固体溶质在超临界三元系统中的溶解度

溶质在超临界流体中的溶解度数据是研究超临界流体技术的基础.本文对纯组分固体溶质有夹带剂存在的超临界流体三元系统中,夹带剂增大溶质溶解度的作用进行了总结,述评了夹带剂增大溶质溶解度的机理和常用的计算模型.此外,针对两种固体混合溶质共存于超临界流体中的三元系统,讨论了混合溶质共存对彼此溶解度的影响及其相关的理论假说和计算模型.     

超临界流体色谱法的进展

当温度在临界温度以上、压力在临界压力以上,此时气体由低密度的流体成为高密度的流体,称为超临界流体。超临界流体既不同于液体,也不同于一般的气体,其特性是密度约为液体的三分之一或很接近;粘度     

有化学作用时气体在液体中的溶解度

在一定温度下,难溶性气体在液体中的溶解度与气相中气体的平衡分压之间的关系用亨利定律描述: P_2=k_mm_2 (1)式中“2”表示气体溶质,P_2是与液体呈平衡的气相中溶质的分压,单位为atm,m_2是溶质的溶解度,     

邻甲氧基苯甲酸在超临界CO2中溶解度测定与研究

邻甲氧基苯甲酸在超临界ＣＯ＿２中溶解度测定与研究柯杰，韩布兴，阎海科，崔孟元Ｄ．Ｙ．Ｐｅｎｇ（中国科学院化学所北京１０００８０）１前言超临界流体是对比温度和对比压力同时大于１的气体。与一般气体和液体相比，这种流体有许多独特的性质。目前超临界技术已在食...     

超临界流体萃取

早在1897年,J. B. Hannay与J. Hogarth就已经发现超临界状态的压缩气体对于固体的特殊溶解作用,在高于临界点的条件下,金属卤化物能分别溶于乙醇或四氯化碳。通过后继的研究工作进一步发现,具有可变密度、介电常数与溶解效能的高压超临界流体C_2H_4、CO_2、NH_3、Cl_2、F_2等,足以作为一种重要的反应介质和溶剂。研究超临界流体理论,对于高压合成氨、甲醇、醋酸、聚乙烯以及羰基合成、费-托合成等工业过程都有意义。超临界流体和液体一样,能溶解固体。在超临界流体介质中,难挥发物质显著地转入流体相。固体对碘氯苯在常压、15℃下,在乙烯     

超临界流体萃取金属离子在环境分析上的应用

固体和液体中的金属离子能在含有有机螯合剂的超临界二氧化碳(SC-CO2)流体中被有效地萃取出来。超临界流体萃取(SFE)金属离子的效率取决于下列因素：螯合剂在SC-CO2中的稳定性和溶解性、金属络合物在SC-CO2中的溶解度、水、pH值、压力、温度及金属离子的化学形式和基质的性质等。     

水杨酸在二氧化碳－正丁醇混合超临界流体中的溶解度

水杨酸在二氧化碳－正丁醇混合超临界流体中的溶解度柯杰，韩布兴，闫海科，赵扬（中国科学院化学研究所，北京１０００８０）超临界流体（ＳＣＦ）是对比温度和对比压力同时大于１的流体。这种流体具有许多特性，如各种性质随温度和压力的变化十分敏感（特别在临界点附近...     

不同温度下气体溶解度的规律性

目前,有关气体在液体里的溶解度的定量关系,常以Henry定律为基础,其内容为:“一定温度下,在稀溶液中,挥发性溶质的平衡分压与溶质在溶液中的摩尔分数成正比。”该定律只运用于稀溶液,且气、液二相中的溶质应具有相     

超临界流体色谱进展

当物质处于其临界温度(Tc)、临界压力(Pc)以上状态时,成为单一相态,既没有液体存在.也不同于通常的气体,称为超临界流体。超临界流体具有极大的溶解能力,能溶解固体物质。早在1879年,Hannay等人就发现了这种溶解性质。后来,这种溶解性质被用来作为分离过程的基础,并发展成新的分离方法——超临界流体萃取法。然而,利用超临界流体的溶解性质作为分析方法,直到1962年才首次由Klesper等人所采用。他们建立了超临界流体色谱(SFC)方法,并成功地分析了卟     

用微扰硬球链理论计算超临界CO-2-溶质二元系的密度

溶质在超临界流体中的溶解度与流体的密度密切相关。本文采用微扰硬球链理论对纯CO2及CO2-正戊烷、CO2-正庚烷、CO2-正癸烷体系在不同条件下的密度进行计算，计算值与文献给出的实验值符合很好。     

A novel hierarchical crystalline structure of injection-molded bars of linear polymer: co-existence of bending and normal shish–kebab structure

