热压烧结Al2O3-ZrB2-SiC复相陶瓷的高温力学性能研究

为提高Al2O3陶瓷的高温力学性能,采用热压烧结工艺(烧结温度1 800℃,烧结压力20 MPa,保温1 h)制备了Al2O3-ZrB2-SiC复相陶瓷(简称AZS),并研究了ZrB2含量对Al2O3基陶瓷高温抗折强度和抗热震性的影响。结果表明:1)在Al2O3基陶瓷中加入第二相ZrB2能有效改善材料的高温抗折强度和高温强度保持率,在1 000和1 200℃时,加入20%体积分数ZrB2的AZS陶瓷试样具有最高的高温抗折强度,而加入24%体积分数ZrB2的AZS陶瓷试样具有最高的高温强度保持率。2)AZS陶瓷的抗热震性能优于纯Al2O3陶瓷。经100℃温差急冷后,加入20%体积分数ZrB2的AZS陶瓷具有最高的残余强度,比纯Al2O3陶瓷提高了17.2%;经300和500℃温差急冷后,加入24%体积分数ZrB2的AZS陶瓷都具有最高的残余强度,比Al2O3陶瓷分别提高了35.3%和20.9%。     

Correlation between crystallinity and thermal expansion in LiAlSiO4 ceramics prepared by spark plasma sintering

LiAlSiO₄ (LAS) ceramics are prepared by using the sol-gel method followed by spark plasma sintering. XRD patterns and SEM images verify that the ceramics contain amorphous and LAS phases and that microcracks appear in the sample prepared at 900 °C due to its larger grain size. Compared with applied pressure and soaking time, sintering temperature has a greater impact on the crystallinity and density of the ceramics during sintering. High-temperature XRD results reveal that the LAS phase exhibits its intrinsic negative thermal expansion independently in all samples regardless of crystallinity. The coefficients of thermal expansion (CTE) measured by the dilatometric method change from positive values in samples prepared at 600 and 650 °C to near zero in samples prepared at 700 and 800 °C and then to a negative value in the sample prepared at 900 °C. The combined effects of an amorphous phase with a positive CTE and the LAS phase with a negative CTE are responsible for the observed transformation of thermal expansion in the samples. The calculated total CTEs of the glass-ceramic bulks are in agreement with the results measured through the dilatometric method in samples prepared at 650–800 °C. Microcracks in the sample prepared at 900 °C cause a more negative bulk CTE than the calculated CTE.     

Microstructure and mechanical properties of ZTA composites fabricated by oscillatory pressure sintering

The influence of sintering temperature on the microstructure and mechanical properties of Al₂O₃?20 wt% ZrO₂ composites fabricated by oscillatory pressure sintering (OPS) was investigated by means of X-ray diffraction, scanning electron microscopy, three-point bending test and Vickers indentation. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The optimum oscillatory pressure sintering temperature was found to be 1600 °C; almost fully dense materials (99.94% of theoretical density) with homogeneous microstructure could be achieved. The highest flexural strength, fracture toughness and hardness of such composites reached 1145 MPa, 5.74 MPa m^1/2 and 19.08 GPa when sintered at 1600 °C, respectively. Furthermore, the oscillatory pressure sintering temperature could be decreased by more than 50 °C as compared with the HP method, OPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Effect of Si4+ substitution on mechanical and thermal expansion properties of Ca0.5Sr0.5Zr4P6O24 ceramics

The Ca_(1+x)/2Sr_(1+x)/2Zr₄P_6-2xSi_2xO₂₄ (CSZP_6-2xS_2x, 0 ≤ x ≤ 0.3) ceramics were prepared using powders synthesized by co-precipitation method, and the effects of Si⁴⁺ substitution on the structure, mechanical, and thermal expansion properties were investigated. The optimum sintering time was 4 hours, which greatly shortened the sintering process. By controlling the appropriate composition and sintering temperature, a single phase with the typical NaZr₂P₃O₁₂ structure was obtained. As a function of x increasing, the parameter a increased and then decreased, while the parameter c and unit cell volume both increased. The mechanical property of CSZP_6-2xS_2x ceramics was affected with increasing amount of Si⁴⁺ content. The Si⁴⁺ substitution could increase the thermal expansion anisotropy and lead to the generation of microcracks, which are responsible for the increase in the amount of hysteresis between heating and cooling curves. The thermal expansion decreased progressively from 1.8 to 0.8 × 10⁻⁶/°C. The investigations indicate that the CSZP_6-2xS_2x ceramics are potential materials in high temperature applications     

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.     

