Increasing viscosity in entangled polyelectrolyte solutions by the addition of salt

The viscosity of several polyelectrolytes is measured in both salt free solutions and solutions in the high salt limit. At low polymer concentrations, the zero shear rate viscosity decreases as much as 100-fold upon addition of a monovalent salt, namely NaCl. However, as polymer concentration increases, the viscosity difference between polymer in salt free and in monovalent salt solution diminishes. Further, the zero shear rate viscosity becomes independent of added monovalent salt at the critical polyelectrolyte concentration c_D. Above c_D, the addition of monovalent salt increases the zero shear rate viscosity of the entangled polyelectrolyte solutions. The viscosity increase agrees with viscosity scaling theory for polyelectrolytes in the entangled regime. Polyelectrolytes exhibiting an increase in viscosity above c_D in the presence of monovalent salt include three natural anionic polyelectrolytes (xanthan, carrageenan, welan), one synthetic anionic polyelectrolyte (hydrolyzed polyacrylamide), and one natural cationic polyelectrolyte (chitosan). Generally, these polyelectrolytes are relatively high molecular weight (>1 M Dalton), which makes c_D experimentally accessible (e.g., c_D = 0.2 wt% for xanthan). The magnitude of the viscosity increase is as high as 300% for xanthan and nearly independent of monovalent salt concentration in the high salt limit. The increase in viscosity in monovalent salt solution and magnitude of c_D appear to be heavily influenced by the molecular characteristics of the polymers such as monomer weight, molecular structure, and chain conformation.     

Rheological behaviour of polystyrene latex near the maximum packing fraction of particles

Additional developments in the comprehension of the rheological behaviour of polymer latices, especially near the high critical concentration ?_c, are presented for two polystyrene latices of average particle diameters close to 200 nm with different electrostatic properties. Not surprisingly, there is a rapid transition in the rheological characteristics over a narrow range of polymer volume fractions as the concentration of the disperse phase increases. By examining twelve different polymer volume fractions a unique value of the critical volume concentration, ?_c, was found for each latex. At this point, the steady shear viscosity, dynamic modulus, and dynamic shear viscosity change dramatically. Furthermore, these critical concentrations are well confirmed by the percolation theory for the dynamic zero shear viscosity as a function of volume fraction. The Cox-Merz rule is not obeyed by these dispersions at the concentrations greater than ?_c. By using a controlled strain Couette rheometer with a gap of 1.2 mm, shear thickening limits were also observed for both latices. The concentration dependence of the onset shear rate for shear thickening changes near ?_c for each of the two latices.     

淮山药黏液稳定性与黏弹响应的关系

研究了淮山药黏液稳定性与黏弹响应的关系,发现在测试频率范围内,储能模量(G)始终大于损耗模量(G″),且均随频率变化不大,呈现出较强的网络结构特征,黏液性质对频率不敏感。黏液的表观黏度(a)与剪切速率(■)的关系可用Carreau模型较好地拟合,增大,黏液发生剪切变稀现象,表明黏液性质对剪切速率的变化较敏感;黏液的增比黏度(ηsp)与浓度(c)的关系为ηsp∝c3.01±0.12,黏液处于亚浓缠结区域。此外,盐度对黏液的黏弹响应影响较大,盐度增加,蛋白质分子间的静电排斥作用被屏蔽,分子间缠结增强,黏液的储能模量、损耗模量以及复数黏度(η*)逐渐上升,对黏液稳定性有一定影响。     

Dependence of thin polystyrene films stability on the thickness of grafted polystyrene brushes

We investigate the stability of thin polystyrene (PS) films on chemically identical grafted brushes of various thickness and grafting density. We observe an essential influence of the brush thickness on the stability of the PS films. For brushes with a thickness of 20-35 nm no de-wetting of the PS film occurs, while considerably thicker or thinner PS brushes lead to de-wetting of the PS top layer. We suggest that in the thin brush-like layers, the unfavorable interactions with underlying silica favor de-wetting. The tendency to de-wet is reduced once the brush is sufficiently thick to insulate the free PS layer from the surface. Beyond that point, the de-wetting process speeds up as the brush becomes thicker and has a higher grafting density with a substantial increase of the interfacial tension between the brush and the free polymer.     

