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1.
The objective of this study is to provide a rheological characterization of binary hydroalcoholic gels made with Carbopol Ultrez 10 (U10) and Hyaluronic Acid (HA) as a function of polymer concentration: U10 (0.0-2.0% w/w) and HA (0.00-0.20% w/w), and to determine the influence of this combination on the thixotropic properties of the resulting binary systems. Interaction of the two polymers was measured using the Viscose Synergy Index (I(S)) and thixotropic analysis, which indicate the structural changes that take place in binary gels attributable to molecular interactions between the gelling agents. The maximum values for viscose synergy (I(S)=1.22-1.44) are obtained for the U10 : HA mixtures with a polymer proportion of 10 : 1. The behavior of the binary gels studied is the result of the formation of a more structured three-dimensional network between the U10 and HA molecules. Shearing of this polymer network requires application of a greater force than is needed to shear the structure of the separate gels. Inclusion of HA in a proportion of 1 : 10 has a fixing effect on the polymer network, resulting in greater resistance to shearing in the compound gel. The relative thixotropic area -A(R)- shows maximum values (A(R)=17.215%) for the same polymer composition. The evolution of the two parameters indicates that restructuring of the molecular interactions for this polymer proportion (10 : 1) takes place; the result is a reinforced three-dimensional structure in the gelled system, which increases the thixotropic properties. The same composition leads to a maximum of thixotropic properties as well as viscose synergy because both characteristics are closely related to structural changes observed in the binary systems of this composition. Thixotropic systems have a very wide area of application in the pharmaceutical industry. For this reason, the results obtained here considerably increase the use of the gels studied. In fact, incorporation of HA significantly improves a property of acrylic gels which has direct repercussions on the ease and efficiency of their application to the skin.  相似文献   

2.
Rheological behavior and structural interpretation of waxy crude oil gels   总被引:5,自引:0,他引:5  
A waxy crude oil which gels below a threshold temperature has been investigated under static and dynamic conditions, using a combination of rheological methods, optical microscopy, and DSC. Particular attention is given in this work to the influence of the mechanical history on gel strength and to describing the time-dependent rheological behavior. The gels display a strong dependence of the yield stress and moduli on the shear history, cooling rate, and stress loading rate. Of particular interest is the partial recovery of the gel structure after application of small stress or strain (much smaller than the critical values needed for flow onset) during cooling, which can be used to reduce the ultimate strength of the crude oil gel formed below the pour point. A second focus of this study is to further develop the physical interpretation of the mechanism by which wax crystallization produces gelation. Gelation of the waxy crude oil studied is suggested to be the result of the association between wax crystals, which produces an extended network structure, and it is shown that the system displays features common to attractive colloidal gels, for one of which, fumed silica (Aerosil 200) in paraffin oil, rheological data are reported. The colloidal gel model provides a simple and economical basis for explaining the response of the gelled oil to various mechanical perturbations and constitutes a fruitful basis from which to develop technologies for controlling the gelation phenomenon, as suggested by the rheological results reported.  相似文献   

3.
Saturated monoglycerides can form firm gels in water. These gels are networks of stiff plate-like beta-crystals of monoglycerides (a "cardhouse"), grown from a space-filling lamellar liquid-crystalline phase. The molecular mechanism of crystallization is discussed in the light of network formation. The concentration dependence of gel development of (shear-cooled) monoglyceride gels has been studied by rheology. A gelation mechanism has been proposed, consisting of two steps: (i) After formation of a nucleus, rapid crystallization in a lateral direction occurs (probably within one bilayer) by which the first space-filling network is formed. (ii) This is followed by reinforcement of the network by which stacks of crystalline bilayers are formed. The plate-like crystals are linked in connective domains or junction zones, probably containing all the material (cosurfactants, diglycerides, etc.) that does not fit in the crystalline array. Small deformation rheology shows that above about 2 wt% monoglyceride a percolating network is formed. The large deformation rheology is typical for a particle gel with a relatively small strain at failure (both in shear deformation and compression). The connective domains or junction zones already fail when relatively small deformations are put on the system.  相似文献   

