高分子稀溶液中溶剂对分子特性与流变性能的影响

本文研究了不同溶剂对离子性和非离子性高分子稀溶液的分子构型和流变性能的影响.在部分水解的聚丙烯酰胺水溶液中加入无机盐,测量并计算了分子扩张因数,特征粘度与盐浓度、盐离子价数、溶液pH值的关系.同时使用不同的有机溶剂测量聚丁烯溶液的Maxwell模型松弛时间和分子扩张因数.研究表明,高分子稀溶液可藉调整溶剂性质的方法以达到期望的流变特性.     

The Rheological Behavior of Salt Tolerant Polyacrylamide Solutions

The rheological behavior of viscoelastic fluids was investigated with regard to the specialty of tertiary oil recovery. Aqueous polyacrylamide solutions at different concentrations were selected to simulate viscoelastic polymer systems, and the Haake RS 150 type rheometer was used to measure the rheological behavior. The experimental results showed that the viscoelasticity was positively influenced by polyacrylamide solution concentrations and negatively affected by solution temperatures. The coefficient of first normal stress deference decreased with increasing shear rate. In addition, the relationship between viscosity and the coefficient of first normal stress with shear rate obeyed a power law model. The viscosity decreased with increasing metal ion concentration and time.     

Rod-Climbing characterization of kaolinite suspended polyisobutylene solutions

The rod-climbing constants of kaolinite-suspended polyisobutylene (PIB) solutions are investigated from rod-climbing experiments. For a low deformation rate, this particle suspended polymer solution can be regarded as a second-order fluid, and the rod-climbing constant for such fluids is correlated with the rheological properties of the particle-suspended polymer solutions. The rod-climbing constants for kaolinite suspended PIB solutions were found to decrease with temperature and increase with PIB concentration, molecular weight of PIB, solvent viscosity, and particle concentration. The rheological properties were measured using rotational rheometer, and the shear viscosity and the first normal stress difference of the kaolinite suspended PIB solution show the Boger-fluid characteristics.     

A rheological study of aqueous separan solutions

The concentration dependence of the rheological response of aqueous Separan solutions was measured. The shear and primary normal stress response in steady shearing flow, and the relaxation of shear stress following cessation of steady shear flow, were measured with four different polymer solution concentrations. Two different nonlinear constitutive equations, Bird-Carreau and Meister, were used to analyse the data. The Bird-Carreau model fit the steady shear data very well and the parameters obtained from steady shear data allow reasonable estimates of the stress relaxation of these systems. The Meister model provided a fit of the transient stress relaxation data and could be used to estimate the steady shear response. No quantitative molecular theory was developed in this work. However, the nature of the concentration dependence of the Bird-Carreau parameters suggests that as the polymer concentration of aqueous Separan solutions decreases from 2.0 to 0.05 weight percent the solutions should be modeled less by an entangled network theory and more as slightly overlapping hydrodynamic units. The concentration where this behavior seems to be changing appears to be about 0.25 percent by weight of polymer.     

Conformation of polyacrylamide in aqueous solution with interactive additives and cosolvents

The viscosity of polyacrylamide (PAM) dilute aqueous solutions with NaCl, glucose, and SDS as additives was measured by Ubbelohde viscometry. There was linear relationship between reduced viscosity vs. PAM concentration in aqueous solutions. The Huggins constant k and intrinsic viscosity [η] were used to study the conformation of the polymer chains and the degree of polymer–solvent interaction. In addition, the viscosity of diluted PAM solutions in water with acetone, ethanol, DMF, and ethylene glycol as cosolvent was measured. It was found that the polymer chain conformation contracted as the acetone, ethanol, and DMF cosolvent composition ratio increased, but there was no distinguishing difference between water–ethylene glycol compositions. The solution properties of PAM were used to estimate the swelling properties of PAM gel in the same external conditions, as gel is formed by crosslinking of linear polymer. In good solvent the polymer chain should be expanded, and gel is expected to have large swelling ratio. In water cosolvent systems, when the linear polymer chain underwent coil–globule transition, PAM gel should have volume phase transition under corresponding external conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3122–3129, 2003     

Comparative studies of rheological properties of polyacrylamide and partially hydrolyzed polyacrylamide solutions

