Polymer electrolyte membranes based on polystyrenes with phosphonic acid via long alkyl side chains

A series of polystyrenes with phosphonic acid ( 5 ) via long alkyl side chains (4, 6, and 8 methylene units) were prepared by the radical polymerization of the corresponding diethyl ω‐(4‐vinylphenoxy)alkylphosphonates, followed by the hydrolysis with trimethylsilyl bromide. The resulting phosphonated polystyrene membranes had a high oxidative stability against Fenton's reagent at room temperature. The membranes prepared from 5 exhibited a very low water uptake, similar to that of Nafion 117 over the wide range of 30 to 80% relative humidity (RH). The proton conductivities of these membranes are lower than that of Nafion 117 in the range of 30 to 90% RH, but comparable or higher than those of the reported phosphonated polymers with higher IEC values, such as the phosphonated poly(N‐phenylacrylamide) (PDPAA, IEC: 6.72 mequiv/g) and fluorinated polymers with pendant phosphonic acids (M47, IEC: 8.5 mequiv/g), at low RH conditions despite the much lower IEC values (3.0–3.8 mequiv/g) of these membranes. These results suggest that the flexible pendant side chains of 5 would contribute to the formation of hydrogen‐bonding networks by considering the very low water uptake of these polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Syntheses and structural characterization of New Tl + and K + complexes of 3,5-dinitrobenzoic acid (HDNB), [Tl(μ-DNB)] n and [K(μ-DNB)(μ-HDNB)] n

Two new Tl⁺ and K⁺ complexes of 3,5-dinitrobenzoic acid (HDNB), [Tl(μ-DNB)] _n and [K(μ-DNB)(μ-HDNB)] _n have been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. Determination of the structure of the [K(μ-DNB)(μ-HDNB)] _n and [Tl(μ-DNB)] _n by X-ray crystallography shows that there are nine coordinate K atoms (KO₉) and eight coordinate Tl atoms (TlO₈). The [Tl(μ-DNB)] _n and [K(μ-DNB)(μ-HDNB)] _n complexes are 2D and 3D coordination polymers, respectively.     

Synthesis and characterization of phenol‐based biaryl proton conducting polymers

Biaryl hydroxy polymers with orthogonal disposition of proton transporting ? OH moieties have been synthesized via conventional free radical polymerization. The polymers are characterized for their thermal stability and proton conductivity, and the results are compared with the corresponding styrenic hydroxy polymers. The orthogonal disposition of ? OH moieties in biaryl polymers does result in lower E_a for proton transport. However, the lower E_a values in biaryl polymers did not translate into a net increase in proton conductivity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

偶氮聚合物薄膜的全光极化研究

报告了分散红共聚物膜HMMM-DR1,HMMM-DR19和偶氮侧链聚合物膜PCN6和PCN2的合成和制备, 并以HMMM-DR1和PCN6为代表比较研究了这两种具有不同吸收性质材料的全光极化特性,研究了他们的实时极化和弛豫过程,对他们的全光极化性质作了最基本的表征.研究了倍频光吸收对薄膜光极化效率的影响,讨论了偶氮聚合物材料光诱导二阶非线性极化率的效率和倍频光透射率之间的折衷关系,这对实用化的全光器件的研制是至关重要的.实验确证了在PCN6薄膜中实现了准相位匹配.对厚膜中光诱导二阶非线性极化率的弛豫抑制效应作出解释.     

Microfabrication of stacks of acoustic matching layers for 15 MHz ultrasonic transducers

This paper presents a novel method used to manufacture stacks of multiple matching layers for 15 MHz piezoelectric ultrasonic transducers, using fabrication technology derived from the MEMS industry. The acoustic matching layers were made on a silicon wafer substrate using micromachining techniques, i.e., lithography and etch, to design silicon and polymer layers with the desired acoustic properties. Two matching layer configurations were tested: a double layer structure consisting of a silicon–polymer composite and polymer and a triple layer structure consisting of silicon, composite, and polymer. The composite is a biphase material of silicon and polymer in 2-2 connectivity. The matching layers were manufactured by anisotropic wet etch of a (1 1 0)-oriented Silicon-on-Insulator wafer. The wafer was etched by KOH 40 wt%, to form 83 μm deep and 4.5 mm long trenches that were subsequently filled with Spurr’s epoxy, which has acoustic impedance 2.4 MRayl. This resulted in a stack of three layers: The silicon substrate, a silicon–polymer composite intermediate layer, and a polymer layer on the top. The stacks were bonded to PZT disks to form acoustic transducers and the acoustic performance of the fabricated transducers was tested in a pulse-echo setup, where center frequency, −6 dB relative bandwidth and insertion loss were measured. The transducer with two matching layers was measured to have a relative bandwidth of 70%, two-way insertion loss 18.4 dB and pulse length 196 ns. The transducers with three matching layers had fractional bandwidths from 90% to 93%, two-way insertion loss ranging from 18.3 to 25.4 dB, and pulse lengths 326 and 446 ns. The long pulse lengths of the transducers with three matching layers were attributed to ripple in the passband.     

