Water absorbance and thermal properties of sulfated wheat gluten films

Wheat gluten films of various thicknesses formed at 30–70°C were treated with cold sulfuric acid to produce sulfated gluten films. Chemical, thermal, thermal stability, and water uptake properties were characterized for neat and sulfated films. The sulfated gluten films were able to absorb up to 30 times their weight in deionized water. However, this value dropped to 3.5 when the film was soaked in a 0.9% (w/w) NaCl solution. The films were also soaked 4 times in deionized water, and each soaking resulted in a reduced water uptake capacity. The temperature of film formation had no effect on the final water uptake properties. Also, thinner films had higher concentrations of sulfate groups than thicker films; this resulted in higher water uptake values. In addition, sulfated gluten films had comparable glass‐transition temperatures but lower thermal stabilities than the neat gluten films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

ESR and FTIR studies on electron beam‐irradiated low‐density polyethylene blends

Low‐density polyethylene (LDPE) composites modified with a resin based on ethylene/methacrylic acid copolymer (surlyn) and/or citric acid were electron beam‐irradiated and investigated by electron spin resonance (ESR) at room temperature. ESR studies were carried out directly after irradiation and after various time intervals up to 72 h postirradiation. The irradiated samples showed the ESR spectrum of seven lines that was assigned to the formation of allyl radical. The nature and yield of the allyl radical of the different LDPE samples were analyzed as a function of time after irradiation. Also, the radical concentration, decay, decay rate, and kinetics of radical decay were evaluated. Fourier transform infrared (FTIR) analysis at a series of different temperatures upon cooling from room temperature to ?175°C and the reverse heating to +125°C was also carried out. The structural changes while cooling and heating of LDPE samples were investigated using FTIR spectrometry. The results showed that cooling of unirradiated LDPE samples to ?175°C results in a decrease of the intensities of IR bands. However, heating the samples from ?175°C up to +125°C led to a consequence increase in the intensities of the IR bands. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3461–3469, 2007     

Reactions between epoxidized natural rubber and palm oil‐based alkyds at ambient temperature

The reactions between epoxidized natural rubber (ENR) and a low‐molecular weight palm oil‐based alkyd (A1) have been investigated. Experimental results (FTIR and toluene swelling tests) showed that the alkyd having both hydroxyl and carboxylic groups could react with the epoxide groups of ENR at ambient temperature to cause crosslinking. To establish the predominant reaction, alkyd A1 was chemically modified to vary the amount of hydroxyl and carboxylic groups. A1 was treated with maleic anhydride under two different temperatures of 130 and 185°C. At 130°C, the anhydride has reacted partially with the hydroxyl groups to produce alkyd A2 with higher carboxylic content and lower hydroxyl content. On the other hand, at 185°C, the anhydride has reacted completely to produce alkyd A3 with similar carboxylic acid content as A1 but lower hydroxyl content. Subsequent reactions of A2 and A3 with ENR under similar conditions have demonstrated that the predominant reaction with epoxide groups was due to the carboxylic groups from the fact that A2 could form higher amount of crosslinkages than A3, which has lower carboxylic content similar to A1. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Water uptake effects in resins based on alkenyl‐modified cyanate ester–bismaleimide blends

The analysis of cured resin blends comprising a commercial dicyanate, bismaleimide and a range of novel alkenyl‐substituted cyanates, to determine the chemical effects of long‐term exposure to water, is reported. The cured resin blends underwent accelerated water uptake by immersion at temperatures of 50 °C and 70 °C, for a period of 14–17 months. The presence of about 10–15% (by weight) of alkenyl‐substituted cyanate in the blend leads to a marked reduction in moisture absorption in comparison with the unmodified bismaleimide/cyanate blend containing a comparable amount of bismaleimide. All samples display non‐Fickian diffusion behaviour at both immersion temperatures, although this is most marked at the higher temperature. Thermogravimetric analysis was performed on alkenyl‐modified neat resin samples before and after the immersion period. The modified samples display thermal stabilities that are indistinguishable from cured resins that have not undergone immersion. Spectroscopy (near infrared Raman and mid‐infrared attenuated total reflectance) was performed on cured resin plaques to determine the sample composition as a function of modifier content. The elemental composition of the samples was also determined before and after the immersion period, and no significant variation in elemental composition was recorded for the modified samples. © British Crown Copyright 2001/DERA. Reproduced with the permission of Her Majesty's Stationery Office. Published for the SCI by John Wiley & Sons, Ltd.     

