Rate coefficients, k1(T), for the gas-phase reaction of the OH radical with furan-2,5-dione (maleic anhydride (MA), C4H2O3), a biomass burning related compound, were measured under pseudo–first-order conditions in OH using the pulsed laser photolysis–laser-induced fluorescence method over a range of temperature (283-374 K) and bath gas pressure (50-200 Torr; He or N2). k1(T) was found to be independent of pressure over this range with k1(283-374 K) = (1.55 ± 0.20) × 10−12 exp[(−410 ± 44)/T) cm3 molecule−1 s−1 and k1(296 K) = (3.93 ± 0.28) × 10−13 cm3 molecule−1 s−1, where the uncertainties are 2σ and the preexponential term includes the estimated systematic error. The atmospheric lifetime of MA with respect to OH reactive loss is estimated to be ∼15 days. The present results are compared with a previous room temperature relative rate study of the OH + MA reaction, and the significant discrepancy between the studies is discussed; the present results are approximately a factor of 4 lower. It is also noteworthy that the experimentally measured k1(296 K) value obtained in this work is nearly a factor of 110 less than estimated by a structure activity relationship based on trends in ionization potential. Based in part on a computational evaluation, an atmospheric degradation mechanism of MA is proposed. 相似文献
To tolerate high processing temperature during the fabrication of low-temperature polycrystalline silicon thin-film transistors (LTPS–TFT) in flexible OLED devices, the polyimide (PI) films, which are used as substrate, should have ultra-high glass transition temperature (Tg > 450°C) and ultra-low coefficient of thermal expansion (CTE at 0–5 ppm K−1). In this paper, two novel heterocyclic monomers, namely, N,N'-(xanthone-2,7-diyl)bis(4-aminobenzamide) (p-DAXBA) and N,N'-(xanthone-2,7-diyl)bis(3-aminobenzamide) (m-DAXBA), which contain a xanthone moiety, are prepared and polycondensed with pyromellitic dianhydride (PMDA), respectively. PI films (PIa and PIb) with intrinsic high Tg and low CTE are designed from the perspective of rigid conjugate xanthone structure and hydrogen bonding interaction. It is found that the PIa films prepared by p-DAXBA have better linear structure of molecular chains and show relatively higher Tg and lower CTE. The Tg of PIa-40 is greater than 450°C, and CTE can reach as low as 2.7 ppm K−1, tensile strength of 179 MPa, modulus of 5.67 GPa, indicating potential application prospect as a flexible OLED substrate. 相似文献
The glass transition and relaxation processes in polystyrene resins with the number average molecular weight ranging from 7.0·102 to 9.8·104 were studied with the positron annihilation technique. The pick-off annihilation lifetime of ortho-positronium (3) and its intensity (I3) were measured in the temperature range from 20 to 430 K. The glass transition temperature (Tg) was determined as an onset temperature coefficient of 3.Tg shows the molecular weight dependence in these samples. BelowTg, local motions were detected by measurements ofI3. The local motions could be observed above 100 K in this experiment.I3 show the minimum at around 250 K and it does not show molecular weight dependence. 相似文献
Rate coefficients for the reactions of OH with n, s, and iso-butanol have been measured over the temperature range 298 to ∼650 K. The rate coefficients display significant curvature over this temperature range and bridge the gap between previous low-temperature measurements with a negative temperature dependence and higher temperature shock tube measurements that have a positive temperature dependence. In combination with literature data, the following parameterizations are recommended: k1,OH + n-butanol(T) = (3.8 ± 10.4) × 10−19T2.48 ± 0.37exp ((840 ± 161)/T) cm3 molecule−1 s−1k2,OH + s-butanol(T) = (3.5 ± 3.0) × 10−20T2.76 ± 0.12exp ((1085 ± 55)/T) cm3 molecule−1 s−1k3,OH + i-butanol(T) = (5.1 ± 5.3) × 10−20T2.72 ± 0.14exp ((1059 ± 66)/T) cm3 molecule−1 s−1k4,OH + t-butanol(T) = (8.8 ± 10.4) × 10−22T3.24 ± 0.15exp ((711 ± 83)/T) cm3 molecule−1 s−1 Comparison of the current data with the higher shock tube measurements suggests that at temperatures of ∼1000 K, the OH yields, primarily from decomposition of β-hydroxyperoxy radicals, are ∼0.3 (n-butanol), ∼0.3 (s-butanol) and ∼0.2 (iso-butanol) with β-hydroxyperoxy decompositions generating OH, and a butene as the main products. The data suggest that decomposition of β-hydroxyperoxy radicals predominantly occurs via OH elimination. 相似文献
The models of rubidium at temperatures of up to 3500 K, degrees of compression of up to Y = V/V0 = 0.3, and pressures of up to 32 GPa were constructed by molecular dynamics (MD) using the interparticle potential ЕАМ. The thermodynamic properties of the MD models agree satisfactorily with experiment in the range of parameters under study at rubidium densities higher than 0.86 g/cm3. The behavior of the models in the range of the van der Waals loop was analyzed; the calculated critical temperature of rubidium Tc is ~2250 ± 25 K, density ~0.41 g/cm3, pressure ~0.019 GPa, and compressibility factor Z = pV/RT ≈ 0.137. The states with the unity factor Z = 1 were observed at pressures of up to 0.30 GPa (at ~3000 K); the temperature dependence of the density of the models with Z = 1 is nearly linear, and the Boyle temperature is TB ≈ 10160 K. The ratio Tc/TB = 0.221 is close to this value for cesium (0.23) and mercury (0.276). In the temperature and pressure ranges under study, the inversion of the Joule–Thomson coefficient did not take place, but should be observed at pressures of ?0.3 GPa and elevated temperatures. It was found that the diffusion coefficient D(T) dependences do not straighten in the usually used coordinates within wide temperature ranges. It was concluded that the structure of the liquid smoothly changes when the rubidium models are compressed and this reveals in the change of the degree of asymmetry of the first peak of the radial distribution function. 相似文献
