Phase transition in polymer gels due to local heating by illumination of light

The volume phase transition in gels induced by visible light and its related properties are presented, the mechanism of which is based on local heating of a polymer network by illumination of light. The gels consist of a covalently cross-linked copolymer network of thermosensitive N-isopropylacrylamide and a chromophore. Without light illumination, the gel volume changes sharply, but continuously at approximately 34°C when the temperature is varied. At a fixed temperature of an appropriate value, a discontinuous volume transition is observed when the light intensity is gradually changed. The phase transitions can be understood in terms of the temperature increment at the immediate vicinity of polymer chains due to the local heating via light absorption and subsequent thermal dissipation of light by the chromophore. The results can be qualitatively described by the Flory-Huggins mean-field equation of state of gels. In order to make clear the mechanism of the light-induced phase transition in the present system, we measured the light transmitting properties and the swelling as well as shrinking kinetics. These preliminary results are described semi-qualitatively by making use of a simple phenomenological model.     

Mri measurements of T1, T2 and D for gels undergoing volume phase transition

Gels consist of crosslinked polymer network swollen in solvent. The network of flexible long-chain molecules traps the liquid medium they are immersed in. Some gels undergo abrupt volume change, a phase transition process, by swelling-shrinking in response to external stimuli changes in solvent composition, temperature, pH, electric field, etc. We report that during volume phase transition changes of NMR longitudinal relaxation time T(1), NMR transverse relaxation time T(2), and diffusion coefficient D of the PMMA gel, and D of the NIPA gel. We describe how the gels were synthesized and the reason of using the snapshot FLASH imaging sequence to measure T(1), T(2), and D. Since T(1), T(2) and D maps have identical field of view and data are extracted from identical areas from their respective maps, these values can be correlated quantitatively on a pixel-by-pixel basis. Thus a complete set of NMR parameters is measured in-situ: the gels are in their natural state, immersed in the liquid, during the phase transition. The results of spectroscopic method agree with that of snapshot FLASH imaging method. For the PMMA gel T(1), T(2) and D decrease when gels undergo volume phase transition between deuterated acetone concentration of 30% and 40%. At its contracted state, T(1) is reduced to a little less than one order of magnitude, T(2) over two orders of magnitude, and D over one order of magnitude, smaller from values of PMMA gel at the swollen state. At an elevated temperature of 54 degrees C the thermosensitive NIPA gel is at a contracted state, with its D reduced to almost one order of magnitude smaller from that of the swollen NIPA at room temperature.     

Temperature Effect on the Elasticity of Acrylamide-n-Isopropylacrylamide Copolymers

Acrylamide (AAm) – N-isopropylacrylamide (NIPA) copolymers were prepared via free radical crosslinking copolymerization with various weight percentages (wt%) of AAm and NIPA. The temperature dependence of the compressive elastic modulus, G, and toughness, U_T, of the PAAm- NIPA copolymers due to a volume phase transition was found using a compressive testing technique. It was observed that the compressive elastic modulus increased comprehensively when the temperature was increased between 30°C and 60°C. The PAAm- NIPA copolymers presented higher values of the compressive elastic modulus than pure NIPA above the lower critical solution temperature (LCST) (NIPA exhibits a volume phase transition from hydrophilic to hydrophobic in water at 31°C) and their compressive elastic modulus and toughness had a strong temperature dependence.     

Thermo-sensitive N-n-propylacrylamide gels

Thermo-sensitive gels were prepared by irradiating aqueous solutions of poly(N-n-propylacrylamide) (NNPA) and its copolymers with acrylic acid (AA) with γ-rays from a ⁶⁰Co source. The equilibrium swelling volume of the gel in water was determined as a function of temperature. NNPA gel showed a discontinuous and reversible volume phase transition. The transition temperature and the volume change at the transition decreased with irradiation time. The transition temperature was approximately 12°C lower than that of poly(N-isopropylacrylamide) gel. A discontinuous volume transition was also observed in the copolymer gels of NNPA and AA. The dependence of the transition temperature on the concentration of carboxyl groups revealed a marked difference depending on whether they were protonated or dissociated. For gels having side groups of COONa, the transition temperature rose and the volume change at the transition was elevated as the COONa concentration increased. In contrast, an increase in the COOH concentration resulted in a decrease in the transition temperature. These results are discussed in terms of an equation of state constructed based on scaling theory.     

