Preparation and properties of microcapsule with EVA core‐PU shell structure

Microcapsule with poly(ethylene‐co‐vinylacetate) (EVA) core‐polyurethane (PU) shell structure was synthesized by interfacial polymerization in aqueous polyol dispersion with ethylene diamine as the chain extender of toluene diisocyanate in poly(vinyl alcohol) aqueous solution as the stabilizing agent. The effects of polyol constituent on the average particle size and distributions, morphologies, color strength, and friction fastness of core‐shell particles were investigated to design microcapsule. The friction fastness of printed fabrics with EVA core‐PU shell microcapsules became the increase to 4–5 grades. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 893–902, 2007     

Fully aliphatic polyimides from adamantane‐based diamines for enhanced thermal stability,solubility, transparency,and low dielectric constant

We have synthesized a series of fully aliphatic polyimides (APIs) from bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BOCA) and various aliphatic diamines, including linear aliphatic, flexible alicyclic, and rigid adamantyl diamines. We performed the polymerization reactions using one‐step syntheses in m‐cresol at elevated temperatures without the isolation of poly(amic) acid. The chemical composition and structure of the polymers were characterized by nuclear magnetic resonance (NMR) and infrared (IR) spectrometry. The characterization data are reported from analyses using gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), and wide‐angle X‐ray diffraction (WXAD) measurements. The polyimides are also subjected to solubility, solution viscosity, tensile strength, transparency, and dielectric constant measurements. The resultant polyimides possess well‐controlled molecular weight, reasonable intrinsic viscosity, good transparency, enhanced solubility, low dielectric constants, and high glass transition temperature, together with marginal thermal and mechanical stability. These properties were enhanced in copolyimides containing equimolar amounts of rigid and flexible moieties. These rigid‐rod APIs derived from the alicyclic dianhydride and aliphatic diamines are promising candidates as advanced materials for future applications in micro‐ and photoelectronic devices. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3316–3326, 2006     

Memory effect of locally ordered α-phase in the melting and phase transformation behavior of β-isotactic polypropylene

Structural changes in β-isotactic polypropylene (β-iPP) during the heating were studied by means of differential scanning calorimetry and real-time in situ X-ray diffraction using a synchrotron source. Crystalline phase transformation and the memory effect caused by residual nuclei of α-iPP were observed during the heating of β-iPP. The memory effect observed in β-iPP during heating and crystallization is believed to be due to the existence of locally ordered α-from in the melt. The effect of local α-form order was probed by studying the behavior under heating of samples with a range of thermal histories. Samples were heated above the equilibrium melting temperature of iPP to remove all residual local order and the memory effect associated with this local order. The samples crystallized isothermally at different temperatures exhibited a significantly different melting and phase transformation behavior during heating. β-iPP is found to be an excellent material for the study of polymorphism, phase transformations, and characteristic memory effects in semicrystalline polymers.     

Morphology-rheology relationship in hyaluronate/poly(vinyl alcohol)/borax polymer blends

In this work, we have prepared bioartificial polymer blends using hyaluronate (HA) as a biological component and poly(vinyl alcohol)-borax association (PVAs) as a synthetic component, and investigated the rheological properties as well as morphology of the blends. When plotted against the blend composition, the rheological properties showed both positive and negative deviation from the linear additive mixing rule depending on thermal history. The blend showed enhanced viscosity at the composition of 20 wt% of HA and 80 wt% of PVAs, when PVA was dissolved at high temperature. The viscosity enhancement was caused by the network formation of HA aggregates in the micrometer scale. In addition, the network structure of HA aggregates was found to be fractal with the fractal dimension of 1.7. As PVA system also forms a network structure in the nanometer scale between hydroxyl groups of PVA and borate anions, the blend system is unique in that it has network structures in both micrometer and nanometer scales in one material. On the contrary, HA formed aggregates but not any network structure in the blend of the same composition but of the negative deviation. In conclusion, we showed that HA/PVAs blend system may have diverse morphology as well as very broad spectrum of rheological properties, and could suggest that the rheology and morphology of HA/PVAs blends can be designed not only by controlling composition but also by controlling thermal and deformation history of the components.     

