Prevention of Cracks in Functionally Graded SiO2‐Mo Materials Fabricated by Uniaxial Compression Casting and Pressureless Sintering

In industrial high‐intensity discharge lamps, cracks and delaminations occasionally develop at the interface between SiO₂ and the Mo foil in the seal. Here, functionally graded SiO₂‐Mo materials for use in these lamps were fabricated by uniaxial compression casting and pressureless sintering. Consequently, vertical cracks developed across the sintered body layers, and interfacial cracks developed between the 100 wt% SiO₂ and 90 wt% SiO₂‐Mo layers. Therefore, the effects of residual stress, difference in the coefficient of thermal expansion (CTE), and difference in the volume shrinkage on these cracks were investigated. Vertical cracks were suppressed when residual stress was relaxed by annealing near the annealing point of silica glass during the cooling step in the sintering process. Interfacial cracks were suppressed when the difference in the CTE of the interface between the 100 wt% SiO₂ and 90 wt% SiO₂‐Mo layers was relaxed by inserting layers of 95 wt% SiO₂‐Mo between them. Furthermore, the suppression effect became stronger when the difference in the volume shrinkage of the layers was relaxed by sintering to join the separately sintered monolayers. Thus, the development of these cracks was influenced by the residual stress, CTE, and volume shrinkage. Therefore, these cracks can be prevented by optimizing these factors.     

Synthesis and characterization of novel saponified guar‐graft‐poly(acrylonitrile)/silica nanocomposite materials

The combination of carbohydrates with silicon‐based ceramic materials offers attractive means of production for high performance materials. Present article describes the synthesis of novel nanocomposites out of SiO₂ and saponified guar‐graft‐poly(acrylonitrile) (SG). Tetraethoxysilane was used as the precursor for silica and growth of SiO₂ phase was allowed concurrently in the presence of SG. The material so obtained was thermally treated at 80°C, 160°C, 500°C, and 900°C to study the effect of thermal curing on its properties. During the curing process, silanol surface groups of silica globules reacted to create the reinforced SiO₂‐SG substance. It was observed that at 900°C, the SiO₂ phase crystallized out in tetragonal shape (similar to Cristobalite form of silica) in presence of SG. The chemical, structural and textural characteristics of the composites were determined by FTIR, XRD, TGA‐DTA, SEM and BET studies. The materials were also evaluated as efficient Zn²⁺ metal binder. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 536–544, 2007     

Cation grain‐boundary diffusivity in SiO2‐ and MgO‐doped Al2O3

Cation grain‐boundary diffusion in undoped and aliovalent‐doped Al₂O₃ is characterized using Cr₂O₃ as a chemical tracer. The compositional depth profiles measured by secondary ion mass spectrometry are fitted to the Whipple‐LeClaire model. The results indicate that cation grain‐boundary diffusivity is insensitive to MgO and SiO₂ dopants between 1100°C and 1300°C.     

Study of surface‐functionalized nano‐SiO2/polybenzoxazine composites

A series of the surface‐functionalized nano‐SiO₂/polybenzoxazine (PBOZ) composites was produced, and an attempt was made to improve the toughness of PBOZ material, without sacrificing other mechanical and thermal properties. A benzoxazine functional silane coupling agent was synthesized to modify the surface of nano‐SiO₂ particles, which were then mixed with benzoxazine monomers to produce the nano‐SiO₂‐PBOZ nanocomposites. The notched impact strength and the bending strength of the nano‐SiO₂‐PBOZ nanocomposites increase 40% and 50%, respectively, only with the addition of 3 wt % nano‐SiO₂. At the same load of nano‐SiO₂, the nano‐SiO₂‐PBOZ nanocomposites exhibit the highest storage modulus and glass‐transition temperature by dynamic viscoelastic analysis. Moreover, the thermal stability of the SiO₂/PBOZ nanocomposites was enhanced, as explored by the thermogravimetric analysis. The 5% weight loss temperatures increased with the nano‐SiO₂ content and were from 368°C (of the neat PBOZ) to 379°C or 405°C (of the neat PBOZ) to 426°C in air or nitrogen with additional 3 wt % nano‐SiO₂. The weight residue of the same nanocomposite was as high as 50% in nitrogen at 800°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Spark Plasma Sintering of Functionally Graded SiO2/Mo Laminated Layer Material

