Strain stiffening and negative normal stress in alginate hydrogels

Alginate hydrogels are polysaccharide biopolymer networks widely useful in biomedical and food applications. Here, we report nonlinear mechanical responses of ionically crosslinked alginate hydrogels captured using large amplitude oscillatory shear experiments. Gelation was performed in situ in a rheometer and the rheological investigations on these samples captured the strain‐stiffening behavior for these gels as a function of oscillatory strain. In addition, negative normal stress was observed, which has not been reported earlier for any polysaccharide networks. The magnitude of negative normal stress increases with the applied strain amplitude and can exceed that of the shear stress at large‐strain. Fitting a constitutive relationship to the stress‐strain curves reveals that the mode of deformation involves stretching of the alginate chains and bending of both the chains and the junction zones. The contribution of bending increases near saturation of G blocks as Ca²⁺ concentration was increased. The results presented here provide an improved understanding of the deformation behavior of alginate hydrogels and such understanding can be extended to other crosslinked polysaccharide networks. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1767–1775     

Synthesis,swelling properties,and network structure of new stimuli‐responsive poly(N‐acryloyl‐N′‐ethyl piperazine‐co‐N‐isopropylacrylamide) hydrogels

Poly(N‐acryloyl‐N′‐ethyl piperazine‐co‐N‐isopropylacrylamide) hydrogels were prepared by thermal free‐radical copolymerization of N‐acryloyl‐N′‐ethyl piperazine (AcrNEP) and N‐isopropylacrylamide (NIPAM) in solution using N, N′‐methylene bisacrylamide as the crosslinking agent. The gels were responsive to changes in external stimuli such as pH and temperature. The pH and temperature responsive character of the gels was greatly dependent on the monomer content, namely AcrNEP and NIPAM, respectively. The gels swelled in acidic (pH 2) and de‐swelled in basic (pH 10) solutions with a response time of 60 min. With increase in temperature from 23 to 80 °C the swelling of the gels decreased continuously and this effect was different in acidic and basic solutions. The temperature dependence of equilibrium water content of the gels was evaluated by the Gibbs–Helmholtz equation. Detailed analysis of the swelling properties of these new gels in relation to molecular heterogeneity in acidic (pH 2) and basic (pH 10) solutions were performed. Water transport property of the gels was studied gravimetrically. In acidic solution, the diffusion process was non‐Fickian (anomalous) while in basic solution, the diffusion was quasi‐Fickian. The effect was more evident in solution of pH 2 than in pH 10. Various structural parameters of the gels such as number‐average molar mass between crosslink (M_c), the crosslink density (ρ_c), and the mesh size (ξ) were evaluated. The mesh sizes of the hydrogels were between 64 and 783 Å in the swollen state in acidic solution and 20 and 195 Å in the collapsed state in basic solution. The mesh size increased between three to four times during the pH‐dependent swelling process. The amount of unbound water (free water) and bound water of the gels was also evaluated using differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Swelling behavior and network structure of hydrogels synthesized using controlled UV‐initiated free radical polymerization

N‐vinyl‐2‐pyrrolidone (VP) and 2‐hydroxyethyl methacrylate (HEMA) copolymeric gels have been synthesized using UV‐initiated photopolymerization to understand their characteristic behavior for development as a bioengineering material, specifically for tissue expansion. The properties of the gels have been investigated by systematic variation of the monomer feed composition and initiator and crosslinker concentrations as well as UV irradiation intensity, which was controlled by various photomasks. The swelling kinetics and network characteristics for the various hydrogels were investigated through the observation of gel swelling behavior in saline solutions and compression modulus determination of the fully swollen hydrogels. The equilibrium swelling ratio (q_e) of the gels increased as expected with increasing VP content and decreasing crosslinker concentration. However, it was found that as the amount of initiator or UV intensity increased, unexpectedly q_e also increased, which indicates a network structure with decreasing effective crosslink density (ν_e) (or increasing average molecular weight between crosslinks (M_c)). Based on this anomalous swelling behavior and thermal analysis of the gels, a molecular structure is proposed consisting of increasing number of dangling chain ends within the polymer network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1450–1462, 2008     

