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1.
The conformational preference of the methyl group of 1-methyl-1-germacyclohexane was studied experimentally in solution (low-temperature 13C NMR) and by quantum chemical calculations (CCSD(T), MP2 and DFT methods). The NMR experiment resulted in an axial/equatorial ratio of 44/56 mol% at 114 K corresponding to an A value (A = G ax G eq) of 0.06 kcal mol?1. An average value for ΔG e→a #  = 5.0 ± 0.1 kcal mol?1 was obtained for the temperature range 106–134 K. The experimental results are very well reproduced by the calculations. CCSD(T)/CBS calculations + thermal corrections resulted in an A value of 0.02 kcal mol?1, whereas a ΔE value of ?0.01 kcal mol?1 at 0 K was obtained.  相似文献   

2.
Glasses having composition 5Li2O5ZnO xBi2O3 (90 ? x) P2O5 (x = 5, 10, 15, 20 and 25 mol%) were prepared by the normal melt quenching technique. Nanocomposite glass containing bismuth phosphate BiPO4 nanocrystals was obtained, which can be attributed to homogeneous nucleation process. The formation of BiPO4 nanocrystals was confirmed and characterized by X-ray diffraction patterns (XRD), transmission electron microscopy (TEM), differential scanning calorimetry, optical absorption (UV–Vis) and micro-hardness studies. The morphological analysis by XRD and TEM microscopy showed the formation of hexagonal BiPO4 nanocrystals, and its estimated nanocrystalline sizes were found to be varying from 5.35 to 11.53 nm depending on the Bi2O3 concentrations. The density (ρ) and molar volume (V m) were also determined and found to be in compositional dependence. Glass transition temperature (T g) and glass crystallization temperature (T c) were obtained and found to be increased (from 240.0 to 337.2 °C) with increasing Bi2O3 up to 20 mol% and then decreased (from 337.2 to 331.8 °C) due to the structural changes in the glass network. Effect of BiPO4 content on the optical properties had been investigated. From the UV–Vis spectra, it was observed that the fundamental absorption edge shifts toward lower wavelengths, i.e., blueshifts with increasing Bi2O3 mol% up to 20 mol%, and then shifts toward higher wavelengths, i.e., redshifts beyond 20 mol%. It was also observed that the obtained E opt (for indirect and direct transitions) increases with gradual increase in Bi2O3 content up to 20 mol% and then decreases beyond 20 mol%. This may be due to the introduction of Bi cations into the glass network as a network former up to 20 mol% causing a decrease in ΔE values, beyond 20 mol%, the introduction of Bi ions into the glass network interstitially leads to increase the values of ΔE. The optical properties of the present nanocrystallized glasses showed a quantum size dependence, in which the optical band gap energy (E opt) was changed as a function of BiPO4 nanocrystalline sizes.  相似文献   

3.
The present study focuses on the proton-conducting polymer electrolytes; poly (N-vinyl pyrrolidone)–ammonium thiocyanate and poly (N-vinyl pyrrolidone)–ammonium acetate prepared by solution casting technique. The XRD analysis indicates the amorphous nature of the polymer electrolytes. The Raman spectra of the C=O vibration of pure polymer PVP at 1,663 cm?1 has been appeared as doublet in the polymer electrolytes. The introduction of this new peak in the salt-doped polymer electrolytes may be due to interaction of the cation with the polymer. The room temperature ionic conductivity σ 303κ has been found to be high, 1.7?×?10?4 S cm?1 for 80 mol% PVP–20 mol% NH4SCN and 1.5?×?10?6 S cm?1 for 75 mol% PVP–25 mol% CH3COONH4. The polymer electrolytes have been tested for their application in Zn–air battery.  相似文献   

4.
Conversion anodes comprising non-stoichiometric black NiO suffer severe capacity fading in Li-ion batteries despite having a high Li+ ion diffusion coefficient. We attribute this capacity fading to (i) its small crystallite size (~?8 nm) and (ii) high charge transfer resistance (Rct ~?60–180 Ω cm2). Small crystallites enhance grain boundaries which promote Li+ ion diffusion without efficient material utilization. In contrast, the stoichiometric green NiO anodes deliver a stable capacity of 280 mAh g?1 over 50 charge-discharge cycles. The comparatively higher capacity of green NiO can be explained from its (i) large crystallite size (~?104 nm) and (ii) negligible Rct values.  相似文献   

