聚碳级双酚A结晶精制过程的研究

研究了以甲苯为溶剂,从双酚A-苯酚的加合物晶体中,用结晶方法制备双酚A的精制工艺,讨论了加合物晶体中苯酚的质量分数、结晶终温、结晶时间、溶剂比对双酚A的结晶收率、产品熔点和产品色号的影响,得出了用甲苯溶剂结晶法从加合物晶体中提纯具有特殊用途的聚碳级双酚A晶体的适宜工艺条件为溶剂摩尔比0∶1,结晶终温38℃,结晶时间190 m in。     

吲哚的结晶提纯研究

以煤焦油中提取的粗吲哚为原料,通过工业常用的结晶提纯技术进行分离精制,考察了不同的溶剂类型、结晶溶剂质量比、溶剂中关键溶剂与惰性溶剂质量比、结晶温度及原料中吲哚质量分数等因素对吲哚结晶产品收率和产品纯度的影响。结果表明:较适宜的溶剂类型为甲醇水混合溶剂,溶剂质量比为1.5,混合溶剂中甲醇与水的质量比为3∶2,结晶温度为0℃,适宜应用结晶进行分离的原料吲哚质量分数应不低于80%,90%以上最佳,在此条件下进行结晶可以获得白色片状吲哚晶体,产品纯度高于99%,产品收率在75%以上。     

球形和片状氯化钠晶习调控研究

晶习会影响晶体的流动性、堆密度等多种性质,目前氯化钠主要以立方晶习存在,导致其在包装和运输等过程中极易结块。为了解决立方氯化钠的结块问题,开发了多品种食用盐,研究了减压蒸发结晶实验中的多个操作条件对氯化钠晶习的影响,探索了立方氯化钠在甲醇-水混合溶剂中的晶习变化,并研究了小规模液体蒸发对于氯化钠晶体生长的影响。结果表明：在减压蒸发结晶实验中,使用优化的工艺条件能够得到球形化较好的氯化钠球形晶体;当用甲醇质量分数为0.5左右的甲醇-水混合溶剂溶解立方形氯化钠晶体时,可获得球形晶习;而通过使用小规模液体蒸发的方法可以得到粒度较大的片状晶体。     

卡马西平多晶型结晶工艺研究

通过生物显微镜、X射线粉末衍射(XRD)、马尔文粒度分析仪,差热分析(DSC)及在线聚焦反射测量仪(FBRM)和粒子成像测量仪(PVM)研究了在卡马西平结晶过程中各种操作参数对产品质量特别是晶型的影响,具体考察了溶剂、晶种、结晶方式、干燥、温度、搅拌速率及冷却速率对晶体产品质量的影响。结果表明,不同溶剂中缓慢结晶,高介电常数溶剂(如醇类)中得到卡马西平晶型Ⅲ,乙醇-水混合物中当乙醇摩尔分数低于40%时结晶产物为二水物,四氢呋喃中结晶得到晶型Ⅱ,其他溶剂得到产品为混合晶型;对于醇类溶剂,蒸发结晶一般得到卡马西平晶型Ⅱ,而缓慢冷却得晶型Ⅲ;以正丙醇为溶剂,加大量颗粒较小的晶种可以得到粒度较均一的产品;晶型Ⅱ产品由于特殊的结构,易于有结晶用溶剂包藏在晶体中,加热到约140℃溶剂逸出;温度是影响晶型的重要因素,在较高温度区间(90~76℃)结晶得晶型Ⅱ,而在低温度区间(52~20℃)得晶型Ⅲ;搅拌速率在较低的温度下对晶型没有影响,搅拌速率大可以避免晶体的聚集,形成较均匀的颗粒;3种降温速率结果显示,产品均为卡马西平晶型Ⅲ,但先慢后快的降温速率可以得到更均匀的颗粒晶体。     

果糖结晶过程优化

通过实验筛选得到适合果糖结晶的混合溶剂,利用中通量结晶仪器Crystalline测定了果糖在水-乙醇（水的摩尔分数为0.39）混合溶剂中的溶解度和介稳区,采用Apelblat方程拟合了溶解度数据。基于热力学数据设计了晶种引晶的果糖冷却结晶工艺,过程优化得到的产品收率可达78.2%以上,纯度可达99%以上,晶体形貌规则,表面光滑,粒度分布窄。当晶体粒径大于100 μm时,利用粒度无关生长的粒数衡算方程建立了果糖连续结晶过程的动力学模型,模型表明晶体生长级数大于成核级数。     

