Retardation of enzymatic degradation of microbial polyesters using surface chemistry: effect of addition of non-degradable polymers

The effects of addition of non-degradable polymers on the rate of enzymatic erosion for the poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] have been studied at 37 °C and pH 7.4 in the aqueous solution of an extracellular PHB depolymerase from Alcaligenes facalis. Polystyrene (PS) or poly(methyl methacrylate) (PMMA) was selected as a minor component (5 wt%) in a blend because of their non-enzymatic activity. Enzymatic degradation behaviors of the “as-cast” and “annealed” blend films were investigated using atomic force microscopy and weight loss measurements. Although the spherulites of P(3HB-co-3HV) cover all blend film surfaces throughout, the retardation of biodegradation in the P(3HB-co-3HV)/PS blend films was detected from morphological observation and weight loss measurement for both as-cast and annealed blend films while there was little difference between the P(3HB-co-3HV)/PMMA blend and pure P(3HB-co-3HV). Since the enzymatic degradation of P(3HB-co-3HV) initially occurs by a surface erosion process, these degradation behaviors were explained by the surface structure of blend films measured by X-ray photoelectron spectroscopy. The surface of P(3HB-co-3HV)/PS blend films revealed an excess of PS, whereas the surface of P(3HB-co-3HV)/PMMA blend films was nearly covered by P(3HB-co-3HV). It was concluded, therefore, that the PS, which exists within P(3HB-co-3HV) spherulites at surface acts as a retardant of enzymatic attack to the surface of the blend film.     

Effects of Modifier Concentration on Structure and Viscoelastic Properties of Copolyester/Clay Nanocomposites

Abstract

Poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate)(PETG)/clay nanocomposites were prepared via melt intercalation technique. The effects of concentration of the organic modifier in the clay on the properties of the nanocomposites were studied. Three clays modified using the same alkyl ammonium modifier, but differing in modifier concentration, are used for this purpose. The nanocomposites are characterized using wide‐angle x‐ray diffraction for their structure. Dynamic mechanical analysis of these nanocomposites is also studied to investigate their viscoelastic behaviors. The x‐ray diffraction study shows an increase in the interlayer spacing of organically modified clays as compared to that of Na⁺ clay. The extent of increase in the interlayer spacing is dependent on the concentration of organic modifier used to modify the montmorillonite. The presence of well‐defined diffraction peaks and the observed increase in the interlayer spacing in the nanocomposites imply the formation of an intercalated hybrid. Dynamic mechanical properties show an increase in the storage modulus of the nanocomposite over the entire temperature range studied, as compared to the pristine polymer. Investigation of the rubbery plateau modulus confirms the reinforcing effect of organically modified clay. The observed enhancement in the modulus was greater for the clay with the lowest content of the organic modifier. These results indicate that in nanocomposites, apart from the compatibility of the organic modifier with the polymer, its concentration in the interlayer also plays a critical role in the structure development and thus in the enhancement of the properties. The nanocomposites showed reduced damping, which was governed by the modifier concentration in the clay.     

P(NIPAM-co-AA)/Clay nanocomposite hydrogels exhibiting high swelling ratio accompanied by excellent mechanical strength

In this paper, a series of P(NIPAM-co-AA)/Clay composite hydrogels (abbreviated as NAC gels) with high swelling ratio and excellent mechanical strength were synthesized and characterized by DMA, SEM, and IR. In NAC gels composed of a unique organic P(NIPAM-co-AA)/inorganic (clay) network, the inorganic clay acts as a multifunctional cross-linker in place of an organic cross-linker as used in the conventional chemically cross-linked hydrogels (abbreviated as OR gels). The NAC gels exhibit excellent swelling ratio, and there was no detectable change in properties on altering the concentration of clay, while the swelling ratio tends to decrease slightly when C _clay increases up to 25 wt%, which was revealed in swelling measurements. IR spectra show that clay has been intercalated by copolymers. Furthermore, results of DMA reveal that the composite hydrogel has an excellent mechanical strength by using a wide range of clay concentration, while the moduli improve with increasing C _clay.     

