Effect of steric hindrance on hydrogen‐bonding interaction between polyesters and natural polyphenol catechin

The phase behaviors for the blends of poly(3‐hydroxypropionate) (PHP), poly(L ‐lactide) (PLLA), poly(D ‐lactide) (PDLA), and poly(D,L ‐lactide) (PDLLA) with catechin were investigated by differential scanning calorimetry. In PLLA/catechin, PDLA/catechin, and PDLLA/catechin blends, two glass transitions were detected when the catechin content was ≥40 wt %, whereas in PHP/catechin blends only one glass transition was observed over the whole range of blend compositions. The former and the latter results should reflect the inhomogeneous and the homogeneous nature of the blends, respectively, in the amorphous phase. These different phase behaviors should arise from the differences in the chemical structures between PHP and PLLA/PDLA/PDLLA, which dominates the strength and the number of intermolecular hydrogen‐bonding interactions between the ester carbonyl groups of polyesters and the phenol groups of catechin. As detected by FTIR spectroscopy, in comparison with PHP, the steric hindrance of side‐chain methyl groups of PLLA, PDLA, and PDLLA might restrain the formation of hydrogen bonds between their ester carbonyl groups and the phenol hydroxyl groups of catechin, even weakening the strength of such hydrogen bonds. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3565–3573, 2004     

Study on the cure behavior of 2,7‐dihydroxynaphthalene dicyanate

The cure behavior of 2,7‐dihydroxynaphthalene dicyanate (DNCY) was studied by means of nonisothermal DSC, isothermal DSC, and FTIR. In nonisothermal DSC, the cure kinetics parameters of DNCY were calculated by the Coats–Redfern method and compared with those of biphenol A dicyanate (BACY). It was revealed that the activation energy of DNCY was enhanced compared with that of BACY because of the presence of naphthalene, and the gelation of DNCY occurred within the conversion range 50–55%, which is lower than that of BACY. In isothermal DSC, a good time–temperature superposition of the conversion profiles of DNCY was obtained during conversions below about 50%. These results were consistent with those obtained by nonisothermal DSC. For the catalyzed system, the autocatalytic behavior prevailed at conversions below 30%, whereas the catalytic behavior occurred only at conversions above 30%. In situ FTIR spectra revealed that a triazine network was formed by cyclotrimerization of the OCN functional group during the cure process for systems with and without catalysts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3927–3939, 2004     

Synthesis and characterization of novel odd–even nylons based on eicosanedioic acid

A series of novel odd–even nylons based on eicosanedioic acid, including nylons 11/20, 9/20, 7/20, 5/20, and 3/20, were prepared through step‐heating melting polycondensation with various diamines, and the products were comprehensively characterized. The results of FTIR, Raman spectra, NMR, and elemental analysis confirmed that the synthesized polyamides had the expected chemical structures. The viscosity‐average molecular weights of the obtained polyamides were in the range of 6.0 × 10³–1.4 × 10⁴. The melting points of the nylons, determined by differential scanning calorimetry, changed from 167 to 194°C. Thermogravimetric analysis gave the decomposition temperatures of the obtained nylons at about 460°C, except for nylon 3/20. Furthermore, dynamic mechanical analysis (DMA) was applied to nylons 11/20, 9/20, 7/20, and 5/20. The glass‐transition temperatures, measured by DMA, ranged from 29 to 52°C. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2066–2071, 2004     

Glass transition and mechanical properties of PLLA and PDLLA‐PGA copolymer blends

The change of the glass transition temperatures (T_g) in the blend of poly(L ‐lactic acid) (PLLA) and the copolymers of poly(D,L ‐lactic acid) and poly(glycolic acid) (PDLLA‐PGA) with different D,L ‐lactic acid and glycolic acid composition ratio (50 : 50, 65 : 35, and 75 : 25) was studied by DSC. Dynamic mechanical measurement and tensile testing were performed at various temperatures around T_g of the blend. In the blend of PLLA and PDLLA‐PGA50 (composition ratio of PDLLA and PGA 50 : 50), T_g decreased from that of PLLA (about 58°C) to that of PDLLA‐PGA50 (about 30°C). A single step decrease was observed in the DSC curve around T_g between the weight fraction of PLLA (W(PLLA)) 1.0 and 0.7 (about 52°C) but two‐step changes in the curve are observed between W(PLLA) = 0.6 and 0.3. The T_g change between that of PLLA and that of PDLLA‐PGA and the appearance of two T_gs suggest the existence of PLLA rich amorphous region and PDLLA‐PGA copolymer rich amorphous region in the blend. A single step decrease of E′ occurs at around T_g of the pure PLLA but the two‐step decrease was observed at W(PLLA) = 0.6 and 0.4, supporting the existence of the PLLA rich region and PDLLA‐PGA rich region. Tensile testing for various blends at elevated temperature showed that the extension without yielding occurred above T_g of the blend. Partial miscibility is suggested for PLLA and PDLLA‐PGA copolymer blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2164–2173, 2004     

