Viscometric and Morphological Properties of Novel Magnesium Electrolyte–Polyacrylamide Composite Polymers in Aqueous Solution

The viscometric properties of novel magnesium electrolyte–polyacrylamide composite polymers in aqueous solutions were investigated using response surface methodology. Independent factors such as concentration of the magnesium electrolyte (magnesium chloride and magnesium hydroxide), concentration of polyacrylamide, and the solution temperature were taken into account for viscometric modeling. Experiments were carried out according to central composite design, which includes factorial, central and axial points of the factors. Solution viscosity was taken as the response variable. A polynomial model for the viscometric properties was developed using ANOVA and non-linear regression analysis, and the R² values are 0.9995 and 0.9996 for aqueous solutions of magnesium chloride–polyacrylamide (MCPAM) and magnesium hydroxide–polyacrylamide (MHPAM) composite polymers, respectively. Two diagnostic plots have been constructed to validate the developed models for the natural logarithm of viscosity of aqueous solutions of the MCPAM and MHPAM composite polymers. The least-squares values show that the developed models are adequate for predictive purposes. TEM was used to investigate the morphological properties of MCPAM and MHPAM composite polymers. Magnesium chloride was impregnated into the polyacrylamide chain while magnesium hydroxide was just adsorbed on the surface of the polyacrylamide chain.     

Reactive Dye Removal Using Inorganic–Organic Composite Material: Kinetics,Mechanism, and Optimization

An inorganic–organic composite material (MCPAM) consisting of magnesium chloride and polyacrylamide, was applied to remove reactive dye (Cibacron Red FN-R) from aqueous solution through coagulation–flocculation process. MCPAM with the ratio of 90% MgCl₂/10% PAM was the best ratio in removing reactive dye. Kinetics of reactive dye removal was investigated using pseudo-kinetics model and it fits pseudo-second-order reaction model. The mechanism of reactive dye removal was investigated through physicochemical properties of supernatant, flocs, and sludge. The change of conductivity and pH denotes the interactions between reactive dye and MCPAM. The chemical structure, settling, and microstructure of sludge indicate the formation of sludge during coagulation–flocculation process. The settled sludge volume and sludge volume index (SVI) that of MCPAM was lower than that of MgCl₂. The flocs formed using MCPAM was also relatively compact and larger in size compared to that of MgCl₂. The reactive dye removal was optimized through central composite design whereby color removal (%) and chemical oxygen demand (COD) reduction (%) were optimized by five operating factors, namely, concentration of dye, pH, dosage of MCPAM, agitation speed, and agitation time. The optimal values reported for color removal (%) and COD reduction (%) were of 97–98% and 60–81%, respectively.     

A study of dilational rheological properties of polymers at interfaces

Viscoelastic properties of two polymers, partially hydrolyzed polyacrylamide and partially hydrolyzed modified polyacrylamide, widely used in chemical flooding in the petroleum industry, were investigated at three interfaces, water-air, water-dodecane, and water-crude oil, by means of a dilational method provided by I.T. Concept, France, at 85 degrees C. Polymer solutions were prepared in brine with 10,000 mg/l sodium chloride and 2000 mg/l calcium chloride. It has been shown that the viscoelastic modulus increases with the increment of polymer concentration in the range of 0-1500 mg/l at the water-air interface. Each polymer shows different viscoelatic behavior at different interfaces. Generally speaking, values of the viscoelastic modulus (E), the real part (E'), and the imaginary part (E") at the crude oil-water interface for each polymer are lower than at the air-water or water-dodecane interface. The two polymers display different interfacial properties at the same interface. Polymer No. 2 gives more viscous interfaces than polymer No. 1. All the information obtained from this paper will be helpful in understanding the interfacial rheology of ultra-high-molecular-weight polymer solutions.     

