Microstructural characterization and optical polarization of glass with needle-like micro–nano silver oriented arrangement

Homogeneous glasses in the Na₂O–B₂O₃–Al₂O₃–SiO₂ system doped with proper amount of AgCl were obtained by melting at a temperature of 1450 °C. Then, with several steps of treatment, including crystallization, elongation and reduction, the glass with oriented arrangement of needle-like micro–nano silver particles was produced. The microstructure and the optical properties of the glass samples in different stages were studied by SEM-EDAX, FE-SEM and UV–Vis spectrum. The results showed that the glass after elongation and reduction exhibits excellent polarization performance in the wavelength range from 600 nm to 900 nm, with an extinction ratio larger than 45 dB. The glass only elongated shows also slight polarizing performance, which may result from the formation of filament structure of Ag during elongation processing.     

Effect of structural relaxation on Curie temperature and magnetostriction investigated by magnetoelastic waves in metglas

Summary Magnetoelastic wave amplitude, a, was measuredvs. the temperature during thermal cycles in Metglas 2826. When the Curie temperature,T _C, has been reached, theA value vanishes due to the fall of the magnetoelastic coupling in the paramagnetic state. This allows evaluation of theT _c temperature. The latter increases after the iterated thermal treatments while the magnetic anisotropyK _u decreases. Also theA amplitude, measured at room temperature after the subsequent thermal treatments, shows an increasing behaviour. The values ofK _u ,T _c andA approach saturation after the same number of thermal cycles; this suggests that the structural relaxation produced by annealing is the microscopic mechanism governing all the three physical quantities. In particular we explain the connection betweenK _u andA by means of the longitudinal magnetostriction.

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Riassunto L'ampiezza delle onde magnetoelastiche,A, è stata misurata in funzione della temperatura eseguendo cicli termici nel Metglas 2826. Raggiunta la temperatura di Curie,T _C l'ampiezzaA si annulla a causa della transizione dell'accoppiamento magnetoelastico nello stato paramagnetico. Ciò ci mette in grado di misurare la temperaturaT _C; quest'ultima aumenta in seguito ai ripetuti trattamenti termici mentre l'anisotropia magneticaK _u diminuisce. Anche l'ampiezzaA, misurata a temperatura ambiente dopo i trattamenti termici, mostra un andamento crescente. I valori diK _u,T _c eA tendono alla saturazione dopo lo stesso numero di cicli termici; ciò suggerisce che il rilassamento strutturale prodotto dalla ricottura è il meccanismo microscopico che regola le tre grandezze fisiche menzionate. In particolare noi mostriamo cheK _u eA sono legati dalla magnetostrizione longitudinale.

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Резюме Измеряется зависимость амплитуды магнитноупругой волны,A, от температуры в течение температурных циклов в металлическом стекле 2826. При достижении температуры Кюри,T _c, величинаA обращается в нуль из-за уменьшения магнитноупругой связи в парамагнитном состоянии. Это позволяет оценить темпаратуру Кюри,T _c. Температура Кюри увеличивается после повторных температурных обработок, тогда как магнитная анизотропияK _u уменьшается. Также отмечается увеличение амплитудыA, измеренной при комнатной температуре после последовательных температурных обработок. ВеличиныK _u,T _c иA приближаются к насьщению после одинакового числа температурных циклов. Это результат предполагает, что структурная релаксация, обусловленная отжигом, представляет микроскопический механизм, определяющий все три физические величины. В частности, мы объсняем связь междуK _u иA с помощью продольной магнитострикции.