Preparation of ordered mesoporous SiCN ceramics with large surface area and high thermal stability

For the first time, highly ordered two-dimensional (2-D) and three-dimensional (3-D) mesoporous SiCN ceramics with high surface area and high thermal stability were prepared by nanocasting a preceramic polymer solution into mesoporous carbon templates, CMK-3 and CMK-8, respectively. As a negative replica of CMK-3 carbon, the obtained mesoporous SiCN ceramic possessed an ordered 2-D hexagonal mesostructure, which is similar to the structure of SBA-15 silica except for the reduced dimensions. An ordered 3-D cubic mesoporous SiCN ceramic was also fabricated using CMK-8 as a template. The wall of the mesoporous SiCN replicas consisted of an amorphous SiCN ceramic phase, which possessed high thermal stability at high temperature up to 1000 °C. N₂-sorption isotherms revealed that these ordered mesoporous SiCN ceramics have high BET surface areas (up to 472 m² g⁻¹) and narrow pore-size distributions, which was preserved even after a re-treatment at 1000 °C in air. The use of carbon template played an important role in the preparation of mesoporous SiCN replicas and enhanced the thermal stability of the SiCN products. It is expected that many other types of ordered mesoporous ceramics can be prepared from nanoporous carbon by nanocasting method.     

Sintering of Al2O3–TiC Composite in the Presence of Liquid Phase

The results obtained from the sintering of Al₂O₃–50TiC (in weight percent) composite in the temperature range from 1650° to 1800°C with addition of Y₂O₃ are presented. Densification is accelerated by the formation of liquid at temperatures above 1750°C, and 99% of theoretical density can be achieved by vacuum sintering at 1800°C for 15 min. The liquid presented at the sintering temperature is crystallized to YAG (Y₃Al₅O₁₂) during cooling.     

A multi-fluid nonrandom lattice fluid model: General derivation and application to pure fluids

A multi-fluid nonrandom lattice fluid model with no temperature dependence of close packed volumes of a mer, segment numbers and energy parameters of pure systems is presented. The multi-fluid nonrandom lattice fluid (MF-NLF) model with the local composition concept was capable of describing properties for complex systems. However, the MF-NLF model has strong temperature dependence of energy parameters and segment numbers of pure systems; thus empirical correlations as functions of temperature were represented for reliable and convenient use in engineering practices. The MF-NLF model without temperature dependence of pure parameters could not predict thermodynamic properties accurately. It was found that the present model with three parameters describes quantitatively the vapor pressure and the saturated density for the pure fluid.     

ELECTROKINETIC EFFECTS: CARBONIC ANHYDRASE AND CO2 ELECTRODE DYNAMICS

It is well known that the dynamic response rate of the Severinghaus-type CO₂ electrode is improved significantly in some cases by addition of the enzyme carbonic anhydrase to the electrode assembly. Hysteresis in the response rate also is reduced. Experimental data and modelling results indicate that catalysis of the CO₂ hydration reaction in the bulk of the bicarbonate layer (the Nernst film) is not responsible for the improved response behavior, Evidence is presented to show that catalysis in the electrostatic double layer region at the glass electrode surface is a possible explanation. This proposed phenomenon may have widespread implications for the optimal design of analytical devices, commercial processes involving electrochemical phenomena, and may also provide insight into electrobiologi-cal processes.     

Encapsulation mechanism of N2 molecules into the central hollow of carbon nitride multiwalled nanofibers

Nitrogen molecules have been encapsulated into the central hollows of vertically aligned carbon nitride (CN) multiwalled nanofibers by dc plasma-enhanced chemical vapor deposition with C₂H₂, NH₃, and N₂ gases on a Ni/TiN/Si(1 0 0) substrate at 650 °C. X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectra showed the existence of nitrogen molecules in CN nanofibers. Elemental mapping images with electron energy loss spectroscopy of the CN nanofiber and catalyst metal, and optical emission spectroscopy spectra of the plasma showed the distribution of nitrogen atoms and molecules in the CN nanofiber, catalyst metal, and gaseous precursor, respectively. These studies showed that atomic nitrogen diffused into the catalytic metal particle because of the concentration gradient and then saturated at the bottom of the particle. Saturated nitrogen atom participated in the formation of the CN nanofiber wall but most of nitrogen was trapped in the central hollow of the nanofiber as molecules.