钨添加对Si3N4陶瓷力学性能的影响及强韧化机理研究

为了增韧Si₃N₄基陶瓷材料,以钨(W)作为第二相材料,Y₂O₃-Al₂O₃作为烧结助剂,采用气压烧结法制备了W/Si₃N₄复合陶瓷材料。研究了W含量对W/Si₃N₄复合陶瓷材料致密性、力学性能以及结构的影响。结果表明:在W含量小于5%(质量分数)时,样品致密度均达97%以上;在W含量为5%(质量分数)时,获得的W/Si₃N₄复合陶瓷材料综合性能最佳,弯曲强度、硬度和断裂韧性分别为(670.28±40.00) MPa、(16.42±0.22) GPa和(8.04±0.16) MPa·m^1/2,相比于未添加金属W的Si₃N₄陶瓷材料分别提高了38.08%、13.08%和44.34%;通过分析W/Si₃N₄复合陶瓷材料样品抛光面和压痕裂纹的微观结构,发现W的引入能促使裂纹在扩展路径上更易发生偏转、分叉等增韧机制,消耗裂纹扩展能量,从而改善Si₃N₄陶瓷的断裂韧性。     

Calculation, Measurement, and Control of Interface Strength in Composites

Strength and energy criteria for interface delamination are given for composite systems involving anisotropic fibers. The tensile strength of planar interfaces is measured with a modified laser spallation experiment involving a laser Doppler displacement interferometer. The technique for achieving desired interface properties is demonstrated on an Nb/Al₂O₃, interface. In the as-deposited state, the strength is determined to be 0.28 GPa. The interface strength is controlled with sputter-deposited Cr and Sb interlayers. The strength of Nb/Al₂O₃ interfaces varies from 0.28 to 0.35 GPa when the Cr layer thickness varies from 1 to 50 Å. The strength is reduced to 0.16 GPa with Sb thickness of 70 Å.     

金刚石增强Na2O-B2O3-Al2O3-SiO2系陶瓷基复合材料的界面研究

以Na₂O-B₂O₃-Al₂O₃-SiO₂系低温玻璃为基础结合剂烧制金刚石增强陶瓷基复合材料,利用扫描电子显微镜、X射线能谱、X射线光电子能谱、拉曼光谱及力学性能测试仪等对其界面结合强度、界面处元素分布及界面化学键进行了表征。结果表明,Na₂O-B₂O₃-Al₂O₃-SiO₂系陶瓷结合剂与金刚石颗粒界面结合强度高,790 ℃煅烧时试样抗折强度达到77.82 MPa。Si、B、Na、Zn各元素在界面位置发生扩散,而Al元素没有明显扩散,元素扩散提升了结合剂对金刚石的把持力。陶瓷结合剂与金刚石在界面处形成C-O、C=O和C-B键,化学成键进一步增进界面结合。另外,790 ℃煅烧的复合材料中金刚石颗粒保存完好,而850 ℃煅烧时金刚石出现石墨化迹象。     

Polymer Viscoelasticity: Relation to Peel Strength in Structural Adhesives

The two tests of most importance in evaluating structural adhesives for metals are (1) lap shear strength and (2) peel strength. Epoxies perform well in the first due to high tensile and shear strength. They are poor in the second unless modified to reduce brittleness. We have developed a urethane modified epoxy for this purpose. By taking climbing drum peel data in which both the temperature and the peel rate are varied, the time-temperature superposition principle can be tested. This principle is most generally applicable to thermoplastic materials between T_θ and T_θ + 100 °C (T_θ = glass transition temperature), and serves as a measure of viscoelastic response in the polymer. First, good agreement was found for a thermoplastic adhesive (PE-AA film). This was done to verify that climbing drum peel data can be used in this manner. Next, data were taken for our urethane modified epoxy. Results showed adherence to the superposition principle only above the heat distortion temperature of the cured polymer. These results indicate, among other things, that our point of failure upon peeling is within the body of the adhesive rather than within a urethane-rich layer at the metal-adhesive interface.     

