The shear degradation of high-molecular-weight flocculant solutions

Solutions of polyacrylamide and poly(acrylamide-co-sodium acrylate) flocculants with varying molecular weights were shear degraded under a range of mixing conditions. The viscosity and flocculant activity of the solutions generally decreased with time to limiting values dependent on the mixing intensity. The activity of 10 and 20% anionic flocculants displayed quite different trends from those for nonionic flocculants of equivalent molecular weight, with less apparent degradation due to mixing, particularly at low dosages. However, viscosity measurements on sheared solutions diluted with a salt buffer suggest that nonionic and anionic flocculants with similar initial molecular weights were degraded to the same degree. Multiangle laser light-scattering measurements were used to confirm that the shearing process resulted in a reduction in molecular weight which was independent of anionic character. The apparent shear resistance of anionic flocculation mechanisms for the nonionic and anionic flocculants. © 1996 John Wiley & Sons, Inc.     

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.     

Aging and loss of flocculation activity of aqueous polyacrylamide solutions

There is a rapid and a slow stage in the decrease of reduced specific viscosity versus time (aging) for a solution of a high intrinsic viscosity polyacrylamide in water. The rapid stage is irreversible and has a fairly high temperature coefficient. Results of the latter type are usually associated with a weak-link scission mechanism, but they can also be reconciled with a disaggregation mechanism. A disaggregation mechanism is also indicated for the rapid stage by an increase in the first-order rate contant with a decrease in the polymer concentration or an increase in the shear rate and by the absence of the rapid stage during the aging of the same sample in formamide. Chemical changes in the polymer are suspected as being responsible for the RSV change during the slow stage in the aging of the high intrinsic viscosity polyacrylamide and also in the aging of a polyacrylamide of low intrinsic viscosity. The aging of the polyacrylamide of high intrinsic viscosity is paralleled by a decrease in the ability of the polymer to increase the subsidence of kaolin suspensions. This decrease in the flocculation activity is attributed to a weakening of the interparticle bridging by a change from a strong adsorption of the bridging polymer to two particles to a strong adsorption of the bridging polymer to one particle but weak adsorption of the bridging polymer to the other particle.     

Polyacrylamides revisited: flocculation of kaolin suspensions and mature fine tailings

A series of acrylamide‐based water‐soluble (co)polymers was synthesized and they were investigated as flocculants of model kaolin suspensions and mature fine tailings of oil sands. The effects of molar mass, charge density, and polymer concentration on flocculation efficiency were studied by monitoring the initial settling rate during sedimentation. Hydrolyzed polyacrylamide (HPAM) with high molar mass and intermediate acrylic acid contents (0.14–0.41 mol/mol (14–41 mol%)) performed better in flocculation tests on kaolin suspensions requiring lower dose for maximum initial settling rate than native polyacrylamide (PAM). Surface force measurements showed that at low polymer concentrations (1 ppm), the partially‐adsorbed polymer induced a bridging attraction between the mica surfaces. Increasing the polymer concentration to 10 and 50 ppm caused purely repulsive forces. The presence of anionic groups in HPAM led to stronger repulsion, which was also demonstrated by the higher viscosity and larger hydrodynamic radius of the charged polymer. The charge‐induced increase in the viscosity of polymer solutions was suppressed by the screening effect of salts in a buffer solution and reducing the viscosity is desirable in the injection of flocculants in the industrial process.     

Untersuchung zur Flockungsfähigkeit von Polyacrylamid-co-acrylaten (0 – 100 mol-% Acrylamid)

The flocculation activity of poly(acrylic acid), poly(acrylamide-co-sodium acrylates) and polyacrylamide, which were prepared in our laboratory, was investigated. The flocculation speed of polyacrylamide was found to increase with increasing molecular weight. The aqueous polyacrylamide solutions as well as the samples stored in the solid state showed, when M_η ≥ 1,5 · 10⁶ g/mol, a time-dependent decrease of the intrinsic viscosity and simultaneously a decrease of flocculation speed. This was accompanied by a diminution of the radius of gyration. These time-dependent facts were caused by a conformational change of the molecular structure and not by molecular degradation. Linear polyacrylamides were better flocculation agents than branched ones (20 branches) with the same total molecular weight. Poly(acrylamide-co-sodium acrylates) exhibited a maximum of flocculation activity at a comonomer degree of about 70 mol-% acrylate.     