5.
Variable-temperature proton magnetic relaxation dispersion (PMRD) profiles are collected in the induced nematic phases of the binary liquid crystalline mixtures composed of smectic mesogens: 5-butyl-2-(4-isothiocyanatophenyl)-1,3-dioxane (4DBT) and 4′-dodecyl-4-cyanobiphenyl (12CB) and the low viscous nematogen 4-(trans-4′-n-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT), with a view to assess the influence of local organisations on the power spectrum of director fluctuation modes. Two distinct compositions of the binary mixture i.e. 50 mol% of 12CB (without a smectic phase) and 70 mol% of 12CB (with a smectic phase) are used. Fast Field Cycling nuclear magnetic resonance relaxometry is employed to measure proton spin-lattice relaxation rates (R1) as a function of Larmor frequency (10 kHz–30 MHz). PMRD data analysis with the choice of a suitable model indicated nematic clusters of moderate size (~200 Å) found in the broad nematic region of 50 mol% 12CB, whose size is almost invariant with temperature. On the other hand, cybotactic clusters, i.e. local smectic organisations of relatively larger size (~2000–3000 Å), are observed near the nematic–smectic transition (T > TAN) of 70 mol% 12CB. Interestingly, the shape geometry of such local organisations accessed from PMRD analysis is weakly anisotropic near TAN, while being isotropic near TNI for 70 mol% 12CB.  相似文献   

6.
Two triads (i.e., 3PTZ–Pt–MNDI and 10PTZ–Pt–MNDI) consisting of 3-phenothiazine (3PTZ) or 10-phenothiazine (10PTZ), bipyridine–diacetylide platinum complex (Pt), and naphthalene diimide (MNDI) chromophores linked by highly twisted biphenylene spacers have been prepared. The formation and decay of the charge-separated (CS) states in toluene were studied by use of picosecond and nanosecond laser photolysis via selective excitation of the Pt moiety. The time required for formation of the CS state, PTZ+–Pt–MNDI?, from PTZ–3Pt*–MNDI was determined to be τ CS = 280 ps for 3PTZ+–Pt–MNDI? and τ CS = 230 ps for 10PTZ+–Pt–MNDI?. The lifetimes of the CS states were determined to be τ CR1 = 75 ns (95 %) and τ CR2 = 285 ns (5 %) for 3PTZ+–Pt–MNDI? and τ CR = 830 ns for 10PTZ+–Pt–MNDI?. Formation and decay of the CS states are discussed in terms the Marcus theory and the spin-correlated radical pair mechanism.  相似文献   

7.
Intrinsic dosimetry is the method of measuring total absorbed dose received by the walls of a container holding radioactive material. By considering the total absorbed dose received by a container in tandem with the physical characteristics of the radioactive material housed within that container, this method has the potential to provide enhanced pathway information regarding the history of the container and its radioactive contents. We report the latest in a series of experiments designed to validate and demonstrate this newly developed tool. Thermoluminescence (TL) dosimetry was used to measure dose effects on raw stock borosilicate container glass up to 70 days after gamma ray, X-ray, beta particle or ultraviolet irradiations at doses from 0.15 to 20 Gy. Two main peaks were identified in the TL glow curve when irradiated with 60Co, a relatively unstable peak around 120 °C and a more stable peak around 225 °C. Signal strength of both peaks decayed with time. The minimum measurable dose using this technique is 0.15 Gy, which is roughly equivalent to a 24 h irradiation at 1 cm from a 50 ng 60Co source. As a result of fading, this dose would be detectable for approximately 1 year post-irradiation. In a more detailed analysis, the TL glow curves were separated into five peaks centered near 120, 160, 225, 300, and 340 °C. Differences in TL glow curve shape and intensity were observed for the glasses from different geographical origins. These differences can be explained by changes in the intensities of the five peaks. This suggests that mechanisms controlling radiation induced defect formation from gamma, beta, X-ray, and UV sources may be similar.  相似文献   

8.
Dilatometric shrinkage data was utilized to study the sintering kinetics of the in-house synthesized nano-crystalline 3-mol% yttria-samaria codoped tetragonal zirconia polycrystal (TZP) ceramics. The objective was to determine activation energy (Q) of sintering and the sintering mechanism (n) relevant to the initial stage of sintering. The product of activation energy and sintering parameter, i.e., “nQ” was calculated from the shrinkage data acquired from the constant rate of heating experiment. The apparent activation energy of sintering (Q) was calculated using modified-“Dorn” method. Modified Johnson’s equation was used to determine value of “n” using the activation energy obtained from the Dorn method. Stepwise isothermal dilatometry technique was utilized as an independent method to determine the “n” value. The activation energy of sintering was in the range of 400–525 kJ mol?1 and found to be dependent on the dopant concentration. The value of “n” was found to be ~0.33 for both 3 mol% yttria-doped (3Y-TZP) and yttria-samaria codoped (3(Y,S)-TZP) TZP, whereas for 3 mol% samaria-doped tetragonal zirconia (3S-TZP), the value of “n” was ~0.40. From the obtained “n” values, it may be concluded that grain boundary diffusion (GBD) was the dominant sintering mechanism in 3Y-TZP and 3(Y,S)-TZP, whereas an intermediate of GBD and volume diffusion influences the initial sintering stage in the 3S-TZP.  相似文献   