The relationship between the strength of an adhesive bond and the thermodynamic properties of its components

Maximum stability of any system is achieved when its free energy is minimum, in accordance with the second law of thermodynamics. Considering the adhesive bond as a thermodynamic system, it is proposed that the minimum interfacial energy coincides with (1) the maximum strength, and (2) the maximum durability, understood as bond resistance to degradation under environmental attack. The thermodynamic properties of bond components which play a key role in promoting conditions for maximum strength of adhesion have been identified. The general pattern of the relationship: STRENGTH = function (interfacial energy and related parameters), has been developed based on experimental data covering a variety of adhesives and substrates such as metals (steel and aluminium), plastics, ceramics and glass fibre composites. The influence of adhesion promoters (eg, silanes) has also been considered.

It is shown that conditions for maximum strength coincide with the minimum interfacial energy of the system, acquired when the ratio of the surface energy of the substrate, γ₁, to that of the cured adhesive, γ₂ (ie, a = γ₁/γ₂), has a specific value denoted a_MIN. Systems with energy ratios a a_MIN were found to have engineering utility, because the strength deficiency for a >a_MIN was found to be significantly less than for a MIN.     

Toughening and Strengthening of NiAl with Al2O3 by the Addition of ZrO2(3Y)

NiAl/10-mol%-ZrO₂(3Y) composites of almost full density have been fabricated via spark plasma sintering (SPS) for 10 min at 1300°C and 30 MPa. The former intermetallic compound, which contains a trace amount of Al₂O₃, has been prepared via self-propagating high-temperature synthesis. The composite microstructures are such that tetragonal ZrO₂ (∼0.2 μm) and Al₂O₃ (∼0.5 μm) particles are located at the grain boundaries of the NiAl (∼46 μm) matrix. Improved mechanical properties are obtained: the fracture toughness and bending strength are 8.8 MPa·m^1/2 and 1045 MPa, respectively, and high strength (>800 MPa) can be retained up to 800°C.     

滑石、CaCO3、BaSO4填充PP复合材料力学性能及界面相互作用对比

以3种白色矿物粉体［颗粒状CaCO₃、BaSO₄,片层状滑石（talc）］为填料,聚丙烯（PP）为基体树脂,通过熔融共混法制备PP复合材料,研究3种矿物粉体在不同含量时对PP复合材料的力学性能、流动性能与断裂形貌的影响规律,并采用Turcasanyi半经验公式计算了矿物填料与PP复合材料力学性能界面相互作用。结果表明,3种矿物粉体的加入均降低了PP的拉伸强度,PP/talc复合材料的拉伸强度明显高于PP/CaCO₃ 与PP/BaSO₄,且talc的加入明显增强了PP的拉伸模量与弯曲模量;CaCO₃ 与BaSO₄的加入使复合材料弯曲强度降低,talc的加入使复合材料弯曲强度提高;CaCO₃对PP断裂伸长率与悬臂梁缺口冲击强度的提升最为明显;talc的加入使复合材料流动性能得到提高,而颗粒状的CaCO₃与BaSO₄的加入对加工性能影响较小;CaCO₃ 与BaSO₄在PP中均存在一定团聚现象,且与PP相容性较差,存在明显界面缺陷;talc与PP间界面较模糊,二者之间有较强的黏结作用。     

Fabrication of Si3N4/SiC Composite by Reaction-Bonding and Gas-Pressure Sintering

Si₃N₄/SiC composite materials have been fabricated by reaction-sintering and postsintering steps. The green body containing Si metal and SiC particles was reaction-sintered at 1370°C in a flowing N₂/H₂ gas mixture. The initial reaction product was dominated by alpha-Si₃N₄. However, as the reaction processed there was a gradual increase in the proportion of β-Si₃N₄. The reaction-bonded composite consisting of alpha-Si₃N₄, β-Si₃N₄, and SiC was heat-treated again at 2000°C for 150 min under 7-MPa N₂ gas pressure. The addition of SiC enhanced the reaction-sintering process and resulted in a fine microstructure, which in turn improved fracture strength to as high as 1220 MPa. The high value in flexural strength is attributed to the formation of uniformly elongated β-Si₃N₄ grains as well as small size of the grains (length = 2 μm, thickness = 0.5 μm). The reaction mechanism of the reaction sintering and the mechanical properties of the composite are discussed in terms of the development of microstructures.     

