硅酸钠与有机硅氧烷前驱体自组装杂化硅基中孔材料

采用有机硅氧烷(RTES)与硅酸钠(Na2SiO3)共水解缩聚合成有机官能化的MSU型硅基中孔材料.考察了合成体系pH值对材料织构性能的影响以及不同有机硅氧烷与硅酸钠在中性条件下的自组装行为.发现在中性条件下，加入NaF可以有效避免带有较小有机基团的有机硅氧烷进入材料孔壁的可能性，而且合成体系的pH值对材料的孔径有一定的调控作用.     

Study of the Influence of Alkaline Ions (Li, Na and K) on the Structure of the Silicate Entities in Silico Alkaline Sol and on the Formation of the Silico-Calco-Alkaline Gel

The study of silico-calco-alkaline gel is essential to warn against the degradation of concrete due to the alkali-silica reaction. In the laboratory, those gels are simulated by the destabilization of a silico-alkaline sol by calcium ions. Their speed of formation depends on the alkali species. The influence of alkaline ions (Li, Na and K) on the structure of silicate entities in sol and on the gel formation has been studied. The state of polymerization of the silico-alkaline sol was determined by NMR and depends on the alkali species and the molar ratio (Rm = [SiO2]/[A2O] with A = Li, Na or K). It appears that lithium enhances the polymerization. By scattering techniques (SAXS and ELS), the evolution of size and number of scattering particles during gelation can be determined from scattering curves with Guinier approximation. The mechanism of gelation appears as a hierarchic structure composed of several discrete sizes.     

Electrophysical characteristics and stability of solid apatite-like electrolytes La x Si6O12 + 1.5x and La x Ge6O12 + 1.5x

Oxygen-ion conduction in apatite-like compounds based on silicates and germanates of lanthanum La _x A₆O_{12 + 1.5x} (A = Si, Ge; x = 9.11–10.22) is studied. The compounds are shown to be purely ionic conductors at 600–900°C and partial oxygen pressures 10^?16 to 10⁵ Pa. The electroconductivity of the best conducting specimens of La _x A₆O_{12 + 1.5x} (A = Si, Ge; x = 9.77–10) exceeds that of electrolyte YSZ at moderate temperatures. The electroconductivity of lanthanum germanate is substantially greater than that of lanthanum silicate, specifically, 7.85 × 10^?2 and 2.35 × 10^?2 S cm^?1, respectively, at 800°C. An inflection is discovered at ～750°C in the temperature dependences of electroconductivity of La _x Ge₆O_{12 + 1.5x} (x = 9.77–10.22). A dilatometric examination points to a second-kind phase transition that may be due to the oxygen sublattice disordering. The behavior of apatite-like electrolytes La _x A₆O_{12 + 1.5x} (A = Si, Ge) during long exploitation periods in the interval of working temperatures of electrochemical devices is studied for the first time ever. The electrolytes’ aging at 800°C in air for 1000 h was investigated by the electroconductivity method. The electroconductivity of lanthanum germanates decayed with time by 5% and that of lanthanum silicates, by 9.5%. The steady-state values of electroconductivity of all compounds studied is reached after 600–700 h. The compounds studied form a class of materials that hold some promise as solid electrolytes for medium-temperature fuel cells and other electrochemical devices.     

Selective Oxidation of Alcohols with a New Reagent: Iron(III) Nitrate Supported on Aluminum Silicate

A selective and effective oxidation of alcohols, except aliphatic alcohols, such as 1‐hexanol or 1‐octyl alcohol, to the corresponding aldehydes and ketones using a new reagent, iron(III) nitrate supported on aluminum silicate, under heterogeneous conditions with reflux with 85–98% yield is described.     