Synthesis and characterization of poly(N‐vinyl formamide) hydrogels—A potential alternative to polyacrylamide hydrogels

The synthesis and characterization of solution‐cast, molded gels of N‐vinyl formamide (NVF) has not been previously reported even though NVF is an isomer of acrylamide (AAm) and polyacrylamide (PAAm) hydrogels have many commercial applications. Aqueous NVF solutions were cross‐linked into gels using a novel cross‐linker, 2‐(N‐vinylformamido)ethylether, and the thermally‐activated initiator VA‐044. For a given formulation, PNVF gels swell up to twice that of PAAm gels cross‐linked with N,N′‐methylenebisacrylamide. From swelling and compression measurements, PNVF gels were found to be more hydrophilic than PAAm gels. Flory‐Huggins solubility parameters were χ = 0.38?₂ + 0.48 for PNVF and χ = 0.31?₂ + 0.49 for PAAm, where ?₂ is the polymer volume fraction. The shear moduli for PNVF and PAAm scale with ? and ? respectively, consistent with good solvent behavior, also suggesting PNVF is more hydrophilic than PAAm. Similarity of mechanical properties for both gels as a function of ?₂ suggests that network structures of PNVF and PAAm gels are similar. Fracture strains of both gels declined with ?₂ by the same linear function while fracture stresses were about 500 kPa regardless of formulation. Since NVF is a liquid monomer, less toxic than AAm and can be hydrolyzed to a cationic form, PNVF gels could become technologically significant. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Organic–inorganic hybrid hydrogels involving poly(N‐isopropylacrylamide) and polyhedral oligomeric silsesquioxane: Preparation and rapid thermoresponsive properties

3‐Acryloxypropylhepta(3,3,3‐trifluoropropyl) polyhedral oligomeric silsesquioxane (POSS) was synthesized and used as a modifier to improve the thermal response rates of poly(N‐isopropylacrylamide) (PNIPAM) hydrogel. The radical copolymerization among N‐isopropylacrylamide (NIPAM), the POSS macromer and N,N′‐methylenebisacrylamide was performed to prepare the POSS‐containing PNIPAM cross‐linked networks. Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) showed that the POSS‐containing PNIPAM networks displayed the enhanced glass transition temperatures (T_g's) and improved thermal stability when compared with plain PNIPAM network. The POSS‐containing PNIPAM hydrogels exhibited temperature‐responsive behavior as the plain PNIPAM hydrogels. It is noted that with the moderate contents of POSS, the POSS‐containing PNIPAM hydrogels displayed much faster response rates in terms of swelling, deswelling, and re‐swelling experiments than plain PNIPAM hydrogel. The improved thermoresponsive properties of hydrogels have been interpreted on the basis of the formation of the specific microphase‐separated morphology in the hydrogels, that is, the POSS structural units in the hybrid hydrogels were self‐assembled into the highly hydrophobic nanodomains, which behave as the microporogens and promote the contact of PNIPAM chains and water. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 504–516, 2009     

Synthesis and chiral recognition properties of poly(N‐propargylamide) gels derived from ornithine and lysine