二硝酰胺铵溶剂效应的理论计算

为研究结晶溶剂在二硝酰胺铵结晶过程中对晶体成核与生长、溶解度、吸湿性的主要影响,基于标准溶解焓理论模拟计算了不同溶剂环境下的晶体成核速率,基于修正附着能模型模拟计算了不同溶剂环境下的晶体形貌特征,并根据吸湿性较低的晶面面积占总晶面面积的比例分析溶剂效应对二硝酰胺铵吸湿性的影响。结果表明,二硝酰胺铵在不同溶剂下的晶体成核速率关系为:环己烷甲苯磷酸三丁酯二氯甲烷正丁醇乙腈γ-丁内酯异丙醇乙醇甲醇丙酮二甲基亚砜水;标准溶解焓与溶解度呈现线性关系;在不同溶剂下的二硝酰胺铵的晶体形貌计算为棱柱状或板片状;计算分析可知,二硝酰胺铵在非极性溶剂中结晶后的吸湿性较低,而在极性溶剂中结晶后的吸湿性较高。     

添加剂调控半水石膏晶体生长研究进展

通过添加剂调控制备形貌各异、结晶良好的半水石膏晶体备受关注。简述了有机添加剂、无机添加剂及复合添加剂调控半水石膏晶体生长成纤维状石膏晶须或短柱状高强α石膏的研究现状;总结并评述了有机、无机两类添加剂对半水石膏晶体成核和生长过程的调控机制;分析了该领域亟待深入研究的问题,为半水石膏晶体及同类晶体材料的结晶生长控制提供了参考。     

FOX-7晶体的制备和热性质

为了解FOX-7晶体形状和尺寸对其热性质的影响,通过冷却结晶和阻溶剂结晶的方法从DMF/H2O、NMP/H2O体系中获得FOX-7晶体.SEM结果表明,得到的晶体基本为延长的四面或六面棱柱和斜方菱晶两种类型,不同溶剂体系中得到晶体的尺寸不同和包含的颗粒数量也不同,超声处理得到的晶体具有单一形状,只是其表面较粗糙.DSC测试结果表明,不同结晶方式和不同溶剂体系中获得的FOX-7晶体的热性质有一定的差别.由此得出,不同的结晶方式和溶剂体系可以获得不同形状、尺寸和热性质的FOX-7晶体,而超声处理可以很好地控制晶体的形状.     

重结晶降低RDX感度研究

采用N-甲基吡咯烷酮、二甲基甲酰胺、二甲基亚砜作溶剂,对普通RDX进行重结晶.研究了不同溶剂对RDX晶体形貌、晶体内空穴、位错、残存溶剂的影响,通过扫描电镜和光学显微镜,分析了重结晶RDX晶体的结晶形貌和内部质量,用密度瓶法测试了晶体密度,用10kg落锤测定了撞击感度.结果表明,用二甲基亚砜重结晶制备的RDX有较好的晶体质量,撞击感度最低(54%),晶体密度达1.823g/cm3.     

译海撷英

一种合成复合晶体的新方法无机合成化学家常致力于通过结晶来合成新的无机材料,以应用于催化和能源生产领域。他们通常将所有反应物溶于溶液中,依靠高温高压来进行反应。一种新的在低温低压下进行的晶体生长方法使得新型多元素复合材料的合成更加简单。当无机化学家Hans-Conrad zur Loye和他在南卡罗来纳大学的研究小组试图通过结晶创建新的结构材料时,他们首先挑选了一种溶剂,并将想要合成的结构所需要的物质溶解在其中。目前为止,该溶解步骤需要在600~1 200℃     

硼酸钙对铜渣中夹杂铜沉降效果的影响

考察了添加剂CaB2O3对转炉铜渣中夹杂铜沉降效果的影响，并结合铜渣的粘度测试及红外光谱表征，研究其影响机理，采用FactSage软件计算了添加剂对铜渣液相线温度的影响。结果表明，随添加剂含量增大，铜渣中夹杂铜的沉降效果逐渐增强，添加剂含量由0增至6wt%时，底部渣含铜量由4.10wt%增至6.85wt%，这是由于添加剂可有效降低铜渣粘度。随添加剂含量增大，渣粘度降低，但降低效果随温度增大而趋于平缓。随添加剂含量增大，铜渣的硅酸盐结构趋于简化，添加剂通过破坏铜渣复杂的硅酸盐结构降低铜渣粘度。铜渣的液相线温度随添加剂含量增大而减小，添加剂通过减少渣中固体颗粒的方式降低铜渣粘度。     

