Silk‐inspired polyurethane containing glyalaglyala tetrapeptide. III. morphological,thermal, and mechanical features of electrosprayed and electrospun deposition

Morphological, thermal, and mechanical features of electrosprayed and electrospun deposition of the silk‐inspired polyurethane (PU) containing GlycineAlanineGlycineAlanine (GlyAlaGlyAla, the featured peptide sequence of silkworm silk fibroin) tetrapeptide, which was synthesized by the traditional liquid‐phase peptide synthesis method and the classical two‐step polymerization method using Boc‐protected amino acids and diisocyanates as starting materials, were characterized. The results show that the synthesized silk‐inspired PU dissolved in tetrahydrofuran (THF) can be easily electrosprayed or electrospun into the film form, although its molecular weight ranging from 13,000 to 15,000 is quite low. Elastomeric fibrous membranes with surface morphologies of “droplets,” “bead‐on‐string,” and “nonwoven fibers” have been obtained by electrospraying and electrospinning the silk‐inspired PU/THF solution of varying concentrations. The thermograms confirm high thermostability of the silk‐inspired PU between 350 and 400°C due to the polar peptide linkages. The tanδ peak of dynamic mechanical analysis curve corresponding to its glass transition temperatures is detected at ?34.3°C. Its elongation at break is about 140–150%, and the breaking tensile strength ranges from 22 to 27 MPa, which is consistent with the data of other PUs containing l ‐alanine residue. Information provided by this study can be used to better understand the correlation between the natural and man‐made silk polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40245.     

Synthesis and optical properties of poss‐based oxadiazole nanohybrids with three‐dimensional molecular conjugated structure

A series of oxadiazole‐containing molecular hybrid materials with three‐dimensional structure ( P1–P3 ) was prepared by Heck reaction based on the octavinylsilsesquioxane. All resultant hybrid materials are soluble in common organic solvents and possess good film‐forming property. Their structures and properties were characterized and evaluated by FTIR, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, MALDI‐TOF, UV–vis, photoluminescence (PL), cyclic voltammetry, and elemental analysis (EA). The results showed that the substituted arm numbers of hybrids ( P2 and P3 ) with pushing electron groups were efficiently controlled. Moreover, the hybrids possessed a steady blue emission and good electron‐injecting property in film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40246.     

Study the factors affecting the performance of organic–inorganic hybrid coatings

In this article, a series of hybrid organic–inorganic coatings based on silica‐epoxy composite resins were prepared with the sol‐gel method by using γ‐aminopropyl triethoxysilane as a coupling agent. Especially, the research emphasized on the factors that influenced on the properties of the prepared hybrid coatings. Firstly, epoxy resin was reacted with γ‐aminopropyl triethoxysilane at a specific feeding molar ratio; subsequently, the asprepared sol–gel precursor was cohydrolyzed with tetraethoxysilane (TEOS) at various contents to afford chemical bondings to form silica networks and give a series of organic–inorganic hybrid coatings. They were loaded and cured on steel panels and characterized for FTIR, TGA, DSC, water contact angles (WCA), pencil hardness, surface & three‐dimensional morphological studies, and potentiodynamic polarization tests. The surfaces of the hybrid coatings showed Sea‐Island or Inverting Sea‐Island morphologies at a certain relative content of two components, which made the coatings possess hydrophobic property. Due to the contribution of organic and inorganic components, the prepared hybrid coatings possess a lot of properties such as pencil hardness, thermotolerance, and corrosion resistance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41010.     

Fabrication and properties of carbon nanotube/styrene–ethylene–butylene–styrene composites via a sequential process of (electrostatic adsorption aided dispersion)‐plus‐(melt mixing)

Carbon nanotube (CNT)/styrene–ethylene–butylene–styrene (SEBS) composites were prepared via a sequential process of (electrostatic adsorption assisted dispersion)‐plus‐(melt mixing). It was found that CNTs were uniformly embedded in SEBS matrix and a low percolation threshold was achieved at the CNT concentration of 0.186 vol %. According to thermal gravimetric analysis, the temperatures of 20% and 50% weight loss were improved from 316°C and 352°C of pure SEBS to 439°C and 463°C of the 3 wt % CNT/SEBS composites, respectively. Meanwhile, the tensile strength and elastic modulus were improved by about 75% and 181.2% from 24 and 1.6 MPa of pure SEBS to 42 and 4.5 MPa of the 3 wt % CNT/SEBS composite based on the tensile tests, respectively. Importantly, this simple and low‐cost method shows the potential for the preparation of CNT/polymer composite materials with enhanced electrical, mechanical properties, and thermal stability for industrial applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40227.     

