the corresponding formation mechanism was elucidated. Results show that the porous mullite ceramics, calcined at 1550 °C for 3 h, possess a porosity of 47%, compressive strength of 31.4 MPa, and thermal conductivity of 0.775 W/(m?K) (at 25 °C), similar to mullite ceramics prepared from pure raw materials. The uniform pore size distribution and sintered neck between the microspheres contribute to the high compressive strength of mullite ceramics, while maintaining high porosity.     

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.     

Mechanical properties and thermal conductivity of dense β-SiAlON ceramics fabricated by two-stage spark plasma sintering with Al2O3-AlN-Y2O3 additives

Fully dense β-SiAlON ceramics with excellent mechanical properties and good thermal conductivity were fabricated by two-stage spark plasma sintering (SPS) processes without and with applying pressure respectively, using α-Si₃N₄ powder and 6 Al₂O₃-3 AlN-6 Y₂O₃ (in wt.%, label with 636), 424 and 422 additives. In the first stage SPS process without pressure, the relative dense β-SiAlON ceramics with interlock microstructures of elongated grains and density of 3.14˜3.18 g cm⁻³, hardness of 14.00˜14.82 GPa and fracture toughness of 6.00˜6.63 MPa m^1/2 were obtained by sintering at about 1600 °C for 20 min. In the second stage SPS process at about 1425 °C for 5 min under pressure of 24 MPa, the fully dese β-SiAlON ceramics with density of 3.22˜3.24 g cm⁻³, high hardness of 15.68˜15.95 GPa, high fracture toughness of 6.38˜7.03 MPa m^1/2 and thermal conductivity of 13.5˜19.6 Wm^-1K^-1 were obtained. The reaction between the samples and the graphite mold can be avoided in this fabrication method.     

Preparation of mullite from alumina/aluminum nitrate and kaolin clay through spark plasma sintering process

In the present study, the in-situ synthesized mullite has been prepared successfully by mixing kaolinite with alumina and aluminum nitrate nonahydrate (ANN) powders through high energy milling followed by spark plasma sintering (SPS). Using a high-energy ball-mill, the stoichiometric compositions of the starting powders, considering their final transformation to Al₂O₃ and SiO₂, have been mixed. The SPS process has been performed at 1400 and 1375?°C for the specimens containing Al₂O₃ and ANN, respectively. XRD patterns of the milled powders after 30?h showed the formation of quartz from kaolinite for both starting batches. The displacement-temperature-time (DTT) curves and the corresponded vacuum changes indicated the dehydration and phase transformation of ANN and kaolinite at different stages of the sintering process. The XRD patterns of the sintered samples revealed the formation of mullite alongside un-reacted Al₂O₃ and crystobalite for the batches containing Al₂O₃ and ANN, respectively. The results of the physical and mechanical properties tests showed higher amounts of bending strength (397?±?18?MPa), Vickers hardness (16.32?±?0.21?GPa) and fracture toughness (3.81?±?0.24?MPa?m^?1/2) alongside a lower porosity (0.070?±?0.02%) for the prepared sample containing Al₂O₃, than those of the sample containing ANN.     

Enhancement mechanical properties of in-situ preparated B4C-based composites with small amount of (Ti3SiC2+Si)

B₄C-based composites were synthesized by spark plasma sintering using B₄C、Ti₃SiC₂、Si as starting materials. The effects of sintering temperature and second phase content on mechanical performance and microstructure of composites were studied. Full dense B₄C-based composites were obtained at a low sintering temperature of 1800 °C. The B₄C-based composite with 10 wt% (TiB₂+SiC) shows excellent mechanical properties: the Vickers hardness, fracture toughness, and flexural strength are 33 GPa, 8 MPa m^1/2, 569 MPa, respectively. High hardness and flexural strength were attributed to the high relative density and grain refinement, the high fracture toughness was owing to the crack deflection and uniform distribution of the second phase.     

Sintering behavior and mechanical properties of Ta4HfC5-based composites with ZrB2 additive

Ta₄HfC₅ powder was synthesized using TaCl₅, HfCl₄ and phenolic resin as raw materials. Then, Ta₄HfC₅–10 vol% MoSi₂ ceramics and Ta₄HfC₅–10 vol% MoSi₂ with different proportions of ZrB₂ (10 – 30 vol%) ceramics were sintered by spark plasma sintering. Zr atoms substituted Ta and Hf atoms in Ta₄HfC₅ during the sintering process at 2000 °C. The sintering behavior and microstructure evolution upon the ceramics are discussed. The mechanical properties of the composites were improved compared to the pure Ta₄HfC₅ ceramics. The hardness of Ta₄HfC₅–MoSi₂ with 30 vol% ZrB₂ increased from around 10 GPa to almost 13 GPa, the flexural strength increased from around 245–435 MPa, and the fracture toughness increased from 2.56 ± 0.12 MPa?m^1/2 to 4.46 ± 0.20 MPa?m^1/2.     

