ZrB2增韧Al2O3陶瓷制备工艺及其对复相陶瓷力学性能影响

Al₂O₃陶瓷因具有很高的强度和耐蚀性受到广泛关注。但由于相对较差的韧性限制了其广泛应用。Al₂O₃陶瓷增韧的方式很多,本文采用微米ZrB₂来增韧氧化铝陶瓷,探讨复相陶瓷烧结工艺,并研究工艺参数对复相陶瓷力学性能及韧性的影响。结果表明：采用单因素法得到两种陶瓷最佳工艺参数分别是纯α-Al₂O₃陶瓷烧结温度为1500℃,成型压力为450MPa,保温时间为8h,球料比为1/2,保压时间为10min;ZrB₂(wt,20%)+α-Al₂O₃ (wt,80%)复相陶瓷烧结温度为1450℃,成型压力为450MPa,保温时间为8h,球料比为1/2,保压时间为10min。其中成型压力、烧结温度和保温时间对复相陶瓷硬度及致密度影响最大。ZrB₂的加入,在降低陶瓷烧结温度的同时,可以将纯α-Al₂O₃陶瓷的断裂韧性由5.2±0.3MPa.m^_1/2提高到6.7±0.2MPa.m^_1/2。     

添加W对ZrB2-SiC复合材料的微观组织、力学性能和氧化行为的影响

通过放电等离子烧结技术制备了添加不同W含量(1%,3%和5%,体积分数,下同)的ZrB₂-SiC复合材料,研究了烧结过程中复合材料的致密化行为,分析了添加W对复合材料微观组织演化、相组成、力学性能和氧化行为的影响。结果表明：W的添加使复合材料的微观组织表现出核壳结构,以ZrB₂晶粒为核,原位形成的(Zr, W)B₂固溶体为壳,有效地促进了复合材料的致密化和晶粒细化。对比不含W的复合材料,含W复合材料的维氏硬度、抗弯曲强度和断裂韧性显著提高,W添加含量在3%时力学性能最优,复合材料表现出最佳的硬度、强度和韧性。随着W添加量从0%增加到5%,复合材料的氧化增重和氧化层厚度逐渐减小。当W添加量为5%时,复合材料的SiC贫化层消失。最后,详细说明了W的添加对复合材料性能的影响机制。     

Al2O3/Ti2AlN复合材料在900℃,1000℃和1100℃空气中的氧化行为

利用综合热分析仪、背散射扫描电镜(BSE)和能谱分析(EDS)对Al₂O₃/Ti₂AlN复合材料在900 ℃,1 000 ℃和1 100 ℃/20 h空气中连续氧化20h后的氧化增重及氧化层截面进行了研究。结果表明：Al₂O₃/Ti₂AlN复合材料在空气中的氧化行为符合抛物线规律,在900 ℃,1 000 ℃和1 100 ℃/20 h氧化增重分别为2.78×10_-2 kg/m₂、10.4 ×10_-2 kg/m₂、21.9 ×10_-2 kg/m₂,抛物线速率常数相应为1.08×10_-8 kg₂/m₄s、1.44×10_-7 kg₂/m₄s、6.56×10_-7 kg₂/m₄s,氧化激活能为274 kJ/mol。氧化层主要由TiO₂和Al₂O₃组成的,连续的Al₂O₃次外层可以提高其抗氧化性能。氧化层结构的改变是由于氧化温度对Ti₄₊、Al₃₊由基体表面向外扩散和O_2-向内扩散的影响,以及TiO₂和Al₂O₃在不同温度下的形核生长速率导致的。对Al₂O₃/Ti₂AlN而言,控制材料与氧化气氛的界面是提高该材料抗氧化性能的关键。     