Optimizing Design for the Traveling Wave Electrodes in Low-Drive High-Speed Electro-Optic Polymer Modulators

Electro-optic (EO) polymer modulators are very promising in the realization of cost-effective and high-performance optical transmissions. In this article, general strategies and specific designs of the traveling wave electrodes in EO polymer modulators were presented to reduce the modulator drive power while maintaining a broadband response. The optimum device parameters and corresponding conditions were estimated using finite element method based on electrode design. In calculating the results, the comprehensive characteristics of polymer modulator with 1.21 V half-wave voltage and 91 GHz bandwidth was demonstrated with electro-optic interaction length is 20 mm, electro-optic coefficient is 55 pm/V, and operation wavelength is 1.319 μm. These results agree with the 0.8 V half-wave voltage and 30 mm electro-optic interaction length reported in Science. In the five designs presented, a hybrid electrode structure combining CPW and microstrip lines were advanced. The characteristics of this structure are like that of microstrip lines with a single-arm electrode on one arm of the waveguide, but it solves the problem of microstrip to coaxial line transition and corona polarization.     

Miscibility of Solution Blends of Unsaturated Polyester Resin with Polystyrene and Polycarbonate

Miscibility studies of unsaturated polyester resin (UPR) blends with two different thermoplastics—polystyrene (PS) and polycarbonate (PC), in a common solvent, chloroform, were carried out by viscosity, ultrasonic velocity, density, and refractive index methods. Two interaction parameters, μ and α were calculated using viscosity data for these blends. The positive interaction parameter values (μ and α > 0) obtained for the UPR/PS blend and the negative interaction parameter values (μ and α < 0) obtained for the UPR/PC blend indicate that the former is a miscible blend and the latter is an immiscible blend. These results were further confirmed by the ultrasonic velocity, density, and refractive index measurements.     

Designing N-halamine based antibacterial surface on polymers: Fabrication, characterization, and biocidal functions

We demonstrate a valuable method to generate reactive groups on inert polymer surfaces and bond antibacterial agents for biocidal ability. Polystyrene (PS) surfaces were functionalized by spin coating of sub-monolayer and monolayer films of poly(styrene-b-tert-butyl acrylate) (PS-PtBA) block copolymer from solutions in toluene. PS-PtBA self-assembled to a bilayer structure on PS that contains a surface layer of the PtBA blocks ordering at the air-polymer interface and a bottom layer of the PS blocks entangling with the PS substrate. The thickness of PtBA layer could be linearly controlled by the concentration of the spin coating solution and a 2.5 nm saturated monolayer coverage of PtBA was achieved at 0.35% (w/w). Carboxyl groups were generated by exposing the tert-butyl ester groups of PtBA on saturated surface to trifluoroacetic acid (TFA) to bond tert-butylamine via amide bonds that were further chlorinated to N-halamine with NaOCl solution. The density of N-halamine on the chlorinated surface was calculated to be 1.05 × 10⁻⁵ mol/m² by iodimetric/thiosulfate titration. Presented data showed the N-halamine surface provided powerful antibacterial activities against Staphylococcus aureus and Escherichia coli. Over 50% of the chlorine lost after UVA irradiation could be regained upon rechlorination. This design concept can be virtually applied to any inert polymer by choosing appropriate block copolymers and antibacterial agents to attain desirable biocidal activity.     

Exploring Microstructures and Interphase Properties of Surface- Grafted Diblock Copolymers in a Homopolymer Melt by Self-Consistent Field Theory Simulations

Polymeric self-consistent field theory is used to investigate microstructures and interphase properties of diblock copolymers grafted onto solid surfaces in a homopolymer melt. The calculations show that the grafted diblock copolymers can self-assemble into hemispherical microstructures at low grafting densities of the diblock copolymers. The morphology transforms into hemicylinder-like and sandwich-like lamellar microstructures with an increase in the chain-grafting density. The effective thickness of the grafted block layer and the interphase width between the homopolymer melt and the grafted copolymers strongly depend on the physicochemical parameters of the system, such as the composition of the grafted copolymer, the chemical incompatibility between the different components, the length ratio of grafted copolymer to homopolymer, and the grafting density of the diblock copolymers. In addition, the above computational results of microphase-separated structures and interphase properties are qualitatively compared with our previous experimental observations. The comparison indicates that our theoretical results not only reproduce the general feature of the experimental observations, but also elucidate the internal structural information and complement the findings in the region of high grafting densities of diblock copolymers.     

Percolation Thresholds in Ternary Polymer Melt Blends with Separate Dispersions of the Inner Phases: Mathematical Model

A mathematical model based on a straightforward geometrical background is developed which enables predictions of a transition of one dispersed phase to a cocontinuous one (i.e., the percolation threshold) on addition of another dispersed phase during melt mixing in ternary polymer blends. The present work concerns only ternary blends with two separate dispersions of the inner phases in which no encapsulation takes place. In addition, in order to simplify the model, one of the inner phases was represented by hard, nondeformable microspheres The expression developed describes well an experimental relationship between the percolation threshold, the concentration above which the former dispersed phase transforms to a continuous one, and concentrations of both inner phases. The results agree well with the experimental data obtained in a previous work.