Preparation and flammability of a novel intumescent flame-retardant poly(ethylene-co-vinyl acetate) system

A phosphorus-containing flame retardant, 4-(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinan-2-yloxymethyl)-2,6,7-trioxa-1-phospha-bicyclo[2.2.2]octane-1-oxide (MOPO), was synthesized successfully and characterized. The flame retardancy and thermal behavior of a new intumescent flame-retardant (IFR) system for EVA, which was made of MOPO and ammonium polyphosphate (APP), were investigated by limiting oxygen index (LOI) test, vertical burning test (UL-94), cone calorimeter, and thermogravimetric analysis (TGA). An LOI value of 28.4 and UL-94 V-0 rating can be achieved when the total loading of MOPO and APP was 30 wt.%. The results from cone calorimeter indicate that both the heat release rate (HRR) and the total heat release (THR) of IFR-EVA decreased significantly compared with those of neat EVA. TG curves showed that the amount of residues increased significantly when intumescent additives were added; it also could be found that the LOI values increased with the increase in char residues. Meanwhile, morphology of the residues obtained from burning IFR-EVA in LOI test was studied through the SEM observations and rich compact char layers could explain the excellent flame retardance.     

Relationship between electrical resistivity and particle dispersion state for carbon black filled poly (ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate)/poly (<Emphasis Type="SmallCaps">L</Emphasis>-lactic acid) blend

It is known that the electrical volume resistivity of insulating polymers filled with conductive fillers suddenly decreases at a certain content of filler. This phenomenon is called percolation. Therefore, it is known that controlling resistivity in the semi-conductive region for carbon black (CB) filled composites is very difficult. When poly (ethylene-co-vinyl acetate) (EVA) is used as a matrix, the percolation curve becomes gradual because CB particles disperse well in EVA. In this study, the relationship between the dispersion state of CB particles and electrical resistivity for EVA/poly (L-lactic acid) (PLLA) filled with CB composite was investigated. The apparent phase separation was seen in the SEM photograph. It was predicted that the CB particles located into the EVA phase in the light of thermodynamical consideration, which was estimated from the wetting coefficient between polymer matrix and CB particles. The total surface area per unit mass of dispersed CB particles in the polymer blend matrix was estimated from small-angle X-ray scattering and the volume resistivity decreased with increasing CB content. The values of the surface area of CB particles in CB filled EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) polymer blends showed a value similar to that of the CB filled EVA single polymer matrix. In electrical volume resistivity measurement, moreover, the slopes of percolation curves of EVA/PLLA (25/75 wt%) and EVA/PLLA (50/50 wt%) filled with CB composite are similar to that of EVA single polymer filled with CB composite. As a result, it was found that CB particles selectively locate in the EVA phase, and then the particle forms conductive networks similar to the networks in the case of EVA single polymer used as a matrix.     

The role of organoclay and matrix type in photo-oxidation of polyolefin/clay nanocomposite films

In this paper the photo-oxidation behaviour of polyolefin/clay nanocomposite films was studied; in particular, the effect of the amount of organo-modifier and the matrix polarity on the photo-oxidation was investigated. Two different organo-modified clays and compositions of LDPE/EVA blend films were used and the photo-oxidation was followed by mechanical and spectroscopic analyses.The organoclay and matrix type strongly influence the photo-oxidative behaviour of nanocomposite films. The films filled with CL15A show a faster loss of mechanical performance and higher carbonyl formation with respect to the films filled with the CL20A. Additionally, the LDPE based nanocomposite undergoes photo-oxidation more rapidly than the EVA based one.     

Co γ-ray irradiation effect and degradation behaviors of a carbon nanotube and poly(ethylene-co-vinyl acetate) nanocomposites

This paper describes the process of manufacturing a new nanocomposite material, which involves adding a carbon nanotube (CNT) to improve EVA's physical characteristics such as weak radiation resistance and thermal properties. We irradiated the prepared samples with doses of 50 kGy, 100 kGy and 200 kGy at a dose rate of 5 kGy/h and examined their thermogravimetric characteristics, activation energy, degradation progress, and CNT dispersion using a thermogravimetric analyzer (TGA), chemiluminescence (CL), and a field emission scanning electron microscope (FESEM). Experimental results indicated that the samples with a CNT had higher DTG 2nd peak temperatures than those without a CNT. Activation energy of the samples reduced as the irradiation dose and the CNT content increased. In the second CL experiment, the CL intensity rapidly declined as the temperature, irradiation dose and the CNT content increased. Finally, examination of the fracture surfaces in the FESEM experiment indicated that the lamella structure of the EVA changed as the irradiation dose increased. We were also able to observe that samples with a CNT were aggregated and dispersed in numerous lumps.     