The hierarchy structures and orientation behavior of high-density polyethylene (HDPE) molded by conventional injection molding (CIM) and gas-assisted injection molding (GAIM) were intensively examined by using scanning electronic microscopy (SEM) and 2D wide-angle X-ray diffraction (2D-WAXD). Results show that the spatial variation of crystals across the thickness of sample molded by CIM was characterized by a typical skin–core structure as a result of general shear-induced crystallization. Unusually, the crystalline morphologies of the parts prepared by GAIM, primarily due to the penetration of secondary high-compressed gas that was exerted on the polymer melt during gas injection, featured a richer and fascinating supermolecular structure. Besides, the oriented lamellar structure, general shish–kebab structure, and common spherulites existed in the skin, sub-skin, and gas channel region, respectively; a novel morphology of shish–kebab structure was seen in the sub-skin layer of the GAIM parts of HDPE. This special shish–kebab structure (recognized as “bending shish–kebab”) was neither parallel nor perpendicular to the flow direction but at an angle. Furthermore, there was a clear interface between the bending and the normal shish–kebab structures, which may be very significant for our understanding of the melt flow or polymer rheology under the coupling effect of multi-fluid flow and complex temperature profiles in the GAIM process. Based on experimental observations, a schematic illustration was proposed to interpret the formation mechanism of the bending shish–kebab structure during GAIM process.     

Morphology and mechanical property of high-density polyethylene parts prepared by gas-assisted injection molding

The crystal morphology, melting behavior, and mechanical properties of high-density polyethylene (HDPE) samples obtained via gas-assisted injection molding (GAIM) under different gas pressures were investigated. Moreover, the non-isothermal crystallization kinetics of HDPE under different cooling rates was also studied. The obtained samples were characterized via differential scanning calorimetry, two-dimensional wide-angle X-ray scattering (2D-WAXS), tensile testing, dynamic mechanical analysis (DMA) and scanning electron microscopy techniques. It was found that the properties were intimately related to each other. Macroscopically, the flow-induced morphology of the various HDPE samples was characterized with a hierarchical crystalline structure, possessing oriented lamellar structure, shish?Ckebab structure, and common spherulites in the skin, sub-skin, and gas channel region, respectively. The 2D-WAXS results demonstrated that the degree of orientation of the high gas pressure sample was larger than that of the low pressure sample at the corresponding layer. The tensile testing results of GAIM parts showed that the mechanical properties of the GAIM parts were improved with an increase of the gas pressure. Furthermore, the DMA was utilized to obtain the dynamic mechanical properties of the GAIM samples, and the results indicated that significant improvement of the orientation was observed with an increase of the gas pressure.     

聚烯烃共混物注射制品的形态控制与多层次结构

从注射制品形态控制和结构表征的角度探讨高分子材料加工-形态-性能之间的关系.研究中采用动态保压成型方法来制备注射样品,在注射成型过程中引入剪切应力场的作用,制得的样品表现出明显的多层次结构,从外向里分别为皮层、剪切层、芯层,表现出不同的相形态、结晶形貌以及取向行为.研究发现,剪切应力对聚烯烃的形态发展和结构变化具有重要影响.在剪切应力的作用下,聚烯烃共混物中分散相会发生变形、取向,从而导致共混物的相转变点发生移动;结晶形态从球晶转变为shish-kebab结构;聚烯烃共混物在高剪切应力下相容,低剪切下发生相分离;HDPE/PP共混物的注射制品中出现附生结晶等现象.     

Role of gas cooling time on crystalline morphology and mechanical property of the HDPE parts prepared by gas-assisted injection molding

In this study, the hierarchical crystalline structures of high-density polyethylene (HDPE) samples molded by gas-assisted injection molding (GAIM) with different gas cooling times were characterized via scanning electron microscopy, two-dimensional wide-angle X-ray scattering, tensile testing techniques, and differential scanning calorimetry, respectively. It was found that the shish-kebab, the oriented lamellae, and common spherulite structures orderly distributed from the skin region to gas channel region of samples. More importantly, the wider area with highly oriented structure (shish-kebab) was obtained in the samples with longer gas cooling time, in that the longer gas cooling time tends to increase the cooling rate of polymer melt, and then much more stretched chains are retained. Although lower crystallinity, the higher degree of orientation, and much more shish-kebab structures lead to significant reinforcement from 28 to 785 MPa of the samples with gas cooling time of 0.5 s to 32 and 879 MPa of the samples with gas cooling time of 20 s for tensile strength and modulus, respectively. Finally, combined the HDPE molecular parameter with characteristic of the GAIM temperature field and flow field, the formation and stability of crystalline morphology in different regions of sample were discussed.     

超临界苯类溶剂对聚苯乙烯降解的影响

在高压间歇反应器中,温度340~370℃,以苯、甲苯、乙苯和对二甲苯为超临界溶剂研究了聚苯乙烯(PS)的降解特性.苯类物质是聚苯乙烯的优良溶剂,在超临界条件下其优异的传质、传热性能使聚苯乙烯快速降解.聚苯乙烯在不同超临界溶剂中降解转化率相近,而降解产物组成差别很大,分析了不同超临界溶剂对聚苯乙烯降解过程的影响.结果表明超临界甲苯对降解过程影响最小,苯乙烯收率最高.聚苯乙烯降解过程中,高分子链断裂和解聚同时进行,结合连续分布理论建立了聚苯乙烯降解的动力学模型,得到在超临界甲苯中聚苯乙烯链端解聚活化能为138.4 kJ.mol-1.     