     

Local entropic effects of polymers grafted to soft interfaces

In this paper, we study the equilibrium properties of polymer chains end-tethered to a fluid membrane. The loss of conformational entropy of the polymer results in an inhomogeneous pressure field that we calculate for Gaussian chains. We estimate the effects of excluded volume through a relation between pressure and concentration. Under the polymer pressure, a soft surface will deform. We calculate the deformation profile for a fluid membrane and show that close to the grafting point, this profile assumes a cone-like shape, independently of the boundary conditions. Interactions between different polymers are also mediated by the membrane deformation. This pair-additive potential is attractive for chains grafted on the same side of the membrane and repulsive otherwise. Received 20 April 2000     

Effect of chain stiffness on the morphology of diblock copolymer melts

The authors have studied the microphase separation of symmetric diblock copolymers with variable block stiffness and different block chain lengths using coarse-grained molecular dynamics simulations. The simulation results show that for symmetric diblock copolymers, a combination of chain length and relative stiffness between the blocks may play the major role in determining the equilibrium morphology of the system. When the variation in stiffness between blocks is small, the equilibrium morphology of the diblock system is found to be lamellar; this is also the case for systems with small chain lengths, regardless of the difference in block stiffness. However, in systems with longer chains with modest variation in stiffness between the blocks, an ordered cylindrical phase is formed in which the stiffer blocks form cylinders completely surrounded by the flexible components. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2556–2565, 2009     

Facile method to prepare monodispersed Ag/polystyrene composite microspheres and their properties

This article presents a facile method to prepare silver/polystyrene composite microspheres. In this approach, monodispersed polystyrene (PS) particles were synthesized with carboxyl acid groups on the surfaces of the PS particles via dispersion polymerization at first. With the addition of [Ag(NH₃)₂]⁺ to the PS dispersion, [Ag(NH₃)₂]⁺ was absorbed to the surfaces of the PS particles, and then by heating the system, [Ag(NH₃)₂]⁺ complex ions were reduced to silver to form the Ag/PS composite microspheres. In the synthesis of PS dispersion, PVP was used as dispersant to stabilize the PS particles, it also acted as reducing agent in the reduction of [Ag(NH₃)₂]⁺ complex ions to silver, so no additional reducing agent was needed. The resulting composite microspheres were characterized by TEM, SEM, XPS, and XRD. The catalytic properties and surface‐enhance Raman scattering (SERS) was studied as well. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4547–4554, 2009     

Control of the microstructure of polymer network and effects of the microstructures on light scattering properties of UV‐cured polymer‐dispersed liquid crystal films

Polymer‐dispersed liquid crystals (PDLC) films were prepared from ultraviolet (UV) irradiation‐induced polymerization of the photopolymerizable monomers in photopolymerizable monomers/nematic liquid crystal (LC) mixtures. The effects of the composition of the mixtures, the curing temperature, and the UV light intensity on the microstructure of the polymer network in the PDLC films were investigated. Furthermore, the effects of the microstructures on the light scattering properties of the PDLC films in the wavelength region of 300–2500 nm were studied experimentally and theoretically based on the combination of three kinds of classical light scattering theories: the Rayleigh‐Gans (RG) approach, the anomalous diffraction (AD) approach, and the geometrical optics (GO) approach. It was found that the sizes of LC domain in PDLC films increased with the increase of the LC content as well as the decrease of the UV curing intensity, while increased at first and then decreased with the increase of the curing temperature. Moreover, smaller LC domain sizes could exhibit strong scattering properties in a smaller VIS wavelength region and the transmittance in NIR region (especially in the wavelength range of 1300–2500 nm) obviously decreased with the increasing sizes of LC domain. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2090–2099, 2008     

Polymerization of higher α‐olefins using a Cs‐symmetry hafnium metallocene catalyst. Kinetics of the polymerization and microstructural analysis

The C_s‐symmetry hafnium metallocene [(p‐Et₃Si)C₆H₄]₂C(2,7‐di‐tert‐BuFlu)(C₅H₄)Hf(CH₃)₂ and tetrakis(pentafluorophenyl) borate dimethylanilinium salt ([B(C₆F₅)₄]^?[Me₂NHPh]⁺) were used as the catalytic system for the polymerization of higher α‐olefins (from hexene‐1 to hexadecene‐1) in toluene at 0 °C. The evolution of the polymerization was studied regarding the variation of the molecular weight, molecular weight distribution and yield with time. The effect of the monomer structure on the polymerization kinetics was established. The role of trioctylaluminum in accelerating the polymerization was investigated. ¹³C NMR spectroscopy was used to study the microstructure of the poly(α‐olefins) by the determination of the pentad monomer sequences. The thermal properties of the polymers were obtained by differential scanning calorimetry, DSC. The results were discussed in connection with the polymer microstructure. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4314–4325, 2009     