Poly(ethylene-co-vinyl alcohol) and poly(methyl methacrylate) blends: Phase behavior and morphology

In this work blends of poly(ethylene-co-vinyl alcohol) (EVOH) with different ethylene contents (27, 32, 38 and 44 mol%) and poly(methyl methacrylate) (PMMA) were prepared by mechanical mixing in the melted state. The miscibility and melting behavior as a function of blend composition and the ethylene content in EVOH copolymers were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The morphology of the cryofractured surfaces was examined by scanning electron microscopy (SEM). DSC and DMTA data show that EVOH/PMMA blends are immiscible, independent of EVOH and blend composition. The SEM analysis in agreement with DMTA analysis indicates that the morphology of phases depends on the blend composition, with phase inversion occurring as the concentration of one or other polymer component increases. However, the copolymer composition apparently does not affect the domain size distribution for blends containing 20 wt% of EVOH or 20 wt% of PMMA. A better phase adhesion is observed mainly for blends with 50 wt% of each polymer component.     

Thermal, ozone and gamma ageing of styrene butadiene rubber and poly(ethylene-co-vinyl acetate) blends

Ageing behaviour of SBR/EVA blends due to the effects of heat, ozone, and gamma radiation was studied with reference to blend ratio, three crosslinking systems (sulfur, peroxide and mixed) and a compatibiliser (SEBS-g-MA). It was found that an increase in the EVA content of the blends enhanced the ageing characteristics. Among the different crosslinking systems, a peroxide cured system exhibited the best retention of properties even after severe ageing. Tensile strength of peroxide cured SBR/EVA blends increased slightly after ageing for three days at 70 °C due to continued crosslinking, whereas tensile strength of all blends decreased on ageing at 100 °C. Compatibilisation with SEBS-g-MA improved the thermal, gamma and water ageing resistance of SBR/EVA blends.     

Contact-angle,ellipsometric, and spin-diffusion solid-state nuclear magnetic resonance spectroscopic investigations of copolymeric stationary phases immobilized on SiO<Subscript>2</Subscript> surfaces

SiO₂ surfaces—silica gel particles and silica wafers—were modified by covalently immobilizing three poly(ethylene-co-acrylic acid) copolymers, (–CH₂CH₂–)_x[CH₂CH/(CO₂H)–]_y, with different chain lengths and mass fractions of acrylic acid. ¹³C solid-state NMR spectroscopy on the modified silica gel particles revealed both mobile gauche and rigid trans aligned alkyl chains in the copolymers. For copolymers attached to silica wafers via a 3-aminopropyltriethoxysilane spacer molecule, ellipsometric measurements revealed a mean value of the layer thickness distribution of 6.5 and 4.3 nm, respectively, for the more acidic and the shorter copolymers with mobile alkyl chains mostly in the gauche conformation. For the longest and least acidic copolymer with more rigid trans ordered alkyl chains, however, a mean phase thickness of 10.6 nm was found. When this copolymer was immobilized via a 3-glycidoxypropyltrimethoxysilane spacer molecule we measured a mean layer thickness of 9.9 nm. A model of the surface morphology of this immobilization strategy was derived using spin-diffusion ¹³C NMR measurements on the corresponding modified silica. It was thereby proven that the trans and gauche-aligned alkyl chains occur in distinct domains of certain sizes on the silica surface. The surface polarity of all modified silica wafers was also investigated by measurement of contact-angle.     

Study on the rapid deswelling mechanism of comb-type N-isopropylacrylamide gels

The shrinking mechanism of comb-type grafted poly(N-isopropylacrylamide) gel was investigated by fluorescence spectroscopy and small-angle X-ray Scattering (SAXS). The SAXS reveals that the microdomain structure with characteristic dimension of 460 Å is developed in the comb-type grafted poly(N-isopropylacrylamide) gel during the shrinking process. Fluorescence spectroscopy together with SAXS observation suggests that the freely mobile characteristics of the grafted chains are expected to show the rapid dehydration to make tightly packed globules with temperature, followed by the subsequent hydrophobic intermolecular aggregation of the dehydrated graft chains. The dehydrated grafted chains created the hydrophobic cores, which enhance the hydrophobic aggregation of the networks. These aggregations of the NIPA chains contribute to an increase in void volume, which allow the gel having a pathway of water molecules by the phase separation.     