Water‐soluble polymers and gels from the polycondensation between cyclodextrins and poly(carboxylic acid)s: A study of the preparation parameters

Native cyclodextrins (CDx) and some of their derivatives were reacted with poly(carboxylic acid)s (PCAs) [citric acid (CTR), 1,2,3,4‐butanetetracarboxylic acid (BTCA), and poly(acrylic acid) (PAA)]. These reactions were carried out in the dry state at a temperature greater than 140°C in air or in vacuo. They resulted in water‐soluble and insoluble polymers formed by polyesterification between CDx and PCA. In this study, the parameters of the reaction were studied, and their influence on the water solubility or swellability of the obtained polymers was investigated. High reaction temperatures, high PCA/CDx molar ratios, and long reaction times preferably yielded insoluble gels, whereas softer conditions resulted in very soluble polymers. The gels could swell up to 10 times their initial volume in water, and the water‐soluble fraction had a solubility of 1 g/mL. A reaction mechanism was proposed that required the use of PCA carrying at least three neighboring carboxylic groups (CTR, BTCA, and PAA), and it was confirmed experimentally by the unsuccessful use of some dicarboxylic acids. A preliminary characterization by Fourier transform infrared spectroscopy and size exclusion chromatography was also conducted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 433–442, 2005     

Reactions of halogenated 1,2-epoxypropanes and diethylaminoethyl cotton

Diethylaminoethyl (DEAE)-cotton has been reacted with epichlorohydrin (1,2-epoxy-3-chloropropane) neat, in alcoholic solvents, and in aprotic solvents at temperatures ranging from 25 to 95°C. Fabric properties and electron micrographs of fibers removed from these chemically treated DEAE cottons have been compared with those obtained when DEAE-cottons were treated under similar conditions with other halogenated 1,2-epoxypropanes, and with 1,2-epoxy-4,4,4-trichlorobutane. For comparative purposes, epichlorohydrin was reacted with an aminized cotton containing primary amine groups, with cotton containing quarternary ammonium groups, and with DEAE-cottons in which the tertiary amine groups had been quaternized. For reaction at 95°C with net epichlorohydrin, greatest increase in conditioned wrinkle recovery was observed with DEAE-cottons. Only with DEAE-cottons were the add-ons and recovery angles imparted by epichlorohydrin affected by the anion associated with the amine groups. None of the halogenated 1,2-epoxypropanes reacted with unmodified cotton in the absence of a basic catalyst. Those that reacted with unmodified cotton in the presence of an external base catalyst did not improve conditioned recovery angles. The mono-, di-, and trichloro-1,2-epoxypropanes all increased the conditioned and wet wrinkle recovery of DEAE-cotton when reacted neat at 95°C. The type of oxirane ring opening of epoxypropanes was shown to be influenced by the degree of chlorination of the carbon alpha to the ring. Both primary amine groups and quaternary amine groups catalyzed the epichlorohydrin–cellulose reaction. Dilution of epichlorohydrin with alcohols or decreasing reaction temperature lowered add-ons and improvements in wrinkle recovery properties. Use of aprotic solvents for the DEAE-cotton-epichlorohydrin reaction gave finished cotton fabrics having only high wet wrinkle recovery properties.     

Study of the Interfacial Reaction of Styrene/Maleic Anhydride Copolymerand (Amine)-Terminated Butadiene-Acrylonitrile Copolymer Using FTIR Imaging Techniques

The interfacial reaction between styrene/maleic anhydride copolymer (SMA) and amine-terminated butadiene-acrylonitrile copolymer (ATBA) was observed using Fourier transform infrared (FTIR) imaging spectroscopy. The anhydride and amine reacted to form an imide. Each component was detected using a characteristic wavenumber, which was 1601 cm ?1 for SMA, 2237 cm ?1 for ATBA, and 1701 cm ?1 for the imide. FTIR images were taken as the reaction proceeded at 150, 160, 170, and 180°C. At low temperatures (150 and 160°C), diffusion-controlled kinetics were observed since interdiffusion between the reactants did not appear in the images. On the other hand, both the diffusion front and the reaction front are observed in the images at high reaction temperatures (170 and 180°C), which indicates that the kinetics became reaction-controlled rather than diffusion-controlled. Absorbance profiles were extracted from the images and used for the calculation of the extent of reaction. The data were analyzed using the Frederickson and Milner theory based on the assumption of diffusion-controlled kinetics, and this theory fit the low reaction temperature data.     