Evolution and properties of antiphase boundaries in silicate minerals

Experimental and observational evidence is reviewed for the mechanisms and kinetics of antiphase domain coarsening in silicate minerals. The expected rate law has the form (domain size)ⁿ ≈ annealing time, but the ideal value of n=2 has been observed in only one of three cases. Values of n≈8 or 10 are interpreted as implying adsorption of impurity atoms onto the antiphase boundaries. Diffusion of these impurities can then provide the rate determining step for boundary migration. Local ordering at the boundaries can also provide some stabilising influence, though this does not appear to affect the coarsening rate law. If the stabilisation is sufficient it might result in the development of an incommensurate superstructure, either as a stable phase or as a metastable phase under non-equilibrium conditions. The effective width of these boundaries appears to be ～ 25°, or approximately two unit cells, and their maximum effective interaction length appears to be ～ 4 times this width.     

A new nonlinear optical silicate carbonate K2Ca[Si2O5](CO3) with a hybrid structure of kalsilite and soda-like layered fragments

Single crystals of a new silicate carbonate, K₂Ca[Si₂O₅](CO₃), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6₃22) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P6₃/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO₄) and the other of the high-temperature soda-like α-Na₂CO₃, Ca substituting for Na. The electro-neutral layer K₂[Si₂O₅] (denoted K) as well as the layer Ca(CO₃) (denoted S) may separately correspond to individual structures. In K₂Ca[Si₂O₅](CO₃) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability.     

Cross‐linked Multilayer Polymer‐Clay Nanocomposites and Permeability Properties

Abstract

Electrostatically layered aluminosilicate nanocomposites have been prepared by the sequential deposition of poly(allylamine hydrochloride)/poly(acrylic acid)/poly(allylamine hydrochloride)/saponite (PAH/PAA/PAH/saponite)₁₀ on poly(ethylene terephtalate) (PET) film. Exfoliated saponite nanoplatelets were obtained by extensive shaking, sonication, and centrifugation of a water suspension. To minimize permeability and improve the mechanical integrity, cross‐linking of composite films was carried out at different temperatures. The formation of amide linkage induced through heating was observed by Fourier Transform Infrared (FT‐IR) and x‐ray photoelectron spectroscopy (XPS). The cross‐linking of nanocomposites (PAH/PAA/PAH/saponite)₁₀ showed 60% decrease in permeability of oxygen when compared with the pristine PET substrate film. In contrast, water permeability of the nanocomposite membrane was not affected by heating temperature and deposition cycles.     

(Ca,Me)La4Si3O13:Eu3+(Me=Sr,Ba)荧光粉的结构和发光特性

采用高温固相法制备了(Ca,Me)La4Si3O13∶Eu3+(Me=Sr,Ba)系列红色荧光体,考察了Eu3+掺杂浓度和Sr2+,Ba2+置换对荧光体结构和发光特性的影响。Eu3+最佳掺杂浓度为nEu3+∶nLa3+=1∶7,5D0-7F2与5D0-7F1跃迁发射强度比为2.55。Eu3+掺杂使晶胞参数a和c呈线性变小,对c的影响大于a,使a/c比增大。Sr2+和Ba2+分别置换基质中的Ca2+可以形成完全固溶体,晶胞参数随Sr2+或Ba2+的置换量增加呈线性增大,使a/c比减小。各发射峰强度在Sr2+置换量为0.4 mol时出现极大值,但随Ba2+置换量的增加而不断增强,全置换后荧光强度最大。荧光体的色坐标为(0.638 5,0.353 0)。     

温和条件下混合碱辅助水热合成硅酸镁纳米管

在混和碱的辅助下, 以普通氢氧化镁和二氧化硅粉末为原料在温和条件下高效合成硅酸镁纳米管。采用XRD, TEM, FTIR, 氮气吸附等多种手段对产物进行了表征, 并对其合成过程进行了研究。结果表明氢氧化钠和氢氧化钾的共融液能提高反应物间的溶解性, 促进反应可以在温和条件下加快进行。250℃下合成硅酸镁纳米管, 传统水热法至少需要7 d, 混合辅助水热合成只需36 h。与传统的水热法相比, 混和碱辅助的水热法是一种温和且高效的过程。     

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses 1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm²) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd