Photocrosslinking kinetics of polymer blends undergoing spinodal decomposition process

Photocrosslinking reaction kinetics of poly(2-chlorostyrene) performed inside the spinodal region of poly(2-chlorostyrene)/poly(vinyl methyl ether) (P2CS/PVME) blends was investigated by means of ultraviolet (UV)-visible absorption spectroscopy. The reaction was performed via photodimerization of anthracene moieties chemically labeled on the P2CS chains. The crosslinking kinetics of (P2CS/PVME) blends submitted to a temperature jump from the one-phase into the spinodal regions was observed by monitoring the irradiation time dependence of the absorbances of anthracene as well as of the blend in two regions of wavelengths. One is inside and the other is outside the absorption range of anthracene. The contribution of the sample cloudiness to the absorbance of anthracene was subtracted from the absorption data by using an empirical power law experimentally established between the incident wavelengths and the absorption of the blends. It was found that the reaction kinetics approximately follows the mean-field kinetics inside the spinodal region, resembling the behavior of the crosslinking reaction performed in the miscible region at relatively low crosslinking densities. On the other hand, the method described here fails to estimate the crosslinking densities when the phase separation proceeds rapidly, overcoming the reaction. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:885–893, 1998     

Numerical simulation of substrate effects on spinodal decomposition in polymer binary mixture: morphology and dynamics

The characteristic features of the morphology and dynamics of binary mixture for substrate-directed spinodal decomposition (SDSD) in three dimensions have been studied using numerical simulations. The simulation results show that the formation of the wetting layer on the substrate interface follows the power-law growth. It is found that the continuous influence of anisotropic diffusive behavior arose by wetting of substrate induces the wetting component spreading onto the interface of the substrate randomly. The phase morphology and averaged size in the vicinity of the substrate fluctuate greatly due to the wetting of the substrate. The self-similar evolution of the cross-sections parallel and perpendicular to the substrate interface is discussed by relevant scale law functions, respectively. And the mechanisms of the growth in both the parallel and perpendicular directions are also investigated.     

The kinetics of phenol decomposition under UV irradiation with and without H2O2 on TiO2, Fe–TiO2 and Fe–C–TiO2 photocatalysts

H₂O₂ used in the photo-Fenton reaction with iron catalyst can accelerate the oxidation of Fe²⁺ to Fe³⁺ under UV irradiation and in the dark (in the so called dark Fenton process). It was proved that conversion of phenol under UV irradiation in the presence of H₂O₂ predominantly produces highly hydrophilic products and catechol, which can accelerate the rate of phenol decomposition. However, while H₂O₂ under UV irradiation could decompose phenol to highly hydrophilic products and dihydroxybenzenes in a very short time, complete mineralization proceeded rather slowly. When H₂O₂ is used for phenol decomposition in the presence of TiO₂ and Fe–TiO₂, decrease of OH radicals formed on the surface of TiO₂ and Fe–TiO₂ has been observed and photodecomposition of phenol is slowed down. In case of phenol decomposition under UV irradiation on Fe–C–TiO₂ photocatalyst in the presence of H₂O₂, marked acceleration of the decomposition rate is observed due to the photo-Fenton reactions: Fe²⁺ is likely oxidized to Fe³⁺, which is then efficiently recycled to Fe²⁺ by the intermediate products formed during phenol decomposition, such as hydroquinone (HQ) and catechol.     

Monolayer and bilayer conducting polymer coatings for corrosion protection of steel in 1 M H2SO4 solution

In this study, monolayer polypyrrole (PPY), polyaniline (PANI), and bilayer PPY/PANI, PANI/PPY coatings were deposited onto steel electrodes by electropolymerization in 0.1 M monomer and 0.3 M oxalic acid solution. Such corrosion parameters of these electrodes, as corrosion potentials, anodic Tafel constants and corrosion current densities were determined by means of current–potential curves as a function of time in 1 M H₂SO₄ solution. These findings were compared to the corrosion parameters of a bare steel electrode in the same acid solution. The monolayer and bilayer polymer coatings were characterized by the Fourier transform infrared (FTIR) spectroscopy and SEM. Bilayer coatings displayed better corrosion inhibition efficiencies than monolayer coatings. Furthermore, the PPY/PANI coatings offered superior corrosion protection than the PANI/PPY coatings.     