A new instrument for measuring the viscoelastic properties of dilute polymer solutions

A new oscillating capillary viscometer has been developed and used for measuring viscoelastic flow properties of dilute polymer solutions. These flow properties are determined from measurements of the pressure to volume flow relationships for sinusoidal flow in cylindrical glass capillaries. The theory for this measurement procedure is based upon the known theory for oscillatory flow of a viscoelastic fluid in circular tubes and which is presented with a few supplementations in this paper.The oscillatory flow is generated by a piezoelectric driver which is dipped directly into the aqueous solution. The advantage of this driver is that the excitation voltage for the piston is a direct measure of the motion of the piston. Changes in pressure are measured with a sensitive low-pressure quartz tranducer.The viscometer was tested with aqueous glycerol solutions and a gelatin gel. The viscoelastic flow properties of dilute polymer solutions (gelatin, gelatin/color-coupler, polyacrylamide) were then investigated in the frequency range 5 Hz to 150 Hz at very small volume flow amplitudes. The results presented illustrate the suitability of the method. The results are also evaluated with regard to the stabilizing action of slightly viscoelastic gelatinous coating liquids in the high-speed coating process in the manufacture of photographic materials.     

Electrophoretic and viscometric studies of the interactions of polymethacrylamide and polyacrylamide with electrolytes in aqueous solutions

Free electrophoresis and viscometry were used to study the effects of salts (perchlorates, thiocyanates, chlorides and sulphates of uni- and bivalent metals) on the properties of polyacrylamide and polymethacrylamide in aqueous solutions. In salt solutions, in the electric field both polymers behave as polyanions. It may be inferred from electrophoretic measurements that both anions and cations are bound on the polymer chain; the degree of binding depends on the nature of the ions. The viscometric data show that there is a pronounced salting-in effect of cations (increasing with increasing surface charge density); the effect of anions is either secondary (for polyacrylamide) or rather unfavourable to dissolution (for polymethacrylamide).     

Rheology of viscoelastic solutions of cationic surfactant. Effect of added associating polymer

Rheological studies were performed with aqueous salt solutions of viscoelastic cationic surfactant erucyl bis(hydroxyethyl)methylammonium chloride (EHAC) and its mixtures with hydrophobically modified polyacrylamide. The solutions of surfactant itself above the concentration of crossover of wormlike micelles exhibit two regions of rheological response. In the first region, they behave like polymer solutions in semidilute regime characterized by viscoelastic behavior with a spectrum of relaxation times. In the second region, unlike polymer solutions their relaxation after shear is dominated by a single relaxation time. Being composed of "living" micelles, the EHAC solutions easily lose their viscosity at the variation of the external conditions. For instance, heating from 20 to 60 degrees C reduces viscosity by up to 2 orders of magnitude, while added hydrocarbons induce a sudden drop of viscosity by 3-6 orders of magnitude. Polymer profoundly affects the rheological properties of EHAC solutions. The polymer/surfactant system demonstrates a 10,000-fold increase in viscosity as compared to pure-component solutions, the effect being more pronounced for polymer with less blocky distribution of hydrophobic units. A synergistic enhancement of viscosity was attributed to the formation of common network, in which some subchains are made up of elongated surfactant micelles, while others are composed of polymer. At cross-links the hydrophobic side groups of polymer anchor EHAC micelles. In contrast to surfactant itself, the polymer/surfactant system retains high viscosity at elevated temperature; at the same time it keeps a high responsiveness to hydrocarbon medium inherent to EHAC.     

Effect of GMA polymer compatibilizers on highly filled composites of low density polyethylene/magnesium hydroxide

Functional polymers such as polyethylene grafted glycidyl methacrylate （PE-g-GMA） and ethylene-methyl acrylate-glycidyl methacrylate terpolymer （E/MA/GMA） were used as compatibilizers in the preparation of highly filled composites of polyethylene/magnesium hydroxide（PE/MH）. Comparative studies were performed on the effect of magnesium hydroxide and stearic acid on the interface within polymer and magnesium hydroxide composites. The effect of polymeric compatibilizers on the properties of the composites was studied using tensile and impact tests, torque rheological analysis, differential scanning calorimetry and environmental scanning electron microscopy （ESEM）. The microstructure of highly filled PE/MH composites changed after the addition of functional polymers. The mechanical properties of the composite material increased after compatibilization. The compatibilization processes of PE-g-GMA and E/MA/GMA were different. The grafted polymer was more compatible with polyethylene, which led to a polar polymer phase. In contrast, the tercopolymer tended to adhere to the surface of MH particles.     

