The effect of microstructure on thermal expansion coefficients in powder-processed Al2Mo3O12

Orthorhombic Al₂Mo₃O₁₂ was investigated as a model anisotropic phase to understand the influence of powder preparation routes and bulk microstructure (mean grain size) on the bulk coefficient of thermal expansion (CTE) and to compare it to the intrinsic CTE of powder samples. A co-precipitation route was used for the synthesis of pure single-phase nanopowders, while a polyvinyl alcohol-assisted sol–gel method was utilized for the synthesis of micron-sized powders. Sintered samples prepared from both powders exhibited different microstructures in terms of mean crystal sizes and porosity. Bulk samples obtained from nanopowders were highly porous and contained crystals of approximately 100-nm diameter, while the bulk pieces produced from the micron-sized powders were denser, contained crystals larger than 5 μm, and showed occasional intergranular and transgranular microcracks. Such different microstructures hugely impact the bulk CTE: the nanometric sample possesses a bulk CTE (0.9 × 10^?6 °C^?1, from 200 to 700 °C) closer to the instrinsic CTE (2.4 × 10^?6 °C^?1) than for the micrometric sample, which showed a negative CTE (?2.2 × 10^?6 °C^?1) from 200 to 620 °C, and an even more negative CTE above 620 °C (?35 × 10^?6 °C^?1). A finite element analysis showed that the local maximum thermal tensile stresses could be as high as 220 MPa when simulating a temperature drop of 700 °C as an example of thermal treatment following sintering. This tensile stress is expected to exceed the tensile strength of Al₂Mo₃O₁₂, explaining the origin of microcracks in bulk samples prepared from the micron-sized powders. The thermal behavior of the microcracks leads to differences between the intrinsic and bulk thermal expansion; we show experimentally that such differences can be reduced by nanostructuring.     

Sc2W3O12/ZrO2可控热膨胀复合材料的制备

采用固相法成功制备了纯度较高的各向异性负热膨胀材料Sc₂W₃O₁₂。将ZrO₂与Sc₂W₃O₁₂按一定体积比混合, 在1200 ℃烧结10 h制备Sc₂W₃O₁₂/ZrO₂复合材料。通过XRD、SEM、EDS和热膨胀仪对合成样品的晶体结构、断面形貌和热膨胀性能进行表征。结果表明: 样品组元为正交相Sc₂W₃O₁₂和单斜相ZrO₂; 在 30~600 ℃内, Sc₂W₃O₁₂/ZrO₂复合材料的热膨胀系数皆线性一致, 并且通过改变Sc₂W₃O₁₂的体积分数, 其热膨胀系数可以控制为正、负或零, 其中60%Sc₂W₃O₁₂/ZrO₂复合材料在30~600 ℃的平均热膨胀系数为0.026×10^-6 ℃^-1, 近似为0。     

Y_2W_3O_(12)/Ni复合材料的制备及热膨胀性能

为研究Ni基Y2W3O12复合材料的热学性能,首先,采用二次焙烧法制备了负膨胀材料Y2W3O12;然后,将Y2W3O12与金属Ni进行混合,并在1 200℃、50 MPa的条件下热压烧结制得40vol%Y2W3O12/Ni复合材料;最后,对复合材料的成分及热膨胀性能进行了研究。结果表明:在热压烧结过程中,由于Ni的还原性比W差,相对于对比试样40vol%Y2W3O12/Cr复合材料中发生的复杂化学反应,40vol%Y2W3O12/Ni复合材料的两相之间并未发生反应,使40vol%Y2W3O12/Ni复合材料保持了较低的热膨胀系数;经数次循环退火释放热应力及去除Y2W3O12相的结晶水后,40vol%Y2W3O12/Ni复合材料在170~800℃温度范围内的热膨胀系数趋于稳定,约为3.4×10-6 K-1,与理论设计值4.0×10-6 K-1相近。     