Solvent dependence of the viscous and viscoelastic properties of a high molecular weight polystyrene in moderately concentrated solution

The steady-flow viscosity and viscoelastic behaviour of two solutions of a sensibly monodisperse polystyrene of high molecular weight (M_w = 498 000) have been measured over a temperature range of 100°C for identical concentrations of 20.55 wt.%. Toluene and methyl ethyl ketone were chosen as the two low viscosity solvents having, respectively, good and marginal thermodynamic affinities. Dynamic viscoelastic measurements were made at a frequency of 41 kHz using travelling torsional waves. At this frequency, both solutions exhibit behaviour characteristic of the rubbery region, and the ratio of the dynamic viscosity normalised by dividing by the corresponding solvent viscosity is independent of the solvent until the onset of the glass transition region with decreasing temperature. The storage shear modulus of the toluene solution in the rubbery region is higher than for the MEK solution, indicating a higher entanglement density in the better solvent and a larger polymer radius. Some features of the results in the poor solvent (MEK) appear to indicate that, as the temperature decreases, partial exclusion of the solvent leads to the formation both of stronger entanglements and of macromolecular aggregates or bundles, as suggested by Dreval and others^6–8,11,22.     

Compatibility studies on solution of polymer blends by viscometric and phase‐separation technique

Solution blending of polystyrene (PS) and natural rubber (NR) was carried out in toluene and chloroform to determine the compatibility. Experimental evidence for the compatibility of these blends was derived from viscometric and phase‐separation studies. The viscometric method was based on the intrinsic viscosities of transfer of polymer in pure and “mixed” solvents. The compatibility of these blends based on the heat of mixing was also examined theoretically. All the experimental and theoretical evidence show that the blends are incompatible at the compositions studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 880–889, 2000     

Characterizations and activities of the nano-sized Ni/Al2O3 and Ni/La–Al2O3 catalysts for NH3 decomposition

A series of nano-sized Ni/Al₂O₃ and Ni/La–Al₂O₃ catalysts that possess high activities for NH₃ decomposition have been successfully synthesized by a coprecipitation method. The catalytic performance was investigated under the atmospheric conditions and a significant enhancement in the activity after the introduction of La was observed. Aiming to study the influence of La promoter on the physicochemical properties, we characterized the catalysts by N₂ adsorption/desorption, XRD, H₂-TPR, chemisorption and TEM techniques. Physisorption results suggested a high specific surface area and XRD spectra showed that nickel particles are in a highly dispersed state. A combination of XRD, TEM and chemisorption showed that Ni⁰ particles with the average size lower than 5.0 nm are always obtained even though the Ni loading ranged widely from 4 to 63%. Compared with the Ni/Al₂O₃ catalysts, the Ni/La–Al₂O₃ ones with an appropriate amount of promoter enjoy a more open mesoporous structure and higher dispersion of Ni. Reduction kinetic studies of prepared catalysts were investigated by temperature-programmed reduction (TPR) method and the fact that La additive partially destroyed the metastable Ni–Al mixed oxide phase was detailed.     

A lattice‐fluid,group‐contribution treatment of the glass transition of homopolymers,copolymers, and polymer solutions

The glass transition temperature of polymers and polymer solutions was approached through a combination of the group‐contribution, lattice‐fluid equation of state and the Gibbs–DiMarzio criterion. The model assumes zero entropy at the glass transition temperature and treats molecules as semiflexible chains. This stiffness is associated with a flex energy obtained from the glass transition temperature at atmospheric pressure. Whereas the application of the model is straightforward for homopolymers and polymer solutions, a new formalism using the dyad concept was developed for copolymers. It takes into account the copolymer composition as well as the sequencing of the monomers. The results obtained are consistent with experimental data. For polymer solutions, the model predictions are semiquantitative depending on the system. The interaction parameter required for binary systems was found to have little effect on the glass transition temperature predictions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 697–705, 2003     

