Swelling behavior and structural characteristics of polyvinyl alcohol/montmorillonite nanocomposite hydrogels

A series of nanocomposite hydrogels based on polyvinyl alcohol containing 0–10 wt % of the organically modified montmorillonite clay were prepared by freezing‐thawing cyclic method. The morphology of the nanocomposite hydrogels was observed by the scanning electron microscopy technique. The structural properties were determined by measuring the network mesh size, crosslinking density, and average molecular weight of polymer chains between crosslinks. The swelling behavior and the effect of swelling medium temperature on the swelling kinetics and characteristics of the nanocomposite hydrogels were also investigated. The results showed that two structural characteristics i.e., network mesh size and average molecular weight of polymer chains between crosslinks have inverse dependence on the clay loading level in the nanocomposite hydrogel, while crosslinking density shows completely direct dependence. Swelling measurements demonstrated a linear relation between the degree of swelling and the square root of immersion time at all swelling medium temperatures. The results indicated that the swelling characteristics of the nanocomposite hydrogels including the equilibrium degree of weight and volume swelling and the equilibrium water content were decreased by increasing the quantity of the clay incorporated into the hydrogel as well as by decreasing the temperature of swelling medium. While, the time required to reach to the equilibrium condition, as another swelling characteristic of the hydrogels, exhibited a completely opposite behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Equilibrium swelling behavior and elastic properties of polymer–clay nanocomposite hydrogels

Nanocomposite hydrogels were prepared by free‐radical polymerization of the monomers acrylamide (AAm), N,N‐dimethylacrylamide (DMA), and N‐isopropylacrylamide (NIPA) in aqueous clay dispersions at 21°C. Laponite XLS was used as clay nanoparticles in the hydrogel preparation. The hydrogels based on DMA or NIPA monomers exhibit much larger moduli of elasticity compared with the hydrogels based on AAm monomer. Calculations using the theory of rubber elasticity reveal that, in DMA‐clay or NIPA‐clay nanocomposites, both the effective crosslink density of the hydrogels and the functionality of the clay particles rapidly increase with increasing amount of Laponite up to 10% (w/v). The results suggest that DMA‐clay and NIPA‐clay attractive interactions are stronger than AAm‐clay interactions due to the formation of multiple layers on the nanoparticles through hydrophobic associations. It was also shown that, although the nanocomposite hydrogels do not dissolve in good solvents such as water, they dissolve in dilute aqueous solutions of acetone or poly(ethylene oxide) of molecular weight 10,000 g/mol, demonstrating the physical nature of the crosslink points. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Swelling kinetics of poly(acrylamide)/poly(mono-n-alkyl itaconates) hydrogels

Hydrogels of mono-n-alkyl itaconate/N-acrylamide have been synthesised. The swelling process at three different pH values (acid, neutral and basic) has been studied. The experimental data indicate that our hydrogels follow second-order swelling kinetics. According to this, the kinetic constant, K_∞, and the swelling capacity at equilibrium, W_∞, have been calculated. The influence of the solvent pH and the molar mass of the mono-n-alkyl itaconate monomeric unit has been analysed. It seems that the general balance between the hydrogen bonding and the hydrophobic interactions regulates the swelling process of these hydrogels.     

Effect of hydrotalcite on the physical properties and drug‐release behavior of nanocomposite hydrogels based on poly[acrylic acid‐co‐poly(ethylene glycol) methyl ether acrylate] gels

A series of nanocomposite hydrogels used for bioadhesive were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and intercalated hydrotalcite (HT) by photopolymerization. The microstructures of the intercalated HT and sample gels were identified by X‐ray diffraction (XRD). The results showed that the swelling ratio for these nanocomposite hydrogels increased with an increase in HT, but the gel strength and adhesive force for these gels decreased with an increase in HT. The XRD results indicated that the exfoliation of intercalated HT was achieved in the xerogels and swollen gels. Finally, the drug‐release behaviors for these gels were also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 692–699, 2004     