Effect of a Novel Polymeric Coupling Agent on the Water Uptake Property and Warp Stability of Poly(vinyl chloride)/Bamboo Flour Composite

Water uptake property and warp stability of poly(vinyl chloride) (PVC)/bamboo flour composite were investigated employing a novel polymeric coupling agent, poly(styrene-co-maleic anhydride)-block-poly(styrene-co-acrylonitrile) {P[(SMA)-b-(SAN)]}. P[(SMA)-b-(SAN)] was synthesized through controlled/'living' radical polymerization (CRP) technique in an one-pot reaction and incorporated into the composite to improve the interfacial adhesion between PVC and bamboo flour. The structure of P[(SMA)-b-(SAN)] was confirmed by ¹H-NMR, FT-IR and GPC. PVC/bamboo flour composite sheets were then prepared from a single screw extruder and two-roll mill in the presence of P[(SMA)-b-(SAN)] coupling agent. As the content of the coupling agent increased, improved interfacial bonding between PVC and bamboo flour filler was observed. Water uptake property and warp stability were also improved in the presence of the coupling agent. These results suggest that the block copolymer successfully acted as a coupling agent in PVC/bamboo flour composites.     

Multifunctional core–shell nanoparticles: superparamagnetic,mesoporous, and thermosensitive

Multifunctional core–shell composite nanoparticles (NPs) have been developed by the combination of three functionalities into one entity, which is composed of a single Fe₃O₄ NP as the magnetic core, mesoporous silica (mSiO₂) with cavities as the sandwiched layer, and thermosensitive poly(N-isopropylacrylamide-co-acrylamide) (P(NIPAAm-co-AAm)) copolymer as the outer shell. The mSiO₂-coated Fe₃O₄ NPs (Fe₃O₄@mSiO₂) are monodisperse and the particle sizes were varied from 25 to 95 nm by precisely controlling the thickness of mSiO₂-coating layer. The P(NIPAAm-co-AAm) were then grown onto surface-initiator-modified Fe₃O₄@mSiO₂ NPs through free radical polymerization. These core–shell composite NPs (designated as Fe₃O₄@mSiO₂@P(NIPAAm-co-AAm)) were found to be superparamagnetic with high r ₂ relaxivity. To manipulate the phase transition behavior of these thermosensitive polymer-coated NPs for future in vivo applications, the characteristic lower critical solution temperature (LCST) was subtly tuned by adjusting the composition of the monomers to be around the human body temperature (i.e. 37 °C), from ca. 34 to ca. 42 °C. The thermal response of the core–shell composite NPs to the external magnetic field was also demonstrated. Owing to their multiple functionality characteristics, these porous superparamagnetic and thermosensitive NPs may prove valuable for simultaneous magnetic resonance imaging (MRI), temperature-controlled drug release, and temperature-programed magnetic targeting and separation applications.     

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.     

Effect of Surfactant Concentration on Thermal and Mechanical Properties of Poly(Butylene Succinate)/Organoclay Composites

Composite materials consisting of poly(butylene succinate) (PBS) and montmorillonite (MMT), modified to various extents using trihexyltetradecylphosphonium chloride (THTDP) cations, were prepared using a simple melt intercalation technique. The surfactant contents were varied, i.e. 0.4, 0.6, 0.8, 1.0, and 1.2 times the cation exchange capacity (CEC) of the MMT. The intercalation of the surfactant molecules into MMT layers, confirmed by the increase in interlayer spacing and significant changes in the morphology of the modified MMT, facilitated the dispersion of the clay in the PBS matrix. The properties of the PBS-based composites were changed with increasing surfactant content. The melting and crystallization temperatures increased and the degree of crystallinity (χ_c) decreased. The storage modulus was significantly enhanced below the glass transition temperature (Tg), and Tg shifted to a higher temperature, with a maximum at a surfactant loading of 0.6 CEC. The mechanical properties, including tensile strength, flexural strength, flexural modulus and impact strength, increased and then decreased with surfactant loading, with the maximum observed also at a surfactant loading of 0.6 CEC. In conclusion, an ideal balance between thermal and mechanical properties can be obtained at a surfactant quantity equivalent to 0.6 times the clay CEC. Moreover, all the composites exhibited obvious improvement in thermal and mechanical properties as compared to those of neat PBS.     

