Dynamic Rheology of Poly(3-hydroxybutyrate-co-4-Hydroxybutyrate) /Clay Biocomposites

Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] composites filled with clay were prepared by a melt blending process. Dynamic rheology of the composites was measured by means of a rotational rheometer. The results showed that the interlayer spacing of the clay increased owing to the presence of the P(3HB-co-4HB) melt in the interlayer regions of the clay. The storage and the loss moduli of the composite samples increased with the increasing frequency, and decreased with the increasing temperature. The addition of the clay enhanced the oscillatory thinning behavior of the composite melts, and improved the processability of the P(3HB-co-4HB) melt. The decrease of the viscosity by increasing both frequency and temperature was feasible and effective for the composites with the clay contents of 1 and 2 wt.%.     

A Study on the Morphology and Mechanical Properties of PVC/nano‐SiO2 Composites

Three methods were used to modify nano‐SiO₂ particles with various interfaces and interfacial interactions between the particles and Poly(vinyl chloride) (PVC) matrix. The experimental results show that direct surface treatment of nano‐SiO₂ particles with a silane coupling agent (KH‐550) is not effective for improving the mechanical properties of PVC/SiO₂ composites. Both ultrasonic oscillations and high energy vibromilling improve the interfacial interactions between SiO₂ particles and PVC matrix. With these methods, the aggregation of SiO₂ particles was inhibited and a good dispersion of SiO₂ particles in PVC matrix was obtained, which improved the mechanical properties of the PVC/SiO₂ composite. The mechanical properties of the PVC/SiO₂ composite with high energy vibromilling modified SiO₂ particles were remarkably improved. Scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), dynamic mechanical analysis (DMA), and theoretical calculations demonstrate these improvements.     

Proton-conducting composite membranes from graft copolymer electrolytes and phosphotungstic acid for fuel cells

New organic–inorganic composite membranes based on poly(vinylidene fluoride-co-chlorotrifluoroethylene)-graft-poly(styrene sulfonic acid) [P(VDF-co-CTFE)-g-PSSA] with embedded phosphotungstic acid (PWA) were prepared. Fourier transform infrared spectra indicated the existence of a specific interaction between P(VDF-co-CTFE)-g-PSSA graft copolymer and PWA particles. PWA nanoparticles were well confined in the polymeric matrix up to 20 wt.%, above which they started to be extracted from the matrix, as revealed by scanning electron microscope analysis. Accordingly, Young’s modulus of membranes also increased with PWA concentration up to 20 wt.%, above which it continuously decreased. Upon incorporation of PWA nanoparticles, the proton conductivity of composite membranes slightly decreased from 0.042 to 0.035 S/cm at room temperature up to 20 wt.%, presumably due to strong interaction between the sulfonic acids of graft copolymer and PWA nanoparticles. The characterization by thermal gravimetric analysis demonstrated the enhancement of thermal stabilities of the composite membranes with increasing concentration of PWA.     

Towards Finding The Best Existing Model for Prediction of Morphology of Ternary Polymer Blends

The goal of this study was to investigate the capability of conceptual models for correct prediction of ternary blends morphology. All existing models, including spreading coefficient, relative interfacial energy, dynamic interfacial energy (DIE), and modified DIE were employed to predict the type of morphology of the polyamide 6/poly(styrene-co-acrylonitrile)/poly(styrene-b-(ethylene-co-butylene)-b-styrene) ternary system. Various samples with different compositions were prepared and predictions of the models were compared with the experimental phase morphology of the samples based on scanning electron microscopy micrographs. Additionally, the effect of elasticity of the matrix component on the both predictions and experimental phase structures of the blends was studied. It was demonstrated that, among the available phenomenological models, the modified DIE can comprehensively represent the most correct predictions for the morphology of ternary polymer blends.     

