Effect of hydrophobic hexafluoroisopropylidene group on the water sorption behaviors of rigid poly(p‐phenylene pyromellitimide) polyimide thin films

We prepared poly(p‐phenylene pyromellitimide) (PMDA–PDA), poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide), and their copolyimides with various compositions to explore the relationship between the water sorption and structure. The water sorption behaviors were gravimetrically investigated as a function of composition and temperature and interpreted with a Fickian diffusion model in films. Overall, the water sorption behaviors were strongly dependent on the changes in morphological structure, which originated from the variations in composition. When the content of the bulky hexafluoroisopropylidene group (6FDA) was increased, the water uptake decreased from 5.80 to 3.18 wt %, whereas the diffusion coefficient increased from 3.6 × 10^?10 to 11.3 × 10^?10 cm²/s. The relatively high water uptake in the PMDA–PDA polyimide film was successfully healed by the incorporation of 6FDA, which may have resulted from the increases in the intermolecular packing order and hydrophobicity. The degree of orientation and crystallinity, which are in‐plane characteristics, were directly correlated to the diffusion coefficient and activation energy in the polyimide film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3442–3446, 2003     

Preparation,characterization, and adsorption properties for metal ions of a novel chelating resin containing sulfoxide and diethylene glycol

A novel chelating resin containing sulfoxide and diethylene glycol, poly{4‐vinylbenzyl‐[2‐2‐(hydroxyethyl)ethoxyl]sulfoxide} (PVESO) was synthesized using chloromethylated polystyrene (PS‐Cl) as material. Its structure was characterized by elemental analysis, infrared spectra, and scanning electron microscopy (SEM). The adsorption capacities of the resin for Hg²⁺, Ag⁺, Cu²⁺, Zn²⁺, and Pb²⁺ at various pH values were determined. The maximum adsorption capacities for Hg²⁺ and Ag⁺ were 1.56 and 0.75 mmol g^?1 respectively. The resin had high selectivity for Hg²⁺ and Ag⁺ over the pH range 1.0–7.0. The adsorption capacities for Hg²⁺ and Ag⁺ under competitive condition were also determined by batch experiment method. In addition, the adsorption kinetics of the resin towards Hg²⁺ at different temperatures was also investigated. The results showed that the adsorption rate was governed by film diffusion at 20°C and 25°C, by particle diffusion at 30°C and 35°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6054–6059, 2006     

Molecular dynamics studies of a model polymer-catalyst-carbon interface

Classical molecular dynamics simulations are performed to obtain insights into structural and dynamical behavior of water and O₂ transport through a model polymer membrane, and at the interface of such hydrated polymer with graphite-supported nanocatalyst platinum particles. Water clustering is observed near the membrane hydrophilic sites constituted by sulfonic groups, which due to their affinity with platinum, are located near the metallic surface. It is found that the diffusion of water through the model hydrated polymer membrane depends strongly on the level of membrane hydration due to contribution from various mechanisms whose relative weights change with the degree of hydration. Possible scenarios for O₂ diffusion are also analyzed.     

Natural rubber–ethylene‐propylene‐diene rubber covulcanization: Effect of reinforcing fillers

Filled covulcanizates of elastomer blend comprising natural rubber (NR) and ethylene‐propylene‐diene rubber (EPDM) of commercial importance were successfully prepared by using a multifunctional rubber additive; namely, bis(diisopropyl)thiophosphoryl disulfide (DIPDIS). A Two‐stage vulcanization technique further improved the physicochemical properties of the blend vulcanizates by restricting, through the formation of polar rubber bound intermediates, the migration of curative and filler from lower to highly unsaturated rubber. Scanning electron microscopy studies indicate homogeneity and coherency in the morphology of the two‐stage vulcanizates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1001–1010, 2002; DOI 10.1002/app.10361     

Sorption,diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) in water–acetic acid mixtures

Sorption, diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) were investigated for water–acetic acid mixtures by using a gravimetric method at 30, 40, and 50°C. The membranes were characterized by X‐ray diffraction and Fourier transform infrared techniques. Concentration‐independent diffusion coefficients were obtained by applying Fick's relationship before completion of equilibrium sorption. Permeation coefficients were calculated from sorption and diffusion coefficients. Concentration profiles of liquids were computed considering the sheet geometry for the membrane by solving Fick's equation under suitable boundary conditions. Arrhenius activation parameters were computed for the transport processes. Experimental results and calculated quantities were discussed to understand membrane–solvent interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1139–1150, 2004     

