Water-induced effects of hydrogen adsorption on Ru(001)

Adsorption and desorption of hydrogen and coadsorption of H₂ with H₂O and CO over Ru(00l) surface have been studied under UHV conditions using the technique of TDS. Surface hydrogen interacts with adsorbed water resulting in an additional desorption state at 510 K which is not easily displaced by CO, but the total number of adsorption sites for hydrogen adsorption is independent of the amount of H₂O predosed at room temperature. Hydrogen adsorption is blocked easily by CO dose (more than 0.5 L) or a small amount of O(a) formed from dissociative adsorption of water, and adsorbed hydrogen formed in the absence of significant water is easily displaced by CO dose at even room temperature.     

Fault identification for process monitoring using kernel principal component analysis

In this research, we develop a new fault identification method for kernel principal component analysis (kernel PCA). Although it has been proved that kernel PCA is superior to linear PCA for fault detection, the fault identification method theoretically derived from the kernel PCA has not been found anywhere. Using the gradient of kernel function, we define two new statistics which represent the contribution of each variable to the monitoring statistics, Hotelling's T²and squared prediction error (SPE) of kernel PCA, respectively. The proposed statistics which have similar concept to contributions in linear PCA are directly derived from the mathematical formulation of kernel PCA and thus they are straightforward to understand. The main contribution of this work is that we firstly suggest a fault identification method especially applicable to process monitoring using kernel PCA. To demonstrate the performance, the proposed method is applied to two simulated processes, one is a simple nonlinear process and the other is a non-isothermal CSTR process. The simulation results show that the proposed method effectively identifies the source of various types of faults.     

Harnessing the Melting Peculiarities of Ultra‐High Molecular Weight Polyethylene Fibers for the Processing of Compacted Fiber Composites

Summary: Compacted fiber composites offer unique properties due to their lack of an extraneous matrix. The conditions of processing ultra‐high molecular weight polyethylene (UHMWPE) fibers were simulated in a heated pressure cell. In situ X‐ray diffraction measurements were used to follow the relevant transitions and the changes in the degree of crystallinity during melting and crystallization. The results strongly support the suggestion that the hexagonal crystal phase, in which the chain conformation is extremely mobile on the segmental level, constitutes the physical basis of compaction technologies for processing UHMWPE fibers into a single‐polymer composite. This report suggests that using a pseudo‐phase diagram outlining the occurrence of different phases during slow heating and the degree of crystallinity can provide valuable insight into the technological parameters relevant for optimal processing conditions.

Degree of crystallinity as a function of pressure and temperature in a region relevant to compaction processes.     

硝化法制备对氨基间硝基苯磺酸的研究

以对氨基苯磺酸为起始原料 ,经过乙酰化、硝化、水解三步来制备标题物。通过正交试验找出了酰化的最佳反应条件为 :对氨基苯磺酸与乙酐的摩尔比为 1∶1.0 5 ,反应总时间为 1.5h ,反应温度为 2 5℃ ,酰化介质为酰化反应前用碳酸钠及水将对氨基苯磺酸完全溶解 ,使混合液 pH值为 5～ 6 ,反应过程中不再补加碳酸钠 ,其酰化转化率可达 99.6 % ,酰化产物的固体收率可达 96 .0 % ;硝化反应的最佳条件为 :硝化剂用 90 .2 %的硝酸 ,对乙酰氨基苯磺酸与硝化剂的摩尔比为 1∶1.0 5 ,反应温度为 10℃ ,浓硫酸与对乙酰氨基苯磺酸的摩尔比为 8.3∶1,其硝化转化率可达 96 .0 % ,硝化反应的选择性好 ,对氨基邻硝基苯磺酸的量不到 1.0 %。     

Non-isothermal laminar pipe flow — II. Experimental

In a previous article [1] theoretical predictions of velocity distributions, pressure drops and mean Nusselt-numbers are given for non-isothermal pipe flow of power-law fluids having a temperature dependent consistency-index. In the present investigation these solutions are checked for Newtonian fluids with extensive experimental data.A flow visualization technique was used for measuring the non-isothermal, laminar velocity profiles of glycerol in a round tube. Furthermore, accurate pressure drop measurements were carried out for non-isothermal tube flow of a viscous. Newtonian liquid. Finally logarithmic mean heat transfer coefficients were measured in laminar flow heat transfer.The experimental velocity profiles, pressure drops and heat transfer coefficients show a good agreement with those predicted theoretically.     

Flaw-Tolerance and R-Curve Behavior of Liquid-Phase-Sintered Silicon Carbides with Different Microstructures

β-SiC powder containing 6 wt% A1₂O₃ and 4 wt% Y₂O₃ as sintering additives was pressureless sintered at 2000°C for 1 h (AYE-SiC) and 3 h (AYP-SiC). AYE-SiC consisted of an equiaxed grain structure and AYP-SiC exhibited a micro-structure with platelike grains as a result of grain growth related to β→α phase transformation during sintering, R -curve behavior and flaw tolerance for these silicon carbides were evaluated by the indentation-strength technique. For comparison, the R -curve behavior of conventional sintered, boron- and carbon-doped SiC (SS-SiC) was evaluated. AYE-SiC and AYP-SiC exhibited rising R -curve behavior with toughening exponents of m = 0.042 and m = 0.135, respectively. AYP-SiC exhibited better flaw tolerance and more sharply rising R -curve behavior than AYE-SiC. The more sharply rising R -curve behavior and the better flaw tolerance of AYP-SiC were attributed mainly to grain bridging of crack faces by platelike grains. Because of the high degree of transgranular fracture, SS-SiC exhibited a flat R -curve despite a microstructural feature with platelike grains.     

