Analysis and modeling for time-dependent behavior of polymers exhibited in nanoindentation tests

Through the arrangement of the applied load, experimental nanoindentation results of polymethylmethacrylate (PMMA) and polyurethane (PU) employed to establish a mechanical model. The proposed model consists of irreversible delayed plastic (viscoplastic) deformation, irreversible viscous deformation, and reversible delayed elastic (viscoelastic) deformations. The phase lag exhibited between the responding depth and the oscillating load is found to be linear proportional to frequency in the range of 1-50 Hz. The residual cavity profile of the PMMA scanned by an atomic force microscope gives a validity of accommodation assumption applied in the present model. The effects of overshooting, which occurred in the dwelling process, are also discussed.     

A theory of coupled diffusion and large deformation in polymeric gels

A large quantity of small molecules may migrate into a network of long polymers, causing the network to swell, forming an aggregate known as a polymeric gel. This paper formulates a theory of the coupled mass transport and large deformation. The free energy of the gel results from two molecular processes: stretching the network and mixing the network with the small molecules. Both the small molecules and the long polymers are taken to be incompressible, a constraint that we enforce by using a Lagrange multiplier, which coincides with the osmosis pressure or the swelling stress. The gel can undergo large deformation of two modes. The first mode results from the fast process of local rearrangement of molecules, allowing the gel to change shape but not volume. The second mode results from the slow process of long-range migration of the small molecules, allowing the gel to change both shape and volume. We assume that the local rearrangement is instantaneous, and model the long-range migration by assuming that the small molecules diffuse inside the gel. The theory is illustrated with a layer of a gel constrained in its plane and subject to a weight in the normal direction. We also predict the scaling behavior of a gel under a conical indenter.     

Electronic Structure and Magnetic Properties of SmCo7-xZrx

The electronic structure and magnetism of SmCo_7-xZr_x alloy are investigated using the spin-polarized MS-X. method. The results show that a few of electrons are transferred to the Sm(5d⁰) orbital due to orbital hybridization between Sm and Co atoms. The exchange interactions between 3d and 5d electrons are more important than the polarization effects of the conductive electrons, thus it is the main reason resulting in the long-range ferromagnetic order in SmCo_7-xZr_x. The Curie temperature of SmCo_7-xZr_x is generally lower than that of corresponding pure Co, which may be explained by the weaker average coupling strength between Co lattices due to some negative couplings mainly occurring of 2e site. The calculated results for the Sm₅Co₃₂Zr₂ cluster may lead to a better understanding of why SmCo_7-xZr_x is stable phase. Since the spin-up DOS peak of d electrons at E_F arises and the bonding of electrons at E_F strengthens with increasing Zr concentration, which results in the internal energy of the system decrease, the stable ferromagnetic order forms in SmCo_7-xZr_x.     

Behaviors of the positive temperature coefficient of resistance of poly(styrene‐co‐n‐butylacrylate) filled with Ni‐plated core‐shell polymeric particles

Conductive composite films of poly(styrene‐co‐n‐butylacrylate) copolymers filled with low‐density, Ni‐plated core‐shell polymeric particles were prepared and their behaviors of positive temperature coefficient of resistance (PTCR) were investigated. When the conductive fillers in the composite film were loaded beyond the critical volume, 10 up to 25 vol %, composite films exhibited a unique electrical resistant transition behavior, which the electrical resistance rapidly increased by several orders of magnitude at the critical temperature. The PTCR transition temperature, in general, occurred before the glass transition temperature of polymer matrix. Further increased the conductive filler loading to 30 vol %, the overpacked conduction paths were formed in the entire composite and the PTCR effects became blurred. While the composite film treated with thermal cycle several times from room temperature up to 120 °C, the electrical resistivity increased accompanied with the shift of the PTCR transition to lower temperature. The reason might have been caused by the formed interfacial cracks within the composite film. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 322–329, 2007     

Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Synthesis of TiO2–SiO2/polymer core–shell microspheres with a microphase‐inversion method

A novel microphase‐inversion method was proposed for the preparation of TiO₂–SiO₂/poly(methyl methacrylate) core–shell nanocomposite particles. The inorganic–polymer nanocomposites were first synthesized via a free‐radical copolymerization in a tetrahydrofuran solution, and the poor solvent was added slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles. The average particle sizes of the microspheres ranged from 70 to 1000 nm, depending on the reaction conditions. Transmission electron microscopy and scanning electron microscopy indicated a core–shell morphology for the obtained microspheres. Thermogravimetric analysis and X‐ray photoelectron spectroscopy measurements confirmed that the surface of the nanocomposite microspheres was polymer‐rich, and this was consistent with the core–shell morphology. The influence of the synthetic conditions, such as the inorganic composition and the content of the crosslinking monomer, on the particle properties was studied in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3911–3920, 2006     

Crystal structure and morphology of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state

A series of crystals of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state were obtained at different isothermal temperatures and were observed directly under transmission electron microscope. The crystals obtained at higher temperatures exhibit more perfect structures than those obtained at lower temperatures. Both the lamella thickness and the crystal size increase with crystallization temperature. The tetraaniline is apt to form larger scale crystals under lower degree of supercooling. However, their crystal structures keep steady with the crystallization temperature. The tetramer was found to adopt a monoclinic lattice with unit cell parameter of a = 13.93 Å, b = 8.82 Å, c = 23.20 Å, and β = 95.03°, as determined using electron diffraction tilting method combined with wide‐angle X‐ray diffraction experiment. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 764–769, 2006     

A highly sensitive and rapid assay for protein determination in human urine and penicillin using a Rayleigh light-scattering technique with benzeneazo-8-acetylamino-1-naphthol-3,6-disulfonic acid sodium salt.

A simple and sensitive method was conducted for the determination of trace amounts of proteins with benzeneazo-8-acetylamino-1-naphthol-3,6-disulfonic acid sodium salt (azophloxine, AP) using a Rayleigh light-scattering (RLS) technique. At pH 2.60 and in the presence of an emulsifier OP microemulsion, the RLS of AP can be greatly enhanced by proteins, owing to the interaction between AP and protein. The enhanced intensity is proportional to the concentration of proteins. Four proteins, including bovine serum albumin (BSA), human serum albumin (HSA), lysozyme (Lys) and gamma globulin (gamma-G) have been tested. For example, the linear range of BSA was 0 - 0.06 microg mL(-1) with detection limits of 2.38 ng mL(-1). The method was applied to the analysis of protein in human urine and penicillin samples with satisfactory results. The relative standard deviation was in all instances less than 4.0%, and the recovery was in the range of 97.5 - 104%.     

男性型秃发患者发中K,Na,Ca,Mg元素含量分析

采用火焰原子吸收法对３０例男性型秃发患者及３８例毛发健康男性对照者发中宏量元素Ｋ、Ｎａ、Ｃａ、Ｍｇ的含量进行了测定。结果表明，男性型秃发患者发Ｋ含量明显高于对照组，具有统计学上的显著差异（Ｐ〈０．０１）。发Ｎａ、Ｃａ、Ｍｇ含量在两组间未见显著差异（Ｐ〉０．０５）。本文提示，体内某些宏量元素变化对男性型秃发可能产生一定影响。