Sinterability of 8Y–ZrO2 powders hydrothermally synthesized at low temperature

Nanometric yttria (8 mol%)-stabilized zirconia powders were hydrothermally synthesized at 110 °C for 7 days in the presence of dilute (0.20 M) or concentrated (2.0 M) solutions of (KOH+K₂CO₃) mineralizer. Zirconia xerogel, crystalline Y(OH)₃, crystalline Y₂O₃ and a xerogel of coprecipitated (Y–Zr) hydroxide were used as starting materials. Setting the content of yttria constant and equal to 8 mol%, three types of mixtures were tested. Zirconia xerogel in mixture with crystalline Y₂O₃, zirconia xerogel in mixture with crystalline Y(OH)₃ and, finally, a xerogel of coprecipitated (Y–Zr) hydroxide were hydrothermally treated.The different characteristics of the resulting powders are discussed in terms of both the mineralizer concentration and the type of Y-based precursor used in the hydrothermal treatments, respectively.Weakly agglomerated cubic ZrO₂ powders with primary particles bigger in size and without any preliminary treatment show better performances when they are directly sintered at 1500 °C.     

Kinetic energy of structural protons in silica xerogels

The kinetic energies of the protons in the silanol groups (Si–OH units) of silica xerogels were deduced by ab initio calculations using the basis set mp2/6-311G**. The silanol groups were simulated using the Si(OH)₄ unit. The calculated result of the H-kinetic energy was found to be 150 meV, which is ~ 50% smaller than a recently reported experimental value for porous silica xerogels. For comparison, the same calculations of the proton kinetic energies of other H-containing molecules such as H₂O and CH₄ (being also ~ 150 meV) were found to be in excellent agreement with measurements. Possible reasons for the huge deviations in the case of the silanols are discussed.     

Self-consistent mapping of the ab initio calculations to the multi-orbital <Emphasis Type="Italic">p</Emphasis>–<Emphasis Type="Italic">d</Emphasis> model: Magnetism in α-FeSi<Subscript>2</Subscript> films as the effect of the local environment

The near infrared transmission spectra of nanoporous SiO₂/Al₂O₃ xerogel have been recorded for the first time in the process of filling of nanopores with ammonia and acetone molecules. It has been found that the physical adsorption of these gases results in a reversible increase in the translucence of xerogel samples at the frequencies of vibrational bands of surface OH groups.     

Properties of Natural Rubber Vulcanizates/Nanosilica Composites Prepared Based on the Method of In-situ Generation and Coagulation

Using the characteristics of silica sol dispersing well in water and easy formation of silica gel when the silica sol is heated, by mixing a system of concentrated natural rubber latex and silica sol, the silica sol can in-situ generate SiO₂ particles when heated. After coagulation of the mixed system, natural rubber/nanosilica composites C(NR/nSiO₂) were obtained. The composites C(NR/nSiO₂) and their vulcanizates were studied using a rubber processing analyzer (RPA), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The influence of silica contents on the C(NR/nSiO₂) vulcanizates mechanical properties, cross-linking degree, Payne effect, dissipation factor (tanδ), and the particle size and dispersion of SiO₂ in NR were investigated. The results obtained were compared with the NR/SiO₂ composites based on traditional dry mixing of bale natural rubber and precipitated silica (white carbon black). The results showed that when using a sulfur curing system with a silica coupling agent (Si69) in C(NR/nSiO₂), the vulcanizate had better mechanical properties, higher wet resistance, and lower rolling resistance than those without Si69. In the composites C(NR/nSiO₂) and their vulcanizates, the SiO₂ particles’ average grain diameter was 60 nm, and the good-dispersion of the in-situ generated SiO₂ in the rubber matrix were a significant contribution to the satisfactory properties of C(NR/nSiO₂) composites and their vulcanizates.     

Gas-phase aggregation of fullerenes by laser ablation of fullerenes in reactive and nonreactive matrices

60 molecules, whereas little or no coalescence was found in the nonreactive mixture. In the negative ion TOF channel the maximum peak of twice C₆₀ coalescence by laser desorption was always located at masses greater than 120 carbon mass units, which is different from all previous reports. We suggest that the formation mechanism was due to strong interactions between the C₆₀ molecules and silica particles or surface species such as the H or OH group existing in the matrix. Received: 6 May 1996/Revised version: 22 July 1996     

Temperature and substrate dependence of structure and growth mechanism of carbon nanofiber

The carbon nanofibers were grown on Ni/Si and Ni/Ti/Si substrates in 1 atm CH₄ atmosphere at 640 °C and 700 °C by thermal chemical vapor deposition method. The carbon nanofibers were characterized by field emission scanning electron microscopy, transmission electron microscopy, and Raman spectrometry for morphology, microstructure, and crystallinity. The electron emission property of carbon nanofibers was also investigated by current-voltage (I-V) measurement. The results showed that the solid amorphous carbon nanofibers could be grown on Ni/Si substrate at 640 °C through tip growth mechanism, the carbon nanotubes could be grown on Ni/Si substrate at 700 °C through tip growth mechanism, and the carbon nanotubes could be grown on Ni/Ti/Si substrate at 700 °C through root growth mechanism.     

