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%。     

杜仲橡胶的环氧化改性研究

采用溶液法对杜仲橡胶（EUG）进行环氧化改性，考察反应条件对环氧化反应的影响，采用红外光谱法、氢核磁共振谱法和差示扫描量热法等研究环氧度（E）对环氧化EUG（EEUG）熔融-结晶行为的影响。结果表明：随着反应温度升高和甲酸用量增大，E逐渐增大；反应温度为50 ℃，n（双键）︰n（甲酸）︰n（双氧水）=1︰0.8︰1时，E较大且无明显的副反应；环氧化反应未改变橡胶分子链构型，EEUG的分子链仍然是反式-1，4-结构，未出现顺式-1，4-结构；随着E增大，EEUG的结晶能力减弱，E为24.8%时EEUG完全失去结晶能力，宏观上由室温下的硬质塑料转变为弹性体。     

Ascorbic acid-assisted hydrothermal route to create mesopores in polymeric carbon nitride for increased photocatalytic hydrogen generation

The facile synthesis of mesoporous polymeric carbon nitride (PCN) can enlarge the surface area and provide mass transport channels, which thus potentially boosts its photocatalytic H₂ generation. However, the formation of mesopores in PCN are mainly relying on the hard and soft templates with tedious operations, and it remains a grand challenge in preparing mesoporous PCN without the assistance of templates. Herein we report on an ascorbic acid-assisted hydrothermal route to effectively create the mesoporous in bulk PCN. The mesopores thus formed a typical IV isotherm with an H3 hysteresis loop, and have a pore size distribution of ∼3.8 nm. Moreover, the crystallinity of mesoporous PCN was improved with ascorbic acid-assisted hydrothermal treatment. Meanwhile, ascorbic acid can be converted to carbon materials under hydrothermal conditions. As a result, an increased photocatalytic H₂ generation was realized under visible light exposure. The highest H₂ generation rate is up to 26.8 μmol h⁻¹ for Pt/CN-A10%, near 10 times higher than that of Pt/PCN (2.7 μmol h⁻¹). This work highlights the effectiveness of organic acid-assisted hydrothermal treatment for synthesizing mesoporous PCN for increased photocatalytic performance.     

Modifying Crystallinity,Morphology, and Photophysical Properties of Carbon Nitride by Using Crystals as Reactants

Here we show a general method to improve the crystallinity of carbon nitride nanosheets by using melamine crystals as reactants for the high temperature synthesis. Additionally, the crystals were calcined in a sealed ampoule, which provides a pressurized environment, yielding crystalline carbon nitride nanosheets that display altered morphology and photophysical properties compared to the reference materials. Electronic microscopy, optical and photoelectrochemical measurements prove the modifications of parameters such like band structure, charge recombination or inter-layer distance. The new growth strategy presented here opens many opportunities for the design of crystalline materials with tailored properties for different applications.     

Nucleation and growth behavior of β-nucleated iPP during shear induced crystallization investigated by in-situ synchrotron WAXS and SAXS

Polymer crystallization under flow was investigated because final properties of polymers strongly depend on the crystalline structure and morphology formed during processing. In-situ synchrotron WAXS and SAXS were used to investigate the structure formation and morphological developments during quiescent and shear-induced crystallization of iPP with 3 different concentrations (0.01, 0.03 and 0.1 wt%) of β-nucleating agent. Under quiescent conditions, a high β-content was obtained at all those concentrations indicating the high β-nucleating efficiency of the nucleating agent. After application of shear, the β-nucleating ability at small concentration was retained, while at larger concentrations it was strongly retarded. Furthermore, the addition of β-nucleating agent was beneficial for the molecular alignment during processing, the anisotropic particles of β-nucleating agent were much more effective to align the molecular chains in the flow direction compared to isotropic ones. A crystallization scheme for the iPP β-nucleating agent under shear was proposed.     

模温和热处理对PET/石墨复合材料导热性能的影响

从影响PET结晶度的角度出发,研究了模具温度和热处理工艺对复合材料热导率的影响,并通过DSC测试对实验结果进行了分析。结果表明:在一定温度范围内,模温升高有利于复合材料中PET结晶的完善和结晶度的提高。选用适当的温度对共混体系进行热处理可使共混材料中的热应力得到松弛,能促进聚合物分子链运动重排,共混物中PET的结晶完善、结晶度提高,提升复合材料的导热性能。     

PVDF/PMMA共混物非等温结晶动力学和晶体结构

通过差示扫描量热仪（DSC）、X射线衍射仪（XRD）对纯聚偏氟乙烯（PVDF）和PVDF/聚甲基丙烯酸甲酯（PMMA）共混物在不同降温速率下的非等温结晶行为和晶体结构进行表征和分析,并采用Jeziorny法和莫志深法研究了各组样品的非等温结晶动力学。结果表明,PMMA含量过多（PVDF/PMMA质量比为6/4和5/5）会完全抑制PVDF结晶;对于纯PVDF和可结晶的共混物（PVDF/PMMA质量比为9/1、8/2、7/3）样品,随着PMMA含量的增加,共混物结晶温度先升高后降低,结晶速率先少许增大后减小,说明少量PMMA起异相成核作用,可促进共混物结晶,而大量PMMA可明显阻碍分子重排,抑制其结晶;PMMA的加入可促进共混物晶体结构向低维转变;共混物晶体结构主要是α晶型,PMMA含量的增加不改变共混物的晶型,且使共混物结晶度先增大后减小。     

电化学沉积法制备氢氧化镁晶体的影响因素研究

以MgCl_2溶液作为电解质,利用电化学沉积方法制备了Mg(OH)_2晶体.研究了电流密度、MgCl_2浓度、沉积时间等因素对沉积产物生长速率、结晶度、微观形貌和孔径分布的影响.结果表明:上述各因素均不影响沉积产物(Mg(OH)_2)的物相组成;电流密度的增大加快了Mg(OH)_2的生长速率,但同时降低了Mg(OH)_2晶体的结晶度,增大了产物中的孔隙率与大孔体积;MgCl_2浓度对Mg(OH)_2结晶度及晶体颗粒大小的影响较小,存在使Mg(OH)_2生长速率达到最大值的最佳MgCl_2浓度;Mg(OH)_2质量随沉积时间增加呈线性增长,生长速率基本维持恒定.