甲苯二异氰酸酯与乙二胺沉淀聚合一步法制备聚脲多孔材料及其表征

以甲苯二异氰酸酯和乙二胺为单体,通过沉淀聚合一步到位制备了富含胺基的聚脲多孔材料.探讨了反应时间、溶剂种类及混合溶剂配比对聚脲多孔材料性能的影响.通过BET和压汞法对聚脲多孔材料的孔结构进行了表征,用扫描电子显微镜表征了材料的形貌,用X-射线衍射仪测试了材料的结晶性能.结果表明,聚合反应进行48 h后多孔材料的胺基含量不再变化,所得聚脲为典型多孔材料且部分结晶.与丙酮相比,以乙腈作反应介质制备的聚脲的比表面积和孔体积较大,孔径分布较宽.以乙腈和丙酮混合溶剂作反应介质,通过改变混合溶剂的配比可以改变材料的孔结构.     

交联聚苯乙烯型多孔吸附剂的中孔性质研究

采用77K温度下的氮气吸附方法,测定了经悬浮聚合制备的不同交联度的交联聚苯乙烯多孔吸附剂的吸附/脱附等温线.根据BET吸附模型计算了比表面,由吸附量计算了总的孔体积,由孔体积和比表面计算出平均孔径,并依据脱附等温线采用BJH方法计算孔径分布.结果表明,交联度对交联聚苯乙烯多孔吸附剂的孔结构均具有显著影响.随着交联聚苯乙烯多孔吸附剂的交联度升高,其孔径变小,比表面增大,而且低交联度吸附剂的中孔接近圆柱形,高交联吸附剂的中孔形状接近“墨水瓶”形.显然,交联度对孔性质的影响与孔结构在交联聚苯乙烯多孔吸附剂制备和后处理过程中的稳定性密切相关.交联度低时,初期形成的小孔不能保持稳定,在后续聚合及后处理过程中合并为大孔,结果造成低交联吸附剂大孔径、低比表面的现象.通过对孔径分布的研究,揭示了不同吸附剂在中孔范围内的孔特征,并对其形成机制进行了分析.     

多阶有序多孔炭的软模板法合成与结构控制

多阶有序多孔炭材料综合了多种多孔炭材料的结构优点,在催化、吸附、储能、电化学等方面具有潜在的重要应用。多阶有序多孔炭材料的合成方法很多,到目前为止,模板法是控制孔结构和调节尺寸的最有效方法。在模板法中,软模板法因为其工艺简单、省时、成本低、环境污染小等优势,近些年来广泛被人们采用。用软模板法合成的多阶有序多孔炭包括:大孔-介孔炭,介孔-微孔炭,介孔-介孔炭,大孔-介孔-微孔炭等。本文对多阶有序多孔炭的软模板法合成与结构控制进行了综述。总结了软模板法在实现上述材料孔结构控制中的影响因素。     

大孔交联甲基丙烯酸缩水甘油酯共聚物的合成及其结构性能研究 …

甲基丙烯酸缩水甘油酯为单体，三烯丙基氰尿酸酯为交联剂，在致孔剂甲苯，正庚烷存在下，用悬浮聚合法制得一系列大孔共聚物。测定了聚物的孔结构性能，讨论了不同交联剂及致孔剂用量和配比对共聚物结构的影响，并初步讨论了特大孔共聚物的形成机理。     

多孔炭物理化学结构及其表征

以碳为基本骨架的多孔炭因具有丰富的孔隙结构和表面化学宫能团,在吸附分离、催化、电子等领域应用广泛.在阐述多孔炭孔结构（物理结构）和表面化学宫能团（化学结构）基础上,重点介绍了透射电镜等可直接观察多孔炭孔结构的表征方法及Dubinin微孔充填理论、平均场密度泛函理论、吸附法、压汞法等表征多孔炭孔结构的主要理论及方法,以及...     