多孔ZrO2-8 wt% Y2O3涂层的制备及性能

航空发动机的效率与转动叶片和机匣之间的间隙密切相关。为了控制转子和静子之间的间隙,需要在机匣表面制备可磨耗的封严涂层。在发动机的高温端,ZrO₂-8wt% Y₂O₃涂层是经常采用的封严涂层基体。涂层中的孔隙可以增加涂层的可磨耗性。本文利用聚苯酯(PHB)增加等离子喷涂的ZrO₂-8 wt% Y₂O₃涂层的孔隙率。为了避免聚苯酯在等离子喷涂过程中的烧损,利用溶胶-凝胶法在聚苯酯颗粒表面沉积一层TiO₂层。文中将讨论采用此方法制成的涂层的形态、孔隙率、硬度和可磨耗性。结果表明,在喷涂粉末中混合包覆型的聚苯酯后,涂层的孔隙率将会得到提升,涂层硬度将会下降。磨耗试验的结果表明涂层的磨耗深度随着涂层孔隙率的增加而增加。     

Ti3AlC2掺杂SPS法制备Ti2AlC/TiAl复合材料的研究

通过2TiC-Ti-1.2Al体系的原位热压反应制备了Ti₃AlC₂陶瓷,然后以59.2Ti-30.8Al-10Ti₃AlC₂(wt%)为反应体系,采用放电等离子烧结技术制备出Ti₂AlC/TiAl基复合材料。借助XRD、SEM分析了产物的相组成和微观结构,并测量了其室温力学性能。结果表明：原位热压烧结产物由Ti₃AlC₂和TiC相组成,Ti₃AlC₂呈典型的层状结构,TiC颗粒分布在其间。SPS法制备的Ti₂AlC/TiAl基复合材料主要由TiAl、Ti₃Al和Ti₂AlC相组成,Ti₂AlC增强相主要分布于基体晶界处,表现为晶界/晶内强化作用。力学性能测试表明：Ti₂AlC/TiAl基复合材料的密度、维氏硬度、断裂韧性和抗弯强度分别为3.85 g/cm₃、5.37 GPa、7.17 MPa?m_1/2和494.85 MPa。     

三元共晶成分Al2O3/YAG/ZrO2粉体及陶瓷的制备与组织性能研究

本文采用醇水共沉淀法制备了三元共晶成分Al₂O₃/YAG/ZrO₂粉体,在600-1350_oC温度范围煅烧后研究其物相转变过程。经1300_oC煅烧后Al₂O₃/YAG/ZrO₂共晶成分粉体的物相由α-Al₂O₃、c-ZrO₂和YAG构成,且具有α-Al₂O₃相包裹c-ZrO₂相的特殊结构。将煅烧粉体在1550_oC下热压烧结,制备具有内晶型结构的共晶成分Al₂O₃/YAG/ZrO₂复相陶瓷,其致密度、室温抗弯强度、断裂韧性和高温(1000_oC)抗弯强度分别为98.8%、420 MPa、3.69 MPa.m_1/2和464 MPa,并对复相陶瓷组织结构的形成机理进行了探讨。     

SNDC/La2Mo2O9复合电解质材料的制备及性能表征

本文采用甘氨酸-硝酸盐法(GNP)和溶胶凝胶法分别合成了Sm_0.1Nd_0.1Ce_0.8O_1.9(SNDC) 和La₂Mo₂O₉(LAMOX)粉末,并用常压烧结的方法制备了不同比例的SNDC和LAMOX的复合材料,通过XRD和SEM等手段表征了不同复合比例样品的物相和表面形貌并测试了烧结样品的电导率。结果表明,复合样品的电导率在相变点前后随着复合量增加变化趋势相反,其中LAMOX含量为20mol%的样品在550℃时的电导率能达到0.01S/cm,高于同温度下SNDC电导率。     

