Decomposition kinetics and recycle of binary hydrogen‐tetrahydrofuran clathrate hydrate

Decomposition kinetics and recycle of hydrogen–tetrahydrofuran (H₂–THF) clathrate hydrates were investigated with a pressure decay method at temperatures from 265.1 to 273.2 K, at initial pressures from 3.1 to 8.0 MPa, and at stoichiometric THF hydrate concentrations for particle sizes between 250 and 1000 μm. The decomposition was modeled as a two‐step process consisting of H₂ diffusion in the hydrate phase and desorption from the hydrate cage. The adsorption process occurred at roughly two to three times faster than the desorption process, whereas the diffusion process during formation was slightly higher (ca. 20%) than that during decomposition. Successive formation and decomposition cycles showed that occupancy seemed to decrease only slightly with cycling and that there were no large changes in hydrate structure due to cycling. Results provide evidence that the formation and decomposition of H₂ clathrate hydrates occur reversibly and that H₂ clathrate hydrates can be recycled with pressure. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Characterisation of the Dynamic Interactions between Complex N-Glycans and Human CD22

CD22 (Siglec-2) is a B-cell surface inhibitory protein capable of selectively recognising sialylated glycans, thus dampening autoimmune responses against self-antigens. Here we have characterised the dynamic recognition of complex-type N-glycans by human CD22 by means of orthogonal approaches including NMR spectroscopy, computational methods and biophysical assays. We provide new molecular insights into the binding mode of sialoglycans in complex with h-CD22, highlighting the role of the sialic acid galactose moieties in the recognition process, elucidating the conformational behaviour of complex-type N-glycans bound to Siglec-2 and dissecting the formation of CD22 homo-oligomers on the B-cell surface. Our results could enable the development of additional therapeutics capable of modulating the activity of h-CD22 in autoimmune diseases and malignancies derived from B-cells.     

Structure and properties of injection‐molded polypropylenes with different molecular weight distribution and tacticity characteristics

Two series of polypropylenes with different molecular weight distribution and tacticity characteristics were injection molded into flexural test specimens by varying cylinder temperature and the effects of the molecular weight distribution and tacticity on the structure and properties of the moldings were studied. Measured propertied were flexural modulus, flexural strength, heat distortion temperature, Izod impact strength, and mold shrinkage and structures studied were crystallinity, the thickness of skin layer, a*‐axis‐oriented component fraction and crystalline orientation functions. The relations between the structures and properties were also studied. It was found that the molecular weight distribution and tacticity characteristics affect the properties mainly through the molecular orientation and crystallinity, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2142–2156, 2002     

Viscoelastic characterization of moderately concentrated polystyrene solutions by dynamic light scattering

The dynamic light scattering measurements were performed for moderately concentrated entangled solutions of atactic polystyrene in benzene (BZ) at 25.0 °C, in cyclohexane (CH) at 34.5 °C (Θ), and in diethyl malonate (DEM) at 35.0 °C (Θ) to characterize their viscoelastic properties. The results have shown that while the mutual diffusion coefficient D increases in the BZ solutions and decreases in the CH and DEM solutions with increasing polymer mass concentration c, the friction coefficient ζ for the three solutions increases with c showing the same power-law behavior irrespective of the weight-average molecular weight M_w and solvent quality. It has been found that the instantaneous longitudinal modulus L₀ for the CH and DEM solutions increases in proportion to c², obeying the familiar relation for the plateau value (4/3)G_N of the longitudinal stress relaxation modulus, but the L₀ values for these solutions are somewhat smaller than the values predicted from the relation. The terminal relaxation time τ_m for the two Θ solvent systems has been found to follow the power-law τ_m∝c^2.7, showing good correspondence to the relation established by rheological measurements.     

Synthesis of Compositionally Homogeneous Sr(CuxZn1−x)1/2W1/2O3

A complex perovskite of Sr(Cu _x Zn_{1- x} )_1/2 W_1/2O₃ (SCZW) is synthesized by a new combination of wet and dry processess. Mixed oxides containing Cu²⁺ and Zn²⁺ (CZ) are prepared by the wet process (coprecipitate method). SCZW is obtained by the dry process (mixed-oxide method) from a mixture of CZ, SrCO₃, and WO₃. SCZW has practically no compositional, unlike solid solutions prepared by the conventional dry method. The wet–dry process method is useful because the wet process is applied to only B-site cations having the same valence.     