Copolymerization of ornithine‐ and lysine‐derived N‐propargylamides, N‐α‐tert‐butoxycarbonyl‐N‐δ‐fluorenylmethoxycarbonyl‐L ‐ornithine N′‐propargylamide ( 1 ), N‐α‐tert‐butoxycarbonyl‐N‐ε‐fluorenylmethoxycarbonyl‐L ‐lysine N′‐propargylamide ( 2 ), N‐α‐fluorenylmethoxycarbonyl‐N‐δ‐tert‐butoxycarbonyl‐L ‐ornithine N′‐propargylamide ( 3 ), and N‐α‐fluorenylmethoxycarbonyl‐N‐ε‐tert‐butoxycarbonyl‐L ‐lysine N′‐propargylamide (4) with dipropargyl adipate was carried out using (nbd)Rh⁺[η⁶‐C₆H₅B^?(C₆H₅)₃] as a catalyst in THF to obtain polymer gels in 80–93% yields. The gels adsorbed N‐benzyloxycarbonyl L ‐alanine, N‐benzyloxycarbonyl L ‐alanine methyl ester, and (S)‐(+)‐1‐phenyl‐1,2‐ethanediol preferably than the corresponding optical isomers. The order of chiral discrimination was poly( 1 ) > poly( 4 ) > poly( 2 ), poly( 3 ) gels. The fluorenylmethoxycarbonyl groups of the gels could be partly removed by piperidine treatment, leading to increase of adsorptivity but decrease of chiral recognition ability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4175–4182, 2008     

Self‐Assembly of Amphiphilic Janus Dendrimers into Mechanically Robust Supramolecular Hydrogels for Sustained Drug Release

Compounds that can gelate aqueous solutions offer an intriguing toolbox to create functional hydrogel materials for biomedical applications. Amphiphilic Janus dendrimers with low molecular weights can readily form self‐assembled fibers at very low mass proportion (0.2 wt %) to create supramolecular hydrogels (G′?G′′) with outstanding mechanical properties and storage modulus of G′>1000 Pa. The G′ value and gel melting temperature can be tuned by modulating the position or number of hydrophobic alkyl chains in the dendrimer structure; thus enabling exquisite control over the mesoscale material properties in these molecular assemblies. The gels are formed within seconds by simple injection of ethanol‐solvated dendrimers into an aqueous solution. Cryogenic TEM, small‐angle X‐ray scattering, and SEM were used to confirm the fibrous structure morphology of the gels. Furthermore, the gels can be efficiently loaded with different bioactive cargo, such as active enzymes, peptides, or small‐molecule drugs, to be used for sustained release in drug delivery.     

Synthesis and characterization of novel biodegradable unsaturated poly(ester amide)/poly(ethylene glycol) diacrylate hydrogels

A series of novel biodegradable hydrogels were designed and synthesized from four types of unsaturated poly(ester amide) (UPEA) and poly(ethylene glycol) diacrylate (PEG‐DA) precursors by UV photocrosslinking. These newly synthesized biodegradable UPEA/PEG‐DA hydrogels were characterized by their gel fraction (G_f), equilibrium swelling ratio (Q_eq), compressive modulus, and interior morphology. The effect of the precursor feed ratio (UPEAs to PEG‐DA) on the properties of the hydrogels was also studied. The incorporation of UPEA polymers into the PEG‐DA hydrogels increased their hydrophobicity, crosslinking density (denser network), and mechanical strength (higher compressive modulus) but reduced Q_eq. When different types of UPEA precursors were coupled with PEG‐DA at the same feed ratio (20 wt %), the resulting hydrogels had similar Q_eq values and porous three‐dimensional interior morphologies but different G_f and compressive modulus values. These differences in the hydrogel properties were correlated to the chemical structures of the UPEA precursors; that is, the different locations of the >C?C< double bonds in individual UPEA segments resulted in their different reactivities toward PEG‐DA to form hydrogels. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3932–3944, 2005     

Relationship between the positive temperature coefficient of resistivity and dynamic rheological behavior for carbon black‐filled high‐density polyethylene

