HfB2-SiC复合材料研究进展

HfB2复合材料是一种性能优异的高温结构材料,具有高熔点、高硬度、高热导率等优良性能,具有广泛的应用前景。本文概述了HfB2-SiC复合材料的研究现状,并对其力学性能进行了评价;总结了近年来国内外在HfB2基复合材料烧结工艺方面的研究进展。     

注凝成型制备HfB2-SiC复合陶瓷

采用注凝成型制备HfB2-SiC复合陶瓷,讨论了分散剂、pH值、固相体积含量对HfB2-SiC复合陶瓷浆料粘度的影响,并采用X射线衍射仪、扫描电镜、能谱等手段对制备烧结体的物相组成和显微结构进行了分析研究。结果表明,在HfB2中添加质量分数为20%的SiC,pH为10.6,分散剂体积分数为8%的条件下,HfB2-SiC复合粉体浆料的固相体积分数为40%,粘度为600mPa.s;在烧结体中HfB2和SiC以主晶相的形式存在于复合材料中,二者存在良好的界面结合,显微结构致密。     

MoSi_2对注凝成型HfB2超高温陶瓷材料性能的影响

在Ph为10.9,分散剂PMAA-NH4为8vol%,固体含量为40vol%的条件下采用注凝成型技术制备了HfB2-(5%～15wt%)MoSi_2超高温陶瓷坯体,密度达到4.25 g/cm~3以上,在氩气气氛下1950 ℃保温30 min烧成.采用X射线衍射仪、扫描电镜等分析方法研究了添加剂MoSi_2对HfB2超高温陶瓷材料性能的影响、烧结体的物相组成和显微结构.结果表明:添加剂MoSi_2可有效促进HfB2超高温陶瓷材料的致密化,随着MoSi_2加入量的提高,HfB2超高温陶瓷材料的力学性能不断提高,当加入量为15%时,可得到显微硬度为9.8 Gpa,抗弯强度为389.7 Mpa,断裂韧性为3.7 Mpa·m~(1/2)的HfB2超高温陶瓷材料.     

Reactive consolidation and high-temperature strength of HfB2–SiB6

During the spark plasma sintering at 1900 °C, SiB₆ decomposes into cubic silicon carbide and boron carbide, owing to the reducing environment of the furnace. For the HfB₂-SiB₆ ceramic improvement in hardness (24.5 ± 0.7 GPa) was attributed to the formation of the B₁₂(C,Si,B)₃. Fracture toughness by indentation (6.8 ± 2.4 MPa·m^1/2), single-edge notched bend specimens (4.6 ± 0.4 MPa·m^1/2) and room-temperature strength (513 ± 21 MPa) of the HfB₂–SiB₆ composite produced by spark plasma sintering was higher or on the same level as the HfB₂–SiC ceramics. The high-temperature flexural strength tests suggested that the strength would decrease monotonically with an increase in temperature. At or below 1600 °C, only a linear stress-strain response was observed, and resulted into a mean strength of ~320 MPa. During the tests at 1800 °C, we observed a nonlinear deformation indicating ongoing plastic deformation which led to a strength decrease down to 230 ± 30 MPa.     

Oxidation of HfB2–SiC ceramics under static and dynamic conditions

The kinetics and the mechanism of oxidation of ceramics based on HfB₂ and SiC, manufactured by elemental self-propagating high-temperature synthesis followed by hot pressing were investigated. The synthesis product contained HfC_(x) and HfO₂ as impurity phases. Depending on the ratio between the main components, the samples were characterized by high structural and chemical homogeneity, porosity of 3–6 vol%, hardness up to 29 GPa, bending strength of 500–600 MPa, fracture toughness of 5.6–8.9 MPa × m^1/2, and thermal conductivity of 86.0–89.7 W/(m × K). The oxidation was performed under static conditions at 1650 °C and upon exposure to a high-enthalpy gas flow. A dense layer consisting of HfO₂/HfSiO₄ grains formed on the surface of the ceramics during both oxidation conditions; the space between the grains was filled with amorphous SiO₂–B₂O₃. The best heat resistance was observed for the ceramics with 16 wt% SiC for static conditions and 8 wt% SiC for gas-dynamic conditions.     