新型AgZrB2 触头材料的制备及电气性能

采用超声、球磨和放电等离子烧结相结合的方法制备了不同ZrB₂含量（3%,5%,7%,质量分数）的新型AgZrB₂触头材料,并通过电接触试验研究了触头材料的电弧侵蚀和材料转移行为。结果表明,ZrB₂含量显著影响AgZrB₂触头材料的耐电弧侵蚀性能。Ag-3% ZrB₂触头材料具有稳定的闭合/分断燃弧能量和持续时间,表现出较好的耐电弧侵蚀性能。但是,过多的ZrB₂会导致更高的闭合燃弧能量和更长的闭合燃弧时间,并且分断燃弧能量和时间会产生较大的波动,电弧侵蚀较为严重,这说明过量的ZrB₂不利于提高触头材料的耐电弧侵蚀性能。此外,Ag-3% ZrB₂和Ag-5% ZrB₂触头材料具有相同的材料转移模式——从阳极向阴极转移,而Ag-7% ZrB₂触头材料则呈现出相反的转移模式——从阴极向阳极转移。     

激光熔覆Ni3Al/Cr3C2复合材料耐磨性能研究

采用激光熔覆技术在304不锈钢基板上制备了Ni_3Al合金和Ni_3Al/Cr_3C_2(25%,质量分数)复合材料耐磨涂层,分析了Ni_3Al合金和Ni_3Al/Cr_3C_2熔覆层的显微组织、硬度和耐磨性能。结果表明,Ni_3Al/Cr_3C_2熔覆层显微组织由基体γ'-Ni_3Al相和原位自生M_7C_3(M=Cr,Fe)型碳化物组成,且细小M_7C_3弥散分布于γ'-Ni_3Al基体。与Ni_3Al合金熔覆层相比较,Ni_3Al/Cr_3C_2熔覆层显微硬度提高了约4000 MPa。650℃时,Ni_3Al/Cr_3C_2熔覆层磨损量仅为对比材料蠕墨铸铁的28%左右,表明Ni_3Al/Cr_3C_2复合材料熔覆层具有良好的耐磨性能。     

Bi2Sn2O7含量对改性Ag/SnO2电接触复合材料性能的影响研究

以SnO2、Bi2Sn2O7为增强相粉体,化学银粉为基体相,采用高能球磨辅助常压烧结工艺制备出系列Bi2Sn2O7改性SnO2增强银基复合材料。考察了Bi2Sn2O7含量、球磨时间、烧结制度对Ag/SnO2-Bi2Sn2O7复合材料物理性能的影响规律。结果表明：随着球磨时间从1h延长至12h,Ag/SnO2-(6 wt.%) Bi2Sn2O7复合粉体从颗粒态向片状结构发生转变,Ag/SnO2-(6 wt.%) Bi2Sn2O7复合材料的电阻率呈逐渐上升趋势而密度呈不断下降趋势。烧结温度的提升和Bi2Sn2O7掺杂量的增加均有助于降低Ag/SnO2-Bi2Sn2O7复合材料的电阻率,且当Bi2Sn2O7掺杂量为12 wt.%、烧结温度900℃时,样品Ag/ (12 wt.%) Bi2Sn2O7的电阻率达到最佳值2.24 μΩ·cm。循环50次的初期电弧烧蚀试验分析可知,相比于纯Ag/SnO2而言,Bi2Sn2O7改性样品表面的烧损面积并未快速扩展至整个表面,且当Bi2Sn2O7含量为6 wt%时,Ag/SnO2-(6 wt.%) Bi2Sn2O7样品表面的烧损面积最小。而当Bi2Sn2O7含量为12 wt.%时, Ag/ (12 wt.%) Bi2Sn2O7表面烧蚀区出现了飞溅现象,这可能归因于其较低的表面硬度(82.38HV0.3)。     

The repeated thermal shock behaviors of a ZrB2-SiC composite heated by electric resistance method

Repeated thermal shocks of ZrB₂-20 vol.% SiC (ZrB₂-SiC) composite was investigated by the electric resistance method with 330 A and 4 V. It was found that the maximum temperature of the specimen center was obtained in 20 s and the specimen was cooled down to room temperature in 10 s due to a coolant system, and then the specimen was heated again. The thermal shock treatment increased the flexural strength with a peak at 20 cycles. Even though 30 cycles showed the minimum strength, it was still higher than that of the unshocked specimen. The increase in the strength was attributed to the formation of the oxide layer and the compression stress that resulted from volume expansion upon conversion of ZrB₂ and SiC, to ZrO₂, B₂O₃ and SiO₂.     

