Sintering dense boron carbide without grain growth under high pressure

Traditionally, densification and grain growth are two competing processes in sintering of ceramics. To improve the density, while limiting grain growth at the same time, an ultrahigh pressure (>1 GPa) is employed here and results in plastic deformation as the dominant densification mechanism during the sintering process. In this way, fully dense boron carbide (B₄C) structural ceramics without grain growth is prepared under the pressure of 4.5 GPa at low temperature of 1300°C in 5 minutes, while showing excellent mechanical properties such as Vickers hardness of 38.04 GPa, Young's modulus of 487.7 GPa, and fracture toughness of 3.87 MPa·m^1/2. This study should also facilitate the development of other structural ceramics for practical applications.     

Pressureless Sintering of Zirconium Diboride: Particle Size and Additive Effects

Zirconium diboride (ZrB₂) was densified by pressureless sintering using <4-wt% boron carbide and/or carbon as sintering aids. As-received ZrB₂ with an average particle size of ∼2 μm could be sintered to ∼100% density at 1900°C using a combination of boron carbide and carbon to react with and remove the surface oxide impurities. Even though particle size reduction increased the oxygen content of the powders from ∼0.9 wt% for the as-received powder to ∼2.0 wt%, the reduction in particle size enhanced the sinterability of the powder. Attrition-milled ZrB₂ with an average particle size of <0.5 μm was sintered to nearly full density at 1850°C using either boron carbide or a combination of boride carbide and carbon. Regardless of the starting particle size, densification of ZrB₂ was not possible without the removal of oxygen-based impurities on the particle surfaces by a chemical reaction.     

防弹装甲用碳化硼陶瓷材料的研究进展

碳化硼陶瓷具有较低的密度、仅次于氮化硼和金刚石的硬度以及优异的耐腐蚀性能,满足防弹材料要求的高强度、高耐磨、高硬度、低密度,简称为"三高一低",当前已经应用于高端装备的防护系统中。然而,碳化硼陶瓷为强共价化合物,且具有低的扩散系数,导致其在制备过程中的主要问题是烧结致密化问题和脆性问题。因此,许多的研究工作集中在碳化硼陶瓷的烧结技术、烧结助剂以及对碳化硼陶瓷进行增韧。本文聚焦防弹装甲用碳化硼陶瓷,首先从碳化硼的晶形结构和相图,综述了碳化硼陶瓷粉体的制备技术以及碳化硼陶瓷的烧结工艺,阐述了改善碳化硼断裂韧性较低的方法,最后分析了碳化硼陶瓷防弹材料的研究现状,并且展望陶瓷防弹装甲的未来研究方向。     

Fabrication of New Cemented Carbide Containing Diamond Coated with Nanometer-Sized SiC Particles

A simple process for depositing a coating of silicon carbide (SiC) crystallites ∼10 nm in size onto diamond particles has been developed. SiO powders react with diamond in a vacuum at 1350°C to form a uniform β-SiC polycrystalline layer ∼60 nm thick. The SiC coating improves the oxidation resistance of the diamond. A cemented carbide material containing 20-vol%-SiC-coated diamond particles was sintered to a relative density of 99.5% by pulsed-electric-current sintering. A Vickers hardness and indentation fracture toughness of 15 GPa and 16.3 MPa·m^1/2, respectively, were obtained. This toughness is two times higher than that of cemented carbide containing no particles. The higher toughness is attributed to deflection and blockage of crack propagation by the diamond particles.     

Sintering and densification mechanisms of tantalum carbide ceramics

Dense tantalum carbide (TaC) ceramics were prepared using TaC nanopowder via spark plasma sintering (SPS). The effects of the sintering temperature and applied pressure on the densification and grain growth behaviour of TaC ceramics were investigated. The results showed that high temperature and pressure promoted sintering densification, while their increase caused an increase in the grain size of TaC ceramics. A highly dense TaC ceramic (∼97.19%) with a fine grain size of 2.67 μm was obtained by sintering at 1800 °C for 10 min under 80 MPa. The Vickers hardness, Young's modulus and fracture toughness were 15.60 GPa, 512.66 GPa and 3.59 MPa·m^1/2, respectively. The densification kinetics were investigated using a creep deformation model. Diffusion and grain boundary sliding were proven to be the dominant densification mechanisms based on the stress and grain size exponents combined with the microstructural characteristics. The apparent activation energy of the mechanism controlling densification was 252.94 kJ/mol.     