纳米Si/C/N复相粉体的微波介电特性

研究了纳米Si/C/N复相粉体在8.2—18GHz的微波介电特性,采用双反应室激光气相合成纳米粉体装置,以六甲基二硅胺烷((Me₃Si)₂NH)(Me∶CH₃)为原料,用激光诱导气相反应法合成纳米Si/C/N复相粉体,复相粉体的粒径为20—30nm.纳米Si/C/N复相粉体与石蜡复合体的介电常量的实部(ε′)和虚部(ε″)以及介电损耗角正切(tan δ=ε″/ε′)随纳米粉体含量的增加而增大,ε′和ε″与纳米粉体体积分数(v)之间符合二次函 关键词： 纳米Si/C/N复相粉体 微波介电常量 微观结构     

Si纳米量子点的LPCVD自组织化形成及其生长机理研究

采用低压化学汽相沉积(LPCVD)方法，依靠纯SiH₄气体分子的表面热分解反应， 在由Si—O—Si键和由Si—OH键终端的两种SiO₂表面上，自组织生长了Si纳米量子点. 实 验研究了所形成的Si纳米量子点密度随SiO₂表面的反应活性位置数、沉积温度以及反应气 压的变化关系. 依据LPCVD的表面热力学过程，定性地分析了Si纳米量子点的形成机理.研究结果对具有密度分布均匀和晶粒尺寸可控的Si纳米量子点的自组织生长，以及Si基新型量子电子器 关键词： Si纳米量子点 LPCVD 自组织化形成 生长机理     

In situ Grafting onto Silica Surface with Epoxidized Natural Rubber via Solid State Method

An in situ solid state grafting reaction between epoxidized natural rubber (ENR) and silica was performed in a Haake internal mixer. Resulting ENR‐grafted silica was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) measurements. Based on these results, it was concluded the silanol groups (Si‐OH) of silica caused the ring opening of ENR oxirane rings so that ENR was grafted onto the silica surface. Transmission electron microscopy (TEM) photographs showed ENR‐grafted silica had better dispersibility and smaller aggregates compared with the original silica. Dynamical mechanical analysis (DMA) of vulcanized rubber compounds contained ENR‐grafted silica showed the glass transition temperature (T _g) of grafted ENR molecules shifted to higher temperature, from ?3°C to 20°C, indicating the mobility of ENR was greatly restricted. As a result, the compounds containing ENR‐grafted silica have higher hysteresis, and can be applied in a much wider field, such as damping materials, tires of racing cars, and so on.     

Synthesis and photoluminescence of aligned straight silica nanowires on Si substrate

Aligned straight silica nanowires (NWs) have been synthesized on Si wafer by thermal evaporation of mixed powders of zinc carbonate hydroxide and graphite at 1100 °C and condensation on Si substrate without using any catalyst. The straight silica NWs have diameters ranging from 50 to 100 nm, and lengths of several micrometers, with cone-shaped tips at their ends. High deposition temperature and relatively high SiO_x vapor concentration near the growth substrate would be beneficial to the formation of the aligned straight silica NWs. Different morphologies of silica nanostructures have also been obtained by varying the deposition temperature and the vapor concentration of the SiO_x molecules. Room temperature photoluminescence measurements on the oriented silica NWs show that two green emission bands at 510 and 560 nm, respectively, revealing that the aligned straight silica NWs might have potential applications in the future optoelectronic devices.     