Melt blends of san with phenoxy

Melt blends of styrene-co-acrylonitrile (SAN) with phenoxy were prepared over a full range of compositions and were evaluated in terms of morphological, rheological, thermal, and mechanical properties. Viscosity-composition plots showed a crossover with the additivity line at 50/50 (SAN/phenoxy by weight), and deviations from semicircles in Cole‐Cole plots were seen for 70/30, 50/50, and 30/70 blends. Scanning electron micrographs (SEM) of the blends showed a two-phase morphology with a finer dispersion and well-elongated fibrils seen when SAN formed the dispersed phase. The glass transition temperature (T _g) of SAN was almost unchanged in the blends, whereas T _g of phenoxy was increased over 5°C. Tensile modulus and strength generally showed synergistic effects in phenoxy-rich blends. In the 10/90 blend, the ultimate elongation was greater than for pure phenoxy, and a dramatic drop of Izod impact strength was observed.     

Superparamagnetic nanocomposites based on poly(styrene-b-ethylene/butylene-b-styrene)/cobalt ferrite compositions

Magnetic nanoparticles were created in or around the sulfonated (s) polystyrene domains in a phase separated poly[styrene-b-(ethylene-co-butylene)-b-styrene)] block copolymer (BCP) using an in situ inorganic precipitation procedure. The sBCP was neutralized with a mixed iron/cobalt chloride electrolyte and the doped samples were converted to their oxides by reaction with sodium hydroxide and further washing with water. Transmission electron microscopy indicated the presence of nanoparticles in the 5–25 nm size range. The metal oxide particle structures were studied using select area electron diffraction, which revealed that they are of the cobalt iron oxide composition (CoFe₂O₄). These nanocomposites were shown, using a superconducting quantum interference device magnetometer, to be superparamagnetic at 300 K and ferrimagnetic at 5 K. Nanocomposites consisting of smaller particles have a blocking temperature of 70 K, whereas it was 140 K for larger particles.     

Preparation of Gold/triblock Copolymer Composite Nanoparticles

A kind of novel gold (Au)/hydroxylated poly (styrene-b-butadiene-b-styrene) triblock copolymer (HO-SBS) composite nanoparticles was synthesized by reduction of tetrachloroaurate ions in HO-SBS micelle. The Au–HO-SBS composite nanoparticles are composed by gold core about 35 nm in diameter and polymer shell about 7 nm in thickness. Formation of the Au/HO-SBS nanoparticles is indentified by infrared (IR) and UV-visible absorption spectroscopies. Transmission electron microscopy (TEM) result shows that the composite nanoparticles tend to aggregate into an ordered hexagonal array on carbon-coated grid.     

Intermacromolecular complexation due to specific interactions. 7. Miscibility and complexation between poly(styrene-co-4-vinyl benzoic acid) and poly[n-butyl methacrylate-co-(4-vinylpyridine)]

The miscibility between poly(styrene-co-4-vinyl benzoic acid), that is, carboxylated PS (CPS), and polyfn-butyl methacrylate-co-(4-vinylpyridine)] (BVPy) was investigated using differential scanning calorimetry (DSC). The results showed that, when the 4-vinyl pyridyl content in BVPy was higher than about 5 mol%, the CPS/BVPy system exhibited miscibility for the carboxyl content in CPS as it varied from 1.6 to 20 mol%. Complexation between CPS and BVPy in non-aqueous solutions was studied by viscometry. It was found that, when the density of hydrogen bonding between the proton-donating and the proton-accepting polymers reached a certain level, an intermacromolecular complex would form as turbidity and/or precipitate in organic solutions such as 2-butanone and THF. Combining the results from DSC and viscometry in 2-butanone, an immiscibility-miscibility-complexation map for the CPS/BVPy system was obtained.     

General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors

A general approach to fabricate nanoparticle arrays of different kinds of materials is demonstrated in this paper. It was found that the center-to-center distance of the nanoparticles or the nanoclusters can be controlled using patterned block copolymer nanoreactors by adding polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin film. The number of the nanoparticles formed in the P4VP nanodomains can also be adjusted by addition of polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer. In fabrication of Au nanoparticle arrays, HAuCl₄ precursor was directly loaded into P4VP nanodomains of the diblock copolymer thin film by using a methanol solvent, which is a good solvent for P4VP but non-solvent for PS. The Au nanoparticle arrays were then obtained by reducing HAuCl₄ with sodium citrate dihydrate, and then in situ transferred to silicon substrate by a two-step calcination method. ZnO and Fe _x O _y nanoparticle arrays were also synthesized by this approach with thermal decomposition and double decomposition reactions, respectively. Additionally, the advantage of using two-step calcination method over the air plasma method was discussed.     

