On an Effect of Fine Ceramic Particles on the Structure of Aerogels

The addition of ferroelectric microparticles embedded in a nanostructured silica aerogel modifies the dry gel microstructure in a measurable way. The pore size distribution changes as well as the specific surface area. This indicates a possible positive effect of particles on the gelation characteristics. These modifications were observed in solutions gelling during a sounding rocket experiment in which approximately three minutes microgravity provided sufficient time for a convection and sedimentation free gelation to occur. The paper describes the synthesis procedures and the microstructures obtained for the gels under microgravity conditions.     

碳化法制备超细碳酸钙反应中凝胶现象的研究

为了研究制备超细碳酸钙过程中凝胶现象对反应过程及产物性能的影响,本文中以碳化法制备超细碳酸钙中的凝胶现象为例,研究了不同工艺参数(温度、石灰乳浓度、碳化气体流量、添加剂)对凝胶现象的影响,探讨了凝胶产生的微观原因,并提出了加入适当成核添加剂以避免凝胶产生的新方法。研究结果表明,避免凝胶出现或减轻凝胶现象的主要方法是在保持产品粒径达到要求的前提下控制反应温度在一定范围内,CO2的气体流量不能过大,石灰乳液浓度不能过高。选择适当的能产生微晶的添加剂来优化反应进程,能够与体系中的反应物作用产生微晶的物质,避免凝胶的发生。     

泡沫分散聚合法制备超大孔水凝胶的工艺探讨

泡沫分散聚合法制备超大孔水凝胶的工艺核心为控制凝胶化过程和泡沫化过程的协同作用效果。探讨各影响因素对泡沫分散聚合工艺的影响,利用电镜、密度和溶胀动力学对材料的结构与性能进行表征。结果表明,以聚氧化乙烯/氧化丙烯和微交联羧甲基纤维素钠复配作为泡沫稳定剂,以碳酸氢钠为发泡剂,用量为10%,以N,N′-亚甲基双丙烯酰胺为交联剂,用量为0.6%,此条件下体系凝胶化时间为28 s左右,泡沫体积可达38 mL,两者的协同作用达到最优情况。乙醇洗涤烘干后,所获得凝胶样品具有大量贯穿,均匀分布的超大孔,1.5 min内即可达到溶胀平衡,且孔隙率越高,其密度越低,溶胀速率和溶胀率均越高。     

基于谷氨酸衍生物和脂肪酸双元有机凝胶的有序纳米结构和组装模式研究

设计研究了具有不同烷基链长度的脂肪酸与谷氨酸衍生物在多种有机溶剂中的双元凝胶行为,在20种溶剂中的凝胶性能测试结果表明是新型双元有机胶凝剂,实验结果表明,烷基链的长度在调控多种有机溶剂中的胶凝剂性能方面起着关键作用,分子骨架中较长的烷基链有助于有机溶剂的胶凝;形貌研究揭示这些凝胶分子随着溶剂的改变自组装形成不同的聚集体,例如片状、棒状、纤维状等;光谱考察表明,取决于分子骨架中酰胺基团和烷基取代链,形成不同的氢键和疏水作用力。此外,使用的溶剂对于这些双元凝胶剂的组装模式和堆积单元也有明显的作用。该工作为设计新型双元有机胶凝剂和软材料提供了新的思路。     

Lipid-bonded conducting polymer layers for a model biomembrane: application to superoxide biosensors

Model biomembranes composed of poly-DATT/DGS/POPA and poly-DATT/DGS/CL were separately prepared on gold electrodes. A monolayer of 1,2-dioleoyl-sn-glycero-3-succinate (DGS) was covalently bonded onto electrochemically grown poly-(3,4-diamiono-2,2:5,2-terthiophene) (DATT) layers (thickness of approximately 300 nm; particle size of approximately 50 to 70 nm). The numbers of unit molecules of the poly-DATT layer and of the DGS immobilized onto the poly-DATT layers were 1.53 x 10(-7) and 1.56 x 10(-9) mol cm(-2), respectively, using a quartz crystal microbalance technique. The lipid bilayers of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphate (POPA) and cardiolipin (CL) were formed onto the poly-DATT/DGS layer using the Langmuir-Blodgett technique. The surface characterizations of each step were investigated by SEM, AFM, and XPS analyses. Cytochrome c (cyt c) was immobilized onto these model biomembranes through the charge interaction between the positive charges of cyt c and the negative charges of phosphate groups in CL or POPA lipids. At the POPA- and CL-modified biomembranes, the formal potentials of the redox couple of the immobilized cyt c were 0.22 and 0.23 V (vs Ag/AgCl), respectively. The redox reaction of the immobilized cyt c at the POPA- and CL-modified biomembranes was quasireversible, and the electron-transfer rate constants were 0.121 s(-1) and 0.133 s(-1), respectively. The applicability of these cyt c immobilized bioimitation membranes as the biosensors was tested for the determination of superoxide.     