Intrinsic viscosity, surface activity, and flocculation of cationic polyacrylamide modified with fluorinated acrylate

A novel cationic polyacrylamide modified with fluorinated acrylate had been synthesized of acrylamide (AM), methacryloxyethyl trimethylammonium chloride (DMC), and 2-(perfluorooctyl)ethyl acrylate (FEA) by free radical micellar copolymerization in aqueous solution utilizing cetyl trimethylammonium bromide (CTAB) as the surfactant and potassium persulfate (KPS)/sodium bisulfite (SBS) as the redox initiator. Some factors affecting synthesis, such as the amount of FEA, CTAB, and KPS, were described. Surface activity and flocculation of the polymer were studied. The results showed that with the incorporation of FEA, the intrinsic viscosity decreased until the modified polymer was not able to dissolve in water; and with the increase of CTAB and KPS, the intrinsic viscosity decreased firstly then increased slowly. The polymer exhibited good surface activity in both water and salt solution. Its flocculation properties were evaluated with kaolin suspensions using a standard jar test. The results demonstrated the superiority of the copolymer over the no-modified cationic polyacrylamide as a flocculant.     

The performance of polymer solutions in enhanced oil recovery: studies on their rheological,interfacial, and porous media behaviors

Four polymeric solutions based on xanthan, high and low molecular weight sulfonated polyacrylamides, and hydrolyzed polyacrylamide were prepared in aqueous solutions and their behaviors in enhanced oil recovery applications were investigated. The effect of thermal aging on polymer solutions was evaluated through rheological measurement. Pendant drop method was also used for measuring the interfacial tension (IFT) between crude oil and brine containing different polymer solutions. Moreover, the zeta potential of the oil reservoir particles treated with oil and polymer was determined by electrophoresis method in a nano-zeta meter instrument. In addition, sand pack and core flooding setup were used for evaluating the effectiveness of the polymer solutions in porous media. Polymer solutions displayed non-Newtonian behavior in almost the whole range of the shear rate applied; a shear thinning behavior was seen. Furthermore, the aging of polymers in formation water decreased the shear viscosity of all the polymers. The oil/water IFT decreased by the addition of polymers to water. The effect of xanthan polymer on zeta potential value was greater than that of the three acrylamide-based polymers. According to sand pack tests, by increasing the polymer concentration, the incremental oil recovery initially increased up to a polymer concentration of 3,500 ppm and then started to fall. Recovery factor increased from 50 to 65 % using the polymer solution in core flooding experiments. By increasing the injection rate from 0.2 to 3 mL/min, the injected fluid had less time to sweep the pores and consequently the amount of recovered oil decreased.     

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     

Novel,rosin‐based,hydrophobically modified cationic polyacrylamide for kaolin suspension flocculation

A novel, hydrophobically modified cationic polyacrylamide (HMPAM) was synthesized via the copolymerization of acrylamide, diallyl dimethyl ammonium chloride (DMDAAC), and diallylmethyl dehydroabietic acid propyl ester ammonium bromide. Optimum conditions for preparing HMPAM were such that the amount of initiator was 0.075 wt % of the total monomer mass, the monomer concentration was 20 wt %, and the amount of DMDAAC was 18 mol % of the total monomer molar mass. HMPAM was characterized with an UV–visible spectrometer, ¹H‐NMR, Ubbelohde viscometer, rotational viscometer, and rotational rheometer. HMPAM solutions exhibited strong hydrophobic associations, and the critical association concentration of the HMPAM aqueous solution was about 0.7 wt %; the HMPAM solutions also showed salt thickening and shear resistance. The surface morphologies of the freeze‐dried HMPAM samples (1 wt %) were also observed via scanning electron microscopy. Compared with unmodified cationic polyacrylamide, Synthesis of HMPAM‐0.5 exhibited a stronger flocculation capacity, and the optimal transmittance of the supernatants was above 95%. HMPAM‐0.5 showed significant flocculation performances for 3–4 and 3–5 wt % kaolin suspensions at 40 and 50 mg/L, respectively. Moreover, the flocculation performance was enhanced with the addition of NaCl and CaCl₂. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46637.     