A functionally graded sintered body consisting of laminated SiO₂/Mo layers was fabricated using spark plasma sintering. A high sintered‐body density was achieved using fine powders of SiO₂ (4.0 μm) and Mo (1.3 μm), which ensured no cracks were formed between layers. The highest joining stress (1.2 MPa) was found to occur at the interface between SiO₂ layers with 0 and 8 vol% Mo, with the electrical resistance decreasing rapidly when the Mo content was increased to 13 and 22 vol%. This is attributed to the use of spark plasma sintering, suggesting further work is needed to fully optimize this process.     

Dibenzothiophene HDS Over Sulphided CoMo on High‐Silica USY Zeolites

USY faujasites (SiO₂/Al₂O₃ = 12, 30 and 80) were used as hydrodesulphurization (HDS) catalyst supports. Mo, Co and P were impregnated at two concentrations: ～12.5, ～3 and ～1.6 mass %; ～18, ～5.5 and ～2.2 mass % (CL and HL series, respectively). Surface acidity decreased after Co‐Mo‐P deposition. Sulphided catalysts were tested in dibenzothiophene (DBT) HDS (320°C, 5.59 MPa). The HDS rate slightly increased with both SiO₂ content and Co‐Mo‐P loading. High selectivity to hydrogenated products suggested deficient Mo promotion in CL solids. Improved Mo promotion by Co (HL series) could be responsible for higher activity and marked selectivity to desulphurization to biphenyl.     

Self‐Generating High‐Temperature Oxidation‐Resistant Glass‐Ceramic Coatings for C–C Composites Using UHTCs

Carbon–carbon (C–C) composites are ideal for use as aerospace vehicle structural materials; however, they lack high‐temperature oxidation resistance requiring environmental barrier coatings for application. Ultra high‐temperature ceramics (UHTCs) form oxides that inhibit oxygen diffusion at high temperature are candidate thermal protection system materials at temperatures >1600°C. Oxidation protection for C–C composites can be achieved by duplicating the self‐generating oxide chemistry of bulk UHTCs formed by a “composite effect” upon oxidation of ZrB₂–SiC composite fillers. Dynamic Nonequilibrium Thermogravimetric Analysis (DNE‐TGA) is used to evaluate oxidation in situ mass changes, isothermally at 1600°C. Pure SiC‐based fillers are ineffective at protecting C–C from oxidation, whereas ZrB₂–SiC filled C–C composites retain up to 90% initial mass. B₂O₃ in SiO₂ scale reduces initial viscosity of self‐generating coating, allowing oxide layer to spread across C–C surface, forming a protective oxide layer. Formation of a ZrO₂–SiO₂ glass‐ceramic coating on C–C composite is believed to be responsible for enhanced oxidation protection. The glass‐ceramic coating compares to bulk monolithic ZrB₂–SiC ceramic oxide scale formed during DNE‐TGA where a comparable glass‐ceramic chemistry and surface layer forms, limiting oxygen diffusion.     