Toughening Effect of Poly(ethene-co-1-butene)-graft-methyl Methacrylate and Acrylonitrile on Styrene-acrylonitrile Copolymer (SAN)

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN), synthesized by suspension grafting copolymerization of methyl methacrylate and acrylonitrile onto PEB, was blended with styrene-acrylonitrile copolymer (SAN). The mechanical properties, phase structure, toughening mechanism, miscibility, and thermal stability of the SAN/PEB-g-MAN blends were studied using a pendulum impact tester, tension tester, scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TG). The results showed that PEB-g-MAN has an excellent toughening effect on SAN resin. The notched impact strength of the blends (containing 25 wt% PEB) was 63.3 kJ/m², which was nearly 60 times that of SAN resin. The brittle-ductile transition of SAN/PEB-g-MAN blends occurred when the weight percentage of PEB was between 17.5 and ～20 wt%. SAN and PEB-g-MAN were partially miscible. The toughening mechanism of the blends changed with the PEB content. When the PEB content was low, the toughening mechanism of the blends was branching and termination of cracks with slight cavitation. As the content of PEB increased, the toughing mechanism gradually changed from branching and termination of crack with slight cavitation to both branching and termination of crack and cavitation, to extensive cavitation, and finally to shear yielding accompanied by cavitation. The phase structure of the blends changed from a “sea-island’’ structure to a cocontinuous structure as the PEB content increased. ATG analysis showed that the thermal properties of the SAN resin in the blends were enhanced by adding the PEB-g-MAN.     

Upgrading poly(butylene succinate)/wood fiber composites by esterified lignin

Aliphatic chains were introduced into the macromolecule of kraft lignin using aliphatic chlorides as esterification reagents. The hydrophobicity of esterified lignin (EL) was enhanced as compared to the original lignin. EL was further used as a macromolecular coupling agent in poly(butylene succinate)/chemi-thermomechanical pulp fiber composites. As a result, the composites with enhanced mechanical performance were obtained, and the tensile strength, impact strength, and bending strength were increased by 25.1, 22.4, and 19.3%, respectively, under 2 wt% EL-treatment (synthesized by palmitoyl chloride, –COCl/–OH = 1.5:1) in comparison with those of the specimen without any coupling agent treatment. Furthermore, the composite prepared with EL-treated fibers shows significant lower water absorption ratio than that of untreated one. A significant increase in storage modulus (E′) was observed upon the incorporation of treated fibers. Furthermore, the improved interfacial bonding between treated fibers and matrix was verified by SEM images. The shear viscosity of composite was increased by the incorporation of EL, but in general, the rheological behaviors of composites are not significantly changed.     

Organic synthesis in water: a green protocol for the synthesis of 2-(cyclohexylamino)-3- aryl- indeno[1,2-b]furan-4-ones

Aldehydes, 1,3-indandione and cyclohexylisocyanide undergo smooth coupling-cyclization in water to produce the corresponding 2-(cyclohexylamino)-3-aryl- indeno [1,2-b] furan-4-ones in good yields. Water was used as a solvent to avoid the use of other highly toxic and environmentally unfavorable solvents for this synthesis.

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Graphical Abstract  A simple and efficient synthesis of 2-(cyclohexylamino)-3-aryl- indeno[1,2-b]furan-4-ones was achieved via a one-pot three-component reaction of cyclohexylisocyanide, aldehydes, and 1,3-indandione in water for 5 h in good yields. zFX

     

The interfacial diffusion of chromium(III) fumarato coordination compound in the formation of aluminum-polyethylene composite film

The aqueous solution of chromium(III) fumarato coordination compound (Volan 82) is a coupling agent developed by DuPont in the early 1970's. The application of Volan 82 in the production of aluminum-polyethylene composite film greatly improves the water-resistance and durability of the composite film. Our previous studies demonstrated the chemical bonding between aluminum oxide and chromium(III) fumarato coordination compound. In this paper, AES is reported for the studies of the solvent-resistance of the interfacial polyethylene of the composite film. The AES sputter depth profile of the aluminum-polyethylene interfacial layer demonstrated that the chromium(III) fumarato coupling agent diffused into the interfacial polyethylene layer during the formation of aluminum-polyethylene composite film. This was confirmed by ESCA, when chromium was detected in the interfacial polyethylene layer. The interfacial diffusion of the coupling agent improves the adhesion between aluminum and polyethylene of the composite film.     

