Proton Diffusion andT1Relaxation in Polyacrylamide Gels: A Unified Approach Using Volume Averaging

The structure of polyacrylamide gels was studied using proton spin–lattice relaxation and PFG diffusion methods. Polyacrylamide gels, with total polymer concentrations ranging from 0.25 to 0.35 g/ml and crosslinker concentrations from 0 to 10% by weight, were studied. The data showed no effect of the crosslinker concentration on the diffusion of water molecules. The Ogston–Morris and Mackie–Meares models fit the general trends observed for water diffusion in gels. The diffusion coefficients from the volume averaging method also fit the data, and this theory was able to account for the effects of water-gel interactions that are not accounted for in the other two theories. The averaging theory also did not require the physically unrealistic assumption, required in the other two theories, that the acrylamide fibers are of similar size to water molecules. Contrary to the diffusion data,T₁relaxation measurements showed a significant effect of crosslinker concentration on the relaxation of water in gels. The model developed using the Bloch equations and the volume averaging method described the effects of water adsorption on the gel medium on both the diffusion coefficients and the relaxation measurements. In the proposed model the gel medium was assumed to consist of three phases (i.e., bulk water, uncrosslinked acrylamide fibers, and a bisacrylamide crosslinker phase). The effects of the crosslinker concentration were accounted for by introducing the proton partition coefficient,K^eq, between the bulk water and crosslinker phase. The derived relaxation equations were successful in fitting the experimental data. The partition coefficient,K^eq, decreased significantly as the crosslinker concentration increased from 5 to 10% by weight. This trend is consistent with the idea that bisacrylamide tends to form hydrophobic regions with increasing crosslinker concentration.     

Effects of continuous water flow on the swelling properties of polyelectrolyte hydrogels

We report the swelling behavior of a polyelectrolyte copolymer gel in water, which consists of poly(N-isopropylacrylamide) and sodium acrylate. The diameter of the cylindrical gels was measured at room temperature under a continuous flow of solvent water (equivalent to an infinite amount of water; open system). After a sufficient water flow, the diameter of the gel in the limited amount of water (closed system) was measured as a function of the temperature. The gel in the open system was found to shrink as a result of the continuous flow of water, and the gel in the closed system began to swell again at the phase transition point by increasing the temperature. The effects of the degree of initial ion exchange by the water flow on the macroscopic swelling behavior were discussed in terms of the exchange of counterions (the ion dissociation of carboxyl groups) and of the creation and destruction of intermolecular forces (hydrogen bonding). It was concluded that the amount of solvent water determines the environmental variables, such as the pH and ion concentration, which affects the swelling properties of polyelectrolyte hydrogels; intermediate re-swollen states can be observed in a closed system.Received: 8 January 2004, Published online: 6 July 2004PACS: 82.35.Jk Copolymers, phase transitions, structure - 82.70.Gg Gels and sols - 82.30.Rs Hydrogen bonding, hydrophilic effects     

Synthetic–Natural Bionanocomposite Hydrogels on the Basis of Polyvinyl Alcohol and Egg White

A series of bionanocomposite hydrogels composed of polyvinyl alcohol, a synthetic polymer, and egg white, a natural protein containing material, were prepared by the freezing- thawing cyclic method. Na-montmorillonite nanoclay (Na-MMT), as a crosslinker and reinforcing agent, with 0, 5, 10, and 15 wt% loadings (based on the dried mass of the bionanocomposite hydrogel) was incorporated in the polyvinyl alcohol and egg white hydrogel matrix. The microstructural characteristics of the prepared bionanocomposite hydrogels were characterized by the X-ray diffractometry, transmission electron microscopy, Fourier transform infrared spectroscopy, scanning electron microscopy and gel fraction measurements. Thermal and mechanical properties of the samples were also studied using differential scanning calorimetry and dynamic mechanical-thermal analysis. The swelling and drying kinetics and mechanisms of the bionanocomposite hydrogels were also studied. The bionanocomposite hydrogels had an exfoliated Na-MMT morphology with an appropriate dispersion of nanoclay layers in the hydrogel matrix. The results showed that the Na-MMT platelets acted as crosslinkers and created a hydrogel network with a smaller pore size in the bio-nanocomposite hydrogels, compared with the clay-free hydrogel. The obtained thermal and mechanical properties confirmed the reinforcing effect of the nanoclay in the bionanocomposite hydrogels. The swelling and drying rates of the bionanocomposite hydrogels exhibited an inverse dependency on the nanoclay loading. In general, it was concluded that the prepared bionanocomposite hydrogels could be used as appropriate biomaterials in biomedical applications, especially in drug delivery, tissue engineering and wound care.     

