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.     

Comparison of ZrB2-SiC ceramics with Yb2O3 additive prepared by hot pressing and spark plasma sintering

This work compared phase composition, microstructures and mechanical properties of ZrB₂—20 vol.% SiC—5 vol.%Yb₂O₃ prepared by hot pressing (HP) and spark plasma sintering (SPS) in vacuum. Despite the same raw material composition, the two densification techniques led to the appearance of different secondary phases. The HP ceramics had coarsened microstructure, predominantly intergranular fracture characteristic and high fracture toughness. The SPS ceramics exhibited refined microstructure, transgranular fracture model and high bending strength.     

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.     

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.     

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。     

High-temperature deformation of ZrB2 ceramics with WC additive in four-point bending

This work investigated high-temperature four-point bending deformation of hot-pressed ZrB₂ ceramics with WC additive at 1900 °C for 0–60 min in argon atmosphere under a static load of 25 MPa. After 60 min bending deformation, about 8% strain was achieved without apparent macroscopic cracks, suggestive of superplastic behavior at 1900 °C. The tensile side and the compressive side of the deformed samples exhibited different microstructural characteristics. On the tensile side, many cavities were observed at the multigrain junctions and the fracture surface was relatively flat. On the compressive side very few cavities occurred and some large cracks were present on the fracture surface. The presence of a secondary W-containing phase formed by the addition of WC, prohibited the coalescence of cavities by its plastic deformation.     

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。     

CVD deposition and characterization of coloured Al2O3/ZrO2 multilayers

Coloured Al₂O₃/ZrO₂ multilayers have been deposited onto WC-Co based inserts by a CVD process. Through physical as well as optical analysis of such multilayers, colour is believed to originate from interference. The coatings are obtained with good process reproducibility. It was found that the ZrO₂ process used in the multilayer, with ZrCl₄ as the only metal chloride precursor, results in a mixture of tetragonal and monoclinic ZrO₂ phases. However by adding a relatively small amount of AlCl₃ during such a process results in ZrO₂ layers being composed of predominantly tetragonal ZrO₂ phase. Corresponding multilayers seem to have a more fine grained and smoother morphology whereas multilayers containing monoclinic ZrO₂ phase seem to be less perfect with existence of larger grains of ZrO₂ which are believed to scatter light and alter the reflectance of such a multilayer. In addition to this, such multilayers were found to be free of or with greatly reduced amount of thermal cracks, normally present in pure CVD grown Al₂O₃ layers.It is believed that, in the studied Al₂O₃/ZrO₂ multilayers, the observed tetragonal ZrO₂ phase is the result of a size effect, where small enough ZrO₂ crystallites energetically favor the tetragonal phase. However as the ZrO₂ crystallite size distribution is shifted to larger sizes it is believed that a mixture of crystallites with both stable and metastable tetragonal phases as well as a stable monoclinic phase is obtained. The proposed metastable tetragonal ZrO₂ phase may in fact explain the absence of thermal cracks in such multilayers through a transformation toughening mechanism, well known in ZrO₂ based ceramics.     

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。     

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。     

载体中ZrO2/Al2O3比对Pt/ZrO2-Al2O3催化剂性能的影响

相比汽油车而言,柴油车具有高效、低油耗的优势已得到广泛应用。本实验以ZrO₂作为改性剂,探究了ZrO₂与Al₂O₃的质量比对催化剂的影响。研究结果表明：随着ZrO₂的加入,Pt粒子先减小后增大;Pt粒子与载体的交互作用先增大后减小。活性实验数据分析表明,ZrO₂的最佳添加量为40 wt%,CO和C₃H₆完全氧化温度分别降低20 _oC 、25 _oC。贵金属在催化剂的分散度以及贵金属与载体的相互作用随着ZrO₂与Al₂O₃质量比的变化而变化。Pt粒子越小,其与载体的交互作用越强,这表明催化剂性能越强。     

