Thermal expansion and mechanical properties of phenolic resin/ZrW2O8 composites

Phenolic resin/ZrW₂O₈ composites were successfully fabricated and their coefficient of thermal expansion (CTE) as well as mechanical properties was investigated. The CTE of the composites decreases from 46 × 10^–6 to 14 × 10^–6 K^?1 when the ZrW₂O₈ volume fraction increases from 0 to 52 vol %. The CTE of the composites is analyzed by some theoretical models; Schapery's upper bound provides the best estimate of the reduction in CTE. The Barcol hardness of the composites increases with an increase in the ZrW₂O₈ volume fraction. The bending strength of the composites with 19–25 vol % of ZrW₂O₈ fillers shows a maximum value of 130 MPa, which is 45% larger than that of phenolic resin without fillers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Fabrication and negative thermal expansion properties of P-substituted ZrV2O7 sintered bodies

Calcined powders of ZrV_1.2P_0.8O₇ (ZVP) and ZrV₂O₇ (ZV) were synthesized by heating gels prepared from NH₄H₂PO₄, NH₄VO₃, and ZrOCl₂ solutions at 500 and 400 °C, respectively. Dense ZV-added ZVP sintered bodies were subsequently fabricated through heating at 850 °C for 20 h, with the addition of ZrV₂O₇ as a sintering additive. The resulting material had a relative density of ca. 92%, while the relative density of pure sintered ZVP was ca. 72%. NH₄H₂PO₄ (NHP) was also added to ZVP along with ZV to obtain a molar ratio of P in NHP for V in ZV = 1. Subsequently, a single phase (NHP, ZV)-added ZVP sintered body was obtained by heating at 850 °C. Thermomechanical analysis showed that the dense ZV-added ZVP sintered body exhibited a positive thermal expansion from 25 to 150 °C and a negative thermal expansion from 150 to 500 °C.     

立方相ZrW1.7Mo0.3O8的制备及其负热膨胀特性研究

以硝酸氧锆、钼酸铵和钨酸铵为原料,采用水合前驱物分解法合成了负热膨胀粉体立方相ZrW_(1.7)Mo_(0.3)O_8。分别采用差热-热重分析(TG-DSC)、X射线粉末衍射、扫描电镜(SEM)等分析测试手段,研究了前驱体的晶化过程、产物的结晶度和形貌。结果表明,采用该方法能合成出纯净的立方ZrW_(1.7)Mo_(0.3)O_8粉体,其负热膨胀系数为-6.16×10~(-6)K~(-1)。     

Avoiding the intermediate phase Zr2WP2O12 to develop a larger-negative-thermal-expansion-coefficient material Zr2W2P2O15

Zr₂W₂P₂O₁₅ with larger-negative-thermal-expansion-coefficient (NTEC, −4.01×10⁻⁶ K⁻¹, 143–673 K) is developed by controlling reaction process to avoid the intermediate phase of Zr₂WP₂O₁₂, whose smaller NTEC limits its application. From 1473 K to1573 K, Zr₂WP₂O₁₂ forms easily but the reaction between Zr₂WP₂O₁₂ and WO₃ to generate Zr₂W₂P₂O₁₅ is difficult even followed by heating up to 1673 K. However, putting raw materials of ZrO₂, WO₃ and NH₄H₂PO₄ into a pipe furnace at sintering temperature 1673 K directly, the Zr₂W₂P₂O₁₅ is formed avoiding the intermediate phase of Zr₂WP₂O₁₂.     

Characterisation of the microstructure and thermal properties of Nd2Zr2O7 and Nd2Zr2O7/YSZ thermal barrier coatings

The microstructure of following thermal barrier coatings (TBC) was characterised in this paper: monolayer coatings Nd₂Zr₂O₇ and 8YSZ; a double ceramic layered (DCL) coating. Coatings were characterised by thicknesses that did not exceed 300 μm and porosities of approx. 5%. The chemical and phase composition analysis of the DCL layers revealed an external Nd₂Zr₂O₇ ceramic layer approx. 80 μm thick, a transitional zone approx. 120 μm thick and an internal 8YSZ layer 100 μm thick. For the case of the monolayer coating, the Nd₂Zr₂O₇ pyrochlore phase was the only one-phase component. The surface topography of both TBC systems was typical for plasma sprayed coatings, and compressive stress state had a value of approx. 5–10 MPa. Measurements of the thermal parameters, i.e., thermal diffusivity, point to considerably better insulative properties for both new types of layers when compared to the standard 8YSZ layers.     

