Swelling and mechanical properties of cellulose hydrogels. III. Temperature effects on the swelling and compliance levels studied by dilatometry and 1H-NMR spectroscopy

The temperature dependence of the swelling and the creep compliance has been investigated for swollen isotropic cellulose hydrogels. The measurements were performed in a high precision type of dilatometer between 5 and 65°C. The thermal expansion of the gels in silicone oil (closed system) and the temperature dependence of the equilibrium swelling in water (open system) were studied. The influence of compressive stress in these experiments was also evaluated. The swelling level in equilibrium with water diminishes slightly with increasing temperature due to migration of water from the gel phase to the surrounding water phase. A secondary transition was found at 35°C where the temperature dependence of the swelling level is changed. When measured at constant gel composition the creep compliance of a highly swollen gel decreases with increasing temperature. The decrease is not, however, large enough for entropy elasticity to dominate over energetic elasticity. The energetic contribution f_U/f was determined to be 0.61 for a gel swollen to 3.9 g water/g dry gel (g/g) and 1.24 for a gel swollen to 1.05 g/g. The swelling and compliance data have also been analyzed in terms of a model where the gels are assumed to behave as a filler-reinforced rubbery network. The amorphous parts of the hydrogels are thus assumed to be described by the statistical theory for polymeric networks. In proton magnetic resonance studies of a gel swollen to 4.4 g/g the spin-lattice relaxation time T₁ was determined to be considerably longer than the spin-spin relaxation time T₂. T₂ has a maximum at 30°C. This maximum marks the onset (on the NMR time scale) of an exchange process between two types of proton species. These species are suggested to be specific hydration water and free gel water, respectively.     

Swelling and mechanical properties of cellulose hydrogels. I. Preparation,characterization, and swelling behavior

Cellulose hydrogels have been synthesized by reacting solutions of cellulose xanthate with different amounts of epichlorohydrin (0–24% w/w on cellulose) after which the cellulose was regenerated. The weight fraction of crystalline cellulose, determined by density measurements, decreases with the extent of chemical crosslinking and was estimated to vary between 30 and 42% for dry gels. The degree of equilibrium swelling in water of the prepared hydrogels varied between 3.05 and 6.33 g water/g dry gel (g/g). The degree of swelling decreases with increasing chemical crosslinking. As a result of the irreversible changes occurring during drying, the degree of swelling in water can be reduced down to 0.74 g/g. According to density gradient column measurements, the partial specific volume of water is 0.865 cm³/g at water contents below 0.13 g/g. It is suggested that water having this partial specific volume is the specific hydration water. At higher water contents, the partial specific volume of gel water equals the specific volume of bulk water. It is implicit in the interpretation of the density data in terms of a two state model of gel water that the crystallinity of cellulose is independent of the water content. Depending on the degree of swelling, heat treatment resulted in either an irreversible increase or decrease of the degree of swelling.     

Adsorption of ammonium and nitrate ions by poly(N‐isopropylacrylamide) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) gel in different states

The adsorption of ammonium and nitrate by temperature‐stimulus‐responsive poly(N‐isopropylacrylamide) (NIPA) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) (NIPA‐CH) gel in different states was investigated. Both the NIPA gel and NIPA‐CH gel could adsorb ammonium and nitrate in a swollen state (swollen gel) and a swelling state (swelling gel), and they adsorbed ammonium more than nitrate. When the gels were shrinking (shrinking gel), they could adsorb a little ammonium from solution, but when the gels were in a shrunken state (shrunken gel), they hardly adsorbed ammonium. The adsorption of both ammonium and nitrate increased for the swelling NIPA gel in comparison with the swollen gel. The NIPA‐CH gel was the opposite in this respect. The difference in the amounts of adsorption of ammonium and nitrate by the swollen and swelling NIPA‐CH gels was more significant than that of the NIPA gels. It was suggested that ions such as ammonium and nitrate could not diffuse into the gels freely. The adsorption of ammonium and nitrate was affected not only by the phase transitions of the gels but also by the electrical charges. The experimental results for the adsorption of ammonium and nitrate during the volume changes of the gels imply that if the gels are applied to the immobilization of microorganisms, they may improve mass transfer between the immobilization matrix and bulk liquid under cyclic temperature changes and promote reactions of the immobilized microorganisms, especially the nitrification of nitrifying bacteria immobilized by the NIPA‐CH gel. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2367–2372, 2005     