Swelling behaviors of ionic poly(N,N‐dimethylacrylamide‐co‐acrylamide) hydrogels in various media

Polyelectrolyte hydrogels were synthesized from N,N‐dimethylacrylamide, acrylamide, and itaconic acid with ammonium persulfate as a free‐radical initiator in the presence of methylene(bis)acrylamide as a crosslinker. The swelling behavior of the ionic poly(N,N‐dimethylacrylamide‐co‐acrylamide) hydrogels was investigated in pure water, in KSCN solutions with pHs 4 and 9, and in water–acetone mixtures according to the itaconic acid content in the hydrogel. The pulsatile swelling behavior of these hydrogels was studied both in water–acetone and in pH 2–9 buffer solutions. Although the equilibrium swelling ratio of the hydrogels with low concentrations of itaconic acid was almost not affected by changes in the temperature, the equilibrium swelling ratio of the hydrogels with high concentrations of itaconic acid increased in the temperature range of 20–50°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2140–2145, 2007     

Effect of montmorillonite on the swelling behavior and drug‐release behavior of nanocomposite hydrogels

A series of nanocomposite hydrogels were prepared from various ratios of N‐isopropylacrylamide (NIPAAm) and organic montmorillonite (MMT). The influence of the extent of MMT in the NIPAAm/MMT nanocomposite hydrogels on the physical properties and drug‐release behavior was the main purpose of this study. The microstructure and morphology were identified by X‐ray diffraction (XRD) and scanning electronic microscopy (SEM). The results showed that the swelling ratios for these nanocomposite hydrogels decreased with increase in the content of MMT. The gel strength and Young's modulus of the gels also increased with increase in the content of MMT. XRD results indicated that the exfoliation of MMT was achieved in the swollen state. Finally, the drug‐release behavior for the gels was also assessed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3652–3660, 2003     

Swelling behavior and diffusion studies of high‐water‐retaining acrylamide/potassium methacrylate hydrogels

Poly(acrylamide‐co‐potassium methacrylate) hydrogels were prepared by free‐radical simultaneous polymerization with aqueous solutions of acrylamide (AAm) and potassium methacrylate (KMA) with a redox initiator. The copolymerization was performed with eight different compositions of KMA at a fixed concentration of oil‐soluble crosslinkers, including 1,4‐butanediol diacrylate and ethylene glycol dimethacrylate (EGDMA). For every composition of AAm/KMA copolymer, the percentage swelling, swelling equilibrium, and diffusion characteristics were investigated. The copolymers were further studied for deswelling properties. The power law relationships of the hydrogels were evaluated for variation in terms of saline concentration. The AAm/KMA copolymers were confirmed by IR spectroscopy. Thermal studies of hydrogels were performed with differential scanning calorimetry and thermogravimetric analysis. EGDMA was found to be a better crosslinker for obtaining higher swelling and deswelling properties for the AAm/KMA hydrogels. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1153–1164, 2005     

Swelling behavior of thermoreversible poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels

Thermoresponsive hydrogels based on N‐isopropylacrylamide and N‐vinylimidazole were synthesized, and their swelling–deswelling behavior was studied as a function of the total monomer concentration. For copolymeric structures with better thermoresponsive properties with respect to poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels, these hydrogels were protonated with HCl and HNO₃, and the copolymer behaviors were compared with those of the unprotonated hydrogels. The temperature was changed from 4 to 70°C at fixed pHs and total ionic strengths. The equilibrium swelling ratio, dynamic swelling ratio, and dynamic deswelling ratio were evaluated for all the hydrogels. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1619–1624, 2004     

Poly(vinyl alcohol)/Clay‐Based Nanocomposite Hydrogels: Swelling Behavior and Characterization

Polymer/clay composite hydrogels were prepared based on PVA hydrogels containing 3–10 wt.‐% MOM. Their microstructure and morphology were studied by FT‐IR, WAXS and SEM, whereas the interactions between MOM and PVA were evaluated by thermal analyses. The swelling ratios for the PVA/MOM hydrogels decrease with increasing MOM content. WAXS results indicate that MOM was intercalates, and DSC results show a strong interaction between PVA and MOM. This interaction results in a stable network, which is confirmed by the elastic modulus and the thermal decomposition behavior of the hydrogels. Therefore, MOM acts as a co‐crosslinker, improving the stability of the network.