Nano‐sio2‐reinforced ultraviolet‐curing materials for three‐dimensional printing

As an additive manufacturing technology, ultraviolet (UV)‐curing three‐dimensional printing, which requires the use of a photocurable resin, is increasingly being used to produce customized end‐user parts of many complex shapes. In this study, to improve the strength and ductility of printing materials, nano‐SiO₂‐reinforced photocurable resins were prepared by a planetary ball mill; then, the morphology, photochemistry, thermal property, and mechanical properties of the nanocomposites were investigated and characterized. Transmission electron microscopy analysis indicated that the modified nano‐SiO₂ was well dispersed in the photocurable resin. The glass‐transition temperature increased from 67.2°C for the unfilled resin to 71.7 and 80.1°C for nanocomposites with nano‐SiO₂ contents of 0.3 and 0.7 wt %, respectively. The tensile strength and impact strength were increased by 46.7 and 165.3% for nanocomposites with 0.3 wt % nano‐SiO₂. The flexural modulus of the nanocomposites increased from 1.7 to 8.0 GPa when 0.7 wt % nano‐SiO₂ was added to the photocurable resin; this appeared to originate from the relatively high level of dispersion and the intimate combination of the nano‐SiO₂ with the matrix. The investigation of the physical and chemical properties of such UV‐curing materials showed that the low filler concentration (<1 wt %) of nano‐SiO₂ did not affect the processability of the nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42307.     

Microstructure evolution and thermomechanical properties of plasma‐sprayed Yb2SiO5 coating during thermal aging

Rare‐earth monosilicates (RE₂SiO₅, RE: rare‐earth elements), such as Yb₂SiO₅, have been developed for potential application as environmental barrier coating (EBC) materials. Yb₂SiO₅ coating would experience microstructure evolution under high‐temperature environment and accordingly its thermomechanical properties would be altered. In this study, Yb₂SiO₅ coating was fabricated by atmospheric plasma spray technique. The phase stability and microstructure change before and after thermal aging at 1300°C, 1400°C, and 1500°C were investigated. The changes in mechanical and thermal properties were characterized. The results showed that the as‐sprayed coating was mainly composed of Yb₂SiO₅ with a small amount of Yb₂O₃ and amorphous phase. Defects in the coating, including interfaces, pores, and microcracks, were greatly reduced with grain growth after thermal treatment. Thermal aging significantly modified the thermal and mechanical properties of the coating. The average CTE was increased by 13.1%, and the hardness and elastic modulus was increased by 42.4% and 49.4%, respectively, after thermal aging at 1500°C for 50 hour. The thermal conductivity of thermal‐aged coating was much higher than that of the as‐sprayed coating, which was still less than 2 W/(m·K). The influence of coating microstructure on the properties was analyzed and related to the failure mechanism of EBCs.     

Fabrication of functionally graded nano‐TiO2‐reinforced epoxy matrix composites

Functionally graded nano‐TiO₂ epoxy matrix composites were successfully fabricated using a centrifugal method. In the preparation of the composite, the aggregation of nano‐TiO₂ occurred during curing, which had a negative effect on the composite performance. To solve this problem, we introduced a silane coupling agent to modify the surface of the nano‐TiO₂, thereby improving the performance and mechanical properties simultaneously. The modified nano‐TiO₂ (s‐TiO₂) had better dispersion in the epoxy resin, making it possible to produce depth gradients of the mechanical properties of functionally graded materials (FGMs). The s‐TiO₂ was characterized with respect to functional groups, morphology, and chemical elements using transmission electron microscopy, X‐ray photoelectron spectroscopy, and Fourier‐transform infrared spectroscopy. The results show that a silane layer was successfully coated on the surface. Also, the gradients of the mechanical and permittivity properties of the FGM indicated that by modifying the surface of the nano‐filler, it is possible to fabricate nano‐filler‐reinforced epoxy matrix FGMs using a centrifugal method. POLYM. COMPOS., 35:557–563, 2014. © 2013 Society of Plastics Engineers     

Novel Low‐Firing Forsterite‐Based Microwave Dielectric for LTCC Applications

A novel low‐temperature sintering microwave dielectric based on forsterite (Mg₂SiO₄) ceramics was synthesized through the solid‐state reaction method. The effects of LiF additions on the sinterability, phase composition, microstructure, and microwave dielectric properties of Mg₂SiO₄ were investigated. It demonstrated that LiF could significantly broaden the processing window (~300°C) for Mg₂SiO₄, and more importantly the sintering temperature could be lowered below 900°C, maintaining excellent microwave dielectric properties simultaneously. The 2 wt% LiF‐doped samples could be well‐sintered at 800°C and possessed a ε_r ~ 6.81, a high Q×f ~ 167 000 GHz, and a τ_f ~ ?47.9 ppm/°C, having a very good potential for LTCC integration applications.     

