Polyimide foams with ultralow dielectric constants

To explore ultralow dielectric constant polyimide, the crosslinked polyimide foams (PIFs) were prepared from 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), 4,4′‐oxydianiline (ODA), and 2,4,6‐triaminopyrimidine (TAP) via a poly(ester–amine salt) (PEAS) process. FTIR measurements indicated that TAP did not yield a negative effect on imidization of PEAS precursors. SEM measurement revealed the homogeneous cell structure. Through using TAP as a crosslinking monomer, the mechanical properties of PIFs could be improved in comparison with uncrosslinked BTDA/ODA based PIF. The crosslinked PIFs still exhibited excellent thermal stability with 5% weight loss temperatures higher than 520°C. In the field with frequency higher than 100 Hz, the dielectric constants of the obtained PIFs ranged from 1.77 to 2.4, and the dielectric losses were smaller than 3 × 10^?2 at 25–150°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1734–1740, 2006     

Effect of incipient removal of hydrogen through palladium membrane on the conversion of methane steam reforming: Experimental and modeling

This paper presents a mathematical model based on the reaction rate expressions to describe the displacement of methane conversion in the steam reforming. The effect of several parameters including weight hourly space velocity (WHSV), load-to-surface ratio, reaction pressure, hydrogen partial pressure in permeate side and reaction temperature were investigated. Simulation and experimental results showed that a conversion higher than 80% could be achieved in a palladium membrane reactor at reaction temperature of 500 °C relative to 850 °C in a conventional fixed bed reactor (FBR). Besides, the yield of CO (<2%) in membrane reactor was much lower than that (>50%) in the FBR, which indicated the significant depression of CO production in use of membrane reactor.     

Crystallization and morphological features of syndiotactic polystyrene induced from glassy state

Spherulitic growth rates and microstructure of syndiotactic polystyrene (sPS) cold-crystallized isothermally at various temperatures, T_c (115–240 °C), have been investigated by small-angle light scattering (SALS), optical microscopy and transmission electron microscopy. The derived activation energy for sPS chain mobility at the crystal growing front is 5.4 kJ/mol, which is relatively lower than that of isotactic polystyrene, 6.5 kJ/mol. In addition, the Hv scattering invariant (Q_Hv) measured by SALS on the crystallized sPS samples displays a pronounced minimum at 150 °C. Despite a wide range of T_c used, however, the sample crystallinity estimated by Fourier transformation infrared spectroscopy remains unchanged. Prior to crystallization, the correlation length derived from the Vv patterns on the basis of Debye–Bueche model is ca. 1.13 μm regardless of T_c used. Interconnected domains with a width of ca. 1.8±0.5 μm are readily observed in all the crystallized samples under phase contrast microscopy and the phase-separated structure is conserved within sPS spherulites whose diameters are increased with increasing T_c.

Based on the above facts, we conclude that the presence of a Q_Hv minimum is ascribed to the resultant events of the two competitive transitions i.e. liquid–solid crystallization, and liquid–liquid demixing resulting from the spinodal decomposition (SD). At lower T_c, the unstable SD transition overwhelms the crystallization. Despite the low chain mobility, the coarsening process driven by the interfacial energies has reached a certain level before crystalline nucleation takes place. At higher T_c, on the other hand, cold crystallization becomes the dominant process due to the enhanced chain mobility, leading to the suppression of ongoing SD coarsening process. At an intermediate T_c range, comparable competition of the phase separation and crystallization prohibits the development of ordered symmetry within spherulites, giving the presence of Q_Hv minimum.     

Identification of organochlorines and organobromines in coals

Four Chinese bituminous coals were extracted with CS₂, n-hexane, benzene, methanol, acetone, tetrahydrofuran (THF) and THF/methanol (1: 3 vol/vol) mixed solvent sequentially. The resulting 28 extracts were analyzed with GC/MS. Six organochlorines (OCs) and two organobromines (OBs) were identified in eight extracts from the coals. Our experiments provide, for the first time, the information on the molecular structure of OCs and OBs in coals.     

浅析计算机网络信息安全问题及对策

随着IT应用在生活中的日益普及,互联网已经覆盖了175个国家和地区的数亿台计算机,用户数量超过lO亿计算机技术广泛应用于各行各业,向着深度和广度不断地发展,构成了各自的网络,为资源共享、信息交换和分布处理提供了良好的环境,企业上网、政府上网、学校用网以及网上购物等计算机的应用表现了一个网络化的社会已经呈现在我们的面前、因此,在增加网络实用性的同时,系统的脆弱性不可避免的显露了出来,使计算机网络面临严重的安全问题。!     

LIQUID PHASE TRANSPORT PROPERTIES IN A HIGH PRESSURE PACKED COLUMN

A mathematical model of fluid flow and mass transfer in a packed bed was derived and used to evaluate the liquid phase axial dispersion and mass transfer coefficients under high pressure conditions. The least-squares method was used to evaluate the rate parameters from experimental breakthrough curves, and the agreement between the concentration curves predicted from rate parameters and those measured experimentally was good. Experiments were performed at 20 and 200°C with water as a solvent and nonporous soda-lime glass beads as packing. Although the axial dispersion coefficient was independent of temperature and pressure, the mass transport parameters were found to be pressure dependent.     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

The viscoelastic properties of rubber–resin blends. III. The effect of resin concentration

The viscoelastic properties of a rubber–resin blend, which influences performance of the blend as a pressure-sensitive adhesive, depend upon the structure of the resin as well as its molecular weight. The effect of the concentration of a compatible resin in the blend was examined using a mechanical spectrometer. Four types of resins were used. These are the rosin esters, polyterpenes, pure monomer resins such as polystyrene and poly(vinyl cyclohexane), and petroleum stream resins. Each was examined in blends with both natural rubber and styrene–butadiene rubber over a range of concentrations. It is shown that the temperature of the tan δ peak for compatible systems can be predicted by the Fox equation, T = W₁T + W₂T, where W₁ and W₂ are the weight fractions of the resin and rubber, respectively, and the T_g's are the tan δ peak temperatures in K. The plateau modulus G for a blend can be identified as the G′ value in the rubbery plateau at the point where tan δ is at a minimum. The relationship between G and G, the plateau modulus for the undiluted elastomer, is shown to be proportional to the volume fraction of the elastomer raised to the 2.3–2.4 power for natural rubber with six different compatible resins. The exponent for styrene–butadiene rubber is 2.5–2.6 with four different resins. Using these relationships, both the tan δ peak temperature and plateau modulus can be predicted for a rubber–resin system from data on the unmodified elastomer and on one typical rubber–resin blend.     

Low-temperature catalytic combustion of methane over MnO x –CeO2 mixed oxide catalysts: Effect of preparation method

The effect of preparation method on MnO _x –CeO₂ mixed oxide catalysts for methane combustion at low temperature was investigated by means of BET, XRD, XPS, H₂-TPR techniques and methane oxidation reaction. The catalysts were prepared by the conventional coprecipitation, plasma and modified coprecipitation methods, respectively. It was found that the catalyst prepared by modified coprecipitation was the most active, over which methane conversion reached 90% at a temperature as low as 390 °C. The XRD results showed the preparation methods had no effect on the solid solution structure of MnO _x –CeO₂ catalysts. More Mn⁴⁺ and richer lattice oxygen were found on the surface of the modified coprecipitation prepared catalyst with the help of XPS analysis, and its reduction and BET surface area were remarkably promoted. These factors could be responsible for its higher activity for methane combustion at low temperature.