9.
Pyrimethamine is an important antiparasitic drug in the treatment of malaria and toxoplasmosis and is often used in combination with either sulfadoxine, sulfalene, or sulfadiazine. Determining the content of pyrimethamine and investigating the related substances is currently possible applying either a compendial monograph utilizing thin layer chromatography as well as liquid chromatographic methods used by the respective manufacturers. To provide a simple method which is capable of determining the content of pyrimethamine and of resolving four of its potential synthetic impurities a very simple, cheap, precise, and accurate isocratic RP-HPLC method was developed. All analytes can be separated within a total runtime of 30 min and the method was linear within the concentration ranges of 0.12–0.740, 0.104–0.621, 0.120–0.710, 2.0–11.8, and 1.01–5.80 µg mL?1 for pyrimethamine, impurity A, impurity B, impurity C, and impurity D, respectively. These substances were separated by employing a Eurospher-II C18H column (250 × 4.6 mm, 5 µm particle size), a mobile phase being a mixture of a 0.05 M KH2PO4 buffer solution (pH 2.6) and methanol in the ratio 40:60 (v/v). The analysis was carried out at 30 °C, applying a flow rate of 1.2 mL min?1, and a detection wavelength of λ = 215 nm. The coefficients of determinations (R 2) for the five analytes were greater than 0.994 for pyrimethamine and all impurities. Results of recovery studies were within the range of 89.1–105.1% for all substances. In all tested genuine batches of pyrimethamine raw material impurities within the specified limits were present which is concurrent with results obtained from using the present manufacturer’s method.  相似文献   

10.
The molecular structure of the axial and equatorial conformers of fluorocyclohexane and 1-fluoro-1-silacyclohexane, H2C(CH2CH2)2XH–F (X = C or Si), as well as the thermodynamic equilibrium between these species were investigated by means of quantum chemical calculations up to MP2/aug-cc-pVTZ level of theory. According to MP2 data, these compounds consist of a mixture of conformers with chair conformation and C s symmetry differing in the axial and equatorial position of the C–F/Si–F bonds (axial = 42/56 mol%, equatorial = 58/44 mol%) at T = 298 K. This corresponds to a free energy difference of A = (G ax ? G eq) = 0.19/?0.13 kcal mol?1 for X = C/Si. NBO analysis revealed that the axial conformer of 1-fluoro-1-silacyclohexane is an example of stabilization of the form that is unfavorable in terms of conjugation effects; stabilization is achieved mainly due to steric interactions. The equatorial conformer of fluorocyclohexane is an example of stabilization of the form that is unfavorable in terms of electrostatic interactions; stabilization is achieved due to steric and conjugation effects.  相似文献   

11.
We report a detailed comparison between RF and microwave (HF) plasmas of N2 and Ar–20 %N2 as well as in the corresponding afterglows by comparing densities of active species at nearly the same discharge conditions of tube diameter (5–6 mm), gas pressure (6–8 Torr), flow rate (0.6–1.0 slm) and applied power (50–150 W). The analysis reveals an interesting difference between the two cases; the length of the RF plasma (~25 cm) is measured to be much longer than that of HF (6 cm). This ensures a much longer residence time (10?2 s) of the active species in the N2 RF plasma [compared to that (10?3 s) of HF], providing a condition for an efficient vibrational excitation of N2(X, v) by (V–V) climbing-up processes, making the RF plasma more vibrationally excited than the HF one. As a result of high V–V plasma excitation in RF, the densities of the vibrationally excited N2(X, v > 13) molecules are higher in the RF afterglow than in the HF afterglow. Destruction of N2(X, v) due to the tube wall is estimated to be very similar between the two system as can be inferred from the γv destruction probability of N2(X, v > 3–13) on the tube wall (2–3 × 10?3 for both cases) obtained from a comparison between the density of N2(X, v > 3–9) in the plasmas to that of the N2(X, v > 13) in the long afterglows. Interestingly enough, densities of N-atoms and N2(A) metastable molecules in the afterglow regions, however, are measured to be very similar with each other. The measured lower density of N2 + ions than expected in the HF afterglow is rationalized from a high oxygen impurity in our HF setup since N2 + ions are very sensitive to oxygen impurity .  相似文献   