Low temperature sintering of Hf0.95Nb0.05B2-based ceramics with submicron-scaled grains and enhanced mechanical properties

Hf_0.95Nb_0.05B₂ ceramics and their composites containing 20 vol% SiC were prepared via high-pressure spark plasma sintering in the study. The densification, microstructures, and mechanical properties of the prepared materials were then investigated. It is challenging to achieve full densification of HfB₂ ceramics, even with markedly refined Hf_0.95Nb_0.05B₂ solid solution powder under the sintering conditions of 2000 °C/30 MPa. However, under the sintering conditions of 1700 °C/200 MPa, a dense microstructure of Hf_0.95Nb_0.05B₂ ceramics was achieved. Moreover, the Hf_0.95Nb_0.05B₂-20 vol% SiC composite was densified at a lower temperature (1500 °C) and exhibited ultrafine grains (300 nm) and high-density defects, including stacking faults, Lomer-Cottrell locks, and twins, thus resulting in exceptional comprehensive mechanical properties, such as ultra-high hardness (32 GPa) and significantly improved fracture toughness (5.2 MPa.m^1/2).     

络合溶胶-凝胶法合成磷酸盐材料CaZr4(PO4)6

用络合溶胶-凝胶法合成了化学组成为CaZr4(PO4)6(CZP)的NaZr2(PO4)3(NZP)族磷酸盐陶瓷的粉体.初步研究了制备条件对粉体物相和粒径及粒径分布的影响.添加ZnO为烧结助剂,将CZP粉体在950℃下烧结成陶瓷,测定和观察所制备陶瓷的相对密度、平均热膨胀系数、抗压强度和显微结构.结果表明:络合溶胶-凝胶法合成的前驱物经700℃煅烧能得到单相CZP粉体,该粉体具有良好的低温烧结活性.在950℃下烧结得到的CZP陶瓷的相对密度达84%,从室温至900℃的平均热膨胀系数为1.4x10-6/℃,属于低热膨胀陶瓷.     

CaZr4（PO4）6（CZP）基复相陶瓷的抗热震性

研究了CaZr4（PO4）6（CZP）基复相陶瓷的抗热震性，在CZP中引入Al2O310wt％、Zr-SiO420wt％后，临界淬冷温差提高，采用SEM对断口形貌进行了分析。     

An oscillatory pressure sintering of zirconia powder: Densification trajectories and mechanical properties

The densification trajectories and mechanical properties of zirconia ceramics obtained by oscillatory pressure sintering (OPS) process were investigated, during the sintering process an oscillatory pressure was applied at three stages. Current results indicated that at intermediate stage the oscillatory pressure revealed a favorable improvement of mechanical properties compared with conventional hot pressing (HP) and pressureless sintering (PS) procedures, while the enhancement was not obvious at initial stage. When the oscillatory pressure was applied at final stage, the OPS specimens exhibited the highest bending strength and hardness of 1455 ± 99MPa and 16.6 ± 0.31GPa compared with the PS and HP specimens. Considering the high elastic modulus and Moiré patterns observed in the OPS specimen, the oscillatory pressure applied at intermediate and final stages was detected to facilitate the sliding of grain boundary, plastic deformation of monolithic grains, the removal of pores and the strengthening of atomic bonds.     

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.     

Effect of dual liquid phase sintering aids on the densification and microstructure of low temperature sintered alumina ceramics

Alumina ceramics was prepared by pressureless sintering technology in which a CuO–TiO₂–Bi₂O₃ mixture (0–4.0 wt% Bi₂O₃ and 4.0 wt% CuO and TiO₂) was added as dual liquid phase sintering aids. The phase compositions, microstructural feature, and sintering behaviour of the alumina ceramics were analyzed. The results showed that adding 2.5 wt% Bi₂O₃ to alumina ceramics can increase the contribution rate of initial stage of sintering to the sintering process. The relative density of the sample reached 97.63% after sintering at 1200 °C for 90 min. Measurements from differential scanning calorimetry, with the addition of CuO–TiO₂–Bi₂O_3, demonstrated the formation of two liquid phase points, 827.4 and 936.8 °C. Notably, the solid solution temperature of TiO₂ and Al₂O₃ ceramics diminished thanks to the dual liquid phase sintering aids, and at the same time the activation energy required also dropped from 368.96 to 137.31 kJ/mol. Research indicates that the combined action of dual liquid phase sintering and solid-state reaction sintering has promoted the densification of alumina ceramics during the sintering process while at the same time inhibiting the growth of abnormal grains so that a homogeneous microstructure can be formed.     

