A Modified Mixing Rule for PSRK Model and Application for the Prediction of Vapor-Liquid Equilibria of Polymer Solutions

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[bij1/2= 1/2(bi1/2+bj1/2)]. The literature reported Soave-Redlich-Kwong equation of state (SRK EOS) parameters ofpure 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.

Prediction of Henry's constant in polymer solutions using PCOR equation of state coupled with an activity coefficient model

In this paper,the polymer chain of rotator(PCOR) equation of state(EOS) was used together with an EOS/G^E mixing rule(MHV1) and the Wilson's equation as an excess-Gibbs-energy model in the proposed approach to extend the capability and improve the accuracy of the PCOR EOS for predicting the Henry's constant of solutions containing polymers.The results of the proposed method compared with two equation of state(van der Waals and GC-Flory) and three activity coefficient models(UNIFAC,UNIFAC-FV and Entropic-FV) indicated that the PCOR EOS/Wilson's equation provided more accurate results.The interaction parameters of Wilson's equation were fitted with Henry's constant experimental data and the property parameters of PCOR,a and b,were fitted with experimental volume data(Tait equation).As a result,the present work provided a simple and useful model for prediction of Henry's constant for polymer solutions.

PREDICTION OF THE RHEOLOGICAL PROPERTIES OF STAR—TYPE BRANCHED POLYMER SOLUTIONS BY MEANS OF THE FIXED SPECTRUM MODEL

The Rouse-Zimm model with slippage was improved and the basic parameters of modelwere modified to explain the rheological properties of star-type branched polymersolutions. The theoretical results show good agreement with experimental data.

Diffusion of Nanoparticles in Semidilute Polymer Solutions： A Multiparticle Collision Dynamics Study

The diffusion of nanoparticles immersed in semidilute polymer solutions is investigated by a hybrid mesoscopic multiparticle collision dynamics method. Effects of polymer concentration and hydrodynamic interactions among polymer monomers are focused. Extensive simulations show that the dependence of diffusion coefficient D on the polymer concentration c agrees with Phillies equation D-exp （-αc^δ） with a scaling exponent δ≈0.97 which coincides with the experimental one in literature. For increasing nanoparticle size, the scaling prefactor α increases monotonically while the scaling exponent always keeps fixed. Moreover, we also study the diffusion of nanoparticle without hydrodynamic interactions and find that mobility of the nanoparticle slows down, and the scaling exponent is obviously different from the one in experiments, implying that hydrodynamic interactions play a crucial role in the diffusion of a nanoparticle in semidilute polymer solutions.

Modified van Laar's Equation and Its Application to VLE of Polymer Solutions

The original van Laar's theory has been modified. The internal pressures of components and mixture are expressed by Frank's relation and the excess entropy for mixing of components is also considered. A new activity coefficient equation, which can be satisfactorily applied to polymer solutions, is obtained. The calculated results for the VLE of 179 polymer solutions show that the accuracy of fit is evidently superior to UNIQUAC equation.

Flow characteristic of polymer solutions in porous media:Influence of the molecular weight and concentration

The polymer solution flow in porous media is a central research topic related to hydraulic fracturing measures,formation damage and fracture propagation.Influenced by molecular weights and concentrations,various flow patterns of polymer in pores are presented,resulting in different filtration loss.In this work,the effectiveness of various polymer solutions for filtration loss was assessed by utilizing the core flooding experiment firstly.The result shows that lesser filtration loss normally is inextricably linked to solutions with high molecular weight and concentration.Subsequently,the flow behaviors of polymer solutions investigated by designed micro pore-throat structure and micro-particle image velocimetry(m-PIV)further confirmed the above result.It was found that the central convergent flow pattern benefiting from higher viscous force loss and less filtration loss was observed at high flow rates(0.5 mL/h),and higher molecular weight and concentration were more prone to convergent flow patterns.The viscosity force loss increases by about 4 times varying the molecular weight of polymer from 5×10^(6)to 18×10^(6)g/mol or the concentration from 0.05 to 0.3%.It interprets higher molecular weight and concentration in core studies and field observations with decreased filtration loss of HPAM.This work provides a theoretical foundation for the application of fracturing fluids as well as fresh perspectives on how to access the filtration loss of fracturing fluids.

A Constitutive Model Describing Molecular Configuration Evolution and Transient Rheological Behavior of Entangled Polymer Solutions

Entanglement network is an important structural feature in concentrated polymer solutions and polymer melts,which has a great influe nee on the transie nt rheological behavior and molecular con figurati on evolution.However,the existi ng constitutive models have limitations in describi ng the influe nee of dyn amic entan glement behavior on molecular chain motion,resulti ng in inaccurate descriptions of the transient rheological behavior.Thus,a molecular con figuration evoluti on model for polymer solutions considering the dyn amic entanglement effect is proposed by introducing an intermolecular force that changes with the orientation of the molecular chain in this work.The intermolecular force is introduced by consider!ng the friction coefficient as anisotropic,and the orientation effect is considered by introducing an excluded volume depende nt an isotropic diffusi on.The proposed model can better describe the stress relaxation,stress growth,and dielectric an isotropy of polymer soluti ons compared with the an isotropy FENE model and FENE model.In addition,the in fluence of different model parameters on the transient and steady shear response of polymer soluti on is investigated,and the results show that the in fluence of volume loss on the fricti on anisotropy factor k0 in creases as the solution concen tration in creases.

