ZrW2O8-doped epoxy as low thermal expansion insulating materials for superconducting feeder system

Epoxy resin insulating materials used in superconducting feeder system of fusion device are required to be low thermal expansion coefficient (TEC). In this paper, negative thermal expansion (NTE) material ZrW₂O₈ filled epoxy resins were fabricated. To improve the dispersion of fillers in epoxy matrix, plasma polymerization was performed on the surface of ZrW₂O₈ powders. Transmission electron microscope (TEM) and surface wettability analysis were performed before and after the surface modification of ZrW₂O₈ powders. The TEC of ZrW₂O₈/epoxy composites were measured from 77 K to room temperature. The results show the doping of ZrW₂O₈ can significantly reduce the TEC of epoxy resins. The sedimentation rate of ZrW₂O₈ before and after modified in epoxy was compared by density measurement. It can be seen that the ZrW₂O₈ surface modified by plasma polymerization can enhance its dispersion properties in epoxy matrix.     

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.     

Investigations on NiAl composites fabricated by matrix coated single crystalline Al2O3-fibers with and without hBN interlayer

The intermetallic compound NiAl has excellent potential for high temperature structural applications but suffers from low temperature brittleness and insufficient high temperature strength. One way to remove these deficiencies is the reinforcement by high strength ceramic fibers. Such intermetallic matrix composites can be conveniently fabricated by the hot pressing of matrix coated fibers. Al₂O₃ single crystal fibers show excellent chemical stability with the NiAl matrix, but the residual thermal compressive stresses during cool down dramatically degrades the fiber strength and thus, renders the composite useless for structural applications. We report on an experimental and computational study to mitigate this problem and to fabricate Al₂O₃/NiAl composites with sufficient high temperature strength. Analytical TEM, mechanical testing and push-out tests were employed to characterize chemistry, microstructure and mechanical properties of the composites. It will be shown that a processing window exists that allows producing intermetallic matrix composites with promising mechanical properties.     

Preparation and thermal properties of zirconium tungstate/copper composites

ZrW₂O₈/Cu composites were prepared by the powder metallurgy method. Electroless plating was used to deposit copper on ZrW₂O₈ powder before sintering. The thermal expansion and thermal conductivity of composites were measured in the temperature range from 25 ^oC to 200 ^oC and compared with those predicted from various theoretical models. The results show that the coefficient of thermal expansion of ZrW₂O₈/ Cu composites with a different volume fraction of ZrW₂O₈ is greater than the theoretically calculated value. The thermal conductivities of ZrW₂O₈/ Cu composites increase with a higher copper content and decrease upon elevated temperature. The thermal conductivity of composites with a different volume fraction of ZrW₂O₈ is lower than the theoretically calculated value.     

Hydration of ZrW2O8 nanopowders under ambient conditions

We report hydration of ZrW₂O₈ under ambient conditions, and its effect on the negative coefficient of thermal expansion (CTE) of ZrW₂O₈. On storing under ambient conditions for six months, about 66% of the outer annular volume was hydrated to ZrW₂O₈·0.35H₂O, while after one year of storage the sample was hydrated to ZrW₂O₈·0.72H₂O. The CTE was determined by in-situ high temperature X-ray diffraction (XRD) measurements in the temperature range from 25 to 200 °C. XPS and TGA were used to characterize the nature of bonding of the water in the ZrW₂O₈ structure. The negative CTE behavior of partially hydrated ZrW₂O₈·0.35H₂O remained intact, while on further hydration to ZrW₂O₈·0.72H₂O, negative CTE was not observed. The bonding of the water molecules to the ZrW₂O₈ structure were stronger than those of adsorbed water molecules but weaker than those of the structural hydroxyl ions.     