Atomistic models of three fluorinated polyimides in the amorphous state

Molecular models of three fluorinated polyimides based on the 4,4′‐(hexafluoroisopropylidene)diphthalic dianhydride (6FDA) have been studied using molecular dynamics (MD) simulations. The respective diamines were 4,4′‐hexafluoroisopropylidene dianiline (6FpDA), 3,3′‐hexafluoroisopropylidene dianiline (6FmDA), and 2,4,6‐trimethyl‐1,3phenylenediamine (DAM). Thirty independent samples were prepared using a hybrid pivot Monte Carlo‐MD generation technique and average densities were found to be in very good agreement with experiment. Model structures also agreed with available wide‐angle X‐ray scattering data. Cohesive energies, Hildebrand solubility parameters, fractional free volumes (FFV), void space distributions and intermolecular as well as intramolecular interactions were analyzed. The differences in bulk properties between both 6FDA‐6FpDA and 6FDA‐6FmDA isomers remain fairly small, although the configurations of the former are more extended. 6FDA‐DAM has a lower density, larger intermolecular distances, and higher free volume than the other two polyimides. Results are discussed with respect to their use as matrices for gas separation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1166–1180, 2009     

Initiator selectivity during free radical copolymerizations of styrene and methyl methacrylate initiated by anaerobic copper(II) oxidation of carbon‐13 labeled acetophenone

Nuclear magnetic resonance (NMR) analysis of the ¹³C‐labeled chain ends of polystyrene, polyMMA, and styrene‐MMA copolymers prepared by polymerizations initiated using ¹³C‐labeled‐phenacyl radicals were investigated. The phenacyl radicals were generated by anaerobic oxidation of acetophenone‐methyl‐¹³C using a Cu(II) octanoate‐pyridine complex in the presence of triethylamine and triphenylphosphine. NMR analysis of the ¹³C‐labeled chain ends of these polymers afforded insight into the initiation mechanism. In copolymerization experiments using ¹³C‐labeled acetophenone initiator, the NMR spectra provided evidence that the phenacyl radical reacts 2.7 times faster with styrene than with MMA. The resonances of the labeled phenacyl carbons also showed that the sequence and stereosequence distributions of monomer units at the chain ends are nearly the same as those that prevail along the polymer chains. Styrene–styrene, styrene–MMA, and MMA–styrene enchainments at the chain ends are equally likely to have meso (erythro) or racemic(threo) configurations but the ratio of meso to racemic MMA‐MMA enchainments is ～ 3/7. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2347–2356, 2008     

A THEORETICAL APPROACH TO P_(co_2) EVOLUTION IN THE ATMOSPHERE BASED ON ASSOCIATIONS OF SEDIMENTARY MINERALS

Based on the theory of pH evolution of sea water and the balance between the seawater and the atmosphere the authors discussed the problems about (i) the method ofcalculating P_(CO_2) in the ancient atmosphere with the associations of sedimentary miner-als; (ii) the evolution of P_(CO_2) values in the geologic history; (iii) the relations of thepH evolution of sea water with carbonate precipitations; and (iv) calculation of the pHlimit for some associations of sedimentary minerals and its corresponding P_(CO_2) valuesin the atmosphere. The authors pointed out that though carbonates had deposited little in the Archaean,the content of CO_2 gas in the Archaean atmosphere was very high and was gradually go-ing up to form a thick CO_2 atmosphere. Up to 2600 Ma ago, the P_(CO_2) had reached a gradeof 10- 50 atm. There was a general trend of evolution that from the early Proterozoicera to the present the depositional horizon of carbonate layers was gradually risingand finally surpassed the horizons of clay min