Catalytic and electrocatalytic production of H2 from propane decomposition over Pt and Pd in a proton-conducting membrane-reactor

In the present study, the C₃H₈ decomposition reaction is studied in a double-chamber proton-conducting cell-reactor. The proton conductor was a strontia–ceria–ytterbia perovskite disk of the form: SrCe_0.95Yb_0.05O₃₋. The working electrode-catalyst was either Pt or Pd, in the form of a polycrystalline film. The reaction temperature varied between 923 and 1023 K and the partial pressure of propane in the feed gas was 2 kPa. The hydrogen produced by the reaction was electrochemically transported through the walls of the proton-conducting disk, to the outer reactor-chamber. The two electrodes (Pt and Pd) are compared in terms of their catalytic and electrocatalytic activities.     

Preparation and characterisation of SrTi1−x−yZrxMnyO3 solid solution powders in relation to their use in combustion catalysis

Mixed oxides with compositions SrTi_1−x−yZr_xMn_yO₃, with 0 ≤ x ≤ 1 and 0 ≤ y ≤ 0.2 have been prepared with a conventional coprecipitation method. Some of them are constituted by very pure perovskite-type solid solution phases, with tetravalent Zr and Mn substituting for Ti in the B site. The addition of Zr to SrTiO₃ tends to increase the surface areas, while the insertion of Mn tends to decrease it. Mn-containing materials are active in the catalytic combustion of 1% methane in air at temperatures higher than 700 K and can be competitive with pure manganite perovskites like LaMnO₃ in spite of the lower Mn content. Pyridine adsorption experiments show that medium strength Lewis acid sites are located at the surface of these materials, and could be involved in the hydrocarbon CH bond activation.     

Synthesis and solution properties of a new sulfobetaine/sulfur dioxide copolymer and its use in aqueous two-phase polymer systems

The zwitterionic monomer, 3-(N,N-diallylammonio)propanesulfonate, was copolymerized with sulfur dioxide in dimethyl sulfoxide using azo-bis-isobutyronitrile (AIBN) to afford the polysulfobetaine (PSB) copolymer in excellent yields. The PSB was converted into the corresponding anionic polyelectrolyte (APE) by treatment with 1 equiv. of sodium hydroxide. The solution properties of PSB and APE were investigated by potentiometric and viscometric techniques. The critical (minimum) salt concentrations (CSC) required to promote water solubility for the PSB at 23 °C have been measured. Basicity constant of the amine functionality in APE is found to be ‘apparent’ and as such follow the modified Henderson-Hasselbalch equation. The composition and phase diagram of the aqueous two-phase polymer systems of PSB (treated with 0.60 equiv. sodium hydroxide) and poly(ethyelene glycol) (PEG) in 0.1N KCl has been studied for the first time for this class of PSB copolymer.     

Synthesis, structural characterization and third-order non-linear optical property of new three-dimensional metal-organic polymer [Fe2(μ10-btc)0.5(μ2-ox)0.5(μ2-O)1.5]n

One new metal-organic polymer formulated as [Fe₂(μ₁₀-btc)_0.5(μ₂-ox)_0.5(μ₂-O)_1.5]_n 1 (btc = 1,2,4,5-benzenetetracarboxylate, pyramellitate; ox = oxalate) has been synthesized by low-temperature solid-state reaction and characterized by single-crystal X-ray diffraction, elemental analyses, TGA, IR spectra and UV–visible spectra. Complex 1 presents the first 3D coordination network structure constructed by bridging btc, ox and O mixed ligands. In 1, carboxyl groups of btc are all deprotonated and they have a new type of μ₁₀-btc coordination mode. The third-order non-linear optical (NLO) properties of the title compound 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 5.98 × 10⁻³⁰ esu for 1 in a 7.45 × 10⁻⁴ mol dm⁻³ DMF solution.     