Formation and Physicochemical Features of Hybrid Threadlike Micelles in Aqueous Solution

We investigate the construction of long, stable hybrid threadlike micelles consisting of polyelectrolytes and oppositely charged surfactants in aqueous solution and examine the physicochemical features such as their structure and viscoelastic behavior in aqueous solution. The most important point for their construction is the careful control of interactions, especially electrostatic interactions, caused between the surfactants and polyelectrolytes. Incorporated polyelectrolytes are fully extended in these hybrid threadlike micelles irrespective of the molecular weight of the polymer. The viscoelastic behavior of the hybrid threadlike micellar solution is similar to that of ordinary threadlike micellar systems consisting of low‐molecular‐weight substances. However, the inclusion of polymers in the micelles causes differences in their mechanical properties.     

Self-assembled networks highly responsive to hydrocarbons

Rheological studies were performed with aqueous salt solutions of anionic surfactant potassium oleate and its mixtures with hydrophobically modified polyacrylamide. Semidilute solutions of the surfactant in the presence of salt (KCl) demonstrate viscoelastic properties due to the formation of a transient network of entangled wormlike micelles. These systems are highly responsive to hydrocarbons: the addition of n-heptane or n-dodecane reduces the viscosity of solutions by up to 4 to 5 orders of magnitude, thus inducing the transition of a gellike system to a fluid one. It is the transformation of cylindrical surfactant micelles into spherical ones upon absorption of hydrocarbon that disrupts the network. The addition of a small amount (0.5 wt %) of associating polymer leads to up to a 5000-fold increase in the zero-shear viscosity and enhances the susceptibility to hydrocarbons. SANS data show that independently of the presence of polymer the radius of wormlike micelles is roughly equal to the length of a surfactant molecule, whereas the radius of spheres formed upon the absorption of hydrocarbon is 2-2.5-fold higher. A possible structure of the spherical micelles is discussed.     

Effect of Thermal History on Rheological Properties of Partially Hydrolyzed Polyacrylamide／Anionic Surfactant SDS Complex Systems

The effects of thermal history on the rheological properties of partially hydrolyzed polyacrylamide/sodium dodecyl sulfate complex aqueous solutions have been studied using both steady shear and dynamic temperature sweep characterizations. An abnormal rheological behavior was found that dynamic moduli of the aqueous solutions increased, while the viscosity decreased after thermal treatment,which could help to gain insight into the micro-phase evolution of the polymer/surfactant complex aqueous solutions and its dependence on temperature     

Apparent relaxation‐time spectrum cutoff in dilute polymer solutions: An effect of solvent dynamics

The apparent short time cutoff of the relaxation‐time spectrum at surprisingly long times for polymers in solution is a well known but not yet understood observation. To elucidate its origins we revisit viscoelastic and oscillatory flow birefringence data for solutions and melts of two linear polymers (polystyrene and polyisoprene) and present new measurements of oscillatory flow birefringence of the latter. Previous measurements have suggested that the “flexibility” of both polymers in solution is smaller than in the melt on the basis of the breadth of the relaxation‐time spectrum of the solution as compared with that of the melt. Our new measurements have explored a higher effective frequency range than was previously possible. This has allowed us to observe the effect of the rotational relaxation time of the solvent on the dynamics of the solution at high frequencies. To obtain the polymer global motion contribution, one now needs to subtract from the solution properties a frequency‐dependent complex solvating environment contribution. We show that the decrease in apparent “flexibility” for solutions arises from the presence of a solvent that exhibits a rotational relaxation time and thus simple viscoelastic behavior somewhat near the frequency window of the experiment. Although recent predictions of a model for a chain in a solvent with a single relaxation time are in qualitative agreement with our results, our data suggest that the solution results may reflect the influence of solvent on the development of the “entropic spring” forces at short times. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2860–2873, 2001     

Swelling equilibrium of poly(acrylamide) gels in aqueous salt and polymer solutions

The influence of some single salts (NaCl, KCl, Na₂HPO₄ and K₂HPO₄) and poly(ethylene glycol) (PEG) on the swelling of aqueous poly(arcylamide)-gels was studied at 25°C in more than 600 experiments. The chlorides and phosphates cause a different behavior at high salt concentrations: The polyacrylamide gels swell in aqueous solutions of sodium and potassium chloride whereas they shrink when chloride ions are substituted by hydrogen phosphate ions. These differences are due to differences in the interactions of chloride and hydrogen phosphate ions with the network groups. In aqueous solutions of poly(ethylene glycol) the gels shrink continuously with increasing polymer concentration. At constant PEG mass fraction in the liquid phase, the swelling of the gel decreases with increasing molecular weight of PEG. The experimental results (degree of swelling, partitioning of solutes to the coexisting phases) are correlated by combining a model for the Gibbs excess energy for aqueous systems of polymers and electrolytes with a modification of the phantom-network theory. The correlation gives a good agreement with the experimental data for the degree of swelling, whereas in most cases, there is only a qualitative agreement for the partitioning of the solutes.     

