Rheological Characterization of Hydrophylic Gels

Rheological characteristics of gels were studied, with the focus on their use as a cosmetic base. Some ideal characteristics can be predicted by the rheological characterization, such as the performance, with easy application and without dripping or forming lumps and bubbles. Moreover, it is possible to detect signs of physical instability. The gels were prepared with sodium carboxymethyl cellulose 3% and 5%, with Carbopol 940 (INCI: Carbomer) and with Carbopol Ultrez (INCI: Acrylates/C10-30 alkyl acrylate crosspolymer). The tests performed were yield stress, stress sweep and creep and recovery. The gel with 3% of sodium carboxymethyl cellulose presented the most appropriated behavior and can be indicated as the most suitable cosmetic base.     

Strain-Dependent Rheological Model and Pressure Wave Prediction for Shut in and Restart of Waxy Oil Pipelines

Waxy oil gelation and rheology is investigated and modeled using strain-dependent viscosity correlations. Rotational rheometry shows a sharp viscosity increase upon gel formation. High creeping flow viscosities are observed at small deformation conditions prior to yielding. A new strain-dependent rheological model, following analogous formulation to the Carreau–Yasuda shear rate-dependent model, captures viscosity reduction associated with yielding. In addition, shear viscosity and extensional viscosity are investigated using a capillary rheometry method. Distinct shear-thinning behavior is observed in the shear mode of deformation, while distinct tension-thinning behavior is observed in the extensional mode of deformation for the model fluid systems. High Trouton ratios are obtained for the gelled model fluid systems, confirming strongly non-Newtonian fluid rheology. Finally, axial pressure wave profiles are computed at real pipeline dimensions for idealized moderate yield stress fluids using a computationally efficient 1D pipeline simulator. The Rønningsen time-dependent gel degradation model is used to emulate the fluid rheology in the simulator. Axial stress localization phenomena are shown to depend on the overall magnitude of gel degradation as established by the reduction in yield value. A high degree of gel degradation serves to afford flow commencement in a timely manner.     

Textural Characterization of Silica and Silica-Alumina Gels: Comparison of Different Techniques

The porous texture of silica and silica-alumina hydrogels has been studied by means of thermoporometry measurements. The texture of the xerogels resulting from spray-drying of silica-alumina hydrogels is then evaluated by different methods: BET, Hg-porosimetry and thermoporometry. As each method is based on different physical principles and assumptions, differences are observed between the results. However, these results are complementary and their comparison leads to a better knowledge of the texture of the catalyst particles. A good agreement is observed between thermoporometry and nitrogen adsorption-desorption measurements, whereas mercury porosimetry results are very different. Silica-alumina gels appear as mainly mesoporous materials.     

Structural Models of Dense Gels

The structural models of gels typically reported concentrate either on the solid space or the pore space of the system. The models described in this paper present a connection between grain and pore spaces, applicable to dense gels with uniform particulate microstructure. The gel structure is depicted as a hierarchy at several levels by means of models built up using the Monte-Carlo technique, on the basis of random close packing (RCP) premises. The pore volume distributions are calculated from the largest sphere radius inscribed within the interstices. These distributions are compared to the pore volume distributions of various RCP classic models and to the pore volume distributions of a series of xerogels measured by means of the Brunauer-Emmett-Teller method. Data on the pore volumes associated with different hierarchical levels (e.g., micro-, meso-, or macropores), the local density of the i-th aggregation level and packing of the successive levels are obtained.     

Programmed Ephemeral Gels: New Types of Biomaterials

Summary: In various biological processes, a solid gel phase is produced which later dissolves. Similar ephemeral protein gels were obtained in vitro using two antagonistic enzymes, one generating and the other cleaving covalent bonds. Alternate sol/gel and gel/sol transitions should occur within such a system, generating transient gel phases. An experimental system consisting of gelatin, transglutaminase and thermolysin was first tested. The various gels obtained were programmed to dissolve after a determined time, without any change in temperature or medium composition, and constitute a completely new type of material which we term “Enzgels”. Varying temperature, but also the protein nature and concentration, the protease specificity, the ratio of the two antagonistic enzymes and, the activity of each enzyme, we were able to generate a full range of ephemeral gels with controlled life times and mechanistic properties.     

Microstructure Evolution of Nonhydrolytic Alumina Gels

Nonhydrolitic sol-gel processes of aluminum chloride and aluminum bromide with isopropyl ether and aluminum sec-butoxide were performed at various temperatures. Based on the Arrhenius type variation of the gelation time with temperature, activation energies for the gelation were found to be in the range 19–25 Kcal/mol range. The energies were found to be sensitive to the nature of the aluminum ligands and the chemical scheme. Due to the large activation energy, it is possible to stop the reaction at any time before gelation by cooling the sol to room temperature. Small angle X-ray scattering (SAXS) of sols from the AlClAlCl₃/Pr O system shows unique development of a fractal like structure with nanometer scale order, demonstrated by discrete peaks in the SAXS data. A fractal dimension D = 1.64 was found. An aggregation scheme is proposed to explain this phenomenon. A fractal dimension of 2.4 without small scale ordering found for xerogels prepared from the AlCl₃/ASB system reflects the effect of the different precursors on the microstructure of nonhydrolytic gels.     