Development of in situ-forming hydrogels for hemorrhage control

We report the preparation of in situ-forming hydrogels, composed of oxidized dextran (Odex) and amine-containing polymers, for their potential use as a wound dressing to promote blood clotting. Dextran was oxidized by sodium periodate to introduce aldehyde groups to form hydrogels, upon mixing in solution with different polymers containing primary amine groups, including polyallylamine (PAA), oligochitosan and glycol chitosan. A series of experiments were conducted to identify the optimum gelation condition for the Odex-PAA system. The polymer concentration appeared to have a major effect on gelation time and the polymer weight ratio affected the resulting gel content and swelling. Other influencing factors included pH of the buffer used to dissolve each polymer, PAA molecular weight, and the type of individual material. The latter also contributed significantly to gel content and swelling. Thromboelastography was used to examine the effects of the in situ gelation on blood coagulation in vitro, where the Odex-PAA combination was found to be most pro-hemostatic, as indicated by a decrease in clotting time and an increase in clot strength. The results of this study demonstrated that in situ-forming hydrogels could promote clotting in vitro; however, further studies are required to determine if the same hydrogel formulations are effective in controlling hemorrhage in vivo.     

Transparent monolithic zirconia gels: effects of acetylacetone content on gelation

Transparent yttria-stabilized zirconia monolithic gels were synthesized under controlled conditions for hydrolysis and chemical polymerization. The influence of acetylacetone on the previous chemical reactions was explored, and a plausible explanation was proposed concerning the outstanding role of this additive during the gelation process. Small-angle X-ray scattering was used to estimate the size of the polymeric species and to investigate the influence of acetylacetone on the structure of the gels prepared.     

Preparation and characterization of keratin-based biocomposite hydrogels prepared by electron beam irradiation

The biocompatible and highly porous keratin-based hydrogels were prepared using electron beam irradiation (EBI). The conditions for keratin-based hydrogel formation were investigated depending on several conditions, including the presence of poly(vinyl alcohol) (PVA), concentration of keratin solution, EBI dose, and poly(ethylene imine) (PEI) additives. The pure keratin (human hair and wool) aqueous solution was not gelled by EBI, while the aqueous keratin solutions blended with PVA were gelled at an EBI dose of more than 90 kGy. Furthermore, in the presence of PEI, the aqueous keratin solution blended with PVA could be gelled at a considerably lower EBI dose, even at 10 kGy. This finding suggests that the PEI additives significantly influence the rate of gelation and that PEIs function as an accelerator during gelation. The resulting keratin-based hydrogels were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), gel fraction, degree of swelling, gel strength, and kinetics of swelling analyses.     

三(氯异丙基)磷酸酯在蒙脱石表面吸附机理的模拟计算

基于密度泛函理论研究了三(氯异丙基)磷酸酯(TCPP)与钠基蒙脱石(NaMMT)凝胶化的机理,在微观水平上建立TCPP和NaMMT的分子模型并计算了在无水和有水状态下TCPP在NaMMT的001表面以及晶层间的吸附参数。结果表明,TCPP在NaMMT的001表面和晶层间均能通过物理作用稳定吸附,钠离子有利于TCPP在NaMMT表面的吸附。在有水分子状态下TCPP与水分子在NaMMT表面协同吸附,水分子作为“桥梁”将TCPP与NaMMT表面连接起来,增强了它们之间的相互作用。实验结果亦表明,水分能明显提高TCPP与NaMMT的凝胶化速度。NaMMT与TCPP通过强相互作用自发溶胀形成物理交联结构,吸收大量的TCPP液体。水分增强了体系的相互作用,使交联网络更容易形成,从而加速凝胶化过程。     

PES制膜体系凝胶时间的研究

提出了拉伸逼近法对PES－NMP制膜体系凝胶时间的定量研究。考察了铸膜液条件、凝胶条件对凝胶时间的影响。研究发现,成膜过程中的凝胶时间随膜液高分子浓度的的增加而增加;随膜液中非溶剂含量的增加而减少;随凝胶液中的溶剂含量增加而增大,并且这种增长在一定范围内出现突跃。这种突跃表明膜液的凝胶过程不仅受传质交换速率控制还不可能受其他因素影响。与延迟分相时间的比较实验揭示了：无论对延迟分相体系或是对瞬间分相体系,成膜过程中的凝胶时间远大于延迟分相时间。说明膜结构不仅取决于分相动力学,也取决于凝胶动力学。     