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.     

Zum abbau von polymerlösungen durch kapillarscherung. Einfluß der kapillarlänge und strömungsform auf den abbau

The dependence of shear degradation of polymer solutions on capillary length at constant shear stress is investigated with solutions of poly(isobutylene) (M_vis=6,1 · 10⁶) in toluene. We examined concentrations of 0.1, 0.25, 1 and 4% and found the degradation to increase with capillary length. In 0,1% solution we found a decreased efficiency of degradation, due to a change in the structure of solution. Flow instabilities, which appear above a critical shear rate D in polymer solutions and pretend a loss in viscosity, are not caused by shear degradation. This result supports our interpretation of unstable flow of polymer solutions as slip flow (spurt).     

Optimising the dewatering behaviour of clay tailings through interfacial chemistry, orthokinetic flocculation and controlled shear

The effect of shear on dewatering behaviour and particle interactions of Na-exchanged smectite and kaolinite clay dispersions has been investigated at pH 7.5, using hydrolysable Ca(II) and Mn(II) ions as coagulants and high molecular weight anionic and non-ionic polyacrylamide (PAM A and PAM N, respectively) and polyethylene oxide (PEO) flocculants. Metal ion addition enhanced the flocculation performance by dramatically reducing the magnitude of the particle zeta potential and, in the case of smectite pulp, suppressing osmotic swelling. Under optimum orthokinetic flocculation conditions of controlled agitation rate and duration, PAM A and PEO-based flocs settled faster than those of PAM N whilst kaolinite pulps produced higher sedimentation rates than smectite pulps. The settling rates are nearly an order of magnitude greater than those observed under standard flocculant-pulp mixing/flocculation methods of inversion and plunging. The difference in the flocculant behaviour is attributed to the more expanded conformation of PAM A and PEO polymer chains in contrast to PAM N, whilst the lower yield stresses, reflecting inter-particle bridging and floc network structure strength that are conducive to faster clarification, were displayed by kaolinite pulps. Following shear, similar consolidation enhancement of ≈ 5-7 wt.% solid for both pulps was achieved at an optimum agitation range of 100-200 rpm. This was accompanied by decreased yield stress in the case of PAM A-based pulps, indicating non-reversible disruption of polymer mediated particle and floc network structure. In contrast, the yield stresses of PAM N and PEO flocculated dispersions indicated similar and stronger particle interactions, respectively, upon consolidation following shear. The findings show clear links between effect of shear, interfacial chemistry and polymer structure on pulp particle interactions and dewaterability.     

Operating window of solution casting. II. Non‐Newtonian fluids

The operating windows of the solution casting of two polymeric liquids were evaluated experimentally. The experimental setup and procedure were the same as used previously for the casting of Newtonian fluids (Journal of Applied Polymer Science 2013, 129, 507–516). Aqueous carboxymethylcellulose/glycerol solutions exhibited pure shear‐thinning behavior at low polymer concentrations but became viscoelastic at high polymer concentrations, whereas polyacrylamide/glycerol solutions showed viscoelastic behavior over a wide range of concentrations. The shear‐thinning behavior, in conjunction with a low level of elasticity, of the casting solution was found to be useful in expanding the stable operating windows. However, an opposite effect on the operating windows was found for highly elastic solutions. The non‐Newtonian effect on the maximum stable casting speed was prominent only when the capillary number exceeded unity. Defects outside of the operating window were mostly similar to those observed in Newtonian solution casting. For highly concentrated solutions, a new rough surface defect was observed. This defect could be attributed to polymer chain entanglement, alignment, or breakup. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41411.     