Swelling and Gelation Time Behavior of Sulfonated Polyacrylamide/Chromium Triacetate Hydrogels

A hydrogel was prepared by crosslinking of aqueous solutions of sulfonated polyacrylamide/chromium triacetate for use in water shut-off operations in oil reservoirs. The effects of pH, salinity, retarder and temperature, as well as co-polymer and crosslinker concentration, on the gelation time were investigated. The results indicated that as temperature increased, gelation occurred more rapidly. The activation energy was measured as about 86 kJ/mol. The effects of initial pH and retarder on the gelation time were also examined. The results showed that addition of retarder and increasing of pH increased and decreased the gelation time, respectively. The increase of co-polymer concentration in solution increased the gel swelling. However, the increase of crosslinker concentration decreased the gel swelling. In the presence of electrolytes, the gel swelling decreased by about 80%. Finally, some usable practical recommendations are offered for the gelling systems in reservoirs.     

Study on the Dynamic Rheometry and Swelling Properties of the Polyacrylamide/Laponite Nanocomposite Hydrogels in Electrolyte Media

Polyacrylamide/laponite/chromium triacetate nanocomposite (NC) hydrogels were prepared by incorporation of the laponite nanoparticles in partially hydrolyzed polyacrylamide followed by cross-linking of their aqueous solutions with chromium triacetate. Influence of nanoparticle, cross-linker, polymer concentrations, and gelation media (water) temperature, salinity, and rheometer frequency on the viscoelastic behavior of the NC hydrogels were studied by probing the network properties. In addition, swelling behaviors of these NC gels in tap and oil reservoir water were evaluated. According to dynamic rheometry of the gelation process, the limiting storage modulus of the NC gels increased with increasing laponite content. The addition of laponite into the polyacrylamide gelling system increased their viscous properties more strongly than the elastic properties. The ultimate elastic modulus of the NC gels increased with increasing water salinity and temperature. Increasing rheometer frequency during gelation retarded the sol–gel transition and decreased the ultimate elastic modulus. The equilibrium swelling ratio of the NC hydrogels in tap water decreased with increasing laponite content. The salt sensitivity of the NC gels in oil reservoir water slightly decreased with increasing laponite content. These results suggest the superiority of the hydrolyzed polyacrylamide (HPAM)/chromium acetate/laponite NC hydrogels for water shut-off applications in oil reservoirs as compared with unfilled HPAM gels.     

Gelatin/Montmorillonite and Gelatin/Polyvinyl Alcohol/Montmorillonite Bionanocomposite Hydrogels: Microstructural,Swelling and Drying Properties

Abstract

Gelatin/montmorillonite bionanocomposite hydrogels containing 0, 5 and 10?wt.% of montmorillonite were prepared via two different techniques, either a cooling or drying method. In addition, gelatin/polyvinyl alcohol/montmorillonite bionanocomposite hydrogels having gelatin/polyvinyl alcohol ratios of 1/1, 1/2 and 2/1, loaded with 0, 5 and 10?wt.% of montmorillonite, were prepared via a cyclic freezing-thawing technique. The microstructural properties of both types of the prepared bionanocomposite hydrogels were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The gel fraction, swelling behavior and drying kinetics of all prepared bionanocomposite hydrogels were also studied. The XRD and SEM results showed a porous structure with a possible exfoliated morphology for both types of the prepared bionanocomposite hydrogels. In addition, the gel fraction of the bionanocomposite hydrogels increased and a more entangled and crosslinked network with a decreased pore size was obtained by increasing the loading level of montmorillonite for both types of the bionanocomposite hydrogels. The swelling ratio and drying rate of both types of the bionanocomposite hydrogels could be increased by decreasing the PVA portion or MMT loading level, while the swelling and drying ability of the gelatin/montmorillonite bionanocomposite hydrogels prepared via the cooling method was higher than those of the corresponding samples prepared via the drying method.     

