Adsorption and desorption kinetics of hydrocarbons in FCC catalysts studied using a tapered element oscillating microbalance (TEOM). Part 2: numerical simulations

The factors affecting the adsorption and desorption kinetics in a TEOM are reviewed in detail with particular attention given to the assumptions required to obtain physical transport parameters from the data. Two models are presented to simulate TEOM adsorption data in the case that concentration differences down the catalyst bed can be neglected, as is appropriate when the amount of catalyst used is small, the carrier gas flowrate is large, and/or the adsorbate partial pressure is low. In the first model, the effective diffusion coefficient, D_e, is taken to be constant. In the second model, the effective diffusion coefficient is assumed to obey the Darken equation, D_e=D₀/(1−θ). The TEOM results obtained on n-hexane, n heptane, n-octane, toluene and p-xylene on a commercial FCC catalyst and on pure rare-earth exchanged zeolite Y under non-reacting conditions (373-) are analysed in detail. It is found that intracrystalline diffusion is not the limiting factor affecting the overall rates of adsorption and desorption for the systems studied. Instead, it is the transport of molecules between the adsorbed and vapour phases at the edge of zeolite crystallites that is the limiting transport step affecting the overall kinetics. For the FCC catalyst, the limiting step is the transport of molecules at the zeolite-matrix interface rather than, say, the matrix-vapour interface. Local rate constants for the desorption of the hydrocarbons at the rate-controlling interface have been obtained.     

Damping of vinyl acetate–n‐butyl acrylate copolymers

A photopolymerization process at room temperature was devised to copolymerize vinyl acetate (VAc) and n‐butyl acrylate (BA) mainly to prepare rubber‐like damping sheet bearing pressure‐sensitive adhesive property in this study. The investigations using both the differential scanning calorimeter and rheometric dynamic analysis show the existence of two glass transition temperatures for each copolymer. The scanning electron microscopic pictures reveal that the degree of microphase separation increases with increasing annealing time at 70°C. It was suggested that the rubbery domain (formed by the PBA blocks) disperses in the glassy domain (constituted by the PVAc blocks), making an effective damping entity. Excellent damping was observed for the copolymer samples, with the tanδ peak values as high as 1.76–1.80 at a certain temperature range and with tanδ> 0.3 at quite wide temperature ranges. In addition, the copolymers containing more VAc tend to have the higher damping. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1396–1403, 2004     

一种支持细粒度并行的SDN虚拟化编程框架

软件定义网络(software defined network,简称SDN)通过集中式的控制器提高了网络的可编程性,成为近年来网络领域非常热门的话题。以Openflow网络为代表的软件定义网络将逻辑控制与数据转发相隔离,为网络虚拟化技术提供了良好的平台。集中式的抽象与控制使得SDN虚拟化框架的处理效率成为主要瓶颈。现有的SDN虚拟化框架由于缺乏对细粒度并行的支持,为编程人员充分利用多核/众核资源、控制更大规模的网络带来了极大的挑战。为了提高SDN虚拟化框架的处理效率,提出一种新的SDN虚拟化编程框架,通过新颖的API和运行时,在框架内部支持细粒度的并行处理。该框架通过对网络中流和网络资源进行抽象,使开发人员可以直接通过划分流空间来定义不同的虚拟网络,利用无锁的编程方式对共享的网络资源和流进行操作。实验结果表明,该框架在逻辑控制的执行效率方面具有良好的可扩展性,可以创建出更大规模的虚拟网络,并对其进行更为复杂的控制。     

Enhanced corrosion prevention effect of polysulfone–clay nanocomposite materials prepared by solution dispersion

A series of polymer–clay nanocomposite (PCN) materials containing polysulfone (PSF) and layered MMT clay were successfully prepared by effectively dispersing inorganic nanolayers of MMT clay in an organic PSF matrix via a solution dispersion technique. The synthesized PCN materials were subsequently investigated with a series of characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The prepared PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in corrosion prevention to those of bulk PSF, based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) in a 5 wt % aqueous NaCl electrolyte. The effects of material composition on the molecular barrier, mechanical strength and optical clarity of PSF and PCN materials, in the form of membranes, was also studied by molecular permeability analysis (GPA), dynamic mechanical analysis (DMA) and UV‐Visible transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 631–637, 2004     

Thermal properties measurements of renatured gelatin using conventional and temperature modulated differential scanning calorimetry