Degradation of drag reducing polymers in aqueous solutions

The performance of drag reducing polymers in turbulent flow is restricted by their mechanical degradation. This study examines how the working fluid can affect the degradation behavior of diluted drag reducing polymeric solutions. Solutions having different proportions of tap water and de-ionized water served as the working fluids. Three commercially available water soluble polymeric agents, namely, an anionic copolymer of polyacrylamide, xanthan gum, and polyethylene oxide, were then added to these solutions. All experiments had identical flow rates corresponding to turbulent conditions in a laboratory scale pipe line. Variation of pressure drop in the pipe line was then measured for 2 hours. It was found that polymer degradation is accelerated in tap water solutions compared to that in de-ionized water solutions. However, this is dependent on the specification of the polymer used, namely, the molecular weight of the polymer and the rigidity of its molecular backbone. Furthermore, a new mathematical relation has been developed to investigate degradation of the polymers over time.     

zeta电位与菌悬液絮凝活性

通过克雷伯杆菌、有机高分子絮凝剂表面zeta电位分析和絮凝实验,初步研究了有机高分子絮凝剂对克雷伯杆菌的絮凝特性和絮凝机理。zeta电位测定表明克雷伯杆菌的等电点大致为2.2,阳离子聚丙烯酰胺（cPAM）表面的零电点约为8.0,非离子聚丙烯酰胺（nPAM）和阴离子聚丙烯酰胺（aPAM）表面均带有少量负电荷。pH<8,cPAM带正电,能与带负电的菌体电中和,显示良好的絮凝效果,最佳絮凝条件为pH7,絮凝率（FR）达94.5%。加入无机电解质后,nPAM絮凝效果变化最明显,pH4时絮凝率达95.1%,结果表明,克雷伯杆菌发酵液絮凝除菌过程是以电性中和为主,吸附架桥为辅。     

VISCOMETRIC MEASUREMENT OF CHROMIUM(III)-POLYACRYLAMIDE GELS†

Gelled polymers are being used increasingly to modify the movement of injected fluids in secondary and enhaced oil recovery processes. A common gelation process involves the reduction of Cr(VI) to Cr(III) in the presence of polyacrylamide. The Cr(III) reacts or interacts with the polymer to form a gel network. Although correlations of gelation time with principal process variables have been obtained, viscometric data have not been reported during or after gelation. These data are needed for fluid flow calculations in surface equipment and estimation of flow behaviour in reservoir rocks.

A Weissenberg Rheogoniometer, with cone and plate geometry, was used to obtain viscometric data for the gelation of polyacrylamide and chromium (III). Solutions consisting of polyacrylamide polymer, sodium dichromate-dihydrate and sodium bisulfite were gelled under a steady shear field at constant temperature. The shear stress versus time profile for the galation process was interpreted to define a gelation time and to determine the apparent viscosity of the gelled fluid. The gelation time decreased as the applied shear rate increased up to about 14.25 sec^?1 and was affected by shear rate history. Viscometric properties of the gelled solutions were determined. Apparent viscosity of the gelled solutions decreased as the shear rate under which they were formed increased.

Post gelation studies indicated that gels exhibited a residual stress at zero shear rate and behaved as Bingham plastics under steady shear. Gels formed at low shear rates were more viscous than gels formed at high shear rates. However, the structure of these gels was susceptible to shear degradation.     