Effect of enhancement of interface performance on mechanical properties of shape memory alloy hybrid composites

Effect of enhancement of interface performance on mechanical properties of shape memory alloy hybrid composites (SMAHCs) was investigated in this work. Composite laminates without Ni-Ti shape memory alloy (SMA) fibers, with Ni-Ti SMA fibers polished, corroded and modified by silane coupling agent KH550 were taken into comparison to investigate the effect of surface treatments. Surface morphology of Ni-Ti fibers under different treatments were observed with scanning electron microscope. The mechanical performance of specimens without Ni-Ti fibers and with Ni-Ti fibers under different treatments were investigated through tensile, three-point bending and low-velocity experiments. The morphology and micromorphology were observed to study the effect of different surface treatment methods. The conclusion shows that embedded Ni-Ti SMA fibers can enhance the mechanical performance of composite laminates. However, the performance of Ni-Ti SMA fibers was restrained by the poor interface performance. After surface treatments, SMAHCs illustrate better mechanical performance owing to the enhanced interface performance. Among all the surface treatment methods, modification with silane coupling agent KH550 shows the best effect.     

The thermal and thermomechanical behaviors of Spartium junceum flour reinforced polypropylene composites: effects of treatment and flour content

The effects of Spartium junceum (SJ) flour content, treatment time on the thermal and thermomechanical properties of polypropylene/Spartium junceum flour (PP/SJ) composites were studied. In order to improve the interfacial adhesion between the PP matrix and the SJ flour, SJ flour was treated with NaOH (2 wt%) for 8, 24 and 48 h at ambient temperature, respectively, and treated by vinyltrimethoxysilane (VTMS) (5 wt%). The results of thermogravimetric analysis (TGA) of SJ flour shows that the treatment improves the thermal stability of SJ flour. DSC analysis measurements illustrates that the addition of SJ flour increase the degree of crystallinity X_c, which indicate that the SJ flour plays a significant role in heterogeneous nucleating of PP matrix. The chemical treatments significantly affect the storage modulus of composite, where E′ increases for composites with treated flour in comparison to the untreated ones.     

Interfacial debonding behavior of a rigid particle-filled polymer composite

Glass beads, non-modified and modified with coupling agent, were filled separately into high density polyethylene to obtain composite materials with different interfacial adhesion strengths. In situtensile tests reveal the damage mechanisms, which are mainly induced by the interfacial debonding. The interfacial debonding process is observed and studied. The debonding stress is found to be linearly related to the opening angle formed at two poles of the particles. Initial and final opening angles, in addition to the corresponding debonding stresses, are measured. The interfacial fracture energy obtained by using the Griffith fracture theory is found to be 0.028 J m^-2 and 0.058 J m^-2 for mechanical anchorage and physical entanglement across the interface, respectively. The stronger the interfacial adhesion, the smaller is the maximum opening angle and greater the debonding stress.     

Fabrication of ceramic oxide-coated SWNT composites by sol–gel process with a polymer glue

The functional copolymer bearing alkoxysilyl and pyrene groups, poly[3-(triethoxysilyl)propyl methacrylate]-co-[(1-pyrene-methyl) methacrylate] (TEPM₁₃-co-PyMMA₃), was synthesized via atom transfer radical polymerization. Attributing the π–π interaction of pyrene units with the walls of single-walled carbon nanotubes (SWNTs), this polymer could disperse and exfoliate SWNTs in different solvents through physical interaction as demonstrated by TEM, UV/Vis absorption, and FT-IR analysis. The alkoxysilyl groups functionalized SWNTs were reacted with different inorganic precursors via sol–gel reaction, and, as a results, silica, titania, and alumina were coated onto the surface of SWNTs, respectively via copolymers as a molecular glue. The nanocomposites of ceramic oxides/SWNTs were characterized by SEM analysis. Dependent upon the feed, the thickness of inorganic coating can be tuned easily. This study supplies a facile and general way to coat SWNTs with ceramic oxides without deteriorating the properties of pristine SWNTs.     