Effect of acids on the morphology and negative thermal expansion analysis of ZrW2O8 powders prepared by the hydrothermal method

Different acids were used to prepare ZrW₂O₈ powders at 570 °C by the hydrothermal method. The products were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, thermogravimetric and differential scanning calorimetry and Fourier transform infrared absorption spectra. The results indicate that among the chosen acids, only HCl and HNO₃ can be used to prepare pure ZrW₂O₈ powders with high crystallinity and rod-like shape. When the hydrothermal temperature reduces to 160 °C, nano-sphere particles with an average diameter of 30 nm is obtained, if prepared by HNO₃ addition. The results of in situ X-ray diffraction measurement indicate that ZrW₂O₈ powders prepared by pure HCl or HNO₃ have strong negative thermal expansion.     

Surface modification of ZrW2O8 and ZrW2O7(OH)·2H2O by in situ polymerization: Enhanced filler particles for use in composites

To explore the effect of negative thermal expansion on the reduction of the coefficient of thermal expansion of polymer with respect to that of chain stiffening, the preparation of polycarbonate composites with ZrW₂O₈ and ZrW₂O₇(OH)₂·2H₂O are attempted. In the process, the dispersion of the filler particles in the polymer needs to be optimized, and the transfer of properties at the interface between the two phases. Therefore, surface modification by in situ polymerization is performed on these two particles. Several parameters of the reaction are optimized to achieve higher surface coverage of oligomer, including reaction time and the amount of monomers and particles. On the basis of the optimized conditions, two modification steps are then used to maximize both recovered amount of modified particles and surface coverage. The composites prepared with modified particles show enhanced dispersion of the particles and interaction at the interfaces. POLYM. COMPOS., 37:1359–1368, 2016. © 2014 Society of Plastics Engineers     

Fabrication and creep properties of eutectic-composition Al2O3/YAG/YSZ sintered composites

Three-phase alumina/YAG/yttria-stabilized cubic zirconia (YSZ) composites were fabricated by a solid-state reaction route starting from commercial powders of Al₂O₃, Y₂O₃ and monoclinic ZrO₂. The final phases Al₂O₃, YAG and YSZ were obtained after calcination of the powder mixtures at 1400 °C. Dense bulk composites were obtained after sintering, with a homogeneous microstructure of fine and equiaxed grains with sizes of 1 μm. Compressive mechanical tests were performed at 1300–1450 °C in air at constant load and at constant initial strain rate. A brittle-to-ductile transition was found with increasing temperature. Grain boundary sliding is the main deformation mechanism in the ductile regime, characterized by a stress exponent of 2 and by the absence of dislocation activity and changes in grain morphology. Alumina seems to be the rate-controlling phase owing to the improvement in creep resistance by the presence of yttrium and zirconium of the other two phases.     

Synthesis and thermal expansion of ZrO2/ZrW2O8 composites

In this work, a ceramic composite of ZrW₂O₈ and ZrO₂ was synthesized, in order to investigate the possibility of compensating the positive thermal expansion of ZrO₂ with the negative thermal expansion (NTE) compound ZrW₂O₈, tailoring the thermal expansion of these composites. The NTE material was mixed with varying amounts of ZrO₂. The thermal expansion coefficients of this series of composites decrease with increasing amounts of ZrW₂O₈. Nevertheless, a negative deviation from the values expected by the rule of mixtures was found to be most pronounced in the middle of the compositional region.     

ZrW2O8负膨胀陶瓷材料进展

叙述了各向同性负膨胀ZrW2O8陶瓷材料的制备、结构、负膨胀机理和应用.     

Thermophysical properties of Yb2O3 doped Gd2Zr2O7 and thermal cycling durability of (Gd0.9Yb0.1)2Zr2O7/YSZ thermal barrier coatings

(Gd_1−xYb_x)₂Zr₂O₇ compounds were synthesized by solid reaction. Yb₂O₃ doped Gd₂Zr₂O₇ exhibited lower thermal conductivities and higher thermal expansion coefficients (TECs) than Gd₂Zr₂O₇. The TECs of (Gd_1−xYb_x)₂Zr₂O₇ ceramics increased with increasing Yb₂O₃ contents. (Gd_0.9Yb_0.1)₂Zr₂O₇ (GYbZ) ceramic exhibited the lowest thermal conductivity among all the ceramics studied, within the range of 0.8–1.1 W/mK (20–1600 °C). The Young's modulus of GYbZ bulk is 265.6 ± 11 GPa. GYbZ/YSZ double-ceramic-layer thermal barrier coatings (TBCs) were prepared by electron beam physical vapor deposition (EB-PVD). The coatings had an average life of more than 3700 cycles during flame shock test with a coating surface temperature of ∼1350 °C. Spallation failure of the TBC occurred by delamination cracking within GYbZ layer, which was a result of high temperature gradient in the GYbZ layer and low fracture toughness of GYbZ material.     