Synthesis and characterization of polyester bionanocomposite membrane with ultrasonic irradiation process for gas permeation and antibacterial activity

Optically active bionanocomposite membranes composed of polyester (PE) and cellulose/silica bionanocomposite (BNCs) prepared with simple, green and inexpensive ultrasonic irradiation process. It is a novel method to enhance the gas separation performance. The novel optically active diol containing functional trifluoromethyl groups was prepared in four steps reaction and it was fully characterized by different techniques. Commercially available silica nanoparticles were modified with biodegradable nanocellulose through ultrasonic irradiation technique. Transmission electron microscopy (TEM) analyses showed that the cellulose/silica composites were well dispersed in the polymer matrix on a nanometer scale. The mechanical properties nanocomposite films were improved by the addition of cellulose/silica. Thermo gravimetric analysis (TGA) data indicated an increase thermal stability of the PE/BNCs in compared to the pure polymer. The results obtained from gas permeation experiments showed that adding cellulose/silica to the PE membrane structure increased the permeability of the membranes. The increase in the permeability of the gases was as follows: P_CH4 (38%) <P_N2 (58%) <P_CO2 (88%) <P_O2 (98%) Adding silica nanoparticles into the PE matrix, improved the separation performance of carbon dioxide/methane and carbon dioxide/nitrogen gases. Increasing the cellulose/silica mass fraction in the membrane increased the diffusion coefficients of gases considered in the current study. Further, antimicrobial test against pathogenic bacteria was carried out.     

Photosynthesis of methanol and methane from CO2 and H2O molecules on a ZnO surface

The photochemical synthesis of CH₃OH and CH₄ from CO₂ and H₂O molecules was observed at 5°C by irradiating ZnO powder with visible light under high pressures of 25 to 35 kg/cm² of CO₂ gas. Under these conditions the water surrounding the ZnO surface is in the clathrate hydrate phase, and this is expected to regulate the surface OH groups and to enhance the interaction of the CO₂ molecules with the OH groups. The surface impurity levels originating from S, Si and P atoms, which are accumulated during the surface activation, play an essential role in the generation of free electrons and holes by visible light. Measurement of the photosurface conductance on the ZnO(101&#x0304;0) surface confirms the above facts. The best conversion efficiency was found to be about 6% with respect to reactant H₂O molecules using a 75 W Xe lamp.     

Scanning tunneling microscopy of fluorinated fullerene molecules on silicon surfaces

Scanning tunneling microscopy (STM) under ultra-high vacuum conditions is used to study the initial stages of adsorption of C₆₀F₁₈ and C₆₀F₃₆ fluorofullerene molecules on Si(111)-7 x 7 and Si(100)-2 x 1 surfaces. Spatially resolved STM images of individual molecules and ab initio calculations show that the fluorofullerene molecules interact with an Si surface, with the F atoms oriented toward the surface. The large electric dipole moment of the molecules induces strong polarization on the surface, but the charge transfer is weak. The presence of C₆₀F₃₆ isomers with different symmetry—T, C ₃, and C ₁—is revealed in STM images for the first time.     

High surface area thermally stabilized porous iron oxide/silica nanocomposites via a formamide modified sol-gel process

Iron oxide/silica (Fe:Si as 1:10 atomic ratio) composite materials have been prepared by calcination for 3 h at different temperatures (400-900 °C) of xerogel precursor obtained via a formamide modified sol-gel process. The process involved TEOS and iron(III) nitrate, nitric acid and formamide. Genesis of the composite materials from the xerogel precursor has been investigated by TGA, DSC, FTIR, XRD, SEM and EDX. Results indicated that all the calcined composites are mainly composed of amorphous iron oxide dispersed as finely divided particles in amorphous silica matrixes. Nitrogen adsorption/desorption isotherms revealed a reversible type I of isotherms indicative of microporosity. However, high S_BET surface area and microsporosity were observed for the calcined composite materials (e.g. S_BET = 625 m² g⁻¹, and S_αs = 556 m² g⁻¹ for the composite calcined at 400 °C). Formation of the porous texture was discussed in terms of the action of formamide, which enhanced strengthening of the silica gel network during evaporation of the more volatile components within the composite body during the drying process.     

Photoluminescence spectra of laser-synthesized Si/C/N ultrafine powders

Ultrafine Si/C/N ceramic powders were synthesized by a CO₂-laser-induced reaction between silane (SiH₄), ammonia (NH₃) and acetylene (C₂H₂). The powders were characterized by infrared (IR) reflection and photoluminescence (PL) spectroscopy. From the infrared reflection spectra of Si/C/N powders, we have identified the causes of the strong photoluminescence present in these powders. The photoluminescence spectra of Si/C/N powders originate from the presence of hydroxylated and amorphous silicon (a-SiO₂) formed at the porous surface of these powders. We have shown that different chemical bonding between Si, C and N atoms, the degree of crystallinity of ternary powders and their porosity strongly influence the processes at their surface, i.e. the formation of amorphous silicon and silanole. Received: 16 June 2000 / Accepted: 24 June 2000 / Published online: 9 November 2000     

