Methane partial oxidation to synthesis gas over bimetallic cobalt/tungsten carbide catalysts and integration with a Mn substituted hexaaluminate combustion catalyst

Co_0.2W_0.8C_x and supported Co_0.2W_0.8C_x catalysts are shown to be active for the partial oxidation of methane to synthesis gas. The catalyst stability is improved by operating at elevated pressure, or in the presence of excess methane. At atmospheric pressure the Co_0.2W_0.8C_x catalysts deactivate by oxidation, as seen by X-ray diffraction. Manganese substituted hexaaluminate catalysts with different Mn contents have been tested as catalysts for the total combustion of methane. In particular BaMn₂Al₁₀O₁₉ is active and stable for the combustion reaction. The temperature rise observed in the reactor was up to 300 K, depending on the reaction conditions, and complete conversion of oxygen in the feed was achieved. A process for stabilising the carbide catalysts is demonstrated, combining the manganese substituted hexaaluminate total oxidation catalyst, in series before the carbide reforming catalyst: this process leads to stable operation, with no carbon formation in the reactor and no carbide catalyst oxidation observed.     

Surfactant-mediated synthesis of metal substituted hexaaluminate from alumina sol

Manganese substituted hexaaluminate has been prepared using environmentally benign surfactants such as Triton X-100, under ambient condition with a commercial alumina sol and metal acetate precursors. The surface area of the pure alumina can be controlled to 10–70 m² g⁻¹ using cetyltrimethylammonium chloride after heating in oxygen flow at 1200°C for 6 h. The crystal structure of the obtained alumina was high purity θ-Al₂O₃. Incorporation of La and Mn leads to the formation of the high purity manganese substituted hexaaluminate with a surface area of 30–40 m² g⁻¹ which is also controllable using organic additives such as urea. The catalytic activity of the manganese substituted hexaaluminate was comparable to the sol–gel derived hexaaluminate catalyst from metal alkoxides.     

Preparation of Thin Mullite Films

Aluminosilicate glass films having compositions approximately that of mullite produced by reactive sputtering of aluminum-silicon alloys are discussed. Data are given on the speed of deposition under certain conditions for a variety of metal and ceramic substrates. Mullite crystals with the needle habit are formed from the initial amorphous film by subsequent heat treatment of about 1 hour at temperatures of 1100° to 1400°C. The number and size of the crystals are affected by firing conditions, composition, and thickness of the film and by nucleating agents such as carbon on the surface of the film as indicated by transmission electron micrographs of unsupported films. The reaction of the oxide films with some supporting ceramic substrates has also been studied.     

The electroformation of Zr metal, Zr–Al alloy and carbon films on ceramic

A method of electroforming Zr metal, Zr–Al alloy and carbon film on ceramic substrates has been developed. Using this method, it is possible to apply these films to ceramic substrates, which are complicated in structure. Zr metal and alloy film are formed in the LiCl–KCl melt containing Zr(II), whereas carbon film is formed in the molten carbonate. The electrode consists of a metal part and the ceramic substrate. The films develop between the metal part and the ceramic substrate and propagate along the surface. To form the film there has to be sufficient initial current density to deposit dendritic Zr, carbon whiskers or cubic carbon particles on the metal part.     

锐钛矿型TiO2溶胶的成膜特性及薄膜性能

使用具有锐钛矿晶粒的TiO2溶胶,在铜质基材、氧化铝陶瓷片、玻璃载玻片、聚碳酸酯(PC)板、聚氯乙烯(PVC)片、聚对苯二甲酸乙二醇酯(PET)膜、涂料涂层、纸片等多种基材表面涂膜。利用扫描电子显微镜观察了各种基材表面的TiO2薄膜形貌,并对以载玻片为基材的TiO2薄膜的光学性能和光催化性能进行了测试。结果表明TiO2溶胶在多种基材上都能较好地成膜;TiO2薄膜透明,不会遮盖基体材料;TiO2薄膜具有较好的光催化活性。     

Fabrication and characterization of aluminum nitride thick film coated on aluminum substrate for heat dissipation

For effective heat dissipation in high-power LED applications, aluminum nitride (AlN) thick films as thermally conductive dielectric layers were developed, which were deposited on an Al substrate by aerosol deposition (AD). The aerosol-deposited AlN thick films on Al substrates have advantages over conventional polymer-based dielectric substrates or ceramic substrate mounted heatsink systems including an epoxy adhesive, such as excellent heat dissipation capacity and low thermal resistance. AD is an effective method to fabricate high-quality AlN thick film without the Al₂O₃ phase because the film is formed at room temperature. Highly dense and well-adhered, pure AlN thick films with thicknesses up to 30 µm were deposited on an Al substrate. AlN-Al₂O₃ and AlN-polyvinylidene fluoride (PVDF) composite films were also deposited on an Al substrate in order to investigate the effect of Al₂O₃ and polymer on the microstructure and thermal properties. Among the films, pure AlN thick film exhibited the highest dielectric strength, the highest thermal conductivity, and the lowest thermal resistance. Therefore, it can be expected that the aerosol-deposited AlN thick film on Al substrate could be used as a powerful heatsink.     