Water absorption and disc cracking in urethane–methacrylate resins

Water absorption at 23 and 100°C has been studied in three materials based on a single type of urethane–methacrylate resin: the neat resin, a rubber-toughened blend containing 15 wt % of core-shell modifier, and a filled rubber-toughened resin containing 46 wt % silica plus 8 wt % core-shell modifier. In all six absorption experiments, water diffusion followed Fick's law. However, in neat resin at 100°C, the period of Fickian diffusion, during which the material appeared to reach saturation, was followed by an additional period of water uptake, which was accompanied by formation of internal disc cracks up to 1 mm in diameter. At both 23 and 100°C, fracture of water-saturated neat resin was defect dominated: cracks were initiated at inorganic impurities between 40 and 80 μm in diameter. The adverse effects of water are attributed to hydration and consequent swelling of these insoluble impurities. No internal cracking was detected in either the rubber-modified or hybrid resin, which have higher a K_ICs than the neat resin. © 1994 John Wiley & Sons, Inc.     

Synthesis of palm oil‐based polyester polyol for polyurethane adhesive production

Palm oil‐based polyester polyol is synthesized by ring opening reaction on epoxidized palm olein by phthalic acid. The reaction is carried out in a solvent free and noncatalyzed condition with the optimal reaction condition at 175°C for 5 h reaction time. The physical state of the product is a clear bright yellowish liquid with low viscosity value of 5700–6700 cP at 25°C and pour point of 15°C. The chemical structure and molecular weight of the polyester polyol were characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, and GPC. The optimal polyol with molecular weight of 36,308 dalton and hydroxyl value of 78.17 mg KOH/g sample was reacted with polymeric 4,4′‐methylene diphenyl diisocyanate (pMDI) at isocyanate index of 1.3 to produce polyurethane adhesive. The lap shear strength of the polyurethane adhesive showed two times higher than the commercial wood adhesives. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39967.     

Crosslinking reaction and properties of two‐component waterborne polyurethane from terpene‐maleic ester type epoxy resin

A two‐component waterborne polyurethane (2K‐WPU) is prepared with the terpene‐maleic ester type epoxy resin‐based polyol dispersion and a hydrophilically modified hexamethylene diisocyanate tripolymer. Laser particle size analyzer and transmission electron microscopy are used to characterize the particle size distribution and the micromorphology of the 2K‐WPU. Crosslinking reaction kinetics of the 2K‐WPU is examined by fourier transform infrared spectrometry (FTIR) spectra. In the preliminary stage of the crosslinking reaction, it shows a very good fit with a second order reaction kinetics, and the apparent activation energy is 94.61 kJ mol^?1. It is also shown from the FTIR spectra that the complete crosslinking reaction of the 2K‐WPU needs 7 h at 70°C. The crosslinked products of the 2K‐WPU have good thermal resistant properties, with glass‐transition temperatures (T_g) in the range of 35–40°C and 10% weight loss temperatures (T_d) in the range of 275–287°C. The films obtained from the crosslinked products have good water‐resistance, antifouling, blocking resistance properties and impact strength of >50 cm, flexibility of 0.5 mm, adhesion of 1 grade, pencil hardness of HB‐2H. The pencil hardness and thermal‐resistant properties of the crosslinked products increase with the molar ratio of isocyanate (? NCO) group to hydroxyl (? OH) group. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Properties of phenol–formaldehyde resin modified with organic acid esters

Properties of liquid and cured phenol–formaldehyde (PF) resin modified with esters were analyzed in this study. Esters with different carbon chain lengths, both in the acid and alcohol groups, were applied in the experiments. It was found that the modification of phenolic resin with applied esters does not deteriorate its pot life at the temperature of 20°C. It results in an increase of its reactivity at higher temperatures, manifested in the shortening of gel time at 130°C and a decrease of activation energy. Results of FTIR tests of polycondensed modified PF resin showed that products of alkali hydrolysis of esters not only catalyze the curing reaction of resin, but also become embedded in its structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modification of vital wheat gluten with phosphoric acid to produce high free swelling capacity

Wheat gluten reacts with phosphoric acid in the presence of urea to produce natural superabsorbent gels. Fourier Transform Infra‐red (FT‐IR) spectroscopy and two‐dimensional gel electrophoresis (2DE) reveal chemical changes from the reaction. Temperatures above 120°C and dry conditions create the opportunity for reaction. FT‐IR analyses confirm the formation of esters, carbamates, and phosphoramides on the gluten samples. 2DE protein composition topographies indicate a shift in the isoelectric point (pI) to lower values along with extensive inter‐protein linkages. A free swelling capacity (FSC) in excess of 85× the mass of the converted gluten is obtainable using a conservative vacuum‐assisted method to recover and quantify the properties of the wet gel. Other methods produce FSC values nearly twice as high. FSC for acid‐treated gluten is lower for solutions containing solutes than the FSC for deionized water. Native gluten produces FSC values that are about 2% of those for treated gluten, but these values are less sensitive to the presence of ionic solutes and increase slightly in the presence of aqueous ethanol up to a mole fraction of 0.25.. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39440.     

