Synthesis of triphenyl phosphine oxide‐containing polymers via atom transfer radical polymerization

Bis[(4 ‐β‐(2‐bromopropanoate)ethoxy)phenyl]phenylphosphine oxide was used for the first time as the initiator of atom transfer radical polymerization of styrene and methyl methacrylate in the presence of CuBr/N, N,N′, N″, N″‐pentamethyldiethylenetriamine as catalyst/ligand and dimethyl sulfoxide as solvent. The presence of phosphine oxide linkages in the backbone gives the polymers special properties; low T_g, high char yield, and decreases the oxygen induction time value. A linear increase of number average molecular weight (M_n) versus monomer conversion was observed, and the molecular weight distribution was relatively narrow (M_w/M_n = 1.1–1.3). FTIR, ¹HNMR, gel permeation chromatography, ultraviolet spectroscopies were used for the characterization of the related polymers. The thermal properties of these polymers were investigated by differential scanning calorimetry and thermogravimetric analysis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of borax addition on the structural modification of bentonite in biodegradable alginate‐based biocomposites

Functionalized next generation biodegradable polymeric systems (bioplastics) that have better compatibility, enhanced relaxation, and thermal properties were designed using bentonite‐added alginate biocomposite films in the presence of borax. A series of bentonite‐added biocomposite films crosslinked with CaCl₂ were characterized by using methods like XRD, FTIR, TGA, DTA/DSC, DMA, and AFM. A plausible structural mechanism with Ca²⁺ crosslinking gel formation known as egg‐box and borate ion complexes was proposed to elucidate the interactions between borax and bentonite/alginate biocomposites. Enhanced compatibility and hybrid properties of raw fillers were confirmed by mineral processing steps involving hydrocyclone purification for bentonite and recrystallization steps for borax. The structure of bentonite and also bentonite hybrid biocomposites were clearly improved upon small additions of borax into the matrix. The presence of borax was found to provide a more intercalated or exfoliated morphology for a given hybrid biocomposite structure. Borate ions dissociated in aqueous solution provided a better effect on the intercalation of bentonite by imparting new hydrogen bonding sites, diol‐complexes, and didiol‐crosslinking gels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

13C‐NMR, 13C‐13C gCOSY,and ESI‐MS characterization of ether‐bridged condensation products in N,N′‐dimethylurea‐formaldehyde systems

The reaction of urea with formaldehyde is the basis for the production of urea‐formaldehyde (UF) resins which are widely applied in the wood industry. The presence of ether‐bridged condensation products in the UF resin reaction system is an open question in the literature. It is addressed in the present work. The N,N′‐dimethylurea‐formaldehyde model system was studied since it is chemically similar to the UF resin reaction system but allows for a simple elucidation of all reaction products. It was analyzed by ¹³C‐NMR spectroscopy and ESI‐MS. In corresponding NMR and MS spectra, peaks due to methoxymethylenebis(dimethyl)urea and its hemiformal were observed. ¹³C‐¹³C gCOSY analysis was conducted using labeled ¹³C‐formaldehyde. The correlation spectra showed evidence for an ether‐bridged compound and mass spectra exhibited peaks agreeing with labeled methoxymethylenebis(dimethyl)urea and its hemiformal. Methoxymethylenebis(dimethyl)urea was characterized in N,N′‐dimethylurea‐formaldehyde systems in acidic and slightly basic media. As urea is very similar to N,N′‐dimethylurea, the results of this work strengthen the assumption that ether‐bridged condensation products are likely to form in UF resins. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of hydrolysis and denaturation of wheat gluten on adhesive bond strength of wood joints

In this study the adhesive bond strength of different wheat gluten modifications and the relationship between molecular weight and adhesive strength was examined. Guanidine hydrochloride and sodium hydroxide were used as denaturation and dispersing agent. Additionally wheat proteins were hydrolyzed by alkaline conditions and enzymes. Effects of different treatments were observed by viscosity measurements and gel electrophoresis. Wood lap joints were prepared with modified proteins and tensile shear strength was tested under dry and wet conditions. In situ hardening of different formulations was analyzed by means of DMA with two‐layered specimens in a three‐point bending test set‐up. Higher solubility had no positive effect on dry bonding strength and wet bonding strength was even reduced. Depending on the degree of hydrolysis, significant improvement of adhesive bond strength was observed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Property enhancement in unsaturated polyester nanocomposites by using a reactive intercalant for clay modification