Swelling Behavior of Physically Cross-Linked Gelatin Gels in Varied Salt Solutions

A series of physically cross-linked gelatin networks were prepared and the effects of salt concentration and chemical valence of the salt ions on the swelling properties of the gelatin gels were studied in detail. It was found that the swelling behaviors as polyelectrolytic or polyampholytic gels depended on the charge distribution on the gelatin chains. The swelling capacity of polyelectrolytic gels with excess positive charges decreased with an increase in salt concentrations. However, the swelling capacity of polyelectrolytic gels with excess negative charges showed a nonmonotonic change with salt concentration. For polyampholytic gels, the equilibrium swelling ratio increased monotonously with the concentration of NaCl and CaCl₂ solutions_. On the other hand, the swelling capacities of the polymer networks increased first and were then followed by a decrease with an increase in the concentration of AlCl₃ solution. Moreover, the swelling kinetics of the gelatin gels in varied salt solutions with different concentrations was also investigated.     

高分子凝胶体积相变中的氢键作用

我们把关联模型(association models)推广应用到高分子凝胶体系,研究高分子与溶剂分子间的氢键和溶剂分子与溶剂分子间的氢键在高分子凝胶体积相变中的作用.首先通过分析凝胶体积分数与温度的关系发现,由于两种氢键作用,随着温度变化高分子凝胶出现连续、不连续体积相变,结果表明在体积相变过程中两种氢键都起着重要作用.其次,对不同氢键分数条件下的旋节线的研究发现,对于高分子凝胶体积相变中出现的UCST和LCST(上临界共溶温度和下临界共溶温度)现象也是由于高分子与溶剂分子间氢键和溶剂分子与溶剂分子间氢键共同作用的结果.     

Temperature Controlled Sequential Gelation in Composite Microgel Suspensions

Depending on the volume fraction and interparticle interactions, colloidal suspensions can exhibit a variety of physical states, ranging from fluids, crystals, and glasses to gels. For microgel particles made of thermoresponsive polymers, both parameters can be tuned using environmental parameters such as temperature and ionic strength, making them excellent systems to experimentally study state transitions in colloidal suspensions. Using a simple two‐step synthesis it is shown that the properties of composite microgels, with a fluorescent latex core and a responsive microgel shell, can be finely tuned. With this system the transitions between glass, liquid, and gel states for suspensions composed of a single species are explored. Finally, a suspension of two species of microgels is demonstrated, with different transition temperatures, gels in a sequential manner. Upon increasing temperature a distinct core–sheath structure is formed with a primary gel composed of the species with lowest transition temperature, which acts as a scaffold for the aggregation of the second species.     

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.     

Gelation,Network Structure and Properties of Physically Crosslinked Gelatin Gels: Effect of Salt Cation Valence

A series of physically cross-linked gelatin networks with and without salts (NaCl, CaCl₂ and CrCl₃) were prepared. The effect of the valence of the cations at the same concentration on the gelation of the gelatin was investigated by a rheometer. It was found that both the gelation temperature and the distance between crosslinks of the networks increased with an increase in valence of the cations. However, the opposite trend was observed for the storage modulus of the gels. Moreover, the influences of the valence and concentration of cations on the swelling and thermal behaviors of the gelatin composite films were studied in detail. It was generally observed that the equilibrium swelling ratio (ESR) decreased with salt concentration for all three cations following the trend ESR for Cr³⁺ <Ca²⁺ <Na⁺. However, the glass transition temperature (T_g) showed an opposite dependence on the valence and concentration of the cations. The relationships between the network structure and the properties of the gelatin composite films are discussed based on two effects (shielding and crosslinking effect), caused by the introduction of the salts.     

