Solvent transport dynamics and its effect on evolution of mechanical properties of nitrocellulose(NC)-based propellants under hot-air drying process

Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics within NC-based propellants was reported,and its effect on the evolution of mechanical properties was not interpreted yet.This study is conducted to gain a comprehensive understanding of hot-air drying for NC-based propellants and clarify the effect of temperature on solvent transport behavior and further the change of mechanical properties during drying.The drying kinetic curves show the drying time required is decreased but the steady solvent content is increased and the drying rate is obviously increased with the increase of hot-air temperatures,indicating hot-air temperatures have a significant effect on drying kinetics.A modified drying model was established,and results show it is more appropriate to describe solvent transport behavior within NC-based propellants.Moreover,two linear equations were established to exhibit the relationship between solvent content and its effect on the change of tensile properties,and the decrease of residual solvent content causes an obvious increase of tensile strength and tensile modulus of propellant products,indicating its mechanical properties can be partly improved by adjustment of residual solvent content.The outcomes can be used to clarify solvent transport mechanisms and optimize drying process parameters of double-based gun propellants.

Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.

Effect of solvent on the initiation mechanism of living anionic polymerization of styrene:A computational study

For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results ofΔG_(TS).Finally,the kinetic characteristics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.

Effect of solvents on the morphology and structure of barium titanate synthesized by a one-step hydrothermal method

Tetragonal barium titanate was synthesized from barium hydroxide octahydrate and titanium tetrachloride through a simple one-step hydrothermal method.The effect of different solvents on the crystal structure and morphology of barium titanate nanoparticles during the hy-drothermal process was investigated.Except for ethylene glycol/water solvent,impurity-free barium titanate was synthesized in pure water,methanol/water,ethanol/water,and isopropyl alcohol/water mixed solvents.Compared with other alcohols,ethanol promotes the formation of a tetragonal structure.In addition,characterization studies confirm that particles synthesized in methanol/water,ethanol/water,and isopropyl al-cohol/water mixed solvents are smaller in size than those synthesized in pure water.In the case of alcohol-containing solvents,the particle size decreases in the order of isopropanol,ethanol,and methanol.Among all the media used in this study,ethanol/water is considered the optimum reaction media for barium titanate with high tetragonality(defined as the ratio of two lattice parameters c and a,c/a=1.0088)and small aver-age particle size(82 nm),which indicates its great application potential in multilayer ceramic capacitors.

Solvent effects on Pt-Ru/C catalyst for methanol electro-oxidation

Alloying degree, particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent（s） used in the preparation process can affect the particle size and alloying degree of the object substance, which lead to a great positive impact on its properties. In this work, three types of solvents and their mixtures were used in preparation of the Pt-Ru/C catalysts by chemical reduction of metal precursors with sodium borohydride at room temperature. The structure of the catalysts was characterized by X-ray diffraction （XRD） and Transmission electron microscopy （TEM）. The catalytic activity and stability for methanol electro-oxidation were studied by Cyclic Voltammetry （CV） and Chronoamperometry （CA）. Pt-Ru/C catalyst prepared in H2O or binary solvents of H2O and isopropanol had large particle size and low alloying degree leading to low catalytic activity and less stability in methanol electro-oxidation. When tetrahydrofuran was added to the above solvent systems, Pt-Ru/C catalyst prepared had smaller particle size and higher alloying degree which resulted in better catalytic activity, lower onset and peak potentials, compared with the above catalysts. Moreover, the catalyst prepared in ternary solvents of isopropanol, water and tetrahydrofuran had the smallest particle size, and the high alloying degree and the dispersion kept unchanged. Therefore, this kind of catalyst showed the highest catalytic activity and good stability for methanol electro-oxidation.

EFFECT OF SOLVENT ON SURFACE ENHANCED RAMAN SCATTERING SPECTRA OF COLLOIDAL SILVER

The effect of solvent on surface enhanced Raman scattering [SERS) of colloidal silver has been studied. Experiments show that the intensity of SERS is related to the polarity and molecular constitution of the solvent. The influence of solvent is due to the change of the adsorption quantity and adsorption intensity.

Growth and Solvent Effects of a Promising Nonlinear Optical Sodium Paranitrophenolate Dihydrate (NO_2-C_H_4-ONa·2H_2O) Single Crystal

Sodium paranitrophenolate dihydrate (NPNa·2H2O) is an excellent semiorganic nonlinear optical (NLO) material, crystallizes both in water and methanol with high degree of transparency. Good optical quality single crystals of dimension upto 18 mm×6 mm×3 mm are obtained by isothermal solvent evaporation technique. The solubility of the crystal in different solvents was measured gravimetrically. The single crystals of NPNa·2H2O show variation in physical properties and growth rate in different solvents. Methanol or ethanol solution yields crystals of bipyramidal shape with clear morphology. However, methanol grown crystal is exhibiting improved hardness parameters and possesses excellent thermal stability as compared to water grown crystals. The effects of solvent on hardness parameter along with thermal and optical properties of NPNa·2H2O was revealed in this paper.