Thermoreversible hydrogels. II. Effect of some factors on the swelling behavior of N,N-dimethylacrylamide and n-butoxymethyl acrylamide copolymeric gels

A series of thermoreversible hydrogels are prepared from the various molar ratios of N,N-dimethylacrylamide (DMA), n-butoxymethyl acrylamide (nBMA), and N,N′-methylenebisacrylamide (NMBA). The influences of the amount of DMA in the copolymeric gels, temperature, and polymerization media on the swelling behaviors in water are investigated. Results indicate that the higher the DMA content in the hydrogel systems the higher the swelling ratio and the gel transition temperature. The effects of the gel thickness on the swelling ratio for DMA/nBMA copolymeric gels indicate that the equilibrium swelling time and diffusion coefficient for the thinner gel (1.5 mm) from the dried state to the completely swollen state are obviously faster than are those for the thicker gels (2.0 and 3.5 mm). The effects of the different polymerization media on the swelling ratio for DMA/nBMA copolymeric gels also show that the larger the solvent molecular size and the poor miscibility of the monomer and solvent the higher the swelling ratio and the diffusion coefficient. The drug release in these copolymeric gel systems are also investigated. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:909–916, 1997     

Influence of water on phase transition and rheological behavior of cellulose/ionic liquid/water ternary systems

The influence of water content on liquid crystalline (LC) gel formation and the rheological behavior of a ternary microcrystalline cellulose (MCC)/1‐ehtyl‐3‐methylimidazolium acetate (EmimAc)/water system was investigated using polarized optical microscopy (POM) and rheometry. POM indicated that the distinct water content range for forming a fully anisotropic LC gel with 14 wt % MCC was 4–10 wt %. Adding water to the MCC/EmimAc system resulted in enhanced complex viscosity and storage and loss moduli, and ultimately LC gel formation. Comparison of creep compliance vs. time revealed that the system without water showed representative viscoelastic behavior, while the time dependence of creep compliance disappeared as the water content increased, suggesting elastic‐solid behavior. Additionally, hydrogen bonding between cellulose and EmimAc weakened as water content increased, whereas the intra‐ and intermolecular hydrogen bonds of cellulose became stronger because of strong self‐association. This strong bonding caused aggregation, chain entanglement, and self‐supporting LC gel network formation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44658.     

Solute diffusion in swollen membranes. IX. Scaling laws for solute diffusion in gels

A scaling law was developed for the diffusion coefficient of spheroidal and ellipsoidal solutes in nonporous, equilibrium-swollen hydrogels. The law relates the solute diffusion coefficient to the solute size, the gel mesh size, and the gel equilibrium volume degree of swelling. The law was verified by appropriate data of low and high molecular weight solute diffusion through hydrogels such as swollen networks of poly(vinyl alcohol), poly(2-hydroxyethyl methacrylate), cellulose, and others. An additional scaling law was developed which relates the rate of release of a small or large molecule from an equilibrium swollen hydrogel with time and with morphological characteristics of the polymeric network.     

