Dynamic layer‐by‐layer self‐assembly of organic–inorganic composite hollow fiber membranes

Multilayer membranes constructed layer‐by‐layer (LbL) is finding increasing importance in many separation applications. The efficient construction of LbL multilayer on to hollow fiber substrates may offer many new opportunities for industrial applications. An organic–inorganic composite hollow fiber membrane has been developed using a dynamic LbL self‐assembly. This poly(acrylic acid)/poly(ethyleneimine) multilayer was dynamically assembled onto the inner surfaces of ceramic hollow fiber porous substrates pretreated by Dynasylan Ameo silane coupling agents. The hollow fibers were subsequently heat crosslinked to obtain stable permselective membranes. The formation of multilayers on the hollow fibers was characterized with a SEM, EDX, an electrokinetic analyzer and IR spectra. The effects of layer number, feed temperature and water content in the feed on the pervaporation performance have been investigated. To the best of our knowledge, this is the first report of LbL assembly of polymer building blocks onto ceramic hollow fiber porous substrates. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3176–3182, 2012     

Synthesis and characterization of organic–inorganic hybrids based on epoxy resin and 3‐glycidyloxypropyltrimethoxysilane

Organic–inorganic hybrid materials based on diglycidyl ether of bisphenol A (DGEBA) and 3‐glycidyloxypropyltrimethoxysilane (GLYMO) were prepared, using a poly(oxypropylene) diamine Jeffamine D230 as a curing agent. Materials were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), infrared spectroscopy, swelling in tetrahydrofurane (THF), and Soxhlet extraction in THF. A dependence of the final conversion of epoxy groups and the final degree of organic phase crosslinking on inorganic phase content was found. The inorganic phase presents a steric hindrance to full crosslinking of epoxy groups. It also immobilizes the organic chains and improves the temperature stability of hybrid materials. Products of GLYMO hydrolysis together with unreacted organic molecules lower the glass transition temperature of hybrid materials. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 498–505, 2004     

Water‐sorption behavior of P‐phenylene diamine–based polyimide thin films

Four different p‐PDA–based polyimide thin films were prepared from their respective poly(amic acid)s through thermal imidization at 400°C: poly(p‐phenylene pyromellitimide) (PMDA‐PDA); poly(p‐phenylene biphenyltetra carboximide) (BPDA‐PDA); poly(p‐phenylene 3,3′,4,4′‐oxydiphthalimide) (ODPA‐PDA); and poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide) (6FDA‐PDA). Water‐sorption behaviors of polyimide films were gravimetrically investigated at 25°C and 22–100% relative humidity by using the modified electromicrobalance (Thin Film Diffusion Analyzer). The diffusion coefficients of water for the polyimides varies in the range of 1.6 to 10.5 × 10⁻¹⁰ cm²/s, and are in the increasing order: BPDA‐PDA < PMDA‐PDA ∼ ODPA‐PDA < 6FDA‐PDA. The water uptakes of polyimides vary from 1.46 to 5.80 wt %, and are in the increasing order: BPDA‐PDA < ODPA‐PDA < 6FDA‐PDA < PMDA‐PDA. The water‐sorption behaviors for the p‐PDA–based polyimides are closely related to the morphological structure; specifically, the diffusion coefficients in p‐PDA–based polyimide thin films are closely related to the in‐plane orientation and mean intermolecular distance, whereas the water uptakes are affected by the packing order. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1315–1323, 2000     

Synthesis and characterization of flame retarding UV‐curable organic–inorganic hybrid coatings

UV‐curable, organic–inorganic hybrid materials were synthesized via sol–gel reactions for tetraethylorthosilicate, and methacryloxypropyl trimethoxysilane in the presence of the acrylated phenylphosphine oxide resin (APPO) and a bisphenol‐A‐based epoxy acrylate resin. The sol–gel precursor content in the hybrid coatings was varied from 0 to 30 wt %. The adhesion, flexibility, and hardness of the coatings were characterized. The influences of the amounts of inorganic component incorporated into the coatings were studied. Results from the mechanical measurements show that the properties of hybrid coatings improve with the increase in sol–gel precursor content. In addition, thermal properties of the hybrids were studied by thermogravimetric analysis in air atmosphere. The char yield of pure organic coating was 32% and that of 30 wt % silicate containing hybrid coating was 30% at 500°C in air atmosphere. This result demonstrates the pronounced effect of APPO on the flame retardance of coatings. Gas chromatography/mass spectrometry analyses showed that the initial weight loss obtained in thermogravimetric analysis is due to the degradation products of the photoinitator and the reactive diluent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1906–1914, 2006     

Water‐soluble cationic polymers and their polymer–metal complexes with biocidal activity: A genotoxicity study