X‐ray tomography of feed‐to‐glass transition of simulated borosilicate waste glasses

High‐level waste feed composition affects the overall melting rate by influencing the chemical, thermophysical, and morphological properties of a cold cap layer that floats on the molten glass where most feed‐to‐glass reactions occur. Data from X‐ray computed tomography imaging of melting pellets comprised of a simulated high‐aluminum feed reveal the morphology of bubbles, known as the primary foam, for various feed compositions at temperatures between 600°C and 1040°C. These feeds were formulated to make glasses with viscosities ranging from 0.5 to 9.5 Pa s at 1150°C, which was accomplished by changing the SiO₂/(B₂O₃+Na₂O+Li₂O) ratio in the final glass. Pellet dimensions and profile area, average and maximum bubble areas, bubble diameter, and void fraction were evaluated. The feed viscosity strongly affects the onset of the primary foaming and the foam collapse temperature. Despite the decreasing amount of gas‐evolving components (Li₂CO₃, H₃BO₃, and Na₂CO₃), as the feed viscosity increases, the measured foam expansion rate does not decrease. This suggests that the primary foaming is not only affected by changes in the primary melt viscosity but also by the compositional reaction kinetic effects. The temperature‐dependent foam morphological data will be used to inform cold cap model development for a high‐level radioactive waste glass melter.     

Ultra‐Low Temperature Sintering and Dielectric Properties of SiO2‐Filled Glass Composites

Ultra low temperature co‐fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and SiO₂ filler was investigated with regard to the phase composition, the microstructure and the dielectric properties as functions of the filler content and sintering temperature. The softening temperature of 554°C and the crystallization temperature of around 650°C for the glass were confirmed by Differential Thermal Analysis result. The X‐ray diffraction results show that all SiO₂‐filled samples were made up of SiO₂, α‐Zn(BO₂)₂, Zn₃B₂O₆ phases. And there was no chemical reaction between SiO₂ and the glass during densification. And then the dielectric constant decreased with the increasing content of SiO₂. At the level of 15 wt% SiO₂ addition, the composites can be densified at a sintering temperature of 650°C for 30 min, and showed the optimal dielectric properties at 1 MHz with the dielectric constant of 6.1 and the dielectric loss of 1.3 × 10^?3, which demonstrates a good potential for use in LTCC technology.     

Synthesis of EP‐POSS mixture and the properties of EP‐POSS/epoxy,SiO2/epoxy,and SiO2/EP‐POSS/epoxy nanocomposite

The hybrid material of EP‐POSS mixture was synthesized by the hydrolysis and condensation of (γ‐glycidoxypropyl) trimethoxysilane. A series of binary systems of EP‐POSS/epoxy blends, epoxy resin modified by silica nanoparticles (SiO₂/epoxy), and ternary system of SiO₂/EP‐POSS/epoxy nanocomposite were prepared. The dispersion of SiO₂ in the matrices was evidenced by transmission electron micrograph, and the mechanical properties, that is, flexural strength, flexural modulus, and impact strength were examined for EP‐POSS/epoxy blends, SiO₂/epoxy, and SiO₂/EP‐POSS/epoxy, respectively. The fractured surface of the impact samples was observed by scanning electron micrograph. Thermogravimetry analysis were applied to investigate the different thermal stabilities of the binary system and ternary system by introducing EP‐POSS and SiO₂ to epoxy resin. The results showed that the impact strength, flexural strength, and modulus of the SiO₂/EP‐POSS/epoxy system increased around by 57.9, 14.1, and 44.0% compared with the pure epoxy resin, T_i, T_max and the residues of the ternary system were 387°C, 426°C, and 25.2%, increased remarkably by 20°C, 11°C and 101.6% in contrast to the pure epoxy resin, which was also higher than the binary systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 810‐819, 2013     

