Concentration effects on irreversible colloid cluster aggregation and gelation of silica dispersions

Effects of particle concentration on the irreversible aggregation of colloidal silica are studied using in situ destabilization via the ionic strength increase derived from the enzymatic hydrolysis of urea by urease. Aggregation is monitored by time-resolved optical density and dynamic light scattering measurements. It terminates at a gel boundary, signaled by a prominent increase of the optical density and incipient non-ergodicity. Raman scattering is used to demonstrate that the enzymatic reaction continues, well beyond gelation for the compositions studied here, until the urea is consumed. Calibration of the ionic conductivity permits for constructing stability diagrams in terms of particle and salt concentration. As with reversible gelation, the process exhibits a collective character in that lower ionic strengths are required for gelation of concentrated dispersions and vice versa. However, light scattering demonstrates that the gel boundary is preceded here by a line marking the transition from reversible to irreversible cluster formation, with the two transition boundaries tracking each other. Comparisons are made with dispersions destabilized by direct addition of salt solutions, which gel under very different conditions.     

Thermoreversible gelation of a polysaccharide with immunological activity: Rheology and dynamic light scattering

The β — 1.3/1.6 glucan schizophyllan is known to suppress tumor growth. Two different schizophyllan samples have been characterized by static and dynamic light scattering in dilute solution of 0.01M NaOH and dimethyl sulfoxide (DMSO). A thermoreversible, optically transparent gel of schizophyllan was obtained on addition of sorbitol to aqueous solution, and the gelation process was followed by low amplitude oscillatory shear and dynamic light scattering (DLS). Power law behavior of storage modulus G'(ω) and loss modulus G”(ω) with the exponent n=0.5 was found at the gel temperature. In the same temperature range intensity time correlation functions (TCF) were measured and the electric field TCFs were calculated, taking into account the heterodyne contributions. The occurrence of two motions gave evidence for inhomogeneities in the gel. The results of the slow motion from DLS agreed surprisingly well with those, estimated by oscillatory rheology. The viscoelastic properties and the influence of sorbitol and schizophyllan concentrations were investigated regarding the pharmaceutical application in cancer therapy.     

Dynamic light scattering in semi-interpenetrating polymer networks based on polyacrylamide and poly(N-vinylcaprolactam)

Semi-interpenetrating networks based on polyacrylamide gel and linear thermosensitive poly(N-vinylcaprolactam) are obtained for the first time and studied via the method of dynamic light scattering. Contributions associated with dynamic fluctuations and frozen inhomogeneities to scattering are determined. It is shown that the ensemble-average scattering intensity strongly depends on the quantity and dimensions of frozen inhomogeneities. As temperature increases, scattering due to both dynamic fluctuations and spatial inhomogeneities tends to increase. At the temperature of the conformational transition of poly(N-vinylcaprolactam), the intensity of scattering increases abruptly, whereas the correlation function assumes the shape of a strongly stretched exponent that corresponds to high relaxation times (??1 s). It is found that the relaxation-time distribution restored with the use of the inverse Laplace transform contains several modes. For all the studied networks, the correlation length of the mode of cooperative motion (the fast mode) is independent of the concentration of poly(N-vinylcaprolactam) and coincides with the correlation length of the mode of collective motion for the polyacrylamide gel.     

Structure of liquid solutions near the critical point

Specific features of the structure of the critical state of binary liquid solutions leading to an anomalous behavior of the Rayleigh line due to a dramatic increase in concentration and density fluctuations are considered. It is shown that an experimental treatment must deal with two fluctuation regions near the critical point of solvent vaporization. In the first region, one can achieve a sufficient degree of accuracy by using theories like selfconsistent field theory. In the second region, which is closer to the critical point than the first region, scaling theory of secondorder phase transitions may be applied. It is found that the anomalous behavior of the Rayleigh line associated with kinetic coefficients is determined by the equilibrium thermodynamic properties and by the radius of fluctuation correlation (rinc). A general theory is developed for calculating thermodynamic potentials, especially the chemical potential and its concentration derivative in the fluctuation region. The results of these calculations are compared with the experimental data briefly described in the paper. Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 655–668, July–August, 1998.     