Al2-xYxW3O12的合成与热膨胀特性的研究

近零及负热膨胀材料有诸多的潜在应用领域,而具有负热膨胀效应的A2M3O12系列材料在较宽的温度范围,易于通过组份变化调整其热膨胀系数.本文首次使用共沉淀法合成了Al2-xYxw3O12(x=0～2)系列粉体材料.经X射线衍射分析证明Al2W3O12和Y2W3O12能完全固溶形成二元固溶体,采用PowderX软件对Al2-xYxW3O12的晶胞参数进行计算,结果表明室温下随着稀土钇(Y)含量的增加,晶体的晶胞参数与晶胞体积逐渐增加.高温X射线衍射结果表明,随着稀土钇(Y)含量的增加,Al2-xYxW3O12的本征热膨胀系数逐渐由正到负变化.热机械分析(TMA)压缩法测定其宏观热膨胀系数,发现通过调整材料的组成,可以将其热膨胀系数控制为一定的正值、负值或零.但是由于其结构的各向异性,多晶陶瓷内部存在的微裂纹使热膨胀曲线出现较大的滞后环.     

Slip casting of Al2O3 and Al2O3/ZrO2 composites

Al₂O₃ and Al₂O₃/ZrO₂ composites have been fabricated by slip casting from aqueous suspensions. The physical and structural characteristics of the starting powders, composition of the suspensions, casting behaviour, microstructure of the green and fired bodies and the mechanical properties of the products were investigated. The addition of ZrO₂ to Al₂O₃ leads to a significant increase in fracture toughness when ZrO₂ particles are retained in the tetragonal form (transformation-toughening mechanism) but when microcracking (due to the spontaneous transformation of ZrO₂ from the tetragonal phase to the monoclinic one) is dominant, an excellent toughness value is accompanied by a drastic drop in strength and hardness.     

Negative thermal expansion in Y2W3O12

Neutron diffraction data were collected on polycrystalline Y₂W₃O₁₂ at seven temperatures from 15 to 1373 K. All three cell edges of orthorhombic Y₂W₃O₁₂ decrease with increasing temperature, giving an average linear thermal expansion coefficient of −7.0×10⁻⁶ K⁻¹. Rietveld refinements of the neutron diffraction data show an apparent decrease in the average W–O distance of 0.05 Å from 15 to 1373 K. This apparent decrease causes the decrease in the cell edges, but it is not an actual decrease of average W–O distances. The apparent shrinkage is instead considered to be caused by the transverse thermal motion of oxygen in the Y–O–W linkages.     

Fabrication of Al/Al2O3 composites and FGM

Al/Al2O3 composites of different ratios were hot-press sintered at 575 similar to 640℃ under a pressure of 30 MPa for 2 h in a vacuum furnace. It was found that the relative density of the Al/Al2O3 composites could be increased evidently with the rise of sinter temperature. No reaction occurred between Al and Al2O3 at the sinter temperatures. Under 640℃-30 MPa-2 h experimental condition, Al/Al2O3 system FGM was successfully fabricated, and its density range changed quasi-continuously from 2.887x10(3) kg/m(3) to 3.1909x10(3) kg/m3 within the middle 1.0 mm thickness range.     

The effect of phase transformation on the thermal expansion property in Al/ZrW2O8 composites

This article studied the effect of phase transformation on the thermal expansion property in Al/ZrW₂O₈ composites. The Al/ZrW₂O₈ composites of low-thermal expansion were fabricated by a squeeze casting method. The coefficient of thermal expansion (CTE) of as-made composites was discovered sharply increased at around 130 °C. The X-ray diffraction (XRD) spectra showed the existence of high-pressure γ-phase in the as-made composites. This high-pressure γ-phase was considered to be induced by the compressive residual stress originated from the thermal mismatch between Al matrix and ZrW₂O₈ particles. The in situ high-temperature XRD and the differential scanning calorimetry technique were used to study this thermally expanded abruption phenomenon. It was found that the phase transformation from high-pressure γ-phase to the low-pressure phases (α/β phase) in the composites should be responsible for fluctuation in the CTE of composites. Furthermore, using a proper heat treatment to eliminate the high-pressure phase in the composite, the Al/ZrW₂O₈ composites of low and uniform CTE (from 20 to 200 °C) could be achieved. And when temperature increased again, the thermal mismatch stresses between the metal matrix and ceramic particles in the composite were not large enough to re-induce the α-γ transformation.     

