Linear viscoelasticity of thermoassociative chitosan-g-poly(N-isopropylacrylamide) copolymer

Chitosan-g-poly(N-isopropylacrylamide) (chitosan-g-PNIPAM) was synthesized and characterized rheologically in aqueous solutions. The copolymer solution exhibits a thermoassociative behavior in which its elastic response dramatically increases when temperature is above the critical temperature or the association temperature, T _assoc. The copolymer at low concentration shows typical solution property. When the temperature is increased up to the critical temperature, the copolymer exhibits a gel-like characteristic due to the formation of physical cross-links between chitosan backbones through the self-aggregation of PNIPAM side chains. At high concentration, the system exhibits a weak elastic response due to the entanglement of the copolymer at 25°C. As temperature is raised above T _assoc, the system shows a strong elastic behavior due to the formation of additional physical cross-links via the aggregation of PNIPAM side chains. Chitosan-g-PNIPAM offers an attractive associating behavior in aqueous solution at temperature close to the body temperature, thus providing potential applications in pharmaceutical and medical industries.     

Acrylamide/2-acrylamido-2-methylpropane sulfonic acid and associated sodium salt superabsorbent copolymer nanocomposites with mica as fire retardants

Acrylamide (AM) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS-H⁺) or its sodium salt (AMPS-Na⁺) were copolymerised by free-radical crosslinking polymerization to obtain poly(AM-co-AMPS-H⁺) and poly(AM-co-AMPS-Na⁺) superabsorbent polymers (SAPs). A maximum water absorbency in deionised water of 1200 g g⁻¹ was achieved for poly(AM-co-AMPS-Na⁺) at a 85% mol of AMPS-Na⁺. The inclusion of mica at 5-30% (w w⁻¹) into the preparation of poly(AM-co-AMPS-Na⁺) SAP leads to an intercalated structure, as detected by XRD and TEM analyses. Poly(AM-co-AMPS-Na⁺)/30% (w w⁻¹) mica SAP nanocomposite showed a tap water absorbency of 593 g g⁻¹ with a better thermal stability, compared to the pure SAP. Cone calorimetric analyses revealed that the wood specimens coated with the prepared poly(AM-co-AMPS-Na⁺) SAP or its 30% (w w⁻¹) mica nanocomposite provided excellent protection in delaying the ignition time after exposure to an open flame when compared to that observed with the uncoated specimen. The maximum reduction in the peak heat release rate and the greatest extension of time at peak heat release rate were observed with the nanocomposite-coated surface, but the total heat release rate was increased. The delayed burning mechanism is brought by the intercalating structure of mica in the SAP nanocomposites, which provided a better shielding effect against external heat sources, and the capability of the SAP nanocomposite in holding a large amount of water.     

Acrylamide–itaconic acid superabsorbent polymers and superabsorbent polymer/mica nanocomposites

Superabsorbent polymer acrylamide (AM)/itaconic acid (IA) and its nanocomposite were synthesized by redox polymerization in an aqueous solution of both monomers with mica used as an inorganic additive. The influences of IA concentration, mica content, and crosslinker concentration on the water absorption and physical properties of the superabsorbent polymer and its nanocomposite were examined. Water absorbency in artificial urine by the synthesized copolymers, and the gel strength of the superabsorbent copolymers and their nanocomposites, were tested with loads of 0.28 or 0.70 psi. Transmission electron micrographs and X‐ray diffraction confirmed that the polymer chains were successfully intercalated into the silicate layers in the mica. The water absorbency and the artificial urine absorbency of the composite with an AM‐to‐IA mole ratio of 95:5, 0.2% mol N‐MBA, and 5% w/w mica were 748 ± 5 and 76 ± 2 g g^?1, respectively, whilst the neat copolymer achieved only 640 ± 7 and 72 ± 2 g g^?1 in water and artificial urine, respectively. The viscoelastic behavior suggested that the swollen gel of the nanocomposites exhibited mechanical stability and elasticity. Copyright © 2009 John Wiley & Sons, Ltd.     

Enhancement of the grafting performance and of the water absorption of cassava starch graft copolymer by gamma radiation

Enhancement of the gamma radiation grafting of acrylonitrile onto gelatinized cassava starch was investigated. Infrared spectrometry was used to follow the chemical changes in the grafting reaction and from saponification. The saponified starch-g-PAN (HSPAN) was then characterized in terms of grafting parameters to provide a guide for the optimum total dose (kGy) and the appropriate ratio of starch/acrylonitrile for a fixed dose rate of 2.5 × 10⁻¹ kGy/min. Other dose rates were also carried out to obtain the appropriate result of grafting copolymerization and of water absorption. A thin aluminium foil, covering the inner wall of the reaction vessel, was found to be far more effective than any other metal films in the enhancement of the grafting reaction and the water absorption as well. Nitric acid in the medium increases the grafting yield and the water absorption. Methyl ether hydroquinone inhibitor was evaluated for its ability to increase homopolymerization and decrease graft reaction. When styrene was used as a comonomer, it hampered the grafting of acrylonitrile onto starch backbone. The water absorption capacity was improved by freeze-drying the HSPAN. The treatment of the HSPAN with aluminium trichloride hexahydrate was found to enhance the degree of wicking, but to decrease the water absorbency.     