4.
The properties of the aged gels of high molecular weight syndiotacticity-rich poly(vinyl alcohol)s (HMW S-PVAs) with different syndiotactic diad (s-diad) contents were investigated. HMW S-PVA gels with s-diad content of 61.5% and 58.2% showed the rapid increases of the syneresis and the turbidity from the early stage of aging time, which is ascribable to the phase separation, while that with s-diad content of 55.7% did not. From the morphological study, it was confirmed that the phase separation in HMW S-PVA gel with s-diad content of 61.5% occurred without the liquid-liquid phase separation in sol state, whereas both the liquid-liquid phase separation in sol state and the subsequent phase separation in gel state occurred in the case of HMW S-PVA gel with s-diad content of 58.2%. On the other hand, HMW S-PVA gel with s-diad content of 55.7% showed neither the liquid-liquid phase separation in sol state nor the phase separation in gel state in the long period of time. It was also confirmed from wide angle X-ray diffractogram that the crystallization was accompanied by the phase separation in gel state in the aging process of PVA gel. However, the crystallization was hindered by the fast network formation at the initial stage of time. Later the syndiotacticity promoted the crystallization. The tensile modulus of HMW S-PVA gel with higher syndiotacticity increased more significantly with time. Received: 2 December 1999/Accepted: 12 July 2000  相似文献   

5.
以非离子表面活性剂单硬脂酸甘油酯(GMS)制备出稳定的微泡沫. 采用偏光显微镜、冷冻断裂蚀刻透射电子显微镜(FF-TEM)、差示扫描量热仪(DSC)和流变仪对其表面活性剂溶液相态、泡沫体系的微观结构、相变行为和流变性进行研究以探索微泡沫的稳定机理. 实验结果表明, 表面活性剂分子吸附在气泡界面, 发生晶化形成有序、紧密排列的层状液晶凝胶相液膜, 该液膜具有较强的刚性, 能抵抗由Laplace附加压力驱使的气泡溶解和聚并行为. 微泡沫可稳定10个月, 无明显的相分离和气泡破裂现象. 其稳定作用机理是通过影响泡沫排液过程, 增强Gibbs-Marangoni效应, 从而提高了气泡液膜强度, 减缓了气相扩散速率.  相似文献   

6.
Poly(ethylene terephthalate) (PET) was rapidly crystallized through thermoreversible gelation in a liquid ethylene glycol oligomer or in epoxy resin. The solutions formed gel rapidly on cooling. Polarized light microscopy and small-angle light scattering showed that these gels contain large, regular PET spherulites. The gels may be formed by two consecutive processes: the phase separation and crystallization, and gelation by formation of a three-dimensional PET network in the oligomer solvents, where the nodes of the network are PET spherulites. The crystallinity of PET recovered from polymer/oligomer gels is near 72% measured by wide-angle X-ray diffraction method, which is about 20% higher than PET samples crystallized by solution crystallization in small molecule solvent, high temperature annealing, and stretching techniques. It takes only a few minutes to form the highly crystalline phase PET in the PET/oligomer system, and the crystallinity of the dried gel is independent of the concentration of the original solution. Excimer-fluoresence and Raman spectroscopic studies indicated that PET recovered from the gels are in an ordered state with few chain entanglements. The entanglement density of the recovered PET recovered from a 20 wt % solution in ethylene glycol oligomer is as low as that of freeze-extracted PET from a 0.5 wt % solution in phenol. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1219–1225, 1998  相似文献   

