离子液体对锯末中纤维素的溶解及再生研究

探讨了离子液体1-(4-磺酸基丁基)-3-甲基咪唑的硫酸氢盐(IL-1)作为催化剂,金属氯化物作为助催化剂时纤维素的水解,利用离子液体IL-1对杨木锯末中纤维素的直接溶解并再生,考察了温度、碱性溶液的浓度以及溶解时间对溶解率的影响,通过傅里叶红外光谱FT-IR、X-射线衍射仪及热失重对处理前后锯末、再生纤维素的结构、结晶性及热性能进行了研究.结果表明,温度为90℃,NaOH质量分数为6%,溶解时间为2 h时,离子液体对杨木锯末具有最佳的溶解性,溶解率可达45%左右.离子液体主要溶解杨木锯末中的纤维素,且为非衍生化的直接溶解,再生后的纤维素结晶形态由纤维素I变为II,热稳定性能有所降低.     

Laser-based optical facility for determination of refractive index of liquids

Refractive index knowledge is an important parameter when physical properties of liquids are investigated. For the easy and fast determination of refractive index of liquids, we established a computer-controlled optical facility in National Metrology Institute of Turkey, based on laser beam deviation technique. Basic components of the established facility are stabilized laser sources, temperature-controlled rectangular cells, servomotor-controlled knife edges and trap detectors. The facility was used to measure the refractive index of four liquids; pure water, acetone, methanol and n-propyl alcohol. Temperature and dispersion characterizations of each liquid were also investigated and are presented in this paper.     

Molecular simulation of a concentrated aqueous KCl solution

A 1.0 M aqueous KCl solution was studied by molecular dynamics simulations at 293 K in order to study the influence of the ionic concentration on the hydration structure of the ions as well as the formation of ion clusters. The hydration structures of the ions are almost independent of the ionic concentration unless in respect to the perturbation that appears due to ionic clustering. Fractions equal to 31.9% of the anions and 37.8% of the cations are associated. Clusters constituted by two, three and four ions were detected. Their mean lifetimes are always affected by thermal effects, reorientational relaxation while the longest lifetimes are a consequence of ionic cloud relaxations. The pairs constituted by two anions or two cations are stabilized by water molecules belonging to the solvation shells of both ions. The neutral K⁺Cl⁻ pairs are formed under the influence of the electrostatic attraction that, however, is small due to the ionic radii of these ions. Consequently, this kind of pairs contains only 8.8% of the ions while the fraction of ions in the negative and positive pairs are equal to 29.2 and 39.3%, respectively, when the same ion can pertain to more than one pair.     

Stabilizing Liquids Using Interfacial Supramolecular Assemblies

Stabilizing liquids based on supramolecular assembly (non-covalent intermolecular interactions) has attracted significant interest, due to the increasing demand for soft, liquid-based devices where the shape of the liquid is far from the equilibrium spherical shape. The components comprising these interfacial assemblies must have sufficient binding energies to the interface to prevent their ejection from the interface when the assemblies are compressed. Here, we highlight recent advances in structuring liquids based on non-covalent intermolecular interactions. We describe some of the progress made that reveals structure–property relationships. In addition to treating advances, we discuss some of the limitations and provide a perspective on future directions to inspire further studies on structured liquids based on supramolecular assembly.     

聚苯乙烯磺酸钠在1-烯丙基-3-甲基咪唑氯盐中的流变行为

研究了聚苯乙烯磺酸钠(Na PSS)在1-烯丙基-3-甲基咪唑氯盐(AmimCl)中的流变行为,并与其在AmimCl/H_2O混合溶剂中的流变行为进行了对比.聚合物浓度单位为每升溶剂中所含链段单元的摩尔数(mol/L).研究发现,Na PSS在AmimCl中表现出与其在无盐、有盐水溶液以及中性聚合物在离子液体(ILs)溶液中不同的流变行为.Na PSS在AmimCl含量不同的AmimCl/H_2O混合溶剂中的流变行为也不相同,随着AmimCl含量的增加,Na PSS在混合溶剂中的特性黏数[η]逐渐降低,表明分子线团逐渐塌缩,溶液的增比黏度随Na PSS浓度变化的标度所表现出的性质由聚电解质无盐水溶液特点逐渐变为中性聚合物溶液在θ状态下特点.当溶剂为纯AmimCl时,0.007~0.8 mol/L的浓度范围在0.29 mol/L处被分成2个浓度区.动态流变行为研究表明c0.29 mol/L浓度区为稀溶液区,溶液的增比黏度和弛豫时间随Na PSS浓度变化的标度关系为:ηsp~c1.4p和τ~c0p,与无盐聚电解质水溶液在缠结区的行为相似;c0.29 mol/L浓度区为溶液的亚浓非缠结区,溶液在该浓度区内增比黏度和弛豫时间随Na PSS浓度变化的标度关系为:ηsp~c3.5p和τ~c1.9p,接近于中性聚合物良溶液在亚浓缠结区的行为.这一特殊现象可能由混合体系中强烈的长程静电耦合作用引起.     