Some properties of aqueous xanthan gels formed under the action of aluminium(III) ions

Aqueous xanthan solutions form gels when aluminium salts are added and the solutions are heated above 45 °C. The gelation process was followed by dynamic light scattering. Characterization was based on the heterodyne and nonergodic approaches. Both techniques gave the same fast relaxation times, but for the slow motion much larger values were found in the heterodyne than in the nonergodic approach. The heterodyne fraction 1-X was found to correlate closely with the plateau height of the time correlation function (TCF) at large delay times in the nonergodic experiments. Three methods of gel point determination are demonstrated: (i) onset of heterodyne/nonergodic behavior, (ii) observation of a sharp maximum for the fast relaxation time at the gel point, (iii) observation of power-law behavior of the TCF. The statistics of nonergodic fluctuations were examined and evaluated. The potential of this procedure for detailed structure evaluation of inhomogeneities in the gel is emphasized.     

Time-resolved,static light scattering: New possibilities in polymer characterization

We have developed a highly sensitive, multi-angle, static light scattering (TRSLS = time resolved static light scattering) instrument, which measures the angular dependent Rayleigh scattering intensity of solutions simultaneously at 38 angles within approximately one second. It is thus suitable as a quick and easy to use static light scattering device for routine polymer and colloid characterization. The time resolution allows the kinetics of many systems to be investigated down to a second time scale, such as polymerization kinetics of linear, branched and crosslinked polymer structures, thermoreversible gelation, growth of colloidal particles, structural changes in micellar systems, etc.     

Effect of surfactants on shear-induced gelation and gel morphology of soft strawberry-like particles

The role of surfactant type in the aggregation and gelation of strawberry-like particles induced by intense shear without any electrolyte addition is investigated. The particles are composed of a rubbery core, partially covered by a plastic shell, and well stabilized by fixed (sulfate) charges in the end group of the polymer chains originating from the initiator. In the absence of any surfactant, after the system passes through a microchannel at a Peclet number equal to 220 and a particle volume fraction equal to 0.15, not only shear-induced gelation but also partial coalescence among the particles occurs. The same shear-induced aggregation/gelation process has been carried out in the presence of an ionic (sulfonate) surfactant or a nonionic (Tween 20) steric surfactant. It is found that for both surfactants shear-induced gelation does occur at low surfactant surface density but the conversion of the primary particles to the clusters constituting the gel decreases as the surfactant surface density increases. When the surfactant surface density increases above certain critical values, shear-induced gelation and eventually even aggregation do not occur any longer. For the sulfonate surfactant, this was explained in the literature by the non-DLVO, short-range repulsive hydration forces generated by the adsorbed surfactant layer. In this work, it is shown that the steric repulsion generated by the adsorbed Tween 20 layer can also protect particles from aggregation under intense shear. Moreover, the nonionic steric surfactant can also protect the strawberry-like particles from coalescence. This implies a decrease in the fractal dimension of the clusters constituting the gel from 2.76 to 2.45, which cannot be achieved using the ionic sulfonate surfactant.     

Tuning the Organogelating and Spectroscopic Properties of a C3-Symmetric Pyrene-Based Gelator through Charge Transfer

Two-component organogels and xerogels based on a C₃-symmetric pyrene-containing gelator have been deeply characterized through a wide range of techniques. Based on the formation of charge transfer complexes, the gelation phenomenon proved to be highly dependent on the nature of the electron poor dopant. This parameter significantly influenced the corresponding gelation domains, the critical gelation concentrations of acceptor dopants, the gel-to-sol transition temperatures, the microstructures formed in the xerogel state and their spectroscopic properties. In particular, titrations and variable-temperature UV–visible absorption spectroscopy demonstrated the key role of donor–acceptor interactions with a remarkable correlation between the phase transition temperatures and the disappearance of the characteristic charge transfer bands. The assignment of these electronic transitions was confirmed through time-dependent density functional theory (TD-DFT) calculations. Eventually, it was shown that the luminescent properties of these materials can be tuned with the temperature, either in intensity or emission wavelength.     