Thermal Stability of Hexaaluminate Film Coated on SiC Substrate for High-Temperature Catalytic Application

A coating of barium hexaaluminate (Ba_0.75Al_11.0O_17.25) on an α-SiC substrate and the thermal stability of the formed film were investigated for a high-temperature catalytic application. The film prepared by sol coating consisted of BaAl₂Si₂O₈ and α-Al₂O₃ phases and always contained many cracks or exfoliations after heating at 1200C. A hexaaluminate porous film was successfully formed by slurry coating without void formation at the interface between the film and the substrate and exfoliation due to the formation of the intermediate layer after heating at 1200°C. The microstructure of the film remained unchanged, even after heating at 1300°C.     

Effect of water content in the precursor solution on the catalytic property and stability of Sr0.8La0.2MnAl11O19 high-temperature combustion catalyst

The effect of water content in the precursor solution on thermal stability in the preparation of Sr-hexaaluminate was examined by XRD, SEM, TEM, BET and XPS analysis. Large water content caused a rapid decrease in the surface area of hexaaluminate. XPS analysis also showed enrichment of the element when large amount of water was added during the hydrolysis step. This result implies that the addition of large amount of water affected the surface properties of hexaaluminate; the instability of the unbalanced surface composition as compared with bulk composition, accelerated the sintering phenomena which resulted in the rapid particle growth and drastic decrease of surface area.     

A study of the initial stages of diamond deposition on ferrous substrates coated by a nitrided chromium interlayer and on nitrided polycrystalline chromium substrates

The use of a nitrided chromium interlayer has been found to improve the interfacial properties of diamond films deposited on ferrous substrates. This is achieved by hindering diffusion process of carbon and iron, good adhesion of the interlayer to the steel substrate, and very stable mechanical and chemical bonding between the interlayer and the diamond film. In the present study the initial stages of diamond deposition on steel substrates coated by a nitrided chromium interlayer and on nitrided polycrystalline chromium substrates are reported. Nitridation of chromium films deposited by electrochemical methods and polycrystalline chromium substrates resulted in the formation of two chromium nitrides phases, CrN and Cr₂N, and a rough surface morphology. The initial stages of diamond deposition were found to be accompanied by carburization of the substrates surface resulting in chromium carbide formation. The incubation time, diamond particle density and growth rate at the very initial stages of the deposition process were found to differ for these two substrates. It is suggested that these differences originate from different carburization rates of the two substrates. Phase transformation, recrystallization and diffusion processes in the near surface regions of both substrates resulted in very stable chemical bonding and good adhesion of the diamond film to the substrates. Raman spectra of the deposited films, on both substrates, show shift of the diamond peak position to higher wave numbers and split of the peak. These effects are associated with compressive stresses in the diamond film. Residual stresses in the deposited films were calculated from the shift of the diamond Raman peak. The residual stresses, as calculated from the Raman spectra, were found to increase with deposition time reaching values of 8.4 and 6.9 GPa for continuous diamond films on steel substrate coated with the nitrided chromium film and on nitrided chromium substrates, respectively. Based on a simple model it was estimated that thermal stress, arising from mismatch between the thermal expansion coefficient of diamond and the underlying substrates, is the major component of the compressive stress in the diamond films.     

Thick Nb-Doped Bismuth Titanate Film with Controllable Grain Orientation

In the current work, we reported a potential approach to obtain thick ceramic films with controllable grain orientation based on magnetic alignment and polymerization techniques. The slurry containing 40 vol% Bi₄Ti_2.96Nb_0.04O₁₂ (BINT) ceramic powder, monomer, initiator, and catalyst was drop coated on a Pt substrate and then moved into a vertical 10 T magnetic field. In 1–2 min, the ceramic particles were aligned by a strong magnetic force in slurry and then in situ locked by polymerization on the substrate. After sintering at 1000°C, a BINT ceramic film (50–80 μm in thickness) with a highly a / b plane orientation was obtained. Theoretically, the grain orientation in the films can be easily controlled by adjusting the magnetic field direction. This approach is readily applicable to other materials with a non-cubic structure and is expected to facilitate the fast preparation of grain-oriented thick films.     