Thermal and flammability performance of polypropylene composites containing melamine and melamine phosphate‐modified α‐type zirconium phosphates

In this article, melamine (MA) and melamine phosphate (MP) have been intercalated into α‐type zirconium phosphate (α‐ZrP) interlayer spaces. The structure and thermal properties of the corresponding powders, MA‐ZrP and MP‐ZrP, were ascertained by X‐ray diffraction, Fourier transform infrared spectra, X‐ray photoelectron spectroscopy measurement, and thermogravimetric analyses (TGA). Furthermore, polypropylene (PP) and its intumescent flame retardant (IFR) composites containing the two organically modified α‐ZrP powders using maleic anhydride‐grafted PP (JPP) as compatibilizer were fabricated by melt blending. The results from TGA and cone calorimetry demonstrated that PP/JPP and PP/JPP/IFR composites containing MA‐ZrP and MP‐ZrP exhibited better thermal stability and burning behavior in comparison with their corresponding counterparts, PP/JPP and PP/JPP/IFR, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40254.     

Rapid fabrication of organic/organic photonic bandgap films with tuneable mechanical properties using blended polymer spheres

In this study, the photonic bandgap (PBG) film with tunable mechanical properties and photonic stop band was prepared by a simple and feasible approach. Colloid polymer spheres with a relatively large diameter (approximate D_n of 200 nm) and different glass transition temperatures (T_g) were blended with small polystyrene (PS) latex (D_n = 20 nm) and were subsequently casted on a substrate for 3 h at 50°C for self‐assembly of the PBG film. The monodispersed polymer spheres were synthesized by soap‐free emulsion polymerization in the boiling state. The T_g values of the spheres were predetermined based on the Fox equation, and designed to fall in the region of ?34°C to 112°C. Small PS could also be synthesized by this approach using the comonomer, sodium p‐styrenesulfonate (NaSS), to ensure the small diameter. The long‐range ordered structure constructed by embedding the small PS in the PBG film was indirectly confirmed on the basis of SEM analysis, from which the monochromatic film color was determined based on Bragg's diffraction law. Tunable film color was achieved by adjusting the diameter of the spheres, as evaluated using UV–Vis. Tunable mechanical properties of the PBG film were also achieved by varying the T_g of the spheres or the filling ratio of small PS. Based on these approaches, the ultimate tensile strength could be tuned in the region between 0.39 to 4.7 Mpa, and the relative strain could be varied from 1236% to 16%, illustrative of the excellent deformability of the film. Furthermore, by variation of these two parameters, the film properties could be changed from typical elastomer behavior to brittle plastic polymer type behavior, greatly extending the prospective application fields. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40276.     

Influence of charge density on rheological properties and dehydration dynamics of weakly charged poly(N-isopropylacrylamide) during phase transition

It is well-known that introduction of charged groups to poly(N-isopropylacrylamide) (PNIPAM) raises its phase transition temperature. However, the influence of charged groups on structural evolution and dehydration dynamics of weakly charged PNIPAM during phase transition still lacks systematic investigation. In the current study, armed with rheometer and two-dimensional Fourier transform infrared spectrometer (2D-FTIR), we investigated on mesoscopic and microscopic scales the phase transition of sodium poly(N-isopropylacrylamide-co-2-acrylamido-2-methylpropanesulfonate), abbreviated as poly(NIPAM-co-NaAMPS), with charge density of 1–10%. At ambient temperature, scaling exponent of poly(NIPAM-co-NaAMPS) varies from that of neutral polymer to polyelectrolytes as charge density increases. Above phase transition temperature, mesoscopic structure of poly(NIPAM-co-NaAMPS) varies from network of physical gel to viscoelastic liquid containing branched aggregates with increase of charge density, indicating increasing hindrance to intra/inter-chain association due to electrostatic repulsion. On a molecular level, poly(NIPAM-co-NaAMPS) exhibits distinctive microdynamic sequence of dehydration during phase transition, in contrast to neutral PNIPAM. In particular, sulfonate groups decouple the cooperative dehydration of alkyl and carbonyl groups, resulting in their distinctive phase transition temperature as well as temperature range. In analogy to hydration of proteins, it is proposed that the microdynamic sequence, implying the hydration stability of each group, is closely related to the density of hydration layer as well as influence of electrostatic field generated by charged groups. For poly(NIPAM-co-AMPS) with charge density of 3%, there still remains 72.3% of hydrogen bonds between carbonyl group and water at 60 °C, meanwhile a highly hydrated network forms with network strands 1–2 times as long as the copolymer chain length.     