7.
Utilizing metal-ligand binding as the driving force for self-assembly of a ditopic ligand, which consists of a 2,6-bis-(1'-methylbenzimidazolyl)-4-oxypyridine moiety attached to either end of a penta(ethylene glycol) core, in the presence of a transition metal ion (Zn(II)) and a lanthanide metal ion (La(III)), we have achieved formation of stimuli-responsive metallo-supramolecular gels. We describe herein a series of experimental studies, including optical and confocal microscopy, dynamic light scattering, wide-angle X-ray diffraction, and rheology, to explore the properties of such gels, as well as the nature of the gelation mechanism. Morphological and X-ray diffraction observations suggest gelation occurs via the flocculation of semicrystalline colloidal particles, which results in the gels exhibiting pronounced yielding and thixotropic behavior. Application of mechanical stress results in a decrease in the particle size, which is accompanied by an increase in gel strength after removal of the stress. Moreover, studies show that the presence of lanthanide(III) perchlorate increases the mechano-responsiveness of the gels, as a consequence of reduced crystallinity of the colloidal particles, presumably due to the different coordination ability of lanthanide(III) and zinc(II), which changes the nature of the self-assembly in these materials.  相似文献   

8.
Cross-linking of polyelectrolytes such as DNA gives gels that are osmotically highly swollen but contract upon addition of electrolytes and, in particular, upon association of oppositely charged cosolutes with the polyelectrolyte chain. The deswelling behavior of cross-linked DNA gels thus reflects the DNA-cosolute interactions and provides a basis for the development of responsive DNA formulations. Gels of both single- and double-stranded DNA have interesting applications, and a comparison between them provides the basis for understanding mechanisms. Denaturation of cross-linked ds-DNA gels was induced by heating them above the melting temperature and then cooling. This process, studied by fluorescence using ethidium bromide, appeared to be reversible when a heating/cooling cycle was performed. The swelling behavior upon addition of different cosolutes, such as metal ions, polyamines, charged proteins, and surfactants, was investigated for different DNA gel samples, including long and short ds-DNA and long and short ss-DNA. The DNA molecular weight was found to have only a slight effect on the deswelling curves, whereas conformation exhibited a pronounced effect. In general, single-stranded DNA gels exhibited a larger collapse in the presence of cations than did double-stranded DNA. This difference was more pronounced with surfactants than with the other cosolutes investigated. The difference between double- and single-stranded DNA was attributed to differences in linear charge density, chain flexibility, and hydrophobicity. For surfactants with different chain lengths, the swelling behavior displayed by ss-DNA can be interpreted in terms of an interplay between hydrophobic and electrostatic interactions, the latter being influenced by polymer flexibility. Increasing hydrophobicity of the network leads to a decreased critical aggregation concentration (cac) for the surfactant/gel complex, as a result of the strengthened hydrophobic attractive force between the surfactant and the gel chain. The swelling of DNA gels appears to be reversible and to be independent of DNA conformation. Surfactant-induced deswelling of DNA gels under some conditions appears to be quite homogeneous, whereas under other conditions, there is a separation into a collapsed region in the outer parts of the gel sample and an inside swollen part. Such "skin" formation is quite different for ss- and ds-DNA, with ss-DNA giving more pronounced skin formation over a wider range of binding ratio, beta. For example, no macroscopic separation into collapsed and swollen regions was observed at intermediate degrees of binding for ds-DNA gels, whereas a dense surfactant-rich surface phase (skin) was found to coexist with a swollen core network for ss-DNA gels with beta>0.5. One explanation for this difference is the large deformation energy required for the compression of the very stiff ds-DNA chains.  相似文献   