Development of WC–ZrO2 Nanocomposites by Spark Plasma Sintering

In the present work, we report the processing of ultrahard tungsten carbide (WC) nanocomposites with 6 wt% zirconia additions. The densification is conducted by the spark plasma sintering (SPS) technique in a vacuum. Fully dense materials are obtained after SPS at 1300°C for 5 min. The sinterability and mechanical properties of the WC–6 wt% ZrO₂ materials are compared with the conventional WC–6 wt% Co materials. Because of the high heating rate, lower sintering temperature, and short holding time involved in SPS, extremely fine zirconia particles (∼100 nm) and submicrometer WC grains are retained in the WC–ZrO₂ nanostructured composites. Independent of the processing route (SPS or pressureless sintering in a vacuum), superior hardness (21–24 GPa) is obtained with the newly developed WC–ZrO₂ materials compared with that of the WC–Co materials (15–17 GPa). This extremely high hardness of the novel WC–ZrO₂ composites is expected to lead to significantly higher abrasive-wear resistance.     

Processing and Properties of TiB2 with MoSi2 Sinter-additive: A First Report

The densification of non-oxide ceramics like titanium boride (TiB₂) has always been a major challenge. The use of metallic binders to obtain a high density in liquid phase-sintered borides is investigated and reported. However, a non-metallic sintering additive needs to be used to obtain dense borides for high-temperature applications. This contribution, for the first time, reports the sintering, microstructure, and properties of TiB₂ materials densified using a MoSi₂ sinter-additive. The densification experiments were carried out using a hot-pressing and pressureless sintering route. The binderless densification of monolithic TiB₂ to 98% theoretical density with 2–5 μm grain size was achieved by hot pressing at 1800°C for 1 h in vacuum. The addition of 10–20 wt% MoSi₂ enables us to achieve 97%–99%ρ_th in the composites at 1700°C under similar hot-pressing conditions. The densification mechanism is dominated by liquid-phase sintering in the presence of TiSi₂. In the pressureless sintering route, a maximum of 90%ρ_th is achieved after sintering at 1900°C for 2 h in an (Ar+H₂) atmosphere. The hot-pressed TiB₂–10 wt% MoSi₂ composites exhibit high Vickers hardness (∼26–27 GPa) and modest indentation toughness (∼4–5 MPa·m^1/2).     

无压烧结制备纳米复合碳化硅陶瓷

以水基喷雾造粒而成含5%(质量分数)纳米氮化钛(TiN)颗粒的碳化硅(SiC)造粒粉为原料,采用无压烧结制备纳米复合SiC陶瓷。分析了烧结温度及保温时间对复合陶瓷烧结特性与显微结构的影响规律。结果表明:采取二步烧结可以实现SiC陶瓷在晶粒不明显长大的前提下实现致密化,二步烧结,即先升温到1950℃保温15min后迅速降至1850℃烧结1h,制备的SiC陶瓷具有较高收缩率、较低质量损失以及较高的致密度;纳米TiN颗粒加入后能与基体(SiC,Al2O3)部分发生反应生成TiC和AlN,明显改善SiC陶瓷的烧结性能,获得等轴状、细晶显微结构和优越的力学性能。     

Densification behavior and related phenomena of spark plasma sintered boron carbide

In this work, boron carbide ceramics were sintered in the temperature range of 1400–1600 °C by spark plasma sintering (SPS). The influence of sintering temperature, heating rate, and holding time on the microstructure, densification process and physical property was studied. The heating rate was found to have greater influence than that of the holding time on the microstructure and the densification of boron carbide. The optimal sintering temperature was 1600 °C under the heating rate higher than 100 °C/min. The relative density, flexural strength, Vickers hardness and fracture toughness of the sample synthesized at 1600 °C were 98.33%, 828 MPa, 31 GPa and 2.66±0.29 MPa m^1/2, respectively. The densification mechanism was also investigated.     