12.
The association reaction between silyl radical (SiH3) and H2O2 has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH3–H2O2 association in the temperature range 250–600 K, k(T) = 6.89 × 10?13 T ?0.163exp(?0.22/RT) cm3 molecule?1 s?1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH2(OH)2 + H, is the major decomposition channel followed by secondary dissociation leading to SiO.  相似文献   

13.
Lyoluminescence (LL) is a good technique for radiation dosimetry of high-energy radiations. Dosimetry of γ rays from 60Co radioactive source has been done using MgB4O7:Mn2+ phosphor material. It was synthesized by simple solid state diffusion method. The material shows good linear LL response with the γ rays for the dose rage of 10 Gy–10 kGy. The studies have also been done for different particle sizes (250–45 µm) and particles having average size ~85 µm were found to be the most suitable for this dosimetry. Effect of solvent pH on LL and fading on storage has also been studied.  相似文献   

14.
The co-efficient of linear thermal expansion (α av) and dose dependence of thermoluminescence (TL) in MgAl2O4(s) were measured. The change in length per unit length was recorded as a function of temperature between room temperature to 1,273 K at a heating rate of 8 K min?1, in flowing argon atmosphere. The average of three measurements was quoted as the α av for MgAl2O4(s). The linear thermal expansion was measured to an accuracy of ±3 %. The dose dependence of the TL was found to be super linear in the dose range of 0–10 kGy with a k value of 0.503 indicating that the MgAl2O4(s) ceramic is ideally suited for the dose estimation of self-irradiated inert matrix fuel in a once through fuel cycle for actinide burning.  相似文献   

15.
Micro- and mesoporous carbide-derived carbons (CDCs) were synthesised from TiC powder via a gas-phase reaction using HCl and Cl2 within the temperature range of 700–1,100 °C. Analysis of X-ray diffraction results show that TiC-CDCs consist mainly of graphitic crystallites. The first-order Raman spectra showed the graphite-like absorption peaks at ~1,577 cm?1 and the disorder-induced peaks at ~1,338 cm?1. The low-temperature N2 sorption experiments were performed, and specific surface areas up to 1,214 and 1,544 m2?g?1 were obtained for TiC-CDC (HCl) synthesised at T?=?800 °C and TiC-CDC (Cl2) synthesised at T?=?900 °C, respectively. For the TiC-CDC powders synthesised, a bimodal pore size distribution has been established with the first maximum in the region up to 1.5 nm and the second maximum from 2 to 4 nm. The energy-related properties of supercapacitors based on 1 M (C2H5)3CH3NBF4 in acetonitrile and TiC-CDC (Cl2) and TiC-CDC (HCl) as electrode materials were also investigated by cyclic voltammetry, impedance spectroscopy, galvanostatic charge/discharge and constant power methods. The specific energy, calculated at U?=?3.0 V, are maximal for TiC-CDC (Cl2 800 °C) and TiC-CDC (HCl 900 °C), which are 43.1 and 31.1 W?h?kg?1, respectively. The specific power, calculated at cell potential U?=?3.0 V, are maximal for TiC-CDC (Cl2 1,000 °C) and TiC-CDC (HCl 1,000 °C), which are 805.2 and 847.5 kW?kg?1, respectively. The Ragone plots for CDCs prepared by using Cl2 or HCl are quite similar, and at high power loads, the TiC-CDC material synthesised using Cl2 at 900 °C, i.e. the material with optimal pore structure, delivers the highest power at constant energy.  相似文献   

16.
We herein report on the calculation of the activation energy (E a) from the thermoluminescence (TL) glow curves performed by the initial rise method that allows us to discriminate between irradiated and non-irradiated sesame seeds. E a values of natural TL (0.68 ± 0.03 eV) and gamma-induced TL (never lower than 0.82 ± 0.02 eV) appear as a complementary criterion to be used differentiating between irradiated and non-irradiated foodstuffs with the position and the intensity of the main peak of the TL emission. In addition, E a values taken from irradiated sesame samples at different doses (1, 5 and 10 kGy) and stored up to 15 months after being processed were compared to a ‘positive’ Spanish blend (i.e. at least one component was commercially irradiated).  相似文献   

17.