Preparation and properties of polyimide nanocomposites with negative thermal expansion nanoparticle filler

Nanocomposites with tunable coefficient of thermal expansion (CTE) were prepared by incorporating cubic zirconium tungstate (ZrW₂O₈) nanoparticles at various volume percentages in a polyimide (PI). Rod-shaped nanoparticles of cubic ZrW₂O₈, which has isotropic negative thermal expansion, were synthesized using a hydrothermal method. The interfacial interaction between the PI and ZrW₂O₈ was enhanced by covalently bonding different organic moieties, including a short aliphatic silane and PI oligomer, to the surface of ZrW₂O₈. Structure–property relationships for the PI–ZrW₂O₈ nanocomposites were investigated for thermal degradation, glass transition, tensile and thermal expansion properties. Addition of ZrW₂O₈ nanoparticles did not alter the thermal degradation and glass transition temperature of the base PI. The addition of ZrW₂O₈ nanoparticles increased the Young's modulus of the polymer, indicating stiffening of the polyimide matrix. The increase was higher for nanocomposites with engineered interfaces due to the efficient load transfer achieved through the presence of linker groups. The addition of ZrW₂O₈ reduced the in-plane CTE of the base PI at all loadings studied. The CTE of the base PI was reduced by around 22% with the addition of ZrW₂O₈ at 15 volume% loading.     

纳米Al2O3改性玻璃纤维增强复合材料低温力学性能研究

简述了纳米Al2O3改性玻璃纤维增强环氧树脂基复合材料的制备,并对其常温、低温力学性能进行实验。结果表明,常温、低温下,复合材料的力学性能随着纳米Al2O3含量的增加都呈现先增强后减弱的趋势。低温处理使复合材料的力学性能得到提升,并且低温下Al2O3的引入对复合材料强度的改善效果比常温下明显,Al2O3含量为1%(质量分数)时,拉伸强度提高比例高达16.61%。其原因是低温下基体强度增大,另外基体热膨胀系数大,收缩明显,界面粘接强度增大,纳米Al2O3颗粒在界面处与树脂基体结合更深入,从而使纳米粒子阻碍微裂纹扩展的能力更强。     

Negative thermal expansion in a zirconium tungstate/epoxy composite at low temperatures

We have investigated a composite of cubic α-ZrW₂O₈ and epoxy with a high ceramic loading for its thermal expansion properties at cryogenic temperatures. The composite was fabricated by allowing the ceramic to sediment in the epoxy resin before curing, using only the dense bottom fraction of the composite for further measurements. Density measurements and thermogravimetric analysis showed that the samples repeatably consisted of approximately 60 vol% tungstate without significant voids. The coefficient of thermal expansion was measured by dilatometry at temperatures from 25 to 300 K, and we found negative thermal expansion occurring at temperatures below about 100 K. The observed behavior is consistent with predictions produced by a variational model, which shows that the high ceramic loading is necessary to reliably achieve negative thermal expansion in the composite. The composite has potential applications as compensators for unwanted thermal expansion at low temperatures and for fiber-optic cryogenic temperature sensors.     

Pressureless sintering of negative thermal expansion ZrW2O8/Zr2WP2O12 composites

Negative thermal expansion material ZrW₂O₈/Zr₂WP₂O₁₂ composite was prepared by liquid phase sintering. The apparent density of ZrW₂O₈ without any sintering additive was about 3.7 g/cm³, corresponding to about 73% of its theoretical density. However, the relative density of the samples, sintered with more than 5 mol% P₂O₅ was about 90%. The identified phases were mainly ZrW₂O₈ with small amounts of WO₃, ZrO₂ and Zr₂WP₂O₁₂ by XRD. The intensity of Zr₂WP₂O₁₂ peaks increased with increasing P₂O₅ content. It was surmised that the melting of ZrO₂-P₂O₅ resulted in liquid phase formation, which is then converted to Zr₂WP₂O₁₂ on the final stage of sintering. Therefore, Zr₂WP₂O₁₂ phase was observed at the gap between the ZrW₂O₈ grains and at the triple junctions. The ceramics sintered with 20 mol% P₂O₅ showed a negative thermal expansion coefficient of − 4.0 × 10^− 6 °C^− 1.     