Interaction and Scale of Mixing in Cellulose Acetate/Poly(<Emphasis Type="Italic">N</Emphasis>-vinyl Pyrrolidone-co-vinyl Acetate) Blends

Binary blends and pseudo complexes of cellulose acetate (CA) with vinyl polymers containing N-vinyl pyrrolidone (VP) units, poly(N-vinyl pyrrolidone) (PVP) and poly(N-vinyl pyrrolidone-co-vinyl acetate) [P(VP-co-VAc)], were prepared, respectively, by casting from mixed polymer solutions in N,N-dimethylformamide as good solvent and by spontaneous co-precipitation from solutions in tetrahydrofuran as comparatively poor solvent. The scale of miscibility and intermolecular interaction were examined for the blends and complexes by solid-state ¹³C-NMR spectroscopy. It was revealed that the formation of complexes was due to a higher frequency of hydrogen-bonding interactions between the residual hydroxyl groups of CA and the carbonyl groups of VP residues in the vinyl polymer component. From measurements of CP/MAS spectra and proton spin-lattice relaxation times (T_1ρ^H) in the NMR study, the existence of the hydrogen-bonding interaction was also confirmed for the miscible blends and the homogeneity of the mixing was estimated to be substantially on a scale within a few nanometers.     

Water transport in aluminium oxide-poly(ethylene-co-butyl acrylate) nanocomposites

Polymer composites with metal oxide nanoparticles are emerging materials for use as insulation in electrical applications. However, the extensive interfacial surfaces and the presence of polar groups on the particle surfaces make these composites susceptible to water sorption. Water sorption kinetics were studied at 23 °C and different relative humidities (18–90%) for composites based on poly(ethylene-co-butyl acrylate) and aluminium oxide (?12 wt.%); the latter being in three different forms: uncoated and coated with either octyltriethoxysilane or aminopropyltriethoxysilane. The equilibrium water uptake increased linearly with increasing overall concentration of polar groups on the nanoparticle surfaces. Composites with well-dispersed nanoparticles showed Fickian diffusion (constant diffusivity and invariant boundary conditions) with a diffusivity that decreased with increasing filler content; the maximum factorial decrease in diffusivity was 300 with reference to that of the pristine polymer. This effect was most pronounced for composites with accessible polar groups on the particle surfaces, suggesting that water saturation of the composites is retarded by dual water sorption. Composites that contained a sizeable fraction of large nanoparticle agglomerates showed a two-stage sorption process: a rapid process associated with the saturation of the matrix phase and a slow diffusion process due to water sorption by the large nanoparticle agglomerates.     

Study on the rapid deswelling mechanism of comb-type N-isopropylacrylamide gels

The shrinking mechanism of comb-type grafted poly(N-isopropylacrylamide) gel was investigated by fluorescence spectroscopy and small-angle X-ray Scattering (SAXS). The SAXS reveals that the microdomain structure with characteristic dimension of 460 Å is developed in the comb-type grafted poly(N-isopropylacrylamide) gel during the shrinking process. Fluorescence spectroscopy together with SAXS observation suggests that the freely mobile characteristics of the grafted chains are expected to show the rapid dehydration to make tightly packed globules with temperature, followed by the subsequent hydrophobic intermolecular aggregation of the dehydrated graft chains. The dehydrated grafted chains created the hydrophobic cores, which enhance the hydrophobic aggregation of the networks. These aggregations of the NIPA chains contribute to an increase in void volume, which allow the gel having a pathway of water molecules by the phase separation.     

The effect of γ-irradiation and polymer composition on the stability of PLG polymer and microspheres

The effects of lactide:glycolide ratio and γ-irradiation on the stability characteristics of poly(d,l-lactide-co-glycolide) (dl-PLG) co-polymer and microspheres were studied. Samples containing 50:50, 65:35, 75:25, 85:15 and 95:5 lactide:glycolide were studied as both the raw polymer and microspheres. The samples were characterised and degradation was monitored using a variety of spectroscopic, chromatographic, thermal and particle analysis techniques. The lactide:glycolide ratio was shown to be an important parameter in controlling the degradation of PLG co-polymer, especially in the microspheres, and the raw polymer samples were observed to be less stable than the microspheres. γ-Irradiation was shown to reduce the molecular weight of the PLG samples without significantly affecting the polydispersity, suggesting a random chain scission degradation mechanism. The detrimental effects of γ-irradiation were shown to continue on storage of the samples for 4 weeks in the solid state at ambient and accelerated conditions.     