Microstructure and mechanical properties of gas pressure sintered Al2O3/TiCN composite

Al₂O₃–30 wt.%TiCN composites have been fabricated successfully by a two-stage gas pressure sintering schedule. The gas pressure sintered Al₂O₃–30 wt.%TiCN composite achieved a relative density of 99.5%, a bending strength of 772 MPa, a hardness of 19.6 GPa, and a fracture toughness of 5.82 MPa m^1/2. The fabrication procedure involves solid state sintering of two phases without solubility to prepare Al₂O₃–TiCN composite. Little grain growth occurred for TiCN during sintering while Al₂O₃ grains grew about three times to an average size of 3–5 μm. The interface microstress arising during cooling from the processing temperature because of the thermal and/or mechanical properties mismatch between the Al₂O₃ and TiCN phase is about 50 MPa. Such a compressive microstress is not high enough to cause grain boundary cracking that may weaken the composite but it can introduce dislocations within grains, which is very good to enhance the composite properties.     

硼酸铝-六钛酸钾晶须复合隔热材料制备与性能

以硼酸、氢氧化铝、六钛酸钾晶须(PTW)等为主要原料,采用固相烧结法制备了硼酸铝-六钛酸钾晶须复合隔热材料,研究了预合成硼酸铝晶须(ABW)对材料显微结构、力学性能及隔热性能等方面的影响。结果表明:随着制备温度的提高,ABW与PTW由点接触转变为晶须间通过K_1.5(Al_1.5Ti_6.5)O₁₆相结合,提高了复合隔热材料的致密度和耐压强度;细小的ABW在PTW之间形成了尺寸更小的孔隙,通过减少对流和辐射传热,显著提高了晶须复合隔热材料的隔热性能。控制PTW、预合成ABW、炭黑质量比为9∶1∶3,在1 100 ℃可制得体积密度为1.11 g/cm³、耐压强度为3.5 MPa、导热系数为0.11~0.16 W/(m·K)(200~800 ℃)的硼酸铝-六钛酸钾晶须复合隔热材料。     

载体含量对NaNO3/硅藻土复合相变储热材料的性能影响规律

采用混合烧结工艺,通过改变硅藻土载体材料的质量分数制备5种不同参数的NaNO₃/硅藻土复合相变储热材料（CPCM）样品,并对其进行抗压强度测试、热物性测试、能谱表征、微观形貌观察及热性能分析。当硅藻土质量分数从30%增加到35%和40%时,样品抗压强度随之增加,表现出脆性材料特征,当达到45%和50%时,则表现出塑性材料特征。硅藻土的加入和混合烧结处理对NaNO₃的相变几乎没有影响。样品的热导率随温度升高而降低,在同一温度条件下,样品热导率均随硅藻土质量分数的升高基本呈上升趋势,但从30%增加到35%时,热导率的增幅大于从35%增加到50%时热导率的增幅,前者约为后者的8倍。与NaNO₃相比,样品在常温-相变前温度段和相变结束-最高温度段的平均比热容随硅藻土质量分数变化均出现先下降后上升的变化。硅藻土质量分数为35%时,样品内部结构致密,NaNO₃充分均匀吸附于硅藻土的分离独立小单元中。硅藻土质量分数为35%时样品具有较好的抗压强度和储热效果。     

The Effect of the Interface on the Impact Strength of Fiber-Reinforced Silicon Nitride Composites

Hot-pressed silicon nitride can offer large gains in gas turbine performance when used as a blade or vane provided the limitation of low impact strength can be overcome. Through the use of fiber reinforcement, energy absorption modes not available in monolithic materials are provided, with the result that the elevated temperature (1300°C) impact strength of an Si₃N₄ composite reinforced with 30 volume percent tungsten wires has been shown to increase ninefold over unreinforced Si₃N₄.To make use of the energy absorbing mechanisms of fiber pullout and/or interfacial splitting, one needs to retain the filament strength and have a fairly weak or low modulus interface or interfacial region between the tungsten and the silicon nitride. At elevated temperatures, this is the case; however, at room temperature the tungsten silicide layer formed at the W-S1₃N₄ interface during hot pressing has been found to render the tungsten reinforcement ineffective as a crack blunting constituent. Efforts are being made to prevent the formation of tungsten silicide through the use of interfacial barrier coatings and/or reducing the fabrication temperature.     