Synthesis of novel amphiphilic pH‐sensitive polyurethane networks through water‐in‐oil soap‐free emulsion polymerization process. I. Microstructural differences and swelling behaviors

pH‐sensitive amphiphilic networks are synthesized from urethane acrylate anionomer (UAA) precursor chains. The microstructures of these networks are very sensitive to the nature of and the amount of solvent used during crosslinking. Whereas dioxane forms relatively homogenous solution, water preferentially interacts with hydrophilic segment of UAA chains, causing the microphase separation between hydrophilic moieties and hydrophobic main chains. This microphase separation was locked‐in by crosslinking reaction, enhancing largely the hydrophilicity of UAA networks and the hydrophobic aggregation. The UAA gels, prepared with water (UAAG) and/or dioxane (UADG), exhibit quite different swelling behaviors in the same dissolution medium because of their completely different microstructures. The improved hydrophilicity of UAAG gels due to the hydrophilic/hydrophobic microphase separation is confirmed by measuring the contact angle to water. These microphase‐separated hydrophilic domains on UAA gel matrix, which are observed by scanning electron microscopy measurement, influence the mechanical property of dried UAA gels as well. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2115–2127, 2000     

Sulfonation studies of copolymers,graft copolymers,and polymeric gels using phase transfer catalysts

A new sulfonation method using phase transfer catalysts was applied to sulfonate a number of polymer matrices in an aqueous two-phase system. The polymer matrices included in this study are (1) styrene (Sty) and acrylonitrile (AN) copolymers with glycidyl methacrylate (GMA), (2) graft copolymers of cellulose with GMA, and (3) polystyrene and polyacrylate gels containing GMA as comonomer. The presence of polar groups such as AN in the polymer matrix makes the sulfonation easier. For cellulose graft copolymers, the extent of sulfonation was not much affected by the phase transfer catalysts, presumably due to the high polarity and high water uptake capacity of the cellulose base. For other polymer gels, the following factors influence the extent of sulfonation: (1) the method of gel synthesis, i.e., gels synthesized by delayed addition of GMA give a higher degree of sulfonation; (2) the nature of the crosslinking agent, i.e., gels with ethylene glycol diacrylate (EGDA) gives a higher degree of sulfonation than gels with divinylbenzene (DVB); (3) the pore size of the gels, i.e., gels with larger pore sizes gave higher degree of sulfonation; (4) increasing polarity of the backbone structure of gels favors increased sulfonation, e.g., MMA–GMA–EGDA gels give 54% sulfonation, whereas Sty–GME–EGDA gives only 38%.     

Swelling and mechanical properties of cellulose hydrogels. IV. Kinetics of swelling in liquid water

The swelling kinetics of cellulose hydrogels have been studied in experiments where partially dried gels were reswollen to equilibrium in liquid water. The swelling interval studied was from the dry state to 3.6 g water/g dry gel, and the temperature range was from 15 to 65°C. The experimental arrangement and the theoretical analysis was based on the unidimensional, unsteady sorption of water into a swelling sheet. The effects of sheet thickness, temperature and the initial degree of swelling were investigated. The integral sorption curves obtained were sigmoid in shape when plotted as the sorbed amount of water versus the square root of time. These anomalous, non-Fickian sorption curves were analyzed under the assumption that the anomalous behavior is due to a slow establishment of concentration equilibrium at the boundary surfaces. Each sorption curve can then be described by a combination of a mutual diffusion coefficient and a surface relaxation rate. The sigmoidicity of the sorption curves is accordingly determined by the ratio of a characteristic diffusion time to a characteristic surface relaxation time. More classical, Fickian-type behavior is then explained by an increase in this ratio. The experimental sorption curves were found to become more nearly classical as the sheet thickness, the temperature and/or the initial degree of swelling was increased. The relaxation process was found to be associated with a higher apparent activation energy than the diffusion process.     