LaNiO3-δ 薄膜中的氧缺位及其对金属输运行为的影响

钙钛矿结构 LaNiO3 因其高电导的金属性输运行为, 有望作为电极材料在今后的氧化物器件工艺中发挥重要作用. 为了细致认识氧缺位对其金属输运的影响, 本文采用溶胶凝胶法在氧气、 空气和真空等气氛下烧结获得具有不同缺氧量的 LaNiO3 -δ 薄膜, 并利用 Mn3 + 的还原性进一步调整其缺氧量δ . 对这些样品的电阻率温度关系测量结果表明, 缺氧量δ > 0. 1 后薄膜的高温电阻率开始超过 Mott-Ioffe-Regel 极限, 变成“坏金属”; 增大δ 至0.2, 薄膜的低温剩余电阻率大幅度上升, 说明氧空位分布无序性导致的载流子局域化有明显作用. 以上样品的金属输运都呈非费米液体行为. 继续增加氧缺位浓度, 样品电阻率在低温a30 K 以下呈绝缘体温度关系, 同时高温金属态转变为费米液体行为, 说明钙钛矿结构镍酸盐的金属-绝缘体转变与费米液体输运之间或存在关联性.     

The effect of inter-cluster interactions on the structure of colloidal clusters

Colloidal systems present exciting opportunities to study clusters. Unlike atomic clusters, which are frequently produced at extremely low density, colloidal clusters may interact with one another. Here we consider the effect of such interactions on the intra-cluster structure in simulations of colloidal cluster fluids. A sufficient increase in density leads to a higher population of clusters in the ground state. In other words, inter-cluster interactions perturb the intra-cluster behaviour, such that each cluster may no longer be considered as an isolated system. Conversely, for dilute, weakly interacting cluster fluids little dependence on colloid concentration is observed, and we thus argue that it is reasonable to treat each cluster as an isolated system.     

Dielectric and conductivity relaxation in mixtures of glycerol with LiCl

We report a thorough dielectric characterization of the α relaxation of glass-forming glycerol with varying additions of LiCl. Nine salt concentrations from 0.1 to 20mol% are investigated in a frequency range of 20Hz-3GHz and analyzed in the dielectric loss and modulus representation. Information on the dc conductivity, the dielectric relaxation time (from the loss) and the conductivity relaxation time (from the modulus) is provided. Overall, with increasing ion concentration, a transition from reorientationally to translationally dominated behavior is observed and the translational ion dynamics and the dipolar reorientational dynamics become successively coupled. This gives rise to the prospect that, by adding ions to dipolar glass formers, dielectric spectroscopy may directly couple to the translational degrees of freedom determining the glass transition, even in frequency regimes where usually strong decoupling is observed.     

Vibrational intensities of liquid N-methylpiperidine

Thin film transmission spectra of liquid N-methylpiperidine were measured in the 4000–500 cm⁻¹ region, using cells of thicknesses ranging from 1 to 8.2 μm. The spectra of both components of the complex refractive index were determined from these data in the mid-IR. Vibrational intensities and other spectral data were calculated from the k(ν) spectrum. In this region 41 bands were detected and quantitatively described. The assignment of numerous bands was carried out. The results were compared with available literature data.     

‘Exact’ integral equation theory and local formulation for excess thermodynamic properties of hard spheres

A hybrid hard sphere bridge function is proposed, which, in combination with the standard Ornstein–Zernike integral equation, can predict extremely accurately hard sphere compressibility, virial pressure, and correlation function. Second, a local formulation for determination of excess chemical potential is derived out, which, in combination with the present hybrid hard sphere bridge function and OZ integral equation, can predict the excess chemical potential also extremely accurately. The resultant excess entropy is in excellent agreement with that from the Carnahan–Starling equation of state. The present formalism performs excellently over the whole density range, i.e. from zero to freezing density, and is largely superior to a formalism available in the literature.