Drying of Granular Ceramic Films: I, Effect of Processing Variables on Cracking Behavior

Drying of binder-free granular ceramic films was studied to identify processing variables which affect their cracking behavior. Films were prepared from electrostatically stabilized suspensions of α-alumina in water. A critical cracking thickness (CCT) was determined, above which films would spontaneously crack during drying. The effects of particle size, liquid surface tension, drying rate, dispersion stability, and sedimentation time were evaluated by a statistical design methodology. The CCT for films prepared on glass substrates was used as a measure of the effect of each variable on cracking. The statistically significant variables were particle size, dispersion stability, and sedimentation time. The effect of substrate constraint was also studied by producing films on a Teflon substrate and a pool of liquid Hg. The observations were consistent with a capillary formed tensile stress acting on the entire film rather than differential stress generated by a moisture gradient over the film thickness.     

Low‐Temperature Co‐Fired Ceramic Substrates for High‐Performance Strain Gauges

Recent advances in the development of high gauge factor thin films for strain gauges prompt the research on advanced substrate materials. A glass ceramic composite has been developed in consideration of a high coefficient of thermal expansion (9.4 ppm/K) and a low modulus of elasticity (82 GPa) for the application as support material for thin‐film sensors. In the first part, constantan foil strain gauges were fabricated from this material by tape casting, pressure‐assisted sintering, and subsequent lamination of the metal foil on the planar ceramic substrates. The accuracy of the assembled load cells corresponds to accuracy class C6. That qualifies the load cells for the use in automatic packaging units and confirms the applicability of the low‐temperature co‐fired ceramic (LTCC) substrates for fabrication of accurate strain gauges. In the second part, to facilitate the deposition of thin‐film sensor structures to the LTCC substrates, pressure‐assisted sintering step is modified using smooth setters instead of release tapes, which resulted in fabrication of substrates with low average surface roughness of 50 nm. Titanium thin films deposited on these substrates as test coatings exhibited low surface resistances of 850 Ω comparable to thin films on commercial alumina thin‐film substrates with 920 Ω. The presented material design and advances in manufacturing technology are important to promote the development of high‐performance thin‐film strain gauges.     

Adherent Zirconia Films by Reactive Ion Implantation

Conventional methods of forming ceramic coatings on metal substrates, such as CVD or plasma spray, typically retain a sharp interface and may have adhesion problems. In order to produce a completely mixed interface for better adhesion, a method using reactive ion implantation was used which can grow a thick stoichiometric film of an oxide ceramic starting from inside the substrate. Zirconium oxide ceramic films have been produced by this technique using a high-energy zirconium ion beam in an oxygen gas ambient. Compositional data are shown based on Auger electron spectroscopy of the film. Tribological properties of the layer were determined from wear and friction measurements using a pin-on-disk test apparatus. The adhesion was measured both by a scratch technique as well as by thermal shock. Results show an extremely adherent ZrO₂ film with good tribological properties.     

Thermal,optical, and electrical characterization of thin film coated RTV 655 bilayer system

Adhesion of thin films to hydrophobic elastomeric substrates is of particular interest in the area of flexible electronics and nano‐sensor technology. Here, nanometer‐thick Au films were deposited directly onto hydrophobic RTV 655 substrates by means of sputtering, thermal evaporation, and electroless techniques without an adhesion‐promoting layer. The bilayer system was exposed to repeat thermal cycling and changes to the surface morphology of the thin film were monitored electrically and optically. Buckle formation in the as‐deposited film was attributed to stress in the film and substrate stiffness rather than thermal coefficient mismatch between films. The Au‐RTV 655 interface was water tight and maintained a strong adhesion despite repeated thermal cycles. Sputtered and thermally evaporated carbon‐coated RTV 655 substrates were also studied in parallel for comparison. Periodic arrays of buckles formed in pre‐strained RTV 655 samples showed reproducibility in their optical properties demonstrating good adhesion between the two layers without an interfacial layer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41396.     

天然气催化燃烧催化剂的研究(Ⅱ)

介绍了天然气催化燃烧钙钛矿型氧化物催化剂、六铝酸盐型催化剂以及负载型非贵金属催化剂的研究现状。对于钙钛矿型氧化物催化剂,利用A位取代或调整B位元素的种类及配比、新的技术和方法制备高比表面积或具有纳米结构的钙钛矿型氧化物,是提高其甲烷催化燃烧活性的重要手段。六铝酸盐型催化剂具有很高的热稳定性和甲烷燃烧活性,但起燃温度较高,通过采用将金属Pd负载到六铝酸盐上或改变制备方法,提高其比表面积,以提高其低温反应活性。负载型非贵金属催化剂研究最多的是过渡族金属,其氧化活性、抗毒性能和耐久性都存在问题,需进一步研究。     

Effects of SiC addition on the structure and properties of reticulated porous mullite ceramics

Reticulated porous mullite ceramics (mullite RPCs) were produced by the polymer replica method using alpha alumina and kaolin to form in situ mullite. Up to 30% particulate silicon carbide (SiCp) was added to ceramic mixtures to explore its effect on the structure and properties of the sintered products. The ceramic slurry was coated onto polyurethane sponge using preset roller method, then recoating was applied by the spray coating technique. The strength of the mullite RPCs was found to depend greatly on the phase composition of the structures and on the amount of SiCp addition.     