Enhancing Toughness in Boron Carbide with Reduced Graphene Oxide

Ceramics typically have very high hardness, but suffer from poor toughness. Here, we use graphene to enhance the toughness of bulk boron carbide ceramics. The reduced graphene oxide (rGO) platelets are homogenously dispersed with boron carbide particles after sintering at 1350°C, under high pressure of 4.5 GPa with a multi‐anvil apparatus. Fracture toughness of the composites is increased ~131% (from ~3.79 to ~8.76 MPa·m^1/2) at 1.5 vol% rGO platelets as a result of a toughing effect of graphene along with a little sacrificing of the hardness and elastic modulus, compared with those of pure boron carbide. The remarkably enhanced fracture toughness in the boron carbide ceramics is associated with graphene sheets crack bridging and graphene interface sliding effect. This study holds much significance for the understanding and development of high‐performance graphene reinforcing ceramics.     

Static and dynamic mechanical properties of boron carbide processed by spark plasma sintering

Spark plasma sintering (SPS) has become a popular technique for the densification of covalent ceramics. The present investigation is focused on the static mechanical properties and dynamic compressive behavior of SPS consolidated boron carbide powder without any sintering additives. Fully dense boron carbide bodies were obtained by a short high temperature SPS treatment. The mechanical properties of the SPS-processed material, namely hardness (32 GPa), Young modulus (470 GPa), fracture toughness K_C (3.9–4.9 MPa m^0.5), flexural strength (430 MPa) and Hugoniot elastic limit (17–19 GPa) are close or even better than those of hot-pressed boron carbide.     

High-Strength Porous Silicon Carbide Ceramics by an Oxidation-Bonding Technique

Porous silicon carbide (SiC) ceramics were fabricated by an oxidation-bonding process in which the powder compacts are heated in air so that SiC particles are bonded to each other by oxidation-derived SiO₂ glass. Because of the crystallization of amorphous SiO₂ glass into cristobalite during sintering, the fracture strength of oxidation-bonded SiC ceramics can be retained to a relatively high level at elevated temperatures. It has been shown that the mechanical strength is strongly affected by particle size. When 0.6 μm SiC powders were used, a high strength of 185 MPa was achieved at a porosity of ∼31%. Moreover, oxidation-bonded SiC ceramics were observed to exhibit an excellent oxidation resistance.     

Fabrication of Mullite and Mullite-Matrix Composites by Transient Viscous Sintering of Composite Powders

Mullite was fabricated by a process referred to as transient viscous sintering (TVS). Composite particles which consisted of inner cores of α-alumina and outer coatings of amorphous silica were used. Powder compacts prepared with these particles were viscously sintered to almost full density at relatively low temperatures (∼1300°C). Compacts were subsequently converted to dense, fine-grained mullite at higher temperatures (∼1500°C) by reaction between the alumina and silica. The TVS process was also used to fabricate mullite/zirconia/alumina, mullite/silicon carbide particle, and mullite/silicon carbide whisker composites. Densification was enhanced compared with other recent studies of sintering of mullite-based composites. This was attributed to three factors: viscous flow of the amorphous silica coating on the particles, avoidance of mullite formation until higher temperatures, and increased threshold concentration for the development of percolation networks.     

无压烧结碳化硼的研究进展

碳化硼陶瓷具有高硬度、高熔点和低密度的特点,是优异的结构陶瓷,在民用、航空和军事等领域都得到了重要应用。本文综述了无压烧结碳化硼陶瓷的国内外研究进展,阐述了不同的烧结助剂、烧结温度和颗粒尺寸等因素对碳化硼陶瓷性能的影响。     

无压烧结碳化硼的研究进展

碳化硼陶瓷具有高硬度、高熔点和低密度的特点,是优异的结构陶瓷,在民用、宇航和军事等领域都得到了重要应用.综述了无压烧结碳化硼陶瓷的国内外研究进展,阐述了不同的烧结助剂、烧结温度和颗粒尺寸等因素对碳化硼陶瓷性能的影响.     

Spark-Plasma Sintering of Silicon Carbide Whiskers (SiCw) Reinforced Nanocrystalline Alumina

The combined effect of rapid sintering by spark-plasma-sintering (SPS) technique and mechanical milling of γ-Al₂O₃ nanopowder via high-energy ball milling (HEBM) on the microstructural development and mechanical properties of nanocrystalline alumina matrix composites toughened by 20 vol% silicon carbide whiskers was investigated. SiC_w/γ-Al₂O₃ nanopowders processed by HEBM can be successfully consolidated to full density by SPS at a temperature as low as 1125°C and still retain a near-nanocrystalline matrix grain size (∼118 nm). However, to densify the same nanopowder mixture to full density without the benefit of HEBM procedure, the required temperature for sintering was higher than 1200°C, where one encountered excessive grain growth. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results indicated that HEBM did not lead to the transformation of γ-Al₂O₃ to α-Al₂O₃ of the starting powder but rather induced possible residual stress that enhances the densification at lower temperatures. The SiC_w/HEBMγ-Al₂O₃ nanocomposite with grain size of 118 nm has attractive mechanical properties, i.e., Vickers hardness of 26.1 GPa and fracture toughness of 6.2 MPa·m^1/2.     