铁尾矿砂基环氧树脂透水材料力学性能及界面特性研究

利用固体废弃物制备透水材料是海绵城市发展新方向,而力学性能差成为固废基透水材料应用的难点之一。为解决该问题,设计了一类用铁尾矿砂作为骨料,环氧树脂作为胶凝材料的聚合物透水材料,研究了环氧树脂含量对透水材料力学性能和透水性能的影响,并探讨了纳米SiO₂、TiO₂、Al₂O₃和硅烷偶联剂KH-560等有机-无机材料对透水材料力学性能的影响。结果表明:当环氧树脂质量分数为6%时,可以得到兼顾力学性能和透水性能的透水材料,抗压、抗折强度和透水速率分别为17.5 MPa、5.3 MPa和1.12 mm/s;同时,当纳米SiO₂、TiO₂、Al₂O₃的添加量分别为环氧树脂的3%、4%、4%(质量分数)时,对透水材料力学性能的提升分别为33.1%、30.5%、28.6%,其原因是纳米粒子在透水材料受压过程中会吸收树脂基体中的部分能量,抑制或消除树脂中微裂纹的扩散;当硅烷偶联剂KH-560的添加量为环氧树脂的0.9%(质量分数)时,透水材料的强度可提升36.5%。SEM和FTIR分析表明,硅烷偶联剂KH-560对改善铁尾矿砂与环氧树脂界面具有显著作用。该研究对研发高性能的固废基透水材料具有重要意义。     

Novel Composites Constituted from Hafnia and a Polymer-Derived Ceramic as an Interface: Phase for Severe Ultrahigh Temperature Applications

HfO₂–SiCN (polymer-derived silicon carbonitride) composites were prepared by two methods. In one case, equal volume fractions of HfO₂ and pyrolyzed powders of SiCN were co-sintered, to create a particulate composite . The second type, called interface composites , were prepared by coating HfO₂ particles with a thin film of the polymer precursor, followed by sintering so that densification and pyrolysis of the precursor occurred simultaneously; this process results in a ∼5-nm-thick grain boundary film constituted from Hf, O, and Si. The fracture properties and environmental degradation (in a humid environment at a velocity of 17.6–35.0 cm/s at 1300°C) of these two composites were measured. They were compared with the properties of a reference material made by sintering HfO₂ powders without any additives, under similar conditions (1450°C for 2 h in air). The interface composite yielded the highest sintered density (0.90), exhibited negligible grain growth, and possessed the highest fracture strength (110 MPa). The strength remained immune to hydrothermal oxidation for several hundred hours. In contrast, the particulate composite suffered severe degradation in strength after hydrothermal exposure. The interface composites, with their highly refractory grain boundaries, represent a new class of ceramics for structural applications in harsh environments and at ultrahigh temperatures.     

冰刀用高强韧Si3N4陶瓷的制备与性能研究

以α-Si₃N₄粉为原料,MgO-La₂O₃-Lu₂O₃为三元复合烧结助剂,采用气压烧结工艺制备Si₃N₄陶瓷条,研究烧结助剂及添加β-Si₃N₄增强相对Si₃N₄陶瓷微观结构及力学性能的影响。结果表明,三元复合烧结助剂促进了烧结的致密化,提高了材料的力学性能,在最高烧结温度1 750 ℃、复合烧结助剂添加量8%(质量分数)时,得到密度为3.172 8 g/cm³、维氏硬度达到15.85 GPa、断裂韧性和抗弯强度分别为9.69 MPa·m^1/2和1 029 MPa的冰刀用Si₃N₄陶瓷。添加β-Si₃N₄材料的断裂韧性得到提高,最高达到10.33 MPa·m^1/2。Si₃N₄陶瓷本身的高硬度与加入的稀土氧化物使得所制备冰刀的硬度与润滑性能得到提高,表面性能优良。     