9.
Twin-dendritic organogelators have been prepared through selective functionalization of N-(3-aminopropyl)-1,3-propanediamine (APPDA) with self-assembling dendrons by using 1,1'-carbonyldiimidazole (CDI). Subsequent modification of the APPDA linker provided an additional degree of structural diversity by which to tailor the gelator self-assembly in bulk or in the gel state. These compounds are able to gel cyclohexane, toluene, n-butyl acetate, ethyl acetate, dichloromethane, and tetrahydrofuran. 3,4-Disubstituted apical branching units provided the most efficient organogelators and show a propensity to form thixotropic gels, wherein the gel recovers its elasticity after being subjected to shear. Structural and retrostructural analysis of the twin-dendritic organogelators reveals the bulk structural characteristics to be indicative of the subsequent gel properties. Diverse self-organized arrays were identified in bulk and all are able to form gels, thus indicating the role of quasiequivalence in mediating self-assembly in the gel state. Furthermore, we have found that porous columnar mesophases provide a strategy by which to prepare thixotropic gels. We demonstrate the importance of weak lateral hydrogen bonding within a column stratum versus hydrogen bonding along the length of the column for forming porous columnar mesophases and, by extension, thixotropic gels.  相似文献   

10.
The gelating ability of an α‐diketo derivative of oleic acid, 9,10‐dioxooctadecanoic acid ( DODA ), is investigated. DODA can gelate aromatic liquids and many other organic liquids. By contrast, none of the liquids examined can be gelated by the methyl ester of DODA. DODA is a more efficient gelator than stearic acid and the monoketo derivative due to its more extensive intermolecular dipole–dipole interactions. Formation of organogels of DODA can be induced by both thermal and mechanical stimuli, during which the luminescent and mechanical properties can be modulated significantly. The emission from DODA in 1‐octanol exhibits a large, reversible, hypsochromic shift (≈25 nm) between its thermally cycled gel and sol states. The emission changes have been exploited to probe the kinetics of the aggregation and deaggregation processes. DODA is the simplest gelator of which we are aware that exhibits a reversible shift in the emission. Although the self‐assembled fibrillar networks of the DODA gels in 1‐octanol, benzonitrile, or silicone oil are crystalline, isothermal mechanical cycling between the gel and the sol states is rapid and can be repeated several times (i.e., they are thixotropic). The single‐crystal structure of DODA indicates that extended intermolecular dipole–dipole interactions are crucial to the thermal and mechanical formation of DODA gels and the consequential changes in emissive and mechanical properties. From analyses of structural information, gelator packing, and morphology differences, we hypothesize that the mechanical destruction and reformation of the gel networks involves interconversion between the 3D networks and 1D fiber bundles. The thermal processes allow the fibrillar 3D networks and their 0D components (i.e., isolated molecules or small aggregates of DODA ) to be interconverted. These results describe a facile approach to the design of mechano‐responsive, thermo‐reversible gels with control over their emission wavelengths.  相似文献   

11.
A hybrid constitutive model is developed to represent the thixotropic behavior of particulate suspension during zeolite crystallization from solution. This model is valid over the complete solid fraction range typical for such a process. It employs two internal variables, agglomeration and contiguity, to describe the degree to which the gel particles form short- and long-range networks. The contiguity is used to weigh the effects of hydrodynamic to chain-like network deformation on the suspension viscosity. Heterogeneous nucleation and surface reaction-controlled crystal growth are assumed to describe the evolution of microstructure and solid fraction of gel and crystals. Such a model successfully captures the thixotropic behavior of zeolite particulate suspension by comparison of the predictions with a set of experimental data.  相似文献   

12.
The influence of addition of small amounts of either citric acid or lactic acid on the formation of crystalline matter in dried gels derived from a multi-component industrial sol–gel silica precursor has been studied. The sols were water-based and had formic acid as the main acid constituent. A pronounced decrease in the extent of crystallization was observed for both acids, with citric acid being more effective than lactic acid. The results are discussed based on the complexation behavior of the corresponding acids under the studied conditions, and the complexation behavior in solution can be directly linked to the extent of crystallization in the dried gels. However, the sol–gel kinetics followed that expected for a purely silica-based sol, which suggests that the kinetics is mainly controlled by the silica portion of the sol. The results are suggested to be of importance for the industrial use of these sols as binders, as pronounced crystallization in the gels upon drying may lead to mechanical stresses, and thus to a decreased binder performance.  相似文献   