基于Rough集理论的知识约简与规则挖掘方法

提出了利用可辨识矩阵和分辨函数自动获取规则的算法,该算法从已知决策系统出发,通过决策系统的可辨识矩阵和分辨函数计算核和所有的约简集,以约简集为初始节点,建立层状节点网络模型,对于各节点,提取符合可信度要求的规则写入规则集中。应用实例表明,文章提供的算法是确实可行的。     

On the fuzzy logic for rule based modeling and process simulation

Some chemical processes are not well understood, and not easy to analyze and simulate with conventional mathematical approaches. A rule based approach is proposed in this paper to model such process units. Conversion between fuzzy and crisp numbers at the input and output of these units is discussed in details and a slicing conversion approach is proposed. It is shown from a case study that the approach provides a way to incorporate fuzzy models into conventional process simulators.     

Light and neutron scattering studies of excess low-angle scattering in moderately concentrated polystyrene solutions

The light scattering (LS) and small-angle neutron scattering (SANS) behaviour of semi-dilute solutions of polystyrene has been determined in both ‘good’ and ‘theta’ solvents. Above a critical concentration related to chain overlap, an excess small-angle scattering component is in evidence for scattering vectors, q, such that qR_g < 1. Application of a number of recent solution scattering theories fails to account for the small-angle scattering observed. The inter- and intramolecular scattering functions are measured experimentally through characterization of the SANS behaviour of solutions containing mixtures of polystyrene and perdeuteropolystyrene. The resultant intermolecular scattering functions depend on the fraction of labelled chains, indicating clearly that the solutions contain large scale fluctuations. LS studies support this hypothesis and further show that the presence of these fluctuations is reproducible, yet dependent on the solution preparation procedure. Similar behaviour is observed in screening length measurements. The excess low-angle scattering is well characterized by the Debye—Bueche random two-phase model, which is subsequently used to estimate the characteristic dimensions of the long-range fluctuations.     

Sequential comparison of two treatments in clinical trials:a decision theoretic approach based on randomized play-the-winner rule

In the context of comparing two treatments in clinical trials randomized play-the-winner rule is used with the goal of treating more patients by the better treatment On its basis we give two decision rules by introducing stopping rule Some performance characteristics of one of the decision rules are discussed and examined .A minimax rule is suggested Finally some exact and asymptotic properties of the decision rule is derived     

PSRK模型的修正混合规则及其应用于聚合物溶液汽液平衡的预测

To extend the PSRK(predictive Soave-Redlich-Kwong equation of state)model to vapor-liquid equilibria of polymer solutions,a new EOS-gE mixing rule is applied in which the term ∑ xi ln(b/bi)in the PSRK mixing rule for the parameter a,and the combinatorial part in the original universal functional activity coefficient(UNIFAC)model are cancelled.To take into account the free volume contribution to the excess Gibbs energy in polymer solution,a quadratic mixing rule for the cross co-volume bij with an exponent equals to 1/2 is applied [b1/2 ij= 1/2(b1/2 i b1/2 j)].The literature reported Soave-Redlich-Kwong equation of state(SRK EOS)parameters of pure polymer are employed.The PSRK model with the modified mixing rule is used to predict the vapor-liquid equilibrium(VLE)of 37 solvent-polymer systems over a large range of temperature and pressure with satisfactory results.     

关联规则的数据挖掘在高校图书馆系统中的应用

简要介绍了关联规则的数据挖掘以及Apriori算法,对Apriori算法优缺点和性能进行分析,并将Apriori算法应用于高校图书馆管理系统,给出了系统的完整实现过程。通过分析数据挖掘的结果,寻找各个学科领域中的一些相互关联的知识、辅助教师的教学工作,优化图书馆的馆藏布局。     

Interfacial tension of demixed polymer solutions near the critical temperature: polystyrene + methylcyclohexane

Interfacial tension between demixed solutions of polystyrene + methylcyclohexane has been measured near the critical temperature as a function of temperature using polystyrenes with molecular weights 9000 ～ 1.26 × 10⁶. The critical exponent for the interfacial tension was determined to be about 1.30 for the lower molecular weight systems. However, for higher molecular weights the exponent could not be obtained because the system departed from critical behaviour. Magnitudes of the interfacial tension were proportional to about N^?0.44, where N is the polymerization index. Experimental results were compared with the recently-proposed theories and found to be in qualitative agreement. The tricritical theory of polymer solutions was also compared with the experimental results.     