Polymeric nanocomposites were synthesized from unsaturated polyester (UPE) matrix and montmorillonite (MMT) clay using an in situ free radical polymerization reaction. Organophilic MMT was obtained using a quaternary salt of coco amine as intercalant having a styryl group making it a reactive intercalant. The resultant nanocomposites were characterized via X‐ray diffraction and transmission electron microscopy. The effect of increased nanofiller loading on the thermal and mechanical properties of the nanocomposites was investigated. All the nanocomposites were found to have improved thermal and mechanical properties as compared with neat UPE matrix, resulting from the contribution of nanolayer connected intercalant‐to‐crosslinker which allows a crosslinking reaction. It was found that the partially exfoliated nanocomposite structure with an exfoliation dominant morphology was achieved when the MMT loading was 1 wt %. This nanocomposite exhibited the highest thermal stability, the best dynamic mechanical performance and the highest crosslinking density, most probably due to more homogeneous dispersion and optimum amount of styrene monomer molecules inside and outside the MMT layers at 1 wt % loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Deducing the Fatigue Crack Growth Rates of Natural Flaws in Silicon Nitride Ceramics: Role of R‐Curves

Fatigue failure is a concern when high‐strength, high‐toughness silicon nitride ceramics are used in mechanical components and the growth of natural flaws will determine the usable upper bound strength. In this study a fracture resistance curve (R‐curve) model is incorporated into an established method for deducing natural flaw growth rates from a combination of strength and fatigue life data for smooth specimens. Experimental data for a commercial silicon nitride, SL200, were examined. When compared with results deduced using a constant fracture toughness model, the new method gives more physically realistic growth rate results. Specifically, by incorporating the R‐curve the deduced fatigue threshold is equal to the reported intrinsic toughness for crack propagation of 2.2 MPa√m, whereas the constant fracture toughness model gives a physically unrealistic threshold value. Furthermore, much better agreement is achieved with the growth rates measured using macroscopic compact‐tension specimens. Overall, it is concluded that the R‐curve effect should not be ignored when deducing the fatigue crack growth rates of natural flaws in high‐toughness silicon nitride ceramics.     

Effect of ZnO on Crystallization of Zircon from Zirconium‐Based Glaze

The promotion of zircon (ZrSiO₄) crystallization by ZnO from a zirconium‐based frit glaze was studied and the possible mechanism was discussed. X‐ray diffraction was used to analyze the relative quantities of zircon and other transitional crystals in the samples. The results show that ZnO can significantly decrease the crystallization temperature of zirconium‐based glaze, depress the formation of Ca₂ZrSi₄O₁₂, and promote the devitrification of transitional crystals t‐ZrO₂ and Ca₂ZnSi₂O₇, as well as lead to the formation of more zircon than the ZnO‐free glaze. It was also found that zircon not only can form from the interaction between t‐ZrO₂ and SiO₂ but also can devitrify directly from the glass phase of zirconium‐based glaze.     

Improvement of Interfacial Adhesion of Glass Fiber/Epoxy Composite by Using Plasma Polymerized Glass Fibers

This study intends to produce plasma polymer thin films of γ-glycidoxypropyltrimethoxysilane (γ-GPS) on glass fibers in order to improve interfacial adhesion of glass fiber-reinforced epoxy composites. A low frequency (LF) plasma generator was used for the plasma polymerization of γ-GPS on the surface of glass fibers at different plasma powers and exposure times. X-ray photoelectron spectroscopy (XPS) and SEM analyses of plasma polymerized glass fibers were conducted to obtain some information about surface properties of glass fibers. Interlaminar shear strength (ILSS) values and interfacial shear strength (IFSS) of composites reinforced with plasma polymerized glass fiber were evaluated. The ILSS and IFSS values of non-plasma polymerized glass fiber-reinforced epoxy composite were increased 110 and 53%, respectively, after plasma polymerization of γ-GPS at a plasma power of 60 W for 30 min. The improvement of interfacial adhesion was also confirmed by SEM observations of fractured surface of the composites.