部分水解聚丙烯酰胺弱凝胶交联动力学的流变学分析

用流变学方法对部分水解聚丙烯酰胺(HPAM)苯酚甲醛间苯二酚交联体系的弱凝胶化过程进行了研究,通过对基团转化率和高分子交联转化率的分析,发现凝胶化过程在接近凝胶点时,处于反应动力学的初期,这使得交联点增加的动力学是比较简单的.通过在不同聚合物浓度和交联剂浓度并在地层温度和矿化度条件下线性粘弹性行为的研究,得到了交联体系凝胶化动力学过程的完整数据,发现聚合物浓度与交联剂浓度对凝胶点与凝胶强度的影响比较类似,反映出交联点增加的共同动力学特征.复数粘度在一个诱导期后,是以指数上升的,类似一个一级反应的特征.产生交联的临界聚合物浓度约为250mg L左右.并提出了剪切粘度数学模型,可以描述凝胶化过程中流变性质的变化.     

Mechanisms of silk fibroin sol-gel transitions

Silk fibroin sol-gel transitions were studied by monitoring the process under various physicochemical conditions with optical spectroscopy at 550 nm. The secondary structural change of the fibroin from a disordered state in solution to a beta-sheet-rich conformation in the gel state was assessed by FTIR and CD over a range of fibroin concentrations, temperatures, and pH values. The structural changes were correlated to the degree of gelation based on changes in optical density at 550 nm. No detectable changes in the protein secondary structure (FTIR, CD) were found up to about 15% gelation (at 550 nm), indicating that these early stages of gelation are not accompanied by the formation of beta-sheets. Above 15%, the fraction of beta-sheet linearly increased with the degree of gelation. A pH dependency of gelation time was found with correlation to the predominant acidic side chains in the silk. Electrostatic interactions were related to the rate of gelation above neutral pH. The overall independencies of processing parameters including concentration, temperature, and pH on gel formation and protein structure can be related to primary sequence-specific features in the molecular organization of the fibroin protein. These findings clarify aspects of the self-assembly of this unique family of proteins as a route to gain control of material properties, as well as for new insight into the design of synthetic silk-biomimetic polymers with predictable solution and assembly properties.     

Comparison of active and passive spectroscopic methods to investigate atmospheric inductively coupled plasmas

A comparison of Thomson and Rayleigh scattering, diode laser absorption and line emission measurements is performed on a 100 MHz atmospheric argon-flowing inductively coupled plasma. The parameters, which are measured in two or more ways, are the electron density, the electron temperature and the heavy particle temperature. The optimized diagnostics show the same behavior for the electron density and temperature. Nevertheless, the Thomson scattering diagnostic is the best at retrieving the radial profile. The heavy particle temperature, as measured by using both Rayleigh scattering and diode laser absorption, is identical within the estimated errors. The technique of measuring the temperature during power interruption, with both Thomson scattering and emission spectroscopy, shows that the electron and heavy particle temperatures are not equal during the period of power interruption.     

流变学法研究部分水解聚丙烯酰胺/Cr(III)交联反应I.浓度的影响

采用流变学法系统地考察了部分水解聚丙烯酰胺（HPAM）/Cr(III)交联体系的 反应动力学。HPAM溶液的粘性模量G”大于弹性模量G’,且其数值随时间不发生变 化,体系为粘性溶液。而HPAM/Cr(III)体系的G’和G”的数值都随时间变化,G” 在反应开始阶段大于G’,当反应进行一段时间后,G’超过G”占据主要地位,体 系成为弹性体系。交联过程可分为三个阶段：第一上升阶段,平缓上升阶段和第二 上升阶段。利用G’～ t曲线可以推测反应机理。实验发现成胶速率随反应物HPAM 和Cr(III)的浓度的增加而增加,而成胶时间缩短。在羧基浓度过量的情况下,交 联反应对Cr(III)浓度的反应级数是1。凝胶的有效弹性交联密度随聚合物浓度的增 加而增,且随凝胶反应的进行而增加。凝胶的交联点间的平均分子量随Cr(III)浓 度的增加和交联反应的进行而下降。     