Methacrylate hydrogels reinforced with bacterial cellulose

Composite hydrogels consisting of nanofibrous bacterial cellulose (BC) embedded in a biocompatible polymeric matrix of various methacrylates were synthesized by UV polymerization using the ‘ever‐wet’ technique. The effect of monomer(s) type and ratio, system dilution at polymerization, monomer(s) hydrophilicity, crosslink density and cellulose/hydrogel ratio was investigated. The effect of BC reinforcement on equilibrium swelling depends on whether the neat gel swells more when brought into contact with water. The major improvement achieved by introduction of 1%–2% BC concerns mechanical properties. Compared with neat gels, the storage shear modulus G′ increased by a factor 10‐20, and the loss part G″ also rose significantly. The compression modulus ranged from 2 to 5.5 MPa for composites swollen to equilibrium (20‐70 wt% water). The BC‐hydrogel composites are considered for application in the tissue engineering area. Copyright © 2012 Society of Chemical Industry     

The effect of PEG(400)DA crosslinking agent on swelling behaviour of acrylamide-maleic acid hydrogels

Summary Acrylamide (AAm)-maleic acid (MA) hydrogels with different monomer ratios were prepared in an aqueous solution by radical polymerization using a new crosslinking agent, polyethyleneglycol (400) diacrylate (PEG (400) DA) and also using N, N’-methylenebisacrylamide (NMBA) for comparison purpose. The hydrogels were characterized by acid group content and FTIR spectroscopy. Their swelling and deswelling behavior were studied as a function of maleic acid content, pH and crosslinking agent. Incorporation of MA in hydrogels significantly increased their swelling ability and their equilibrium degree of swelling (EDS) values changed between 100–269 g water/g polymer in water while AAm polymers swollen less (22–23 g water/g polymer). The AAm hydrogels showed Fickian type diffusion but the all AAm-MA hydrogels showed non-Fickian type behavior. Their swelling degree increased with the increase of pH of the external medium and an instantaneous increase was observed near a pH value of 7.0. The use of PEG (400) DA instead of NMBA as a crosslinking agent also increased the swelling rate and capacity of the gel. The swelling constant (K) and the diffusion coefficient (D) of hydrogels were also increased. The swelling-deswelling cycles in acidic-basic solutions showed that they could be used as pH responsive gels without any decrease in swelling capacity.     

pH-response of chitosan, κ-carrageenan, carboxymethyl cellulose sodium salt complex hydrogels

We synthesized the polyelectrolyte complex hydrogel consisting of chitosan, κ-carrageenan, and carboxymethyl cellulose sodium salt (NaCMC) and investigated the swelling properties of the gel varying with carrageenan/NaCMC compositions. In a lower composition of carrageenan, heterogeneous gels were obtained indicating strong electrostatic interactions among these polyelectrolytes. Oppositely, in a higher composition of carrageenan, a gelation did not occur. It was cleared that a homogeneity of the gel strongly depended on the carrageenan/NaCMC composition. The degree of swelling at the equilibrium decreased proportional to the carrageenan composition. The gels showed a maximum degree of swelling in the range of pH 11-12. The maximum degree of swelling discontinuously decreased with increasing the NaCMC composition and was independent of the composition at a higher composition of NaCMC. Swelling properties in pure water and in alkaline solutions were also affected by salt concentrations of each polyelectrolyte aqueous solutions.     

Swelling of sodium chloride filled polybutadiene networks in water,water/ acetone and water/THF mixtures

The swelling of polybutadiene (PB) networks of different cross-link densities filled with finely divided sodium chloride (NaCI) particles are studied in water, water/acetone and water/THF mixtures. Swelling over periods of 2 months are recorded. The degree of swelling was observed to increase continuously in water during this period, whereas in water/acetone mixtures it reached a peak followed by deswelling and it converged to a maximal value in water/THF mixtures. The highly cross-linked samples exhibited unusually high degrees of swelling, and calculations indicated full stretching of the network chains. The enthalpic contribution to the chemical potential of the networks in equilibrium with solvent was determined using the phantom network model of rubber elasticity theory. The swollen network-salt system was approximated by the lattice model of polymer solutions. The positive contributions of water and acetone to the chemical activity of the swollen network were offset by the negative contribution of dissociation of salt in water, resulting in a small negative enthalpy of mixing. The highest rate of diffusion of solvent was observed for the PB/water/THF ternary system. Diffusion rates of pure water and water/acetone mixture were much smaller and of comparable magnitude. Mechanical measurements of stress and strain at break, and dynamic mechanical measurements of storage and loss moduli of filled and unfilled samples showed that filling with NaCl did not change the mechanical properties of the networks significantly, in spite of the dramatic change in the swelling behaviour.     