超分子凝胶在催化有机反应中的应用

超分子凝胶是有机小分子通过分子间非共价作用形成的使溶剂固定的三维网络结构胶体。 综述关注了近年来超分子凝胶在催化有机反应中一个新的应用方向,依据凝胶剂结构特征和催化反应的类型对迄今报道的小分子凝胶催化剂进行了深入的总结与归类,揭示凝胶催化的独特性,并对其存在的问题和发展趋势进行了讨论。     

Photo-Deformation of Syndiotactic Polystyrene Gels

We report a usual and novel phenomenon that an excitation light beam of a spectrofluorometer produced a black mark in gels of syndiotactic polystyrene (SPS). This mark whose shape is identical with that of an excitation light beam was found to appear in SPS/chloroform gel just after only irradiation at 260 nm for 5 to 10 min. The heating of the gel with the mark at 80°C diminished the mark and recovered uniformly the gel to be as it had been before irradiation. We discuss what the black mark is and why it is produced by light irradiation.     

Numerical Study of Pore Sizes Distribution in Gels

We introduce a new numerical technique for the calculation of the pore size distribution in two-dimensional disordered systems. Our method is based on a triangulation technique which allows a closer measurement of pores surface without any morphological hypothesis.In this work, we focus our calculations in simulated gels. Such materials are modeled in two different conditions: by means of the Diffusion-Limited and Reaction-Limited Cluster-cluster Aggregation algorithms, DLCA and RLCA, respectively. In both situations, when the particles concentration decreases, the average pores size increases. The more compact cluster in RLCA, compared with DLCA, is consistent with the pore size distribution we have calculated. The simulated mean pore size is quantitatively in agreement with experimental data from literature.     

新型刺激响应性纤维素基含能凝胶的流变性能

研究了以不同基团含量的羧甲基纤维素硝酸酯(CMCN)为胶凝剂的含能凝胶细微结构与流变行为的关系.探讨了凝胶的形成机理,并采用线性的流变学方法研究了凝胶的屈服性、触变性、蠕变性及温敏性等动态黏弹性质,分别利用Herschel-Bulkley模型、Burger模型及Carreau-Yasuda模型对凝胶的流动曲线、蠕变曲线和频率曲线进行了数据拟合.研究发现,CMCN凝胶是由其分子结构上两亲性基团通过分子链间氢键及疏水键等非共价键相互作用形成的一种结构均匀的物理交联网络型凝胶.凝胶的非牛顿系数n均小于0.5.随着亲水性羧酸基团含量的增加,凝胶的屈服应力逐渐增大,触变恢复性逐渐增强,弹性与黏性柔量均减小,但其比值增加,蠕变的黏性响应性逐渐减弱而弹性响应性逐渐增强.凝胶的温敏性变化有一个力学松弛转变区,随着羧酸基团含量的增加,松弛转变区愈发明显,凝胶的温敏性也逐渐增强.     

Hybrid Gels as Host Matrices of Perfumed Essences

The variety of SiO₂-gel structures allows the use of sol-gel derived materials as host matrices for prolonged release of chemicals. In this work, the release of perfumed essences is studied in the case of hybrid SiO₂ materials obtained from alkyl-modified silicon alkoxides. Thermogravimetric analysis in isothermal conditions at various temperatures provide data on the kinetic release process. The effects of physical parameters (porosity reduction, vapour pressure) and chemical interactions (organic molecules with matrix) are discussed for the interpretation of the results.     

基于脲基氢键组装的功能超分子凝胶

有机小分子化合物在分子间氢键、π-π堆积、亲疏水作用、范德华力等非共价键弱相互作用力驱动下,自组装形成三维网络结构的物理凝胶称为超分子凝胶。含有脲基的凝胶因子由于其强氢键缔合能力以及与阴离子、金属离子、卤素化合物等作用的可调变多样性,成为组装超分子凝胶中特别有效的氢键组装单元。本文分别从单脲基、双脲基和多脲基的凝胶因子分类综述了基于脲基氢键组装的功能超分子凝胶的研究工作,特别是近几年来的重要进展。对一些成功例子,从分子设计及成胶操作条件控制等方面的精细调谐如何解决聚集-溶解这对主要矛盾,从而实现溶胶-凝胶的转化及其可能的应用前景进行了评述。本文展望了该领域的发展方向与趋势,指出超分子凝胶研究经过多年的快速发展,深化对其蕴含机制以及动力学过程的认识与调控以实现具有多种刺激响应、多重信号输出的多组分复合功能凝胶体系的加工制备是发展趋势与必然要求,展现出广泛的应用前景也极富挑战性。     