Comparison of experimental DPR and viscosity cross sections

It has previously been shown that the shape of the depolarized Rayleigh line in gases is governed by a correlation function exhibiting a spread in correlation times. Here it is shown that effective cross sections obtained from data on flow birefringence and the field dependence of the viscosity are in agreement with the DPR results. Moreover, the non-lorentzian behaviour of the H/p dependence of the viscosity, is fully interpretable in terms of the non-exponential behaviour of the DPR correlation function.     

用探针粒子示踪微流变法测量明胶的动态不均匀性

利用探针粒子示踪微流变法对明胶溶液等温凝胶化过程的动态不均匀性进行了观测.通过向体系中引入探针粒子,利用广义的Stokes-Einstein关系由探针粒子的位移建立了体系结构的空间分布.进而利用van Hove函数和非高斯因子描述了凝胶化转变前后动态不均匀性的变化,结果表明在凝胶化后体系动态在空间和时间尺度上都是不均匀的,与凝胶化前相比,凝胶化后的快动态有更高的贡献.为了进一步探究这种动态不均匀性在空间和时间上相关的变化,本工作在粒子示踪技术的基础上,实现了四点相关函数和极化率的测量.实验结果表明,凝胶化前体系的快松弛可以原位独立完成,而慢松弛则需要周围的结构单元协同完成;凝胶化后体系的快松弛和慢松弛均需要协同完成.     

Local density augmentation and dynamic properties of hydrogen-and non-hydrogen-bonded supercritical fluids: a molecular dynamics study

The local density inhomogeneities in neat supercritical fluids were investigated via canonical molecular dynamics simulations. The selected systems under investigation were the polar and hydrogen-bonded fluid methanol as well as the quadrupolar non-hydrogen-bonded carbon dioxide one. Effective local densities, local density augmentation, and enhancement factors were calculated at state points along an isotherm close to the critical temperature of each system (T(r)=1.03). The results obtained reveal strong influence of the polarity and hydrogen bonding upon the intensity of the local density augmentation. It is found that this effect is sufficiently larger in the case of the polar and associated methanol in comparison to those predicted for carbon dioxide. For both fluids the local density augmentation values are maximized in the bulk density region near 0.7rho(c), a result that is in agreement with experiment. In addition, the local density dynamics of each fluid were investigated in terms of the appropriate time correlation functions. The behavior of these functions reveals that the bulk density dependence of the local density reorganization times is very sensitive to the specific intermolecular interactions and to the size of the local region. Also, the estimated local density reorganization time as a function of bulk density of each fluid was further analyzed and successfully related to two different time-scale relaxation mechanisms. Finally, the results obtained indicate a possible relationship between the single-molecule reorientational dynamics and the local density reorganization ones.     

Variation of Microenvironment around Auramine O Molecules Doped in Silica Prepared from Tetramethoxysilane

Silica gel doped with Auramine O (AuO), which is known as a microscopic viscosity probe through fluorescence spectra, was prepared by the sol-gel method using tetramethoxysilane (TMOS) as a starting alkoxide. Fluorescence spectra from the starting solution to the dry gel were measured to pursue the variation of microscopic viscosity around the AuO molecules during the sol-gel process. The fluorescence intensity of AuO did not change at the gelation point, indicating that the microscopic viscosity around AuO did not change during the sol-to-gel transformation. The intensity was, however, increased largely in the drying process; the internal motion of AuO molecules became largely restricted by the surrounded silica matrix during the drying process.     