Modeling of solid—liquid adsorption: Effects of adsorbent loads on model parameters

The adsorption of cobalt phthalocyanine dye onto activated carbon in a continuous stirred tank adsorber was studied. The variables investigated were: adsorbent mass, adsorbent particle size and fluid flowrate. Several models based on film, pore and surface diffusion were constructed and fitted to the experimental data. Experimental results showed: (i) the increasing importance of the film mass transfer resistance for increasing adsorbent loads; (ii) the increasing importance of the surface diffusion mechanism for increasing adsorbent loads; and (iii) the better discrimination among different models for higher adsorbent loads and lower flowrate.     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. I. Effect of orientation

The present study examined poly(ethylene terephthalate) (PET) and a series of statistical and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate by copolymerization and melt blending, respectively. Some level of transesterification during processing of melt blends resulted in blocky copolymers, as confirmed by NMR. Random and blocky copolymers exhibited similar properties in the glassy state, including a single glass transition, due to miscibility of the blocks. However, random copolymerization effectively retarded cold‐crystallization from the glass whereas blocky copolymers readily cold‐crystallized to a crystallinity level close to that of PET. The polymers were oriented at four temperatures in the vicinity of the T_g and characterized by oxygen transport, wide‐angle X‐ray diffraction, positron annihilation lifetime spectroscopy, and infrared spectroscopy. Orientation of all the copolymers resulted in property changes consistent with strain‐induced crystallization. However, blocky copolymers oriented more easily than random copolymers of the same composition and after orientation exhibited slightly lower oxygen permeability, higher density, and higher fraction trans conformers. Analysis of oxygen solubility based on free volume concepts led to a two‐phase model from which the amount of crystallinity and the amorphous phase density were extracted. Dedensification of the amorphous phase correlated with the draw temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1615–1628, 2005     

Effects of Y2O3 and ZrO2 on the Densification of Si3N4-Zr(Y)O2 Composites

The effects of ZrO₂ and Y₂O₃ on the densification of hotpressed Si₃N₄-Zr(Y)O₂ composites have been studied. High density could not be obtained by the addition of pure or 3-mol%-Y₂O₃-doped ZrO₂ in this composite; however, nearly full density (>97%) could be obtained in Si₃N₄ using 6- and 8-mol%-Y₂O₃-doped ZrO₂. It is concluded that Y₂O₃ diffusing out from the added Zr(Y)O₂ promoted the densification and that ZrO₂ also had some role in the formation of an oxynitride glass.     

Swelling of pH‐sensitive chitosan–poly(vinyl alcohol) hydrogels

The swelling properties of different chitosan–poly(vinyl alcohol) (PVA) hydrogels were investigated as functions of the medium pH and salt concentration. The maximum swelling ability of the hydrogels was at a buffer pH of approximately 3, regardless of the PVA content in the hydrogels. The maximum mass of the swollen hydrogels was about 13 times that of their contracted counterparts. The cyclical swelling and contraction between pH 3 and pH 7 buffers and pH 3 and pH 3 buffers with salt confirmed the Donnan swelling mechanism of these hydrogels. The swelling mechanism was considered the transfer of water molecules driven by a concentration gradient. This was represented by a simplified mass‐balance model, which neglected the effect of the ionization reaction, for the initial swelling period. The effective mass‐transfer coefficient of water molecules during swelling, estimated with this model, gradually decreased with increasing PVA content in the hydrogels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4665–4671, 2006     

炼厂外排污水回用于循环冷却水腐蚀影响因素初探

从单因素、多因素和复杂水系考察了炼厂外排污水回用于循环冷却水腐蚀的影响因素，结果表明，碳钢腐蚀的主要影响因素取决于离子特性、氧化膜的形成和溶解氧的扩散等综合协同作用，其中以离子特性的,影响为最大（如：Cl^-、Ca^2 、CO3^2-的腐蚀性较强）。碳钢腐蚀反应又可由以上三种主要影响因素分为三个反应控制区，而当电导率在0．1－2．0mS/cm范围时，其水质属于腐蚀危险高发区。从而也进一步说明水质的低电导率处理，其防腐效果并不理想，相反在高电导率情况下却表现出相对较好的低腐蚀性能。