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1.
An electron paramagnetic resonance (EPR) study of the photoexcited triplet state of four free base porphyrins is presented. The zero field splitting parameters (ZFS) |D| and |E| were calculated from the EPR spectra of the porphyrins dissolved in n-octane matrices at 80°K. |D| = 0.0359 cm?1, |E| = 0.0079 cm?1 for tetra phenyl porphyrin (H2 TPP), |D| = 0.0432 cm?1, |E| = 0.0037 cm?1 for tetra (per-fluoro) phenyl porphyrin H2T (per-F) PP, |D| = 0.0366 cm?1, |E| = 0.0078 cm?1 for tetra (para-chloro) phenyl porphyrin H2T(P-Cl)PP, |D| = 0.0369 cm?1, |E| = 0.0076 cm?1 for tetra (para-methyl) phenyl porphyrin H2T(P-Me)PP. The transient behavior of the EPR signal intensities in the last two porphyrins is discussed. The depopulation rate constants of the triplet sublevels kp, the ratio between the population rate constants Ap (at zero field, p = x,y,z), and the spin lattice relaxation rate W within the triplet manifold, were calculated. kx = (12 ± 2) × 102 sec?1, ky = (0.5 ± 0.1) × 102 sec?1, kz = (1.2 ± 0.4) × 102 sec?1, Ax:Ay:Az ? 0.63:0.01:0.33, W = (0.4 ± 0.1) × 104 sec?1 for H2T(P-Cl)PP, kx = (7 ± 2) × 102 sec?1, ky = (4 ± 1) × 102 sec?1, kz = (1.5 ± 0.5) × 102 sec?1, Ax:Ay:Az ? 0.56:0.31:0.13, W = (1.7 ± 0.4) × 103 sec?1 for H2T(P-Me)PP.  相似文献   

2.
Reduced graphene oxide nanosheets modified by conductive polymers including polythiophene (GPTh), polyaniline (GPANI) and polypyrrole (GPPy) were prepared using the graphene oxide as both substrate and chemical oxidant. UV–visible and Raman analyses confirmed that the graphene oxide simultaneously produced the reduced graphene oxide and polymerized the conjugated polymers. The prepared nanostructures were subsequently electrospun in mixing with poly(3‐hexylthiophene) (P3HT)/phenyl‐C71‐butyric acid methyl ester (PC71BM) and poly[bis(triisopropylsilylethynyl)benzodithiophene‐bis(decyltetradecylthien)naphthobisthiadiazole] (PBDT‐TIPS‐DTNT‐DT)/PC71BM components and embedded in the active layers of photovoltaic devices to improve the charge mobility and efficiency. The GPTh/PBDT‐TIPS‐DTNT‐DT/PC71BM devices demonstrated better photovoltaic features (Jsc = 11.72 mA cm?2, FF = 61%, Voc = 0.68 V, PCE = 4.86%, μh = 8.7 × 10?3 cm2 V–1 s?1 and μe = 1.3 × 10?2 cm2 V–1 s?1) than the GPPy/PBDT‐TIPS‐DTNT‐DT/PC71BM (Jsc = 10.30 mA cm?2, FF = 60%, Voc = 0.66 V, PCE = 4.08%, μh = 1.4 × 10?3 cm2 V–1 s?1 and μe = 8.9 × 10?3 cm2 V–1 s?1) and GPANI/PBDT‐TIPS‐DTNT‐DT/PC71BM (Jsc = 10.48 mA cm?2, FF = 59%, Voc = 0.65 V, PCE = 4.02%, μh = 8.6 × 10?4 cm2 V–1 s?1 and μe = 7.8 × 10?3 cm2 V–1 s?1) systems, assigned to the greater compatibility of PTh in the nano‐hybrids and the thiophenic conjugated polymers in the bulk of the nanofibers and active thin films. Furthermore, the PBDT‐TIPS‐DTNT‐DT polymer chains (3.35%–5.04%) acted better than the P3HT chains (2.01%–3.76%) because of more complicated conductive structures. © 2019 Society of Chemical Industry  相似文献   