Effect of fire retardant on flammability of acrylamide and 2-acrylamido-2-methylpropane sodium sulfonate copolymer composites

Poly[acrylamide-co-(2-acrylamido-2-methylpropane sodium sulfonate)] superabsorbents and superabsorbent composites (SAPCs) with zinc borate and/or melamine as fire retardants were synthesized. Water absorbencies decreased inversely to added amount of fire retardant. Thermal stability of SAPC/zinc borate increases with increasing zinc borate. Incorporating melamine improved thermal stability of the SAPC until 300 °C. Flammability analysis demonstrated that wood surface coated with SAP or SAPC emulsions extended time to ignition of the wood. Peak heat release rate and total heat release are smallest in specimens coated with SAPC/30% melamine. Wood coated with SAPC incorporating 20% zinc borate/10% melamine mixture gave the longest time to ignition at 4½ min.     

Rheological and morphological characterizations on physical stability of gamma-oryzanol-loaded solid lipid nanoparticles (SLNs)

In the present study, gamma-oryzanol was incorporated into glycerol behenate (Compritol 888 ATO) nanoparticles (SLNs) at 5 and 10% (w/w) of lipid phase. Increasing lipid phase concentration resulted in increased consistency and particle diameter of SLNs. Upon storage over 60 days at 4, 25 and 40 °C, the instability was observed by rheological analysis for all samples due to the formation of gelation. Rheological measurement revealed the increase in storage modulus and critical stress during storage at all temperatures. However, at 40 °C, the pronounced instability was observed from the highest increase in storage modulus and a formation of rod-like network structure from scanning electron micrographs. An increase in crystallinity, determined by differential scanning calorimetry, was also found during storage at all temperatures, confirming the instability of SLNs. Particle diameters and zeta potentials of both concentrations at all storage conditions failed to explain the observed instability. These investigations may help to develop formulations of solid lipid nanoparticles, which are optimized with respect to the desired rheological properties.     

Gel strength and swelling of acrylamide‐protic acid superabsorbent copolymers

The viscoelastic and swelling properties of polyacrylamide‐based superabsorbent copolymers were investigated as a function of the ionic comonomer structure. Superabsorbent copolymers were synthesized by free‐radical crosslinking copolymerization of acrylamide and one of the monoprotic acids (acrylic acid and crotonic acid) or the diprotic acids (maleic acid and itaconic acid) as the investigated ionic comonomer. The reaction composition of all components, i.e. monomer, comonomer, initiator, co‐initiator, and crosslinker, was fixed to be the same for the synthesis of all four superabsorbent copolymer systems. Viscoelastic measurements were performed in all systems where the particles were closely packed. The network structures of all systems were evaluated via viscoelastic and swelling measurements. The results indicated that superabsorbent polymers (SAPs) with high water absorbency were accompanied by low gel strength and the calculated high value of molecular weight between crosslinks ($\bar {M}{}_c$ ) and low value of effective crosslinking density (ν_e). Diprotic acid‐containing SAPs showed higher water absorbency over monoprotic acid‐containing and non‐ionic ones. The differences in $\bar {M}{}_c$ and ν_e values of each system were explained with respect to the differences in the monomer reactivity ratio and hydrophilicity of the comonomers. Copyright © 2010 John Wiley & Sons, Ltd.     

Ultraviolet Protection Characteristics of Silicone/Titanium Dioxide Composite Sheets

Silicone/titanium dioxide (TiO₂) composite sheets were prepared from TiO₂ particles and silicone elastomer by a compression-molding process at 140 °C. The particles were produced through sol-gel method, and emulsion technique consecutively. The prepared composite sheets with thickness of 0.8 mm had ultraviolet radiation protection property such that the transmission of ultraviolet (UV) B ray through the sheets was less than 1%. The UVA ray transmitted the sheets in the range of 0.02–4% at 320 nm and 2–43% at 400 nm, depending on the amount of TiO₂ emulsion presented in the silicone elastomer. The composite sheets still remained transparent since the transmission of the visible light through the sheets was up to 60%. On the other hand, the transmissions of UVB ray, UVA ray, and visible light through the pure silicone elastomer sheets were in the range of 47–58%, 58–71%, and 71–88%, respectively. Comparable with silicone elastomer sheets, the addition of TiO₂ emulsion resulted in the composite sheets with higher strain and lower modulus; however, these differences in tensile properties were up to the amount of the emulsion in the silicone elastomer.