超临界CO2冷却换热特性数值模拟

采用L-B低雷诺数模型对超临界二氧化碳在竖直圆管内的冷却对流换热特性进行了数值模拟.通过分析得到了管内不同截面的径向流体温度、速度、湍动能分布,并进一步分析了二氧化碳和冷却水进口雷诺数对超临界二氧化碳对换热的影响.研究表明,对流传热系数峰值出现在接近准临界温度的截面内,此时截面内湍动能最大,跨过该截面流速小于进口流速;...     

超临界CO2抗溶剂法制备聚乳酸药物缓释微球

以L-聚乳酸为模型体系,超临界CO2为抗溶剂,采用超临界流体抗溶剂法制备聚乳酸微球.考察了压力、温度、溶液浓度、溶液流速、二氯甲烷-丙酮混合溶剂、聚合物分子量等参数对制备微球的形态、粒径及其分布的影响.结果表明,改变工艺参数,可在一定范围内调控微球粒径,所制微球平均粒径0.67～6.64μm,溶液浓度及其流速为主要影响因素;实验条件一定时,采用二氯甲烷-丙酮混合溶剂及强制分散溶液法制备得较小粒径微球.释放度实验结果表明,微球按一级释放方程释药,具缓释效果.     

超临界二氧化碳渗透成核剂至聚乳酸的分散及对基体性能的影响

通过超临界二氧化碳渗透的方法将成核剂分子输运到聚乳酸基体中,使其达到与传统挤出共混方法相比更为均匀、粒度更小的分散,从而进一步细化聚乳酸的球晶尺寸,改善其结晶行为。球晶尺寸的降低增加了球晶界面的结合强度,提高了聚乳酸的冲击强度。     

用超临界异丙醇流体制备TiO2/活性炭复合材料

在存在超临界异丙醇介质的条件下,将钛酸异丙酯与活性炭反应生成具有光催化与吸附性能协同效应的TiO2/活性炭复合材料.产生协同效应,可使低浓度污染物快速地表面富集和吸附净化,加快了污染物的光催化降解速率,TiO2的光催化作用又促使被活性炭吸附的污染物向TiO2表面迁移,使活性炭吸附能力得以恢复,实现了吸附剂的原位再生.     

Synthesis of ultra-small hollow silica nanoparticles using the prepared amorphous calcium carbonate in one-pot process

The ultra-small hollow silica nanoparticles were synthesized using the prepared amorphous calcium carbonate (ACC) particles as a template. The ACC particles were firstly prepared by carbonation method, which procedure was conducted in the methanol solvent to form the Ca(OCH₃)₂ layers on the ACC particles. An effect of methanol concentration on the morphology of ACC particles was also investigated. The prepared ACC particles were directly coated by silica through adding tetraethoxysilane (TEOS) into the methanol solvent. Hence, the ACC-silica core-shell particles were obtained since the ACC particles have a positive charge and interact with hydrolyzed TEOS. The ACC particles could be stabilized through the reaction between methanol and calcium ions when the methanol concentration was increased over than 40?vol%.     

超临界CO2方法制备纳米蒙脱土/氢化丁腈橡胶复合材料

比较了超临界CO₂方法与机械共混法制备的纳米蒙脱土/氢化丁腈橡胶复合材料的结构与性能,以验证超临界CO₂方法在氢化丁腈橡胶复合材料制备中的有效性。并研究了超临界CO₂处理条件对蒙脱土分散情况的影响。XRD及TEM研究表明,与机械共混法相比,超临界CO₂处理有效提高了氢化丁腈分子向蒙脱土层间扩散的能力,使层间距进一步增大,最大达3.93 nm。同时,蒙脱土片层能够均匀无规地分散于氢化丁腈橡胶基体中,且具有较高的剥离程度。而超临界处理时,温度和压力的变化对蒙脱土的分散情况影响不大。蒙脱土加入后,蒙脱土/氢化丁腈橡胶复合材料的拉伸强度显著提高,从14.4 MPa分别增加到16.3 MPa（机械共混法）和19.6 MPa（超临界CO₂方法）,断裂伸长率也略有增加。超临界CO₂方法比机械共混法所制备复合材料的力学性能要高,且在介质浸泡前后,仍能够保持较好的力学性能。     

新型CO2可逆离子液体体系制备纤维素膜的结构与性能

以新型CO2可逆离子液体CO2/DBU/DMSO体系经溶解、沉积制备出纤维素膜,系统探究了沉积浴的种类、溶剂组成及溶解时间对纤维素膜结构与性能的影响。研究表明,经该体系充分溶解并水沉积得到的纤维素膜具有Ⅰ型与Ⅱ型结晶并存的结构,与原纤维素的固有结晶结构相近。所得纤维素膜具有良好的力学性能,拉伸强度达到55.9MPa,断裂伸长率为9%。因此,新型CO2可逆离子液体体系的运用,为简便易行制备性能良好的纤维素膜提供了重要的技术途径。     