3.
A novel polyion complex membrane was synthesized for direct methanol fuel cell application through the blending of the natural biopolymer sodium alginate (SA) with the synthetic polymer Pebax [poly(ether‐block ‐amide)]. The blend was covalently crosslinked with glutaraldehyde (GA) and sulfonated with sulfuric acid (H2SO4), after which characterization by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffractometry, thermogravimetric analysis, and universal testing machine techniques was carried out. The SA–Pebax–GA–H2SO4 membrane exhibited a high ion‐exchange capacity of 2.1 mequiv/g, an optimum water sorption of 17.3%, and a low methanol sorption of 9.5%. A desirably low methanol permeability of 9.25 × 10?8 cm2/s and a high proton conductivity of 0.067 S/cm were obtained as against corresponding values of 1.82 × 10?6 cm2/s and 0.077 S/cm reported for a commercial Nafion 117 membrane. Moreover, a high selectivity of 6.5 × 105 Ss/cm3 with a power density of 0.17 W/cm2 was achieved with the indigenous blend membrane at a potential of 0.34 V. Molecular dynamics simulation was performed along with the estimation of fractional free volume to explain the transport behavior of water and methanol molecules through the membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44485.  相似文献   

4.
Static and dynamic light‐scattering techniques were used to study biodegradable thermoplastic poly(hydroxy ester ether) in N,N‐dimethylacetamide (DMAc). A weight‐average molecular weight MW = 6.4 × 104 g/mol, radius of gyration RG = 9.4 nm, second‐virial coefficient A2 = 1.05 × 10?3 mol mL/g2, translational diffusion coefficient D = 1.34 × 10?7 cm2/s, and hydrodynamic radius RH = 8.3 nm are reported. In addition, the effect of H2O on the polymer chain's conformation and architecture in a DMAc/H2O solution is evaluated. Results suggest that H2O makes the mixed solvent poorer as well as promotes polymer chain branching via intramolecular transesterification. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1737–1745, 2001  相似文献   

5.
A tossa variety of jute fiber (Corchorus olitorious) treated with soap–glycerol micelles is characterized by infrared (IR) spectroscopy, X‐ray diffraction method, and tensilometry. The IR spectra for jute fibers treated with soap–glycerol micelles show a reduced absorption band due to O H stretching at a frequency of 3420 cm−1 with almost absent OH bending frequencies, prominent CH2 stretching and bending frequencies at 2915 and 1440 cm−1 and reduced skeletal vibration at 1060 cm−1. The percentage crystallinity measured by the X‐ray diffraction method increases from 45 to 53% on treated jute fibers. The tensile strength and strain percent at maximum load, Young's modulus, and work done per unit volume within an elastic limit (resilience) for treated fibers increased from 1.8 ± 0.2 to 3.43 ± 0.2 GPa, from 3.98 ± 0.1 to 4.75 ± 0.1, from 75 ± 2 to 113 ± 5 GPa, and from 26 ± 2 to 74 ± 3 MJ m−3, respectively. Using a stabilizing agent (2%) and a swelling agent (2% KOH), the tensile strength, strain percent, Young's modulus, and resilience increase to 4.02 ± 0.2 GPa, 4.85 ± 0.3, 154 ± 5 GPa, and 95 ± 4 MJ m−3, respectively. Under natural weathering at 12–30°C and 30–80% relative humidity over a prolonged period of 8 weeks, all the tensile properties for micelle‐treated fibers increase during the first 2 weeks of exposure and then decrease exponentially to the starting values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 852–856, 2000  相似文献   