Microstructure and mechanical properties of laminated ZrB2-SiC ceramics with ZrO2 interface layers

Laminated ZrB₂-SiC ceramics with ZrO₂ interface layers were successfully prepared by tape casting, laminating and hot pressing. The flexural strength and fracture toughness are 561 ± 20 MPa and 14.4 ± 0.3 MPa m^1/2 for parallel direction, and 432 ± 18 MPa and 5.8 ± 0.3 MPa m^1/2 for perpendicular direction. The fracture toughness for parallel direction is improved significantly compared to monolithic ZrB₂-SiC ceramics. The toughening mechanism was attributed to the deflection and branch of the crack and the new microcracks, which would increase the propagation path and fracture work.     

La2O3改性ZrB2-SiC涂层C/C复合材料全温域抗氧化行为研究

采用高温反应熔渗工艺制备了ZrB2-SiC和La2O3改性ZrB2-SiC涂层C/C复合材料,对比了2种涂层试样在中温(7001100℃)、高温(12001500℃)和超高温(2000℃以上)3个温域范围内的抗氧化性能。结果表明:7001100℃范围内,随着温度的升高,La2O3改性涂层试样的抗氧化性能提升幅度在逐渐提高。1200℃1500℃范围内,涂层均表现出良好的长时抗氧化性能,La2O3改性ZrB2-SiC在1200℃下恒温氧化250 h后,仍保持微量的增重;涂层复合材料良好的高温抗氧化性能主要其在是由于氧化过程中涂层表面形成的La-Si-O复合玻璃层和钉扎相ZrSiO4的协同作用提升了氧化膜的高温稳定性。在2000℃以上的氧乙炔火焰烧蚀环境下,La2O3的添加使得ZrB2-SiC涂层的质量烧蚀率和线烧蚀率均降低了近50%,其主要归因于表层La-Si-O和ZrO2玻璃层对烧蚀缺陷的愈合作用。     

Mechanochemical and volume combustion synthesis of ZrB2

Formation of ZrB₂ by volume combustion synthesis (VCS) and mechanochemical process (MCP) from ZrO₂-Mg-B₂O₃ was studied. Production of ZrB₂ by VCS in air occurred with the formation of side products, Zr₂ON₂ and Mg₃B₂O₆ in addition to MgO and ZrB₂. Zr₂ON₂ formation was prevented by conducting VCS experiments under argon. Wet ball milling was applied to the VCS products before leaching for easier removal of Mg₃B₂O₆ phase. MgO and Mg₃B₂O₆ were removed from wet ball-milled products by leaching in 5 M HCl for 2.5 h. In MCP, 30-hour ball milling was found to be sufficient for the formation of ZrB₂ with no minor phase formation. Leaching of MCP products in 1 M HCl for 30 min was sufficient to remove MgO. Complete conversion of ZrO₂ to ZrB₂ did not take place in both production methods, even with excess amounts of Mg and B₂O₃. Therefore, formed ZrB₂ contained residual ZrO₂.     