Pore-size distributions of cationic polyacrylamide hydrogels of different compositions maintained at the same swelling capacity

Pore-size distributions have been measured for cationic acrylamide-based hydrogels of different compositions maintained at the same swelling capacity (27.8 ± 0.7 g swollen gel/g dry gel) by varying the ionic strength of the surrounding solution. Swelling equilibria were measured at about 6°C in pure water and aqueous sodium azide solutions ranging in concentration from to 10^?3 to 10^?1 M. The mixed-solute-exclusion method (introduced by Kuga) was used to obtain the experimental solute-exclusion curve, which represents the amount of imbibed liquid inside the gel inaccessible to a solute of radius r. The pore-size distribution was obtained by using Casassa's Brownian-motion model and numerically solving the Fredholm integral equation. The modes of the pore radii range from 20.4 to 47.1 Å for acrylamide-based hydrogels containing varying amounts of cationic comonomer (1.5 and 4.0 %M), crosslinker (0.3 and 1.0 %C), and initial concentration of total monomer (15 and 35 % T).     

Preparation and Characterization of Hyaluronic Acid Hydrogel Blends with Gelatin

Porous hydrogel blends composed of various weight ratios of hyaluronic acid (HA) and gelatin (Gel) were fabricated by a freeze-drying method. The 1-ethyl-3(3-dimethylaminopropyl) carbodiimide (EDC) was used as a crosslinker to improve their biostability. The effect of the component and crosslinker content on the morphology, swelling ratio (SR), and mechanical properties were investigated. The results indicated that after chemical crosslinking the hydrogel showed a smoother and denser surface with less pores and a crosssection with smaller pores than that without crosslinking. The crosssection morphologies of the HA/Gel hydrogels changed from a sheet-like appearance to a fiber-like appearance with increasing HA content. The addition of HA improved the swelling property, but reduced the compressive strength. As the crosslinker content increased, the SR decreased; however, the compressive strength of the HA/Gel hydrogels increased. All these results suggest that HA/Gel hydrogel crosslinked by EDC is a potential candidate for tissue engineering scaffolds.     

Effect of κ-carrageenan on volume phase transition for polyacrylamide (PAAm) hydrogel using the fluorescence technique

Steady-state fluorescence (SSF) technique was employed for studying swelling of polyacrylamide (PAAm) gels with various content of κ-carrageenan (κC). Disc shaped composite hydrogels were prepared by free-radical crosslinking copolymerization of acrylamide (AAm) with various amounts κC. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as crosslinker and initiator, respectively. Pyranine was introduced as a fluorescence probe. Fluorescence intensity of pyranine was monitored during in situ swelling processes of composite gels. It was observed that fluorescence intensity values decreased as swelling is proceeded. Li–Tanaka equation was used to determine the swelling time constants, τ and cooperative diffusion coefficients, D from intensity variations during the swelling processes. It was shown that swelling time constants, τ decreased and diffusion coefficients, D increased as the κC content in the composites are increased.     

Dynamic Theory of Die Swell for Entangled Polymeric Liquids in Tube Extrusion: Correlations of Total and Ultimate Extrudate Swell Effects to Growth Time, Shear Stress and Aspect Ratio Under the Free States

利用挤出胀大动力学理论研究稳态剪切流下HDPE 和PBD液体的挤出胀大行为,建立了自由动态下线团回复和挤出胀大增长时间的回复机制和动力学. 结果表明在自由回复过程中自由线团回复和挤出物胀大增长可分为两个区域(瞬间和推迟区)、三个增长阶段(瞬间、推迟和最终阶段). 证明了自由线团回复和挤出胀大增长可表征为增长时间、剪切应力和长径比的函数。从而从动力学理论推倒出了三种挤出胀大效应(瞬间、推迟和最终)同分子结果参数和挤出操作条件间的相关性. 并建立了总合(TESE)和最终(UESE)两组挤出胀大效应的普适方程.     