Thermal properties of homogenous lanthanum hexaaluminate/alumina composite ceramics

Lanthanum hexaaluminate has the potential to be applied in thermal barrier coatings due to its relative low thermal conductivity and low sinterability at temperatures higher than 1100 °C. One of the main problems in developing this material as a thermal barrier coating is difficulty in controlling the microstructure in order to combine the low thermal conductivity with high structural reliability.The idea behind this study was to take advantage simultaneously of the low thermal conductivity of lanthanum hexaaluminate and of the high mechanical properties of alumina by developing alumina-rich and lanthanum hexaaluminate-rich alumina/lanthanum hexaaluminate ceramic composites. The thermal properties of the alumina/hexaaluminate ceramic composites were compared as a function of temperature and lanthanum hexaaluminate content (20–80 vol.%). The results showed that the alumina/lanthanum hexaaluminate ceramic composites have sufficient low thermal conductivity to be used in thermal barrier coatings.     

Annealing‐promoted unidirectional migration of organic‐modified nanoparticles embedded two‐dimensionally in polymer thin films

The spatial structures of oleic acid‐modified CeO₂ nanoparticles in polystyrene (PS) thin films spin‐coated on silicon substrates were observed by transmission electron microscopy, when the films underwent thermal annealing above the glass‐transition temperature of PS. Before annealing, the nanoparticles have segregated to the surface of the films, and formed two‐dimensional spatial structures in the PS films. Then, the nanoparticles migrated away from the film surface to the substrate/film interface during thermal annealing, maintaining the two‐dimensional spatial structures. In addition, we demonstrated that such unidirectional migration of nanoparticles across the PS film occurs regardless of the characteristics of the substrate surface, the concentration of nanoparticles, and the thickness of the films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42760.     

Diamond coating of coloured Si3N4 ceramics

The effect of Si₃N₄ secondary phases on chemical vapour deposition (CVD) diamond film growth was analyzed. Silicon nitride substrates were obtained by pressureless sintering, placing the green samples inside a powder bed of Si₃N₄/BN. Local variations in the sintering atmosphere led to samples with different grey colouration as well as chemical and physical characteristics, determined by X-ray diffraction and thermal conductivity tests, which affected the diamond film growth. A complete characterization of the films, including thickness, average crystal size, surface roughness, texture and adhesion, was done. The Si₃N₄ substrate with glassier phase gave thicker diamond films, with smaller crystal sizes and better film adhesion to the substrate than the diamond films grown on ceramic substrates with less vitreous phase.     

Fabrication of Pb(Zr,Ti)O3 thin films utilizing unconventional powder magnetron sputtering (PMS)

Pb(Zr,Ti)O3 (PZT) ferroelectric ceramic films exhibit highly superior ferroelectric, pyroelectric and piezoelectric properties which are promising for a number of applications including non-volatile random access memory devices, non-linear optics, motion and thermal sensors, tunable microwave systems and in energy harvesting (EH) use. In this research, a thin layer of PZT was deposited on two different substrates of Strontium Titanate (STO) and Strontium ruthenate (SRO) by powder magnetron sputtering (PMS) system. The preliminary powders, consisting of PbO, ZrO₂ and TiO_2, were manually mixed and placed into the target holder of the PMS. The deposition was performed at an elevated temperature reaching up to 600 °C via a ceramic heater. This high temperature is required for PZT thin film crystallinity, which is never achieved in conventional physical vapour deposition processes. The phase structure, crystallite size, stress-strain and surface morphology of deposited thin films were characterized using X-ray Diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM). The composition of the PZT thin films were also analysed by X-ray photoelectron spectroscopy (XPS). The mechanical properties of the thin films were evaluated with micro-scratch adhesive strength and micro hardness equipment. FESEM results showed that the PZT thin films were successfully deposited on both SRO and STO substrates. The surfaces of the coated samples were free from cracks, relatively smooth, uniform and dense. The profile of X-ray diffraction confirmed the formation of single-c-domain/single crystal perovskite phase grown on both substrates. The XPS analysis have shown that the PZT thin film grown by this method and that a target of PZT+10% PbO is a proper target for growing nominal PZT thin films. The adhesion strength and micro hardness results have confirmed the stability and durability of the thin film on the substrates, although higher values have been reported for thin film of PZT deposited on SRO surfaces.