The present work is concerned with experimental results of rheological characteristics of polyacrylamide (PAM) and of partially hydrolyzed polyacrylamide (HPAM) (degree of hydrolysis up to 80%) in aqueous and aqueous/sodium chloride solutions with changing experimental conditions such as polymer concentration, temperature, solvent quality, and shear rate applied. It has been observed that the all‐aqueous and aqueous/NaCl solution of PAM and of HPAM exhibited the non‐Newtonian behavior with shear‐thinning and shear‐thickening areas. The onset of shear‐thickening at depends mainly on the degree of HPAM hydrolysis, as well as on solution concentration, temperature, solvent quality, and polymer molecular weight. Rheological parameters from power law (Ostwald de Waele model) and activation energy of viscous flow (E_a) are determined and discussed. The changes in apparent shear viscosity during aging of solutions of PAM and HPAM are also described. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2235–2241, 2007     

非牛顿流体在周期性突扩突缩通道中的流动阻力特性

以聚丙烯酰胺水溶液（２００ｗｐｐｍ，５００ｗｐｐｍ，１４００ｗｐｐｍ）为介质，实验研究了此粘弹性流体在直管充分发展段和周期性突扩突缩充分发展段的流动阻力特性。雷诺数变化范围为５×１０３～７×１０４。实验结果表明此浓度范围内的聚丙烯酰胺溶液在直管中的阻力系数可比纯水中的降低４０％，而在周期性突扩突缩通道中无明显的减阻现象     

The flow of non-Newtonian solutions through packed beds

The rheological behavior of aqueous solutions of Separan AP-30®, polymethylcellulose, and polyvinylpyrrolidone was studied experimentally. These solutions exhibit non-Newtonian flow behavior in simple shear, and are characterized by one of several 2, 3, or 4 parameter rheological equations. The equations used included the power law, the Ellis model, Spriggs equation, the Herschel-Bulkley equation, and Meter's model. The power law model fits the data for each of the solutions over a limited range of shear rates, whereas the other models, which include either a lower shear rate limiting Newtonian viscosity, and/or an upper shear rate limiting Newtonian viscosity, or a yield stress, fit the data well over a wide range of shear rates from 0.00675 to 1076 sec^?1. The pressure drop-flow rate data for the same aqueous solutions flowing through packed beds were correlated well by the Ergun equation using the various rheological models applied in this work to evaluate a modified fluid viscosity. In each case it was found that the rheological model which best fit the viscometric data also gave the best packed bed friction factor correlation, and that no one model, such as the powerlaw, or the Ellis model, is the best one to use in all cases for all solutions. For polyvinylpyrrolidone solutions large deviations between experimental values of friction factor and those from the Ergun equation occurred for modified Reynolds numbers greater than one. A pseudo viscoelastic parameter was used to improve the friction factor correlation empirically at high Reynolds numbers.     

Highly elastic-constant vicosity fluids

The rheological properties of three types of fluids that exhibit large normal stresses are examined and compared. These fluids have a constant or nearly constant viscosity and can be used as model viscoelastic fluids, covering a range of viscosity from 0.1 to 124 Pa.s. One lubricant, Emkarox FC 31-45000, is shown to have the characteristics of a second-order fluid. Series difficulties encountered in measuring the rheological properties of the Separan—corn syrup solutions (Boger fluids) are reported. The Emkarox and solutions of polyacrylamide (Pusher 700) in mixtures of glycerine and water are proposed as better model fluids.     

Factors effecting a loss of flocculation activity of polyacrylamide solutions: Shear degradation,cation complexation,and solution aging

Polyacrylamide and poly(acrylamide-co-acrylic acid) flocculant solutions were subjected to shear degradation in a rotating cone instrument. At constant shear rate, shear degradation was minimized (highest limiting intrinsic viscosity) by the use of a lower solution concentration and high ionic strength of the polymer solution. Resistance to shear degradation also increased with increasing anionic character of the polyacrylamide. Sheared polymers showed reduced performance as flocculants of coal preparation plant tailings, their major commerical application in the U.K. Partially anionic polyacrylamide solutions were completely inactivated in the presence of certain multivalent cations. Aluminium, iron_III, lead, copper, and zinc ions formed complexes with the carboxyl groups on the polymer, resulting in zero flocculation activity. Nonionic polyacrylamides were unaffected. Viscosity–aging of polyacrylamide solutions was observed over a period of several months, but was insufficient to affect the flocculation activity. In the presence of 3% ethanol or methanol, no aging was observed in solutions stored for over a year.     