不同层Cu/ZrW2O8梯度薄膜的制备和性能

采用ZrO2、WO3复合氧化物和Cu靶材,利用磁控溅射法,通过改变溅射功率在单晶硅基片上分别制备1、3、5层Cu/ZrW2O8复合薄膜.通过X射线衍射、扫描电镜和原子力显微镜表征不同层薄膜的物相组成和表面形貌:采用划痕仪和应力测试仪分别测量薄膜的结合力和热应力.结果表明:未退火处理的薄膜为非晶态钨酸锆和铜的复合薄膜:在...     

Flower-like Sc2Mo3O12 nanosheet clusters: Synthesis,thermal expansion and photocatalytic properties

In this work, Sc₂Mo₃O₁₂ has been synthesized via one-pot hydrothermal reaction. The effects of process conditions on the crystal structure, morphology, photocatalytic activity and negative thermal expansion (NTE) behaviors of flower-like Sc₂Mo₃O₁₂ were systematically investigated. Results indicate that orthorhombic flower-like Sc₂Mo₃O₁₂ assembled by nano-size flaky crystal grains can be synthesized by one-pot hydrothermal reaction at a temperature as low as 120 °C for 2 h. The hydrothermal reaction temperature and time have no obvious effects on the crystal structure and morphology. However, the photocatalytic property of synthesized Sc₂Mo₃O₁₂ is sensitive to the above parameters. The sample synthesized at 200 °C for 2 h shows the best photocatalytic degradation of methyl orange, and the degradation rate is 73.32% in 2 h ¹The coefficient of thermal expansion (CTE) of Sc₂Mo₃O₁₂ is ?1.99 × 10^?6 °C^?1 in 50–500 °C tested using TMA. The high-temperature XRD analysis reveals that Sc₂Mo₃O₁₂ exhibits anisotropic NTE and the intrinsic CTE is measured to be ?2.09 × 10^?6 °C^?1 in 25–800 °C.     

Thermophysical properties of carbon/carbon composites and physical mechanism of thermal expansion and thermal conductivity

Five different carbon/carbon composites (C/C) have been prepared and their thermophysical properties studied. These were three needled carbon felts impregnated with pyrocarbons (PyC) of different microstructures, chopped fibers/resin carbon + PyC, and carbon cloth/PyC. The results show that the X-Y direction thermal expansion coefficient (CTE) is negative in the range 0-100 °C with values ranging from −0.29 to −0.85 × 10⁻⁶/K. In the range 0-900 °C, their CTE is also very low, and the CTE vs. T curves have almost the same slope. In the same temperature range composites prepared using chopped fibers show the smallest CTE values and those using the felts show the highest. The microstructure of the PyC has no obvious effect on the CTE for composites with the same preform architecture. Their expansion is mainly caused by atomic vibration, pore shrinkage and volatilization of water. However, the PyC structure has a large effect on thermal conductivity (TC) with rough laminar PyC giving the highest value and isotropic PyC giving the lowest. All five composites have a high TC, and values in the X-Y direction (25.6-174 W/m K) are much larger than in the Z direction (3.5-50 W/m K). Heat transmission in these composites is by phonon interaction and is related to the preform and PyC structures.     

Characterization of microstructure and thermal properties of Gd2Zr2O7-type thermal barrier coating

We present herein a characterization of the microstructure and thermal properties of thermal barrier coatings (TBCs), which we obtained via plasma spraying of powder Gd₂Zr₂O₇. By using X-ray diffraction (XRD) and electron backscatter diffraction (EBSD), we evaluated the phase composition of a ceramic layer and estimated the ceramic-layer stress state by the sin²ψ method. The tests revealed that the TBC layer consisted of a single-phase structure of Gd₂Zr₂O₇, namely, an Fd3m lattice. The thermal diffusivity of the outer ceramic layer was determined based on a bilayer model and corrected with a factor to account for the presence of pores. The results reveal that the use of the standard parameters in a standard spraying process gives good-quality Gd₂Zr₂O₇ TBCs with a thermal conductivity considerably lower than 8YSZ-type TBCs.     