6.
In this work, hydrogen (H2) permeation fluxes through 230 nm‐thick graphene oxide (GO) membrane deposited on porous YSZ hollow fiber were measured and correlated to an explicit H2 permeation model. H2 fluxes through such GO‐YSZ hollow fiber membrane increased from 4.83 × 10?8 mol cm?2 s?1 to 2.11 × 10?7 mol cm?2 s?1 with temperature rise from 20 to 100 °C. The activation energy of H2 permeation was determined by the linear regression of the experimental data and was applied in the theoretical calculations. The model predictions fit well the temperature dependent and the argon sweep gas flow rate dependent H2 fluxes data. Using the derived permeation model, the effects of vacuum pressure at lumen side and H2 partial pressure at shell side, membrane area, and GO membrane film thickness on the membrane performance were simulated and discussed to provide insights for practical applications. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2711–2720, 2018  相似文献   

7.
The diffusion coefficient of the perhydroxyl ion (HO?2) was determined in 4.5 M LiOH supporting electrolyte. Over the range of concentration 0.2–0.8 M H2O2 it was found to be independent of concentration and had a value of 5 ± 0.2 × 10?6 cm2/s at 293 K. The experimental data were obtained chronoamperometrically used a rde. At the limiting current, O2 evolution was found to be almost entirely suppressed and the current limiting species was therefore assumed to be the HO?2 ion. The electrochemical mechanism for the perhydroxyl reduction reaction was invoked to explain the experimental results.  相似文献   

8.
High pyroelectric performance and good thermal stability of pyroelectric materials are desirable for the application of infrared thermal detectors. In this work, enhanced pyroelectric properties were achieved in a new ternary (1?x)(0.98(Bi0.5Na0.5)(Ti0.995Mn0.005)O3–0.02BiAlO3)–xNaNbO3 (BNT–BA–xNN) lead‐free ceramics. The effect of NN addition on the microstructure, phase transition, ferroelectric, and pyroelectric properties of BNT–BA–xNN ceramics were investigated. It was found that the average grain size decreased as x increased to 0.03, whereas increased with further NN addition. The pyroelectric coefficient p at room temperature (RT) was significantly increased from 3.87 × 10?8Ccm?2K?1 at = 0 to 8.45 × 10?8Ccm?2K?1 at = 0.03. The figures of merit (FOMs), Fi, Fv and Fd, were also enhanced with addition of NN. Because of high p (7.48 × 10?8Ccm?2K?1) as well as relatively low dielectric permittivity (~370) and low dielectric loss (~0.011), the optimal FOMs at RT were obtained at = 0.02 with Fi = 2.66 × 10?10 m/V, Fv = 8.07 × 10?2 m2/C, and Fd = 4.22 × 10?5 Pa?1/2, which are superior to other reported lead‐free ceramics. Furthermore, the compositions with  0.03 exhibited excellent temperature stability in a wide temperature range from 20 to 80°C because of high depolarization temperature (≥110°C). Those results unveil the potential of BNT–BA–xNN ceramics for infrared detector applications.  相似文献   

9.
This article deals with the development of kinetic parameters for bisphenol acetophenone–polycarbonate made by melt transesterification with diphenyl carbonate. The understanding of the influence of borosilicate glass of the reactor construction materials on the accuracy of the kinetic data is reported. During the development of analytical methods, the use of high performance liquid chromatography‐mass spectrometry (HPLC‐MS) was proven to be a valid tool to determine the oligomers existing in the reaction mixture. Accurate kinetics parameters were obtained by elimination of the interference of the construction materials. We provide the rate expressions, kinetic parameters [forward reaction frequency factor = 2.456 × 1013 ± 0.01 (cm3/mol)2/min, forward reaction activation energy = 45.69 ± 0.2 kJ/mol, reverse reaction frequency factor = 2.068 × 1014 ± 0.01 (cm3/mol)2/min, and reverse reaction activation energy = 56.37 ± 0.1 kJ/mol], and equilibrium constants at various temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4072–4079, 2007  相似文献   

10.
Composites of styrene–butadiene rubber were prepared with three different types of lead oxide, namely, monolead oxide (PbO), lead dioxide (PbO2), and red lead oxide (Pb3O4). Concentrations of Pb3O4 ranging between 17 and 88 wt % were utilized, whereas 87 wt % was used for PbO and PbO2. The prepared composites were investigated for their gamma radiation shielding properties. Moreover, physical and mechanical properties, and electrical conductivity were measured for both the unirradiated and irradiated composites. The highest value obtained for the linear absorption coefficient was 0.424 cm?1 for 88% Pb3O4.  相似文献   