Microstructural evolution of HfB2 based ceramics during oxidation at 1600–2000°C

HfB₂–2?wt-%-La₂O₃, HfB₂–20?vol.-%SiC and HfB₂–20?vol.-%SiC–2?wt-%La₂O₃ were sintered by spark plasma sintering for 5?min between 1900 and 2000°C. Oxidation studies were carried out in static air on sintered ultra high temperature ceramics at 1600, 1800 and 2000°C, and the weight change and microstructure changes after oxidation were examined. LaBO₃ formed on the surface after oxidation for 1?h above 1600°C in all La₂O₃ containing materials, and the cross-section microstructure shows growth of LaBO₃ fibres from pores due to vapour phase reaction. Addition of La₂O₃ altered the oxidation kinetics of HfB₂, significantly increasing the oxidation layer thickness above 1600°C. However, above 1800°C reaction has occurred between the sample and the zirconia crucible.     

Efficient multiscale strategy for toughening HfB2 ceramics: A heterogeneous ceramic–metal layered architecture

A multiscale structural design was innovatively adopted herein to increase the toughness of monolithic HfB₂ ceramics. SiC whiskers (SiC_w) and graphene oxide (GO) were used as fillers for the HfB₂ matrix, whereas a ductile W foil was introduced as an interlayer to synthesize laminated HfB₂-SiC_w-rGO/W ceramics. Monolithic HfB₂-SiC_p (particulate) and laminated HfB₂-SiC_p/W ceramics were prepared using the same routes and used as controls. Following tape casting and spark plasma sintering at 1800°C, the toughness of the prepared laminated HfB₂-SiC_w-rGO/W samples was increased to 14.2 ± 0.6 MPa·m^1/2, with minimal sacrifice in flexural strength (421 ± 16 MPa). Morphological analysis of the fracture surface revealed the synergistic effects of micro-toughening (including bridging and pullout of whiskers and rGO) and macro-toughening (including crack deflection, bifurcation, and delamination) mechanisms responsible for improving the fracture toughness of the laminated HfB₂-SiC_w-rGO/W composites.     

Mechanical and physical behaviors of short pitch-based carbon fiber-reinforced HfB2–SiC matrix composites

Short Pitch-based carbon fiber-reinforced HfB₂ matrix composites containing 20 vol% SiC, with fiber volume fractions in the range of 20–50%, were manufactured by hot-press process. Highly dense composite compacts were obtained at 2100 °C and 20 MPa for 60 min. The flexural strength of the composites was measured at room temperature and 1600 °C. The fracture toughness, thermal and electrical conductivities of the composites were evaluated at room temperature. The effects of fiber volume fractions on these properties were assessed. The flexural strength of the composites depended on the fiber volume fraction. In addition, the flexural strength was significantly greater at 1600 °C than at room temperature. The fracture toughness was improved due to the incorporation of fibers. The thermal and electrical conductivities decreased with the increase of fiber volume fraction, however.     

Influence of mechanical activation of reactive mixtures on the microstructure and properties of SHS-ceramics MoSi2–HfB2–MoB

In this work, the influence of modifications of SHS-process on the microstructure and performance characteristics of composite ceramics MoSi₂-HfB₂-MoB with two-level structure was studied. Partial texturing of MoSi₂ grains in samples obtained by force SHS pressing technology was revealed. The effect of preliminary mechanical activation on the macrokinetic parameters of combustion and on the microstructure of the synthesized ceramics was studied. A significant grinding of the synthesized ceramics grain and an increasing of physical-mechanical properties are achieved by increasing the velocity and lowering the combustion temperature of the activated mixtures. The sample obtained by hot pressing of SHS powder from MA reaction mixture showed the most optimal combination of hardness (19.5 GPa), porosity (0.4%) and oxidation resistance (1.82∙10^-6 mg/(cm²∙s)).     

