Effect of restrictive diffusion on hydrodesulfurization of heavy residue oils over CoMo/Al2O3

The effect of the ratio of reactant molecular diameter to catalyst pore diameter (λ) on the restrictive diffusion under hydrodesulfurization (HDS) reactions of heavy residue oils over CoMo/Al₂O₃ catalysts was investigated. A series of Al₂O₃ with various pore structures were used as supports of CoMo sulfide. The HDS reaction was carried out in a semi-batch Carberry type reactor at 648 K and 10.3 MPa. Two empirical correlations for restrictive diffusion under HDS reaction conditions were developed depending on the value of λ. The results showed that the restrictive diffusion effect under HDS reaction conditions is severe for the lower values of λ. However, this effect seems not prominent for higher values of λ. The order of the magnitude of the effective diffusivity was in the range of 10^?6-10^?7 cm²/s for the sulfur-containing compounds of residue oil in CoMo/Al₂O₃ catalysts at 648 K.     

吖啶橙受溶液pH和浓度变化的光谱研究

利用荧光光谱分析仪研究吖啶橙受溶液pH和浓度变化的吸收光谱和荧光光谱的变化。实验表明,当改变吖啶橙溶液pH和浓度时,它的吸收光谱和荧光光谱发生位移。吖啶橙为1×10-6mol/L时,不同pH的吖啶橙溶液均在(490±3)nm出现一个强吸收峰,pH=6.5,吸收光谱的λm ax=430 nm,发生蓝移;而荧光光谱的λm ax随pH增大发生红移,荧光强度减弱。在浓吖啶橙溶液中,不同pH的吖啶橙溶液的吸收光谱的形状基本相同,出现两个吸收峰,λm ax1分别为(455±3)nm和(430±3)nm,λm ax2分别为(505±4)nm和(510±2)nm,吸收光谱红移;荧光光谱的λm ax均为(535±2)nm,荧光强度荧光很弱。pH相同或相近时,吖啶橙溶液的吸收光谱蓝移和荧光光谱红移,浓度越大,荧光强度越弱。还探讨了吖啶橙在水溶液中的赋存状态,结果表明,在稀溶液中,吖啶橙主要以单体的形式存在;在高浓度吖啶橙溶液中则以吖啶橙单体、二聚体,甚至多聚体形式存在。这说明溶液pH主要影响到吖啶橙分子基态的质子化和氢键的形成能力,使得分子的基态与激发态之间的能量间隔发生了变化,吖啶橙被质子化,则引起发光光谱向短波方向移动,而离解作用,则引起发光光谱向长波方向移动;吖啶橙浓度变化影响吖啶橙在水溶液赋存状态,引起吸收光谱向短波方向移动或向长波方向移动。     

Magnetic Resonance Imaging Correlates of White Matter Gliosis and Injury in Preterm Fetal Sheep Exposed to Progressive Systemic Inflammation

Progressive fetal infection/inflammation is strongly associated with neural injury after preterm birth. We aimed to test the hypotheses that progressively developing fetal inflammation leads to neuroinflammation and impaired white matter development and that the histopathological changes can be detected using high-field diffusion tensor magnetic resonance imaging (MRI). Chronically instrumented preterm fetal sheep at 0.7 of gestation were randomly assigned to receive intravenous saline (control; n = 6) or a progressive infusion of lipopolysaccharide (LPS, 200 ng intravenous over 24 h then doubled every 24 h for 5 days to induce fetal inflammation, n = 7). Sheep were killed 10 days after starting the infusions, for histology and high-field diffusion tensor MRI. Progressive LPS infusion was associated with increased circulating interleukin (IL)-6 concentrations and moderate increases in carotid artery perfusion and the frequency of electroencephalogram (EEG) activity (p < 0.05 vs. control). In the periventricular white matter, fractional anisotropy (FA) was increased, and orientation dispersion index (ODI) was reduced (p < 0.05 vs. control for both). Histologically, in the same brain region, LPS infusion increased microglial activation and astrocyte numbers and reduced the total number of oligodendrocytes with no change in myelination or numbers of immature/mature oligodendrocytes. Numbers of astrocytes in the periventricular white matter were correlated with increased FA and reduced ODI signal intensities. Astrocyte coherence was associated with increased FA. Moderate astrogliosis, but not loss of total oligodendrocytes, after progressive fetal inflammation can be detected with high-field diffusion tensor MRI.     