Thermal properties of La2Zr2O7 double-layer thermal barrier coatings

La₂Zr₂O₇ is a promising thermal barrier coating (TBC) material. In this work, La₂Zr₂O₇ and 8YSZ-layered TBC systems were fabricated. Thermal properties such as thermal conductivity and coefficient of thermal expansion were investigated. Furnace heat treatment and jet engine thermal shock (JETS) tests were also conducted. The thermal conductivities of porous La₂Zr₂O₇ single-layer coatings are 0.50–0.66?W?m^?1?°C^?1 at the temperature range from 100 to 900°C, which are 30–40% lower than the 8YSZ coatings. The coefficients of thermal expansion of La₂Zr₂O₇ coatings are about 9–10?×?10^?6?°C^?1 at the temperature range from 200 to 1200°C, which are close to those of 8YSZ at low temperature range and about 10% lower than 8YSZ at high temperature range. Double-layer porous 8YSZ plus La₂Zr₂O₇ coatings show a better performance in thermal cycling experiments. It is likely because porous 8YSZ serves as a buffer layer to release stress.     

Fabrication of surface-treated BN/ETDS composites for enhanced thermal and mechanical properties

The ceramic/polymer composites based on epoxy-terminated dimethylsiloxane (ETDS) and boron nitride (BN) were prepared for use as thermal interface materials (TIMs). 250 µm-sized BN was used as a filler to achieve high-thermal-conductivity composites. To improve the interfacial adhesion between the BN particles and the ETDS matrix, the surface of BN particles were modified with silica via the sol–gel method with tetraethyl orthosilicate (TEOS). The interfacial adhesion properties of the composites were determined by the surface free energy of the particles using a contact angle test. The surface-modified BN/ETDS composites exhibited thermal conductivities ranging from 0.2 W/m K to 3.1 W/m K, exceeding those of raw BN/ETDS composites at the same weight fractions. Agari׳s model was used to analyze the measured thermal conductivity as a function of the SiO₂-BN concentration. Moreover, the storage modulus of the BN/ETDS composites was found to increase with surface modification of the BN particles.     

磁控溅射法制备ZrW2O8/Cu梯度薄膜

在单晶硅基片上用磁控溅射法制备ZrW2O8/Cu梯度薄膜.用X射线衍射分析薄膜的物相组成,用原子力显微镜和扫描电镜对薄膜的表面形貌进行观察和分析,利用X射线光电子能谱技术对薄膜中各元素沿深度的分布情况进行检测.结果表明:溅射所得薄膜为非晶态钨酸锆与氧化铜的复合薄膜,快速热处理和氢气还原后得到立方相钨酸锆与铜的复合薄膜,在760 ℃下热处理钨酸锆的结晶度最好,而在740 ℃热处理的薄膜质量最佳,薄膜中各成分沿厚度方向呈梯度分布.     

负热膨胀材料ZrW2O8制备方法的研究进展

各向同性负热膨胀氧化物ZrW2O8是极具应用潜力的结构、功能材料.由于其热力学稳定的温度范围窄,材料合成困难,因此,如何提高产物纯度、降低生产成本是今后该材料研究的主要方向之一,也是改善ZrW2O8的性能和应用的关键因素.本文综述了ZrW2O8粉体、薄膜、单晶及其复合材料制备方法的研究现状,比较了不同制备方法的优缺点,分析了不同制备方法对ZrW2O8形貌及材料性能的影响,并展望了ZrW2O8制备方法的发展趋势及材料的应用前景.     

Thermal cycling behavior and bonding strength of single-ceramic-layer Sm2Zr2O7 and double-ceramic-layer Sm2Zr2O7/8YSZ thermal barrier coatings deposited by atmospheric plasma spraying

The single-ceramic-layer (SCL) Sm₂Zr₂O₇ (SZO) and double-ceramic-layer (DCL) Sm₂Zr₂O₇ (SZO)/8YSZ thermal barrier coatings (TBCs) were deposited by atmospheric plasma spraying on nickel-based superalloy substrates with NiCoCrAlY as the bond coat. The mechanical properties of the coatings were evaluated using bonding strength and thermal cycling lifetime tests. The microstructures and phase compositions of the coatings were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The results show that both coatings demonstrate a well compact state. The DCL SZO/8YSZ TBCs exhibits an average bonding strength approximately 1.5 times higher when compared to the SCL SZO TBCs. The thermal cycling lifetime of DCL SZO/8YSZ TBCs is 660 cycles, which is much longer than that of SCL 8YSZ TBCs (150 cycles). After 660 thermal cycling, only a little spot spallation appears on the surface of the DCL SZO/8YSZ coating. The excellent mechanical properties of the DCL LZ/8YSZ TBCs can be attributed to the underlying 8YSZ coating with the combinational structures, which contributes to improve the toughness and relieve the thermal mismatch between the ceramic layer and the metallic bond coat at high temperature.