EFFECTS OF OPERATIONAL CONDITIONS ON DRYING CHARACTERISTICS IN CLOSED SUPERHEATED STEAM DRYING

The effects of operational conditions on the drying performance in closed superheated steam drying were examined theoretically and experimentally. The vapor generated from the sample was circulated in the drying chamber. In the theoretical analysis, the replacement of air with vapor in drying chamber and the convective vapor transfer in sample were considered. At the start of drying, the drying chamber was filled with air. As the drying proceeded, the air was replaced with the vapor generated from sample. The calculated results explained the characteristics of experimental data. The pore diameter of sample had little effect on the drying characteristics. During the internal evaporation period, the evaporation occurred in the narrow zone, which moved from the surface to the bottom of sample. The convective vapor transfer in sample had a significant influence on the drying performance. The excess increments in temperature and velocity of drying gas hardly contributed to shortening the drying time.     

EFFECT OF FLUIDIZING PARTICLE ON DRYING CHARACTERISTICS OF POROUS MATERIAL IN FLUIDIZED BED

The drying characteristics of porous material in fluidized bed were examined theoretically and experimentally. The brick ball was used as the sample and immersed in the fluidized bed. The glass beads were used as the fluidizing particles and the particle diameters were changed. When the pore diameter of sample was relatively large, the fluidizing particles were adhered on the sample surface. In the theoretical analysis, the heat and mass transfers in adhered particle layer were considered. The fluidizing particles were adhered on the sample surface during the earlier period of drying. The sample temperature largely decreased when the mass of adhered particle decreased. The calculated results are in good agreement with experimental data. The diameter of fluidizing particle had a small effect on the drying time. The excess increments in drying gas temperature hardly contributed to shortening the drying time.     

Hydrogen and carbon dioxide adsorption with tetra‐n‐butyl ammonium semi‐clathrate hydrates for gas separations

Gas adsorption rates of H₂, CO₂, and H₂‐CO₂ gas mixture (H₂/CO₂ = 3.4) with tetra‐n‐butyl ammonium salt (bromide, chloride, and fluoride) semi‐clathrate hydrate particles were measured at 269 K to assess their properties for gas separation. Equilibrium gas occupancies in the S‐cages of the particles were in order of (high to low) for hexagonal structure‐I, tetragonal structure‐I, and superlattice of cubic structure‐I structures with the maximum fractional occupancy by CO₂ being about 40%. The CO₂ diffusion rate depended on the anion size of the salt, which is attributed to distortion of the S‐cage that is close to the molecular size of CO₂. Simulations of semi‐clathrate hydrate particles with theory showed that H₂/CO₂ selectivities could be as high as 36 (3.0 mol% TBAF) and that selectivities for an ideal membrane (3.3 mol% TBAF) could be >100 (269 K, 0.3–4.5 MPa). Semi‐clathrate hydrates have wide application as separation media for gas mixtures. © 2014 American Institute of Chemical Engineers AIChE J, 61: 992–1003, 2015     

A novel spin-finishing method for antistatic modification of polyester fiber. Surface reaction onto amine-containing copoly(amide-ethers) blended with polyester fiber

Copoly(amide-ethers) containing two types of tertiary amine units were made as antistatic modifiers for poly(ethylene terephthalate) (PET) fibers. The filaments of the copolymers were melt-spun and reacted with three alkylating agents in order to quaternize the tertiary amine into a sulfo-betaine, a carbobetaine, and an ammonium ion. The apparent electric resistivity of the filaments was greatly reduced by this reaction, being in the range of 10⁶ to 10⁸ Ω/cm. However, because these quaternized copolymers incurred decomposition during blend spinning with PET, a blend PET fiber containing one type of copoly(amide-ether) was melt-spun and subjected to quaternization of the amino groups as well as to surface crosslinking with various alkylating and epoxy agents. The quaternized blend fibers obtained showed improved antistatic properties compared with the original blend fiber. Particularly, the fibers crosslinked with epoxy compounds were found to have the best antistatic properties that had ever been attained with this type of modification. The antistatic properties were retained even after dyeing, because both hydrophilic and ionic groups had been effectively immobilized on the surface. Since this quaternization and crosslinking could be conducted on-line with spinning and drawing within a short reaction time, this modification technique is called “spin-finishing method”, which should be superior to the conventional methods in terms of cost performance and productivity.