Chemische Zusammensetzung und Mikrostruktur polymerabgeleiteter Gläser und Keramiken im System Si–C–O. Teil 2: Charakterisierung der Gefügeausbildung mittels hochauflösender Durchstrahlungselektronenmikroskopie und Feinbereichsbeugung

Chemical Composition and Microstructure of Polymer‐Derived Glasses and Ceramics in the Si–C–O System. Part 2: Characterization of microstructure formation by means of high‐resolution transmission electron microscopy and selected area diffraction Liquid or solid silicone resins represent the economically most interesting class of organic precursors for the pyrolytic production of glass and ceramics materials on silicon basis. As dense, dimensionally stable components can be cost‐effectively achieved by admixing reactive filler powders, chemical composition and microstructure development of the polymer‐derived residues must be exactly known during thermal decomposition. Thus, in the present work, glasses and ceramics produced by pyrolysis of the model precursor polymethylsiloxane at temperatures from 525 to 1550 °C are investigated. In part 1, by means of analytical electron microscopy, the bonding state of silicon was determined on a nanometre scale and the phase separation of the metastable Si–C–O matrix into SiO₂, C and SiC was proved. The in‐situ crystallization could be considerably accelerated by adding fine‐grained powder of inert fillers, such as Al₂O₃ or SiC, which permits effective process control. In part 2, the microstructure is characterized by high‐resolution transmission electron microscopy and selected area diffraction. Turbostratic carbon and cubic β‐SiC precipitate as crystallization products. Theses phases are embedded in an amorphous matrix. Inert fillers reduce the crystallization temperature by several hundred °C. In this case, the polymer‐derived Si–C–O material acts as a binding agent between the powder particles. Reaction layer formation does not occur. On the investigated pyrolysis conditions, no crystallization of SiO₂ was observed.     

声光效应拉曼-内斯方程矩阵级数解法及声光调制器优化设计

提出一种求解正常声光相互作用拉曼 内斯 (Raman Nath)方程的矩阵级数解法 ,该解法直观方便且具有普遍性。计算结果表明 ,对Q =4 1π ,Bragg衍射的效率只有 97 5 % ;对非对称入射 ,以往的Raman Nath近似解误差较大 ;指出提高Bragg衍射效率的有效途径在于提高声光频率比并给出计算声光器件最优长度的计算公式。     

Biodegradation of monoaromatic hydrocarbons in aquifer columns amended with hydrogen peroxide and nitrate

The ability of indigenous microorganisms to degrade benzene, toluene, ethylbenzene and xylenes (BTEX) in laboratory scale flow-through aquifer columns was tested separately with hydrogen peroxide (110 mg/l) and nitrate (330 mg/l as NO₃⁻) amendments to air-saturated influent nutrient solution. The continuous removal of individual components from all columns relative to the sterile controls provided evidence for biodegradation. In the presence of hydrogen peroxide, the indigeneous microorganisms degraded benzene and toluene (> 95%), meta- plus para-xylene (80%) and ortho-xylene (70%). Nitrate addition resulted in 90% removal of toluene and 25% removal of ortho-xylene. However, benzene, ethylbenzene, meta- and para-xylene concentrations were not significantly reduced after 42 days of operation. Following this experiment, low dissolved oxygen (< 1 mg/l) conditions were initiated with the nitrate-amended column influent in order to mimic contaminated groundwater conditions distal from a nutrient injection well. Toluene continued to be effectively degraded (> 90%), and more than 25% of the benzene, 40% of the ethylbenzene, 50% of the meta- plus para-xylenes and 60% of the ortho-xylene were removed after several months of operation.     

Chemical leaching and magnetic properties of non-equilibrium Al(Co–Cu) powders produced by rod milling

We report upon the chemical leaching and magnetic properties of nanoscale crystalline Al_0.6(Co₂₅Cu₇₅)_0.4 alloy powders produced by rod milling. X-Ray diffractometry (XRD), transmission electron microscopy, differential scanning calorimetry, vibrating sample magnetometry, and superconducting quantum interference device magnetometry were used to characterize the as-milled and leached specimens. After 400 h of milling, only the b.c.c. phase of the intermetallic compound γ-Al_3.892Cu_6.10808 was detected by XRD. After annealing the leached specimen at 600 °C for 1 h, the nanoscale crystalline phase was transformed into the f.c.c. Cu phase, and this was accompanied by a change in the magnetic properties. The peaks of the magnetization shifted towards lower temperature with increasing external field. The temperature behavior at T_f (45 K) for direct current (d.c.) magnetic susceptibility measurements was quite different for field cooling and zero-field cooling. After cooling the leached specimen from 800 °C, magnetization increased gradually.     

The microstructure of Cu films deposited by the self-ion assisted technique

The microstructures of Cu films deposited by the self-ion assisted, partially ionized beam (PIB) deposition technique under two different accelerating potentials, 0 KeV and 6 KeV, are compared. The 6 KeV film shows a bimodal (111) fiber and (100) fiber texture with an abundance of twin boundaries and a relatively large average grain size with a typical lognormal distribution. The 0 KeV film consists of small, mostly (111) oriented grains with islands of abnormally large (100) grains. The controlling factors for the abnormal growth of the (100) grains are discussed in relation to the observed microstructures, showing that all factors necessary for abnormal (100) growth are present in the films.     