二维编织C/SiC复合材料的热膨胀系数预测

根据二维编织 C/ SiC复合材料的细观结构及其制备工艺特点 , 提出了一种预测该材料面内热膨胀系数的单胞模型。模型充分考虑了编织结构复合材料中的纤维束弯曲和 CVI工艺制备陶瓷基复合材料产生的孔洞对热膨胀系数的影响。利用单胞模型预测了二维编织 C/ SiC的结构参数、 纤维体积含量、 孔洞含量对复合材料热膨胀系数的影响规律 , 结果表明 : 随着纤维束扭结处产生间隙与纱线宽度比值的增大 , 热膨胀系数增大 ; 当其它参数不变时 , 随着纤维体积含量的增大 , 热膨胀系数反而下降; 随着孔洞含量的增加 , 热膨胀系数也出现了下降的趋势。利用 DIL402C热膨胀仪测试了二维编织 C/ SiC复合材料纵向热膨胀系数 , 试验结果与模型预测结果吻合较好。     

The coefficient of thermal expansion of biomimetic composites

The excellent mechanical properties of biocomposites has attracted a lot of research attention, and people have started attempting to fabricate biomimetic staggered composites. In this paper, the relationship between the equivalent coefficient of thermal expansion (CTE) and the microstructure of a biomimetic staggered composite is investigated. A shear-lag based thermalelastic analytical model is developed and is found to agree well with the finite element simulations. It is found that besides the volume fraction and the material constants of the constituent phases, the aspect ratio of the hard platelet plays an important role in the CTE of biocomposites. Hence, there are additional design parameters in staggered composites that can be used to adjust the CTE, which makes this type of composite promising in thermalelastic loading.     

Temperature dependence of flexural strength and microstructure of Al2O3/Y3Al5O12/ZrO2 ternary melt growth composites

New Al₂O₃/Y₃Al₅O₁₂(YAG)/ZrO₂ ternary Melt Growth Composites (MGCs) with a novel microstructure have been fabricated by unidirectional solidification. These MGCs displayed superior high-temperature strength characteristics. The flexural strength increases progressively in the range 650–800 MPa with a rise in temperature from room temperature up to 1873 K. These excellent high-temperature characteristics are closely linked to such factors as: a microstructure consisting of three-dimensionally continuous and complexly entangled single-crystal Al₂O₃ with a hexagonal structure, single-crystal YAG with a garnet structure and fine ZrO₂ with a cubic structure; characteristic dimensions of the microstructure of Al₂O₃/YAG/ZrO₂ ternary eutectic ceramics of around 2–3 m for YAG, around 2–3 m for Al₂O₃ and around 0.4–0.8 m for ZrO₂; and the fact that no amorphous phase is formed at interfaces between any of the phases.     

The coefficient of thermal expansion of biomimetic composites

The excellent mechanical properties of biocomposites has attracted a lot of research attention, and people have started attempting to fabricate biomimetic staggered composites. In this paper, the relationship between the equivalent coefficient of thermal expansion (CTE) and the microstructure of a biomimetic staggered composite is investigated. A shear-lag based thermalelastic analytical model is developed and is found to agree well with the finite element simulations. It is found that besides the volume fraction and the material constants of the constituent phases, the aspect ratio of the hard platelet plays an important role in the CTE of biocomposites. Hence, there are additional design parameters in staggered composites that can be used to adjust the CTE, which makes this type of composite promising in thermalelastic loading.     

Carbon fiber-reinforced cyanate ester/nano-ZrW2O8 composites with tailored thermal expansion

Fiber-reinforced composites are widely used in the design and fabrication of a variety of high performance aerospace components. The mismatch in coefficient of thermal expansion (CTE) between the high CTE polymer matrix and low CTE fiber reinforcements in such composite systems can lead to dimensional instability and deterioration of material lifetimes due to development of residual thermal stresses. The magnitude of thermally induced residual stresses in fiber-reinforced composite systems can be minimized by replacement of conventional polymer matrices with a low CTE, polymer nanocomposite matrix. Zirconium tungstate (ZrW(2)O(8)) is a unique ceramic material that exhibits isotropic negative thermal expansion and has excellent potential as a filler for development of low CTE polymer nanocomposites. In this paper, we report the fabrication and thermal characterization of novel, multiscale, macro-nano hybrid composite laminates comprising bisphenol E cyanate ester (BECy)/ZrW(2)O(8) nanocomposite matrices reinforced with unidirectional carbon fibers. The results reveal that incorporation of nanoparticles facilitates a reduction in CTE of the composite systems, which in turn results in a reduction in panel warpage and curvature after the cure because of mitigation of thermally induced residual stresses.     

Characterization of Al2O3 composites with fine Mo particulates,I. Microstructural development

Alumina based composites containing nano- or submicron-meter Mo grains in the amounts of 20 vol% or less were prepared through a dissolution of molybdenum oxide in ammonium solution, followed by spray-drying, hydrogen reduction and sintering with or without hot-pressing. The properties of alumina/molybdate solutions and the ζ-potential of alumina particles in the solution were measured. By using electron microscopic and quantified X-ray diffraction techniques, the microstructural features and the evolution of Mo paniculate in spray-dried powder and sintered bodies were analyzed. The time dependent exponent and activation energy of grain growth of Mo between 600 to 900 °C were determined. There is no glassy phase or reaction at the interfaces between Mo/Al₂O₃ of dense composites. Only one coherent interface was found, and the others are incoherent. The results reveal that submicrometric Mo grains may grow by surface diffusion in reduction stage (≤ 900 °C) and greatly retard the densification and reduce the grain size of alumina matrix in sintering stage.     

光悬浮区熔定向凝固Al2O3/Er3Al5O12和Al2O3/Yb3Al5O12共晶陶瓷的制备与性能研究

本研究探索了光悬浮区熔法制备Al₂O₃/Er₃Al₅O₁₂(ErAG)和Al₂O₃/Yb₃Al₅O₁₂(YbAG) 定向凝固共晶陶瓷。在10 mm/h的抽拉速率下成功获得了凝固组织均匀、内部无裂纹或孔洞的高质量共晶陶瓷。通过高分辨三维X射线衍射仪研究了Al₂O₃和RE₃Al₅O₁₂在三维空间的分布与组织结构; 利用电子背散射衍射技术分析了定向凝固末期Al₂O₃和RE₃Al₅O₁₂两相的晶体学择优取向和相界面关系。力学性能表征结果显示, Al₂O₃/ErAG和Al₂O₃/YbAG具有优异的力学性能, 二者的维氏硬度分别为(13.5±0.4)和(12.8±0.1) GPa;断裂韧性分别为(3.0±0.2)和(3.2±0.1) MPa·m^1/2。     

Cyclic oxidation of FeCrAlY/Al2O3 composites

Abstract

Three-ply composites consisting of a FeCrAlY matrix and continuous single crystal Al₂O₃ (sapphire) fibers were cyclically oxidized at 1,000° and 1,100°C for up to 1,000 1-h cycles. FeCrAlY matrix only samples were also fabricated and tested for comparison. Fiber ends were exposed at the ends of the composite samples. Following cyclic oxidation, cracks running parallel to and perpendicular to the fibers were observed on the large surface of the composite. In addition, there was evidence of increased scale damage and spallation around the exposed fiber ends, particularly around the middle ply fibers. This damage was more pronounced at the higher temperature. The exposed fiber ends showed cracking between fibers in the outer plies, occasionally with Fe and Cr-rich oxides growing out of the cracks. Large gaps developed at the fiber–matrix interface around many of the fibers, especially those in the outer plies. Oxygen penetrated many of these gaps resulting in significant oxide formation at the fiber–matrix interface far within the composite sample. Around several fibers, the matrix was also internally oxidized showing Al₂O₃ precipitates in a radial band around the fibers. The results show that these composites have poor cyclic oxidation resistance due to the CTE mismatch and inadequate fiber–matrix bond strength at temperatures of 1,000°C and above.