Hydrophilic gels based on copolymers of 2-hydroxyethyl methacrylate with methacrylamide and acrylamide

Copolymerization of 2-hydroxyethyl methacrylate with methacrylamide or acrylamide and a crosslinking agent in the presence of water or other diluents yielded transparent hydrogels with a varying degree of swelling and varying sorption properties. The equilibrium degree of swelling increases with increasing content of amide groups and exhibits a maximum at ca. 60 wt-% methacrylamide. The temperature dependence of swelling at 25–50°C changes from negative to positive with growing content of methacrylamide in the copolymer. The effect of the introduction of the amide groups can be interpreted by a weakening of the extent of hydrophobic interactions and by an increase in the role played by the hydrogen bonds. At the same time, the swelling-in effect of the salting-in anions decreases and the sensitivity to the sorption of metal cations increases. The increasing content of methacrylamide is reflected in an increase in the modulus, tensile strength, and elongation-at-break in gels swollen to the same degree. In gels swollen in water to equilibrium, the positive effect of methacrylamide units is compensated for by the negative effect of the increasing degree of swelling, so that the mechanical properties of these gels do not depend too much on the composition of the copolymer. The increasing content of acrylamide in the copolymer strongly raises the degree of swelling, which is reflected in poorer mechanical properties compared to poly(2-hydroxyethyl methacrylate).     

In situ synthesis of ferrites in ionic and neutral cellulose gels

The filaments of a tyrecord rayon were modified by two methods to enhance the degree of swelling of the material: (1) carboxyl and sulfonic acid substituents were introduced into the rayon and (2) the filaments were swollen in sodium hydroxide. The water-swollen filaments were rendered magnetic by in situ synthesis of ferrites and the resulting magnetic filaments were characterized by transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). Two other non-ionic, highly swollen cellulose gels were used as matrices for in situ synthesis of ferrites: a never-dried, wet-spun model cellulose filament and a never-dried bacterial cellulose membrane. TEM micrographs of thin cross-sections of the magnetic gels showed that the nanometre-sized ferrites were uniformly distributed whereas the treated rayon filaments had ferrites predominantly at the filament surface. All the materials were superparamagnetic as determined by VSM. However, a ferrimagnetic component was detected after several reaction cycles for the bacterial cellulose membrane by Mössbauer spectroscopy.     

Swelling studies in electrochemically prepared acrylamide/N,N′ methylene bisacrylamide gels

Acrylamide/N,N′ methylene bisacrylamide gels were prepared at different voltages electrochemically. The dependence of the swelling properties on the preparation voltage was investigated. A set of gel samples was swollen as prepared and another set was swollen after being dried to constant weight. Swelling versus time curves were all in stretched exponential form, rather than pure exponential form, indicating that the gels are of heterogeneous nature. Maximum swelling increased with the preparation voltage in both gel types. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1398–1401, 2006     

Phase transition in swollen gels 30. Temperature-induced phase transition in positively charged poly(N-isopropylacrylamide) hydrogels in water and aqueous NaCl solutions