温敏性聚(N-异丙基丙烯酰胺)水凝胶的合成与表征

以不同粒径的硅胶颗粒为致孔剂制备了多孔的聚(N-异丙基丙烯酰胺)(PNIPAAm)水凝胶,用DSC对其相转变温度进行了表征,并测定了不同温度下达到溶胀平衡时水凝胶的溶胀率,研究了水凝胶的退胀机理及收缩凝胶的再溶胀机理。实验证明,多孔凝胶相对于无孔凝胶其溶胀性能有较大提高,孔结构的存在大幅度提高了水凝胶的响应速率,尤其是退胀速率。     

部分水解聚(丙烯酸甲酯─醋酸乙烯酯─甲基丙烯酸甲酯)多孔载体合成与结构的研究

该文以二乙烯苯和双丙烯酸多缩乙二醇酯为交联剂，制备了部分水解聚（丙烯酸甲酯-醋酸乙烯酯-甲基丙烯酸甲酯）多孔载体。用电镜、压汞仪、红外、X射线衍射仪等测定了载体的结构与孔结构。     

一步碳化多孔有机材料制备多孔碳及其性能的研究

开发并利用清洁的、可再生的能源是解决环境污染问题和能源短缺的有效方法.碳化含碳量较高的多孔有机材料制备的多孔碳,具有较高的比表面积,良好的物化稳定性,优良的机械性能等优点,在清洁能源的存储、分离、能量的存储与转化领域有广泛的应用.常见的由多孔有机材料制备多孔碳的方法主要是非活化碳化法和活化碳化法.不同的制备方法得到的多孔碳形貌,孔结构各不形同.多孔碳材料自身的结构性质可以影响其应用.合理的设计并调控多孔碳的“孔”,发挥孔尺寸的“筛分效应”可以有效地对气体进行存储和分离.在锂电等能量转化领域,“限域效应”是影响锂电性能的重要因素.多孔碳材料中较小的孔可以限域活性成分,而较大的孔可以快速传输,两种孔的协同效应可以使锂电性能大大提升.本综述系统地归纳了一步碳化多孔有机材料制备多孔碳的方法及其优势,详细地介绍了其在气体吸附、存储、分离以及电化学等领域的应用.最后,结合多孔碳材料的研究现状,提出由多孔有机材料制备多孔碳材料所面临的挑战,同时也展望了多孔碳材料的应用前景.     

铝合金熔体在多孔介质中的渗流过程及多孔铝合金

以高技术需求的多孔铝合金为研究对象,揭示了铝合金熔体在多孔介质中的渗流过程及影响规律;根据相似原理采用渗流模拟法揭示了模拟液在多孔介质中渗流的规律,与熔体渗流过程结果吻合良好;建立了熔体在多孔介质中渗流,控制多孔铝合金孔结构的物理模型并与实验吻合,以控制孔结构;在上述单一孔径多孔铝合金基础上,发展了梯度孔径及周期调制的新型多孔铝合金,获得了更佳的声学性能.     

PP/HDPE 共混物及其纳米复合材料超临界流体微孔发泡

通过间歇法制备了聚丙烯(PP)/高密度聚乙烯(HDPE)共混物及其纳米复合材料的微孔塑料.用扫描电镜对发泡样品的泡孔结构进行表征,研究了纳米粒子的类型和含量对泡孔结构的影响.结果表明:在PP中加入25%的HDPE可改善泡孔结构;在 PP/HDPE 共混物中加入纳米粒子可使泡孔的直径减小、密度增加、泡孔分布更均匀;泡孔直径随着纳米粒子含量的增加会出现先减小后增加的趋势.     

Precise control of agarose media pore structure by regulating cooling rate

A porous structure is the key factor to successful chromatography separation. Agarose gel as one of the most popular porous media has been extensively used in chromatography separation. As the cooling process in the agarose gelation procedure can directly influence the pore structure, ten kinds of 4% agarose media with different cooling rates from 0.132 to 16.7°C/min were synthesized, and the pore structure was determined accurately by using low‐field NMR spectroscopy. The curves of pore structure and cooling rate can be divided into two stages with the boundary of 6°C/min. In stage I, the pore structure met a power equation with the decrease of the cooling rate, and in stage II, the process reached a plateau. Confirmatory experiments proved that, by adjusting the cooling rate, a precise control of the pore structure of agarose media can be realized, furthermore, cooling rate optimization was an effective way to control the pore size of agarose media and can further tailor the pore structure for more effective separation of different proteins.     

