(Ti,Zr,Hf)B2粉体的制备及B4C含量对中熵陶瓷高温弯曲强度的影响

高熵陶瓷是陶瓷领域近几年的研究热点，过渡金属硼化物中熵、高熵陶瓷以其优异的性能、化学反应惰性和极高的熔点，成为耐极端环境的重要候选材料。本工作首次研究了B₄C过量含量对中熵硼化物粉体合成、陶瓷致密化、微结构演变和高温弯曲强度的影响，确定了低氧含量、高烧结活性(Ti,Zr,Hf)B₂粉体的制备工艺。采用热压烧结工艺在1800℃制备的(Ti,Zr,Hf)B₂中熵陶瓷致密度高达99%以上。B₄C过量15wt%的(Ti,Zr,Hf)B₂陶瓷晶粒尺寸为5.0±2.1μm，随着B₄C过量含量增加到25wt%，晶粒尺寸明显细化至2.4±0.7μm。过量的B₄C一部分与球磨引入的Si₃N₄原位反应生成BN相，另一部分B₄C以第二相形式存在，BN和B₄C相的引入可以有效抑制中熵陶瓷烧结过程中的晶粒生长，同时也提升了材料的高温弯曲强度。B₄C过量...     

B4C陶瓷中原位生成TiB2及其对力学性能的强化机制

以 TiO₂为烧结助剂,采用反应烧结法在 B₄C 陶瓷中原位生成 TiB₂,制备出致密的 B₄C 陶瓷,并对其强化机制进行了分析。结果表明：随着 Ti O₂添加量的增加,B₄C 陶瓷的致密度和抗弯强度先增大后减小,断裂韧性不断增大。当 Ti O₂添加量为 5% (质量分数)、烧结温度为 1 700 ℃时,B₄C 陶瓷致密度达到 99.6%;当 TiO₂加入量为 15%时,B₄C 陶瓷的 Vickers硬度为 36.0 GPa,断裂韧性为 4.38 MPa·m^1/2,抗弯强度为 405 MPa,综合性能最优。原位生成的 TiB₂抑制了 B₄C 陶瓷晶粒长大,消除了裂纹尖端应力,使裂纹产生偏转和分叉,对 B₄C 陶瓷起到细晶强化和增韧作用。     

硼化钛对无压烧结碳化硼结构和性能的影响

利用无压真空烧结炉,选用C和Si作为烧结助剂,将不同含量的TiB₂作为第二相添加到B₄C基体中,在不同温度下进行无压烧结制备出B₄C–Ti B2复相陶瓷。研究了B₄C–TiB₂成分配比和烧结温度对复相陶瓷微观结构和力学性能的影响,以及B₄C–TiB₂复相陶瓷的增韧机理。结果表明:当烧结温度为2 200℃、Ti B2含量为30%时,所制复相陶瓷的致密度及综合力学性能最高,致密度为94.59%,洛氏硬度、抗弯强度和断裂韧度分别为87.62、182 MPa、3.97 MPa·m^1/2;TiB₂颗粒能有效的钉扎晶界,抑制B₄C晶粒的长大,起到细晶强化的作用,TiB₂和叠层状石墨相阻碍了裂纹扩展,提高复相陶瓷的断裂韧性。     

TiB2对无压烧结B4C–TiB2复相陶瓷结构和性能的影响

以碳化硼(B₄C)、二硼化钛(TiB₂)、碳化钛(TiC)为原料,采用无压烧结法在2 130℃制备了含20%(质量分数)和30%TiB₂的B₄C基复相陶瓷,分析所制样品的密度、硬度、弯曲强度和断裂韧性。结果表明:在2 130℃,直接加入30%的TiB₂亚微米颗粒,复相陶瓷的抗弯强度和断裂韧性分别达到277.6 MPa和5.38 MPa·m^1/2。陶瓷中颗粒拔出和裂纹微桥接对复相陶瓷增韧作用显著。B₄C–TiB₂复相陶瓷的增韧机理主要是由于TiB₂与B₄C热膨胀系数不匹配产生的残余应力导致的微裂纹增韧和裂纹偏转增韧。     

无压烧结碳化硼中Y2O3和Al2O3助剂的助扩散机制研究

采用无压烧结工艺，添加质量分数9.5%的Y₂O₃作为烧结助剂，进行了碳化硼陶瓷的2100℃、2200℃和2250℃烧结2h实验，对样品进行了体积密度、显气孔率、维氏硬度、表面形貌和晶体结构测试，并与纯碳化硼2250℃烧结的样品进行了比较。实验表明，添加Y₂O₃助剂2250℃烧结2h的样品的体积密度、气孔率、硬度指标比纯碳化硼粉2250℃烧结2h的样品有较大幅度提升；在碳化硼晶粒扩散时，Y₂O₃助剂和碳化硼晶粒协同扩散，使碳化硼晶粒趋向于致密化烧结；Y₂O₃助剂的介入使碳化硼晶粒生长(运动)机制发生了变化。     