Preparation and Properties of Polylactide/Poly(ethylene-co-octene)/nano-SiO2 Ternary Composites

Polylactide (PLA)/poly(ethylene-co-octene)(POE) blends with various contents of nano-SiO₂ were prepared via melt mixing. The structure and properties of the PLA/POE/nano-SiO₂ ternary composites were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), rheometry, and tensile testing. The particle size of the dispersed POE phase first decreased with increasing nano-SiO₂ content and then remained constant. Nano-SiO₂ played an important role in the heterogeneous nucleation of PLA, which resulted in an increase of the crystallinity of PLA. The synergistic effect of both POE and nano-SiO₂ can significantly improve the toughness, strength, and modulus of PLA. When the ratio of PLA/POE/nano-SiO₂ was 90/10/0.5, PLA/POE/nano-SiO₂ composite had the best comprehensive properties.     

Preparation and Combustion Behavior of Polyamide 6/Polypropylene/Clay Nanocomposites

Polyamide 6(PA 6)/Polypropylene (PP) blends as well as PA 6/PP/clay composites were prepared by melt compounding. The distribution of clay was characterized by transmission electron microscopy. The combustion surface morphology as well as product composition after burning were studied by scanning electron microscopy along with electro-probe microanalysis. Moreover, the flame retardance and thermal stability were evaluated by a cone calorimeter together with thermogravimetric analysis. The results showed that the clay was selectively located in the PA6 phase. It is proposed that, in the presence of clay, the combustion surface changed from a branch-shaped structure to a compact carbonaceous–silicate structure. When the clay content was 3 phr, the layered silicates became enriched on part of the surface and formed an island-like structure; the islands displayed a loose cinders structure with much higher silicon content, in contrast to a branch-shaped surface with low silicon content of the surrounding polymer substrate. As the clay content continued to increase, the char covered most of the combustion surface and more clay accumulated on the burning surface. In addition, the clay particles promoted the formation of the carbonaceous–silicate structure. The peak of the heat release rate of the PA6/PP blend decreased with increasing addition of clay and the thermal stability of the PA6/PP blend also improved.     

Epoxy-organoclay nanocomposites: morphology,moisture absorption behavior and thermo-mechanical properties

The morphology and moisture barrier characteristics are studied of epoxy-based nanocomposites reinforced with layered silicates. Two different types of organoclay, including the quaternary alkylamine modified montmorillonite (KH-MT) and the octadecylamine modified montmorillonite (I30P), were studied. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that the I30P system exhibited a large increase in interlayer d -spacing from 3.39 mm to over 8 nm during the curing process, whereas the KH-MT system showed negligible changes in reflection angle and d -spacing, with the final interlayer distance of 3.39 nm after cure. The moisture absorption behaviour was different for different organoclays: the moisture absorption rate was similar for the neat polymer and the KH-MT system, which could be fitted to Fick's second law. The moisture absorption rate of the I30P system was much lower than the two systems, which was predicted using a non-Fickian model based on the ID Langmuirian solution. The deviation from the Fickian diffusion for the latter system is associated with exfoliated morphology and more uniform dispersion of clay particles, which altered the diffusion path of water molecules in the nanocomposite. The moisture diffusivity of nanocomposites in general decreased with increasing clay content, the reduction being more pronounced for the I30P system. The normalized permeability also showed a systematic degradation with increasing clay content, which agrees well with the prediction based on the tortuous path model.     

Electrical properties of expanded graphite/poly(styrene-co-acrylonitrile) composites

A four probe method was used to measure the electrical conductivities of poly(styrene-co-acrylonitrile)/expanded graphite composites. The composites showed excellent electrical conductivities in both a- and c-axes. The different effects of temperature and the applied current on the conductivities in a-axis and in c-axis were observed. It was found that the conductive behaviors of the composite were different from those of semiconductor and carbon black loaded polymer composites. All these differences and excellent conductivity were considered to be related to the structure of the composites.     

Dynamic rheological and dynamic thermomechanical properties of poly(trimethylene terephthalate)/short carbon fibre composites

The dynamic rheology and thermomechanical properties of poly(trimethylene terephthalate) (PTT)/short carbon fibre (CF) composites at different mechanical states were investigated by a rotational rheometer and a dynamic mechanical analyzer (DMA). At molten state, the composite melts were pseudo-plastic fluids, and the complex viscosity of the composite melts decreased much with increasing CF content because of the poor adhesion at the fiber/matrix interface. The viscous behavior was predominant rather than elastic behavior in the composites melt and viscous behavior was increased with increasing CF at low shearing frequency. An apparent slope change in storage modulus and loss modulus plot suggested that a structure change occurred in the melt that was dependent on shearing frequency. At glassy state, the storage modulus increased with increasing CF content, suggesting that CFs had good reinforcing effect on PTT. At glass transition region, the increasing loss modulus indicated a better toughness of the composites, and the elastic behavior was predominant rather than viscous behavior. Moreover, the glass-transition temperatures of the composites increased with 10% CF content. The composites have larger cold-crystallization rate than pure PTT.     