Solid phase enzymatic glycerolysis of beef tallow resulting in a high yield of monoglyceride

A mixture of mono-, di- and triglycerides was obtained when beef tallow was reacted with glycerol using lipase enzyme as a catalyst. The reaction was carried out batchwise in a small vessel with agitation by magnetic stirring. The yield of monoglyceride (MG) was greatly influenced by the reaction temperature—at higher temperatures (48–50°C) a yield of approximately 30% MG was obtained, while at lower temperatures (38–46°C) a yield of approximately 70% MG was obtained. A sharp transition was observed between the high and low yield equilibrium states. The temperature at which this transition occurred is called the critical temperature (T_c) and was found to be 46°C in the case of tallow. During the course of the reaction, when approximately 40% MG had been synthesized, the reaction mixture became solid but the reaction continued until approximately 70% MG had been synthesized. A yield of 70% MG also was obtained with tallow at 42°C when a glycerol/tallow mole ratio ranging from 1.5 to 2.5 was used. The free fatty acid content at equilibrium depended on the water concentration in the glycerol phase and varied from 0.5% to 11.0% when the water content ranged from 0.6% to 12.5%. Above 8% water content, the yield of MG was reduced. Of the commercially available lipases that were investigated, lipase fromPseudomonas fluorescens orChromobacterium viscosum resulted in the highest yield of MG.     

Reinforcement effect of nanodiamond on properties of epoxy matrix

Epoxy/nanocrystalline diamond nanocomposites composites were prepared by dispersing ultrasonically, 0.4, 0.7, 1.0, and 4.0 wt% acid‐treated nanocrystalline diamond (NCD) powder in epoxy matrix. Fourier infrared spectroscopy was utilized to study the moieties attached to the nanodiamond particles. The trace elements present in NCD powder before and after acid treatment were analyzed by ion beam techniques. Thermomechanical properties of the nanocomposites showed that incorporation of low content (0.4 wt%) of nanodiamond powder into epoxy matrix enhanced the storage modulus, loss modulus, and hardness by ∼68, ∼55, and ∼86%, respectively, over neat epoxy. By increasing the concentration of modified NCD to 0.7 wt% resulted in lower values of hardness and thermomechanical properties but still remain higher than neat epoxy. An increasing trend in properties was again observed at 4 wt% concentration of modified nanofiller. The glass transition temperature was up shifted to ∼110°C over neat epoxy. The mechanisms responsible for enhanced properties of epoxy matrix are also discussed in detail. POLYM. COMPOS., 34:811–818, 2013. © 2013 Society of Plastics Engineers     

Online monitoring of reaction temperature during cationic ring opening polymerization of epichlorohydrin in presence of BF3 and 1,4‐butanediol

This work introduces cationic ring opening polymerization of polyepichlorohydrin (PECH) produced under various reaction conditions (set temperature: ?10 to 40°C, [C]/[I] ratio: 0.1–1, monomer feed rate: 1–4 mL/min). In addition, a correlation between the exothermic reaction temperature and the performance of the PECH was obtained by utilizing a reaction temperature monitoring system, GPC, ¹H‐NMR, and FTIR. During the polymerization, an induction period which affects the polydispersity was observed below 10°C. At lower temperatures and lower [C]/[I] ratios, a higher induction period was observed. The monomer feed rate did not affect the induction period but it highly affected the polydispersity when the induction period occurred. The total molecular weight of PECH increased with decreasing set temperature even though the amount of low molecular weight cyclic oligomer increased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39912.     

Hot-Air Drying and Rehydration Characteristics of Red Kidney Bean Seeds

The effects of pretreatments such as citric acid and hot water blanching and air temperature on drying and rehydration characteristics of red kidney bean seeds were investigated. Drying experiments were carried out at four different drying air temperatures of 50°C, 60°C, 70°C, and 80°C. It was observed that drying and rehydration characteristics of bean seeds were greatly influenced by air temperatures and pretreatments. Four commonly used mathematical models were evaluated to predict the drying kinetics of bean seeds. The Weibull model described the drying behaviour of bean seeds at all temperatures better than the other models. The effective moisture diffusivities (D_eff) of bean seeds were determined using Fick's law of diffusion. The values of D_eff were between 1.25 × 10^?9 and 3.58 × 10^?9 m²/s. Activation energy was estimated by an Arrhenius-type equation and was determined as 24.62, 21.06, and 20.36 kJ/mol for citric acid, blanch, and control samples, respectively.     