Partitioning of anionic/nonionic polysaccharides in a segregative system of anionic polyelectrolyte mixtures in aqueous solution: Effects of polymer charge density and ionic strength of solution

The partitioning of three polysaccharides, Dextran sulfate (DxS), λ‐Carrageenan (CAR), and Dextran (Dx), and its dependence on polymer charge density and ionic strength have been investigated in the segregative mixture of poly(sodium styrene sulfonate) (NaPSS) and sodium polyacrylate‐acrylamide copolymers, NaP(AA/AM), of variable charge density, in aqueous solutions. It is shown that the solubility of all the three may be zero or finite in one or both phases, but the preferred phase is determined by the charge density on the copolymer. When charge densities are equal on the phase forming polymers, the saccharides CAR and Dx favor the phase rich in PSS, but they have greater affinity for the polymer of lower charge density when the charge densities on phase polymers are unequal. The partitioning behavior of DxS is the opposite of the other two polysachharides with respect to which phase it has the greatest affinity for. The values of the partitioning coefficients show that the system may be potentially useful for the purification of polysaccharides and other macromolecules, if appropriate conditions are selected. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1728–1734, 2006     

Formation process of diamond from supercritical H2O–CO2 fluid under high pressure and high temperature conditions

The formation process of diamond from supercritical H₂O–CO₂ fluid was studied using ¹³C-graphitic carbon and oxalic acid dihydrate, (COOH)₂·2H₂O, as starting materials under a diamond stable high pressure–high temperature (HP–HT) condition of 7.7 GPa and 1600°C. The exchange reaction between ¹³C-graphitic carbon and ¹²CO₂ in the supercritical H₂O–CO₂ fluid, which was first formed by the decomposition of oxalic acid dihydrate, occurred very rapidly and became nearly equilibrated after 6 h. At the same time, graphite was recrystallized and coexistent with the fluid until traces of diamond were first observed after 8 h. All graphite transformed into diamond after 17 h, showing that a considerably long induction time was present for the formation of diamond in this fluid system.     

Photoresponse and AC impedance characterization of TiO2–SiO2 mixed oxide for photocatalytic water decomposition

TiO₂–SiO₂ mixed oxides were prepared by sol–gel processes with one-stage (mix up fully hydrolyzed titania- and silica-sol), two-stage (with pre-hydrolysis) and modified two-stage synthesis routes. The photoresponse and AC impedance characterization of the derived catalysts are studied and correlated for the first time with the photocatalytic activities in water decomposition under UV illumination. Synergistic effects in terms of photocatalytic activity and electronic properties including band-gap energy, flat band potential and doping density were observed on atomically mixing TiO₂ and SiO₂ by the two-stage synthesis route. Meanwhile, the decline of photocurrent density were found on TiO₂–SiO₂ relative to bare TiO₂, which could be attributed to low quality crystalline structure of the former compared to that of the latter. The superior photocatalytic performance of TiO₂–SiO₂ is ascribed to the higher flat band potential, band-gap energy, and doping density than those of bare TiO₂.     

Crystallinity, morphology, mechanical properties and conductivity study of in situ formed PVdF/LiClO4/TiO2 nanocomposite polymer electrolytes

Nanocomposite polymer electrolytes composed of poly(vinylidene fluoride) (PVdF), lithium perchlorate (LiClO₄) and TiO₂ nanoparticles were prepared by a solution-cast method. The nanosized ceramic filler, TiO₂, was synthesized in situ by a sol-gel process. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis revealed that the crystalline phase and crystallinity were slightly decreased with the addition of TiO₂ to the PVdF/LiClO₄ system. Scanning electron microscopy (SEM) micrographs showed that the PVdF/LiClO₄/TiO₂ solid polymer electrolyte (SPE) membranes had a porous structure to a certain extent, and that the pore size decreased with increasing TiO₂ content. The overfull nanoparticles tended to aggregate on the surface and inside the pores at TiO₂ content above 15 wt.% so that the porosity decreased. Regarding mechanical properties, the strength of the PVdF/LiClO₄/TiO₂ electrolytes decreased after the uptake of EC/PC solution. In contrast to the conductive behavior of wet PVdF/LiClO₄/TiO₂ membranes relative to the uptake of EC/PC solution, the conductive mechanism of the solid membranes, after the lithium ion of LiClO₄ had already been installed in the PVdF solid polymer network, was mainly influenced by the TiO₂ nanoparticles. At a TiO₂ content of 10 wt.%, the solid and wet PVdF/LiClO₄/TiO₂ systems had the maximum conductivity values of 7.1 × 10⁻⁴ and 1.8 × 10⁻³ S/cm, respectively.     