11.
《分离科学与技术》2012,47(1):164-178
Abstract

The adsorption of different metal ions on acrylamidezirconium (IV) arsenate has been studied. The effect of surfactant concentration (Tween 80‐R and Tritron X‐100) on sorption of different metal ions acrylamidezirconium (IV) arsenate was explored. The effect of experimental parameters such as contact time, temperature, and pH on adsorption of Pb2+ions was studied. The promising feature of the material is its specificity for Pb2+ ions. A new PVC based Pb2+ ion‐selective electrode using acrylamidezirconium (IV) arsenate as electro‐active material has been fabricated. The electrode works well over a wide range of concentration 1×10?1 M–1×10?7 M with a Nerstian slope of 30±1 mV per decade. The sensor shows the short response time of 20 seconds and can operate in the pH range of 2–7. The sensor can be used for the period of over 4 months with out deviation in response characteristics. The electrode has been successfully used as an indicator electrode for potentiometric titration of Pb2+ ions in solution against EDTA solution.  相似文献   

12.
《分离科学与技术》2012,47(1):203-222
Abstract

The decontamination of lead ions from aqueous media has been investigated using styrene‐divinylbenzene copolymer beads (St‐DVB) as an adsorbent. Various physico‐chemical parameters such as selection of appropriate electrolyte, contact time, amount of adsorbent, concentration of adsorbate, effect of foreign ions, and temperature were optimized to simulate the best conditions which can be used to decontaminate lead from aqueous media using St‐DVB beads as an adsorbent. The atomic absorption spectrometric technique was used to determine the distribution of lead. Maximum adsorption was observed at 0.001 mol L?1 acid solutions (HNO3, HCl, H2SO4 and HClO4) using 0.2 g of adsorbent for 4.83×10?5 mol L?1 lead concentration in two minutes equilibration time. The adsorption data followed the Freundlich, Langmuir, and Dubinin‐Radushkevich (D‐R) isotherms over the lead concentration range of 1.207×10?3 to 2.413×10?2 mol L?1. The characteristic Freundlich constants i.e. 1/n=0.164±0.012 and A=2.345×10?3±4.480×10?5 mol g?1 have been computed for the sorption system. Langmuir isotherm gave a saturated capacity of 0.971±0.011 mmol g?1, which suggests monolayer coverage of the surface. The sorption mean free energy from D‐R isotherm was found to be 18.26±0.75 kJ mol?1 indicating chemisorption involving chemical bonding for the adsorption process. The uptake of lead increases with the rise in temperature. Thermodynamic parameters i.e. ΔG, ΔH, and ΔS have also been calculated for the system. The sorption process was found to be exothermic. The developed procedure was successfully applied for the removal of lead ions from real battery wastewater samples.  相似文献   

13.
Poly(ethylene terephthalate) (PET) filament yarns were photostabilized by addition of 0.5–4.0 mole % dimethyl 4,4′-biphenyldicarboxylate (4,4′-BPDC) to the polymerization feed. The mechanism of photostabilization is proposed to be a triplet–triplet energy transfer from excited terephthalate units to ground-state biphenyldicarboxylate units. The mechanism of transfer is reported to be via an electron exchange mechanism, with the “quenching sphere” calculated to be 14.9 Å. Kinetic studies show the “pseudo” zero-order rate constant of initial photodegradation to decrease from 3.4 × 10?19 for the PET homopolymer to 2.0 × 10?19% breaking strength loss/quantum exposure/cm2 for the copolyester containing 4.0 mole % of the 4,4′-biphenyldicarboxyl moieties. The photophysical processes available to the dimethyl 4,4′-biphenyldicarboxylate monomer were characterized by absorption and luminescence studies. In solution, dimethyl 4,4′-biphenyldicarboxylate was shown to emit an intense fluorescence from a 2(π,π*) state and a weaker (~10?2×) phosphorescence from a 1(π,π*) state derived from the 1A→supn1Lb absorption. The copolymer yarns were shown to exhibit both fluorescence and phosphorescence from the biphenyldicarboxylate units: the fluorescence from direct excitation, the phosphorescence by sensitized transfer.  相似文献   