Porous epoxy thermosets obtained by a reaction-induced process and their characterizations

A novel reaction-induced method with the aid of solvent for porous thermosetting epoxy was first carried out. Investigations of pore structure using scanning electron microscope （SEM） showed that porous epoxy networks with average pore size ranging from 3 to 20 μm were obtained. The pore structure generated by this method can be tailored by changing the solvent content.     

聚苯乙烯-co-聚(2,3,4,5,6-五氟苯乙烯)共聚物: 合成及其多孔薄膜的制备

利用原子转移自由基聚合(ATRP)方法, 分别在三氟甲苯、含氟离子液体以及三氟甲苯/含氟离子液体混合溶剂体系中合成了聚苯乙烯-co-聚(2,3,4,5,6-五氟苯乙烯)(PS-co-PPFS)共聚物, 通过¹H NMR、¹⁹F NMR、元素分析以及凝胶渗透色谱法(GPC)对所得聚合物的分子链结构和组成进行了分析和表征. 随后, 利用静态呼吸图法分别在CS₂, CHCl₃ 和CH₂Cl₂ 中制备了有序多孔薄膜, 用扫描电子显微镜(SEM)观察其表面形貌, 并与利用分子量大小相当的聚苯乙烯均聚物(PS)制备的多孔薄膜进行了对比. 研究结果表明: 在三氟甲苯和含氟离子液体溶剂体系中, 均可利用ATRP 聚合方法获得窄分子量分布的PS-co-PPFS 共聚物(M_n＝5200～7900 g·mol^-1, i>M_w/M_n＝1.12～1.22). 对聚合物薄膜的扫描电子显微镜(SEM)观察和分析显示: 分别以CS₂, CHCl₃ 和CH₂Cl₂ 作为溶剂, 利用静态呼吸图法均可制备出PS-co-PPFS 共聚物多孔薄膜. 然而, 与在CHCl₃ 和CH₂Cl₂ 中制备的PS 均聚物多孔薄膜的表面形貌不同的是, PS-co-PPFS 共聚物多孔薄膜呈现出无序排列、平均孔径大小不同的两种孔结构; 在CHCl₃ 中制备所得薄膜的孔结构有序性相对较好, 两种孔的平均孔径分别为0.75 和0.37 μm.     

Capillary Rise in Granitic Rocks: Interpretation of Kinetics on the Basis of Pore Structure

The capillary transport of water into granitic rocks has been interpreted on the basis of the structure of its porous network. An effective pore radius has been calculated from a three-sized single-pore model proposed by F. A. L. Dullien, El-Sayed, and V. K. Batra (J. Colloid Interface Sci. 60, 497, 1977) Considering the porous network of granites as consisting of fissures grouped in two size types, macro- and microfissures, an effective radius was found from the characteristic radii for each type and the average of these two values. Good agreement between the effective radius calculated and the radius estimated using a capillary rate value measured experimentally provides a suitable basis for identifying interrelationships between the pore structure and moisture capillary rise. In fact, it is possible to predict the process rate from only two characteristic pore sizes, corresponding to the radii of macrofissures and microfissures. The abnormally low rate of capillary rise observed in one of the granites studied could be easily interpreted as due to the involvement exclusively of the macrofissures of its porous network in capillary transport. Copyright 2000 Academic Press.     

In-situ cryo-SEM investigation of porous structure formation of chitosan sponges

Aiming at better understanding of porous structure formation unique in-situ experiments on freeze-drying the chitosan-based solvents were carried out by cryo-SEM method. It allowed us to visualize the lyophilization process and to follow the formation of the porous structure in the chitosan sponge. It was clearly shown that the chitosan solutions just after freezing possess an evident microstructure consisting of the walls of the future pores and of the frozen solvent filling the space between them. The diameter of the pores and their wall thickness are controlled be pre-freezing temperature. An incorporation of nanofillers (chitin nanofibrils and montmorillonite) into the chitosan solution did not affect the pore size and wall thickness. However, they can promote the formation of the layered structure of the pore walls.     