Processing and mechanical properties of B4C-SiCw ceramics densified by spark plasma sintering

Homogenous distribution of whiskers in the ceramic matrix is difficult to be achieved. To solve this problem, B₄C-SiC_w powder mixtures were freeze dried from a slurry dispersed by cellulose nanofibrils (CellNF) in this work. Dense B₄C ceramics reinforced with various amounts of SiC_w up to 12 wt% were consolidated by spark plasma sintering (SPS) at 1800 °C for 10 min under 50 MPa. During this process, CellNF was converted into carbon nanostructures. As iron impurities exist in the starting B₄C and SiC_w powders, both thermodynamic calculations and microstructure observations suggest the dissolution and precipitation of SiC_w in the liquids composed of Fe-Si-B-C occurred during sintering. Although not all the SiC_w grains were kept in the final ceramics, B₄C-9 wt% SiC_w ceramics sintered at 1800 °C still exhibit excellent Vickers hardness (35.5 ± 0.8 GPa), flexural strength (560 ± 9 MPa) and fracture toughness (5.1 ± 0.2 MPa·m^1/2), possibly contributed by the high-density stacking faults and twins in their SiC grains, no matter in whisker or particulate forms.     

Microstructure and mechanical properties of B4C based ceramics with Fe3Al as sintering aid by spark plasma sintering

B₄C based ceramics were fabricated with different Fe₃Al contents as sintering aids by spark plasma sintering at relatively low temperature (1700 °C) in vacuum by applying 50 MPa pressure and held at 1700 °C for 5 min. The effect of Fe₃Al additions (from 0 to 9 wt%) on the microstructure and mechanical properties of B₄C has been studied. The composition and microstructure of as-prepared samples were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe microanalyzer (EPMA) equipped with WDS (wavelength dispersive spectrometry) and EDS. The mixtures of B₄C and Fe₃Al underwent a major reaction in which the metal borides and B₄C were encountered as major crystallographic phases. The sample with 7 wt% of Fe₃Al as a sintering aid was found to have 32.46 GPa Vickers hardness, 483.40 MPa flexural strength, and 4.1 MPa m^1/2 fracture toughness which is higher than that of pure B₄C.     

Microstructure and mechanical properties of multiwalled carbon nanotube toughened spark plasma sintered ZrB2 composites

ZrB₂ based composites containing 10 vol.-% carbon nanotubes (CNTs) are synthesised by spark plasma sintering at temperatures ranging from 1600 to 18008C and at an applied pressure of 25?MPa. The effects of sintering temperature on densification behaviour, microstructural evolutions and mechanical properties are presented. Results indicate that ZrB₂-CNT composites fabricated at 16508C have the optimal combination of dense microstructure and properties. The fracture toughness is sensitive to the temperature change and reaches 7.2?MPa m^1/2 for the CNT toughened ZrB₂ ceramics, which is higher than the measured result for monolithic ZrB₂ (3.3?MPa m^1/2). The crack deflection and CNT pullout are the dominant toughening mechanisms.     

The preparation and properties of high-strength porous mullite ceramics by a novel non-toxic gelcasting process

A novel approach to fabricate porous mullite ceramics with homogeneous pore size and high-strength using green non-toxic and cost-effective poly-γ-glutamic acid (γ-PGA) gelling system was reported for the first time. Effect of γ-PGA addition, additive amount and solid loading on rheological behavior of the slurries, and microstructure and properties of samples were investigated systematically. By optimizing the solid loading of mullite samples, we are able to get the sample with small pores (< 200 µm) dominating (93.3% of the total pores), and compressive strength of the sample reaches up to 26.62 MPa. In addition, the mullite ceramics exhibited high porosity of 75.7% with low thermal conductivity of 0.279 W/(m·K) at room temperature. This study not only provides a green and non-toxic gelling system but also offers porous mullite ceramics with low thermal conductivity and excellent mechanical strength as an energy-saving thermal insulation material.     

An optimized method for synthesizing phase-pure Ti3AlC2 MAX-phase through spark plasma sintering

So far many attempts have been made to synthesize phase-pure Ti₃AlC₂ MAX-phase. But still the challenge posed by the presence of TiC and Ti-Al based intermetallic transient impurity phases in the final product is a persisting problem. Spark plasma sintering (SPS) technique has been the most successful method to decrease the impurity content of the final product. Even so, synthesis of phase-pure Ti₃AlC₂ MAX-phase, without any TiC and Ti-Al based intermetallic impurities, has not been achieved and reported in literature with substantial evidences. Further, high purity Ti₃AlC₂ MAX-phase synthesized using SPS technique has shown lack of phase and microstructural stability above 1350°C temperature. In this work, we have reported an optimized method for producing phase-pure Ti₃AlC₂ MAX-phase (having more than 99 % purity) using commercial grade Ti, Al and C elemental powders through SPS technique. The final product also showed very good high temperature stability up to 1500°C under flowing Argon inert atmosphere.     