Effect of the chemical characteristics of mesoporous silica MCM‐41 on morphological,thermal, and rheological properties of composites based on polystyrene

Mesoporous silica nanoparticles (MCM‐41) with an average diameter of ～ 20 nm were synthesized by a sol‐gel method using binary surfactant system. Polystyrene (PS) composites containing mesoporous silica nanoparticles were prepared by in situ polymerization of styrene monomers. Similar in situ polymerized PS composites were prepared based on the modified silica functionalized with methyl and vinyl groups. The effects of silylation on thermal and rheological properties of the PS/silica composites are investigated. Of particular importance is that the in situ polymerization of monomers within the mesoporous silica may trap some polymer chains, if not all, thereby affording a greater physical interaction between polymer and the porous fillers, whereas the chemical modification of silica surface promotes the polymer–filler interaction, which in turn enhances the thermal stability of composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

An experimental investigation of the large-strain tensile behavior of neat and rubber-toughened polycarbonate

The large-strain tensile behavior of polycarbonate and polycarbonate filled with several volume fractions (f) of rubber particles is studied via an optical technique. Digital image correlation is used to determine, in two dimensions, the local displacement gradients and full-field displacements during a uniaxial tension test. Full-field strain contours, macroscopic true stress-strain behavior, and local volumetric strain are reduced from the raw test data. Full-field strain contours exhibit a decreasing degree of localization with increasing f. The true stress-strain results show a decrease in modulus, yield stress, post-yield strain softening, and subsequent strain hardening with increasing f. The volumetric strain decreases with increasing f as well. In the case of the neat polymer, comparisons are made to a three-dimensional finite element simulation.     

Conducting polymer blends of polypyrrole with polyvinyl acetate,polystyrene, and polyvinyl chloride based toxic gas sensors

Blends of the conducting polymer, polypyrrole (PPy), and in the insulating host polymers, polyvinyl acetate (PVAc), polystyrene (PS), and polyvinyl chloride (PVC) resin, have been prepared chemically. Threshold conductivities occur at about 5% for PPy in blends with host polymers. The characterizations of these blends were done by FTIR, UV‐visible, differential scanning calorimetric (DSC), scanning electron microscopy (SEM), and thermal gravimetric analysis (TGA). The products of the blends have electrical conductivity comparable to PPy and mechanical properties similar to hosting polymers. The response mechanism of the conducting blends to a selection of gases and vapors was investigated using two techniques, measurement of conductance and mass changes using a four‐point probe method, and a X‐ray fluorescence (XRF) device, respectively. These responses of blends to toxic gases and vapors are more well explained. Prepared films were exposed to hydrogen halides (HCl, HBr, and HI), hydrogen cyanide, halogens (Cl₂, Br₂, and I₂), monochloroacetic acid (MCAA), 1‐3‐5 trichloromethyl benzene (TCMB), methylbenzyl bromide (MBB), bromoacetone (BA), and cyanogen bromide (CB). The changes of conductivity of polymers frequently observed are partly due to one stage in the two‐stage sorption, perhaps involving the swelling of the polymer, then diffusion gases into polymer chains. The swelling of polymers is a slow process, therefore, preswelled polymer films tend to decrease the response times of blends with respect to gases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 49–62, 2003     

Prediction of viscosity of mixed electrolyte solutions based on the Eyring's absolute rate theory and the semi-ideal hydration model

The mixing behavior of viscosities of electrolyte solutions under isopiestic equilibrium has been studied for the first time using the Eyring's absolute rate theory and the semi-ideal hydration model. The concentration dependence of the change in molar free energy of activation for flow has been formulated and discussed based on the concept of average hydration number and the structure-making or structure-breaking nature of the ion species. Coupling of the Erying's theory and the semi-ideal hydration model yields very simple mixing behavior of viscosities of electrolyte solutions under isopiestic conditions and thus yields new simple equations for viscosity, which can provide predictions for mixed solutions using only information on the single solute solutions. The new equations have been tested by comparisons with the experimental results for 15 systems and the existing equations reported in literature. The present equations improve the predictions considerably and the agreement with experimental results is in general quite good. The effect of different contributions accompanying the mixing process on the predicted results has been studied. The viscosities of the mixed electrolyte solutions can be well predicted only by using the additive contribution from the viscosities of binary solutions under isopiestic condition. The addition of the mixing term in this simple additive equation yields better predictions for mixed solutions mainly consisting of the structure-making ions. The inclusion of the density term has little effect on the predicted results.     

An experimental study of the influence of carbon black on the rheological properties of a polystyrene melt

A broad range of experiments on carbon black filled polystyrene melts shows the reinforcing effect of the filler. This study represents one of the most extensive investigations of a series of highly filled polymer melts. Stress relaxation and dynamic experiments characterize the small strain behavior while the steady state shear viscosity, normal stresses, and elongational flow experiments describe the large strain deformation rate response. Extrudate swell and unconstrained shrinkage of extrudates are also measured. Highly filled systems exhibit yield values. This is seen in the dynamic experiments and in the shear and elongational viscosities. Viscosity does not level off at finite values with decreasing deformation rate but continues to increase in an approximately inverse manner. This corresponds to yield values of order 5 × 10⁵ dynes/cm². The storage modulus also does not tend to zero at low frequencies. The small strain dynamic properties and stress relaxation results suggest high memories for small strain experiments. Txtrudate swell values are however small and the systems exhibit minimal delayed recovery. The implications of this are considered. Generally it is argued that at volume loadings between 10 and 20 percent, the system takes on the characteristics of a gel and the response is similar to that of a Schwedoff body.     