Microstructure characterization of fibrous HAp-(20 vol.% t-ZrO2)/Al2O3-(25 vol.% m-ZrO2) composites by multi-pass extrusion process

Core-shell structured HAp-(t-ZrO₂)/Al₂O₃-(m-ZrO₂) composites were fabricated using a multi extrusion process. The shell of Al₂O₃-(m-ZrO₂) phases was selected due to their excellent biocompatibility and mechanical properties and the core was designed with t-ZrO₂ dispersed in the HAp matrix. The t-ZrO₂ and m-ZrO₂ particles (< 400 nm) were homogeneously dispersed in the HAp and Al₂O₃ phases, respectively. In the HAp-(t-ZrO₂) core region, a heavy strain field contrast was observed due to the mismatch of their thermal expansion coefficients. The values of relative density, bending strength and Vickers hardness of the third pass fibrous HAp-(t-ZrO₂)/Al₂O₃-(m-ZrO₂) composites, which were sintered at 1400 °C, were about 93%, 169 MPa, and 792 Hv, respectively.     

Synthesis of zirconium tungstate–zirconia core–shell composite particles

In this work, ZrW₂O₈–ZrO₂ core–shell composite particles were synthesized. ZrW₂O₈ that was used in the core is a material with negative coefficient of thermal expansion, and it was synthesized from a high-pH precursor based on use of tungstic acid and zirconium acetate. Shell layer was composed of ZrO₂ nanocrystallites and precipitated from an aqueous solution by urea hydrolysis. While volume of the shell was effectively controlled by the initial zirconium ion concentration in the solutions, the rate of precipitation was a function of the ratio of initial concentrations of urea to zirconium ions. It is hypothesized that isolation of the ZrW₂O₈ within a layer of ZrO₂, will be a key element in solving problems associated with reactivity of ZrW₂O₈ towards other components in sintering of ceramic–ceramic composites with tuned or zero thermal expansion coefficient.     

Effects of TiO2 doping on microstructure and properties of directed laser deposition alumina/aluminum titanate composites

ABSTRACT

Al₂O₃-based composite ceramics have excellent high temperature performance and are ideal materials for preparing hot end components. However, poor fracture toughness and thermal shock resistance limit its applications. Based on the excellent low thermal expansion characteristics and thermal shock resistance of Al₂TiO₅ ceramic, different composition ratios of Al₂O₃/Al₂TiO₅ composite ceramics were prepared by directed laser deposition (DLD) technology. Effects of TiO₂ doping amount on microstructure and properties of the composite ceramics were investigated. Results show that α-Al₂O₃ phase is discretely distributed in the continuous aluminum titanate matrix when TiO₂ doping amount between 2 and 30?mol%. With the increase of TiO₂ doping amount, content of Al₂O₃ gradually decreases and its morphology changes from cellular to dendritic. When TiO₂ doping amount reaches 43.9?mol%, the microstructure transforms into fine Al₂TiO₅/Al₆Ti₂O₁₃ eutectic structure. Property test results show that Al₂O₃/Al₂TiO₅ composite ceramics have good comprehensive mechanical properties when TiO₂ doping amount between 2 and 6?mol%.     

Cryogenic properties of SiO2/epoxy nanocomposites

SiO₂/epoxy nanocomposites were prepared using diglycidyl ether of bisphenol-F (DGEBF) type epoxy and tetraethylorthosilicate (TEOS) via the sol-gel process. Silica nanoparticles were collected after burning off the matrix resin and the silica nanoparticles were observed using TEM. The cryogenic tensile properties at 77 K and thermal expansion coefficient of the nanocomposites were studied. The tensile properties at room temperature were also given to compare with the cryogenic tensile properties. The fracture surfaces were examined with scanning electron microscopy (SEM). The effects of silica nanoparticle content have been studied on the cryogenic tensile and thermal properties of the nanocomposites. In addition, the dependence of the glass transition temperature on the silica nanoparticle content has also been examined.     