13.
We study gel formation in a mixture of equally-sized oppositely charged colloids both experimentally and by means of computer simulations. Both the experiments and the simulations show that the mechanism by which a gel is formed from a dilute, homogeneous suspension is an interrupted gas-liquid phase separation. Furthermore, we use Brownian dynamics simulations to study the relation between gel formation and the equilibrium phase diagram. We find that, regardless of the interaction range, an interrupted liquid-gas phase separation is observed as the system is quenched into a state point where the gas-liquid separation is metastable. The structure of the gel formed in our experiments compares well with that of a simulated gel, indicating that gravity has only a minor influence on the local structure of this type of gel. This is supported by the experimental evidence that gels squeezed or stretched by gravity have similar structures, as well as by the fact that gels do not collapse as readily as in the case of colloid-polymer mixtures. Finally, we check whether or not crystallites are formed in the gel branches; we find crystalline domains for the longer ranged interactions and for moderate quenches to the metastable gas-liquid spinodal regime.  相似文献   

14.
A silver ion (Ag+)‐triggered thixotropic metallo(organo)gel of p‐pyridyl‐appended oligo(p‐phenylenevinylene) derivatives (OPVs) is reported for the first time. Solubilization of single‐walled carbon nanohorns (SWCNHs) in solutions of the pure OPVs as well as in the metallogels mediated by π–π interactions has also been achieved. In situ fabrication of silver nanoparticles (AgNPs) in the SWCNH‐doped dihybrid gel leads to the formation of a trihybrid metallogel. The mechanical strength of the metallogels could be increased stepwise in the order: freshly prepared gel<dihybrid gel<trihybrid gel. Microscopic studies of the trihybrid gel indicate the formation of three distinct morphologies, that is, nanoscale metal–organic particles (NMOPs), flowerlike aggregates of SWCNHs and AgNPs, and also their integration with each other. Detailed studies suggest lamellar organizations of the linear metal–ligand complexes in the NMOPs, which upon association create a three‐dimensional network that eventually immobilizes the solvent molecules.  相似文献   

15.
A transition from hierarchical pore structures (macro- and meso-pores) to uniform mesopores in monolithic polymethylsilsesquioxane (PMSQ, CH(3)SiO(1.5)) gels has been investigated using a sol-gel system containing surfactant Pluronic F127. The precursor methyltrimethoxysilane (MTMS) undergoes an acid/base two-step reaction, in which hydrolysis and polycondensation proceed in acidic and basic aqueous media, respectively, as a one-pot reaction. Porous morphology is controlled by changing the concentration of F127. Sufficient concentrations of F127 inhibit the occurrence of micrometer-scale phase separation (spinodal decomposition) of hydrophobic PMSQ condensates and lead to well-defined mesoporous transparent aerogels with high specific pore volume as a result of the colloidal network formation in a large amount of solvent. Phase separation regulates well-defined macropores in the micrometer range on decreasing concentrations of F127. In the PMSQ-rich gelling domain formed by phase separation, the PMSQ colloidal network formation forms mesopores, leading to monolithic PMSQ gels with hierarchical macro- and meso-pore structures. Mesopores in these gels do not collapse on evaporative drying owing to the flexible networks and repulsive interactions of methyl groups in PMSQ.  相似文献   

16.
By the interaction of a water–glycol solution of poly(ethylene glycol) (PEG) with calcium chloride dihydrate, a gel was produced. It was determined that, below a certain shear rate, this gel is a Newtonian fluid; however, above a certain shear rate, which depends on the gel viscosity, the properties of this gel are anomalous: the gel flow instantaneously completely stops. The viscosity of the gels was found to exponentially increase with increasing concentration of the cross-linking metal at constant PEG concentration. The density of the gels linearly increases with increasing concentration of the cross-linking metal at constant PEG concentration.  相似文献   