Studies on the relationship between resistivity and dynamic rheological properties of carbon black‐filled high‐density polyethylene (CB/HDPE) composites were carried out. Change of resistivity ρ is associated with the dynamic modulus before the positive temperature coefficient/negative temperature coefficient (PTC/NTC) transition temperature. When the temperature approaches the melting point of HDPE, ρ increases rapidly with a decreasing modulus, corresponding to PTC transition. The resistivity‐dynamic viscoelasticity relationship in the PTC region can be divided into two parts in which the changes of ρ with storage modulus G′ and loss modulus G″ can be described by the scaling laws given by the critical storage modulus and loss modulus G′_c and G″_c; adjustable parameters ρ′_1c, ρ′_2c, ρ″_1c and ρ″_2c; and nonlinear exponents n and m, respectively. The accordance between the experimental data and the scaling functions of the dimensionless quantities (G′/G′_c ? 1) and (G″/G″_c ? 1) in the PTC transition region suggests that the ρ jump may be the result of a modulus‐induced percolation. G′_c and G″_c increase, but the four scaling resistivitis, ρ′_1c, ρ′_2c, ρ″_1c, and ρ″_2c, decrease with increasing CB concentration, implying that the microstructure change of the composites is the determinant factor for the PTC behavior and the resistivity‐dynamic modulus relationship. However, ρ′_2c and ρ″_2c exhibit no scaling dependence. It is suggested that a threshold concentration exists for the modulus of the composites on the basis of examining the plot of both G′_c and G″_c against CB concentration. The scaling laws G′ ～ Φ^x and G″ ～ Φ^y hold for the concentration dependence of the critical modulus when Φ > Φ_c and the estimated values of x and y are 1.10 ± 0.10 and 0.89 ± 0.29, respectively. The resistivity‐dynamic modulus can shift to form a master curve. The horizontal factors a_G′ and a_G″ and the vertical factors a′ and a″ are relevant to the concentration dependence of the dynamic modulus or PTC behavior. It is believed that the former would be involved in changing the mechanical microstructure formed by the complicated interaction of CB particle and polymer segments, and the latter would be involved in the overall changes of conducting a network during the PTC transition region. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 983–992, 2003     

Synthesis and characterization of polyhedral oligomeric silsesquioxane hybrid co‐crosslinked poly(N‐isopropylacrylamide‐co‐dimethylaminoethyl methacrylate) hydrogels

Polyhedral oligomeric silsesquioxane hybrid temperature and pH double‐responsive hydrogels with organic–inorganic co‐crosslinked networks are synthesized by in situ, free‐radical polymerization of N‐isopropylacrylamide and dimethylaminoethyl methacrylate in the presence of both organic crosslinker N,N′‐methylenebis(acrylamide) (BIS) and inorganic crosslinker octavinyl polyhedral oligomeric silsesquioxane (OvPOSS) in tetrahydrofuran media. The resulting hydrogels (OR‐OvP gels) display obvious temperature and pH double responsiveness, OvPOSS particles dispersed in polymer make a dominant effect on the properties of gels. With the increase of OvPOSS, the aggregation of particles on nano‐ or microscale happens and causes a considerable change on the properties of gels, such as the lower critical solution temperature and better compression strength. Specially, the interconnected microporous structure of gels ascribed to the microphase separation results in faster deswelling rate, which makes the gel become attractive. Besides, the crosslink by BIS intensifies the heterogeneity of gels significantly, which could also be used to adjust the properties of gels. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1494–1504     

Thermorheological analysis of PVC blends

The effect of temperature on dynamic viscoelastic measurements of miscible poly (vinyl chloride) (PVC)/ethylene‐vinyl acetate–carbon monoxide terpolymer (EVA‐CO) and immiscible PVC/high‐density polyethylene (HDPE) and PVC/chlorinated polyethylene (CPE) molten blends is discussed. PVC plasticized with di(2 ethyl hexyl) phthalate (PVC/DOP) and CaCO₃ filled HDPE (HDPE/CaCO₃) are also considered for comparison purposes. Thermorheological complexity is analyzed using two time–temperature superposition methods: double logarithmic plots of storage modulus, G′, vs. loss modulus, G″, and loss tangent, tan δ, vs. complex modulus, G*, plots. Both methods reveal that miscible PVC/EVA‐CO and PVC/DOP systems are thermorheologically complex, which is explained by the capacity of PVC to form microdomains or crystallites during mixing and following cooling of the blends. For immiscible PVC/HDPE and PVC/CPE blends the results of log G′ vs. log G″ show temperature independence. However, when tan δ vs. log G* plots are used, the immiscible blends are shown to be thermorheologically complex, indicating that the morphology observed by microscopy and constitued by a PVC phase dispersed in a HDPE or CPE matrix, is reflected by this rheological technique. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 469–477, 2000     