Preparation of Silica/Poly(divinylbenzene) Composite Particles by Dispersion Polymerization in Supercritical Carbon Dioxide

Silica/poly(divinylbenzene) (PDVB) composite particles were synthesized by the dispersion polymerization of divinylbenzene (DVB) with ultrafine silica particles in supercritical carbon dioxide (scCO₂). Silica particles of average diameter 130 nm were pretreated with 3-(trimethoxysilyl) propyl methacrylate in order to be well dispersed in CO₂ and participated in the polymerization. Random copolymeric dispersant, poly(diisopropylaminoethyl methacrylate-co-heptafluorobutyl methacrylate) was used as a stabilizer to provide sufficient stabilization to latexes in scCO₂ and the silica/PDVB composite powder was obtained in high yield from the polymerization. SEM analysis revealed that the composite particles prepared at 5% silica loading ratio and 6% stabilizer concentration with respect to monomer have the average diameter of 1.60 μm with uniform and spherical morphology. The composites were also characterized by FTIR spectroscopy and TGA.     

Electromagnetic shielding of multiwalled,bamboo-like carbon nanotube/methyl vinyl silicone composite prepared by liquid blending

Multiwalled, bamboo-like carbon nanotube (BCNT)/methyl vinyl silicone (MVQ) composites with different concentrations of BCNT were fabricated by liquid blending method with an aim to investigate the behavior of such composites as effective electromagnetic interference shielding material in the frequency range of 1–6?GHz. The morphology and structure of BCNT were characterized and elucidated. Scanning electron microscopy examination showed that the BCNTs homogeneously dispersed in MVQ. The electrical conductivity (σ) and shielding effectiveness (SE) of the composite were measured and discussed. The results showed that the BCNTs/MVQ composites had a relatively low percolation threshold at 0.92?wt. % BCNT, and the σ showed a decreasing linear relation with temperature, i.e., the σ slightly decreased with increasing temperature. The BCNTs/MVQ composites with SE of 33–38?dB were obtained at 7?wt. % BCNT loading. Shielding mechanism was studied by resolving the total incident energy into absorbed, reflected, and transmitted contribution, and the result showed that the dominated shielding mechanism was reflection loss.     

Charge transport properties of composites of multiwalled carbon nanotube with metal catalyst and polymer: application to electromagnetic interference shielding

We report charge transport properties such as d.c. conductivity (σ_DC) and its temperature dependence for composites of poly(methyl methacrylate) (PMMA) and multiwalled carbon nanotubes (MWCNTs). The MWCNTs were synthesized through chemical vapor deposition with Fe or Co as catalyst. The MWCNTs were homogeneously dispersed in PMMA matrix through sonication to prepare MWCNT–PMMA composite films. We controlled mass concentration of MWCNTs in the composites, and the thickness of MWCNT–PMMA composite films was 20–400 μm. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy were used to study structure and homogeneity of the composites. The σ_DC at room temperature of MWCNT–PMMA composites increased as mass concentration of MWCNTs increased, which followed percolation theory. Electromagnetic interference (EMI) shielding efficiency (SE) of MWCNT–PMMA composites was measured in the frequency range of 50 MHz–3.5 GHz. We observed the increase of EMI SE of MWCNT–PMMA composites with increasing the concentration of MWCNTs.     

Synthesis and tribological properties of AA5052-base insitu composites

Abstract

It is important to optimize the properties of a material for a particular application, hence, to find the suitable material for tribological applications, the wear and friction behaviour of AA5052 in situ composites with different kind of reinforcements have been investigated. For present study, three in situ formed composites have been produced with different reinforcements namely Al₃Zr, ZrB₂ and combination of both (Al₃Zr + ZrB₂) by direct melt reaction (DMR) technique. The as-cast composites and base alloy have been characterized by X-ray diffraction (XRD), optical microscopy, electron microscopy, tensile testing, hardness and dry sliding wear and friction tests. XRD results indicate the successful formation of second phase reinforcement particles in all composites. Wear test results indicate that the cumulative volume loss increases with an increase in sliding distance while coefficient of friction shows a fluctuating tendency, whereas with increasing applied load, wear rate shows an increasing trend while coefficient of friction shows decreasing trend. The variation of wear rate with composites indicates that the composite with multiple reinforcement (Al₃Zr + ZrB₂) has lowest wear rate among all as-cast composites and base alloy, while coefficient of friction is higher. The responsible mechanisms concerned with wear and friction results have been discussed in detail with the help of the observation on worn surface analysis by scanning electron microscope (SEM) and 3D-profilometer. All tribological results have been correlated with the microstructural properties, strength parameters and bulk hardness of the composites.     