Effect and Mechanism Analysis of Solvent on the Electron Transition of Fluoroquinolones Based on Quantum Chemical Calculation

Ciprofloxacin（CIP）, moxifoxacin（MOX） and enrofloxacin（ENR） were selected as typical fluoroquinolones（FQs） to analyze the excitation-enhancing effect and mechanism of solvents on FQs＇ electron transition based on quantum chemical calculations. The UV spectra of three FQs in gas and five different solvents（water, cyclohexane, dimethylsulfoxide, methanol, acetone） were calculated using Gaussian 09 software. The transition mechanisms of FQs＇ main electron transitions were analyzed by natural bond orbital（NBO） theory, and the solvent effect on each electron transition was assessed qualitatively and quantitatively by sensitivity analysis and an established index system. The excitation enhancing mechanism of solvent on electron transitions of FQs was analyzed from the view of photo-induced reactions between solvent and FQs molecules. The results show that there are two main transitions located in the spectrum ranges of 300~380 and 240~300 nm for each FQ in any medium, which are assigned as n →π＊ and π→π＊ electron transitions, respectively. By comparison, the n →π＊ transition is more sensitive to solvent because of the energy transfer between solvent molecules and FQs, but the solvent effect on the π→π＊ transition is stronger than on the n →π＊ transition. The sequence of affected extent of solvent effect on electron transition was CIP 〉 MOX 〉 ENR, and the sequence of solvent effect was water 〉 DMSO 〉 methanol 〉 acetone 〉 cyclohexane（stronger solvent effect with increasing the dielectric constant of solvent）. From the view of photo-induced reactions, the reaction between FQs＊T1 and solvent＊T1 has the decisive regulatory effect on the n →π＊ transition of FQs in solvent, and the reaction between FQsS0 and solvent＊TI has an enhancing effect on the π→π＊ transition.

Solvent effects on infrared spectra of 2-methyl-4,5-dimethoxy-3-oxo-2H-pyridizine： Part 1. Single solvent systems

Infrared spectroscopy studies of 2-methyl-4,5-dirnethoxy-3-oxo-2H-pyridlzine (MDOP) in 12 pure organic solvents were undertaken to investigate the solvent-solute interactions. The frequencies of the carbonyl (C = O) of MDOP were correlated with solvent properties such as solvent acceptor number (AN) and the linear solvation energy relationships (LSER). These frequencies showed a good correlation with the solvent acceptor number (AN) and the LSER.

A reaction density functional theory study of solvent effect in the nucleophilic addition reactions in aqueous solution

Whereas the proper choice of reaction solvent constitutes the cornerstone of the green solvent concept,solvent effects on chemical reactions are not mechanistically well understood due to the lack of feasible molecular models.Herein,by taking the case study of nucleophilic addition reaction in aqueous solution,we extend the proposed multiscale reaction density functional theory(RxDFT)method to investigate the intrinsic free energy profile and total free energy profile,and study the solvent effect on the activation and reaction free energy for the nucleophilic addition reactions of hydroxide anion with methanal and carbon dioxide in aqueous solution.The predictions of the free energy profile in aqueous solution for these two nucleophilic addition reactions from RxDFT have a satisfactory agreement with the results from the RISM and MD-FEP simulation.Meanwhile,the solvent effect is successfully addressed by examining the difference of the free energy profile between the gas phase and aqueous phase.In addition,we investigate the solvent effect on the reactions occurred near solid-liquid interfaces.It is shown that the activation free energy is significantly depressed when reaction takes place in the region within 10A distance to the substrate surface owing to the decrease of hydration free energy at the solid-liquid interface.

Physical Diffusion and Electron-transfer Dynamics of Electroactive Solutes in Polymer Electrolytes Ⅲ. Effect of the Polymer Solvents

The diffusion coefficients(Dapp) and the heterogeneous electron transfer rate constants(ks)for ferrocene in several polymer solvents were determined by using steady-stae voltammetry. Thetemperature dependence of the two parameters indicates Arrhenius behavior. The polymer solventeffects on diffusion and electron transfer dynamics of ferrocene were discussed

Solvent effects on hydrogen bonding between primary alcohols and esters

The interaction by hydrogen bond formation of some primary alcohols (1-heptanol, 1-octanol and 1-decanol) with esters (methyl methacrylate, ethyl methacrylate and butyl methacrylate) was investigated in non-polar solvents viz., n-heptane, CCl4 and benzene by means of FTIR spectroscopy. Formation constants and free energy changes of complex formation were determined. The dependence of the equilibrium constants and free energy changes of complex formation on the alkyl chain length of both the alcohols and esters are discussed. The solvent effect on the hydrogen bond formation is discussed in terms of specific interaction between the solute and solvent.