Rheological Investigation of Thermal-Induced Gelation of Polyacrylonitrile Solutions

In this article, thermal-induced gelation of polyacrylonitrile (PAN) solutions in dimethylformamide was studied through rheological measurements. The entangled and non-entangled states were delimited for an overlap parameter of macromolecular coils of 2.7. In temperature sweep experiments, two types of gelation processes were identified for PAN entangled solutions at: (1) a reversible gelation in the region of low temperatures (below 15°C) due to the formation of a crosslinked structure with a small region of order that dissolves completely in an excess of solvent, and (2) an irreversible gelation at high temperatures (above 60°C) and this gel is insoluble in an excess of solvent, due to the formation of a chemical three-dimensional network. Physical PAN gels with good elastic properties were also obtained by the freezing and thawing method. The gel properties depend on the thermal history of the solution (freezing time, aging time, and aging temperature), its composition (concentration and molar mass of the polymer), and gelation conditions (freezing rate). The gelation was attributed to the formation of junction zones via an aggregation process between a certain number of chain segments due to attractive dipole–dipole interactions.     

Poly(HEMA) hydrogels with controlled pore architecture for tissue regeneration applications

The technique for fabrication of soft porous hydrogels, in which both the size and the orientation of inner pores can be controlled, was developed. Three-dimensional hydrophilic gels based on poly[2-hydroxyethyl methacrylate] are designed as scaffolds for regeneration of soft tissues, e.g., nerve tissue. Anisotropic macropores of the size ranging from 10 to 50 μm were formed (1) by using a porogen-leaching method with a solid organic porogen, (2) by phase-separation during gelation in solvent-nonsolvent mixture, or (3) by combination of solid porogen elimination and phase-separation. As a porogen, poly(l-lactide) fibers were applied and consequently washed away under mild conditions to obtain desired spatial orientation of pores. Highly water-swollen polymer gels were characterized with high pressure (low vacuum) scanning electron microscopy (AquaSEM). The morphology of voids remaining after removing the solid PLLA porogen (the macropores) was clearly shown.     

Fibrin gels and their clinical and bioengineering applications

Fibrin gels, prepared from fibrinogen and thrombin, the key proteins involved in blood clotting, were among the first biomaterials used to prevent bleeding and promote wound healing. The unique polymerization mechanism of fibrin, which allows control of gelation times and network architecture by variation in reaction conditions, allows formation of a wide array of soft substrates under physiological conditions. Fibrin gels have been extensively studied rheologically in part because their nonlinear elasticity, characterized by soft compliance at small strains and impressive stiffening to resist larger deformations, appears essential for their function as haemostatic plugs and as matrices for cell migration and wound healing. The filaments forming a fibrin network are among the softest in nature, allowing them to deform to large extents and stiffen but not break. The biochemical and mechanical properties of fibrin have recently been exploited in numerous studies that suggest its potential for applications in medicine and bioengineering.     

凝胶介质对聚酰亚胺膜凝胶速率及膜断面结构的影响

以一种可溶性的新型聚酰亚胺ODPA—BAPP为膜材料,N-甲基吡咯烷酮（NMP）为溶剂,采用浸入凝胶相转化法制备非对称膜．分别以水乙醇正丙醇异丙醇正丁醇以及正戊醇作为凝胶介质,用凝胶动力学测定装置和相分离动力学测定仪分别对其成膜过程中的凝胶速率和相分离时间进行测定．研究结果表明：（1）凝胶介质对凝胶速率大小影响的排序依次为：水〉乙醇〉正丙醇〉异丙醇〉正丁醇〉正戊醇;（2）瞬时相分离易生成指状结构的膜,延时相分离易生成海绵状结构的膜,与相关文献报道一致．     

Screening the fabrication conditions of ultrafiltration membranes by using the uniform design and regression analysis methods

In this work, the concerned casting conditions for the fabrication of the ultrafiltration (UF) membrane from polysulfone were the gelation medium used, the temperature of the gelation bath, the gelation period, and the evaporation time of the cast sheet. The uniform design method was applied to substantially reduce the number of experiments for studying the influence of each of four casting conditions introduced in the preparation of UF-membranes. The pure water flux and the molecular weight cutoff (MWCO) of each of the four macromolecule-standards, namely egg white lysozyme, egg white albumin, bovine serum albumin and bovine γ-globulius, of each prepared UF-membrane were determined. These experimental responses were then analyzed by using a non-linear model with the backward regression method. The results of this work showed that the uniform design-non linear model (UD-NLM) method can substantially reduce the number of experimental runs for predicting the influences of the studied casting conditions on the ultrafiltration performance of the prepared asymmetric polysulfone membranes.     