Rheology of Water-Soluble Polymers: A Comparative Study on the Effect of Monovalent Salt

A comparative study was conducted on three commercial water-soluble polymers: partially hydrolyzed polyacrylamide (Separan AP30—Dow Chemicals), polyethylene oxide (Polyox Coagulant—Union Carbide), and xanthan gum (Keltrol—Kelco). Both the steady shear and the dynamic properties were examined. The presence of salt significantly reduces the viscous and elastic properties of Separan AP30. Negligible changes were observed for Polyox Coagulant. However, some marginal reduction in these properties was evident for xanthan gum at low salt concentration up to c_s of 0.05 M, beyond which no effect was observed. The relationship between the rheological properties of the polymers and the salt concentration is governed by the charged characteristics of the polymer chains. The present study suggests that it is more desirable to use xanthan gum than polyacrylamide in a high-salt environment. Polyethylene oxide is usually avoided due to its cost and low resistance to mechanical degradation.     

Mechanical stability of high‐molecular‐weight polyacrylamides and an (acrylamido tert‐butyl sulfonic acid)–acrylamide copolymer used in enhanced oil recovery

High‐molecular‐weight partially hydrolyzed and sulfonated polyacrylamides are widely used in enhanced oil recovery (EOR). Nonionic polyacrylamide and polyacrylamide‐based microgels are also used in water shut‐off treatments for gas and oil wells. A comparative study of the mechanical degradation for three linear polyacrylamides and a microgel is presented. Mechanical degradation is quantified from the loss of the viscosity of the polymer solution as it passes through a stainless steel capillary with a length of 10 cm and an internal diameter of 125 µm. The critical shear rate above which degradation increases exponentially was found to depend on the chemical structure of the polymer, molecular weight, and electrolyte strength. The nonionic polyacrylamide shows higher degradation and lower critical shear rate compared with a sulfonated polyacrylamide with similar molecular weight. Moreover, the nonionic polyacrylamide with a higher molecular weight results in lower mechanical degradation. The higher mechanical stability of the sulfonated polymer is attributed to the higher rigidity of its molecules in solution. On the other hand, the ability of the high‐molecular‐weight polymers to form transient, flow‐induced microgels boost their mechanical stability. This ability increases with the increase in the molecular weight of the polymer. Indeed, the microgel solution used in this study demonstrates exceptional mechanical stability. In general, mechanical stability of linear polymers used in chemical enhanced oil recovery can be enhanced by tailoring a polymer that has large side groups similar to the sulfonated polyacrylamide. Also, polyacrylamide‐based microgels can be applied if high mechanical stability is required. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40921.     

凹凸棒土/丁苯胶乳纳米复合材料的制备与表征

以凹凸棒土(AT)和丁苯胶乳(SBR)为原料,通过与阴离子型聚丙烯酰胺、非离子型聚丙烯酰胺(NPAM)、氯化钠、乙醇等絮凝,制备了性能优异的凹凸棒土/丁苯胶乳复合材料。研究了各种添加剂对凹凸棒土和丁苯胶乳混合液絮凝效果的影响,同时考察了添加剂类型、用量对凹凸棒土/丁苯胶乳复合材料的力学性能的影响,确定了混合液最佳絮凝条件。结果表明:非离子型聚丙烯酰胺对混合液絮凝效果最好,同时凹凸棒土经硅烷偶联剂KH590改性后有利于提高凹凸棒土在丁苯胶乳基体中的分散性及复合材料中的结合橡胶量,从而提高凹凸棒土/丁苯胶乳复合材料的力学性能。     

The flocculation of kaolin by cationic polyacrylamides and the effect of cationic surfactant on this process

The flocculation of kaolin suspended in a dilute salt solution was studied as a function of the addition of cationic surfactant and cationic polyacrylamide (CPAM) added separately, consecutively, or simultaneously. Cationic polyacrylamide caused flocculation by bridging when added in low concentrations, but at higher concentrations, charge neutralization became the dominant mechanism and the flocculation rate was highly dependent on the charge density of the polymer. Adsorption of sufficient polymer or surfactant (cetyl pyridinium chloride) prevented immediate adsorption of the other, although surfactant could replace polymer after extended agitation. The adsorption of polymer was greatest when small flocs were formed by charge neutralization or by prolonged shaking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2382–2389, 2002