Synthesis,microstructure and mechanical properties of high-entropy (VNbTaMoW)C5 ceramics

High-entropy ceramics (HEC) with a fixed composition of (VNbTaMoW)C₅ were prepared by spark plasma sintering (SPS) from 1500 °C to 2200 °C. XRD, TEM, HRTEM, SAED and EDX were used to investigate effects of the sintering temperatures on compositional homogeneity, constituent phases and microstructure of the HECs. The results showed that single-phase HEC formed at a temperature as low as 1600 °C while ultimate elemental distribution homogeneity could be obtained at 2200 °C. Elemental distribution homogenization was accompanied by microstructural coarsening and oxide impurities aggregating at grain boundaries as temperature increased. SPS at 1900 °C for 12 min could yield uniform HECs (VNbTaMoW)C₅ with Vickers hardness, nanohardness, fracture toughness and Young’s modulus reaching 19.6 GPa, 29.7 GPa, 5.4 MPa m^1/2 and 551 GPa, respectively. The resultant HECs showed excellent wear resistance when coupled with WC at room temperature.     

Solid state sintering of very low and negative thermal expansion ceramics by Spark Plasma Sintering

Lithium aluminosilicate powder precursors of compositions Li₂O:Al₂O₃:SiO₂ as 1:1:2; and 1:1:3.11 were synthesized and sintered by the Spark Plasma Sintering technique. The sintering conditions were adjusted to obtain dense ceramic materials in an attempt to avoid the presence of a glassy phase. XRD and SEM images were employed for composition and microstructure characterization. The coefficient of thermal expansion of the sintered samples was studied down to cryogenic conditions. Rietveld quantification was performed with the use of an external standard. Pure β-eucryptite of different compositions in dense ceramic bodies was obtained with a negative expansion coefficient.     

Effects of Pr6O11 on the microstructure and mechanical properties of Ti/Al2O3 composites prepared by pressureless sintering

Ti/Al₂O₃ composites with different volume percentages of Pr₆O₁₁ added (0–12.0  vol.%) were prepared by pressureless sintering at 1600 °C for 1.5 h. The influences of Pr₆O₁₁ on the composition, microstructure and mechanical properties of the composites were characterized and investigated. The results showed that Pr₆O₁₁ could promote the sintering of the composites by generating some new interfacial reaction products, such as AlTiO₂, Pr₂Ti₂O₇ and PrAlO₃. Pr₆O₁₁ could also inhibit the production of TiAl and Ti₃Al by the same mechanism. Additionally, Pr₆O₁₁ changed hexagonal alumina to tetragonal alumina. The latter could improve the mechanical properties of the composites by the effects of crack deflection and particle pullout when it was present in proper amounts. Composites showed satisfactory comprehensive properties when the content of Pr₆O₁₁ was no more than 3.0 vol.%.     

The microstructure and mechanical properties of Ni/Al2O3 composites by in-situ generated CaAl12O19 and ZrO2 via hot pressing sintering

Ni/Al₂O₃ composites with a varying mass fraction of CaZrO₃ (0–12 wt%) were prepared by vacuum hot pressing sintering at 1650 °C under a pressure of 30 MPa for 30 min to investigate how CaZrO₃ affect the mechanical properties and morphology of the composites. The results show that CaZrO₃ can react with Al₂O₃ and form new strengthening and reinforcing phases of CaAl₁₂O₁₉ and ZrO₂, which can promote complete densification and solve the problem of uneven distribution due to the poor wettability between Al₂O₃ and Ni. Additionally, composites showed satisfactory mechanical properties when 6.0–9.0 wt% CaZrO3 was added and the major toughening mechanism involved the typical fracture of delamination and the transgranular mode.     

On the fabrication and mechanical properties of Si3N4 ceramics with low content sintering additives

Si₃N₄ ceramics were prepared by hot pressing (HP) and spark plasma sintering (SPS) methods using low content (5 mol%) Al₂O₃–RE₂O₃(RE = Y, Yb, and La)–SiO₂/TiN as sintering additives/secondary additives. The effects of sintering additives and sintering methods on the composition, microstructures, and mechanical properties (hardness and fracture toughness) were investigated. The results show that fully density Si₃N₄ ceramics could be fabricated by rational tailoring of sintering additives and sintering method, and TiN secondary additive could promote the density during HP and SPS. Besides, SN-AYS-SPS possesses the most competitive mechanical properties among all the as-prepared ceramics with the Vickers hardness as 17.31 ± .43 GPa and fracture toughness as 11.07 ± .48 MPa m^1/2.     

