Effect of carbon nanotubes on the crystallization and properties of polypropylene

The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005     

Surfactant‐Stabilized Small Hydrogel Particles in Oil: Hosts for Remarkable Activation of Enzymes in Organic Solvents

Hydrogels of amino acid based cationic surfactant having C₁₆ tails were used to immobilize heme proteins and enzyme. These hydrogel‐entrapped proteins/enzyme showed remarkable activation when dispersed in organic solvent. The activation effect (ratio of the activity of the hydrogel‐entrapped enzyme in organic solvent to the activity of the native enzyme in water) of cytochrome c increased up to 350‐fold with varying protein and gelator concentration. Hydrogel‐entrapped hemoglobin and horseradish peroxidase (HRP) also showed markedly improved activity in organic solvent. Alteration in the structure of the gelator and its supramolecular arrangement showed that the protein immobilized within amphiphilic networks with larger interstitial space exhibited higher activation. This striking activation of hydrogel‐entrapped proteins stems from the following effects: 1) the hydrophilic domain of the amphiphilic networks facilitates accessibility of the enzyme to the water‐soluble substrate. 2) the surfactant, as an integral part of the amphiphilic network, assists in the formation of a distinct interface through which reactants and products are easily transferred between hydrophilic and hydrophobic domains. 3) Surfactant gelators help in the dispersion and stabilization of gel matrix into small particles in organic solvent, which enhances the overall surface area and results in improved mass transfer. The activation was dramatically improved up to 675‐fold in the presence of nongelating anionic surfactants that helped in disintegration of the gel into further smaller‐sized particles. Interestingly, hydrogel‐immobilized HRP exhibited about 2000‐fold higher activity in comparison to the activity of the suspended enzyme in toluene. Structural changes of the entrapped enzyme and the morphology of the matrix were investigated to understand the mechanism of this activation.     

Effects of TEMED and EDTA on the structural and mechanical properties of NIPAAm/Na+MMT composite hydrogels

N‐isopropyl acrylamide (NIPAAm) hydrogels are known as thermosensitive crosslinked polymer networks. In this work, the network parameters of their composites, i.e., NIPAAm/sodium montmorillonite (NIPAAm/Na⁺MMT) hydrogels synthesized by free radical solution polymerization in the presence of two different types of accelerator (tetramethyl ethylenediamine (TEMED) and ethylenediamine tetraacetic acid (EDTA)) and initiator (potassium persulphate (K₂S₂O₈) and cerium ammonium nitrate ((NH₄)₂Ce(NO₃)₆), Ce(IV)) using five different clay content (in the range of 1.0–5.0 wt % of total monomer concentration) at 25 °C were presented and discussed. FTIR spectra, XRD patterns, SEM photographs, and network parameters of the samples indicated that the presence of COOH groups on EDTA molecules was resulted in the formation of exfoliated structures and the activity of EDTA/KPS redox pair was higher than those of TEMED/KPS and EDTA/Ce (IV) pairs. The compression moduli (G) of the hydrogels initiated with EDTA/Ce(IV) redox pair showed smooth and continual changings with increase in Na⁺MMT content (for swelling equilibrium at 25 °C) on the contrary of EDTA/KPS and TEMED/KPS pairs. It might be related to low initiator efficiency of cerium ammonium nitrate than KPS molecules, having higher effective crosslinking density with increasing clay content. On the other hand, the G moduli of NIPAAm/Na⁺MMT hydrogels (above their phase transition temperature) initiated with TEMED/KPS redox pair were higher than the others because of the more hydrophobic nature of TEMED molecules. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1256–1264, 2010     

Swelling behavior of chemically crosslinked PVA gels in mixed solvents

We report the swelling behavior of chemically crosslinked polyvinyl alcohol (PVA) gels with different degrees of hydrolysis in water, several organic solvents, and their mixed solvents. The gels were dried after gelation and were put into their respective solvents. The gel volume in pure water decreased with increasing temperatures, and the total changes increased with decreasing degrees of hydrolysis. The swelling ratio depends on the solvent and its concentration. In the cases of mixed solvents of methanol–water, ethanol–water, and acetone–water, the gels shrank continuously with increasing concentrations of solvents and reached the collapsed state in the pure organic solvent. In the case of dimethyl sulfoxide (DMSO), on the other hand, the gels shrunk, swelled, and finally reached the swollen state in pure DMSO. Results of measurements using Fourier Transform infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) suggested that crosslinks and microcrystallites were formed due to hydrogen bonds during the drying process after gelation. The hydrogen bonds were partly destroyed in a rich solvent, but the residual hydrogen bonds had an essential role in determining the swelling behavior in a poor solvent. The swelling behavior and the possible phase transition of the present system are discussed in terms of the solubility of polymers with different degrees of hydrolysis in given mixed solvents and in terms of the formation and destruction of physical crosslinks in the chemical PVA gels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1978–1986, 2010     

New hydrogels from interpenetrated physical gels of agarose and chemical gels of polyacrylamide: Effect of relative concentration and crosslinking degree on the viscoelastic and thermal properties

In this article, we report on the viscoelastic and thermal properties of agarose–polyacrylamide (PAAm) interpenetrating polymer hydrogels (IPHs) and semi‐IPHs as a function of agarose concentration and PAAm crosslinking degree. The results demonstrated that the agarose is able to gel in the presence of crosslinked and linear IPHs. In addition, the reticulation of PAAm in the presence of agarose is confirmed for the case of IPHs giving rise to systems with dimensional stability at high temperatures. The formation of a fully IPH was ascertained at low agarose concentrations. A study of the morphology and nanoscale elasticity of the different systems has been carried out with atomic force microscopy/ultrasonic force microscopy (UFM). UFM data provide further evidence of interpenetration, allowing us to visualize—if present—phase‐separated domains with nanoscale resolution for the various crosslinking degrees and PAAm and agarose concentrations used during the formation of the IPHs. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Thermoresponsive super water absorbent hydrogels prepared by frontal polymerization