Interpenetrating thermophobic and thermophilic dual responsive networks

Poly(N‐acryloyl glycinamide) (PNAGA)/poly(N‐isopropyl acrylamide) (PNIPAAm) interpenetrating network (IPN) hydrogels were made by UV‐light initiated radical polymerization in two‐steps. The IPN hydrogels showed a double thermoresponsive behavior due to the combination of PNIPAAm (thermophobic) and PNAGA (thermophilic) networks. Increasing the content of the thermophobic PNIPAAm network leads to a change from a broad thermophilic volume phase transition temperature of PNAGA to a thermophilic–thermophobic‐type dual transition for the prepared IPN. Due to the double thermoresponsive character of the IPN gels, the mechanical properties are dependent upon temperature as demonstrated by performing tensile tests in water at 15 and 50 °C. Furthermore, the IPN hydrogels were characterized using turbidity measurements, SEM, and the determination of the equilibrium swelling ratio. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 539–544     

Compression elastic modulus of neutral,ionic, and amphoteric hydrogels based on N‐vinylimidazole

Several hydrogels of N‐vinylimidazole and sodium styrenesulfonate have been prepared by radical cross‐linking copolymerization in aqueous solution, using N,N′‐methylene‐bisacrylamide as crosslinker. Depending on composition, these hydrogels were neutral, amphoteric, cationic or anionic. Compression‐strain measurements were performed on samples as‐synthesized and swollen in deionized water or in acid aqueous solutions, with and without salt. It was thus found that the cross‐linking densities determined by compression measurements on as‐synthesized samples are in good accordance with those calculated by means of the model of polymer networks with pendant vinyl groups. A non‐Gaussian parameter (β) was introduced to explain that the elastic moduli (G) of samples swollen at equilibrium are larger than predicted by the Gaussian model. The β values of the neutral or ionized systems increase with swelling and fall into a single curve, which denotes a common behavior. Swelling has two opposite effects on G; on the one hand G decreases because the polymer volume fraction diminish and the system shifts from the affine limit to the phantom one; on the other, β increases and contributes to increasing G. The balance of those two opposite effects determines the variation of G with swelling. The possible contribution of ionic crosslinks to ν_e for the polyampholyte and for the polycation wearing divalent counteranions was discussed. A peculiar system is poly(sodium styrenesulfonate), whose cross‐linking density is much lower than expected. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1078–1087, 2009     

Small‐angle x‐ray scattering study of thermoreversible poly(vinyl chloride) gels

Poly(vinyl chloride) (PVC)/bis(2‐ethylhexyl)phthalate (DOP) gels were prepared at room temperature from tetrahydrofuran solutions of PVC and DOP. PVC/DOP gels of different molecular weights at various PVC concentrations (c) were investigated with small‐angle X‐ray scattering (SAXS). The mean distance between two neighboring inhomogeneities (D) and two characteristic lengths, the intrainhomogeneity distance (d₁) and interinhomogeneity distance (d₂), were evaluated from Bragg's law and the distance distribution function, respectively. Both D and d₂ can be expressed by a power‐law relation (e.g., D and d₂ ∝ c^?0.5). After a period of rapid cooling to 25 °C from the sol state, the structural evolution was examined with time‐resolved SAXS measurements. An Avrami analysis with the SAXS invariant data revealed that the growth kinetics of PVC/DOP gels was one‐dimensional growth from predetermined nuclei, regardless of c. These results suggest that the PVC/DOP gels are constructed from a fibrillar structure that forms gel structures at high concentrations or low temperatures. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2340–2350, 2001     