Allyl ether‐modified unsaturated polyesters for UV/air dual‐curable coatings. I: Synthesis and characterization of the oligomers and their cured films

Allyl ether (AE)‐modified unsaturated polyester oligomers were synthesized from polyethylene glycol (PEG), maleic anhydride (MAH), and trimethylolpropane mono allyl ether (TMPAE), and characterized by Fourier transform infrared (FTIR) spectra. The UV/air dual‐curable coatings were prepared from the oligomers using vinyl ether (VE) as a reactive diluent. FTIR spectra showed that C?C bonds in the coating composition had polymerized partially after cured by UV or air. The investigation of rheological behavior of the dual curable composition suggested that all the systems belonged to pseudoplastic fluid, and the increasing allyloxy content in oligomer resulted in a higher viscosity. Differential scanning calorimetry (DSC) analysis showed that the increasing TMPAE‐PEG molar ratio resulted in lower T_g, and all samples had the same glass transition temperature irrespective of the type of curing. The results of TGA for cured films indicated that UV‐cured film had better thermal stability than the air‐cured one. The air‐cured film showed superior pencil hardness, impact strength, and flexibility to the UV‐cured counterpart. However, the air‐cured film had poor adhesion and electric resistance properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2765–2770, 2004     

Modeling the curing kinetics for a modified bismaleimide resin using isothermal DSC

The kinetics of curing for a modified bismaleimide (BMI) resin was investigated to ascertain a suitable cure model for the material. The resin system used in this study was composed of 4,4′‐bismaleimidodiphenylmethane (BMIM) and 0,0′‐diallyl bisphenol A (DABPA, DABA). The BMIM was the base monomer and the DABPA was the modified agent. A series of isothermal DSC runs provided information about the kinetics of cure in the temperature range 170–220°C. Regardless of the different temperatures, the shape of the conversion curves was similar, and this modified BMI resin system underwent an nth‐order cure reaction. Kinetic parameters of this BMI resin system, including the reaction model, activation energy, and frequency factor, were calculated. From the experimental data, it was found that the cure kinetics of this resin system can be characterized by a first‐order kinetic model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3338–3342, 2004     

Comparative Study of Ultrasonication-Induced and Naturally Self-Assembled Silk Fibroin-Wool Keratin Hydrogel Biomaterials

This study reports the formation of biocompatible hydrogels using protein polymers from natural silk cocoon fibroins and sheep wool keratins. Silk fibroin protein contains β-sheet secondary structures, allowing for the formation of physical cross-linkers in the hydrogels. Comparative studies were performed on two groups of samples. In the first group, ultrasonication was used to induce a quick gelation of a protein aqueous solution, enhancing the ability of Bombyx mori silk fibroin chains to quickly entrap the wool keratin protein molecules homogenously. In the second group, silk/keratin mixtures were left at room temperature for days, resulting in naturally-assembled gelled solutions. It was found that silk/wool blended solutions can form hydrogels at different mixing ratios, with perfectly interconnected gel structure when the wool content was less than 30 weight percent (wt %) for the first group (ultrasonication), and 10 wt % for the second group (natural gel). Differential scanning calorimetry (DSC) and temperature modulated DSC (TMDSC) were used to confirm that the fibroin/keratin hydrogel system was well-blended without phase separation. Fourier transform infrared spectroscopy (FTIR) was used to investigate the secondary structures of blended protein gels. It was found that intermolecular β-sheet contents significantly increase as the system contains more silk for both groups of samples, resulting in stable crystalline cross-linkers in the blended hydrogel structures. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to analyze the samples’ characteristic morphology on both micro- and nanoscales, which showed that ultrasonic waves can significantly enhance the cross-linker formation and avoid phase separation between silk and keratin molecules in the blended systems. With the ability to form cross-linkages non-chemically, these silk/wool hydrogels may be economically useful for various biomedical applications, thanks to the good biocompatibility of protein molecules and the various characteristics of hydrogel systems.     