14.
Poly(vinyl chloride) (PVC)—poly(butyl methacrylate) (PBMA) blended polymer electrolytes with lithium perchlorate (LiClO4) as the complexing salts are prepared by solution casting technique. The addition of PBMA into PVC matrix is found to induce considerable changes in physical and electrical properties of the polymer electrolytes. Addition of PBMA into PVC matrix is found to increase the conductivity by two orders of magnitude (1.108 × 10?5 S cm?1) when compared with that of the pristine PVC polymer electrolyte (10?7 S cm?1). Structural, thermal, mechanical, morphological, and polymer–salt interactions are ascertained from X‐ray diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA), mechanical analysis, scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) respectively. A thermal stability upto 250 °C is asserted from the TG/DTA analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44939.  相似文献   

15.
The aim of the present work is to provide information about the migration of phthalate and non‐phthalate plasticizers generally used in flexible polyvinyl chloride (PVC) applications. Plastisols (pastes) were prepared by mixing PVC, plasticizer, and thermal stabilizer. The plasticized PVC (p‐PVC) films are obtained by gelation at 160°C for 15 min. The p‐PVC films were heat treated at 50, 85, 100, 130, and 160°C up to 420 min to follow the mass loss to find out diffusivity of plasticizer out of films into air and to determine related activation energies. The films having di‐octyl terephthalate (DOTP) and di‐isononyl 1,2‐cyclohexanedicarboxylic acid (DINCH) exhibited the lowest mass loss in general, among the phthalate and non‐phthalate plasticizer having p‐PVC films, respectively, as confirmed by FTIR investigation. The same tendency was observed for diffusion coefficients and for the activation energies of migration. The diffusion coefficients were found to be around 3.5 × 10?18–2.1 × 10?17 m2/sec for the studied plasticizers in PVC at 50°C and around 4.0 × 10?15–9.9 × 10?14 m2/sec at 160°C. The activation energies for 85–160°C interval were determined to be between 70 and 153 kJ/mol (0.72–1.58 eV) for the plasticizers used herein those could be treated as a homologous series as deduced from the related compensation factors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

16.
Crosslinked hydroxyl‐conductive copolymer/silica composite membranes based on addition‐type polynorbornene, poly(dodoxymethylene norbornene‐co‐norbornene‐3‐(trimethylpropyl ammonium)‐functionalized silica (QP(DNB/NB‐SiO2), were prepared by a sol–gel method. Copolymer composite membranes with different degree of quaternary ammonium functional silica, designated as QP(DNB/NB‐SiO2‐X) (X = 5, 10, 15 and 25 wt%, respectively), displayed good dimensional stabilities with low in‐plane swelling rate of 1.32–3.7%, good mechanical properties with high elastic modulus of 605.4–756.8 MPa and high tensile strength of 13.2–20 Mpa. The achieved copolymer composite membranes could self‐assemble into a microphase‐separated morphology with randomly oriented long‐range aliphatic chain/cylinder ionic channels that were imbedded in the hydrophobic PNB matrix. Among these membranes, the QP(DNB/NB‐SiO2‐25) showed the parameter with ionic conductivity of 9.33 × 10?3S cm?1, methanol permeability of 2.89 × 10?7cm2 s?1, and ion‐exchange capacity(IEC) of 1.19 × 10?3 mol g?1. A current density of 82.3mA cm?2, the open circuit voltage of 0.65 V and a peek power density of 32 mW cm?2 were obtained. POLYM. ENG. SCI., 58:13–21, 2018. © 2017 Society of Plastics Engineers  相似文献   