Summary The swelling and mechanical behaviour of ionized networks of N-isopropylacrylamide with an ionic comonomer, (2-acrylamidoethyl)trimethylammonium chloride (mole fractions x _S= 0−0.1), in the presence of a crosslinker, N,N'-methylenebisacrylamide, was investigated in water as a function of temperature and in aqueous NaCl solutions (c _NaCl= 10⁻⁵− 1 M) at 23 °C. On heating, a continuous decrease in the swelling degree in water, Q _w, was observed; increasing x _S shifts the volume transition temperature, T _tr, (from the swollen to collapsed state) to higher temperatures. The expected decrease in the swelling degree, Q, with increasing NaCl concentration in aqueous NaCl solutions was observed and two shrinking regions in ionic gels were found. The decrease in Q _w with increasing temperature and the decrease in Q with increasing c _NaCl are accompanied by an increase in equilibrium shear modulus of gels, so that the mechanical behaviour of gels is predominantly determined by the swelling degree. The experimental swelling behaviour could be, in the first approximation, described by the theory of polyelectrolyte networks in which repulsion of charges on the chain and finite chain extensibility were considered. Received: 7 June 2001 / Accepted: 21 September 2001     

Thermo-sensitive swelling behavior in crosslinked N-isopropylacrylamide networks: Cationic,anionic, and ampholytic hydrogels

Crosslinked polymer networks of N-isopropylacrylamide (NiPAAm) containing small amounts of either anionic or cationic comonomers, or mixtures of both were fabricated and characterized in terms of their aqueous swelling and critical behavior. These gels demonstrate critical transition temperatures in aqueous media between a highly solvated, swollen gel state and a collapsed, dehydrated network over temperature ranges comparable to that of pure NiPAAm, with modifications of gel critical points and respective temperature ranges dependent upon comonomer type and content. Copolymer gel swelling ratios are significantly larger than those reported for pure homopolymer NiPAAm gels, even when only 0.5 mol % of comonomer is incorporated. At temperatures exceeding the collapse transition point, all copolymer gels collapse to a state of nearly complete dehydration, demonstrating short-time collapsed-state swelling ratios far lower than those of pure NiPAAm networks. Collapse kinetics for the ionomeric gels are much more rapid than those of pure NiPAAm, achieving collapse state equilibrium on time scales of seconds. Swelling behavior as a function of pH, buffer type, ionic strength, crosslinking, and temperature is detailed over a range of copolymer compositions. © 1993 John Wiley & Sons, Inc.     

Molecular weight decrease in the early pyrolysis of crystalline and amorphous cellulose

Samples of ordinary “ash-free” cellulose papers and similar samples decrystallized by swelling in liquid ammonia were pyrolyzed in vacuo to a weight loss ranging from <0.1% to nearly 20%. The samples were then nitrated and their molecular weight distributions determined by gel permeation chromatography. When weight loss reached 1%, both the ordinary and the ammonia-swelled celluloses showed a large drop in average degree of polymerization (D.P.). However, the ordinary cellulose showed this sharp drop long before there was any measurable weight loss; the ammonia-swelled cellulose changed D.P. only gradually in the early stages. Further, x-ray diffraction measurements showed that by the time the D.P. of the ammonia-swelled cellulose had dropped appreciably, the material had developed a significant crystalline pattern. These results support the suggestion that initial rupture of the cellulose molecule occurs at strain points at the crystalline–amorphous boundaries.     

Studies on preparation and swelling properties of the N-isopropylacrylamide/chitosan semi-IPN and IPN hydrogels

Semi-interpenetrating network (semi-IPN) polymer gels and interpenetrating network (IPN) polymer gels with thermosensitivity were prepared by introducing a biodegradable polymer, chitosan, into the N-isopropyacrylamide (PNIPAAm) gel system. The swelling behavior, temperature sensitivity, pH sensitivity, gel strength, and drug-release behavior of PNIPAAm/chitosan semi-IPN and IPN hydrogels were investigated. The results indicated that the NIPAAm/chitosan semi-IPN and IPN hydrogels exhibited pH and temperature-sensitivity behavior and could slow drug release and diffusion from the gels. From the stress–strain curves of the hydrogels, the compression moduli of IPN gels containing crosslinked chitosan were higher than those of semi-IPN gels. This is because IPN gels have a more compact structure. The morphology of PNIPAAm/chitosan hydrogels was also investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2487–2496, 2001