Iodine reaction of vinyl acetate – vinyl propionate copolymers I. Molar absorption coefficients of the copolymer-iodine complexes

Poly(vinyl propionate) was found to form a weak iodine-complex in an aqueous solution of potassium iodide. The complex was colorless under usual conditions differing from the poly(vinyl acetate)iodine complex which had a red-violet colour. Random and block copolymers of vinyl acetate (VAc) and vinyl propionate (VPr) also formed colored iodine complexes. The maximum absorption wave-length (λ_max) of the complex shifted to shorter wave-lengths with decrease in the VAc-fraction of copolymers and to longer wave-lengths with increase in the concentration of added iodine. This shift of λ_max was discussed in connection with the chain length of the polyiodine in the complex. The molar absorption coefficient (?_max) of the complex (defined as absorbance per bound iodine molecule) depended remarkably upon the polymer composition. The dependence of ?_max upon the copolymer composition could be explained by the assumption that the complex consists of two different parts, a strongly colored and a weakly colored one.     

Diffusion behavior of poly(ethylene imine) into keratin fibers using microspectrophotometry

In order to investigate the diffusion behavior of poly(ethylene imine) (PEI) into keratin fibers, cross‐sectional samples of bleached white human hair treated with PEI were prepared. We were successful in developing a method for analyzing the diffusion behavior of PEI into human hair, which to our knowledge is a first. The diffusion pattern of PEI into human hair, which cannot be determined by optical microscopy, can be determined by our method. After the treatment, the cross‐sectioned hair samples were dyed with Orange II and the cross‐sectional intensity scans were measured at a wavelength of 487 nm (λ_max of Orange II) with a microspectrophotometer. In our method, the diffusion pattern of PEI at pH 11.1 showed Fickian type characteristics. This suggests that the diffusion coefficient of PEI is essentially independent of the PEI concentration. By calculating the diffusion coefficient from the PEI concentration profile, the diffusion coefficient of PEI [number‐average molecular weight (M_n) = 300 and 600] into the bleached human hair was found to be on the order of 10^?10 cm²/s. In addition, the diffusion coefficient of PEI (M_n = 600) with urea added increased twofold in comparison with that of PEI without urea added. This experiment demonstrated that urea acts as a penetration accelerator for PEI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 65–71, 2005     

Induced anisotropy of thermal conductivity of polymer solids under large strains

A simple analytical form of induced anisotropy of heat conductivity k_ij(λ₁,λ₂λ₃,T) of initially isotropic polymer solids results from employing the simplified theory of the three-chain model of the non-Gaussian network. The analytical form appears to be valid up to a stretch ratio of λ = 2.65, which is the limit of existing experimental data. The effect of induced anisotropy on the temperature distribution, due to the large deformations, is illustrated for a highly expanded spherical shell and a cylindrical tube under a steady-state heat flow using the derived analytical form of the strain-dependent heat conductivity.     

Estimation on thermal conductivities of filled polymers

A new thermal conduction model is proposed for filled polymer with particles, and predicted values by the new model are compared with experimental data. The model is fundamentally based on a generalization of parallel and series conduction models of composite, and further modified in taking into account that a random dispersion system is isotropic in thermal conduction. The following equation is derived from the new model; log λ = V · C₂ · log λ₂ + (1 ? V) · log(C₁ · λ₁). Therefore, when thermal conductivities of polymer and particles (λ₁, λ₂) are known, thermal conductivity of the filled polymer (λ) can be estimated by the equation, with any volume content of particles (V). The new model was proved by experimental data for filled polyethylene, polystyrene and polyamide with graphite, copper, or Al₂O₃.     

Temperature dependence of the thermal conductivity and thermal diffusivity of treated oil‐palm‐fiber‐reinforced phenolformaldehyde composites

The effective thermal conductivity (λ_e) and effective thermal diffusivity (χ_e) of oil‐palm‐fiber‐reinforced treated composites were measured simultaneously with the transient plane source technique from 50 to 110°C. The fibers of the composites were treated with sodium hydroxide alkali, silanol, and acetic acid. The experimental results for the different treated composites showed that there were variations in λ_e and χ_e over this temperature range. However, the maximum values of λ_e and χ_e were observed at 90°C, in the vicinity of the glass‐transition temperatures of these composites. An effort was also made to predict the temperature dependence of λ_e and χ_e through the development of an empirical model. The theoretically predicted values of λ_e and χ_e for these composites were in excellent agreement with the experimental results over the entire range of investigated temperatures. Sudden increases in λ_e and χ_e in the glass‐transition region of these composites were indicative of the fact that the crosslinking density decreased and was at a minimum at the temperature at which λ_e and χ_e showed their maxima. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3458–3463, 2003     

Thermal conductivity of a polymer composite filled with mixtures of particles

A new thermal conduction model is proposed for a polymer system filled with a mixture of several types of particles. Predicted values by the new model are compared with experimental data. The model is derived by extending a model that was previously proposed for a two-phase system. The following equation is derived from the new model: log λ = V · (X₂ · C₂ · log λ₂ + X₃ · C₃ · log λ₃ + (1 ? V) log (C₁ · λ₁. When the thermal conductivities of polymer and particles (λ₁, λ₂, λ₃, …) and a mixing ratio of particles (X₂, X₃, …) are known, thermal conductivity of the filled polymer (λ) with several types of particles can be estimated from the equation, with any volume content of particles (V). Furthermore, from each polymer–filler composite (two-phase system) data, the thermal conductivity of a composite filled with different filler particles can be estimated.     

Multivariate Genetic Structure of Externalizing Behavior and Structural Brain Development in a Longitudinal Adolescent Twin Sample

Externalizing behavior in its more extreme form is often considered a problem to the individual, their families, teachers, and society as a whole. Several brain structures have been linked to externalizing behavior and such associations may arise if the (co)development of externalizing behavior and brain structures share the same genetic and/or environmental factor(s). We assessed externalizing behavior with the Child Behavior Checklist and Youth Self Report, and the brain volumes and white matter integrity (fractional anisotropy [FA] and mean diffusivity [MD]) with magnetic resonance imaging in the BrainSCALE cohort, which consisted of twins and their older siblings from 112 families measured longitudinally at ages 10, 13, and 18 years for the twins. Genetic covariance modeling based on the classical twin design, extended to also include siblings of twins, showed that genes influence externalizing behavior and changes therein (h² up to 88%). More pronounced externalizing behavior was associated with higher FA (observed correlation r_ph up to +0.20) and lower MD (r_ph up to −0.20), with sizeable genetic correlations (FA r_a up to +0.42; MD r_a up to −0.33). The cortical gray matter (CGM; r_ph up to −0.20) and cerebral white matter (CWM; r_ph up to +0.20) volume were phenotypically but not genetically associated with externalizing behavior. These results suggest a potential mediating role for global brain structures in the display of externalizing behavior during adolescence that are both partially explained by the influence of the same genetic factor.     

ION EXCHANGE CHARACTERISTICS OP A NEW MANGANESE OXIDE : SELF-DIFFUSION AND TRACE COMPONENT DIFFUSION

The kinetics of self-diffusion and trace component diffusion of Na+ and Cs+ in a new manganese oxide, having the chemical formula Na₄Mn₁₇O₂₇.13 H₂O, was studied. A uniform diffusion process was observed in all cases. The diffusion coefficients increase with particle size at the relatively large sizes, which is attributed to the conglomeration of small particles. The self-diffusion coefficient of Na+ is lower than that of Cs+ whereas the trace diffusion coefficients follow a reverse trend. Besides, the self-diffusion coefficients are not equal to the trace diffusion ones and opposite differences are observed for Na+ and Cs+. These results were tentatively explained in terms of the oxide water content and ion hydration.     

Generalized Diffusion Tensor Imaging (GDTI): A Method for Characterizing and Imaging Diffusion Anisotropy Caused by Non-Gaussian Diffusion

For non-Gaussian distributed random displacement, which is common in restricted diffusion, a second-order diffusion tensor is incapable of fully characterizing the diffusion process. The insufficiency of a second-order tensor is evident in the limited capability of diffusion tensor imaging (DTI) in resolving multiple fiber orientations within one voxel of human white matter. A generalized diffusion tensor imaging (GDTI) method was recently proposed to solve this problem by generalizing Fick's law to a higher-order partial differential equation (PDE). The relationship between the higher-order tensor coefficients of the PDE and the higher-order cumulants of the random displacement can be derived. The statistical property of the diffusion process was fully characterized via the higher-order tensor coefficients by reconstructing the probability density function (PDF) of the molecular random displacement. Those higher-order tensor coefficients can be measured using conventional diffusion-weighted imaging or spectroscopy techniques. Simulations demonstrated that this method was capable of quantitatively characterizing non-Gaussian diffusion and accurately resolving multiple fiber orientations. It can be shown that this method is consistent with the q-space approach. The second-order approximation of GDTI was shown to be DTI.     