     

Effect of preshearing on the structure and properties of poly(methyl methacrylate)/clay nanocomposite panels

The effect of preshearing resin mixtures prior to casting on the structure and properties of in situ polymerized poly(methyl methacrylate)/clay nanocomposite panels was investigated. The preshearing was performed with a mechanical stirrer and controlled by varying mixing time. The structure, thermomechanical, and optical properties of the panels prepared with different preshearing times were analyzed by XRD, TEM, DMA, and UV/visible spectrophotometer. The properties of the panels increased with preshearing time because of improved intercalation and exfoliation of the clay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and electrorheological characterization of suspensions of poly(urethane acrylate)/clay nanocomposite particles

Micron‐sized poly(urethane acrylate) (PUA)/clay nanocomposite particles were synthesized by suspension polymerization. UA containing a poly(ethylene oxide) group in the main chain was first inserted into the silicate layers of montmorillonite clay through mixing the UA with the clay. Then, ethylene glycol dimethacrylate and an oil‐soluble initiator were added into this UA/clay mixture, followed by the emulsification of the monomer mixture in an aqueous solution of polymeric stabilizer. Suspension polymerization was carried out at 60°C for 12 h to obtain the PUA/clay composite particles. The incorporation of clay into the polymer phase was verified by FTIR spectroscopy, and the intercalation structure of the clay composite was confirmed by X‐ray diffraction analysis. Other characterizations including thermal analysis, morphological observation, and dielectric analysis were also performed. After suspensions of bare PUA and PUA/clay nanocomposite particles in silicone oil were prepared, their electrorheological properties were measured under various electric fields and compared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 458–464, 2003     

Effect of intercalant content of mica on the various properties for the charged nanocomposite poly(N‐isopropyl acrylamide) hydrogels

In this study, we intend to adjust the charge properties of the poly(N‐isopropylacrylamide) [Poly(NIPAAm)] gel by using anionic clay and cationic monomer. Hence, two series of nanocomposite hydrogels bearing different charges were designed from NIPAAm, intercalated mica (IM) (NIM‐series) and NIPAAm, IM, trimethyl (acrylamido propyl) ammonium iodide (TMAAI) (NTIM‐series), respectively. The mica was first intercalated with different contents of intercalant, trimethyl (acrylamido propyl) ammonium chloride (TMAACl), based on the cationic exchange capacity (CEC) of mica. The effect of the CEC value of IM and IM content on the charge property, swelling behaviors, mechanical properties, and drug‐release behaviors of the present gels were investigated. Results showed that the negative charges for NIM series gels decrease with increase in CEC values of the IM (from ?11 to ?6 mV), the positive charges for NTIM series gels also decrease with increase in CEC values of the IM (from +36 to +18 mV). The swelling behaviors and mechanical properties for the NTIM gels were significantly enhanced by IM content and CEC values of the IM. The microstructures, morphologies, and drug‐release behaviors in these two series gels are also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2277–2287, 2007     

Swelling behavior of anionic acrylamide-based hydrogels in aqueous salt solutions: Comparison of experiment with theory