凝胶渗透色谱多孔硅胶吸附问题的研究

本文以端基为羟基的聚二甲基硅氧烷为测试样品,甲苯为淋洗液,研究了凝胶色谱柱填料多孔硅胶的表面羟基含量等与吸附效应的关系。说明采用对硅胶进行表面处理和在淋洗液中加入吸附抑制剂的方法,不能避免吸附。建议采用端基封闭剂(如三甲基氯硅烷)处理聚合物的活性端基——羟基的方法,解决吸附问题。     

Comments on the size of the adsorbed phase in porous adsorbents

An alternative to the conventional ‘pore filling model’ for describing Gibbsian surface excess (GSE) isotherm from a liquid mixture on a porous adsorbent is proposed where the adsorbed phase volume is treated as a variable. The new model is tested using GSE isotherm data on various micro and mesoporous adsorbents. The adsorbed phase volume is found to be system specific but always less than the adsorbent pore volume, irrespective of the pore size.     

聚乳酸蜂窝状多孔膜的形成与控制

以单一组分聚L-乳酸(PLLA)为成膜材料,利用水辅助法制备了聚乳酸(PLLA)蜂窝状多孔膜.利用扫描电镜(SEM)和原子力显微镜(AFM)观察多孔膜形貌.研究溶剂、溶液浓度、环境温度和湿度等因素对所成多孔膜结构的影响.实验结果表明,高湿度环境和具有一定浓度的聚合物溶液是制备蜂窝状多孔膜的必要条件.溶剂的挥发性是形成规整蜂窝状孔结构的关键因素.环境相对湿度由43%增加到91%,PLLA多孔膜的孔径由(1.75±0.24)μm增加到(11.50±1.43)μm,且孔呈现六边形的蜂窝状结构.扫描电镜断面和AFM表明:膜表面形成了深度约为1.8μm的单层孔结构.通过控制溶液浓度、环境温度和湿度等因素来控制膜的表面形貌及其所成蜂窝状孔的大小.最佳的成膜条件为溶剂CH2Cl2,湿度75%RH,温度34℃,浓度3 wt%.讨论了蜂窝状多孔膜的形成机理.     

Application of a micro/macro‐homogenization procedure to the investigation of the mechanical behavior of ionomer membranes for fuel cells

A microhomogenization/macrohomogenization procedure is proposed to compute the mechanical and swelling behavior of ionomer (Nafion) membranes for fuel cells under external compression loads. The membrane is viewed as a periodic porous media composed of a charged solid phase saturated by an aqueous electrolyte solution. We establish the equation of state in a single membrane pore based on a rigorous treatment of thermodynamic, electrostatic (Poisson–Boltzmann equation) and of mechanical equilibrium. The homogenization technique is then applied to propagate the information available in the pore‐scale model to the macroscale. Numerical experiments are performed to illustrate the results in a cylindrical pore geometry. The results show that the swelling pressure can be approximated by the osmotic pressure, which depends on the charge density at the pore walls and the pore radius. The model predicts the water content of liquid equilibrated membrane under various compression loads and the results are consistent with literature data. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1496–1509     

Capillary filling in nanostructured porous silicon

An experimental study on the capillary filling of nanoporous silicon with different fluids is presented. Thin nanoporous membranes were obtained by electrochemical anodization, and the filling dynamics was measured by laser interferometry, taking advantage of the optical properties of the system, related with the small pore radius in comparison to light wavelength. This optical technique is relatively simple to implement and yields highly reproducible data. A fluid dynamic model for the filling process is also proposed including the main characteristics of the porous matrix (tortuosity, average hydraulic radius). The model was tested for different ambient pressures, porous layer morphology, and fluid properties. It was found that the model reproduces well the experimental data according to the different conditions. The predicted pore radii quantitatively agree with the image information from scanning electron microscopy. This technique can be readily used as nanofluidic sensor to determine fluid properties such as viscosity and surface tension of a small sample of liquid. Besides, the whole method can be suitable to characterize a porous matrix.