Intrinsic viscosity of polymer solutions: fresh ideas to an old problem

Intrinsic viscosity is one of the most fundamental properties of dilute polymer solutions; its study forms an integral part of the cornerstone of the modern macromolecular theory. However, a general theory applicable to any chain architectures and solvent conditions has remained elusive, due to the formidable challenges in the theoretical treatment of the long-range, many-body and accumulative hydrodynamic effects. Recently, Lijia An and coworkers at the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, has developed a new approach that largely overcomes these challenges. Their new theory provides a simple and unified theoretical framework for describing the intrinsic viscosity of polymers with arbitrary architectures under any solvent conditions and forms the theoretical basis for inferring the polymer chain structure from intrinsic viscosity measurements. Comparisons with existing experimental data yield extensive, quantitative agreement.

Rheological Behavior for Polymer Melts and Concentrated Solutions——Part Ⅶ: A Quantitative Verification for the Molecular Theory of Non-linear Viscoelasticity with Entanglement Constraints in Polymer Melts

Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.

Rheological Behaviour for Polymer Melts and Concentrated Solutions Part Ⅰ:A New Multiple Reptation Model to Predict the Nonlinear Visco-elasticity with Nagai Chain Constraints in Entangled Polymer Melts

An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results

ASSOCIATION OF ETHYLENE VINYL ACETATE COPOLYMER IN DILUTE SOLUTIONS IV. SOLVENT MIXTURE AND ADDITIVE EFFECT ON C_A

Critical association concentration (Ca) of ethylene-vinyl acetate copolymer (EVA) in selective solvent mixtures of 1,2-dichloroethane (DCE) (polar solvent) and cyclohexane (CYH) (non-polar solvent) was investigated. DCE is a good solvent for polyvinyl acetate (PVAc) and a poor solvent for paraffin, whereas CYH is a good solvent for the paraffin and a precipitant for PVAc. Viscosities of EVA in different compositions of the solvent mixture with and without additives were measured. Viscosity results were used to determine the C-A value of the systems. It is shown that C-A was markedly dependent on the composition of the solvent mixture and concentration and structure of the additive. Solvation and competition between hydrogen bonding and micellisation were suggested for qualitative description of the changing of C-A value observed.

Study of action mechanisms and properties of Cr^(3+) cross-linked polymer solution with high salinity

Performance characteristics of partially hydrolyzed polyacrylamide （HPAM） and cross- linked polymer （CLP, Cr^3＋ as the cross linker） solutions have been investigated. A Brookfield viscometer, rheometer, dynamic light scattering system, and core flow device have been used to measure the viscosity, viscoelasticity, polymer coil dimensions, molecular configuration, flow characteristics, and profile modification. The results show that, under conditions of high salinity and low HPAM and Cr^3＋ concentrations, cross-linking mainly occurred between different chains of the same HPAM molecule in the presence of Cr^3＋, and a cross-linked polymer （CLP） system with a local network structure was formed. Compared with an HPAM solution of the same concentration, the apparent viscosity of the CLP solution increased slightly or remained almost unchanged, but its viscoelasticity （namely storage modulus, loss modulus, and first normal stress difference） increased, and the resistance coefficient and residual resistance coefficient increased significantly. This indicates that the CLP solution exhibits a strong capability to divert the sequentially injected polymer flood from high-permeability zones to low- permeability zones in a reservoir. Under the same HPAM concentration conditions, the dimensions of polymer coils in the CLP solution increased slightly compared with the dimensions of polymer coils in HPAM solution, which were smaller than the rock pores, indicating that the cross-linked polymer solution was well adapted to reservoir rocks. Core flood experiments show that at the same cost of reagent, the oil recovery by CLP injection （HPAM-1, Cr^3＋ as the cross linker） is 3.1% to 5.2% higher than that by HPAM- 2 injection.

A NOVEL INTERPRETATION OF CONCENTRATION DEPENDENCE OF VISCOSITY OF DILUTE POLYMER SOLUTION

The concentration dependence of the reduced viscosity of dilute polymer solution is interpreted in the light of a new concept of the self-association of polymer chains in dilute solution. The apparent self-association constant is defined as the molar association constant divided by the molar mass of individual polymer chain and is numerically interconvertible with the Huggins coefficient. The molar association constant is directly proportional to the effective hydrodynamic volume of the polymer chain in solution and is irrespective of the chain architecture. The effective hydrodynamic volume accounts for the non-spherical conformation of a short polymer chain in solution and is a product of a shape factor and hydrodynamic volume. The observed enhancement of Huggins coefficient for short chain and branched polymer is satisfactorily interpreted by the concept of self-association. The concept of self-association allows us to predict the existence of a boundary concentration C-s(dynamic contact concentration) which divides the dilute polymer solution into two regions.