Modeling viscoelastic properties of triblock copolymers: A DPD simulation study

Gel systems based on self‐assembled, amphiphilic ABA triblock copolymers in midblock‐selective solvent form stable, spatially extended networks with controllable morphology and tunable viscoelastic behavior. In this work, we systematically evaluate the mechanical properties of these gels using morphology calculations, and a nonequilibrium oscillatory shear technique based on the dissipative particle dynamics (DPD) method. Our simulations demonstrate that low molecular weight triblock copolymers with incompatible blocks self‐assemble into micelles connected with bridges and loop‐like chains comprised of the solvent‐selective polymer midblocks. The fraction of bridges, ?_b, generally increases with increasing relative volume of the midblock, x, defined as the ratio of midblock and endblock volumes ( ). For our model, ?_b reaches a plateau at approximately x > 9 for a strongly selective solvent. At this limit, the value of ?_b increases from 0.40 to about 0.66 as the copolymer concentration, c, increases from 0.2 to 0.5; however, this increase is less significant at higher concentrations. The elastic response of the gel studied here is comparable with the Rouse modulus. The elastic modulus increases with polymer concentration, and it exhibits a broad peak within 6 < x < 12. Finally, we present an approximate method to predict the elastic modulus of unentangled ABA triblock copolymers based solely on the morphology of the micellar gel, which can be gleaned from equilibrium DPD simulations. We demonstrate that our simulation results are in good qualitative agreement with other theoretical predictions and experimental data. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 15–25, 2010     

Synthesis of transition‐metal‐ion‐selective poly(N‐isopropylacrylamide) hydrogels by the incorporation of an Aza crown ether

A functionalized cyclam was synthesized by the attachment of a polymerizable acryloyl group to one of the four nitrogens on the cyclam molecule. The polymerization of the functionalized cyclam was performed with N‐isopropylacrylamide and N,N′‐methylene bisacrylamide, and the gels obtained were studied in the presence of different transition‐metal‐ion solutions. There was a drastic difference in the phase‐transition temperature (T_c) of the poly(N‐isopropylacrylamide) (PNIPAAm)/cyclam gel in comparison with the pure PNIPAAm gel. For the described system, a T_c shift of 15 °C was obtained. The presence of functionalized cyclam increased the hydrophilicity and T_c of the aforementioned polymer gels in deionized water (at pH 6) because of the presence of protonated amino moieties. The PNIPAAm/cyclam gels showed a dependence of the swelling behavior on pH. T_c of the pure PNIPAAm gel was weakly influenced by the presence of any transition‐metal ions, such as Cu²⁺, Ni²⁺, Zn²⁺, and Mn²⁺. The addition of Cu²⁺ or Ni²⁺ to the PNIPAAm/cyclam gel reduced T_c of the polymer gel, and a shift of approximately 12 °C was observed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1594–1602, 2003     

Rheology of (±)‐camphor‐10‐sulfonic acid doped polyaniline‐m‐cresol conducting gel nanocomposites

The rheological behavior of polyaniline‐(±champhor‐10‐sulfonic acid)_0.5‐m‐cresol [PANI‐CSA_0.5‐m‐cresol] gel nanocomposites (GNCs) with Na‐montmorillonite clay (intercalated tactoids) is studied. The shear viscosity exhibits Newtonian behavior for low shear rate (<2 × 10^?4 s^?1) and power law variation for higher shear rate. The zero shear viscosity (η₀) and the characteristic time (λ) increase but the power law index (n) decrease with increase in clay concentration. In the GNCs storage modulus (G′) and loss modulus (G″) are invariant with frequency in contrast to the pure gel. The G′ and G′ exhibit the gel behavior of the GNCs up to 105 °C in contrast to the melting for the pure gel at 75.7 °C. The percent increase of G′ of GNCs increases dramatically (619% in GNC‐5) with increasing clay concentration. The conductivity values are 10.5, 5.65, 5.51, and 4.75 S/cm for pure gel, GNC‐1, GNC‐3, and GNC‐5, respectively, promising their possible use in soft sensing devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 28–40, 2008     