Isothermal decomposition behavior and dynamic mechanical properties of in situ‐reinforcing elastomer composites based on thermoplastic elastomers and thermotropic liquid crystalline polymer

In situ‐reinforcing composites based on two elastomer matrices very different in melt viscosity, styrene–(ethylene butylene)–styrene triblock copolymer (Kraton G1650), and styrene–(ethylene propylene) diblock copolymer (Kraton G1701), and a thermotropic liquid crystalline polymer (TLCP), Rodrun LC3000, were prepared using a twin‐screw extruder. The isothermal decomposition behavior and dynamic mechanical properties of the extruded strands were investigated by means of thermogravimetry (TG) and dynamic mechanical analysis (DMA), respectively. No significant change in the shape of TG curves for the neat matrices and their LC3000‐containing blends was observed under isothermal heating in nitrogen. In air, G1650 and G1701 showed a single weight‐loss stage and rapid decomposition whereas their blends with 30 wt % LC3000 showed different profiles of weight loss depending on isothermal temperatures. The calculated kinetic parameters indicated that the thermal stability of the polymers is much higher in nitrogen than in air and suggested an enhancement of thermal resistance of the elastomer matrices by addition of TLCP. DMA results showed a great enhancement in dynamic moduli for the blend with 10 wt % LC3000 when compared with the neat matrix. The tan δ peaks corresponding to the elastic and hard phases in both matrices mostly shifted to the lower temperature with LC3000 loading. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 917–927, 2007     

CO_2离心式压缩机高压缸转子变转速、变流量工况下轴向推力的计算与分析

在测量ＣＯ２离心式压缩机高压缸转子各级叶轮性能曲线的基础上,研究了变转速、变流量工况下高压缸转子轴向推力的变化规律,揭示了ＣＯ２压缩机高压缸转子在启动过程中容易发生窜轴事故的原因。针对５２万ｔ／ａ尿素装置实际生产过程的特点,提出了控制轴向推力大小、防止窜轴事故的措施     

Solid-Solution Ranges of the n= 2 and n= 3 Superconducting Phases in Bi2(SrxCa1 −x)n+1CunOy and the Effect on Tc

The cation solubility limits of the n = 2 and n = 3 superconducting phases in the Bi₂(Sr _x Ca_{1 − x} ) _{n +1}Cu _n O _y system were established along tie lines with compatible phases via electron probe microanalysis on bi- (or poly-) phasic samples prepared at 860°C. Pb additions (15 mol% of the Bi content) were used to facilitate formation of the n = 3 phase. In each case football-shaped volumes in composition space were established as the solubility limits which bordered on the nominal compositions 2212 or 2223 (Bi:Sr:Ca:Cu) with the long axis parallel to the Sr-Ca side of the quaternary (i.e., Sr-to-Ca intersolubility) but also extending toward Bi and Cu. This means that, for the most part, the superconducting phases are alkaline-earth deficient relative to the ideal 2212 and 2223 compositions. The Pb content in the 2223 phase is typically 10% of the Bi content. T _c variations could be correlated with variations in Sr or (Sr + Bi) content and the length of the c -axis parameter.     

The roles of Cu, Zn and Mn in Cu0.5Zn0.5Mn2O4 spinel-lattice catalyst for methanol decomposition

Cu_0.5Zn_0.5Mn₂O₄ spinel-lattice catalyst has been studied for methanol decomposition by in situ infrared (IR) spectroscopy analysis and micro reactor study. Methoxy species is formed by dissociative adsorption of methanol which subsequently converts into formate species via step-wise dehydrogenation process. The activities of surface intermediates on reduced CuO, ZnO and Mn₂O₃ catalysts are strongly affected by the ease of hydrogen desorption from the site, the strength of C–H bonding and the availability of oxygen. A synergism between Cu and MnO whereby the Cu serves as a sink for reverse hydrogen atoms spillover from MnO has been proposed. The micro reactor analysis correlates well with the IR results.