Influence of dissolved oxygen content on oxidative stability of linked polymer solution

The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at the same temperature, the degree of the oxidative degradation of the LPS increased and the rapidity of the oxidative degradation was accelerated with the increase of the dissolved oxygen content. Consequently, the size of linked polymer coils (LPCs) of the LPS became small, and the plugging capability of the LPS decreased. At a fixed content of dissolved oxygen, with increasing degradation temperature, almost the same results were observed, namely, an increased degree of oxidative degradation, accelerated rapidity of the oxidative degradation and decreased plugging capacity, with decreased oxidative stability of LPS. At 90 °C, in the presence of oxygen, LPS lost its plugging capability after having been degraded for a period of time. But at 40 °C, LPS with low dissolved oxygen content could be stable for a long time. The decreased plugging ability of LPS after oxidative degradation is mainly caused by the decreased size and number of the LPCs due to the breaking of hydrolyzed polyacrylamide (HPAM) molecule segments and the structural changing of HPAM molecules.

Deformation of Linked Polymer Coils

Linked polymer solution (LPS) is defined as the solution of linked polymer coils (LPCs) dispersed in water, composed of low concentration partially hydrolyzed polyacrylamide (HPAM) and aluminum citrate (crosslinker). In the work, the conformational changes of LPCs under different conditions were investigated by the methods of membrane filtering under low pressure, dynamic light scattering and core flooding experiments. The results showed that in some conditions the LPCs could be compressed mechanically to 1/158.5 of their original volume because of relatively lower HPAM cross-linking. The hydration property of LPCs was similar to that of normal polymer coils. The deformation of LPCs was more restricted than that of ordinary polymer coils under the flow shear stress or the shift of hydration equilibrium caused in the variation of the electrolyte concentration which is responsible for the effective plugging in the throats of porous media when LPCs are used for deep diverting.

EFFECT OF ADSORPTION ON THE VISCOSITY OF DILUTE POLYMER SOLUTION

Careful measurements of the dilute solution viscosities of polyethylene glycol and polyvinyl alcohol in water were carried out. The reduced viscosities of both polymer solutions plot upward curves at extremely dilute concentration levels similar to the phenomena observed for many polymer solutions in the early 1950's. Upon observation of the changes of the flow times of pure water in and the wall surface wettability of the viscometer after measuring solution viscosity, a view was formed that the observed viscosity abnormality at extremely dilute concentration regions is solely due to the effect of adsorption of polymer chains onto the wall surface of viscometer. A theory of adsorption effect based on the Langmuir isotherms was proposed and a mathematical; analysis for data treatment was performed. The theory could adequately describe the existing viscosity data. It seems necessary to correct the viscosity result of dilute polymer solutions measured by glass capillary viscometer by taking into account the effect of adsorption in all cases.

SOLID STATE VOLTAMMETRY OF ELECTROACTIVE SOLUTES IN POLYMER SOLVENTS(PEO)AT MICROELECTRODE

The present paper describes experiments aimed at delineating significant chemical characteristics of electrochemical reactions in polymeric solutions, including how rigid solvent environments affect mass transport rates, and also discusses the possibility that the microelectrode coated with poly(ethylene oxide)(PEO) film can be used as gas sensor.

Physical Diffusion and Electron-transfer Dynamics of Electroactive Solutes in Polymer Electrolytes Ⅲ. Effect of the Polymer Solvents

The diffusion coefficients(Dapp) and the heterogeneous electron transfer rate constants(ks)for ferrocene in several polymer solvents were determined by using steady-stae voltammetry. Thetemperature dependence of the two parameters indicates Arrhenius behavior. The polymer solventeffects on diffusion and electron transfer dynamics of ferrocene were discussed

COMPUTER SIMULATION OF POLYMER SOLUTION THERMODYNAMICS

The statistical counting method for the computer simulation of the thermodynamic quantities of polymer solution has been reviewed. The calculating results for a single athermal chain confirm the theory of the renormalization group. The results for the athermal solution are consistent with the scaling law of the osmotic pressure with the exponent 2.25. The results for a single chain with the segmental interaction are in a good agreement with the exact results obtained by the direct counting method. The results for the polymer solution show us that the Flory-Huggins parameter is strongly dependent on both the polymer concentration and the interaction energy between segments. (Author abstract) 15 Refs.

Pressure Effects on Thermodynamics of Phase Behavior in Polystyrene/Methylcyclohexane Solutions

The calculations presented in this paper are based on the Sanchez-Lacombe（SL）lattice fluid theory.The interaction energy parameter,g12/k,required in this approach was obtained by fitting the cloud points of polystyrene（PS）/methylcyclohexane（MCH）polymer solutions under pressure.The SL lattice fluid theory was used to calculate the spinodals,the binodals,and the Flory-Huggins（FH）interaction parameter of the solutions.The calculated results show that the SL lattice fluid theory can describe the dependences of thermodynamics of PS/MCH solutions on temperature and pressure very well.However,the calculated enthalpy and the excess volume changes indicate that the Clausius-Clapeyron equation cannot be suitable to describe pressure effect on PS/MCH solutions.Further analysis on the thermodynamics of this system under pressure shows that the role of entropy is more important than the excess volume in the present case.