Gelation Rheology and Water Absorption Behavior of Semi-Interpenetrating Polymer Networks of Polyacrylamide and Carboxymethyl Cellulose

Gelation rheology and swelling behavior of novel semi-interpenetrating polymer network (semi-IPN) hydrogels based on polyacrylamide are described. These hydrogels were prepared by solution cross-linking of partially hydrolyzed polyacrylamide and carboxymethyl cellulose (CMC), using chromium triacetate. Effects of CMC content on the gelation process and swelling behavior in tap water and different electrolyte solutions were investigated. Study of the gelation behavior using dynamic rheometery showed that the limiting storage modulus of the semi-IPN gels increased with increasing CMC content. Enhancement of storage modulus was more than two times for the semi-IPN gels containing 50 wt% CMC. It was also found that increasing the CMC content decreased the loss factor, indicating that the elastic properties of this gelling system increase more strongly than the viscous properties. The swelling ratio of the semi-IPN gels in tap water, NaCl and CaCl₂ solutions, and synthetic oil reservoir water slightly decreased as the concentration of the CMC increased. The improved storage modulus and slightly decreased swelling capacity in oil reservoir water make these semi-IPN hydrogels potentially good candidates for excess water treatment in oil recovery applications.     

Studies on mechanical and swelling behavior of polymer networks on the basis of the scaling concept. 6. Gels immersed in polymer solutions

In order to describe the mechanical and swelling behavior of gels immersed in polymer solutions, theoretical considerations based on both classical and scaling theories are discussed and compared with experimental findings. Three situations are studied: (1) the gel is separated from the surrounding solution by a semipermeable membrane; (2) the gel is immersed in the semidilute solution of a chemically identical polymer; (3) the gel is directly immersed in the semidilute solution of a chemically different polymer. An attempt is made to take into account the effect of the penetrating polymer on the elastic modulus and the swelling pressure of the gel. Experimental data referring to chemically cross-linked poly(vinyl alcohol) and poly(vinyl acetate) networks are presented. It was found that the concentration of the free chains inside moderately cross-linked networks may be considerable even for polymers having relatively long chains (27,000 < < M _n < 130,000). Experimental results indicate that the presence of free chains only slightly alters the elastic modulus; however, the swelling pressure is considerably affected by the penetrating polymer. The analysis of mechanical and equilibrium deswelling measurements carried out on several series of gel homologues shows that scaling theory satisfactorily describes the experimental data.     

Synthesis and Properties of Polyacrylamide-Based Conducting Gels with Enhanced Mechanical Strength

A nanocomposite conducting hydrogel, polyacrylamide/MWNT/clay (abbreviated as PAM/MWNT/clay), prepared through in situ free radical aqueous polymerization and crosslinked by both clay, as a functional physical crosslinker, and N,N′-methylenebisacrylamide (MBA) as a chemical crosslinker, is reported. The morphology of the gels was characterized by scanning electron microscopy (SEM). The mechanical properties and electrical conductivity were also studied. The results show that the prepared hydrogels had the expected chemical components, with a highly porous structure, and the gels also showed high mechanical strength. The mechanical strength and electrical conductivity value increased with increasing content of multi-walled nanotube (MWNT), and decreased with increasing content of water.     

缠结高分子液体在管中挤出胀大动力学理论：一组新的增长和最终挤出胀大比方程

基于O-W-F本构方程和自由回复机制，从Poioeuille流出发建立了一种新的缠结高分子液体挤出胀大动力学理论，该理论能有效地预测高分子流体的动静态挤出胀大行为同高分子粘弹性参数和成型条件间的相关性. 基于稳态剪切量可分解为自由“回复线团”和“不可回复热耗”两部分事实，定义了一个稳态剪切下自由“回复线团”和“不可回复热耗”的配分函数和它们两者间分配指数上可回复和不可回复构象分数，从而在理论上得到了瞬时、推迟和最终三者可回复形变量和可回复线团量同配分函数、分配指数上可回复构象分数、分子粘弹性参数和成型条件     

Polyelectrolyte gels in poor solvent: Elastic moduli

We study theoretically using scaling arguments the behavior of polyelectrolyte gels in poor solvents. Following the classical picture of Katchalsky, our approach is based on single-chain elasticity but it accounts for the recently proposed pearl necklace structure of polyelectrolytes in poor solvents. The elasticity both of gels at swelling equilibrium and of partially swollen gels is studied when parameters such as the ionic strength or the fraction of charged monomers are varied. Our theory could be useful to interpret recent experiments performed in Strasbourg that show that if identical gel samples are swollen to the same extent at different pH the sample with the highest charge has the lowest shear modulus. Received 7 April 2000     