Al2TiO5添加量对MgO-Al2TiO5复合陶瓷烧结及抗热震性的影响

以纳米MgO粉为原料,选用以纳米Al2O3粉和纳米TiO2粉经1500℃保温3 h烧结制备的Al2TiO5为添加剂,采用固相烧结法经1500℃保温3 h制备了Al2TiO5质量分数分别为0、5%、10%和20%的MgO-Al2TiO5复合陶瓷,并采用XRD、SEM和EDS等研究了Al2TiO5添加量对MgO-Al2TiO5复合陶瓷烧结性能及抗热震性能的影响。结果表明:添加Al2TiO5有利于促进复合陶瓷的烧结,其体积密度和线收缩率随Al2TiO5添加量的增加而增大,当Al2TiO5添加量为20%(w)时,其体积密度和线收缩率分别为3.68 g·cm-3和22.07%;当Al2TiO5添加量为10%(w)时,其抗热震性能最佳。Al2TiO5位于方镁石晶粒交界处,抑制方镁石晶粒生长,阻碍裂纹扩展,使MgO-Al2TiO5复合陶瓷的抗热震性能得到改善。     

Ca0.6Mg0.4Zr4（PO4）6陶瓷的抗热震性

Ｃａ０．６Ｍｇ０．４Ｚｒ４（ＰＯ４）６（简称ＣＭ）陶瓷热震后的强度变化与裂纹扩展依赖于材料的热膨胀系数和轴向膨胀特性。以ＭｇＯ作为烧结助剂的ＣＭ１陶瓷，当热震温差ΔＴ＝８００℃时，残留强度与原始强度相关。作者提出裂纹部分闭合模式解释了上述现象。以ＺｎＯ作烧结助剂的ＣＭ２陶瓷，其强度降低和裂纹扩展符合Ｈａｓｓｅｌｍａｎ提出的脆性陶瓷热震理论。     

Nano-structured MgAl2O4 spinel consolidated by high pressure spark plasma sintering (HPSPS)

Nano-structured transparent polycrystalline magnesium aluminate spinel (PMAS) was fabricated using a high pressure (up to 1000 MPa) spark plasma sintering (HPSPS) apparatus and various properties of the spinel, such as transparency, micro-structure and mechanical properties (specifically, hardness and fracture toughness), were tested. Using a creep densification model, it was concluded that densification in the final stage of HPSPS is controlled by grain boundary sliding (GBS), rather than by oxygen diffusion. The average grain size of PMAS fabricated under 400 MPa pressure at 1200 °C was about 170 nm, while for samples fabricated under 1000 MPa at 1000 °C the average grain size was remarkably smaller (about 50 nm). HRTEM analysis clearly demonstrated clean grain boundaries and triple points with no evidence for the existence of amorphous regions. Fully dense specimens displayed in-line transmittance higher than 80%. It was moreover established that hardness and fracture toughness values did not depend on the indentation load applied. Finally, hardness values for grains sized between tens of microns and tens of nm strictly followed the Hall-Petch relationship.     

Cost effective preparation of Si3N4 ceramics with improved thermal conductivity and mechanical properties

High-purity silicon powder is used as the starting material for cost-effective preparation of silicon nitride ceramics with both high thermal conductivity and excellent mechanical properties using RE₂O₃ (RE=Y, La or Er) and MgO as sintering additives. Nitridation is a key procedure that would affect the properties of green bodies and the sintered samples. The β: (α+β) ratio can be increased as the samples nitrided at 1450ºC and a large amount of long rod-like β-Si₃N₄ grains were developed in the samples. It was found that the addition of Er₂O₃-MgO could help to improve the mechanical properties of the sintered Si₃N₄ ceramics, the thermal conductivity, flexural strength and fracture toughness of the sample were 90 W/(m∙K), 953±28.3 MPa and 10.64±0.61 MPa·m^1/2, respectively. The RE³⁺ species with larger ionic radius tended to increase the oxygen of nitrided samples and decrease N/O ratio (triangle grain boundary) of sintered samples.