Effect of La2O3 addition on long-term oxidation kinetics of ZrB2–SiC and HfB2–SiC ultra-high temperature ceramics

Long-term oxidation kinetics of SiC-reinforced UHTCs and La₂O₃-doped UHTCs over an intermediate temperature range (1400–1600 °C) reveal partially protective behavior for the former characterized by an oxidation kinetic exponent 1 < n < 2. In addition, unstable oxidation behavior was observed in HfB₂-based UHTCs due to the presence of SiC agglomerates. On the other hand, La₂O₃-doped UHTCs were found to be protective over the whole temperature range studied (n = 2), in particular at 1600 °C, where oxidation kinetic exponents as high as 8 were observed as a consequence of formation of new oxidation protective particles, MeO_xC_y, where Me is Zr, Hf or Si. Adsorption of oxygen-containing species formed protective MeO_xC_y phases, which enhanced the thermal stability of the oxide scale as well as providing protection against oxidation for long exposure times at 1600 °C.     

SnO_2-SbO_2-IrO_2/SnO_2-SbO_2-CeO_2电极制备及其电化学性能研究

采用涂层热分解法制备含中间层Sn O_2-Sb O_2-Ir O_2、中间层Ti/Sn O_2-Sb O_2-Ir O_2/Sn O_2-Sb O_2-Ce O_2电极,研究了中间层数对电催化性能的影响。结果表明含有5层中间层的电极,可有效提高活性层的比表面积,使活性层变得更致密,会使电极的使用寿命和催化活性提高,含有5层中间层的电极寿命是不含中间层的25倍。在Na Cl溶液中降解亚甲基蓝的效果比在Na_2SO_4溶液中好,最佳的降解条件为0.1 mol/L的Na Cl溶液中,槽压为4.0 V。     

Fe2+/H2O2体系O2生成路径

掌握Fe²⁺/H₂O₂体系O₂的生成路径,可为避免H₂O₂无效分解,开发经济高效的Fe²⁺/H₂O₂体系利用技术指明方向。采用添加自由基捕获剂的方法,探究Fe²⁺/H₂O₂体系内各种自由基对O₂生成速率的影响,进而确定O₂的生成路径。结果表明:Fe²⁺/H₂O₂体系内不会产生大量O₂^-·,O₂^-·不是生成O₂的主要反应物质;O₂^-·被全部捕获后,体系中仍产生大量O₂^-·,但此时无O₂生成,证明生成O₂的反应由·OH和HO₂·两种自由基直接参与。分析认为反应·OH+HO₂·-H₂O+O₂是体系内O₂生成的主要路径。控制Fe²⁺/H₂O₂体系定向生成·OH,抑制HO₂·的产生,是提高Fe²⁺/H₂O₂体系中H₂O₂利用率的有效手段。     

Li2O-Na2O-K2O-CaO-MgO-Al2O3-SiO2系统乳浊釉的研究

对Li2O-Na2O-K2O-CaO-MgO-Al2O3-SiO2系统釉进行了较全面的正交试验研究,找到了影响该系统釉乳浊及釉面质量的主次因素,获得了性能良好的乳浊釉及其较优乳浊釉配方.     

Fe~(2+)/H_2O_2体系O_2生成路径

掌握Fe~(2+)/H_2O_2体系O_2的生成路径,可为避免H_2O_2无效分解,开发经济高效的Fe~(2+)/H_2O_2体系利用技术指明方向。采用添加自由基捕获剂的方法,探究Fe~(2+)/H_2O_2体系内各种自由基对O_2生成速率的影响,进而确定O_2的生成路径。结果表明:Fe~(2+)/H_2O_2体系内不会产生大量O_2~-·,O_2~-·不是生成O_2的主要反应物质;·OH被全部捕获后,体系中仍产生大量HO_2·,但此时无O_2生成,证明生成O_2的反应由·OH和HO_2·两种自由基直接参与。分析认为反应·OH+HO_2=H_2O+O_2是Fe~(2+)/H_2O_2体系内O_2生成的主要路径。控制Fe~(2+)/H_2O_2体系定向生成·OH,抑制HO_2·的产生,是提高Fe~(2+)/H_2O_2体系中H_2O_2利用率的有效手段。     

PbCl_2-ZnCl_2-H_2O和CaCl_2-PbCl_2-H_2O三元体系373K相平衡

采用等温溶解平衡法研究了两个三元体系PbCl_2-ZnCl_2-H_2O和CaCl_2-PbCl_2-H_2O在373 K时的相平衡,测定了平衡溶液的溶解度和密度,并根据溶解度数据和对应的平衡固相绘制了相图和密度-组成图,根据相图对单变量曲线和结晶区进行了讨论。研究发现,两个三元体系均为简单共饱和型,均无复盐和固溶体生成,有一个共饱点,两条单变量曲线,两个结晶区。平衡液相对应的固相由XRD确定,并对实验结果进行了简要的讨论。     