Y2O3对高热导率Si3N4陶瓷显微结构和性能的影响

以氧含量相对较高的“平价”Si₃N₄粉体(氧含量1.85%(质量分数))为原料,Y₂O₃-MgO作为烧结助剂,制备低成本高热导率Si₃N₄陶瓷,研究Y₂O₃含量对Si₃N₄陶瓷致密化、显微结构、力学性能及热导率的影响。结果表明,适当增加Y₂O₃的加入量不仅可以促进Si₃N₄陶瓷的致密化和显微结构的细化,还有助于晶格氧含量的降低和热导率的提升。Y₂O₃含量为7%(质量分数)的样品在1 900 ℃烧结后的综合性能最佳,其相对密度、抗弯强度、断裂韧性和热导率分别为99.5%、(726±46) MPa、(6.9±0.2) MPa·m^1/2和95 W·m^-1·K^-1。     

振荡压力烧结氮化硅陶瓷微观形貌及其力学性能

在氮化硅粉料中引入Al₂O₃、Y₂O₃和TiC,采用振荡压力烧结技术制备氮化硅陶瓷材料。研究了不同温度(1 700、1 725、1 750、1 775℃)氮化硅的微观形貌、晶粒尺寸的变化及其对氮化硅力学性能的影响。探讨了第二相TiC的加入对粉体致密化及界面结合性能的影响。结果表明:在振荡压力烧结工艺下氮化硅陶瓷在1 725℃时即可达到完全致密化并获得高的抗弯强度与硬度,其抗弯强度、Vickers硬度值分别为(1 421±59)MPa和(16.1±0.3)GPa。试样晶粒的长径比同样是随着温度的升高先增大后降低,其中,晶粒长径比最大的是1 725℃烧结的试样,当温度继续升高至1 775℃时,晶粒的长径比下降明显,晶粒粗化。氮化硅的抗弯强度与硬度在温度高于1 725℃时开始也随着长径比下降而减小。     

TiO2晶型对微波加热制备TiB2粉体的影响

为探究TiO₂晶型(锐钛矿型和金红石型)对微波加热制备TiB₂粉体的影响,分别以锐钛矿型和金红石型TiO₂为钛源,B₄C为硼源,炭黑为碳源,在微波加热的条件下通过硼热/碳热还原法快速制备了TiB₂粉体,探讨了TiO₂晶型对微波加热制备TiB₂粉体的物相组成、显微结构以及C和O杂质含量的影响。结果表明：在微波加热条件下,2种晶型TiO₂原料在1 450℃反应20 min后均可制备纯相TiB₂粉体,其中金红石型TiO₂制备的TiB₂粉体呈规则的六方片状结构,晶粒发育较为完善。而锐钛矿型TiO₂制备的TiB₂则为近似球状结构。相比较,金红石型TiO₂作为硼源更有利于制备高纯度、晶型完整的TiB₂粉体。     

不同改性剂对ZrO2陶瓷烧结性能与微观结构的影响

通过在ZrO₂陶瓷粉体中添加不同量的CeO₂、MgO、Y₂O₃,探讨了不同改性剂对ZrO₂陶瓷烧结性能与微观结构的影响规律。结果发现,添加CeO₂作为改性剂能有效细化ZrO₂的陶瓷晶粒,并提高陶瓷的体积密度,但不能消除陶瓷中裂纹的产生;适量MgO的添加,可以有效防止ZrO₂陶瓷中出现裂纹,但对陶瓷晶粒的细化作用有限,且添加量过大后将导致陶瓷晶粒发生急剧生长;少量Y₂O₃的添加,即可有效细化ZrO₂陶瓷的晶粒大小并消除陶瓷中裂纹的产生,其最佳添加量在3mol%。适量MgO的添加可以将陶瓷的致密化温度降至1450℃,而添加Y₂O₃陶瓷的致密化温度均在1550℃以上。     

金属离子和柠檬酸的配比对Y2O3-MgO纳米粉体及其纳米复相陶瓷性能的影响

纳米粉体的团聚程度影响纳米复相陶瓷的微观结构,进而影响其光学与力学性能。本文采用溶胶-凝胶法合成Y₂O₃-MgO纳米粉体,结合热压烧结(HP)技术制备出光学及力学性能优异的Y₂O₃-MgO复相陶瓷。研究了前驱体中金属离子与柠檬酸的摩尔比(m/c)对纳米粉体团聚程度及复相陶瓷显微结构、光学及力学性能的影响。研究结果表明,当金属离子和柠檬酸摩尔比为0.75时,粉体团聚程度最低,该粉体经过热压烧结后制备出的Y₂O₃-MgO陶瓷具有均匀的相域,晶粒尺寸约为140 nm,3~6 μm波段的透过率达到80%,维氏硬度及断裂韧性分别为10.90 GPa、2.21 MPa·m^-1/2,抗弯强度为226 MPa。     

