Impact of non‐solvent on regeneration of cellulose dissolved in 1‐(carboxymethyl)pyridinium chloride ionic liquid

Cellulose dissolved in ionic liquid (1‐(carboxymethyl)pyridinium chloride)/water (60/40 w/w) mixture is regenerated in various non‐solvents, namely water, ethanol, methanol and acetone, to gain more insight into the contribution of non‐solvent medium to the morphology of regenerated cellulose. To this end, the initial and regenerated celluloses were characterized with respect to crystallinity, thermal stability, chemical structure and surface morphology using wide‐angle X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. According to the results, regardless of non‐solvent type, all regenerated samples have the same chemical structure and lower crystallinity in comparison to the initial cellulose, making them a promising candidate for efficient biofuel production based on enzymatic hydrolysis of cellulose. The reduction in crystallinity of regenerated samples is explained based on the potential of the non‐solvent to break the hydrogen bonds between cellulose chains and ionic liquid molecules as well as the affinity of water and non‐solvent which can be evaluated based on Hansen solubility parameter. The latter also determines the phase‐separation mechanism during the regeneration process, which in turn affects surface morphology of the regenerated cellulose. The pivotal effect of regenerated cellulose crystallinity on its thermal stability is also demonstrated. Regenerated cellulose with lower crystallinity is more susceptible to molecular rearrangement during heating and hence exhibits enhanced thermal stability. © 2019 Society of Chemical Industry     

硅渣和玻璃粉直接烧结制备多孔材料的气孔结构与力学性能

以硅渣和玻璃粉为原料,采用粉体直接烧结法制备多孔材料,研究了烧结温度(700~900℃)、烧结时间(15~120min)和升温速率(10~100℃·min^-1)对多孔材料表观密度、气孔率、物相组成、抗压强度的影响。结果表明:气孔结构均匀性随烧结温度的升高而降低;表观密度随烧结温度的升高先减小后增大,随保温时间的延长而增大,随升温速率的增大而减小,气孔率的变化趋势与表观密度的相反;多孔材料的主要物相为玻璃相和硅、SiC、SiO2、Ca2Al2SiO7等结晶相,且结晶度随烧结温度的升高而降低;抗压强度随烧结温度的升高呈先增大后减小的趋势;当烧结温度为750℃,升温速率为30℃·min^-1,烧结时间为30 min时,多孔材料的主晶相为硅和Ca2Al2SiO7,抗压强度最大(1.60MPa),表观密度为0.43g·cm^-3,气孔率为80%。     

Peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis: a continued work

Previous work has shown that the enzymatic hydrolysis of sugarcane bagasse could be greatly enhanced by peracetic acid (PAA) pretreatment. There are several factors affecting the enzymatic digestibility of the biomass, including lignin and hemicelluloses content, cellulose crystallinity, acetyl group content, accessible surface area and so on. The objective of this work is to analyze the mechanism of the enhancement of enzymatic digestibility caused by PAA pretreatment. Delignification resulted in an increase of the surface area and reduction of the irreversible absorption of cellulase, which helped to increase the enzymatic digestibility. The Fourier transform infrared (FTIR) spectrum showed that the absorption peaks of aromatic skeletal vibrations were weakened or disappeared after PAA pretreatment. However, the infrared crystallization index (N.O'KI) was increased. X‐ray diffraction (XRD) analysis indicated that the crystallinity of PAA‐treated samples was increased owing to the partial removal of amorphous lignin and hemicelluloses and probable physical change of cellulose. The effect of acetyl group content on enzymatic digestibility is negligible compared with the degree of delignification and crystallinity. The results indicate that enhancement of enzymatic digestibility of sugarcane bagasse by PAA pretreatment is achieved mainly by delignification and an increase in the surface area and exposure of cellulose fibers. Copyright © 2008 Society of Chemical Industry     

Effects of a Nd—Fe—B magnetic filler on the crystallization of poly(phenylene sulfide)

The crystallization of poly(phenylene sulfide) (PPS) in a polymer–magnetic Nd—Fe—B powder suspension was studied. Isothermal crystallization behavior was analyzed by way of differential scanning calorimetry, and the kinetics were described via the Avrami equation. The Avrami parameters and the crystallization times were strongly affected by both the particle size and the presence of a coupling agent coated on the filler particles. The small Nd—Fe—B particles exhibited long induction and half‐times, whereas the large particles tended to have short crystallization times. Particles ranging from 38 to 150 μ appeared to have similar crystallization times and to have no significant change in the value of Avrami index with melt crystallization temperature. As a result of these analyses, the dynamic mechanical properties were determined to correlate the fundamental polymer crystallization characteristics and the physical properties of the PPS binder. The enhancement of the wetting of the filler to the binder was promoted through the coupling agent, as confirmed by dynamic mechanical testing performed on the samples. The storage modulus typically decreased because of the presence of the uncoated small particles. Conversely, the loss modulus was enhanced because of the presence of the coated small particles in the PPS binder. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1091–1102, 2002     