Water soluble acrylamide polymers, 2. Aging and viscous flow of aqueous solutions of polyacrylamide and hydrolyzed polyacrylamide

The aging of aqueous solutions of polyacrylamide which appears experimentally as a decrease of solution viscosity and which is probably caused by microorganisms may be prevented by the addition of a small amount (0.02 wt.-%) of an antimicrobial agent such as sodium azide. Aluminium chloride causes a very strong decrease of the viscosity during a prolongated storing time. The addition of aluminium ions to the polymer solution leads to a complexing of amidic groups with aluminium cations and probably also to decrease of the dimensions of individual polymer coils. The viscous flow of aqueous solutions of polyacrylamide and hydrolyzed polyacrylamides was studied as a dependence of the shear gradient D on the shear stress τ and was described by the relation D = k · τⁿ, where k and n denote constants. Both constants depend on the polymer concentration, the degree of polymerization and the content of carboxylic groups in the polymer. The greatest deviations from the Newtonian behaviour were found in the range of molecular weights over 2 · 10⁶ g/mol and practically no deviations were observed for polyacrylamide with molecular weights below 1 · 10⁶ g/mol. The dependence of the viscosity on the shearing time at different shear rates (300, 600 and 1200 s^?1) which was observed in solutions of polyacrylamide, hydrolyzed polyacrylamide and poly-(N,N-dimethyl)-acrylamide was explained by an entanglement model.     

Comparative properties of hyaluronan and chitosan in aqueous environment

In this paper, our objective is to compare the physico-chemical properties of chitosan (CHIT) and hyaluronic acid (HA), two important polysaccharides often used in biomedical or cosmetic applications. Polymer-polymer interactions as well as polymer-solvent interactions, studied by experiments and by molecular modeling, are discussed for the two biopolymers in presence of aqueous environments. HA and CHIT have similar non-freezing water content, although HA retains more water than CHIT at large degree of relative humidity (RH). Thermal degradation is larger for HA. The specific viscosity at zero shear rate of CHIT deviates from the master curve, whereas that of HA superimposed nicely. The solution viscosity of concentrated solutions of CHIT continuously decreases in the shear rate range between 0.5 up to 100 s^?1, whereas HA shows a Newtonian plateau at low shear rates. Dynamic rheology of semi-diluted solutions of HA shows storage modulus G?? lower than the loss modulus G?? up to 30 g/L but that of CHIT at 20 g/L shows G?? > G?? at nearly the same overlap parameter. The viscosity of CHIT solution is less influenced by temperature than that of HA. These results clearly underline the importance of interchain interactions for CHIT in a good solvent. Molecular modelling is used to provide insights on both the aggregated state and solution state of the two polysaccharides. Interchain interactions in the organized models were predicted larger for CHIT than for HA whereas the interaction between the polysaccharide and the solvent molecules are larger for HA than for CHIT. This approach rationalizes the experimental observations: the higher solvation of HA and the higher ability to aggregate for CHIT.     

Flow properties of aqueous solution of methylcellulose

Flow properties of aqueous solution of methylcellulose, especially nonlinear viscoelasticity, were investigated. The peculiar flow properties of the aqueous solution of methylcellulose were compared with the existing theories of non-Newtonian viscosity of concentrated polymer solutions and the experimental results obtained for the aqueous solution of sodium alginate which behaves as polyelectrolyte in solution. The characteristic time for the formation of entanglement couplings between molecular chains was mainly examined. To investigate the elastic behavior under steady-shear flow, normal stress difference was measured with a coaxial cylinder apparatus, and extinction angles were determined with a flow birefringence apparatus. The values of normal stress difference obtained by the mechanical and the optical methods coincided with each other. For the aqueous solution of methylcellulose as reported for solutions of nonpolar polymers, the relation between normal stress difference and shear stress was represented by a single curve irrespective of temperature and concentration. Non-Hooken behavior was observed for the relation between recoverable shear and shear stress and attributed to the strong intermolecular interactions and the stretching-out effect of structural networks.     

Nonlinear rheological behavior of a novel oil displacing agent

In this work, the shear and elongational rheologies have been investigated for a newly developed oil displacing agent, polymeric surfactant‐PSf. It was found that the PSf solutions exhibited Newtonian, shear‐thinning, and shear‐thickening behavior, respectively, depending on the polymer concentration and shear rate, and Cox–Merz rule was not applicable to these systems. The first normal stress difference (N₁) versus shear rate plots for PSf were complicated, which varied with the composition of the solutions. The uniaxial elongation in capillary breakup experimental results indicated that Exponential model could be used to fit the experimental data of the PSf solutions at lower polymer concentrations. In addition, it was found that PSf was more effective in improving shear viscosity than partially hydrolyzed polyacrylamide, but not in the case of elongational viscosity. The experimental results indicated that the microstructural mechanisms are responsible for the rheological behavior of the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40813.     