Effect of Alumina on the Structure and Mechanical Properties of Spark Plasma Sintered Boron Carbide

Uniform densification of relatively thick (~7 mm) consolidated boron carbide plates at relatively low temperatures (e.g. 1800°C) and low facture toughness are two of the primary challenges for further development of boron carbide applications. This work reports that these two challenges can be overcome simultaneously by adding 5 wt% alumina as a sintering aid. Nearly fully dense (97%), fine grained boron carbide (B₄C) samples were produced using spark plasma sintering at 1700°C and above in the B₄C‐5 wt% Al₂O₃ system. The alumina and boron carbide matrix reacted to form an Al₅O₆BO₃ (a mullite‐like phase) during sintering. The Al₅O₆BO₃ phase facilitated uniform densification via liquid phase sintering. This secondary phase is dispersed throughout the intergranular pores, providing obstacles for crack propagation and resulting in tougher boron carbide ceramics.     

Crack tolerant silicon carbide ceramics prepared by liquid-phase assisted oscillatory pressure sintering

Silicon carbide ceramics were prepared by liquid-phase assisted oscillatory pressure sintering (OPS) with graphene and in-situ synthesized SiC whisker as the reinforcements. The effects of sintering temperature on the densification, morphology and mechanical performances of the SiC_p-SiC_w-graphene ceramics were investigated. In the temperature range from 1700 to 1800 °C, the densification rate of SiC_p-SiC_w-graphene ceramics was accelerated, ascribing to the reduction in viscosity of the glassy phase. At 1800 °C, the flexural strength and fracture toughness of the OPS ceramics corresponded to 697 MPa and 5.8 MPa m^1/2, respectively, which were higher than that of the hot-pressed ceramics under the same temperature conditions. Multiphase toughening mechanisms, such as whisker bridging and pullout, graphene bridging and delamination, were considered as the primary mechanisms. This work demonstrates an effective strategy to prepare silicon carbide ceramics at low sintering temperature.     

Improvement of sinterability and mechanical properties of ZrB2 ceramics by the modified borothermal reduction methods

Starting from ZrO₂ and boron (molar ratio: 1:4), four ZrB₂ powders were synthesized by borothermal reduction method, three of which were designed to introduce minor modifications by combining solid solution with Ti and/or water-washing. The sinterability, microstructures, mechanical properties and thermal conductivity were investigated. In comparison with the conventional borothermal reduction, the modified methods offered significant improvement in terms of densification of ZrB₂ ceramics, particularly the mixture that included water-washing. Owing to the refined particle size and boron residues, ZrB₂ ceramics from the modified borothermal reduction which included water-washing demonstrated nearly full densification, Vickers hardness of 14.0 GPa and thermal conductivity of 82.5 W/mK after spark plasma sintering at 2000 °C for 10 min. It was revealed that the properties of ZrB₂ ceramics could be enhanced utilizing the proposed minor modification, starting from the same raw materials and adopting the same sintering conditions.     

Processing of a Silicon-Carbide-Whisker-Reinforced Glass-Ceramic Composite by Microwave Heating

A calcium magnesium aluminosilicate-based glass that contained 10 wt% of silicon carbide whiskers (SiC _w ) as reinforcement was prepared by tape casting, followed by sintering either in a conventional furnace or in a microwave oven. The results were consistent with retardation of glass sintering through whisker bridging. The glass, by itself, was sintered to almost-full density at 750°C for 4 h by conventional furnace sintering; the best sintered composite, with an estimated density of ∼90%, was obtained at 800°C with a dwell time of 4 h. Sintering at a temperature of >800°C did not improve the densification but rather resulted in severe whisker oxidation. A reduced densification rate was observed for the samples that were sintered in nitrogen. By contrast, in the microwave oven, almost-full density for the glass and ∼95% of the theoretical density for the composite were obtainable at 850°C for 15 min, which represented a reduction of ∼10 h of the total processing time and a reduced SiC _w oxidation.