17.
CO2 reforming, oxidative conversion and simultaneous oxidative conversion and CO2 or steam reforming of methane to syngas (CO and H2) over NiO–CoO–MgO (Co: Ni: Mg=0·5: 0·5:1·0) solid solution at 700–850°C and high space velocity (5·1×105 cm3 g−1 h−1 for oxidative conversion and 4·5×104 cm3 g−1 h−1 for oxy-steam or oxy-CO2 reforming) for different CH4/O2 (1·8–8·0) and CH4/CO2 or H2O (1·5–8·4) ratios have been thoroughly investigated. Because of the replacement of 50 mol% of the NiO by CoO in NiO–MgO (Ni/Mg=1·0), the performance of the catalyst in the methane to syngas conversion process is improved; the carbon formation on the catalyst is drastically reduced. The CoO–NiO–MgO catalyst shows high methane conversion activity (methane conversion >80%) and high selectivity for both CO and H2 in the oxy-CO2 reforming and oxy-steam reforming processes at ⩾800°C. The oxy-steam or CO2 reforming process involves the coupling of the exothermic oxidative conversion and endothermic CO2 or steam reforming reactions, making these processes highly energy efficient and also safe to operate. These processes can be made thermoneutral or mildly exothermic or mildly endothermic by manipulating the process conditions (viz. temperature and/or CH4/O2 ratio in the feed). © 1998 Society of Chemistry Industry  相似文献   

18.
Copolymerizations of butadiene (Bd) with styrene (St) were carried out with catalytic systems composed of a rare‐earth compound, Mg(n‐Bu)2 (di‐n‐butyl magnesium) and halohydrocarbon. Of all the rare earth catalysts examined, Nd(P507)3–Mg(n‐Bu)2–CHCl3 showed a high activity in the copolymerization under certain conditions: [Bd] = [St] = 1.8 mol l?1, [Nd] = 6.0 × 10?3 mol l?1, Mg/Nd = 10, Cl/Nd = 10 (molar ratio), ageing for 2 h, copolymerization at 50 °C for 6–20 h. The copolymer of butadiene and styrene obtained has a relatively high styrene content (10–30 mol%), cis‐1,4 content in butadiene unit (85–90%), and molecular weight ([η] = 0.8–1 dL g?1). Monomer reactivity ratios were estimated to be rBd = 36 and rSt = 0.36 in the copolymerization. © 2002 Society of Chemical Industry  相似文献   

19.
Solid polymer electrolytes comprising blends of poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) as host polymers and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as dopant salt were prepared by solution‐casting technique. The ionic conductivity and dielectric behavior were investigated by using AC‐impedance spectroscopy in the temperature range of 298–353 K. The highest ionic conductivity of (1.11 ± 0.09)×10?6 S cm?1 is obtained at room temperature. The temperature dependence of ionic conductivity plots showed that these polymer blend electrolytes obey Arrhenius behavior. Conductivity–frequency dependence, dielectric relaxation, and dielectric moduli formalism were also further discussed. Apart from that, the structural characteristic of the polymer blend electrolytes was characterized by means of horizontal attenuated total reflectance–Fourier transform infrared (HATR–FTIR) spectroscopy. HATR–FTIR spectra divulged the interaction between PMMA, PVC, and LiTFSI. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

20.
Lead‐free sodium bismuth titanate–aluminate bismuth [0.97(Na0.5Bi0.5)TiO3–0.03BiAlO3] solid‐solution films deposited on (100) Pt/TiO2/SiO2/Si substrates by a sol–gel process were pyrolyzed and annealed at different temperatures. The film annealed at 725°C with a pyrolysis temperature of 410°C exhibited the optimal electrical properties and excellent piezoelectric properties, with a remanent polarization 2Pr of 38 μC/cm2 and a leakage current density of 10?7–10?6 A/cm2 (E < 200 kV/cm). The values of the dielectric constant and dissipation factor at 100 kHz were 422 and 0.039, respectively. The piezoelectric coefficient of the film after poling at 168 kV/cm was found to be 57 pm/V, making the BNT‐BA films a viable lead‐free alternative to the lead‐based materials in such as biosensors and ultrasonic transducers.  相似文献   

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