Porous SiC/SiCN composite ceramics fabricated by foaming and reaction sintering

Porous SiC/SiCN composite ceramics with heterogeneous pore structure and rod-like SiCN grains were fabricated by foaming and reaction sintering. The mixture slurry containing SiC and silicon as raw materials, cornstarch as binder, Y₂O₃ as sintering additive and an electrosteric dispersant was stirred with foams derived from pre-foaming using foaming agent. The casted green body was sintered at 1650 °C under nitrogen atmosphere. The results demonstrated that the porous SiC/SiCN ceramics exhibited hierarchical vias ranging from 1 μm to 1 mm and the rod-like crystalline SiCN grains generated in the SiC matrix.     

Preparation and characterization of porous mullite ceramics via foam-gelcasting

Porous mullite ceramics were prepared via foam-gelcasting using industrial grade mullite powder as the main raw materials, Isobam-104 as the dispersing and gelling agent, sodium carboxymethyl cellulose as the foam stabilizing agent, and triethanolamine lauryl sulfate as the foaming agent. The effects of processing parameters such as type and amount of additive, solid loading level and gelling temperature on rheological properties and gelling behaviors of the slurries were investigated. The green samples after drying at 100 °C for 24 h were fired at 1600 °C for 2 h, and the microstructures and properties of the resultant porous ceramic samples were characterized. Based on the results, the effects of foaming agent on the porosity level, pore structure and size and mechanical properties of the as-prepared porous mullite ceramics were examined. Porosity levels and pore sizes of the as-prepared samples increased with increasing the foaming agent content up to 1.0%, above which both porosity levels and pore sizes did not change. The compressive strength and flexural strength of the as-prepared sample with porosity of 76% and average pore size of 313 μm remained as high as 15.3±0.3 MPa and 3.7±0.2 MPa, respectively, and permeability increased exponentially with increasing the porosity.     

Microstructure and mechanical behaviour of transient liquid phase spark plasma sintered B4C–SiC–TiB2 composites from a B4C–TiSi2 system

Almost fully-dense B₄C–SiC–TiB₂ composites with a high combination of strength and toughness were prepared through in situ reactive spark plasma sintering using B₄C and TiSi₂ as raw materials. The densification, microstructure, mechanical properties, reaction, and toughening mechanisms were explored. TiSi₂ was confirmed as a reactive sintering additive to promote densification via transient liquid-phase sintering. Specifically, Si formed via the reaction between B₄C and TiSi₂ that served as a transient component contributed to densification when it melted and then reacted with C to yield more SiC. Toughening mechanisms, including crack deflection, branching and bridging, could be observed due to the residual stresses induced by the thermoelastic mismatches. Particularly, the introduced SiC–TiB₂ agglomerates composed of interlocked SiC and TiB₂ played a critical role in improving toughness. Accordingly, the B₄C–SiC–TiB₂ composite created with B₄C-16 wt% TiSi₂ achieved excellent mechanical performance, containing a Vickers hardness of 33.5 GPa, a flexural strength of 608.7 MPa and a fracture toughness of 6.43 MPa m^1/2.     

Enhanced electromagnetic shielding property of cf/mullite composites fabricated by spark plasma sintering

Aiming to prepare high-performance electromagnetic interference (EMI) shielding materials, chopped carbon fibers were incorporated into mullite ceramic matrix via rapid prototyping process of spark plasma sintering (SPS). Results indicate that C_f/mullite composites with only 1 wt% of carbon fibers exhibit highest shielding effectiveness (SE_T) over 40 dB at a small thickness of 2.0 mm, showing great advantages both in terms of performance and thickness compared with many mature carbon/ceramic composites. The high EMI shielding properties mainly depend on two mechanisms of absorption and reflection in this present work. The enhanced absorption and reflection of electromagnetic wave are ascribed to the promotional electrical conductivity arising from the formation of conductive network by introduction of carbon fibers. Regarding enhanced electrical conductivity, notable intensified interfacial polarization on a large number of interfaces between mullite matrix and carbon fibers is also the key factor to the improved absorption, which makes absorption play a dominant role in the significant improvement of EMI SE_T. The C_f/mullite composites with excellent EMI shielding properties and thin thickness show great potential application as EMI materials.