17.
The thixotropic properties ofthermoreversible organogels composed ofN-3-hydroxypropyl dodecanamide and various apolar fluids have been investigated by X-ray scattering, light microscopy, and rheo-optics experiments. This revealed that gel formation occurs via a precipitation process. Depending upon the cooling rate, large interconnected aggregates are formed and induce an elastic behavior. When submitted to a shear flow, these aggregates disentangled and became aligned in the direction of the velocity. Nevertheless, shear does not alter the structure of the individual aggregate and connections between the aggregates are quickly rebuilt due to gravity and thermal fluctuations when the applied flow is stopped. The alignment under flow and the reformation of the connections after the cessation of the shear induces the thixotropic behavior.  相似文献   

18.
Preparation of affinity polyacrylamide gels containing immobilized Fe(III) ions for the separation of proteins exhibiting metal ion binding properties is described. The presented method enables uniform distribution of immobilized metal ions in the affinity part of the polyacrylamide separating gel. Affinity gels prepared by this way are suitable to follow the effect of different concentrations of metal ions immobilized in polyacrylamide gel on a protein electrophoretic behavior. Polyacrylamide gels containing immobilized Fe(III) ions were used to study the electrophoretic behavior of two model proteins differing in their phosphate group content: chicken ovalbumin and bovine α‐casein. For the electrophoretic separation, both the native and the denaturating conditions were used.  相似文献   

19.
We present the case of a nonchiral organogelator that forms hollow fibers and encapsulates silver nanoparticles (SNP) and a dye molecule. The biscarbamate molecule (a model compound for polyurethanes), which has two hydrogen-bonding motifs symmetrically attached to n-dodecyl side chains (C(12)), gels benzonitrile with hollow fibrillar morphology. The C(12) molecules form sheets that eventually wrap into hollow fibers to form the gel network. Herein, two-component gels were prepared with C(12) as one component and SNP, phthalocyanine (Pc), or perylene (Pe) as the other. Microscopic analysis and partial melting experiments confirmed the inclusion of the silver nanoparticles and phthalocyanine into the hollow fibers. On the other hand, Pe molecules tend to form crystals at the outer surface of the C(12) fibers, which results in a significant increase in the width of the gel fibers. This difference in the behavior of Pc and Pe molecules were accounted for by their crystal geometry and significantly different crystal growth rate compared with that of C(12) fiber formation in the gels. Pc crystallizes in a needle shape that facilitates occlusion in the gel fibers, whereas Pe forms large platelets. X-ray diffraction and spectroscopic analysis of the two-component gels along with their neat components confirmed that there was no change in the packing behavior of the Pc and Pe molecules in the gels. Therefore, these are examples of two-component physical gels in which the Pc crystals are occluded within the hollow fibers of C(12) by physical mixing of the components without the aid of any inter-molecular interactions between the different components. We have thus shown that lumen-loaded gel fibers with nanoparticles and dye molecules can be prepared by the two-component gel route, provided that the above growth rate, shape, and size conditions are satisfied.  相似文献   

20.
The hydrogel consisting of an oligomeric electrolyte, poly[pyridinium-1,4-diyl-iminocarbonyl-1,4-phenylenemethylene chloride] ( 1-Cl) underwent self-healing at temperatures lower than its gelation temperature after destruction of the gel network in a shear flow. The self-healing mechanism was investigated by rheological measurements on three different kinds of gels including a low-molecular weight organogelator and a polymeric hydrogelator. Although all of the three gels exhibited thermo-reversible hysteresis loops in the shear moduli, only 1-Cl hydrogel recovered its mechanical properties after vigorous agitation. It is conjectured that the self-healing is due to formation of network structure via a chlorine ion mediated hydrogen bond for which the activation energy is on the order of 10 kJ/mol.  相似文献   

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