Water‐soluble polyelectrolytes containing ammonium and sulfonic groups, their polymer–Ag(I) complexes, and silver nitrate were investigated as bactericidal compounds for Staphylococcus aureus (Collection No. ATCC 28922) and Escherichia coli (Collection No. 6538P) according to the National Committee for Clinical Laboratory Standards (NCCL) method. All the compounds, except Ag(I), showed bactericidal activity only for S. aureus. Ag(I) showed high bactericidal activity for both bacteria. No important effect of the molecular weight or macromolecular size on the maximum bactericidal concentration value was observed. The genotoxicity was studied using the rec assay. None of the macromolecular compounds showed genotoxicity, except silver ions, whose value was borderline. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 452–457, 2003     

Water‐swellable hydrophobic porous copolymer resins based on divinylbenzene and acrylonitrile. I. Water‐swelling behavior

Hydrophobic porous copolymer resins based on divinylbenzene (DVB) and acrylonitrile (AN) could be prepared as directly swellable in water by using purified DVB (98.8%) and technical DVB (79.3%) in the presence of 1,2‐dichloroethane as porogen. Compared with the resins based on DVB and methyl acrylate (MA/DVB resins), the AN/DVB resins thus obtained are water‐swellable over a wider range of copolymer compositions, and the swelling ability of the AN/DVB resins in water was further confirmed by investigating the water‐swelling behavior of the AN/DVB resins undergoing solvent treatment. The copolymer composition (AN and DVB contents) of the resins and the property of the porogen affect the water‐swellable behavior of the AN/DVB resins profoundly. The results in this paper provide additional evidence to support the hypothesis that the swelling ability of a hydrophobic porous copolymer in water originates from the existence of the inner stresses in the strained polymer network of the resins and the weak interaction between polymer and water that is negligible in the case of a conventional hydrophobic polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2041–2049, 2004     

Preparation and water absorbency of a novel poly(acrylate‐co‐acrylamide)/vermiculite superabsorbent composite

A novel poly(acrylate‐co‐acrylamide)/expanded vermiculite (EVMT) superabsorbent composite was synthesized by aqueous solution polymerization method. The water absorbency of the superabsorbent composite still reaches 850 g/g when 50 wt % EVMT is added, which is significant in decreasing the production cost of the superabsorbent composites. By controlling the molar ratio of acrylic acid monomer and acrylamide monomer, and neutralization degree of acrylic acid, the hydrophilic groups on the composite can be adjusted, and it is found that the collaborative absorbent effect of ? CONH₂, ? COOK, and ? COOH groups is superior to that of single ? CONH₂, ? COOK, or ? COOH group. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 735–739, 2007     

Water absorption by acrylic‐based latex blend films and its effect on their properties

The absorption of moisture, from liquid as well as gaseous states of water, is known to strongly influence the properties of many polymeric materials. In this article, we examine the unusually high affinity for water of acrylic‐based latex blend films, which lose their transparency and turn white upon water absorption. Composed of rubbery and glassy phases at room temperature, these blends absorb significant amounts of water, which results in only a minor plasticization of the glassy component. When redried at elevated temperatures, the blend films return to their original transparent state but remain white and opaque when freeze‐dried at −70°C. Scanning electron micrographs of the freeze‐fractured surfaces of wet samples exhibit micron‐sized holes that suggest clusters of water inside the bulk of the films. A qualitative model associates these water clusters to residual surfactant inside the samples that is left behind after the drying of original latices. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1407–1419, 1999     

Synthesis and characterization of organic–inorganic hybrid polymers with a well‐defined structure from diamines and epoxy‐functionalized polyhedral oligomeric silsesquioxanes

A new class of organic‐inorganic hybrid polymers with well‐defined structure was prepared by reacting diepoxyhexavinyl polyhedral oligomeric silsesquioxanes (DehvPOSS) with diamines of different chain lengths. The structures and properties of these hybrid polymers were well characterized by FTIR, ²⁹Si‐NMR, GC‐MS, and TGA. A modeling characterization was employed to help identify the structures of organic tethers linked between the POSS cages. The results indicated that at the stoichiometric ratio of DehvPOSS to diamine, well‐defined organic–inorganic hybrid polymers with controlled variation of the organic tether architecture can be made, and each organic tether connected four POSS cages. Thermal stability (T_dec) increased with an increase in the tether length of the diamine molecules, and the highest T_dec was obtained with butanediamine (rather than propanediamine or ethanediamine) as the organic tether. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3730–3735, 2006     

Enhanced wettability and thermal stability of polypropylene separators by organic–inorganic coating layer for lithium‐ion batteries

Organic–inorganic coating polypropylene separators were developed by introducing SiO₂ nanoparticles through sol–gel process, where polydopamine was used as an intermediate layer. Scanning electron microscopy results showed the coating layers have highly porous structure, which was beneficial for liquid electrolyte uptake. Compared with pristine polypropylene separator, the ceramic separators showed improved thermal stability, higher ionic conductivity, and lower interfacial impedance. The cells employing the ceramic separators delivers excellent discharge capacity (retention = 75%) and coulombic efficiency up to 98% at 2 °C rate after 100 cycles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46478.     