Microstructure and properties of (SiC, TiB2)/B4C composites by reaction hot pressing

(SiC, TiB₂)/B₄C composites were fabricated by reactive hot-pressing B₄C, Si₃N₄, -SiC and TiC powders, with (Al₂O₃ + Y₂O₃) as sintering additives. According to the thermodynamics principles, the possible reaction equations and the reaction products for the system were determined. By means of XRD, SEM of surface thermally etched and TEM the phase composition was determined. It was shown that the phase composition of sintered body was B₄C, -SiC, BN and TiB₂, and the matrix was B₄C and -SiC. The typical values of hardness, bending strength, fracture toughness and the relative density of the composites can reach HRA 88.6, 554 MPa, 5.6 MPa m^1/2 and 95.6%, respectively. Furthermore, the microstructures of the composites were analyzed by TEM, SEM and energy spectrum methods. The results show the presence of laminated structure and a clubbed frame dispersion phase and bunchy dispersion phase among the matrix. Some intragranular structures were also found in the B₄C grains. Microstructural analysis indicates that the new formed phase, uniform and fine grains, and the layered and clubbed structure play an important role in improving the properties of the composites. Fractography and crack propagation suggest that crack deflection and crack bridging are the possible toughening mechanisms.     

The preparation and performance of high-temperature adhesives for graphite bonding

Two kinds of high-temperature adhesives (HTAs) were prepared. One was composed of phenol-formaldehyde (PF) resin and boron carbide (PF+B₄C), the other was composed of PF resin, B₄C and fumed silica (PF+B₄C+SiO₂). Graphite materials were bonded by the above adhesives and heat-treated at temperatures ranging from 200 to 1500 °C. The joining strength was tested at room temperature. The results show that the graphite joints exhibit satisfactory bonding strength and that ceramics fillers show a marked property modification effect. The strength of graphite joints bonded by PF+B₄C and PF+B₄C+SiO₂ adhesive and treated at 1500 °C are 9.3 and 17.1 MPa, respectively. The property modification mechanism of ceramics fillers is also discussed in this paper. A strong chemical bonding force is introduced at the bonding interface and the volume shrinkage is restrained, which can be responsible for the good adhesive properties of HTAs for graphite bonding.     

无压烧结氮化硅陶瓷的物理性能研究

以α-Si₃N₄粉末为原料,Y₂O₃和MgAl₂O₄体系为烧结助剂,采用无压烧结方式,研究了烧结温度、保温时间、烧结助剂含量以及各组分配比对氮化硅致密化及力学性能的影响。结果表明:以Y₂O₃和MgAl₂O₄为烧结助剂体系,氮化硅陶瓷在烧结温度为1 600 ℃,保温时间为4 h,烧结助剂含量为12.5%(质量分数),Y₂O₃和MgAl₂O₄质量比为1∶1时,综合性能最好;氮化硅陶瓷显气孔率为0.21%,相对密度为98.10%,抗弯强度为598 MPa,维氏硬度为15.55 GPa。     

Yb2O3 and Y2O3 co-doped zirconia ceramics

A suspension stabilizer-coating technique was employed to prepare x mol% Yb₂O₃ (x = 1.0, 2.0, 3.0 and 4.0) and 1.0 mol% Y₂O₃ co-doped ZrO₂ powder. A systematic study was conducted on the sintering behaviour, phase assemblage, microstructural development and mechanical properties of Yb₂O₃ and Y₂O₃ co-doped zirconia ceramics. Fully dense ZrO₂ ceramics were obtained by means of pressureless sintering in air for 1 h at 1450 °C. The phase composition of the ceramics could be controlled by tuning the Yb₂O₃ content and the sintering parameters. Polycrystalline tetragonal ZrO₂ (TZP) and fully stabilised cubic ZrO₂ (FSZ) were achieved in the 1.0 mol% Y₂O₃ stabilised ceramic, co-doped with 1.0 mol% Yb₂O₃ and 4.0 mol% Yb₂O₃, respectively. The amount of stabilizer needed to form cubic ZrO₂ phase in the Yb₂O₃ and Y₂O₃ co-doped ZrO₂ ceramics was lower than that of single phase Y₂O₃-doped materials. The indentation fracture toughness could be tailored up to 8.5 MPa m^1/2 in combination with a hardness of 12 GPa by sintering a 1.0 mol% Yb₂O₃ and 1.0 mol% Y₂O₃ ceramic at 1450 °C for 1 h.     