Comparative rheological study of ionic semi-IPN composite hydrogels based on polyacrylamide and dextran sulphate and of polyacrylamide hydrogels

Ionic semi-interpenetrating polymer networks composite hydrogels were synthesized by free-radical polymerization using dextran sulphate (DxS), acrylamide as monomer and N,N′-methylene(bis)acrylamide as cross-linking agent. The viscoelastic properties of these composite hydrogels were investigated by oscillatory shear measurements under small deformation conditions comparative with those of polyacrylamide gels. Changes of the rheological properties of composite hydrogels have been studied in terms of polymerization temperature, cross-linker ratio, initial monomer concentration and molar mass of DxS. The results showed that the stability of the composite hydrogels obtained at room temperature (22?°C) was relatively low because the storage modulus (G′) was only eight times higher than the loss modulus (G″), while for those obtained by cryopolymerization (?18?°C), the stability was improved, the G′ values being about 30 times higher than those of G″. This behaviour indicated that, by conducting the synthesis of hydrogels below the freezing point of the reaction solutions, an enhancement of the hydrogels elasticity was achieved. The network parameters, i.e. the average molecular weight between two cross-links and the cross-link density of the composite hydrogels prepared at ?18?°C, were estimated from rheological data.     

Synthesis and thermal properties of a novel lactose‐containing poly(N‐isopropylacrylamide‐co‐acrylamidolactamine) hydrogel

An improved, simple, and efficient method for the synthesis of lactose‐containing monomer acrylamidolactamine (LAM) has been reported. Free radical copolymerization of this monomer with N‐isopropylacrylamide (NIPAM) in the presence of the crosslinking reagent N,N′‐methylenebisacrylamide (BisA) (1.2 mol %) proceeded smoothly in an aqueous solution using potassium persulfate (KPS) and N,N,N′,N′‐tetramethylethylenediamine (TMEDA) as the initiating system and gave transparent hydrogels. Reactivity ratios were estimated from copolymerization reactions carried out in solution without BisA crosslinker and at low conversion, by using both linearization and nonlinearization methods. They were found to be r_LAM = 0.75 and r_NIPAM = 1.22. The swelling behavior of the hydrogels was studied by immersion of the hydrogels in deionized water at different temperatures. Equilibrium water uptake was increased when the LAM content was higher than 47 mol %, and reached ≈ 44‐fold with 100 mol % LAM at room temperature. Depending on the composition, the gels showed sharp swelling transitions with small changes in temperature. Differential scanning calorimetry (DSC) was used to characterize the swelling transition and the organization of water in the copolymer hydrogels. The amounts of freezable water in these hydrogels ranged from 81 to 89%, and was not correlated to the content of the sugar monomer. These gels have potential applications as biocompatible materials. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1393–1402, 1999     

Charge‐Functionalized and Structurally Enhanced (Cryo)Hybrids from Acrylic (Co)Monomers and Kaolin: Altering Physicochemical Properties via Cryotropic Gelation

The potential to improve mechanical, structural, and mechanochemical properties of charge‐functionalized poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA)‐based hybrid cryogels is investigated. The simple and versatile synthesis of hybrid cryogels with high strength and toughness using cationic DMAEMA and ionic comonomer 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid has been proposed via in situ free‐radical crosslinking (cryo)polymerization by which the properties of virgin polymer can be modulated to required applications by incorporation of inorganic filler kaolin (KLN). Two factors affecting swelling and elasticity of hybrid gels (referred as PDA/KLNm), KLN content and gel preparation temperature, are studied. The optimum KLN concentration for desired swelling and modulus of elasticity is determined as 0.80% (w/v). Effective crosslinking density of hybrid hydrogels increases with KLN addition and this dependence is expressed by a quadratic polynomial as a function of KLN concentration. The results show that obtained hybrid gels with multiresponsive properties could be regarded as “smart materials” in sensing and actuation applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1758–1778