形状记忆聚氨酯的结构与性能研究

以 2 ,4 -甲苯二异氰酸酯 (2 ,4 -TDI)、不同分子量的聚己二酸丁二醇酯 (PBAG)和 1,4-丁二醇 (BDO)为原料合成了具有形状记忆功能的聚氨酯材料。通过DSC、弯曲实验和力学实验 ,研究了形状记忆聚氨酯的性能 ,发现软段高度结晶和硬段聚集形成硬段微区是其具有较好形状记忆性能的必要条件。     

高阻值Cd1-xZnxTe晶体的生长及其性能测试

通过适当的工艺措施，采用Bridgman法生长了直径为30mm的X射线及γ射线探测器级的Cd.9Zn0．1Te晶锭．测试结果表明：该晶锭结晶质量良好，位错密度低，成分均匀，杂质含量低，红外透过率和电阻率都十分接近本征Cd.9Zn0．1Te的值．并从晶体的生长特性、缺陷和杂质的角度，分析了生长高性能晶体的条件，研究了生长Cdl-xZnxTe晶体的x值与缺陷和杂质浓度之间的关系．     

Effect of Preparation Methods and Condition of Precursors on the Phase Composition of Yttria-Stabilized Zirconia Powders

An yttria-stabilized zirconia powder, free of monoclinic phase, may be prepared by an oxalate method in an ethanol solution at strong acidity. This study demonstrates that the control of pH in the preparation of precursors has a significant effect on the ability of precursors to crystallize and hence plays an important role in determining the formation and fraction of various crystalline phases in the resulting yttria-stabilized zirconia powder. With the increase of pH, a precursor with a certain crystalline form may be transformed into an amorphous precursor, and a monoclinic phase appers in the phase composition of the resulting powder. The results of XRD analysis and Raman spectroscopy are discussed.     

N.m.r. study of the ferroelectric phase transition in a 7030mol% copolymer of vinylidene fluoride (VF2) and trifluoroethylene (TrFE)

Nuclear magnetic resonance (n.m.r.) studies of ¹⁹F nuclei in a $\text{70}\text{30}\text{mol}\text{\%}$ random copolymer of vinylidene fluoride and trifluoroethylene were performed at 9.14 MHz and 20.0 MHz. The free induction decays (FIDs) were analysed in terms of two T₂ components attributed to the amorphous and crystalline portions of the polymer. The changes in crystallinity as well as the effects of the ferroelectric transition were observed during cycles of heating and cooling between 20°C and 140°C. The crystalline component of the FID lengthens by a factor of 2 at 100°C on heating and decreases by this factor at 60°C on cooling, thus exhibiting the thermal hysteresis of this ferroelectric transition. The spin-lattice relaxation was also investigated. From measurements at 9.14 MHz the observed longitudinal relaxation time T₁ appears to be dominated by the dynamics of the amorphous phase and exhibits no anomaly through the phase transition. However, from measurements at 20 MHz, well defined minima of T₁ were observed, which are associated with the ferroelectric transition (especially after repeated annealing of the samples). Results are discussed in terms of the crystalline phase structure, which appears dynamically disordered above the ferroelectric phase transition. An analogy is considered with the plastic phase transitions encountered in molecular crystals.     

Studies on chitin 3—effect of coagulants and annealing on the preparation and the properties of chitin membrane

Chitin membrane was prepared by casting a N,N-dimethyl acetamide, N-methyl 2-pyrrolidone and lithium chloride (DMA-NMP-LiCl)solution of chitin and coagulating with several media. The effect of the coagulants on membrane formation was studied. 2-Propanol was found to be more favourable than methanol, ethanol, acetone and mixtures of 2-propanol and water. The membrane obtained in 2-propanol was subjected to annealing. Annealing made the membrane dense and strong. The tensile strength of the membrane annealed at 145°C for 2hr was about twice that of an unannealed membrane. The solute permeability of the annealed membranes was lower than that of the original one. These phenomena could be clearly interpreted in terms of crystallinity.     

Nuclear Magnetic Resonance Studies of Silicon Carbide Polytypes

The ²⁹Si MAS NMR spectra of the 2H, 4H, 6H, and 3C polytypes of silicon carbide are presented. An attempt is made to correlate differences in the chemical shifts with local atomic environment. The results of the analysis of the spectra of pure polytypes are used as a basic for the interpretation of the spectra of mixed polytypes and a discussion of the crystallinity and impurity levels of different samples. Carbon-13 chemical shifts obtained from spectra of the same polytypes are also tabulated.