空气反应钎焊ZrO2与GH3536接头组织与力学性能

采用Al₂TiO₅颗粒增强的Ag-CuO-Al₂TiO₅复合钎料,在钎焊温度为1050 ℃保温30 min工艺参数下,对ZrO₂陶瓷与GH3536合金进行了空气反应钎焊(RAB),分析了钎焊接头的界面结构及其形成机制;同时研究了接头在800 ℃氧化不同时间的组织演变规律及其对连接性能的影响。结果表明,钎焊过程中Al₂TiO₅颗粒分解产生Al₂O₃和TiO₂,TiO₂与ZrO₂陶瓷反应生成ZrTiO₄相。GH3536侧金属元素发生氧化形成尖晶石层,并分别与钎缝中的Al₂O₃、CuO反应,在钎缝中生成细密分布的NiAl₂O₄相及紧邻尖晶石层的团块状NiCuO₂相。ZrO₂/GH3536接头高温氧化1000 h后,钎缝中NiAl₂O₄呈团块状分布,Cr₂O₃薄层保持稳定;尖晶石层内部元素均匀化,厚度有明显增加。接头强度随着氧化时间的延长先降低后稳定在20 MPa。     

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.     

等离子喷涂制备ZrB_2-SiC涂层及其抗氧-丙烷焰流烧蚀性能

为提高C/C复合材料的抗高温烧蚀性能,利用大气等离子喷涂技术在C/C复合材料表面制备ZrB_2-SiC复合涂层,并对其进行抗高温氧-丙烷焰流烧蚀试验。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)及能谱分析仪(EDS)对涂层的物相成分、微观形貌等进行检测分析。结果表明:大气等离子喷涂能在C/C复合材料表面制备出均匀致密的ZrB_2-SiC复合涂层,涂覆有ZrB_2-SiC涂层的C/C复合材料分别承受1 600、1 700和1 800℃的氧-丙烷焰流烧蚀300 s后依次增重0.63%、0.76%和0.71%,而烧蚀600s后试样质量烧蚀率分别为9.42×10~(-5)、2.04×10~(-4)和1.04×10~(-3)g/s。ZrB_2-SiC涂层显著提高了C/C复合材料的抗烧蚀性能,涂层氧化生成的玻璃态SiO_2能有效填充孔隙。直到SiO_2耗尽,涂层烧蚀后的孔洞成为环境中的氧进入基体的通道,导致基体烧蚀。     

原位合成ZrO2/MgO膜层及自修复裂纹研究

微弧氧化熔融冷却成膜过程出现的裂纹将影响膜层的强韧性和磨损性能。本研究利用ZrO₂自身的强韧性,原位合成具有自修复裂纹作用的ZrO₂/MgO膜层,研究原位合成的ZrO₂对膜层磨损性能的影响。结果表明,微弧氧化原位合成的ZrO₂在高温放电通道发生相变产生体积膨胀使得氧化锆界面萌生微裂纹并阻碍裂纹尖端的裂纹扩展,从而实现了膜层裂纹的自修复。通过控制锆源含量实现了对膜层中ZrO₂含量的调控,膜层中原位ZrO₂含量为32%时,ZrO₂/MgO膜层裂纹呈现细小分散化,裂纹密度较传统膜层下降63.4%,摩擦系数减小53.4%,磨损量降低66.7%。研究认为,原位合成的ZrO₂在膜层制备过程实现裂纹自修复并有效降低摩擦系数和磨损量,改善ZrO₂/MgO膜层表面磨损性能。     

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。     

Dielectric and microwave properties of ZrO2 doped CaO-SiO2-B2O3 ceramic matrix composites

The behavior of dielectric and microwave properties against sintering temperature has been carried out on CaO-SiO₂-B₂O₃ ceramic matrix composites with ZrO₂ addition. The results indicated that ZrO₂ addition was advantageous to improve the dielectric and microwave properties. X-ray diffraction (XRD) patterns show that the major crystalline β-CaSiO₃ and a little SiO₂ phase existed at the temperature ranging from 950 °C to 1050 °C. At 0.5 wt% ZrO₂, CaO-SiO₂-B₂O₃ ceramic matrix composites sintered at 1000 °C possess good dielectric properties: ?_r = 5.85, tan δ = 1.59 × 10⁻⁴ (1 MHz) and excellent microwave properties: ?_r = 5.52, Q · f = 28,487 GHz (11.11 GHz). The permittivity of Zr-doped CaO-SiO₂-B₂O₃ ceramic matrix composites exhibited very little temperature dependence, which was less than ±2% over the temperature range of −50 to 150 °C. Moreover, the ZrO₂-doped CaO-SiO₂-B₂O₃ ceramic matrix composites have low permittivity below 5.5 over a wide frequency range from 20 Hz to 1 MHz.