Characteristics of tissue equivalent gels intended for passive test procedures of ultrasonic scanner performance

The ultrasonic qualities of hydrophobic gels with various cross-linked internal structures were investigated. It was found that thermally and mechanically stable gels with ultrasonic properties resembling many mammalian tissues can be produced and may be useful as a reference among hospital clinics in quality assurance tests and training of personnel on diagnostic ultrasound scanners. This paper summarizes some of the results of these studies.     

CRITICAL SCALING THEORY OF GENERALIZED PHASE TRANSITION AND ITS UNIVERSALITY

Generalized phase transition (GPT) refers to the transition process of material systems from one steady-state to another. It includes equilibrium phase transition (EPT) and nonequilibrium phase transition (NPT), and phase transitions intermediate between them. In this paper some results on the study of critical scaling relations of the NPT and EPT are obtained. We developed the critical scaling theory of EPT and advanced a universal critical scaling theory of GPT. The critical scaling relations(scaling laws) has more niversality. The critical exponents calculated from our theory are identical with the results of experiments and other theories about EPT and NPT systems. Because the basic model of the theory does not depend on the concrete material system, it has a certain unversality. Its results thus can be applied to generlized phase transition systems, such as the electrorheological fluid and magnetorheological fluid systems.     

Swelling of cross-linked polyelectrolyte gels

A model of a cross-linked polyelectrolyte gel has been examined using Monte Carlo simulations. The simple model contained a charged defect-free network represented by linked charged beads and explicit counterions. Pressure-density relations for the polyelectrolyte gel, a corresponding non-ionic polymer gel, and several partly or fully degraded gels have been determined. The polyelectrolyte gel displayed a very large swelling capacity, in agreement with experiments. The swelling mechanism and chain properties are discussed and foundations of current theories on gel swelling are examined.     

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     

Morphology and chain dynamics during collapse transition of PNIPAM gels studied by combined imaging, relaxometry and 129Xe spectroscopy techniques

The temperature-induced shape transition of poly(N-isopropylacrylamide) gels of different cross-link densities was investigated by a combination of NMR techniques allowing the characterization of both the macroscopic collapse as well as the changes on a molecular scale related to the expulsion of water from the gel network. The proton-containing gel phase was visualized by swelling in heavy water, and the volume change was monitored by proton imaging for cross-link densities between 0.5% and 2.5%. Above the transition temperature of 35 degrees C, gel collapse led to a volume change of up to a factor of 17 for the gel of smallest cross-link density. Two spectral lines of 129Xe are found in the gel state and are assigned to the hydrophobic and hydrophilic parts of the network. In the collapsed state, the hydrophobic peak shows a strong shift while the hydrophilic peak disappears. A considerable shortening of both T1 and T2 of the gel protons upon collapse was found at a field of 4.7 T. At lower fields, the effect becomes more pronounced and qualitatively different dispersion behaviors between the swollen and the collapsed states are observed.     

Critical swelling of particle-encapsulating vesicles

We consider a ubiquitous scenario where a fluctuating, semipermeable vesicle is embedded in solution while enclosing a fixed number of solute particles. The swelling with increasing number of particles or decreasing concentration of the outer solution exhibits a continuous phase transition from a fluctuating state to the maximum-volume configuration, whereupon appreciable pressure difference and surface tension build up. This criticality is unique to particle-encapsulating vesicles, whose volume and inner pressure both fluctuate. It implies a universal swelling behavior of such vesicles as they approach their limiting volume and osmotic lysis.     