石墨烯/纳米Al2O3增韧Ti(C,N)基金属陶瓷的力学及摩擦磨损性能

采用真空热压烧结工艺制备了石墨烯(GNPs)和纳米Al₂O₃增韧的Ti(C,N)基金属陶瓷复合刀具材料(TAG)。研究了GNPs和纳米Al₂O₃对复合陶瓷材料微观结构、力学性能和摩擦磨损性能的影响。研究表明,GNPs和纳米Al₂O₃的添加对复合陶瓷材料的力学性能有明显的提高,当GNPs和纳米Al₂O₃含量(质量分数)为1%和5%时,复合刀具陶瓷材料(TA5G1)综合力学性能最优,其硬度、抗弯强度和断裂韧性分别为21.50 GPa、810.80 MPa和10.51 MPa·m^1/2。研究了复合刀具材料的摩擦磨损性能和磨损机理,研究结果表明,在TAG复合刀具材料中,TA5G1的摩擦磨损性能最优,其摩擦系数和磨损率分别为0.338和4.921×10^-6 mm³/(N·m),复合刀具材料的主要磨损形式为磨粒磨损和黏着磨损。     

Effects of nano-Al2O3 additions on microstructure development and hardness of Sn3.5Ag0.5Cu solder

This work investigates the effects of nano-Al₂O₃ on the microstructure and microhardness of the Sn3.5Ag0.5Cu composite solder alloy. In comparison with solder without the addition of nano-Al₂O₃ particles, the formation of primary β-Sn phase, the Ag₃Sn phase average size, and the spacing lamellae decreased significantly in the composite solder matrix. In addition, the eutectic areas of the composite solder were wider than that of the Sn3.5Ag0.5Cu solder. This is attributed to the adsorption of nano-Al₂O₃ particles with high surface free energy on the grain surface during solidification. The wettability property was improved by 0.25–0.5 wt.% addition of nano-Al₂O₃ particles into the Sn3.5Ag0.5Cu solder. However, when the nano-Al₂O₃ particles concentration up to over 1.0 wt.% decreased the beneficial influence. Microhardness improved with the addition of nano-Al₂O₃ particles. This improved mechanical property was due to the composite microstructure, which is close to the theoretical prediction from dispersion strengthening theory.     

A study of the erosion-corrosion behavior of nano-Cr2O3 particles reinforced Ni-based composite alloying layer in aqueous slurry environment

To investigate the role of nano-Cr₂O₃ particles on the erosion-corrosion behavior of composite alloying layer, a nano-Cr₂O₃ particles reinforced Ni-based composite alloying layer was fabricated onto AISI 316L stainless steel (SS) via a duplex surface treatment, consisting of Ni/nano-Cr₂O₃ predeposited by electric brush plating, and subsequent Ni-Cr-Mo-Cu multi-element surface alloying by a double glow process. The microstructure and composition of composite alloying layer were characterized by means of X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS). The results indicated that the added nano-Cr₂O₃ particles were homogeneously distributed in the alloying layer and didn’t decompose or react with surrounding metal matrix under alloying temperature (1000 °C) condition. A series of electrochemical techniques, including potentiodynamic polarization, open circuit potential (OCP), current response and electrochemical impedance spectroscopy (EIS), was employed to evaluate the corrosion properties of nano-Cr₂O₃ particles reinforced composite alloying layer under various hydrodynamic conditions. Erosion-corrosion tests were conducted in 3.5% NaCl solution plus sand particles with varying concentration (50-150 g/L) at different rotation speeds (600-1100 rpm). To estimate the influence of the nature of different nano-particles on the erosion-corrosion property of composite alloying layer, nano-SiO₂ particles reinforced Ni-based composite alloying layer, single alloying layer and 316L SS was selected as the reference materials for all the corrosion and erosion-corrosion tests.     