Statistical thermodynamics of polymer solutions. VIII. Effect of intermolecular correlations on rayleigh scattering

The effect of intermolecular correlations on the angular dependence of the intensity of Rayleigh scattering from a dilute solution of a flexible-chain polymer in a good solvent is studied for an approximate model that retains the random-flight intramolecular segment-pair correlation while probabilities of multiple intermolecular contacts are simplified as products of probabilities of single contacts, all conditional on a common “initial” contact. This model, unlike one in which a polymer chain is represented as a spherically symmetrical cloud of segments, gives very little deviation from Zimm's “single-contact” approximation in light scattering: i.e., the initial concentration dependence of the concentration/intensity ratio is almost the same at all scattering angles. This behavior, which appears to underestimate the intermolecular correlations, can be accounted for by the symmetry of the bimolecular cluster as represented by the model.     

Gel to glass transition in simulation of a valence-limited colloidal system

We numerically study a simple model for thermoreversible colloidal gelation in which particles can form reversible bonds with a predefined maximum number of neighbors. We focus on three and four maximally coordinated particles, since in these two cases the low valency makes it possible to probe, in equilibrium, slow dynamics down to very low temperatures T. By studying a large region of T and packing fraction phi we are able to estimate both the location of the liquid-gas phase separation spinodal and the locus of dynamic arrest, where the system is trapped in a disordered nonergodic state. We find that there are two distinct arrest lines for the system: a glass line at high packing fraction, and a gel line at low phi and T. The former is rather vertical (phi controlled), while the latter is rather horizontal (T controlled) in the phi-T plane. Dynamics on approaching the glass line along isotherms exhibit a power-law dependence on phi, while dynamics along isochores follow an activated (Arrhenius) dependence. The gel has clearly distinct properties from those of both a repulsive and an attractive glass. A gel to glass crossover occurs in a fairly narrow range in phi along low-T isotherms, seen most strikingly in the behavior of the nonergodicity factor. Interestingly, we detect the presence of anomalous dynamics, such as subdiffusive behavior for the mean squared displacement and logarithmic decay for the density correlation functions in the region where the gel dynamics interferes with the glass dynamics.     

The orientational correlation parameter g2 of symmetrical benzene derivatives

Values for the orientational correlation parameter of liquid 1,3,5-trifluorobenzene and 1,3,5-trimethylbenzene at 295 K are reported. The results were obtained by combining the Cotton-Mouton constants and the intensity of the reorientational contribution to the depolarized Rayieigh scattering. The g₂ values are compared with the ratio of Rayleigh and single-particle rerorientation times, to which they are related in some models of molecular reorientation.     

Time evolution of density fluctuation in supercritical region. I. Non-hydrogen-bonded fluids studied by dynamic light scattering

The time evolution of the density fluctuation of molecules inhomogeneously dispersing in a mesoscopic volume is investigated by dynamic light scattering in several fluids in supercritical states. This study is the first time-domain investigation to compare the dynamics of density fluctuation among several fluids. The samples used are non-hydrogen-bonded fluids in the supercritical states: CHF(3), C(2)H(4), CO(2), and xenon. These four molecules have different properties but are of similar size. Under these conditions, the relationship between dynamic and static density inhomogeneities is studied by measuring the time correlation function of the density fluctuation. In all cases, this function is characterized by a single exponential function, decaying within a few microseconds. While the correlation times in the four fluids show noncoincidence, those values agree well with each other when scaled to a dimensionless parameter. From the results of this scaling based on the Kawasaki theory and Landau-Placzek theory, the relation between dynamics and static structures is analyzed, and the following four insights are obtained: (i) viscosity is the main contributor to the time evolution of density fluctuation; (ii) the principle of corresponding state is observed by the use of time-domain data; (iii) the Kawasaki theory and the Landau-Placzek theory are confirmed to be applicable to polar, nonpolar, and nondipolar fluids that have no hydrogen bonding, at temperatures relatively far from critical temperature; and (iv) the density fluctuation correlation length and the value of density fluctuation are estimated from the time-domain data and agree with the values from other experiments and calculations.