High temperature controlled atmosphere experiments for catalysts in a transmission electron microscope

A new transmission electron microscopy (TEM) specimen preparation procedure for high temperature experiments using a controlled atmosphere specimen holder (HTCASH) has been developed. It is designed for studying the microstructure of catalyst specimens before and after treatments in various gases. The procedure involved (1) finding a new formula for the embedding material, (2) devising a new method of making specimen supports, and (3) developing a method for removing the embedding material after the specimen has been microtomed. These techniques were then brought together to produce the ideal specimens for the HTCASH experiments. As an extra benefit, this procedure is also suitable for preparing specimens for ultrahigh resolution imaging experiments. The application of the new procedure in HTCASH experiments is illustrated through a high temperature reduction of a Co/SiO₂-923 catalyst.     

Preparation, Characterisation and Catalytic Behaviour of a New TeVMoO Crystalline Phase

TeM_xMo_1.7O mixed oxides (M = V and/or Nb; x = 0-1.7) have been prepared by calcination of the corresponding salts at 600 °C in an atmosphere of N₂. A new crystalline phase, with a Te/V/Mo atomic ratio of 1/0.2-1.5/1.7, has been isolated and characterised by XRD and IR spectroscopy. This phase is observed in the TeVMo or TeVNbMo mixed oxide but not in the TeNbMo mixed oxide. The new crystalline phase shows an XRD pattern similar to Sb₄Mo₁₀O₃₁ and probably corresponds to the M1 phase recently proposed by Aouine et al. (Chem. Commun. 1180, 2001) to be present in the active and selective MoVTeNbO catalysts. Although these catalysts present a very low activity in the propane oxidation, they are active and selective in the oxidation of propene to acrolein and/or acrylic acid. However, the product distribution depends on the catalyst composition. Acrolein or acrylic acid can be selectively obtained from propene on Nb-free or Nb-containing TeVMo catalysts, respectively. The presence of both V and Nb, in addition to Mo and Te, appears to be important in the formation of acrylic acid from propene.     

Influence of Edible Films upon the Moisture Loss and Microstructure of Dietetic Sucrose-Free Sponge Cakes during Storage

The kinetics of changes in the bound water content in dietetic sucrose-free sponge cakes (DC) during storage was investigated. The effect of edible films of polymyxan, pectin, xanthan, and carboxymethylcellulose upon this kinetics was also investigated. The quantitative changes in both states of water (slightly bound water and strongly bound water) were registered by combined dynamic analysis (thermogravimetry analysis, TGA, and differential thermal analysis, DTA). The moisture changes in DC crumb were analyzed by drying out to constant mass. The rate constants were determined according the equation q = q_oe^-kt. The values of rate constants 'k', in day^-1, concerning the different edible films were as follows: for crumb moisture is (8.00 ≤ k ≤ 12.47) × 10^-3, for bound water is (3.07 ≤ k_w ≤ 6.26) × 10^-2, for slightly bound water is (4.22 ≤ k₁ ≤ 8.49) × 10^-2 and for strongly bound water is (2.02 ≤ k₂ ≤ 5.62) × 10^-2 as compared to 18.53 × 10^-3, 7.16 × 10^-2, 9.04 × 10^-2, and 5.36 × 10^-2 in the uncovered DC, respectively. The best water-retaining effect in respect to crumb moisture during storage was ascertained in the use of polymyxan and xanthan films. The lowest rate constant values for bound water and its two states were measured for DC covered with pectin. The relation between the kinetics of both bound water states during storage and ageing of the crumb of DC covered with different edible films and the crumb microstructure was represented. By means of scanning electron microscope was read the smallest change in crumb microstructure of pectin-covered DC on the sixth day of storage.     

Influence of accelerated ageing on methacrylate‐based denture resins heterogeneity as viewed by ESR‐spin‐probe method

The electron‐spin‐resonance (ESR) spin‐probe method, was used to study the heterogeneity of denture resins based on poly(methyl methacrylate). Results for three resins processed by microwave energy, conventional curing and cold curing (depending on the curing procedure and exposed to ageing in various environmental conditions) were compared. All three cured resins were stored over the same time (1200 h) in distilled water at ambient temperature and in artificial saliva at 348 K. The temperature‐dependent ESR spectra of a spin probe dispersed in the denture resins are analyzed in terms of line‐shapes and line‐widths. The appearance of two spectral components was taken as an indication of resin heterogeneity. The results reveal that the cold‐cured resin has a lower local density in comparison with microwave and conventionally cured resin. The amount of residual monomer also contributes to the local motion of polymer segments. The change of denture resins exposed to ageing is influenced both by the structure of the original resin and the ageing conditions. Restricted motion of a spin probe incorporated into the acrylic resins exposed to accelerated ageing suggests additional crosslinking of polymer chains. The differences are observed for all the investigated resins, but the highest change is observed with the cold‐cured resin. The ESR results are accompanied by T_g and T_m measurements. Copyright © 2005 Society of Chemical Industry