In order to develop a new functional product from lignin, sodium lignosulfonate (LS)-based polyurethane (LSPU) hydrogels were prepared from LS and hexamethylene diisocyanate (HDI) derivatives in water. Isocyanate/hydroxyl group ratio (NCO/OH ratio) was varied from 0.05 to 0.8 mol mol−1, and water content (Wc = mass of water/mass of dry sample) of the obtained LSPU hydrogels was varied from 0 to 3.0 g g−1. Phase transition behavior of hydrogels with various Wc’s was investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG). In DSC heating curve of LSPU hydrogels, glass transition, cold crystallization, melting and liquid crystallization were observed. Cold crystallization, two melting peaks and variation of melting enthalpy indicate that three kinds of water, i.e., non-freezing water, freezing bound water and free water, exist in LSPU hydrogel. Glass transition temperature (Tg) decreased from 230 to 190 K in a Wc range where non-freezing water was formed in the hydrogel. Tg increased when freezing bound water was formed in the system. Tg leveled off in a Wc range where normal ice was formed. The effect of NCO/OH ratio on molecular motion of LSPU hydrogel is examined based on Tg and heat capacity difference at Tg (ΔCp). Water vaporization curve measured by TG also indicates the presence of bound water which evaporates at a temperature higher than ca. 410 K. By atomic force microscopic observation, the size of molecular bundle of LSPU hydrogel is calculated and compared with that of LS-water system. By cross-linking, the height of molecular bundle decreased from ca. 3–1 nm and lignin molecules extend in a flat structure.
The kinetics of OH reactions with furan (k1), thiophene (k2), and tetrahydrothiophene (k3), have been investigated over the temperature range 254–425 K. OH radicals were produced by flash photolysis of water vapor at λ > 165 nm and detected by timeresolved resonance fluorescence spectroscopy. The following Arrhenius expressions adequately describe the measured rate constants as a function of temperature (units are cm3 molecule?1 S?1): k1 = (1.33 ± 0.29) × 10?11 exp[(333 ± 67)/T], k2 = (3.20 ± 0.70) × 10?12 exp[(325 ± 71)/T], k3 = (1.13 ± 0.35) × 10?11 exp[(166 ± 97)/T]. The results are compared with previous investigations and their implications regarding reaction mechanisms and atmospheric residence times are discussed. 相似文献
Low‐temperature heat capacities of gramine (C11H14N2) were measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 401 K. A polynomial equation of heat capacities as a function of temperature was fitted by least squares method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15 K were calculated and tabulated at 5 K intervals. The constant‐volume energy of combustion of the compound at T=298.15 K was measured by a precision oxygen‐bomb combustion calorimeter as ΔcU=−(35336.7±13.9) J·g−1. The standard molar enthalpy of combustion of the compound was determined to be ΔcHm0=−(6163.2±2.4) kJ·mol−1, according to the definition of combustion enthalpy. Finally, the standard molar enthalpy of formation of the compound was calculated to be Δ;cHm0=−(166.2±2.8) kJ·mol−1 in accordance with Hess law. 相似文献
Three novel diamines, incorporating benzimidazole and amide moieties, namely 4-amino-N-(5-amino-benzimidazol-2-yl)-benzamide (6a), 4-amino-N-(5-amino-1- methyl-benzimidazol-2-yl)-benzamide (6b), and 4-amino-N-(5-amino-1-phenyl -benzimidazol-2-yl)-benzamide (6c), were designed and synthesized. A series of poly(benzimidazole-amide-imide) (PBIAI) films were prepared from the resulting diamines and 4,4-biphthalic dianhydride (BPDA). These flexible polyimides (PIs) showed high glass transition temperatures (Tg = 353–379°C), low coefficients of thermal expansion (CTE = 3.7–12.3 ppm K−1) and good mechanical properties (σ = 152–207 MPa and E = 4.5–7.7 GPa), promising candidates for applications in flexible-display substrates. Furthermore, the data guided a feasible method to enhance Tg and reduce CTE by introducing benzimidazole and amide units into PI main chains, and the effect of different N-substituents on performance was revealed. 相似文献
Thermophysical and mechanical properties of two conjugated polymers, poly(p‐phenylene vinylene) (PPV) and polyacetylene (PA), are predicted using molecular dynamics simulations and compared with results obtained from differential scanning calorimetry, nanoindentation, and dynamic mechanical analysis experiments. Glass transition temperature (Tg) is calculated from the changes in the slopes of the specific volume versus temperature and cohesive energy density versus temperature plots, obtained from constant pressure and constant temperature simulations (NPT ensemble). The effects of temperature on the torsion angle distributions and characteristic ratio are analyzed. PPV is found to have a Tg of 416 ± 8 K. PA does not exhibit a glass transition in the temperature range of 120 to 500 K. Using the static deformation method, the values of Young's modulus are calculated to be 1.81 ± 0.34 GPa for PA and 9.20 ± 0.57 GPa for PPV at 298 K. These values are in good agreement with the experimental measurements, validating the suitability of these techniques in the prediction of the polymer properties.