Effect of temperature during vital gluten adhesive preparation and application on shear-bond strength

If protein-based adhesives are to become a competitive bio-based alternative to synthetic adhesives, the preparation and application methods have to be considerable improved to reduce process time and thereby improve the economy of the adhesive system. The purpose of this study was to investigate the impact of the temperature during preparation and application on the shear-bond strength of an adhesive based on vital gluten for use in wood applications. Vital gluten was used in its natural form and mixed with water of different temperatures (preparation temperature 0 °C or 20 °C), and applied on beech veneer at different temperature (application temperature –10, 20, 60 and 100 °C). Tensile shear-bond strength samples were prepared and tested according to EN 205. The results showed that an increase in veneer temperature during application of the adhesive led to a decrease in the shear-bond strength, but that the preparation temperature of the adhesive had no influence on the strength.     

Preparation and properties of polyhedral oligomeric silsesquioxane/epoxy hybrid resins

Octaaminophenyl polyhedral oligomeric silsesquioxane (OAPS) was synthesized using three‐step method and used to modify o‐cresol‐novolac epoxy resin (ECN) for printed circuit board. The influence of OAPS on the reactivity and the final properties of the hybrid networks were evaluated. The intercrosslinking reaction between ECN and OAPS was confirmed by Fourier transform infrared spectra. The ECN/OAPS hybrids have better impact strength, higher electrical resistivity and thermal stability, lower water absorption than the unmodified ECN. The volume resistivity and surface resistivity of the hybrids increase by an order of magnitude or more compared to the neat epoxy. The thermal stability of the hybrids improves by the incorporation of OAPS; the initial decomposition temperature and char yield show an increasing tendency up to 4 wt% loading of OAPS. The hybrids exhibit higher storage modulus and glass transition temperature (T_g) than the neat epoxy. The T_g of the hybrids greatly improves up to 153.3°C at 3 wt% content, much higher than 119.4°C of the neat epoxy. POLYM. COMPOS., 34:1753–1760, 2013. © 2013 Society of Plastics Engineers     

The effects of tension on the absorbance of water into neat and glass-bead-filled,cross-linked polyester

The effects of tension on the absorbance of water at 60°C into neat and glass-bead-filled, cross-linked polyester are reported. Experimental apparatus and procedure to determine water uptake for these materials subjected to three tensile stresses in the range of 0 to 30 percent of the breaking stress of the neat dry polyester are described. It was found, for bead-filled samples, that a load of approximately 4.9 × 10⁶ N/m² caused the absorption level to increase by 30 percent over that of an unloaded sample. Tensile load was found to have no effect on the absorption characteristics of neat polyester. However, breaking stress was reduced to less than 15 percent of that in the dry neat material. Optical microscope examinations of damage at the fracture surfaces and at the sample cores indicate that the excess moisture uptake in bead-filled samples was not due to microcrack formation.     

Development of composites based on recycled polyethylene/sugarcane bagasse fibers

In this work, sugarcane bagasse fibers were used as filler in composites having recycled high‐density polyethylene (PEr) as matrix. Because of the poor interaction between fibers surface and the PEr, the surface of bagasse was chemically modified. This modification consists of washing with water at 80°C, a mercerization process using sodium hydroxide and acetylation reaction with acetic anhydride. The chemical modification was characterized by Fourier transform infrared–horizontal attenuated total reflectance (FTIR‐HATR) and ¹³C nuclear magnetic resonance spectroscopies (NMR), thermogravimetric analysis (TGA), and scanning electronic microscopy (SEM). The composites were prepared from modified and unmodified fibers into PEr matrix, containing 5, 10, and 20% (w/w) of fiber. The samples were processed by extrusion and molds were prepared by injection process in order to perform mechanical tests. These materials were analyzed by SEM, TGA, and the water uptake was evaluated. Also, their mechanical properties were analyzed. Morphological analysis indicated that the chemical modification of sugarcane bagasse increased the compatibility between matrix and reinforcement. Tensile, flexural, and impact tests showed that the mechanical properties of the composite were improved compared to PEr due to the presence of the fibers. POLYM. COMPOS., 35:768–774, 2014. © 2013 Society of Plastics Engineers