Zero-<Emphasis Type="Italic">trans</Emphasis> shortening using palm stearin and rice bran oil

Several pilot-scale trials reported in this paper, using palm stearin-rice bran oil (PS-RBO) blends, obviously did not contain trans FA (TFA), whereas the commercial products were found to contain 18–27% TFA. The effects of processing conditions such as rate of agitation, crystallization temperature, and composition of the blends on the crystal structure of shortenings were studied. The products were evaluated for their physicochemical characteristics using DSC, X-ray diffraction (XRD), HPLC, and FTIR techniques. The formulation containing 50% PS and 50% RBO showed melting and cooling characteristics similar to those of hydrogenated commercial “vanaspati” samples. Analysis of the FA composition revealed that the formulated shortenings contained 15–19% C_18∶2 PUFA. Tocopherol and tocotrienol contents of the experimental shortenings were in the range of 850–1000 ppm with oryzanol content up to 0.6%. XRD studies demonstrated that the crystal form in the shortenings was predominantly the most stable β′ form, and there was less of the undesirable β form.     

DSC and synchrotron-radiation X-ray diffraction studies on crystallization and polymorphic behavior of palm stearin in bulk and oil-in-water emulsion states

The crystallization and polymorphic behavior of palm stearin (PS) in a bulk state and in oil-in-water (O/W) emulsion droplets (average diameter, 1.7±0.3 μm) was observed by using DSC, optical microscopy, and in situ X-ray diffraction with synchrotron radiation (SR-XRD). For the bulk sample the DSC measurements revealed three main exothermic peaks at approximately 31 (large), 21 (small) and 3°C (medium) on cooling, and broad endothermic peaks at approximate −3 (small), 8, 15 to 25 (medium), and 37 and 53°C upon heating. The SR-XRD patterns taken during cooling from 60 to −5°C clarified that the DSC exothermic peaks around 31 and 3°C corresponded to crystallization of the α form of high-melting and low-melting fractions, respectively, and that the occurrence of β′ corresponded to the small exothermic peak around 21°C. The XR-XRD patterns taken during heating from −5 to 60°C demonstrated that the DSC endothermic peaks corresponded to the following transformation processes: melting of α of the low-melting fraction (−3°C), melt-mediated transformation from α to ∇′ (15–25°C), melting of β′ (36°C), and melting of β (53°C) of the high-melting fraction. As for the O/W emulsion sample, the DSC and SR-XRD measurements during the cooling and heating processes exhibited basically the same behavior as that of PS in the bulk state, except that β′ did not crystallize during the cooling process, and the temperatures of crystallization of α, melt-mediated α→β′→β transformation, and melting of β were lower in the emulsion droplets than in the bulk state.     

Reversible,repeatable and low phase transition behaviour of spin coated nanostructured vanadium oxide thin films with superior mechanical properties

Smooth, uniform and crystalline vanadium oxide thin films were deposited on quartz by spin coating technique with four different rpm i.e., 1000, 2000, 3000 and 4000 and subsequently post annealed at 350, 450 and 550?°C in vacuum. Transmission electron microscopy (TEM), Field emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) techniques were utilized for microstructural characterizations and phase analysis, respectively, for vanadium oxide powder and deposited film. Nanorods were observed to be grown after vacuum annealing. X-ray photoelectron spectroscopy (XPS) technique was utilized to study the elemental oxidation state of deposited vanadium oxide films. Thermo-optical and electrical properties such as solar transmittance (τ_s), reflectance (ρ_s), absorptance (α_s), infrared (IR) emittance (ε_ir) and sheet resistance (R_s) of different thin films were evaluated. Based on the optical characteristics the optimized condition of the film processing was identified to be spin coated at 3000?rpm. Subsequently, the nanoindentation technique was utilized to measure hardness and Young's modulus of the optimized film. The measured nanomechanical properties were found to be superior to those reported for sputtered vanadium oxide films. Finally, temperature dependent phase transition characteristics of optimized vanadium oxide films were studied by differential scanning calorimetry (DSC) technique. Reversible and repeatable phase transition was found to occur in the range of 44–48?°C which was significantly lower than the phase transition temperature (i.e., 68?°C) of bulk VO₂.