Influence of different alcohols on the swelling behaviour of hydrogels

The swelling equilibrium of cross-linked poly(N-isopropylacrylamide) (PNIPAAm) hydrogels in alcohol solutions as a function of temperature, alcohol concentration, kind of alcohol (C₁OH–C₃OH) and gel properties was investigated experimentally. Additionally, the swelling degree as a function of the alcohol concentration was modelled with the UNIQUAC-Free Volume model in combination with the Phantom Network theory. The experiments show that, in pure water, the transition temperature is between 303.15 and 308.15?K depending on the properties of the gel and hence on the polymerization conditions. The transition from a swollen to a shrunken state is caused by the polymeric network and the change of polymer chain localization. In a system with hydrogel?+?water?+?alcohol, the swelling degree decreases with increasing alcohol concentration until the shrunken state is reached and increases again by further addition of alcohol at constant temperature. With increasing carbon number of the alcohols, the transition from a swollen to a shrunken state and vice versa shifts to lower concentrations at constant temperature. The use of the UNIQUAC-Free Volume model with Phantom Network theory leads to results in good agreement with the experimental data.     

Preparation and Swelling Behavior of Partially Hydrolyzed Polyacrylamide Nanocomposite Hydrogels in Electrolyte Solutions

In this research, nanocomposite hydrogels were prepared by cross‐linking of partially hydrolyzed polyacrylamide/sodium montmorillonite aqueous solutions with chromium triacetate. The gelation process and influence of nanoclay content and salt concentration on swelling behavior were investigated. Study of gelation behavior using dynamic rheometry method showed that increasing the nanoclay content decreases the storage modulus, due to the partial adsorption of polymer chains onto the clay surface and ionic interaction between negative layers of sodium montmorillonite and Cr.³⁺ By increasing the cross‐linker concentration of the gelation system, the viscous energy dissipation properties of the nanocomposite gel decreases. Swelling ratio of the nanocomposite gels in distilled water decreased as the concentration of the nanoclay increased. However, nanocomposite gels showed lower salt sensitivity in electrolyte media compared with unfilled gels.     

Fracture of a biopolymer gel as a viscoplastic disentanglement process

We present an extensive experimental study of mode-I, steady, slow crack dynamics in gelatin gels. Taking advantage of the sensitivity of the elastic stiffness to gel composition and history we confirm and extend the model for fracture of physical hydrogels which we proposed in a previous paper (Nature Mater. 5, 552 (2006)), which attributes decohesion to the viscoplastic pull-out of the network-constituting chains. So, we propose that, in contrast with chemically cross-linked ones, reversible gels fracture without chain scission.     

Static and time-dependent properties of polymer gels around the volume phase transition

Recent progress in the study of the volume phase transition of polymer gels is reviewed. The phenomenological theories of swelling equilibrium and phase transition of gels are summarized, and some basic experimental results on poly-N-isopropylacrylamide (NIPA) gels are compared with the prediction from these theories. Special attention is paid to the elastic properties of the gel network near the volume phase transition. The effect of external stresses on the swelling and the phase transition is analyzed. Some anomalous and unique characteristics revealed in NIPA gels such as shape- and size-dependent swelling and phase transition properties, curious phase coexistence, and domain structure are presented. Experimental results on some time-dependent phenomena such as phase separation, spinodal decomposition, and pattern formation are also presented and discussed. Some problems inherent to gels from biological bodies are briefly discussed.     

Synthesis and Properties of Tannic Acid-Based Hydrogels

Hydrogels were synthesized by using tannic acid (TA) as a chemical cross-linker for the copolymer of allylglycidyl ether and acrylamide. The swelling ratio of the hydrogels increased with increasing amount of TA and decreased with increasing amounts of allylglycidyl ether. The hydrogels exhibited pH sensitivity; the swelling ratio increased with pH. Adsorption experiments of the hydrogel for Cu (II) ions suggested that the hydrogels can be used as an adsorbent for removal of Cu (II) heavy metal ions from dilute aqueous solutions.