Water‐soluble polymers. LXXXII. Shear degradation effects on drag reduction behavior of dilute polymer solutions

Drag reduction measurements were conducted on extensively characterized poly(ethylene oxide) and poly(acrylamide) utilizing a fully automated rotating disk rheometer equipped with an optical tachometer, torque transducer, and software allowing real‐time data acquisition. The instrument sensitivity allowed the study of concentrations as low as 0.1 ppm. In addition, previously immeasurable concentration‐ and time‐dependent shear degradation effects were readily observed. A power law equation was shown to adequately correlate the percentage of drag reduction and the volume fraction for each polymer. Furthermore, an empirical shift factor was utilized to superimpose data from all the systems that were studied. By conducting measurements in the proper concentration and time domains, it was possible to extract the minimal concentration for the maximum drag reduction efficiency in the absence of shear degradation. The resulting values were significantly higher than those previously reported by our laboratories for poly(ethylene oxide) and poly(acrylamide). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1211–1221, 2001     

Water‐Soluble Gold–N‐Heterocyclic Carbene Complexes for the Catalytic Homogeneous Acid‐ and Silver‐Free Hydration of Hydrophilic Alkynes

Water‐soluble gold(III/I) N‐heterocylic carbene complexes behave as efficient catalysts for the hydration of terminal alkynes in neat water. The transformation proceeds in the absence of Brønsted acids or halide scavengers and is suitable for sensitive substrates. Kinetic profiles and DFT studies provide a clear picture of intermediates present during catalysis.

     

增效过磷酸钙的增效机制及其对玉米生长的影响

利用猪毛、风化煤和腐植酸钠的水解液为增效剂制备了一种增效过磷酸钙,探讨了增效过磷酸钙的增效机制及其对玉米生长的影响。结果表明,蒸馏水浸提条件下,增效过磷酸钙能减缓水溶磷的释放,具备较高的pH值缓冲性。与普通过磷酸钙相比,增效过磷酸钙处理的玉米生物量平均增加了41.9%,吸磷量和吸钙量分别增加了61.7%和27.8%,根系活力增加了24.3%。该研究结果对过磷酸钙生产的技术改进具有指导意义。     

A new approach to chemically modified carboxymethyl chitosan and study of its moisture‐absorption and moisture‐retention abilities

A new approach to prepare chemically modified carboxymethyl chitosan (CM) derivatives was reported, from which initially CM was prepared from chitosan, then N‐quaternary ammonium group was introduced by the reaction of CM with 2,3‐epoxypropyl trimethylammonium. The structures of the derivatives were characterized by FTIR, XRD, ¹³C‐NMR, and gel permeation chromatography. The capability of moisture‐absorption and moisture‐retention was investigated. It was found that the moisture‐absorption and moisture‐retention ability of the new derivatives quaternized carboxymethyl chitosan (CMQ) are higher than not only that of CM but also that of chitosan quaternary (Q) and carboxymethyl group and quaternary ammonium group are in synergistic effect. Relationships between molecular structures (including degree of substitution of carboxymethylation group, degree of substitution of quaternary group, and molar mass) and functions of CMQ were also studied. The moisture absorption kinetics of CMQ was discussed and the diffusion of water molecules in it looks likely to be non‐Fickian type. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1303–1309, 2006     

Preparation of a starch‐graft‐acrylamide/kaolinite superabsorbent composite and the influence of the hydrophilic group on its water absorbency

A novel starch‐graft‐acrylamide/kaolinite superabsorbent composite with water absorbency 4000 times (g ) was synthesized by a graft copolymerization reaction among acrylamide, potato starch and kaolinite ultrafine powder, followed by saponification with NaOH. The influence of the hydrophilic group on water absorbency was investigated. It was found that the combined absorbent effect of —CONH₂, —COONa and —COOH groups was superior to that of a single group, and the composite with the molar ratio of 8:6:3 for the —CONH₂, —COONa and —COOH groups exhibits the highest water‐absorbent ability. Copyright © 2003 Society of Chemical Industry     

Optimized synthesis of carrageenan‐ graft‐poly(sodium acrylate) superabsorbent hydrogel using the Taguchi method and investigation of its metal ion absorption