软凝聚态物质物理学

软物质是指其某种物理性质在小的外力作用下能产生很大变化的凝聚态物,典型的例子包括液晶、高分子体系、胶体、微乳液等。软物质的结构和性质主要不是由内能,而是由熵来决定,较通俗地介绍了软物质的概念,仔细分析了熵在软物质中所起的作用,同时详细介绍了聚合物体系、胶体及生物膜等几种典型的软物质,通过硫化橡胶和无管虹吸等十分有趣的例子。说明了聚合物对流变性质的影响;通过分析硬球胶体的相变及相分离等行为说明了熵力的概念;仔细分仔了电稳定胶体的相互作用,并介绍了DLVO理论以及近年来发现的对这一理论的偏离,特别是约束条件下同号带电胶球的长程吸引相互作用及其对此现象的一些解释;对生物膜也作了初步介绍。人们对软物质的研究和理解目前还处于一个非常原始的阶段,深入研究和理解软物质的各种性质必将促进人类对自然和人类自身的认识。     

Influence of environmental solution pH and microstructural parameters on mechanical behavior of amphoteric pH-sensitive hydrogels

Amphoteric hydrogels contain both ionizable acidic and basic groups attached on the polymer chains, which can change their volume in response to the slight alteration of the surrounding environmental p H. In this paper, a theory of equilibrium swelling of amphoteric p H-sensitive hydrogels which is an extension of the formalism proposed by Marcombe et al. and a new hybrid free-energy density function of amphoteric hydrogels composed of the Edwards-Vilgis slip-link model and the Flory-Huggins solution theory as well as the contributions of mixing the mobile ions with the solvent, and dissociating the acidic and basic groups are presented for the prediction of the influence of environmental solution p H, microstructural parameters and geometric constraints on mechanical behavior. The calculations were modeled on chitosan-genipin gels, and the results were compared to experimental data. Numerical calculations show that the model is able to predict the dependence of swelling on p H and crosslinker qualitatively well and quantitatively close to the experimental data. Each gel shows minimal swelling at low p H but an increase in swelling until a maximum was reached; for most of the p H range, a good fit was achieved except for where the maximum swelling occurs; for experimental data, the maximum swelling appears at about pH = 4 , but for modeled data the maximum swelling appears between pH = 4 and pH = 6 ; each gel swell decreasing with increasing crosslinker concentration was also successfully predicted. The calculated results also show that microstructural parameters and geometric constraints have a significant impact on the mechanical behavior of the amphoteric hydrogels; the gel swells less when the network is more densely entangled and the maximum swelling ratio of the gels under biaxial constraint is only about one-third of the maximum when the gels swell freely. The theory developed here is valuable for the design and optimization of a drug delivery system.     

Fractal Dimensions of κ-Carrageenan Gels during Gelation and Swelling

A photon scattering technique for research on the sol-gel and gel-sol transitions in κ-carrageenan-water systems with various carrageenan contents (CC) was utilized for characterizing the fractal dimensions during gelation and swelling. It was observed that the scattered photon intensity, I_sc, increased at all temperatures with an increase in the CC when I_sc was monitored against temperature. Additionally, the sol-gel transition temperatures were found to be much lower than the gel-sol transition temperatures, causing hysteresis of the phase transition loops. I_sc increased with an increase in CC at all test temperatures, which is attributed to the formation of a fractal-like carrageenan gel. After drying, the gels were used in swelling experiments where the gels were immersed in water at room temperature, reswelling to the original structure. It was observed that I_sc from the carrageenan gels increased as the CC was increased. The fractal dimension, d, during gelation was found to increase as the gelation temperature was increased. On the other hand, the d values during swelling decreased as the swelling time was increased.     

Temperature-sensitive poly(N-Isopropyl-Acrylamide) microgel particles: A light scattering study

We present a light scattering study of aqueous suspensions of microgel particles consisting of poly(N-Isopropyl-Acrylamide) cross-linked gels. The solvent quality for the particles depends on temperature and thus allows tuning of the particle size. The particle synthesis parameters are chosen such that the resulting high surface charge of the particles prevents aggregation even in the maximally collapsed state. We present results on static and dynamic light scattering (SLS/DLS) for a highly diluted sample and for diffuse optical transmission on a more concentrated system. In the maximally collapsed state the scattering properties are well described by Mie theory for homogenous hard spheres. Upon swelling we find that a radially inhomogeneous density profile develops.     

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.