n-Hexane sorption in poly(ethylene-co-1-octene)s: Effect on phase composition and character

Diffusion of small-molecule penetrants in semi-crystalline polymers is retarded by two factors: penetrant detour bypassing impenetrable crystals and the constraining effect of the crystals on the amorphous component. Previous experiments have shown that the latter factor becomes much less important at higher penetrant concentration in the polymer. Structural changes in a series of poly(ethylene-co-1-octene)s occurring on saturation in n-hexane at 296 K, covering a wide range of crystallinity (17-75 wt.%), were studied by wide-angle X-ray scattering, Raman spectroscopy and NMR spectroscopy. Densification of the crystal unit cell and partial dissolution of the interfacial component on n-hexane sorption are the main experimental findings. The conclusion is that the penetrant molecules increase the mobility of the polymer chain segments adjacent to the crystal interface, enabling better packing of the crystal stems and importantly also causes a reduction in the constraining factor (β) for diffusion.     

Water and polymer dynamics in poly(hydroxyl ethyl acrylate-co-ethyl acrylate) copolymer hydrogels

Water and polymer dynamics in hydrogels based on random copolymers of hydrophilic poly(hydroxyl ethyl acrylate) (PHEA) and hydrophobic poly(ethyl acrylate) (PEA), in wide ranges of composition, were investigated by means of two dielectric techniques, thermally stimulated depolarization currents (TSDC) and, mainly, broadband dielectric relaxation spectroscopy (DRS) at several levels of relative humidity/water content. Water sorption of the hydrogels was studied by equilibrium sorption isotherms (ESI). Two secondary relaxations (γ and β_sw) and the primary (segmental) α relaxation associated with the glass transition of the copolymer matrix were followed and analyzed against copolymer composition and water content. The results show that the copolymers are homogeneous at nm scale, except at very high PEA content. Correlations were observed between results on the organization of water in the hydrogels and on water effects on polymer dynamics. Distinct changes in the dielectric response, in particular in the time scale and the dielectric strength of the β_sw relaxation, at the water content of the completion of the first hydration layer indicate that water molecules themselves contribute to the dielectric response at higher water contents. Proton conductivity of the hydrogels at various levels of water content was also studied and correlation to segmental dynamics (decoupling) was analyzed.     

Controlling the size of poly(hydroxybutyrate-co-hydroxyvalerate) nanoparticles prepared by emulsification–diffusion technique using ethanol as surface agent

Poly(hydroxybutyrate-co-hydroxyvalerate) (PHBHV) nanospheres and oily nanocapsules were prepared by emulsification–diffusion technique. Controlled particle sizes were obtained employing binary mixtures of solvents (chloroform:ethanol) in the organic phase. Ethanol was chosen because of its dipole–dipole interaction with chloroform and its hydrogen bond with water. The smallest particles (from 253 to 493 nm) were obtained using a mixture of solvents composed of 70% ethanol and 30% chloroform (v/v) in the organic phase, while the largest particles (from 896 to 1568 nm) were obtained using chloroform exclusively. Independently of the organic phase composition, the nanoparticles showed unimodal distributions. Optical microscopy showed that the size of the primary emulsion droplets of the nanosphere formulations decreased with increasing ethanol concentrations in the organic phase. A simple empirical equation was developed correlating the nanoparticle diameters with the surface tension gradient coefficient multiplied by the ethanol molar concentration in the organic phase. The strategy showed that the control of the nanoparticle diameters, using emulsification–diffusion technique, could be achieved by adjusting the surface tension of the organic phase.     

Solid-state C NMR and SAXS characterization of the amorphous phase in low-molecular weight poly(ethylene oxide)s

Low-molecular weight poly(ethylene oxide)s (PEO) with extended, once or twice folded chains (as characterized by SAXS), were investigated by solid-state ¹³C NMR spectra measured under conditions to detect only the signal of the narrow line component. The direct detection and integrated intensities of the signals from hydroxy-terminated chain-end units in these spectra confirm that the narrow line component corresponds to the noncrystalline (amorphous) phase. The NMR line of PEO carbons adjacent to the hydroxy end-groups was used as an intensity standard to obtain information on the mean number of carbons per chain contributing to the amorphous phase. Assuming that amorphous phase is formed by chain ends (cilia) and folds it follows from the spectra that the length of folds is 6-7 monomer units; cilia are 2-3 monomer units long.     