Dielectric Properties of Polymer Composites Filled with Different Metals

Electrically conductive composite systems based on polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA) filled with metal powders of Al and Cu have been studied. The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer matrix. Dependence of the dielectric and conductivity properties of the PVC and PMMA/fillers was studied over a broad range of frequency and volume fraction of metal fillers. The experimental results could be explained by means of the conductivity of fillers and the interface polarization between polymers and fillers. Percolation was also seen in this study when the volume fraction of conducting fillers was close to critical value, in which the composites undergo an insulator‐conductor transition. The relation among the dielectric property and the fillers with different conductivity was proposed.     

Dynamic mechanical properties of plasticized poly(vinyl chloride). Linear free energy relationship in the poly(vinyl chloride)–ester system

A considerable number of quantitative attempts have been made to predict the properties of solutions containing polar polymers and polar solvents. Thermodynamic approaches have generally failed to accurately describe these systems. This can be be ascribed to the difficulty in determining structural characteristics arising from the variety of secondary interactions present in these highly complex solutions. A linear free energy relationship has been used here to explore changes encountered in solutions of monofunctional esters in poly(vinyl chloride) undergoing mechanical deformation. This treatment appears valid only for the rubbery region of the viscoelastic spectrum of this polymer. The data indicate that the observed changes are a function of corresponding changes in polymer intramolecular interactions.     

Zeolite-Polymer Composite Materials as Water Scavenger

The influence of the charge compensating cation nature (Na⁺, Mg²⁺) on the water adsorption properties of LTA-type zeolites used as filler in composite materials (zeolite/polymers) was investigated. Large scale cation exchanges were performed on zeolite powder at 80 °C for 2 h using 1 M magnesium chloride (MgCl₂) aqueous solutions. XRF, ICP, and EDX analyses indicate a successful cationic exchange process without the modification of the zeolite structure as shown by XRD and solid-state NMR analyses. Composite materials (granulates and molded parts) were manufactured using to extrusion and injection processes. In the case of MgA zeolite, nitrogen adsorption–desorption experiments allowed us to measure a microporous volume, unlike NaA zeolite, which is non-porous to nitrogen probe molecule. SEM and EDX analyses highlighted the homogeneous distribution of zeolite crystals into the polymer matrix. Water adsorption capacities confirmed that the trends observed in the zeolite powder samples are preserved after dragging zeolites into composite formulations. Granulates and molded parts composite samples containing the magnesium exchanged zeolite showed an increase of their water adsorption capacity up to +27% in comparison to composite samples containing the non-exchanged zeolite. The MgA composite is more promising for water decontamination applications due to its higher water adsorption properties than the NaA composite.     

Characterization of the drag-reducing nature of long-chain polymer–water solutions through atomization

Inclusion of minute concentrations of elongated long chain polymers is known to exhibit drastic reduction in frictional losses for turbulent fluid flows. The polymer chains interact with solvent molecules to act as eddy stress absorbers causing reduction in drag and inducing the viscoelastic nature in the fluid layer. In this work, we propose a characterization method for viscoelastic behavior of polymer-water solutions using a spray atomization experiment. The methodology is demonstrated for polyacrylamide and polyethylene oxide-based aqueous solutions. The experimental technique assesses the nature of the fluid using a predefined parameter, impact ratio (R). Computational fluid dynamics simulations of spray atomization are performed to validate the experimental values of the impact ratio. The simulation results indicate coherence with the experimental data, and are concordant with the reported behavior of such solutions in the literature.     