Thermal decomposition behavior of γ‐irradiated poly(vinyl acetate)/poly(methyl methacrylate) miscible blends

Miscible polymer blends based on various ratios of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were prepared in film form by the solution casting technique using benzene as a common solvent. The thermal decomposition behavior of these blends and their individual homopolymers before and after γ‐irradiation at various doses (50–250 kGy) was investigated. The thermogravimetric analysis technique was utilized to determine the temperatures at which the maximum value of the rate of reaction (T_max) occurs and the kinetic parameters of the thermal decomposition. The rate of reaction curves of the individual homopolymers or their blends before or after γ‐ irradiation displayed similar trends in which the T_max corresponding to all polymers was found to exist in the same position but with different values. These findings and the visual observations of the blend solutions and the transparency of the films gave support to the complete miscibility of these blends. Three transitions were observed along the reaction rate versus temperature curves; the first was around 100–200°C with no defined T_max, which may arise from the evaporation of the solvent. The second T_max was in the 340–380°C range, which depended on the polymer blend and the γ‐irradiation condition. A third transition was seen in the rate of reaction curves only for pure PVAc and its blends with PMMA with ratios up to 50%, regardless of γ‐ irradiation. We concluded that γ‐irradiation improved the thermal stability of PVAc/PMMA blends, even though the PMMA polymer was degradable by γ irradiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1773–1780, 2006     

Poly(trimethylene terephthalate) nanocomposite fibers comprising different organoclays: Thermomechanical properties and morphology

Poly(trimethylene terephthalate) (PTT) nano composites were synthesized by in situ polymerization at high temperature with two thermally stable organoclays: 1,2‐dimethylhexadecylimidazolium‐montmorillonite (IMD‐MMT) and dodecyltriphenyl phosphonium‐MMT (C₁₂PPh‐MMT). PTT hybrid fibers with various organoclay contents were melt‐spun at various draw ratios (DRs) to produce monofilaments. The thermomechanical properties and morphologies of the PTT hybrid fibers were characterized using differential scanning calorimetry, thermogravimetric analysis, wide‐angle X‐ray diffraction, electron microscopy, and mechanical tensile properties analysis. The nanostructure of the hybrid fibers was observed by both scanning and transmission electron microscopy, which showed that the clay layers were well dispersed into the matrix polymer, although some clusters or agglomerated particles were also detected. Unlike the hybrids containing IMD‐MMT, the clay layers of the C₁₂PPh‐MMT hybrid fiber were more dispersed into the matrix polymer. The thermal stability and tensile properties of the hybrid fibers increased with increasing clay content for DR = 1. However, as DR increased from 1 to 9 the ultimate strength and initial modulus of the hybrid fibers with IMD‐MMT increased slightly whereas those of C₁₂PPh‐MMT hybrid fibers decreased slightly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4535–4545, 2006     

Contraction stress build‐up of anisotropic conductive films (ACFs) for flip‐chip interconnection: Effect of thermal and mechanical properties of ACFs

The important mechanical mechanism for the electrical conduction of anisotropic conductive films (ACFs) is the joint clamping force after the curing and cooling processes of ACFs. In this study, the mechanism of shrinkage and contraction stress and the relationship between these mechanisms and the thermomechanical properties of ACFs were investigated in detail. Both thickness shrinkages and modulus changes of four kinds of ACFs with different thermomechanical properties were experimentally investigated with thermomechanical and dynamic mechanical analysis. Based on the incremental approach to linear elasticity, contraction stresses of ACFs developed along the thickness direction were estimated. Contraction stresses in ACFs were found to be significantly developed by the cooling process from the glass‐transition temperature to room temperature. Moreover, electrical characteristics of ACF contact during the cooling process indicate that the electrical conduction of ACF joint is robustly maintained by substantial contraction stress below T_g. The increasing rate of contraction stresses below T_g was strongly dependent on both thermal expansion coefficient (CTE) and elastic modulus (E) of ACFs. A linear relationship between the experimental increasing rate and E × CTE reveals that the build‐up behavior of contraction stress is closely correlated with the ACF material properties: thermal expansion coefficient, glassy modulus, and T_g. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2634–2641, 2004     

Morphology and activity of nanosized NdCl3 catalyst for 1,3‐butadiene polymerization

The binary lanthanide catalyst for 1,3‐butadiene was invented for 40 years ago. However, it has not been employed in commercial application due to its poor solubility and low activity. Nanosized neodymium chloride (NdCl₃) was prepared in tetrahydrofuran (THF) medium through dissolution, chelation, and colloidal formation steps. Anhydrous NdCl₃ was dissolved in THF, and ca. 1.5 THF molecules were coordinated. In the colloidal formation step, THF was slowly replaced with the addition of cyclohexane, and pale blue nuclei, nanosize below 200 nm, were formed. The structural studies for NdCl₃ · xTHF using X‐ray powder diffraction (XRD) and scanning electron microscope (SEM) indicate that high ordered crystallinity is decreased with reduced particle size from trigonal prismatic to porous sphere structure. Nano NdCl₃, obtained as colloidal state in cyclohexane, was activated with Al(iBu)₃ and Al(iBu)₂H at room temperature and employed for 1,3‐butadiene solution polymerization. The nanosized Nd catalysts showed high activity (1.0 ～ 1.3 × 10⁵ g/Nd mol · h), which is comparable to that of the ternary neodymium catalyst Nd(neodecanoate)₃/AlEt₂Cl/Al(iBu)₃. The microstructures of polybutadiene, cis, trans, and vinyl, are about 96.0, 3.5, and 0.5%, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1279–1283, 2005