Preparation of a novel polymer gel electrolyte based on N-methyl-quinoline iodide and its application in quasi-solid-state dye-sensitized solar cell

Using poly(acrylonitrile-co-styrene) as polymer host, 1,2-propanediol carbonate, dimethyl carbonate and ethylene carbonate as mixture solvent, N-methyl-quinoline iodide and iodine as the source of I⁻/I₃ ⁻, a novel polymer gel electrolyte with ionic conductivity of 5.12 × 10⁻³ S· cm⁻¹ at 25°C was prepared by sol-gel and hydrothermal methods. Based on the polymer gel electrolyte, a quasi-solid-state dye-sensitized solar cell was fabricated. The solar cell possess better long-term stability and light-to-electrical energy conversion efficiency of 4.04% under irradiation of 100 mW· cm⁻². The influences of polymer host, solvent, N-methyl-quinoline iodide and temperature on ionic conductivity of the polymer gel electrolyte and the performance of the dye-sensitized solar cell was discussed.     

Hypercrosslinking: new approach to porous polymer monolithic capillary columns with large surface area for the highly efficient separation of small molecules

Monolithic polymers with an unprecedented surface area of over 600 m(2)/g have been prepared from a poly(styrene-co-vinylbenzyl chloride-co-divinylbenzene) precursor monolith that was swollen in 1,2-dichloroethane and hypercrosslinked via Friedel-Crafts reaction catalyzed by ferric chloride. Both the composition of the reaction mixture used for the preparation of the precursor monolith and the conditions of the hypercrosslinking reaction have been varied using mathematical design of experiments and the optimized system validated. Hypercrosslinked monolithic capillary columns contain an array of small pores that make the column ideally suited for the high efficiency isocratic separations of small molecules such as uracil and alkylbenzenes with column efficiencies reproducibly exceeding 80,000 plates/m for retained compounds. The separation process could be accelerated while also improving peak shape through the use of higher temperatures and a ternary mobile phase consisting of acetonitrile, tetrahydrofuran, and water. As a result, seven compounds were well separated in less than 2 min. These columns also facilitate separations of peptide mixtures such as a tryptic digest of cytochrome c using a gradient elution mode which affords a sequence coverage of 93%. A 65 cm long hypercrosslinked capillary column used in size exclusion mode with tetrahydrofuran as the mobile phase afforded almost baseline separation of toluene and five polystyrene standards.     

Stabilization of proteases by entrapment in a new composite hydrogel

A new one-step procedure for entrapping proteases into a polymeric composite calcium alginate-poly(N-vinyl caproladam) hydrogel was developed that provided 75–90% retention of the activity of entrapped enzymes compared to soluble ones. Properties of entrapped carboxypeptidase B, trypsin, and thrombin were investigated. The immobilized enzymes were active within a wide pH range. The temperature optima of entrapped trypsin and carboxypeptidase B were approx 25°C higher than that of the soluble enzymes, and the resistance to heating was also increased. The effects of various polar and nonpolar organic solvents on the entrapped proteases were investigated. The immobilized enzymes retained their activity within a wide concentration range (up to 90%) of organic solvents. Gel-entrapped trypsin and carboxypeptidase (CPB) were successfully used for obtaining human insulin from recombinant proinsulin. The developed stabilization method can be used to catalyze various reactions proceeding within wide pH and temperature ranges.     

Multiresidue determination of (fluoro)quinolone antibiotics in chicken by polymer monolith microextraction and field-amplified sample stacking procedures coupled to CE-UV

Simultaneous determination of 9 (fluoro)quinolone antibiotics (FQs) was accomplished by capillary electrophoresis-ultraviolet (CE-UV) based on poly(methacrylic acid-co-ethylene glycol dimethacrylate) (MAA-EGDMA) monolith microextraction (PMME) coupled with on-line preconcentration technique of field-amplified sample stacking (FASS). The effects of composition of the acid and organic solvent in the sample solution, sampling time, and voltage on the efficiency of the sample stacking have been systematically investigated. Several parameters that influence extraction efficiency for PMME such as pH of sample solution, extraction volume, and wash and desorption conditions were optimized. In the proposed method, a substantial increase in sensitivity for all the FQs tested was achieved by the combination of PMME procedure with on-line preconcentration of FASS prior to CE analysis. Good linearities were obtained for the 9 tested FQs with the correlation coefficients (R) above 0.9954. The limits of detection (S/N = 3) were found to be 2.4-34.0 ng g⁻¹ and the recoveries ranged from 81.2 to 100% with relative standard deviations less than 11.3%. The proposed PMME-FASS-CE method was applied to the determination of FQs residues in chicken samples.