聚酰亚胺/SiO_2纳米复合抗原子氧气凝胶的合成与性能

以3,3′,4,4′-联苯四酸二酐(sBPDA)和2,2′-二甲基-4,4′-二氨基联苯胺(DMBZ)为聚合单体,八(氨基苯基)聚倍半硅氧烷(OAPS)为交联剂,SiO2纳米粒子为填料,采用超临界二氧化碳干燥工艺制备了一系列聚酰亚胺(PI)/SiO2纳米复合气凝胶(CPIA-SiO2-0~CPIA-SiO2-7)。研究表明:SiO2纳米粒子的引入对PI气凝胶的耐热性能未产生显著的影响。然而,随着SiO2纳米粒子含量的增加,PI气凝胶的孔隙率从89.6%逐渐降低至79.4%,BET表面积也随之从425.5m2/g降低至380.2m2/g,纳米泡孔孔径分布呈现出变宽的趋势。SiO2的引入显著提高了PI气凝胶的抗原子氧侵蚀能力,含量为7%(质量分数,下同)的PI/SiO2复合气凝胶CPIA-SiO2-7的原子氧侵蚀率(2.6%)仅为不含SiO2气凝胶CPIA-SiO2-0的原子氧侵蚀率(12.3%)的1/5左右。     

白炭黑粒子对三元乙丙橡胶硫化性能、黏弹性及泡孔结构的影响

采用4种不同种类的白炭黑粒子(A200,H2000,R812S,T36-5)分别作为三元乙丙橡胶(EPDM)的增强填料,并通过超临界CO₂发泡法制备具有微孔结构的EPDM泡沫材料。通过扫描电子显微镜和橡胶加工分析仪对不同白炭黑/EPDM基体的黏弹性、硫化性能及泡孔结构等进行测试和表征。结果表明:以气相法白炭黑(A200,H2000,R812S)作为增强填料的EPDM基体流变性能好,利于形成泡孔结构,且泡孔密度随交联度的提高而增加。而以沉淀法白炭黑T36-5作为增强填料的EPDM基体的模量和黏度过高,只在较窄的预硫化区间内形成泡孔结构。其中以白炭黑A200作为增强填料的EPDM基体在不损失良好流变性能的前提下仍能够获得较高的交联度,且A200能够提供更好的异相成核作用,明显提高泡孔密度,减小泡孔尺寸。     

超临界二氧化碳流动和换热研究进展

综述了国际上对超临界二氧化碳管内换热和压降特征的研究。提供了多种公开发表的超临界流体在冷却工况下的换热关联式及单相压降关联式,将实验关联式的计算结果与文献中的实验数据进行对照,在此基础上对关联式的准确性进行了讨论。同时指出了现有研究内容的不足。     

CO_2插层作用下有机蒙脱土膨胀/结构行为的分子模拟

运用蒙特卡洛分子模拟方法,依据能量最小原则,从微观水平研究了二氧化碳环境下钠蒙脱土及表面活性剂改性有机蒙脱土的膨胀性能和层间结构。模拟结果表明,蒙脱土晶面间距随着层间二氧化碳含量增加而膨胀增大,其中有机蒙脱土表现出更强烈的膨胀性能。通过结构分析,层间二氧化碳随着蒙脱土晶面间距的增大而出现明显的多层分布现象,其中层间表面活性剂随着二氧化碳含量的变化而形成不同的结构形态。     

直接电解法制备二氧化锰正极的研究

首次通过电解方法直接制得二氧化锰-碳电极.通过恒电流放电、XRD 衍射、差热-热重实验以及环境扫描电镜等现代实验方法研究了合成条件与放电性能的关系.结果表明,在二氧化锰-碳电极上经过420℃处理的二氧化锰具有四方结构(空间群 P42/mnm).以0.1C的电流倍率放电时放电容量达到219mAh/g.不必涂敷粘结剂,二氧化锰就可以与石墨集电极牢固的结合在一起,直接作为正极使用.     

聚乙烯亚胺型吸附纤维的制备及其对二氧化碳的吸附性能

以玻璃纤维作为基质复合聚乙撑亚胺（PEI），制得含多胺基的复合型吸附纤维。表征了该吸附纤维的化学结构，评价了不同PEUEP比例、涂布质量以及吸附气体中CO2浓度对CO2吸附容量的影响。研究表明，在饱和水蒸汽环境中，CO2吸附量随PEUEP比例的增加而增加，对二氧化碳的吸附量最高可达89．11mgCO2／g-吸附纤维，相当于276．96mg CO2／g-PEI，但CO2吸附量随涂布质量的增加而降低。吸附气中CO2含量对CO2吸附容量的影响较大，随吸附气中CO2含量的增加，吸附纤维对CO2的吸附容量也增加。     