Structure and photoluminescence properties of Er3+-doped TiO2-SiO2 powders prepared by sol-gel method

Er 3+-doped TiO 2-SiO 2 powders are prepared by the sol-gel method,and they are characterized by high resolution transmission electron microscopy (HR-TEM),X-ray diffraction (XRD) spectra,and Raman spectra of the samples.It is shown that the TiO 2 nanocrystals are surrounded by an SiO 2 glass matrix.The photoluminescence (PL) spectra are recorded at room temperature.A strong green luminescence and less intense red emission are observed in the samples when they are excited at 325 nm.The intensity of the emission,which is related to the defect states,is strongest at the annealing temperature of 800 C.The PL intensity of Er 3+ ions increases with increasing Ti/Si ratio due to energy transfer between nano-TiO 2 particles and Er 3+ ions.     

Hybrid Polyurethane-Poly(2-hydroxyethyl methacrylate) Semi-IPN–Silica Nanocomposites: Interfacial Interactions and Glass Transition Dynamics

Polyurethane-poly(2-hydroxyethyl methacrylate) semi-IPN-silica nanocomposites with low content (0.25 and 3 wt%) of differently functionalized 3-D fumed silica nanoparticles were studied using a combined AFM/DSC/CRS approach over the ?100 to 160°C range. The pronounced heterogeneity of the PHEMA and PU glass transitions’ dynamics and the effects of considerable suppression of dynamics and increasing elastic properties by silica additives were shown. It was caused by formation of peculiarly cross-linked structures due to “double hybridization,” in particular via selective covalent bonding of the silica surface, functionalized by ?OH, ?NH₂ or ?CH?CH₂ groups, with the matrix constituents. The silica dispersion remained unchanged in these nanocomposites; therefore the relationships between interfacial interactions and dynamics/modulus behavior could be followed.     

Electrical and thermoelectric properties of the SiC/Si biomorphic composite at high temperatures

The electrical resistivity ρ and the thermopower coefficient α of a SiC/Si biomorphic composite fabricated from a porous carbon matrix [prepared through pyrolysis of wood (white eucalyptus)] by infiltrating molten Si into the empty channels of the matrix were measured in the temperature ranges 100–950 and 100–750 K, respectively. Silicon reacts chemically with the carbon of the matrix to produce 3C-SiC, which, in combination with the excess Si unreacted with carbon, forms the SiC/Si biomorphic composite. The SiC/Si samples studied had a concentration of “excess” Si of ～30 vol % and a porosity of ～13–15 vol %. Measurements of ρ were carried out on samples cut either along (ρ_∥) or across (ρ_⊥) the tree growth direction, and α was measured on a sample cut along the tree growth direction.     

Carbon nanostructures produced by pyrolysis under high pressure inside a nanosize silica matrix

In this work, the pyrolysis under high pressure of hydrocarbons dispersed inside a nanosized silica matrix (Aerosil) was investigated. The samples consisted of hydrophobic nanometric silica powder terminated by methyl groups with carbon contents ranging from 0.7 to 4 wt%. The pyrolysis was carried out in the temperature range from 1000 to 1600 °C under high pressure (1.25 up to 7.7 GPa) to keep the two‐dimensional distribution of carbon atoms originally at the silica grain boundaries. Evidences from Raman spectroscopy and transmission electron microscopy suggested that the resulting carbon nanostructures were actually graphene‐like nanoflakes. The size of the nanostructures calculated from the I_D/I_G ratio increased from 6 to 30 nm for processing temperatures increasing from 1000 to 1600 °C under pressure, respectively. The results revealed that the very good dispersion of the methyl groups inside the nanosize silica matrix, and the confinement under high pressure during the pyrolysis, played both a relevant role in the resulting carbon nanostructures. Copyright © 2012 John Wiley & Sons, Ltd.     

溶胶-凝胶法制备纳米多孔SiO2薄膜

以正硅酸乙酯(TEOS)为原料，采用旋转涂敷的方法，结合溶胶-凝胶技术在硅衬底上制备超低介电常数多孔SiO₂薄膜.采用两种不同的改性方法对薄膜表面进行改性，傅里 叶变换红外光谱分析发现改性后薄膜中含有大量的—CH₃键，从而减少了孔洞塌陷.用扫 描电子显微镜观察薄膜的表面形貌，发现薄膜内孔洞尺寸在70—80 nm之间.调节溶胶pH值，发现pH值越小凝胶时间越长.对改性样品热处理的结果表明，在300 ℃时介电常数最低达2.05. 关键词： 2')" href="#">多孔SiO₂ 低介电常数 溶胶-凝胶