Ablation resistance of SiC‐modified ZrC coating prepared by SAPS for SiC‐coated carbon/carbon composites

This study evaluated the ablation resistance of ZrC/SiC coating for carbon/carbon (C/C) composites at different temperatures and heat fluxes, which improved the researches on ultra‐high temperature oxidation of ZrC/SiC system. Results showed that the protection of coating depended on temperature and heat flux. Ablation test for 120 seconds under heat flux of 2.4 MW/m² at 2270°C revealed a good ablation resistance, with the linear ablation rate reduced by 96.4% and the mass gain rate increased by 383.3% compared with those of pure ZrC coating. The good ablation resistance was attributed to the formation of dense oxide scale surface. SiC could improve the compactness of the oxide scale at this temperature by forming SiO₂. A dense scale could not form at 2105°C after ablation for 120 seconds, resulting in a dissatisfactory ablation resistance of the coating. After ablation for 120 seconds at 1738°C, the coating was integrated due to the protection of glassy SiO₂ encapsulated ZrO₂. The coating could not resist the strong shear force from the flame at heat flux of 4.2 MW/m² and was severely damaged after ablation for 60 seconds.     

Preparation of poly(methyl methacrylate‐co‐maleic anhydride)/SiO2?TiO2 hybrid materials and their thermo‐ and photodegradation behaviors

The optically transparent poly(methyl methacrylate‐co‐maleic anhydride) P(MMA‐co‐MA)/SiO₂? TiO₂ hybrid materials were prepared using 3‐aminopropyl triethoxysilane as a coupling agent for organic and inorganic components. Real‐time FTIR was used to monitor the curing process of hybrid sol, indicating that imide group formation decreased with increasing titania content. scanning electron microscopy, atomic force microscopy, and differential scanning calorimetry results confirmed their homogeneous inorganic/organic network structures. TGA analysis showed that incorporated titania greatly prohibits the thermodegradation of hybrid films, especially at the content of 5.3 wt %, showing an increase of about 32.6°C at 5% loss temperature in air. The UV degradation behavior of P(MMA‐co‐MA) studied by quasi‐real‐time FTIR showed that TiO₂ incorporated in the hybrid network provides a photocatalytic effect rather than a UV‐shielding effect. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1714–1724, 2005     

High‐Selectivity Y2O3‐Doped SiO2 Nanocomposite Membranes for Gas Separation in Steam at High Temperatures

Asymmetric structures were fabricated by depositing Y₂O₃‐doped SiO₂ (Si/Y) membranes onto γ‐Al₂O₃ supported by tubular α‐Al₂O₃. The thickness of the Y₂O₃‐doped SiO₂ deposits was approximately 100 nm. The deposits/membranes have micropores with a pore diameter ~ <0.40–0.55 nm. Pore size distribution measurements were conducted directly on the membranes before and after hydrothermal treatment with a nano‐permporometer. The gas permeance properties of the membranes were measured in the temperature range 100°C–500°C. The Y‐doped SiO₂ membrane (Si/Y = 3/1) was found to exhibit asymptotically stable permeances of 2.39 × 10^?7 mol/m²/s/Pa for He and 6.19 × 10^?10 mol/m²/s/Pa for CO₂, with a high selectivity of 386 (He/CO₂) at 500°C for 20 h in the presence of steam. The Y‐doped silica membranes exhibit very high gas permeances for molecules with smaller kinetic diameters. The apparent activation energies of the H₂ permeance at 400°C were 24.2 ± 0.2 and 21.3 ± 0.7 kJ/mol for SiO₂ and Si/Y, respectively.     