Novel three-dimensional in-cavity transient temperature measurements in injection molding and fluid-assisted injection molding

This report presents novel experimental set-ups which allow the measurement of three-dimensional temperature fields in the depths of injection molding cavities throughout molding cycles. Two specific molds equipped with two types of temperature measuring devices, i.e., a mesh type device consisting of thermocouples mounted on metal wires and a tubular type device consisting of tubular needles guiding embedded micro-thermocouples inside the cavities, have been designed and built. Temperature distributions in both injection molding and fluid assisted injection molding processes, including gas and water assisted injection molding, were measured and recorded by a data acquisition system on a personal computer. It was found that the tubular type device induced much less flow disturbance and provided accurate temperature profiles. Among the processes, the water assisted injection molding process required the least time to cool the parts, followed by gas assisted injection molding and conventional injection molding. In addition, the experimental results also suggested that the shear heating by viscous dissipation in the runners leads to a significant increase in melt temperature. A precise measurement of the in-depth temperature profile can be helpful to better understand the molding phenomena, to validate numerical simulation results, as well as to optimize the parameters for the molding processes.     

在低频振动场中注射成型HDPE试样的力学性能及其形态控制

利用自行研制的低频振动注射实验装置探讨HDPE振动注射试样力学性能和微观形态之间的关系 .实验中对常规注射和振动注射成型的试样力学性能和微观形态进行了对比实验 .SEM实验结果显示 ,振动注射制件芯层的形态由常规注射的球晶转变为垂直于振动波传递方向排列的片晶结构 ,在剪切层中同时存在串晶或柱状堆砌的片晶结构 .频率的改变 (0 相似文献   

Role of gas delay time on the hierarchical crystalline structure and mechanical property of HDPE molded by gas-assisted injection molding

The relationship among the processing parameters, crystalline morphology, and macroscopic properties in injected molded bar becomes very complicated due to existence of temperature gradient and shear gradient along the sample thickness. To enhance the shear strength, gas-assisted injection molding (GAIM) was utilized in producing the molded bars. The aim of our research was to explore the relationship between processing conditions and the spatial variation of the hierarchy structure as well as the mechanical properties of high-density polyethylene (HDPE) obtained via GAIM. In our previous work [Wang L, Yang B, Yang W et al (2011) Colloid Polym Sci 289:1661–1671], we found that the enhancement of the gas pressure can remarkably increase the degree of molecular orientation in the HDPE samples, which turns out to improve the mechanical performances of GAIM parts. In this work, the hierarchy structure, orientation behavior, and mechanical properties of molder bars under different gas delay time were investigated using a variety of characterization techniques including rheological experiments, scanning electron microscope, tensile testing, differential scanning calorimetry, and two-dimensional wide-angle X-ray scattering. Moreover, the temperature field during the short shot stage of GAIM process was simulated using an enthalpy transformation approach. Our results indicate that these properties were intimately related to each other, and with prolonged gas delay time, GAIM samples with higher degree of orientation and improved mechanical properties were obtained.     

On-line multidimensional supercritical fluid chromatography/capillary gas chromatography

A new analytical technique combining on-line supercritical fluid chromatography with capillary gas chromatography has been developed. The supercritical fluid sample effluent is decompressed through a restrictor directly into a conventional capillary gas chromatographic injection port. This technique allows for not only direct (100%) sample transfer from the supercritical fluid chromatograph to the gas chromatograph but also for selective or multi-step heartcutting of various sample peaks as they elute from the supercritical fluid chromatograph. Heartcut times are determined by monitoring the responses from the flame ionization or ultraviolet absorbance detectors on the supercritical fluid chromatograph. This report describes the operational setup and provides the results of heartcut reproducibility experiments using normal hydrocarbon and aromatic test mixtures. Results from studies where operational parameters were varied, such as GC injector temperature, will also be provided. The potential usefulness of this new technique for selective heartcutting will also be demonstrated using complex hydrocarbon streams.     

WAXS analysis of structural changes of poly(ethylene terephthalate) fibers induced by supercritical-fluid dyeing

 Supercritical CO₂ fluid, a new environmentally friendly dyeing medium, changes the fiber structure to a certain extent in dependence on the treatment temperature and pressure used. Therefore the changes of crystalline structure in poly(ethylene tereph-thalate) (PET) fibers as brought about under the influence of supercritical CO₂ fluid were investigated. For the data collection of wide-angle X-ray diffraction full patterns a two-circle goniometer, equipped with a position sensitive detector, was used. From the observed two-dimensional fiber diffraction patterns the crystallinities of various treated fibers were evaluated. The equatorial scanning yielded the dimensions of crystallites. To elucidate the fiber-surface morphology changes SEM analyses were performed. The supercritical fluid dyeing of PET fibers with highly developed microfibrillar structure under taut-ends conditions promotes changes which are characterized by an increase in crystallinity and by diminution of the apparent crystallite dimensions. Some changes of surface morphology of dyed fibers were observed as well. Received: 14 May 1997 Accepted: 23 September 1997