Localized Yielding Around Crack Tips of Double‐Network Gels

Double‐network (DN) gels, a type of interpenetrating polymer network (IPN) consisting of rigid and flexible polymer components, exhibit two outstanding mechanical behaviors: yielding deformation of the entire specimen in tensile tests and quite high fracture energy in tearing tests. In this study, atomic force microscope (AFM) measurements were conducted on DN gels to determine the local Young's moduli immediately below the fracture surfaces E_f and below the usual molded surfaces E_m, and compare the local modulus with bulk Young's moduli measured before and after the yielding deformation, denoted as E_h and E_s, respectively. E_m and E_h are around 0.1 MPa; E_f and E_s, around 0.01 MPa, one order lower than the former two moduli. The order relation indicates that yielding deformation occurred locally around the crack tip of the DN gel during fracture. This supports the basic assumption of phenomenological models recently proposed to explain high fracture energy of DN gels. (H. R. Brown, Macromolecules 2007 , 40, 3815–3818; Y. Tanaka, Europhys. Lett. 2007 , 78, 56005).

     

Anisotropy in Longitudinal Modulus of Polymer Gels Containing Ferrite

The effects of magnetization direction on the longitudinal modulus of magnetic gels, which consist of magnetized barium ferrite and poly(vinyl alcohol), have been investigated using 10 MHz ultrasonic waves. The modulus change due to magnetization depends on both the crosslinking density and magnetization direction. The modulus change increased and decreased when the strain direction was perpendicular and parallel to magnetization, respectively.     

Opal Gels Templated Synthesis of Structured Titania Materials

Summary: Core/shell opal gels of sulfonated polystyrene were used as templates to synthesize structured crystalline titania materials. Under acidic conditions, opal materials with hollow spheres of controllable shell thickness and cavity size were prepared. Under neutral conditions, inverse opal inorganic materials with a tunable pore size were prepared. It is crucial that proton ions induce a preferential sol/gel process, forming titania in the gel.

Scanning electron micrograph of the interior region of a structured titania material derived from the G1 template used here. The inset shows broken spheres in which the internal cavity can be observed.     

Supramolecular Gels by Design: Towards the Development of Topical Gels for Self‐Delivery Application

Following a supramolecular synthon approach, simple salt formation has been employed to gain access to a series of supramolecular gelators derived from the well‐known non‐steroidal anti‐inflammatory drug (NSAID) ibuprofen. A well‐studied gel‐inducing supramolecular synthon, namely primary ammonium monocarboxylate (PAM), has been exploited to generate a series of PAM salts by reacting ibuprofen with various primary amines. Remarkably, all of the salts ( S1 – S7 ) thus synthesized proved to be good to moderate gelators of various polar and nonpolar solvents. Single‐crystal and powder X‐ray diffraction studies established the existence of the PAM synthons in the gel network, confirming the efficacy of the supramolecular synthon approach employed. Most importantly, the majority of the salts ( S2 , S3 , S6 , and S7 ) were capable of gelling methyl salicylate (MS), an important ingredient found in many commercial topical gels. In vitro experiments (MTT and PGE₂ assays) revealed that all of the salts (except S3 and S7 ) were biocompatible (up to 0.5 mm concentration), and the most suited one, S6 , displayed anti‐inflammatory ability as good as that of the parent drug ibuprofen. A topical gel of S6 with methyl salicylate and menthol was found to be suitable for delivering the gelator drug in a self‐delivery fashion in treating skin inflammation in mice. Histological studies, including immunohistology, were performed to further probe the role of the gelator drug S6 in treating inflammation. Cell imaging studies supported cellular uptake of the gelator drug in such biomedical application.     

胆酸超分子凝胶化学

胆酸来源丰富,价格低廉,在生命过程中发挥着重要的作用。与胆固醇不同,胆酸以其结构和修饰途径的多样性,以及独特的双亲结构备受超分子化学工作者关注。近年来以胆酸为基本构筑单元的小分子胶凝剂创制及其相关凝胶的研究取得了重要的进展。本文从胆酸衍生物结构设计到胆酸衍生物凝胶构建,概要介绍了胆酸超分子凝胶及其性能研究进展。在此基础上,简要阐述胆酸超分子凝胶材料的潜在应用。     

超分子凝胶中的光化学反应

超分子凝胶中的光化学反应是比较特殊的一类反应,通常是将具有光响应活性的基团或分子引入到超分子凝胶的自组装体系中,因此,能够将超分子凝胶独特的性质与光化学反应的优势有效地结合起来,构筑新型的光功能材料,这使得此类超分子凝胶在光信息存储、光开关及光转换器件等前沿领域具有广阔的应用前景.本文主要总结近年来国内外包括作者课题组对超分子凝胶中光化学反应方面的研究进展,以及其在多重响应凝胶、手性光学开关以及手性合成方面的应用.