Electrical,optical and fluorescence percolations in P(VAc-co-BuA)/MWCNT composite films

Effects of multiwall carbon nanotube (MWCNT) addition on the electrical conductivities, optical transparencies and fluorescence emissions of poly(vinyl acetate-co-butyl acrylate) (P(VAc-co-BuA))/MWCNT composite films were studied. Optical transmission, fluorescence emission and two point probe resistivity techniques were used to determine the variations of the optical, fluorescence and electrical properties of the composites, respectively. Transmitted photon intensity (I _tr), fluorescence emission intensity (I _fl) and surface resistivity (ρ _s) of the composite films were monitored as a function of MWCNT mass fraction (M) at room temperature. All these measured quantities of the composites were decreased by increasing the content of MWCNT in the composite. The conductivity and the optical results were attributed to the classical and site percolation theories, respectively. The fluorescence results, however, possessed both the site and classical percolation theories at low and high MWCNT content regions, respectively.     

Phase composition, microstructure and electrical properties of alumina-zirconia eutectic composites

Oxide eutectic composites prepared by a directional solidification are noticeable for their good mechanical properties and high temperature stability in oxidizing environments. In this paper we study the influence of stabilizers (Y, Sc) on the phase composition, microstructure and electrical properties of Al₂O₃ - ZrO₂ eutectic composites. At a hypereutectic composition of the melt, we have prepared the composites with tetragonal ZrO₂, which possesses conductivities comparable to those of the composites containing cubic ZrO₂. An addition of Sc₂O₃ improves the ionic conductivity of the Al₂O₃ - (Y₂O₃)ZrO₂ eutectic composite at high temperatures. Both the microstructure and ionic conductivity do not change along the composite (grown at a constant growth rate). Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Synthesis and characterization of MnFe2O4-BiFeO3 multiferroic composites

The mixed spinel-perovskite composites of xMnFe₂O₄-(1-x)BiFeO₃ with x=0, 0.1, 0.2, 0.3 and 0.4 were prepared by solid state reaction method. The structure and grain size were examined by means of X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM), respectively. The XRD results showed that the composites consisted of spinel MnFe₂O₄ and perovskite BiFeO₃ phases after being calcined at the temperature 950 °C for 2 h. The grain size ranged from 0.8 to 1 μm. Magnetization was found to increase with increasing concentration of ferrite content. The variation of dielectric constant and dielectric loss with frequency showed dispersion in the low frequency range. Magnetocapacitance was also observed in the prepared composites, which may be the sign of magnetoelectric coupling in the synthesized composites at room temperature.     

Dielectric, ferroelectric and piezoelectric properties of 0-3 barium titanate–Portland cement composites

In this work, barium titanate (BT) and cement composites of 0-3 connectivity were produced with BT concentrations of 30%, 50% and 70% by volume using the mixing and pressing method. The dielectric constant (ε _r ) and the dielectric loss (tan δ) at room temperature and at various frequencies (0.1–20 kHz) of the ferroelectric BT-Portland cement composites with different BT concentrations were investigated. The results show that the dielectric constant of BT-PC composites was found to increase as BT concentration increases, and that the highest value for ε _r —of 436—was obtained for a BT concentration of 70%. In addition, the dielectric loss tangent decreased with increasing BT concentration. Moreover, several mathematical models were used; the experimental values of the dielectric constants are closest to those calculated from the cube model. The 0-3 cement-based piezoelectric composites show typical ferroelectric hysteresis loops at room temperature. The instantaneous remnant polarization (P _ir ), at an applied external electrical field (E ₀) of 20 kV/cm (90 Hz) of 70% barium titanate composite, was found to have a value ≈3.42 μC/cm². Furthermore, the piezoelectric coefficient (d ₃₃) was also found to increase as BT concentration increases, as expected. The highest value for d ₃₃ was 16 pC/N for 70% BT composite.