Kinetic studies of a composite carbon nanotube-hydrogel for tissue engineering by rheological methods

Here we used rheological methods to study the gelation kinetics of silanized hydroxypropylmethylcellulose (HPMC-Si) hydrogel for tissue engineering. Firstly, the gelation time was determined from the independence of tan δ on frequency, and the Arrhenius law was applied to obtain the apparent activation energy of gelation, which was found to be about 109.0 kJ/mol. Secondly, the gelation process was monitored by measuring the sample storage modulus. The results showed that the gelation process could be well classified as a second-order reaction. In addition, a composite HPMC-Si/MWNTs hydrogel system for potential cartilage tissue engineering was investigated. The comparison of pure HPMC-Si hydrogel and composite HPMC-Si/MWNTs systems indicated that the addition of MWNTs could increase the mechanical strength of hydrogel without changing the gelation mechanism of the system.     

Sol-gel derived PbTiO3

Lead titanate gels have been prepared by adding an aqueous nitric acid solution to a Pb-Ti complex alkoxide. A systematic study was made to examine the effects of process parameters such as amounts of water and acid alkoxide molarity on the gelation time as well as on the structure of the gels obtained. The gel structure was characterized by the elastic modulus which was determined via sound wave propagation through the gels. It was found that an increase in both the amount of water and alkoxide molarity caused rapid gelation. Acid additions not only suppressed gelation but also reduced the elastic moduli of the resultant gels. Gels having a low elastic modulus were found to be desirable for the suppression of cracking during ageing and drying. Addition of an excessive amount of acid, however, prevented the formation of a large scale polymer-network and resulted in a powder-like gel. The porosity and dielectric constant of dried gels are also reported.     

Rapid synthesis and characterization of maghemite nanoparticles

Fe2O3-SiO2 nanocomposites were prepared by a sol-gel method using various evaporation surface to volume (S/V) ratios ranging from 0.03 to 0.2. The Fe2O3-SiO2 sols were gelated at various temperatures ranging from 50 degrees C to 70 degrees C, and subsequently they were calcined in air at 400 degrees C for 4 hours. The structure and the magnetic properties of the prepared Fe203-SiO2 nanocomposites were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), differential thermal analysis (DTA), and vibrating sample magnetometer (VSM) measurements. The gelation temperature of the Fe2O3-SiO2 sols influenced strongly the particle size and crystallinity of the maghemite nanoparticles. It was observed that the particle size of maghemite nanoparticles increased with the increasing of the gelation temperature of the sols, which may be due to the agglomeration of the maghemite particles at elevated temperatures inside the microporosity of the silica matrix during the gelation process, and the subsequent calcination of these gels at 400 degrees C resulted in the formation of large size iron oxide particles. Magnetization studies at temperatures of 10, 195, and 300 K showed superparamagnetic behavior for all the nanocomposites prepared using the evaporation surface to volume ratio (S/V) of 0.1, 0.2, 0.09, and 0.08. The saturation magnetization, Ms, values measured at 10 K were 5.5, 8.5, and 9.5 emu/g, for the samples gelated at 50, 60, and 70 degrees C, respectively. At the gelation temperature of 70 degrees C, gamma-Fe2O3 crystalline superparamagnetic nanoparticles with the particle size of 9 +/- 2 nm were formed in 12 hours for the samples prepared at the S/V ratio of 0.2.     

黏度法测定聚偏氟乙烯溶液凝胶分相温度

采用黏度法测定了聚偏氟乙烯/N,N-二甲基乙酰胺/一缩二乙二醇体系的凝胶分相温度,考察了黏度计转子的转速、高分子浓度、溶液的邻近比及熟化时间对溶液凝胶分相温度的影响.结果显示高分子溶液凝胶分相温度与黏度计转子的转速无关,但随着高分子浓度、溶液的邻近比及熟化时间的增加而升高.黏度法来确定PVDF溶液的凝胶分相温度是一种简...     

块状TiO_2气凝胶的形成过程及其对品质的影响

研究了ＴｉＯ２气凝胶形成过程中制备条件和凝胶化过程对块状ＴｉＯ２气凝胶宏观性质的影响,结果表明所得气凝胶是由粒度约为４～６ｎｍ的ＴｉＯ２非晶态微粒连结而成的具有均匀网络结构的多孔性超轻量级块状材料,通过严格控制制备过程中凝胶化过程的条件及状态,可以获得不同密度不同品质的ＴｉＯ２气凝胶．