Dimensional changes during solvent-induced crystallization of poly(ethylene terephthalate) films

The sample dimensional changes accompanying diffusion with induced crystallization in amorphous poly(ethylene terephthalate) (PET) films are analyzed. Initially, the film's lateral area remains practically constant, but near the end of the process, it increases rapidly, consistent with non-Fickian models for diffusion. The ultimate relative thickness increase is about double that for the lateral dimension, implying that plastic deformation in the thickness direction accompanies the sorption. Plots of fractional area increase (ΔA/ΔA_∞) vs. fractional weight gain (W/W_∞) indicate severe softening of the polymer by the penetrant.     

The Effect of Foreign Ions on Separation of Hafnium from Zirconium on Diphonix® Resin

The weight distribution coefficients (λ_M) of the most often occurring in zirconium salts ions (M(II), M(III) and M(IV)) have been determined in established earlier optimal conditions for separation of zirconium from hafnium by means of Diphonix® resin. Their values range from 21 (λ_Zn(II)) to 1830 (λ_Ti(IV)) and depend on the charge of M ion as well as on its radius. For ions of the highest λ_M (Ti(IV) and Fe(III)) their influence on hafnium – zirconium separation has been studied. Ti(IV) ions at concentration of 1% (in relation to Zr) has been found to noticeably affect separation of hafnium from zirconium by means of Diphonix® resin.     

Material constraint-based laser performance estimation of Yb3+-doped phosphate fibers

Based on the material properties of 47 Yb³⁺-doped phosphate fibers with different sizes and lengths, a laser performance estimation model was established to estimate the laser wavelength just above the threshold (λ_th), the laser threshold (P_th), and the laser slope efficiency (η). This model was solved via a numerical computing method with an accuracy of 0.01. Under the material constraints of this model, λ_th, P_th, and η were investigated by sensitivity analysis and Monte Carlo numerical simulation. The results show that short fibers with a small core diameter may more easily produce a shorter λ_th. Additionally, for constant material properties, fibers with a longer λ_th may have a lower P_th and higher η than other fibers. Verifying the above conjecture, an output power of 8.7 W with 35% enhancement in slope efficiency was obtained from an optimized phosphate fiber for an optical path in which the output of the short-wave laser was inhibited. This model can be extended to simulate the lasing wavelength of multi-composition fibers, providing a theoretical basis for special laser bands, laser material preparation, and fiber structure design.     

Thermal properties of carbon fibers at very high temperature

Thermal properties such as specific heat C_p, thermal diffusivity a, and thermal conductivity λ of carbon fibers are important parameters in the behaviour of the carbon/carbon composites. In this study, the specific heat and the thermal diffusivity are measured at very high temperatures (up to 2500 K). The experimental thermal conductivity estimated by the indirect relation λ = aρC_p is presented as a function of the temperature. Validations are carried out on isotropic metallic (tungsten) and ceramic (Al₂O₃) fibers. Measurements were obtained on three carbon fibers (rayon-based, PAN-based and pitch-based). Thermal conductivity results allow us to classify fibers from the most insulated to most conductive. The main result is that insulated carbon fibers have an increasing thermal conductivity when the temperature and the heat treatment temperature rise. Relationships between thermal conductivity and the structural properties (L_c and d₀₀₂) of such carbon fibers are studied. We also describe the influence of heat treatment on the thermal conductivity of carbon fibers.     

The effect of grain size on the lattice thermal conductivity of an individual polyacrylonitrile-based carbon fiber

The lattice thermal conductivity (λ_L) of general purpose grade polyacrylonitrile (PAN)-based carbon fibers with a crystallite size (L_a) of several nanometers was examined. Using a modified 3ω method, the λ_L of the fibers with different heat-treatment temperatures were detected, and it was found that the λ_L was linearly dependent on −1/L_a. Based on phonon scattering theory, this observation can be attributed to the combined effect of boundary scattering and point-defect scattering. The constant for point-defect scattering (A) was evaluated and a formula was derived.     