Effect of nanoclay on relaxation and breakup of polyamide 6 threads in polystyrene matrix

In this work, we investigate the compatibilizing mechanism of nanoclay in binary polymer blends by measuring the interfacial tension of polystyrene/polyamide 6, PS/PA6, as a typical system, in the presence of nanoclay. The interfacial tension of PA6 nanocomposites and PS are determined with the breaking thread method by employing the Tomotika theory. The interfacial tension is reduced when organoclay is incorporated in the PA6 phase. To investigate the effect of the localization of nanoclay, nanoclay is intentionally located at the interface of PA6 and PS. Microscopic observations show that PA6 fiber remain unchanged and does not go through break-up process; therefore, one can deduce that the apparent interfacial tension of the system reduces significantly when nanoclay particles saturate the interface.     

Effect of montmorillonite modification on the behaviour of polyamide/polystyrene blends

BACKGROUND: In nanocomposites with multiphase matrices, the addition of layered silicate not only has a reinforcing effect, but also changes significantly the morphology, namely the size and the structure of the dispersed phase. In this paper, we focus on systems with polyamide 6 (PA6)/polystyrene (PS) matrices. The effect of clay was studied over the whole composition range together with the simultaneous variation of basic parameters influencing the structure and mechanical behaviour, i.e. the clay treatment type and mixing protocol. RESULTS: At all compositions, remarkable refinements of both particulate and co‐continuous structures by clay were found. This effect and a significant shift of the glass transition temperature of blend components were more pronounced for clay with less polar treatment as a result of distinct localization of clay in the interfacial area (due to its lower affinity for PA6 phase). An increase in modulus was found at all compositions, whereas strength and toughness were enhanced at low PS contents only, as a consequence of small particle size and enhanced interfacial bonding. CONCLUSIONS: The results presented indicate that nanosilicates can effectively influence the structure and properties of PA6/PS blends. Copyright © 2008 Society of Chemical Industry     

Theoretical and experimental testing of a scaling rule for air current segregation of alumina powder in cylindrical silos

Air current segregation (ACS) is one segregation phenomenon that has been identified to contribute significantly to the separation of fines (particles < 42 µm) from coarse material during the filling of industrial silos. This paper describes investigations of ACS for alumina powder based on experiments conducted in an industrial silo, in the laboratory and by computation, using the commercial computational fluid dynamics code Fluent.For the industrial silo, the extent of ACS has been measured using the accumulation of fine material at the wall as an indicator. Based on these results, modifications to the feeding system were undertaken which showed that ACS is promoted if the material is fed in a dilute form. Experiments in the laboratory confirmed this effect visually. In order to be able to compare numerically the extend of ACS, a segregation index has been developed. It was found that a dilute particle jet leads to more ACS than dense particle jet.The effects of solids feeding rate and air extraction rate on ACS have been investigated in the laboratory silo and the results clearly show that low solids feeding rates promote ACS. It was further found that an increase in the air extraction rate has a mild effect in suppressing ACS. These effects were confirmed by the Fluent simulations, which showed an unexpectedly good agreement with the experiments.     

Prediction of viscosity of mixed electrolyte solutions based on the Eyring's absolute rate theory and the equations of Patwardhan and Kumar

The mixing behavior of viscosities of electrolyte solutions at constant ionic strength has been studied for the first time using the Eyring's absolute rate theory and the equations of Patwardhan and Kumar. Coupling of the Eyring's theory with the equations of Patwardhan and Kumar yields simple mixing behavior of viscosities of electrolyte solutions at constant ionic strength, and thus permits the establishment of new simple equations for viscosity, which can provide predictions for mixed solutions using only information on the single solute solutions. The new equations have been compared with the experimental results for fifteen systems and the existing equations reported in literature. The present equations generally give the best predictions and the agreement with experimental results is in general quite good. The effect of different contributions accompanying the mixing process on the predicted results has been studied. The viscosities of the mixed electrolyte solutions can be well predicted only by using the additive contribution from the viscosities of binary solutions at constant ionic strength. The addition of the mixing term in this simple additive equation yields better predictions. The inclusion of the density term has little effect on the predicted results.