A series of hydrogels were prepared from acrylamide and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) monomers with 0–80 mol % AMPS and using N,N′-methylenebis(acrylamide) as the crosslinker. The swelling capacities of hydrogels were measured in water and in aqueous NaCl solutions. The volume swelling ratio q_v of hydrogels in water increases sharply when the mole fraction f_c of AMPS increases from 0 to 0.06. At higher values of f_c from 0.06 up to 0.18, no change in the swelling capacities of hydrogels was observed; in this range of f_c, q_v becomes nearly constant at 750. However, as f_c further increases, q_v starts to increase again monotonically over the entire range of f_c. At a fixed value of f_c, the swelling ratio of hydrogels decreases with increasing salt concentration in the external solution. The results of the swelling measurements in aqueous salt solutions were compared with the predictions of the Flory–Rehner theory of swelling equilibrium. It was shown that the theory correctly predicts the swelling behavior of hydrogels up to 80 mol % charge densities. The method of estimation of the network parameters was found to be unimportant in the prediction of the experimental swelling data. The network parameters used in the simulation only correct the deficiency of the swelling theory. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 567–575, 1998     

Swelling–deswelling kinetics of ionic poly(acrylamide) hydrogels and cryogels

A series of ionic poly(acrylamide) (PAAm) gels was prepared by free‐radical crosslinking copolymerization of acrylamide and N,N′‐methylenebisacrylamide in aqueous solutions. The gels were prepared both below and above the bulk freezing temperature of the polymerization solvent water, which are called as the cryogels and the hydrogels, respectively. The deswelling behavior of swollen gels in acetone as well as the reswelling behavior of the collapsed gels in water were investigated. It was shown that the cryogels respond against the external stimuli much faster than the hydrogels. The interior morphology of the cryogel networks exhibits a discontinuity and a two‐phase structure, compared to the continuous morphology of the hydrogel networks. Introduction of the ionic units in the network chains further increased the response rate of the cryogels. In contrast to these advantages of cryogels, they exhibit lower swelling capacities than the conventional hydrogels. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 319–325, 2006     

Rheology of poly(propylene)/clay nanocomposites

The linear and nonlinear shear rheological behaviors of poly(propylene) (PP)/clay (organophilic‐montmorillonite) nanocomposites (PP/org‐MMT) were investigated by an ARES rheometer. The materials were prepared by melt intercalation with maleic anhydride functionalized PP as a compatibilizer. The storage moduli (G′), loss moduli (G″), and dynamic viscosities of polymer/clay nanocomposites (PPCNs) increase monotonically with org‐MMT content. The presence of org‐MMT leads to pseudo‐solid‐like behaviors and slower relaxation behaviors of PPCN melts. For all samples, the dependence of G′ and G″ on ω shows nonterminal behaviors. At lower frequency, the steady shear viscosities of PPCNs increase with org‐MMT content. However, the PPCN melts show a greater shear thinning tendency than pure PP melt because of the preferential orientation of the MMT layers. Therefore, PPCNs have higher moduli but better processibility compared with pure PP.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2427–2434,2004     

Poly(acrylamide/laponite) nanocomposite hydrogels: Swelling and cationic dye adsorption properties

Super adsorbent polyacrylamide (PAAm)/nanoclay (laponite, Lap) hydrogels were prepared by in situ free radical polymerization of AAm in an aqueous solution with clay as a crosslinker. The swelling properties and water‐soluble cationic dye adsorption behaviors of the PAAm/laponite (PAAm/Lap) nanocomposite (NC) hydrogels were investigated. The parameters of swelling and diffusion of water in dye solutions were evaluated for the PAAm/Lap NC hydrogels. The adsorption behavior of the monovalent cationic dyes such as Basic Blue 12 (BB 12), Basic Blue 9 (BB 9), and Basic Violet 1 (BV 1), were studied on the NC hydrogels. The effects of the clay content of the hydrogel on its cationic dye uptake behavior were studied. The adsorption studies indicated that the rates of dye uptake by the NC hydrogels increased in the following order: BB 9 > BB 12 > BV 1. This order is similar to the swelling results of the PAAm/Lap NC hydrogel in the dye solutions. The equilibrium uptakes of the different dyes by the PAAm/Lap NC hydrogel were nearly the same. In the dye absorption studies, S‐type adsorption in the Giles classification system was found for the BB 12 and BV 1 dyes, whereas L ‐type was observed for the BB 9 dye. After the heat treatment of PAAm/Lap, the rate of dye uptake and equilibrium dye uptake were increased. The NC hydrogels may be considered as a good candidate for environmental applications to retain more water and to remove dyes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties and morphology of poly(L‐lactide)/clay composites according to the clay modification