Thermal Properties of Rare‐Earth Monosilicates for EBC on Si‐Based Ceramic Composites

Rare‐earth (RE) monosilicates are promising candidates as environmental barrier coating (EBC) materials for ceramic matrix composites for aerospace applications. Five rare‐earth monosilicate materials have been investigated: Y₂SiO₅, Gd₂SiO₅, Er₂SiO₅, Yb₂SiO₅, and Lu₂SiO₅ produced from RE oxides and silica starting materials pressed and sintered at 1580°C under flowing air. Relative densities above 94% were obtained for all samples and ceramics were made containing 85–100 wt% of the RE monosilicate according to X‐ray diffraction (XRD) with RE disilicates as the second phase in the Gd, Yb, and Lu silicate systems. Microstructures were characterized using scanning electron microscopy and XRD, and thermal properties measured including specific heat, thermal expansion, and thermal diffusivity. For the first time, specific heat capacity values are reported for the monosilicates [0.45–0.69 J·(g·K)^?1]. Thermal expansion coefficients (TECs) of the dense samples ranged between 5.9 and 10.3 × 10^?6 K^?1 measured for 473 to 1473 K. All EBCs have low thermal conductivities [1.8 W·(m·K)^?1 or less] making them excellent EBC insulators.     

Organic–inorganic hybrid boron‐containing phenol–formaldehyde resin/SiO2 nanocomposites

The organic–inorganic hybrid boron‐containing phenol–formaldehyde (BPFR) resin/SiO₂ nanocomposites was synthesized in‐situ from boric acid, phenol, and tetramethoxysilane. The structure of BPFR modified and the distributions of silicon element were studied by Fourier‐transform infrared spectroscopy, energy dispersive X‐ray spectrometry, and transmission electron microscope, respectively. The glass transition temperature (T_g) was determined by torsional braid analysis. The results show that silicon element distribution is homogeneous, and the size of nanosilica is about 40–60 nm. The thermal stability and kinetics parameters of thermal degradation were determined by thermogravimetry analysis (TGA). TGA results show that the resin modified has higher heat resistance property when the additive quantity of SiO₂ was 3 wt%. The temperature of 5% weight loss is 487.7°C, which is 12.4°C higher than that of common BPFR. The residual ratio of 3 wt% SiO₂/BPFR was 62.3% at the temperature of 900°C, which is 11.2% higher than that of common BPFR. The mechanics loss peak T_p of 3% SiO₂/BPFR is 33°C higher than common BPFR. Fiberglass‐reinforced BPFR modified by 3 wt% SiO₂ has better mechanical and dielectric properties than that of common BPFR. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Carbon nanotube/graphene oxide‐added CaO‐B2O3‐SiO2 glass/Al2O3 composite as substrate for chip‐type supercapacitor

A CaO‐B₂O₃‐SiO₂ (CBS) glass/40 wt% Al₂O₃ composite sintered at 900°C exhibited a dense microstructure with a low porosity of 0.21%. This composite contained Al₂O₃ and anorthite phases, but pure glass sintered at 900°C has small quantities of wollastonite and diopside phases. This composite was measured to have a high bending strength of 323 MPa and thermal conductivity of 3.75 W/(mK). The thermal conductivity increased when the composite was annealed at 850°C after sintering at 900°C, because of the increase in the amount of the anorthite phase. 0.25 wt% graphene oxide and 0.75 wt% multi‐wall carbon nanotubes were added to the CBS/40 wt% Al₂O₃ composite to further enhance the thermal conductivity and bending strength. The specimen sintered at 900°C and subsequently annealed at 850°C exhibited a large bending strength of 420 MPa and thermal conductivity of 5.51 W/(mK), indicating that it would be a highly effective substrate for a chip‐type supercapacitor.