Frontal polymerization was used as an alternative technique for the preparation of super water absorbent hydrogels obtained from acrylamide and 3‐sulfopropyl acrylate, potassium salt (SPAK) in the presence of N,N′‐methylene‐bisacrylamide as a crosslinker. All samples were synthesized in dimethyl sulfoxide, and their swelling behavior in water was investigated. It was found that their features are dependent on the monomer ratio used, which influenced the porous morphology, and consequently, the swelling capability. The swelling ratio ranges from about 1000% for the acrylamide homopolymer up to 14,000% for the sample containing 87.5 mol % of SPAK, thus indicating that this parameter can be easily tuned by using the appropriate monomer ratio. The affinity towards water was eventually confirmed by contact angle analysis. Polymer hydrogels made from at least 62.5 mol % SPAK exhibit a thermoresponsive behavior, with a lower critical solution temperature of ～30 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2486–2490, 2010     

Reducibly degradable hydrogels of PNIPAM and PDMAEMA: Synthesis,stimulus‐response and drug release

Reducibly degradable hydrogels of poly(N‐isopropylacrylamide) (PNIPAM) and poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) were synthesized by the combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and click chemistry. The alkyne‐pending copolymer of PNIPAM or PDMAEMA was obtained through RAFT copolymerization of propargyl acrylate with NIPAM or DMAEMA. Bis‐2‐azidyl‐isobutyrylamide of cystamine (AIBCy) was used as the crosslinking reagent to prepare reducibly degradable hydrogels by click chemistry. The hydrogels exhibited temperature or pH stimulus‐responsive behavior in water, with rapid response, high swelling ratio, and reproducible swelling/shrinkage cycles. The loading and release of ceftriaxone sodium proved the feasibility of the hydrogels as the stimulus‐responsive drug delivery system. Furthermore, the presence of disulfide linkage in AIBCy favored the degradation of hydrogels in the reductive environment. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3604–3612, 2010     

Investigation of clay modifier effects on the structure and rheology of supercritical carbon dioxide‐processed polymer nanocomposites

Superior property enhancements in polymer–clay nanocomposites can be achieved if one can significantly enhance the nanoclay dispersion and polymer–clay interactions. Recent studies have shown that nanoclays can be dispersed in polymers using supercritical carbon dioxide (scCO₂). However, there is need for a better understanding of how changing the clay modifier affects the clay dispersability by scCO₂ and the resultant nanocomposite rheology. To address this, the polystyrene (PS)/clay nanocomposites with “weak” interaction (Cloisite 93A clay) and “strong” interaction (Cloisite 15A clay) have been prepared using the supercritical CO₂ method in the presence of a co‐solvent. Transmission electron microscopy images and small‐angle X‐ray diffraction illustrate that composites using 15A and 93A clays show similar magnitude of reduction in the average tactoid size, and dispersion upon processing with scCO₂. When PS and the clays are coprocessed in scCO₂, the “dispersion” of clays appears to be independent of modifier or polymer–clay interaction. However, the low‐frequency storage modulus in the scCO₂‐processed 15A nanocomposites is two orders of magnitude higher than that of 93A nanocomposites. It is postulated that below percolation (solution blended composites), the strength of polymer–clay interaction is not a significant contributor to rheological enhancement. In the scCO₂‐processed nanocomposites the enhanced dispersion passes the percolation threshold and the interactions dictate the reinforcement potential of the clay–polymer–clay network. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 823–831, 2010     

Fabrication of Bienzymatic Glucose Biosensor Based on Novel Gold Nanoparticles‐Bacteria Cellulose Nanofibers Nanocomposite

An exploration of gold nanoparticles–bacterial cellulose nanofibers (Au‐BC) nanocomposite as a platform for amperometric determination of glucose is presented. Two enzymes, glucose oxidase (GOx) and horseradish peroxidase (HRP) were immobilized in Au‐BC nanocomposite modified glassy carbon electrode at the same time. A sensitive and fast amperometric response to glucose was observed in the presence of electron mediator (HQ). Both of GOx and HRP kept their biocatalytic activities very well in Au‐BC nanocomposite. The detection limit for glucose in optimized conditions was as low as 2.3 µM with a linear range from 10 µM to 400 µM. The biosensor was successfully applied to the determination of glucose in human blood samples.     

Development of poly(vinyl chloride)/montmorillonite nanocomposites using chelating agents

Different chelating agents such as poly(ethylene glycol), propylene glycol monooctadecanoate and palm oil were used for modification of the surface-treated montmorillonite (MMT). The work also included the development of a technique for mixing chelating agents with MMTs using different methods and different proportions of MMT/chelating agent/ethanol. Evaluation of the result of mixing was performed by thermogravimetric analysis, X-ray diffraction and high-resolution scanning electron microscopy (HR-SEM). The results showed that the chelating agents used were intercalated in MMT, increasing the interlayer spacing. The OMMT was used in the manufacture of composites with rigid PVC using a microcompounder. The master batch concept turned out to be promising in terms of dispersion and delamination of clay, as observed in HR-SEM photographs. However, despite good dispersion and exfoliation of MMT, poor compatibility between clay platelets and PVC matrix remains to be solved to enable full exploitation of its engineering potential. Despite this drawback, good thermal stability and mechanical properties have already been achieved.