The thermal properties of amorphous gelatin films and gelatin films with renatured structural order were measured by using conventional and temperature modulated differential scanning calorimetry (DSC). Different amounts of gelatin structural order associated with a melting enthalpic change in the DSC measurement were prepared based on different gelatin drying conditions. Two consecutive heating and cooling DSC measurements on the gelatin films showed that there was no change in the glass‐transition temperature (T_g) for the amorphous gelatin but there was a decrease in the T_g for the structural gelatin on the second DSC scan. This decrease was attributed to the plasticizing effect from the release of originally hydrogen‐bonded water associated with the structural gelatin. In addition, a reversing endotherm observed upon melting of the structural gelatin during a temperature modulated DSC measurement indicated that the transition of bound water to free water occurred as the partial triple‐helix gelatin melted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1795–1801, 2006     

Micromechanical properties on the surface of PVC/SBR blends spatially resolved by a nanoindentation technique

The microhardness and micromodulus on the surface of poly(vinyl chloride) (PVC)/styrene‐butadiene rubber (SBR) blends were determined using a nanoindenter. A flat surface was obtained by microtoming the sample at ?100°C in liquid nitrogen. Dozens of indents along a line with a spatial interval of 0.5 μm were performed. From the loading and unloading curves of each indentation, the stiffnesses of the unloading curve and the contact area between the sample and the indenter were evaluated, and the local modulus and hardness were calculated. Profiles of the local hardness and modulus were obtained from the lines of indents. Pure PVC and a miscible PVC/acrylonitrile‐butadiene rubber (NBR) (40/10) blend showed constant modulus and hardness values. In the case of an immiscible PVC/SBR (50/50) blend, which has a morphology of elongated PVC droplets in the SBR matrix, the hardness and modulus profiles showed regions of the different phases. At the interface between the SBR and PVC phases, a step change in the modulus and hardness profiles was observed. The force required to deform the material at the same displacement increased systematically across the interface from the SBR to the PVC phase because of the increasing contribution of the PVC phase. Polym. Eng. Sci. 44:609–614, 2004. © 2004 Society of Plastics Engineers.     

基于二维广义Logistic映射的图像加密算法

提出一个基于广义Logistic方程构造的二维混沌映射,采用Feigenbaum常数、相图、分岔图分析的方法,研究该混沌映射的非线性动态特性;然后利用该方程生成混沌序列,将混沌序列进行优化改进,生成密钥序列;最后采用输出反馈的加密方式,改变图像的像素值,达到加密的目的。实验仿真表明,该加密算法对密钥非常敏感,有效地提高了抵御选择明文攻击的能力,密文图像信息熵为7.996 94,非常接近理想值8。加密图像像素值具有类随机均匀分布特性,加密图像和明文图像之间的相关性非常接近于0,相邻像素具有零相关特性,而且密钥空间达到299比特。加密方法大大改变了明文图像的像素值,使得密文能够抵御统计攻击。     

丙烯酸酯类聚合物乳液法修饰纳米SiO2粒子研究

采用带有羧基活性官能团的丙烯酸酯类聚合物乳液对纳米SiO2进行表面修饰.并用透射电镜、红外、热失重、接触角、粒径分析对处理效果进行了表征.结果表明所制备的含羧基基团的共聚物乳胶粒子在机械搅拌作用下,与粒径为15～20nm左右的无机SiO2纳米粒子的作用过程中,实现了对SiO2表面修饰和分散的效果.当复合温度(65℃)高于改性用聚合物的Tg(45℃)时,柔软的聚合物乳胶粒子变形、黏附在SiO2纳米粒子周围,并通过羧基的化学吸附作用最终实现对SiO2粒子的包覆;当复合温度(25℃)低于改性用聚合物的Tg(45℃)时,乳胶粒子仍保持其基本形状,SiO2粒子黏附在乳胶粒子周围.     

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.     

电磁振动给料机内颗粒物料的定量加料特性

为提高电磁振动给料机定量加料性能，采用离散单元法建立振幅和闸门开度双重控制参数下电振机的计算模型，从颗粒群运动状态和力学特性的角度研究控制参数对加料流量快速性和稳定性的影响，并通过实验验证了计算模型的可靠性。结果表明：加料流量均值随振幅、闸门开度的增加分别呈二次曲线和线性增长，且料层厚度的变化引起加料速度的改变使得振幅与闸门开度间存在交互因子；提升振幅，闸门内侧外层颗粒紊流区域增加，闸门口弧状流流速加快；减小振幅至2.0mm或增大闸门开度至16mm，都能有效降低颗粒与颗粒、颗粒与槽面之间法向、切向上的平均接触力和最大接触力，颗粒群流动密实性增加，颗粒体系受力更为均衡，流动一致性更好，进而使加料流量变异系数减小，定量加料快速性和稳定性综合性能提高。