耐温抗盐驱油聚合物溶液黏弹性

对3种不同结构类型的耐温抗盐驱油聚合物〔高分子量聚丙烯酰胺(HPAM)、磺化聚丙烯酰胺(S-HPAM)和疏水缔合聚丙烯酰胺(A-HPAM)〕的溶液黏弹性能进行了研究。在温度85℃下,通过稳态剪切和动态剪切试验,考察了质量浓度和矿化度对聚合物溶液黏弹性的影响。结果表明,随剪切速率增加,溶液表观黏度逐渐降低。质量浓度越高,溶液的储能模量(G')和损耗模量(G″)越大。由动态剪切实验数据,计算得到第一法向应力差(N1)。随质量浓度增加,聚合物溶液的N1逐渐增大;随矿化度增加,聚合物溶液的N1出现不同盐敏感区域,说明不同结构类型的驱油聚合物溶液对矿化度的弹性响应不同。研究结果为高温高盐油藏聚合物驱剂的选择及开发提供了理论参考。     

Spectral and thermal characterization of polyaniline–oxalic acid salt

Polyaniline–oxalic acid salts were prepared at 5 and 30°C by chemical polymerization of aniline using different concentration of oxalic acid. Polyaniline base was obtained from the corresponding polyaniline salt by dedoping using aqueous ammonium hydroxide solution. Conductivity measurements, elemental analysis, Infrared, electronic absorption, electron paramagnetic resonance spectral, and thermogravimetric analysis were performed on the polyaniline salts and bases. Composition and the extent of dopant in polyaniline salt systems where determined. The value of composition of polyaniline: oxalic acid is 4: 1.6 and the polymer yield is around 66%. The value of conductivity, polymer yield and composition of polyaniline–oxalic acid salt is independent of concentration of oxalic acid used and also the synthesis temperature. The results are compared with polyaniline–hydrochloride salt prepared by chemical polymerization. The conductivity of polyaniline–oxalic acid salt is three orders of magnitude lower than that of polyaniline-hydrocholoride salt. © 1995 John Wiley & Sons, Inc.     

Preparation,swelling behaviors and application of polyacrylamide/attapulgite superabsorbent composites

A series of superabsorbent composites, polyacrylamide/attapulgite (PAMA), were prepared from acrylamide (AM) and attapulgite micropowder in aqueous solution, using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator and then saponified with sodium hydroxide solution. This paper focuses on swelling behaviors of the PAMA superabsorbent composites in various saline solutions. The results indicate that saline solutions can weaken the swelling abilities of the PAMA compsites greatly. Water absorbency of the PAMA composites with 20 and 40 wt% attapulgite in aqueous chloride salt solutions has the following order: Li⁺ = Na⁺ = K⁺, Mg²⁺ > Ca²⁺ = Ba²⁺ all through the range of concentration investigated. However, swelling properties of the composites are complicated in CuCl_2(aq), AlCl_3(aq) and FeCl_3(aq) solutions and are related to saline solutions concentration. The deswelling behavior of PAMA composites is more obvious in univalent chloride salt solutions than in divalent and trivalent ones. The influence of kind and valence of anions on swelling ability of the composites is limited and almost the same. Moreover, reswelling capability, practical water retention ability in sand soil of the composites and the effect of pH on water absorbency of the PAMA composites were investigated. The PAMA composite shows good water retention and reswelling ability in sand soil, and may be used as a recyclable water‐managing material for the renewal of arid and desert environment. Copyright © 2006 John Wiley & Sons, Ltd.     

纳米阻燃氢氧化镁/聚氧化乙烯复合聚合物电解质

合成了纳米氢氧化镁作为聚氧化乙烯(PEO)基聚合物电解质的增塑剂和阻燃剂,并对其进行X射线衍射(XRD)、透射电子显微镜(TEM)和热重(TG)分析研究.制得的氢氧化镁为片状六方晶体,尺寸在50-80nm之间,纳米氢氧化镁在340℃时开始热分解.对纳米氢氧化镁/PEO复合聚合物电解质的电化学研究结果显示:纳米氢氧化镁/PEO复合聚合物电解质的离子电导率随着添加纳米氢氧化镁的质量分数的增加先增大后减小,其在5%-10%之间时,复合聚合物电解质的离子电导率达到最大值.纳米氢氧化镁的添加使复合聚合物电解质的阳极氧化电位有一定程度的提高,纳米氢氧化镁具有改善PEO阳极抗氧化能力的作用.