The Taguchi method, a robust experimental design, was used for the optimization of the synthesis of a novel biopolymer‐based superabsorbent hydrogel, carrageenan‐graft‐poly(sodium acrylate). The Taguchi method was applied for the experiment and standard 16 orthogonal arrays with five factors and four levels for each factor were used. In the synthesis of the superabsorbent hydrogel, N,N′‐methylene bisacrylamide (MBA) was used as crosslinker, ammonium persulfate as initiator, and acrylic acid as monomer. Neutralization percent and reaction temperature were used as important factors. The analysis of variance results showed that the most important factor in this synthesis was MBA concentration. Under the optimized conditions determined, the maximum capacity of swelling in distilled water was found to be 1383 (g (g dried gel)^?1). Furthermore, the absorption capacity of the hydrogel towards bivalent metal ions was evaluated. The hydrogel may be considered as a candidate to develop an efficient absorbent biopolymer in water treatment applications. Copyright © 2006 Society of Chemical Industry     

Physical and electrochemical properties of low molecular weight poly(ethylene glycol)‐bridged polysilsesquioxane organic–inorganic composite electrolytes via sol–gel process

A new class of ionic conducting organic/inorganic hybrid composite electrolyte with high conductivity, better electrochemical stability and mechanical behavior was prepared through the sol–gel processing between ethylene‐bridged polysilsesquioxane and poly(ethylene glycol) (PEG). The composite electrolyte with 0.05 LiClO₄ per PEG repeat unit has the best conductivity up to 10^?4 S/cm at room temperature with the transference number up to 0.48 and an electrochemical stability window as high as 5.5 V versus Li/Li⁺. Moreover, the effect of the PEG chain length on the properties of the composite electrolyte has also been studied. The interactions between ions and polymer have also been investigated for the composite electrolyte in the presence of LiClO₄ by means of FTIR, DSC, and TGA. The results indicated the interaction of Li⁺ ions with the ether oxygen of the PEG, and the formation of transient crosslinking with LiClO₄, resulting in an increase of the T_g of the composite electrolyte. The VTF‐type behavior of the ionic conductivity implied that the diffusion of the charge carriers was assisted by the segmental motions of the polymer chains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2752–2758, 2007     

Water‐soluble polymers. LXXXIII. Correlation of experimentally determined drag reduction efficiency and extensional viscosity of high molecular weight polymers in dilute aqueous solution

The extensional viscosity for aqueous solutions of high molecular weight poly(acrylamide) copolymers and poly(ethylene oxide) homopolymers was measured using a laboratory‐designed screen extensional rheometer. A Bingham model was developed to estimate the average local polymer coil extensional viscosity (η_coil). A strong correlation was found between the measured η_coil values and the polymer extensional viscosity predicted by a bead‐spring model. The dilute aqueous solution drag reduction was measured with a rotating disk instrument under conditions minimizing the effects of shear degradation. Extensional viscosity and drag reduction measurements were performed in deionized water and in 0.514M sodium chloride. The relative drag reduction efficiency values (Δ) in both solvents were found to strongly correlate with measured η_coil values. This is the first report of the accurate prediction of drag reduction behavior for a wide range of polymer types in various solvents from the independently measured molecular parameters η_coil and [η]C. The often‐used relative drag reduction efficiency expressed as the product of [η]C and Δ can now be replaced by the absolute drag reduction efficiency [η]Cη_coil. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1222–1231, 2001     

Influence of reaction parameters on water absorption of neutralized poly(acrylic acid‐co‐acrylamide) synthesized by inverse suspension polymerization

Highly water‐absorbing polymers of neutralized poly(acrylic acid‐co‐acrylamide) were synthesized in an effort to investigate the influences of reaction parameters on water absorption. In addition, the extent of water absorption and the absorption rate were studied to determine their relationship with the reaction parameters. This article explains the synthesis technique, characterization of the water‐absorbing copolymers, and their properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1349–1366, 1999     

不同增效氮肥品种及用量对玉米幼苗生长、光合特性及养分吸收的影响

采用盆栽试验,研究3种增效氮肥(海藻寡糖尿素、腐植酸尿素、聚能网尿素)及其用量对玉米幼苗生长、光合特性及养分吸收的影响。结果显示,3种增效尿素对玉米幼苗生长的促进作用均好于普通尿素,且海藻寡糖尿素对玉米生长的综合促进效果最优;进一步研究显示,海藻寡糖尿素可提高玉米功能叶片叶绿素含量和净光合速率,还能促进玉米对氮、磷、钾的吸收,同等施氮条件下其施用效果优于其他2种增效氮肥。