Effect of Iron and Boron Carbide on the Densification and Mechanical Properties of Titanium Diboride Ceramics

The effect of Fe and B₄C on the sintering behavior and mechanical properties of TiB₂ ceramics have been studied. Sintering was performed in an Ar atmosphere at 2000° using attrition-milled TiB₂ powder (mean particle size = 0.8 μm). When a small amount of Fe (0.5 wt%) was added, abnormal grain growth occurred and the sintered density was low. In the case of B₄C added along with 0.5 wt% Fe, however, abnormal grain growth was remarkably suppressed, and the sintered density was increased up to 95% of theoretical. But with excess Fe addition (5 wt%), B₄C grains did not act as a grain growth inhibitor, and B₄C grains were frequently trapped in large TiB₂ grains. The best mechanical properties were obtained for the TiB₂–10 wt% B₄C–0.5 wt% Fe ceramics, which exhibited a three-point bending strength of 400 MPa and a fracture toughness of 5.5 MPa · m^1/2.     

Properties of ZrB2–SiC Ceramics by Pressureless Sintering

Pressureless sintering was used to densify ZrB₂–SiC ultra-high temperature ceramics. The physical, mechanical, thermal, electrical, and high temperature properties were investigated. This comprehensive set of properties was measured for ZrB₂ containing 20 vol% SiC in which B₄C and C were used as the sintering aids. The three-point flexural strength was 361±44 MPa and the elastic modulus was 374±25 GPa. The Vickers hardness and fracture toughness were 14.7±0.2 GPa and 4.0±0.5 MPa·m^1/2 respectively. Scanning electron microscopy studies of the microstructure of ZrB₂–SiC showed that SiC particles were distributed homogenously in the ZrB₂ matrix with little residual porosity.     

Preparation and Properties of （Na0.50＋xK0.50-2xLix）Nb0.9Ta0.1O3 Lead-Free Piezoelectric Ceramics by Sol-Gel Method

采用溶胶–凝胶法制备Li＋取代（K0.5Na0.5）＋及Ta5＋取代Nb5＋的（K0.5Na0.5）NbO3陶瓷粉体,采用无压烧结工艺制备（Na0.50＋xK0.50–2xLix）Nb0.9Ta0.1O3（x=0,0.02,0.04）陶瓷样品。研究了前驱体煅烧温度对陶瓷粉体物相组成的影响。分析了不同Li＋掺杂量对样品物相组成、微观结构、体积密度及电学性能的影响。结果表明：前驱体的最佳煅烧温度为600℃,通过透射电子显微镜分析陶瓷粉体的粒径为49nm;不同Li＋掺杂量制备的（Na0.50＋xK0.50–2xLix）Nb0.9Ta0.1O3陶瓷样品均为正交相钙钛矿结构;随着Li＋掺杂量的增加,（Na0.50＋xK0.50–2xLix）Nb0.9Ta0.1O3陶瓷的体积密度先增大后减小,介电常数逐渐升高,压电常数先降低再升高,剩余极化强度逐渐升高。Li＋掺杂量x为0.04时样品的压电常数（d33=94pC/N）、相对介电常数（εr=684.33）及剩余极化强度（Pr=98.27μC/cm2）较好。     

镧掺杂PMN-PT陶瓷在准同型相界处的相组成调控

采用两步预烧工艺制备Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_1-zTi_zO₃(z=0.28、0.29、0.30、0.31)陶瓷,其准同型相界(MPB)的化学组成位于PbTiO₃含量为0.29 mol和0.30 mol附近。选取准同型相界两侧的化学组成,制备四方晶相Pb(Mg_1/3Nb_2/3)_0.66Ti_0.34O₃和三方晶相Pb_1-1.5xLa_x(Mg_1/3Nb_2/3)_1-yTi_yO₃(x=0.083 3~0.041 7,y=0.206 7~0.273 3)陶瓷粉体。将两种晶相粉体按照设计比例(三方晶相摩尔分数w=0.3、0.4、0.5、0.6)混合,干压成型,烧结成化学组成相同、晶相占比不同的Pb_{0.962 5}La_0.025(Mg_1/3Nb_2/3)_0.70Ti_0.30O₃陶瓷。研究了晶相组成对陶瓷压电性能、介电性能、铁电性能的影响。结果表明,高温烧结后,陶瓷中的三方晶相和四方晶相占比与配料比基本一致。当w=0.5时,1 250 ℃烧结陶瓷中三方晶相与四方晶相含量占比分别为0.47、0.53,晶粒平均尺寸为(5.24±0.23) μm,相对密度为96.76%。陶瓷的压电应变常数d₃₃、径向机电转换系数k_p、厚度机电转换系数k_t、相对介电常数ε_r、剩余极化强度P_r和场致应变系数S(1 Hz、3.5 kV/mm)分别为1 014 pC/N、0.67、0.64、10 955、24 μC/cm²和0.21%。该方法可人为调控化学组成位于准同型相界的陶瓷的晶相占比。