Rheological properties of UHMWPE/HDPE blend gels and morphology and mechanical properties of gel-spun fibers

To produce polyethylene (PE) fibers with relatively high tensile strength but low cost, ultra-high-molecular-weight polyethylene (UHMWPE)/high-density polyethylene (HDPE) (UH) blend gels were prepared from paraffin oil and further fabricated into UH blend fibers by gel spinning. This research focused on the rheological properties of UH blend gels with high solid contents (SCs) ranging from 25 to 100 g/L, as well as morphology and mechanical properties of resultant gel-spun UH blend fibers. The rheological measurements indicated that the apparent viscosity, shear storage, and loss moduli of the UH blend gels were not markedly increased compared with those of the UHMWPE gel with much less SC. No obvious solid–liquid phase separation occurred in UH blend gels at a temperature above the sol–gel transition temperature. UH blend fibers were prepared by drawing as-spun fibers (draw ratio [λ] = 3) at 110°C to λ = 15, 45, 60, and 80, respectively. The orientation degree of fibril structure in UH blend fibers increased with increasing λ but the length of fibrils (L_fibril) showed a complex change. The L_fibril of UH blend fibers became larger due to chain arrangement in company with the transformation of the kebab structure to the extended shish structure when the λ was less than 45 but decreased during further elongation (λ = 60 and 80) because of fibril breakage and recrystallization. The change in morphological behavior led to the corresponding change in mechanical properties of resultant gel-spun UH blend fibers. The tensile strength of gel-spun UH55-45 blend fiber (UHMWPE/HDPE = 5/5 and λ = 45) reached 15.6 cN/dtex, which could fulfill the requirement of mechanical properties in common application.     

Influence of two‐stage drawing conditions on ultradrawing behavior of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends

The influence of two‐stage drawing conditions on the ultradrawing behavior of the gel films of ultrahigh‐molecular‐weight polyethylene/low‐molecular‐weight polyethylene blends is reported in this article. The critical draw ratios (λ_c) of the gel films prepared near their critical concentrations were found to depend significantly on the draw ratio attained in the first drawing stage (D_1r) and on the temperature utilized in the second drawing stage (T_sec). After drawing the gel films to a fixed draw ratio in the first drawing stage, each two‐stage drawn gel film was made to exhibit a maximum λ_c (λ_cmax) by drawing the drawn gel film at its corresponding optimum T_sec. In addition, the optimum T_sec was found to increase significantly with the D_1r value of the drawn gel films. It is worth noting, on the other hand, that the λ_cmax of two‐stage drawn gel films increased consistently with an increasing D_1r until its value reached an optimum value of 160. These results clearly suggest that, as T_sec and D_1r are increased to their optimum values, the λ_cmax of the two‐stage drawn gel films can be improved further so as to be higher than those of the corresponding one‐stage drawn gel films. These interesting phenomena were investigated in terms of reduced viscosities of the solutions and by an analysis of the thermal, birefringence, and tensile properties of the drawn gel films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1890–1901, 2001     

Equilibrium and Kinetic Studies on Lithium Adsorption from Geothermal Water by λ-MnO2

The adsorption equilibria of lithium from geothermal water were investigated by using both powdery and granulated forms of λ-MnO₂ derived from spinel-type lithium manganese dioxide. Optimum amounts of adsorbents were 1.0 g adsorbent/L-geothermal water for powdery λ-MnO₂ and 6.0 g adsorbent/L-geothermal water for granulated λ-MnO₂. The adsorbents exhibited the promising adsorption capacities and their adsorption equilibria of lithium agreed well with the Langmuir adsorption isotherm model. The kinetic data of lithium adsorption have been evaluated using pseudo-first-order, pseudo-second-order kinetics models, as well as Elovich kinetic model. In addition, intra-particle diffusion model has been used for evaluating the kinetic data to evaluate the adsorption mechanism. The adsorption kinetic process was attributed to the gradual adsorption stage where intra-particle diffusion was found as the rate-controlling step.