Effects of Hydrogen-bonding Interaction and Polarity on Emission Spectrum of Naphthalene-Triethylamine in Mixed Solvent

The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of the naphthalene-triethylamine system consists of two emission bands, the fluorescence band of naphthalene(band A, 329 nm) and the emission band of the exciplex(band B, 468 nm). The intensities of both the emission bands decrease with increasing the solvent polarity. The intensity of band B also decreases due to the hydrogen-bonding interaction between triethylamine and protic solvent, while that of band A increases. It is thus suggested that the quenching of naphthalene fluorescence by triethylamine in THF occurs through the charge transfer and electron transfer reactions. The spectral changes upon the increase of solvent polarity can be explained by the dependences of the equilibrium constant between exciplex and ion-pair and the rate constant for the electron transfer reaction from triethylamine to the excited naphthalene on the relative permittivity of solvent. It is shown that the formation of intermolecular hydrogen-bonding between triethylamine and protic solvent suppresses the quenching reaction by the decrease in free amine. Acetonitrile has only a polar effect and trichloroacetic acid only a hydrogen-bonding(or protonation) effect, while alcohols have both the effects. The effects of alcohols could be separated into the effects of solvent polarity and intermolecular hydrogen-bonding interaction quantitatively.

Solvent Effects on Extraction of Rare Earth Metals with HDEHP

オhe extraction of Pr, Nd, Sm, Dy, Ho and Yb with HDEHP were studied in hexane, cyclohexane, carbon tetrachloride, toluene, benzene and chloroform at 298±1 K. The apparent and thermodynamic extraction equilibrium constants and the solubility parameters of the extraction complexes were obtained. The relationship between apparent equilibrium constants Kex and the physical parameters of solvents can be derived. The results indicated that the different solvents affect the apparent extraction equilibrium constants. The solubility parameters of the extraction complexes are nearly the same and not sensitive to rare earth ions.

Solvent effects on structure and optical properties of a D-π-A azobenzene dye

Time-dependent hybrid density functional theory in combination with Onsager reaction field model and super-molecular model has been applied to study solvent effects on the geometrical and electronic structures, as well as one/two-photon absorption properties, of 4-（N-（2-hydroxyethyl）-N-methyl）-amino-4＇-nitroazobenzene. It is found that the short-range interaction has a large effect on the electronic structure of the solute molecule, namely, large red-shift of the maximum one-photon absorption is induced by hydrogen bonding. The solute molecule has a large two-photon absorption cross section, which is enhanced by the solvent effect. The computational results are in good agreement with measurements.

Studies on the Solvent Effect of N-Carbamoyl-N-(1-Oxyl 2,2,5,5-Tetramethyl-Pyrrolin-3-yl) Ureas

The electron spin resonance spectra of N-carbamoyl-N-(l-oxyl-2,2,5,5-tetramethyl-pyrrolin-3-yl) urea compounds in ten solvents with different polarities were determined. It was found that the hyperfine splitting constant AN and spin density pN. as well as the energy difference between two adjacent energy levels E of different pyrroline nitroxides in the same solvent increase with the increase of electron-withdrawing α-bility of the substituted groups on the aromatic ring. There was a linear correlation between AN and Reichardt ET value, and between AN and Z value as well. Such a linear correlation was also found between solvent viscosity n and ESR rotational correlation time r. On the other hand, the correlation between T and the relative height hr of peak on high field was reverse. The results are discussed in the paper.

Responsive mechanism of three novel hypochlorous acid fluorescent probes and solvent effect on their sensing performance

Optical properties and responsive mechanisms of three newly synthesized fluorescent probes for hypochlorous acid （HOC1） are investigated by employing time-dependent density functional theory. The computational results show that the absorption and emission properties of these probes change obviously when they react with hypochlorous acid. It is found that the probe FHZ has the best performance according to the probing behavior. Moreover, the responsive mechanisms of the probes are studied by analyzing the distributions of molecular orbitals and charge transfer, which are shown as the photon- induced electron transfer （PET） for FHZ and the intramolecular charge transfer OCT） for the other two probes. Specially, solvent effect on optical properties of the probe FHZ before and after reaction is studied within the polarizable continuum model （PCM）. It is shown that performance of the probe depends crucially on the solvent polarity. Our computational results agree well with the experimental measurement, and provide information for design of efficient two-photon fluorescent probes.

Solvent effects on optical properties of a newly synthesized two-photon polymerization initiator： BPYPA

Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.