利用核桃壳的形态结构优化Al2O3多孔材料的孔结构和性能

首先将质量分数为5%的ZrO₂溶胶、7%的Al₂O₃溶胶、3%的SiO₂溶胶作为浸渍试剂对核桃壳粉（WSP）浸渍处理。然后以α-Al₂O₃微粉为主原料,以处理后的WSP为造孔剂,制备了Al₂O₃多孔材料。研究了溶胶浸渍处理后WSP对多孔材料孔结构、热导率和力学性能的影响。结果表明,在Al₂O₃多孔材料的孔中可以清楚地观察到WSP的形变,这是优化陶瓷孔结构的重要因素。通过使用质量分数为3%的SiO₂溶胶浸渍处理的WSP,可以获得低热导率(200℃,0.297 W·m^-1·K^-1)和高耐压强度（43.5 MPa）的Al₂O₃多孔材料,并在孔中发现了莫来石的交叉网络结构。     

Fabrication, Microstructure, and Mechanical Properties of Cr2O3/ZrO2(2.5Y) Composite Ceramics in the Cr2O3-Rich Region

Intimate mixtures of Cr₂O₃/ZrO₂(2.5Y) in the Cr₂O₃-rich region are produced at low temperatures from amorphous materials prepared by the hydrazine method. Spark plasma sintering (SPS) has been performed for 10 min at 1300°C and 30 MPa. Composite ceramics with homogeneously dispersed fine ZrO₂ (0.2 µm) give 99.8% of theoretical densities. Their mechanical properties are examined in connection with increased ZrO₂ content. A high fracture toughness of 9.3 MPam^1/2 and an excellent bending strength of 1290 MPa are achieved in the composite ceramics containing 50 mol% ZrO₂.     

Wettability and Adhesion Characteristics of Plasma-Treated Carbon Fibers

The surface free energy (γ_s) of modified carbon fibers was determined by tensiometry and effects of CF₄-O₂ plasma treatment were evaluated. The treatment with the gas mixture in which oxygen was above 40% accelerated preferentially the oxidation of fiber surfaces and the nondispersive component of the surface free energy, γ^P_S, increased to about three times that of the untreated fiber. On the other hand, the treatment with the gas containing CF₄ above 80% induced fluorination and surface species such as - CF, - CF₂, or - CF₃ were formed. The γ^P_S values decreased to almost zero and the dispersive component became about 18 mJ/m². The calculated work of adhesion between various fibers and the epoxy resin was well correlated with the interfacial shear strength of the composites formed with these materials.     

High-Temperature Strength and Fracture Toughness of Y2O3-Partially-Stabilized ZrO2/Al2O3 Composites

The temperature dependence of bending strength, fracture toughness, and Young's modulus of composite materials fabricated in the ZrO₂ (Y₂O₃)-Al₂O₃ system were examined. The addition of A1203 enhanced the high-temperature strength. Isostatically hot-pressed, 60 wt% ZrO₂ (2 mol% Y₂O₃)/40 wt% Al₂O₃ exhibited an extremely high strength, 1000 MPa, at 1000°C.     

Strength of Green Ceramics with Low Binder Content

Acrylic-based polymers are common binders that impart high green strength (>2 MPa) at low concentrations (<5.0 vol%). Strength at low binder concentrations may be determined by chemical bonding at the ceramic–polymer interface. We have studied the binding mechanisms as a function of ceramic surface chemistry using a cross-linkable binder, which is based on a soluble poly(acrylic acid) (PAA, MW = 60 000) and glycerol. The cross-linked PAA binder system has been integrated into a solid freeform fabrication process, which provides a means of fabricating very reproducible green bodies, including SiO₂, TiO₂, Al₂O₃, multicomponent oxides, and non-oxides, with uniform density and composition. The ceramic parts contain only 2.5 vol% binder (solids basis), which increases the strength of the ceramic systems by at least a factor of 8 while the strength of Al₂O₃ components increases by a factor of ∼24 (0.3 to 7.6 MPa). Addition of the binder improves the toughness of the ceramic bodies by an order of magnitude with SiO₂ representing the largest relative increase (2.8 × 10⁻³ to 4.4 × 10⁻² MPa·m^1/2). The mechanical properties are dictated by two binding mechanisms: binder adsorption and mechanical interlocking. High green strengths result from adsorption of the binder onto the ceramic surface whereas toughness is enhanced by poor adhesion of the binder to the ceramic surface.