Low-temperature sintering of ZrW2O8–SiO2 by spark plasma sintering

Amorphous ZrW₂O₈ powder and amorphous SiO₂ powder were prepared by a sol–gel process as raw materials, and high-density ZrW₂O₈–SiO₂ were successfully prepared at a much lower temperature of 923 K for a much shorter holding time of 10 min by spark plasma sintering (SPS) method rather than by conventional melt-quenching method. The relative densities of 0.85ZrW₂O₈–0.15SiO₂ and 0.70ZrW₂O₈–0.30SiO₂ were 99.4% and 96.6%, respectively. The combined technique of a sol–gel process and SPS should enable us to prepare the varied types of high-density composites of ZrW₂O₈ without severe thermal cracking caused by melt-quenching. The thermal expansion properties and dielectric properties of ZrW₂O₈–SiO₂ were also investigated.     

Synthesis, structure and exchange bias in Cr2O3/CrO2/Cr2O5 particles

We report on the synthesis, structure and magnetic properties of a novel exchange bias system with Cr₂O₃/CrO₂/Cr₂O₅ interfaces. Chromium oxide particles with mixed chromium valences were prepared by sintering CrO₃ in air. X-ray diffraction patterns show that CrO₃ lost its oxygen gradually with increasing temperature and time through Cr₃O₈, Cr₂O₅, CrO₂, and finally Cr₂O₃ at temperatures above 760 K. X-ray photoelectron spectra indicate a low CrO₂ content and a binding energy of 579.3 eV for Cr 2p_3/2 photoelectrons in Cr₂O₅. Chromium dioxide was found to stably coexist with Cr₂O₃ and Cr₂O₅ in the particles. Magnetic measurements show hysteresis loop shifts in the sample, indicating an exchange bias induced by antiferromagnetic Cr₂O₃/Cr₂O₅ in ferromagnetic CrO₂. An exchange bias of 9 mT at 5 K and a coercivity of 26.3 mT were observed in the chromium oxide particles containing CrO₂.     

Microstructure and mechanical properties of ZrB2-SiC composites

A ZrB₂-based composite containing 20 vol.% nanosized SiC particles (ZSN) was fabricated at 1900 °C for 30 min under a uniaxed load of 30 MPa by hot-pressing. The microstructure and mechanical properties of the composite were investigated. It was shown that the grain growth of ZrB₂ matrix was effectively suppressed by submicrosized SiC particles located along the grain boundaries. In addition, the mechanical properties of ZSN composite were strongly improved by incorporating the nanosized SiC particles into a ZrB₂ matrix, especially for flexural strength (925 ± 28 MPa) and fracture toughness (6.4 ± 0.3 MPa•m^1/2), which was much higher than that of monolithic ZrB₂ and ZrB₂-based composite with microsized SiC particles, respectively. The formation of intragranular nanostructures plays an important role in the strengthening and toughening of ZrB₂ ceramic.     

(Mg2B2O5w+ND)/ZK60镁基复合材料的摩擦磨损性能研究

在湿球磨条件下以600 r/min高能球磨混粉,并将球磨后的粉末经过热压烧结-热挤压成型制备(Mg2B2O5w+ND)/ZK60镁基复合材料。研究了(Mg2B2O5w+ND)/ZK60镁基复合材料在不同载荷和转速下的干摩擦磨损性能。结果表明:干摩擦条件下,材料的摩擦系数随着滑动距离的增加会经历跑和阶段和稳定阶段;材料的质量磨损率随着转速的增大而降低,随着载荷的增大而增大,且基体镁合金的质量磨损率始终低于复合材料。随着摩擦载荷和转速的增加,材料的摩擦系数减小,然后逐渐趋于平稳。混杂增强的镁基复合材料相比基体合金具有更低的摩擦系数。