Influence of injection molding on the electrical properties of polyamide 12 filled with multi-walled carbon nanotubes

Microinjection-molded and compression-molded polyamide (PA12) matrix composites filled with 0.67, 1.33, 2 and 4 wt% multi-walled carbon nanotubes (MWNTs) were prepared from twin-screw extruded pellets. The compression molded samples have an electrical percolation threshold close to 1.2 wt%. Coupled rheological and electrical measurements show that their electrical properties start decreasing as soon as shear begins and are partially restored during flow, suggesting successively breakage and reconstruction of a percolating network. On the other hand, the electrical properties of the microinjection molded composites are close to the matrix ones, showing that cooling is too fast for the MWNTs to form a network. There is some electrical anisotropy in these composites, as evidenced by a greater conductivity measured in the flow direction. However polarized Raman spectroscopy analysis does not reveal a significant orientation of the MWNTs.     

Thermal stability of modified end‐capped poly(lactic acid)

The influence of functional end groups on the thermal stability of poly(lactic acid) (PLA) in nitrogen‐ and oxygen‐enriched atmospheres has been investigated in this article using differential scanning calorimetry, thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA). Functional end groups of PLA were modified by succinic anhydride and l ‐cysteine by the addition–elimination reaction. PLA was synthesized by azeotropic condensation of l ‐lactic acid in xylene and characterized by nuclear magnetic resonance. The values of the activation energies determined by TGA in nitrogen and oxygen atmospheres revealed that the character of functional end groups has remarkable influence on the thermal stability of PLA. Moreover, DMA confirmed the strong influence of functional end groups of PLA on polymer chains motion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41105.     

Preparation and characterization of carboxymethyl starch under ultrasound‐microwave synergistic interaction

Using native cassava starch as raw materials, carboxymethyl starch (CMS) was prepared by ethanol solvent method under the ultrasound‐microwave synergistic interaction. And the structure of CMS was characterized employing Fourier transform infrared (FTIR) spectrometer, scanning electron microscopy (SEM), X‐ray diffraction (XRD) and thermogravimetric analyzer. Typically, the optimal synthesis conditions for the preparation process confirmed by orthogonal experiment L₁₈ (6¹ × 3⁶) were shown as follows: the ultrasonic treatment temperature was fixed to 35°C and two steps alkalization was employed; the ultrasonic time was 40 min before alkalizing and the ultrasonic power was 220 W; the amount of sodium hydroxide was 8.8 g, the microwave alkalization time was 2 min; the amount of monochloroacetic acid was 11.34 g; the amount of 95% (v/v) ethanol was 70 mL; the microwave etherification time was 3 min. The degree of substitution of prepared CMS was 1.089 ± 0.041, which was increased 30.4% compared with the prepared sample without ultrasound‐microwave synergistic treatment. FTIR results showed that the strong ? COO? characteristic absorption peaks of the stretching vibration were observed at 1613 and 1421 cm^?1, which proved that the carboxymethylation of cassava starch was occurred. SEM results suggested that there were many cracks and dents on CMS granules; and, XRD results indicated that the carboxymethylation of starch occurred both in amorphous region and crystalline region, the noticeable damage of crystalline region by carboxymethylation was observed. Thermogravimetric analysis (TG) and derivative TG showed that thermal stability of CMS changed better compared with native starch. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40906.