Maintenance of highly interfacial shear strength by diblock copolymer between carbon fiber and epoxy resin in hostile environment

The environmental resistance properties of carbon fiber (CF), with various surface modifications, reinforcing epoxy resin composites have been studied by a microbond test. The results of cooling–heating cycling between ?40 and 95?°C indicate that the introduction of the flexible poly(n-butyl acrylate) (PnBA) blocks into the interface can effectively decrease the interfacial degradation rate, induced by interfacial thermal stress. After 50 cooling–heating cycles, the interfacial shear strength between CF and epoxy resin was still as high as 32.69?±?2.13?MPa. The results of hygrothermal treatment by immersing the composites in hot water show that assembly morphology of the diblock copolymer hydroxyl-terminated poly(n-butyl acrylate-b-glycidyl methacrylate) (OH-PnBA-b-GMA) at the interface can decrease the interfacial water absorption and thus increase the hygrothermal resistance of the composite. Besides, the length of PnBA block in the diblock copolymer influenced the interfacial properties of the composite in a hygrothermal environment.     

Spontaneous condensation in DNA-polystyrene- b-poly(l-lysine) polyelectrolyte block copolymer mixtures

We investigated the condensation of calf thymus DNA by amphiphilic polystyrene_m-b-poly(l-lysine)_n block copolymers ( PS_m-b- PLys_n, m, n = degree of polymerization), using small-angle X-ray scattering, polarized optical microscopy and laser scanning confocal microscopy. Microscopy studies showed that the DNA condenses in the form of fibrillar precipitates, with an irregular structure, due to electrostatic interactions between PLys and DNA. This is not modified by the presence of hydrophobic PS block. Scattering experiments show that the structure of the polyplexes corresponds to a local order of DNA rods which becomes more compact upon increasing n. It can be concluded that for DNA/ PS_m-b- PLys_n polyplexes, the balance between the PLys block length and the excess charge in the system plays an essential role in the formation of a liquid crystalline phase.     

Intermacromolecular complexation due to specific interactions. 6. Miscibility and complexation between Poly{Styrene-co-[p-(2-Hydroxypropan-2-yl)Styrene]}and poly[n-butyl Methacrylate-co-(4-vinylpyridine)]

In recent years, considerable attention has been focused on polymer miscibility and Complexation due to hydrogen bonding. Monodisperse, proton-donating polystyrene (PS), that is, poly{styrene-co-[p-(2-hydroxypropan-2-yl)styrene]} [PS(t-OH)], was synthesized via chemical modification of polystyrene. Poly[n-butyl methacrylate-co-(4-vinylpyridine)] (BVPy), as a proton acceptor, was prepared by free-radical copolymerization of the corresponding monomers at low conversion. In organic solutions of PS(t-OH)/BVPy blends, viscometry was employed to study the Complexation behavior. Solvents with different proton-accepting abilities were used and hence proved to exert distinctive effects on solution complexation. In very dilute solutions, the complex aggregate was observed by static and dynamic light scattering (LS). Differential scanning calorimetry (DSC) investigation proved that miscibility could be greatly enhanced when a small amount of hydrogen bonding was introduced into the originally immiscible PS/PBMA (polybutyl methacrylate) system. Although it was found that the T _g of the hydrogen-bonding polymer complexes occurred at higher temperatures with respect to linear weight-average value, DSC measurement alone could not accurately distinguish polymer complexes from ordinary miscible blends. Based on the data of miscibility from DSC and complexation from vis-cometry in 1,2-dichloroethane for a few tens of blends, which cover broad ranges of the contents of interaction sites, a map showing the immiscibility-miscibility-complexation transitions by strengthening the hydrogen bonding for the system of PS(t-OH)/BVPy was successfully constructed.