Inorganic/organic nanocomposite coatings: The next step in coating performance

Inorganic/organic hybrid materials have considerable promise and are beginning to become a major area of research for many coating usages, including abrasion and corrosion resistance. Our primary approach is to prepare the inorganic phase in situ within the film formation process of the organic phase. The inorganic phase is introduced via sol-gel chemistry into a thermosetting organic phase. By this method, the size, periodicity, spatial positioning, and density of the inorganic phase can be controlled. An important aspect of the inorganic/organic hybrid materials is the coupling agent. The initial task of the coupling agent is to provide uniform mixing of the oligomeric organic phase with the sol-gel precursors, which are otherwise immiscible. UV-curable inorganic/organic hybrid systems have the advantages of a rapid cure and the ability to be used on heat sensitive substrates such as molded plastics. Also, it is possible to have better control of the growth of the inorganic phase using UV curing. It is our ultimate goal to completely separate the curing of inorganic and organic phases to gain complete control over the morphology, and hence optimization of “all” the coating properties. Thus far, it has been found that concomitant UV curing of the inorganic and organic phases using titanium sol-gel precursors afforded nanocomposite coatings which completely block the substrate from UV light while maintaining a transparent to visible light. Also, it has been found that the morphology of the inorganic phase is highly dependent on the concentration and reactivity of the coupling agent. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL.     

Charakterisierung von Suspensionen nanoskaliger Partikel mittels Ultraschallspektroskopie und elektroakustischer Methoden

Technical control over dispersions with particles in the nanometer size realm should bring about a boost in innovations for some parts of industry. Requirements for the development of these new products is the accurate characterization of the various materials systems. A characterization should always include a determination of the particle size distribution, since it is coupled to the specific effects of these systems. Ultrasound measurement techniques and electroacoustics are two if the available techniques that allow determination of the size distribution and zeta potential of particles with dimensions up to 10 nanometers. A further fundamental advantage of the method is the possibility of carrying out measurements in high‐concentration materials systems. This report describes ultrasound spectroscopy for the measurement of fine‐ and very‐fine‐dispersion particles, and the known theoretical concepts for the interpretation of spectra. In addition, experiences in the use of currently available measurement techniques are presented.     

Trapping the western pine beetle at and near a source of synthetic attractive pheromone Effects of trap size and position

Western pine beetles were caught on unbaited sticky traps placed near a source ofexo-brevicomin, frontalin, and myrcene. Size of trap, distance and direction from the source of attractant, and height from the ground were varied. Significant differences in trap catch were observed in relation to each of the variables. Traps close to the source of attractant caught more beetles than traps farther from the source. Traps downwind of the source of attractant caught more beetles than did upwind traps. More males than females were trapped close to the source of attractant.Based in part on a thesis submitted by the senior author to the University of California, Berkeley, California, in partial fulfillment of the requirements for the degree Master of Science in entomology, December 1976. These studies were supported by the U.S. Forest Service and in part by the Rockefeller Foundation and a joint grant (NSF GB-34718/BMS 75-04223) from the U.S. National Science Foundation and the U.S. Environmental Protection Agency to the University of California. The findings, opinions, and recommendations are not necessarily those of the University of California or the funding agencies.Trade names and commercial enterprises or products are mentioned solely for information and do not constitute endorsement by the U.S. Department of Agriculture or University of California.     

Mechanical Means of Enhancing Drying Rates: Effect on Drying Kinetics and Quality

The effect of various pretreatments on drying kinetics as well as quality parameters of selected vegetables and fruits was studied experimentally in a convective dryer. The pretreatments tested include application of pinholes and drilled holes of different diameters and densities, blanching and freezing. Potato, cassava, dragon fruit and red chilli were used as the sample drying materials. As expected, increase of the diameter and density of the holes under fixed drying conditions increased the drying rate. Samples with drilled holes showed better drying performance than those with pinholes. The improvement of the drying rate was found to be dependent on the physical properties and the initial moisture content of the material. Results show that the drying performance of the products that possess a skin of low moisture diffusivity, such as chilli, can be improved significantly by blanching and making perforations in the skin. Overall changes of color and volume shrinkage during drying of the samples with and without holes were similar. The effect of different modes of heat input, such as convection, conduction and radiation, on the drying performance of the treated samples was also experimentally investigated. On-off type controllers were used to regulate the power of the heaters and maintain the product temperature within a range of pre-set values. Convection combined with radiation displayed the highest drying rate.     