Montmorillonite (MMT) was modified with dodecylamine, 1,12‐diaminododecane, and 1,11‐aminoundecanoic acid to prepare CHMMT, NHMMT, and COMMT, respectively. The three clays were mixed with poly(L ‐lactide) (PLLA) with the aid of chloroform. Depending on the modifiers, PLLA/MMT composites exhibited different mechanical properties and morphology. A completely exfoliated morphology was observed in the PLLA/COMMT composite (PLACO). The PLACO exhibited the best tensile properties among the tested composites because of the finest dispersion of the clay layers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4983–4988, 2006     

温度及pH敏感共聚/粘土纳米复合水凝胶的合成与性能研究

以无机粘土为交联剂制备了具有温度、pH双重敏感性的聚（N-异丙基丙烯酰胺-co-甲基丙烯酸-β-羟乙酯）/粘土纳米复合水凝胶（P（NIPA-co-HEMA）/clay）,并用红外和X衍射对其结构和形态进行了表征。在弱碱性（pH=7.4）和25℃条件下,分别研究了温度和不同pH缓冲溶液对该凝胶溶胀度的影响,测定了纳米复合水凝胶的力学性能。结果表明：水凝胶的粘土已被剥离成单片层,且均匀分散在凝胶网络中,起交联作用;P（NIPA-co-HEMA）/clay具有良好的温度、pH双重敏感特性;凝胶的断裂伸长率〉1000%。     

Crystalline morphology and isothermal crystallization kinetics of poly(ethylene terephthalate)/clay nanocomposites

A poly(ethylene terephthalate) (PET)/montmorillonite clay nanocomposite was synthesized via in situ polymerization. Microscopic studies revealed that in an isothermal crystallization process, some crystallites in the nanocomposite initially were rod‐shaped and later exhibited three‐dimensional growth. The crystallites in the nanocomposite were irregularly shaped, rather than spherulitic, being interlocked together without clear boundaries, and they were much smaller than those of neat PET. With Avrami analysis, the isothermal crystallization kinetic parameters (the Avrami exponent and constant) were obtained. The rate constants for the nanocomposite demonstrated that clay could greatly increase the crystallization rate of PET. The results for the Avrami exponent were consistent with the observation of the rodlike crystallites in the PET/clay nanocomposite during the initial stage. Wide‐angle X‐ray scattering and Fourier transform infrared studies showed that, in comparison with neat PET, the crystal lattice parameters and crystallinity of the nanocomposite did not change significantly, whereas more defects may have been present in the crystalline regions of the nanocomposite because of the presence of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1381–1388, 2004     

Suspension polymerization of poly(methyl methacrylate)/clay nanocomposites

Polymer/clay nanocomposites (PCNs) of poly(methyl methacrylate) and an organically modified clay, Cloisite 15a, were synthesized in situ with a suspension polymerization technique. The amount of clay present in the PCNs was varied to provide a better understanding of the effect of the clay on the properties of the polymer matrix. However, unexpectedly, we found that the concentration of clay had a dramatic impact on the molecular weight of the polymer matrix, and a relationship between the clay concentration and polymer molecular weight was determined. The PCNs were characterized with size exclusion chromatography (SEC), X‐ray diffraction, transmission electron microscopy, and oscillatory shear rheology. From oscillatory shear rheology, the full master curves for the PCNs were obtained by application of the time–temperature superposition principle. To enable the effect of the clay on the rheology to be quantified, the experimental data was compared to the time‐dependent diffusion model of des Cloizeaux for polydisperse polymer melts, which enabled the polydispersity to be incorporated through the use of the molecular weight distribution obtained via SEC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009