The oxidation of aniline with silver nitrate in 1 mol L−1 acetic acid at 20 °C yielded a composite of two conducting components, polyaniline and silver; the acceleration with 1 mol% of p-phenylenediamine is needed for efficient synthesis. The yield and molecular weight increased when aniline was copolymerized with 10 mol% p-phenylenediamine. Such product displayed metallic conductivity below 180 K and semiconductor type above this temperature. As the result, the conductivity was the same at 100 and 300 K. The oxidation of p-phenylenediamine alone with silver nitrate also produced a conducting composite having the conductivity of 1,750 S cm−1 despite the assumed nonconductivity of poly(p-phenylenediamine). The present study demonstrates that all oxidations proceeded also in frozen reaction mixtures at −24 °C, i.e., in the solid state. In most cases, molecular weights of polymer component increased, the conductivity of composites with silver improved, to 2,990 S cm−1 for poly(p-phenylenediamine)–silver, and remained high after deprotonation with 1 mol L−1 ammonium hydroxide.

  相似文献   

18.
An ab initio variational grand-canonical electronic structure mean-field method, based on the Gibbs–Peierls–Bogoliubov minimum principle for the Gibbs free energy, is applied to the di-lithium (Li+Li) system at temperatures around T ≈ 104 K and electronic chemical potential of μ ≈ ?0.1E h . The method is an extension of the Hartree–Fock approach to finite temperatures. We first study the Li2 molecule at a frozen inter-nuclear distance of R = 3 Å as a function of temperature. The mean-field electronic structure changes smoothly as temperature increases, up to 104 K, where a sharp spontaneous spin-polarization emerges as the variational mean-field solution. Further increase in the temperature extinguishes this polarization. We analyze the mean-field behavior using a correlated single-site Hubbard model and show it arises from an attempt of the mean-field to mimic the polarization of the spin–spin correlation function of the exact solution. Next, we keep constant the temperature at 104 K and examine the electronic structure as a function of inter-nuclear distance R. At R = 3.7 Å, a crossing between two free energy states occurs: One state is “spin-unpolarized” (becomes lower in energy when R > 3.7 Å), while the other is “spin polarized”. This crossing causes near-discontinuous jumps in calculated properties of the system and is associated with using the noninteracting electron character of our mean-field approach. Such problems will likely plague FT-DFT calculations as well. We use second-order perturbation theory (PT2) to study effects of electron correlation on the potential of mean force between the two colliding Li atoms. We find that PT2 correlation free energy at ~104 K is larger than at 0 K and tends to restore the spin-polarized state as the lowest free energy solution.  相似文献   

19.
A detailed thermal analysis of iron and cobalt surfactant complexes of the type [M(CH3COO)4]2?[C12H25NH3 +]2 has been carried out using Thermogravimetric (TG) analysis at different heating rates (i.e., 5, 10, 15, and 20 °C min?1). It has been observed that iron complex decomposes by a different mechanism compared to other transition metal complexes. Metal is the final product instead of metal oxide. Combining the results from our previous study, first row transition metal complexes exhibit an order of stability in agreement with the famous Irving Williams series, i.e., the apparent activation energy, E for thermal decomposition varies as: E Fe > E Co < E Ni < E Cu > E Zn (exception being iron because of different decomposition mechanism). Thermal decomposition parameters have been measured and compared using the multiple heating rate method of Flynn–Wall–Ozawa. Further, molecular modeling calculations have been carried out to compare the experimental TG data with theoretical computations for the synthesized metal surfactant complexes. Minimum energy optimized structures for the complexes have been obtained using Gaussian software.  相似文献   

20.
Blends of cardanol-based bisbenzoxazine (BZc) and 4,4′-bisitaconimidodiphenyl ether (BIM) having nine different mass ratios (i.e. 100:0, 90:10, 75:25, 60:40, 50:50, 40:60, 25:75, 10:90 and 0:100) were prepared and their curing behaviour was studied by differential scanning calorimetry (DSC) and fourier transform infrared spectroscopy. A curing mechanism comprising two-steps: (1) homopolymerization and co-curing reaction of itaconimide with alkyl side chain double bonds of cardanol BZc at lower temperature (~443 K) and (2) ring-opening polymerization of oxazine at higher temperature (~453–483 K) has been proposed. The T g of the cured resin blends was determined by DSC and the increase in BIM content in the blend resulted in an increase in T g from 408 K BZc to 474 K BIM. Increase in bisitaconimide content resulted in improvement of char yield at 1,073 K as well as an increase in mass loss temperatures (5 and 10 %). Compared to BZc, the blends showed a higher thermal stability. The lap shear strength of these blends in metal–metal joints was investigated at 323, 523 and 573 K.  相似文献   

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