氮气幕对瓦斯爆炸进行阻爆实验

为阻断瓦斯爆炸在管道方向上的传播，保护管道后方区域，本文采用氮气幕来进行阻爆，所设计的实验装置在爆炸发生后能自动喷出氮气。主要研究了氮气的喷气压力和喷气时刻对阻爆功能的影响。结果表明，在喷气压力为0.1MPa时，氮气幕仅起到抑制作用，爆炸火焰能穿过整个实验管道。在喷气压力为0.2MPa时，仅部分实验能够阻爆，氮气幕产生不稳定的阻爆效果。在喷气压力为0.3MPa时，阻爆位置均稳定在左喷头和右喷头之间区域，氮气幕产生稳定地阻爆效果。喷气压力超过0.4MPa后，阻爆位置稳定在右喷头附近。在较低氮气压力0.2MPa下，喷气时刻对阻爆效果产生显著影响。随着喷气时刻延迟，氮气喷出量减小，氮气幕由不稳定阻爆变为不阻爆。喷气时刻延迟到198ms后，氮气幕便丧失阻爆功能。在喷气压力超过0.3MPa后，氮气幕阻爆效果便不受喷气时刻的影响，喷气压力对能否阻爆起决定作用。     

水平及竖直基底上微小固着液滴的蒸发特性分析

为揭示非水平表面上微小蒸发液滴的传热传质特性,本文在准稳态模型的假设下构造三维液滴模型,综合考虑了蒸气扩散、蒸发冷却以及气相域中的自然对流这3种传输机理,对水平以及竖直基底上液滴的蒸发过程进行数值研究。通过分析气液界面上温度分布、蒸发通量分布及总蒸发率的变化,重点探究了基底过热度以及重力的改变对液滴蒸发特性的影响。结果表明：与水平基底上温度的对称分布不同,竖直基底上气液界面温度分布表现出明显的非对称性,且非对称性随基底过热度的升高而增强,最低温度点不再位于液滴顶点,而向一侧偏移。此外,水平基底上气液界面局部蒸发通量呈对称分布,各截面分布相似,而竖直基底上局部蒸发通量分布则呈现出显著的非对称性以及各截面异性,非对称性随着基底过热度的升高而增强,这是重力改变后气相域自然对流发生改变的结果。与水平基底相比,竖直基底上蒸发率更高,总蒸发时间更少。最后,基底由水平变为竖直时,液滴内部流场由对称双涡转变为非对称单涡,单涡流速显著大于双涡流速,液滴内流速随基底过热度的上升而增大,单涡环流造成了气液界面温度分布的改变以及最低温度点的偏移。     

Kinetics of base-catalyzed transesterification of triglycerides from Pongamia oil

The kinetics of transesterification of Pongamia oil using methanol at 60°C were studied. The forward as well as the reverse rate constants of all three steps involved in the transesterification of Pongamia oil are reported for the first time. Among the forward rate constants, the one governing the conversion of TG to DG was the highest and the one for DG to MG was the lowest. A distinct feature of the present work is the direct estimation of the equilibrium constants of all three steps by measuring the concentrations of TG, DG, and MG at very long reaction times. This reduced the number of parameters to be, determined from the kinetic data by one-half, thereby leading to more accurate estimation of the rate constants. The equilibrium constant of the final step involving the conversion of MG to methyl ester and glycerol was at least an order of magnitude greater than that of the first two reaction steps. A detailed comparison was made with kinetic parameters reported in literature. The trend in the relative magnitudes of the rate constants appears to be unique to Pongamia oil.     

Breakage patterns of agglomerates

The experimental information available in the literature regarding the patterns of breakage of agglomerate materials is scarce, particularly in dynamic loading. The primary objective of this paper is to present our findings on the breakage patterns of the agglomerates and the interparticle bond. A high-speed digital video imaging technique is used here to gain an insight into the impact behaviour of individual agglomerates against a target plate. Several breakage patterns are observed. Agglomerates may suffer localised damage only, with the disintegration of the damaged zone into very fine debris, or localised damage combined with fracture. The frequency of occurrence of these patterns depends on the impact velocity and agglomerate structure. The pattern of breakage affects significantly the size distribution of the impact product. An investigation of the breakage of individual interparticle bonds is also presented. Two forms of failure are observed, internal (cohesive) and interfacial (adhesive) failure. The morphology of the fractured surface depends greatly on the type of breakage. Internal breakage shows irregular surfaces due to crack jumping, whereas interfacial failure produces clean, smooth fracture surfaces. These observations should provide the necessary foundation for the development of a fundamental model of agglomerate breakage.     

Functional properties of proteins in foods

The measurement of functionality of protein food ingredients has developed somewhat haphazardly, probably due to the wide range of proteins used as ingredients and the diversity of foods. Studies of the physiochemical properties of proteins should enable prediction of a proteins response to process environments and prove more fruitful than many of the empirical measurements of functionality. The effects of pH, salt type and concentration on the phase behaviour of the oilseed globulin and arachin, demonstrates the complexity of protein solubility and the inadequacies of simple tests that have arisen. Studies of the effects of salts and conditioning on meat fibres, coupled with measurement of the location of water in pellets from water holding tests enable the latter to be applied with increased confidence. Comparison of the endothermic transitions observed on heating with the development of storage and loss moduli allow the contributions of domains of skeletal muscle myosin to gel structure to be investigated.