用超临界CO2法制备聚乳酸三维多孔支架材料

在超临界CO2(SC—CO2)条件下制备了生物相容性良好的聚乳酸(PLA)多孔材料，研究了PLA的分子量、SC—CO2的压力、温度和处理时间对多孔材料的结构形态、孔隙率和玻璃化温度的影响。结果表明：支架材料的孔洞分布、结构形态和孔隙率不仅与聚乳酸的分子量有关，而且与处理样品的压力、温度和时间关系密切；经超临界CO2处理后材料的玻璃化温度(Tg)有所升高，与传统的方法所制得的材料相比较，多孔材料不仅杂质少，孔径孔率分布均匀，孔洞表面粗糙，而且在大孔之间几乎布满了直径为10—20μm的微孔，该结构提供了营养物质和新陈代谢的通道，且细胞和生长因子也能通过。     

超临界CO2流体干燥合成ZrO2气凝胶及其表征

以无机盐为原料,采用沉淀法结合超临界CO2流体干燥技术成功地制备了ZrO2气凝胶.借助TG/DSC、XRD、TEM、DLS以及N2物理吸附等手段对其性能进行表征.结果显示,超临界CO2流体干燥可以有效地防止干燥过程中胶体粒子之间的硬团聚作用,在基本保持湿凝胶网络结构的情况下实现液相的脱除,从而使合成的ZrO2具有高比表面积和大孔体积等特点.此外,样品的TEM和DLS分析显示,纳米ZrO2颗粒首先形成具有空间网络结构的簇团,尺寸为数百个纳米的簇团堆积形成ZrO2气凝胶;气凝胶的空间网络结构特征在中等温度的热处理过程中不会遭到完全破坏.     

Wear resistance of Fe-based amorphous coatings prepared by AC-HVAF and HVOF

Fe₆₃Cr₈Mo_3.5Ni₅P₁₀B₄C₄Si_2.5 amorphous coatings have been prepared by the activated combustion high velocity air fuel (AC-HVAF) and high velocity oxygen fuel (HVOF) processes. The microstructure and wear resistance of the amorphous coatings are comparatively studied. The wear volume loss of the AC-HVAF coating is approximately seven times less than that of the HVOF coating, indicating that the AC-HVAF coating exhibits better wear resistance. Detailed analysis on the worn surface indicates that the enhanced wear resistance of the AC-HVAF coating is mainly attributed to the formation of a more stable oxide tribolayer and smoother worn surface, which result from the dense and complete amorphous microstructure of the AC-HVAF coating. The wear mechanism of the amorphous coatings is dominated by oxidation wear.     

Water vapor adsorption properties of amorphous cefditoren pivoxil evaluated by adsorption isotherms and microcalorimetry

Water vapor adsorption of ground cefditoren pivoxil was studied. The amount of water adsorbed increased with a decrease in the crystallinity of cefditoren pivoxil. It was found from the microcalorimetric measurements that the differential heat of water vapor adsorption at 1.5% adsorbed water increased with decreasing crystallinity of cefditoren pivoxil, suggesting that hygroscopicity of cefditoren pivoxil was enhanced by grinding. These results indicated that hydrophilic adsorption sites in cefditoren pivoxil increased through the grinding process. The results of infrared (IR) spectra examination suggested that the increment of hydrophilic adsorption sites through the grinding process resulted from the change of the environment of the carbonyl groups in two esters and amide.     

Production of few-layer graphene by supercritical CO2 exfoliation of graphite

In this study, the authors report a supercritical CO₂ processing technique for intercalating and exfoliating layered graphite. Few-layer graphene is produced by immersing powdered natural graphite in supercritical CO₂ for 30 min followed by rapidly depressurizing the supercritical fluid to expand and exfoliate graphite. The graphene nanosheets are collected by discharging the expanding CO₂ gas directly into a solution containing dispersant sodium dodecyl sulfate (SDS) to avoid restacking. Atomic force microscopy (AFM) shows that the typical graphene sheet contains about 10 atomic layers. This technique offers a low-cost, simple approach to large-scale production of pure graphene sheets without the need for complicated processing steps or chemical treatment.     

Application of the Taylor dispersion method in supercritical fluids

This paper describes some of the experimental and theoretical problems encountered when the Taylor dispersion method is applied to the measurement of diffusion coefficients near gas-liquid critical points. We have used our own measurements of diffusion of benzene and toluene in supercritical carbon dioxide, along with measurements from several other sources, to illustrate some of the experimental challenges. Special attention is given to the peak shape. The intercomparisons are greatly simplified by comparing the experimental data as functions of density, rather than pressure. We find large and unexplained discrepancies between the various experimental sources. We discuss the theoretical predictions for the relationships between the diffusion coefficients and diffusivities obtained from Taylor dispersion and dynamic light scattering in fluids near critical points. We conclude that there is no strong reason to press for Taylor dispersion measurements near the gas-liquid critical point of the carrier gas.Paper dedicated to Professor Joseph Kestin.