Investigation of Polymer Adsorption on Rock Surface of Highly Saline Reservoirs

Blocking or reducing water production from oil wells is a serious problem in oil industry. Two types of polymers, namely, polyacrylamide (PAA) and polysaccharides (xanthan) have been investigated in this paper. The viscosity of both polymer solutions was first evaluated at different salinities, shear rates and concentrations. Afterwards, the solutions were injected into core samples to examine the adsorption on the rock surface by calculating the resistance factor as well as the residual resistance factor. Also, the effect of the injection rate of the polymer solutions has been studied. The results show that xanthan solution is tolerant of high salinity (20 %), while PAA solution is very sensitive to salt. Both polymer solutions show a pseudoplastic flow as a function of the shear rate. The core sample experiments show that both polymer solutions suffer a reduction in the adsorption rate with salinity increase. However, xanthan shows acceptable values even with a salinity up to 20 % and a temperature of 60 °C. Therefore, xanthan can be recommended to shut off water in high salinity and high temperature reservoirs. It was also found that the lower the injection rate the higher the adsorption on the rock surface.     

顺丁橡胶生产中胶液浓度、平均分子量及门尼粘度与胶液物性常数关联的探索研究

本文通过对顺丁胶抽余油溶液的折射率及粘度的测定来预计胶液浓度、平均分子量及门尼粘度,并得出相应的关联式。为在生产上实现这三个参数的自动控制提供了一种可供参考的方法。     

Preparation, characterization, solution properties and rheological behaviour of polyacrylamide

In this report a survey is given on structure and properties of polyacrylamide homopolymers (PAAm) in solution. However the review is restricted to all those papers, where a molecular characterization of the polymers has been achieved as a basis to correlate this fundamental information with applicational properties.

Different polymerization methods are summarised in brief, the preparation and solution structure of long chain branched polyacrylamides as well as chemical modification reactions of linear PAAm are also mentioned. A number of experimental characterization methods (GPC, ultracentrifugation, intrinsic viscosity, and light scattering measurements) are described with special emphasis on the difficulties of the different procedures including some proposals for properly designed experimental techniques. The state of solution is discussed in view of experimental data obtained with different solvents. Moreover viscosity constant ø is calculated for aqueous solution and the unperturbed dimensions are estimated. All available data on cross correlations (e.g. [η] - M, S₀ - M, 2>^1/2 - M) are collected with the intention to give a survey of established relations and, comparing the given relationships, to suggest the reliable ones of them.

The phenomenon of long-term viscosity decrease of aqueous PAAm solutions has been investigated and discussed with regard to its molecular origin.

The viscoelastic properties are discussed in dependence on molecular weight, concentration, solvent quality, and shear rate (10⁶ · s⁻¹). Based on these data a simple equation was developed oped for the η₀-c-M relationship, which can be applied to other polymer systems as well. It is further described that the elastic nature (first normal stress difference) may overwhelm the viscous nature (shear stress) at relatively low shear rates. This high elasticity can cause deviation from laminar flow conditions. Moreover, it can be demonstrated — based on instationary measurements as well as the comparison of steady shear flow with dynamic rheology — that energetic interactions (H-bonds) strongly influence the rheological behaviour.     

碱溶性羟乙基纤维素在复合溶剂体系中的流变性能

使用平行板流变仪,以氢氧化钠/硫脲/尿素/水溶液作为碱溶性羟乙基纤维素(HEC)的复合溶剂,研究了HEC在该溶剂体系中的流变性能,并考察了剪切速率、温度及溶液浓度对溶液的非牛顿指数、结构黏度指数及黏流活化能的影响。结果表明:溶液属于切力变稀型假塑性流体,随溶液温度下降及浓度增加,溶液的表观黏度和结构黏度指数增大,非牛顿性增强;该溶液的黏流活化能随着剪切速率的增加而下降。     

Comments on the accuracy of zero shear intrinsic viscosity of high molecular weight polyacrylamide

The intrinsic viscosity of a polymer is traditionally measured with a capillary tube viscometer where the shear rate range is moderately high. Such method is valid when the polymers are non-ionic and have low to moderate molecular weight. The viscosity-shear rate curves obtained for dilute aqueous solutions of two high molecular weight polyacrylamides using two rotational viscometers indicate a strong shear-dependent viscosity in the medium to high shear rate regions. The zero shear intrinsic viscosity of the polymers determined by extrapolation from the high shear rate region to the zero shear condition may result in large errors. Its implication in predicting the molecular weight of polymers using the Mark-Houwink-Sakurada equation is discussed. A rheological equation for intrinsic viscosity as a function of shear rate is proposed.     

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.