PbCl2-ZnCl2-H2O和CaCl2-PbCl2-H2O三元体系373K相平衡

采用等温溶解平衡法研究了两个三元体系PbCl₂-ZnCl₂-H₂O和CaCl₂-PbCl₂-H₂O在373 K时的相平衡,测定了平衡溶液的溶解度和密度,并根据溶解度数据和对应的平衡固相绘制了相图和密度-组成图,根据相图对单变量曲线和结晶区进行了讨论。研究发现,两个三元体系均为简单共饱和型,均无复盐和固溶体生成,有一个共饱点,两条单变量曲线,两个结晶区。平衡液相对应的固相由XRD确定,并对实验结果进行了简要的讨论。     

SiO_2-ZrO2-Na_2O玻璃中SiO_2、TiO_2、ZrO_2受碱侵蚀的研究

吴正明等在1986年曾报道(76-x)SiO_2·XZrO_2·6 TiO_2·5CaO·10.4Na_O·2.6K_2O(氧化物前的系数为重量百分数,X为引入ZrO_2的重量百分数)玻璃随ZrO_2含量的变化受碱侵蚀前后试样失重百分数的变化.为进一步查明在上述系列玻璃中,当以ZrO_2代替等重量的SiO_2后,系统中各主要氧化物(SiO_2,TiO_2,ZrO_2)受碱侵蚀的变化,特开展了本次试验.     

S2O^2-8／ZrO2-Al2O3-SiO2固体超强酸

采用共沉淀法制备S2O^2-8／ZrO2-Al2O3-SiO2固体超强酸催化剂。通过单因素实验考察了三种金属最佳配比、陈化时间S2O^2-8的最佳浓度、浸泡时间、焙烧温度、焙烧时间等对固体酸酸强度的影响。研究表明,固体超强酸S2O^2-8／ZrO2-Al2O3-SiO2的最佳制备条件是：n（Zr）：n（Al）：n（Si）=1：2：1,陈化时间5h,S2O^2-8的浓度为0．75mol／L,浸渍时间3h,焙烧温度400℃,焙烧时间4h。此外,还利用红外光谱对样品结构进行了表征,利用酯化反应对其催化活性进行了初步研究。     

Al2O3-SiO2-TiO2-ZrO2复合膜及其微观结构

研究采用Sol-gel法研制了一种新型的Al2O3-SiO2-TiO2-ZrO2复合陶瓷膜。复合膜由γ-Al2O3，TiO2，ZrO2和Al2SiO3等多相组成，改变体系组成各相含量时膜的主晶相也随之变化，从而影响到膜的微观结构。利用原子力显微镜(AFM)分析法重点研究了膜的表面性质及其形貌，并探讨了修饰物添加剂对膜的形貌和性能的影响。     

PbBr2-PbCl2-PbF2-PbO-P2O5系统玻璃性能研究

研究了ＰｂＢｒ２ － ＰｂＣｌ２－ ＰｂＦ２ － ＰｂＯ－ Ｐ２Ｏ５ 系统的玻璃转变温度、密度、耐水性和透光率．ＰｂＢｒ２ － ＰｂＣｌ２ － Ｐ２Ｏ５ 系统的玻璃转变温度低达１４６ ℃,密度高达４ ．７５ ｇ／ｃｍ３ ． 加入ＰｂＦ２ 和／ 或ＰｂＯ 可显著提高玻璃的转变温度和密度,其中ＰｂＯ 的影响更为显著,可使玻璃的密度增加到５ ．４８ ｇ／ｃｍ３ ． 多数ＰｂＢｒ２ － ＰｂＣｌ２ － ＰｂＦ２－ ＰｂＯ－ Ｐ２Ｏ５ 系统玻璃的耐水性都很好,在水中的溶解速率为１０－５ ｍｍ／ｄａｙ． 玻璃的透光性较好,加入ＰｂＢｒ２ 使玻璃的紫外截断波长明显向长波方向移动．