Investigations on synthesis of ZrB2 and development of new composites with HfB2 and TiSi2

This paper presents the results of experimental investigations carried out on the synthesis of pure ZrB₂ by boron carbide reduction of ZrO₂ and densification with the addition of HfB₂ and TiSi₂. Process parameters and charge composition were optimized to obtain pure ZrB₂ powder. Monolithic ZrB₂ was hot pressed to full density and characterized. Effects of HfB₂ and TiSi₂ addition on densification and properties of ZrB₂ composites were studied. Four compositions namely monolithic ZrB₂, ZrB₂ + 10% TiSi₂, ZrB₂ + 10% TiSi₂ + 10% HfB₂ and ZrB₂ + 10% TiSi₂ + 20% HfB₂ were prepared by hot pressing. Near theoretical density (99.8%) was obtained in the case of monolithic ZrB₂ by hot pressing at 1850 °C and 35 MPa. Addition of 10 wt.% TiSi₂ resulted in an equally high density of 98.9% at a lower temperature (1650 °C) and pressure (20 MPa). Similar densities were obtained for ZrB₂ + HfB₂ mixtures also with TiSi₂ under similar conditions. The hardness of monolithic ZrB₂ was measured as 23.95 GPa which decreased to 19.45 GPa on addition of 10% TiSi₂. With the addition of 10% HfB₂ to this composition, the hardness increased to 23.08 GPa, close to that of monolithic ZrB₂. Increase of HfB₂ content to 20% did not change the hardness value. Fracture toughness of monolithic sample was measured as 3.31 MPa m^1/2, which increased to 6.36 MPa m^1/2 on addition of 10% TiSi₂. With 10% HfB₂ addition the value of K_IC was measured as 6.44 MPa m^1/2, which further improved to 6.59 MPa m^1/2 with higher addition of HfB₂ (20%). Fracture surface of the dense bodies was examined by scanning electron microscope. Intergranular fracture was found to be a predominant mode in all the samples. Crack propagation in composites has shown considerable deflection indicating high fracture toughness. An oxidation study of ZrB₂ composites was carried out at 900 °C in air for 64 h. Specific weight gain vs time plot was obtained and the oxidized surface was examined by XRD and SEM. ZrB₂ composites have shown a much better resistance to oxidation as compared to monolithic ZrB₂. A protective glassy layer was seen on the oxidized surfaces of the composites.     

Interface and defect characterization in hot-pressed ZrB2-SiC ceramics

ZrB₂ is interesting for thermal protection materials because of favorable thermal stability, mechanical properties and oxidation resistance. ZrB₂-20 vol.% SiC composite was prepared by hot-pressing at 2000 °C and 30 MPa. Microstructures and interfacial characterization were investigated by high resolution transmission electron microscopy. SiC polytype was formed as 6H structure in hot-pressed ZrB₂-SiC ceramics. Numerous edge dislocations were found in ZrB₂ grains. There was no interfacial amorphous layer or transition layer at the ZrB₂/6H-SiC interface. Note also that since only one of the constituents (ZrB₂ or SiC) was oriented along a proper zone axis, no evident orientation relationship was observed between SiC or ZrB₂.     

ZrB_2-SiC粉末与等离子射流场的相互作用

为了探究等离子喷涂制备ZrB_2-SiC涂层组织结构疏松、致密性差的原因,采用去离子水对经过射流场加热的粉体进行收集,对比前后粉体的组织结构特征以及物相变化。设计单颗粒沉积试验探究粉体的熔化状态以及变形颗粒的形貌特征,并与等离子喷涂制备涂层进行对应分析。结果表明,由于"涡流效应"使得经过等离子射流场的ZrB_2-SiC粉体与卷入的氧气发生反应,粉体出现轻微氧化现象。经过等离子射流场后,ZrB_2-SiC粉体呈现3种形貌特征:表面光滑型、表面多孔型、表面团聚型。其原因与等离子射流温度场非均匀性以及粉体的飞行路径有关。变形颗粒呈现与之相对应的3种形貌特征:熔化充分颗粒、团聚堆积颗粒、以及介于两者间的半熔融半疏松颗粒。共晶组织包裹的ZrB_2颗粒容易在涂层中形成致密区,而团聚堆积的ZrB_2和SiC颗粒是涂层形成疏松区的主要原因。