The Effect of CTBN Concentrations on the Kinetic Parameters of Decomposition of Blends of Epoxy Resins Modified with Carboxyl-Terminated Liquid Copolymer

Diglycidyl ether of bisphenol—A (DGEBA)—based epoxy resin was blended in the ratio of 3:1 (weight basis) with cycloaliphatic epoxy (CAE) resin. The prepared blend sample was further blended with different weight percentages of carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) ranging between 0 and 25 wt% with an interval of 5 wt% and cured with stiochiometric amounts of 4, 4’- diamino diphenyl sulphone (DDS) cure agent. Structural changes during blending were studied by Fourier-transform infra-red (FTIR) spectroscopic analysis. The kinetic parameters, viz., order of decomposition reaction (n), activation energy (E), pre-exponential factor (Z) and rate decomposition constant (k), for the decomposition of the samples were calculated by applying Coats-Redfern equation over thermogravimetric (TG) data. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. Further, the blend sample had higher initial degradation temperature and activation energy than its respective pure epoxy resin indicating that the CTBN acted as thermal stabilizer for epoxy resin which improved the thermal stability.     

Characterization of Environmentally Friendly Polymers by Inverse Gas Chromatography: I Amylopectin

Amylopectin, as a potato starch based polymer, with a molecular weight of six million gram/mol was characterized using the Inverse Gas Chromatography Method (IGC). DSC method was also used to measure the glass and melting temperatures. Both DSC and IGC agreed well on a T_g of 105°C and T_m of 160–166°C. Nineteen solutes (solvents) were injected onto a chromatographic column containing amylopectin. These solutes revealed the interaction of alkanes with AP, and the wettability and water intake of AP. Alkanes showed exothermic values of interaction parameters which were increased as the temperature increased and as the number of carbons in the alkane series decreased. Retention diagrams of these solutes in a temperature range of 80–200°C revealed two zones, crystalline and amorphous. T_g and T_m were measured using these zones which complimented the DSC values. The two zones were used to calculate the degree of crystallinity below the melting temperature which ranged from 85% at 104°C to 0% at 161°C. The dispersive component of the surface energy of amylopectin was measured using alkanes which ranged from 25.35 mJ/m² at 80°C to 8.47 mJ/m² at 200°C. This is attributed to the weak crystalline surface of AP at 80°C and when the surface melted at 160°C the surface energy decreased due to the thermal expansion of the surface.     

Renewable Resource-Based Composites of Acorn Powder and Polylactide Bio-Plastic: Preparation and Properties Evaluation

Renewable resource-based composites were prepared with acorn powder and Thermoplastic resin poly(lactic acid) (PLA) by twin-screw extrusion followed by injection molding processing or hot-compression molding processing. The study of the composites microstructure showed poor adhesion between acorn powder and PLA matrix. The hygroscopicity, mechanical properties and melt flow property of composites were promising even though the composites had a 70 wt% content of acorn powder. Silane coupling agent, 4,4′-Methylenebis (phenyl isocyanate) and PLA grafted with maleic anhydride did not show obvious effect on mechanical properties of composites. The impact resistance strength of reinforced composites with steel fiber webs were improved greatly in comparison with those having no steel fiber webs. Thermal properties results of DSC and DMA showed that the presence of acorn powder significantly affected the crystallinity, crystallization temperature (T_c), glass transition temperature (T_g) and melting temperature (T_m) of PLA matrix. The study results proved that composites had superior mechanical properties, enough to partially replace the conventional thermoplastic plastics.     

Influence of Polyol Plasticizers on the Properties of Polyvinyl Alcohol Films Fabricated by Melt Processing

In this work, high-alcoholysis polyvinyl alcohol (PVA) films were fabricated by melt processing and the plasticizing effect of compound polyol plasticizers on PVA were investigated with X-ray diffraction (XRD), differential scanning calorimetry (DSC), rheological measurements, mechanical tests etc. Hydrogen bonding interactions occurred between PVA and plasticizer. With the increase of plasticizer, the flowability of PVA was improved and reached the maximum value at the plasticizer of 20%. Glass transition temperature (T _g) and melting point (T _m) decreased with the increase of plasticizer content. For the heterogeneous nucleation effect of plasticizer, new polymorph of PVA formed. The viscosity was sensitive to the shear rates. The incorporation of plasticizers into PVA resulted in the increase of elongation at break and impact strength, as well as the decrease of tensile strength.     

Synthesis and Properties of Polyesters from Waste Grapeseed Oil: Comparison with Soybean and Rapeseed Oils

The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917^®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. T _g’s of the polyesters ranged from ?36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher T _g polymers (?17 to 17 °C) than soybean (?25 to 6 °C) and rapeseed (?36 to ?27 °C). Grapeseed oil showed similar properties to soybean oil in terms of T _g, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.     

Investigation on Miscibility of Sodium Alginate/Pullulan Blends

Miscibility studies of Sodium alginate (NaAlg)/Pullulan have been carried out in different percentage of blend components. The ultrasonic velocity, viscosity, density and refractive index were measured at 30 and 40 °C. Further the blend films of NaAlg and Pullulan were prepared by solution casting method and characterized by differential scanning calorimetric (DSC), fourier transition infrared spectroscopic (FTIR), and scanning electron microscopic (SEM) methods. Using the viscosity data, interaction parameters were computed to determine the miscibility. The data suggest that the blend is miscible in the entire composition range. The change in temperature had no significant effect on the miscibility of NaAlg/Pullulan blends. The miscibility is confirmed by SEM, DSC, ultrasonic velocity, density, and refractive index methods. The specific interactions of hydrogen bonding type of the blends were investigated by FTIR.     

Compatible Blends of Zein and Polyvinylpyrrolidone

Blends of zein and polyvinylpyrrolidone (PVP) were compared based on their tensile properties, thermal properties and morphology. Zein was blended with polyvinylpyrrolidone of varying molecular weights (10, 55, and 1,300 kDa) and films were cast from ethanol solutions. Films cast using the higher molecular weight polymers showed an improvement in tensile strength, up to a 24% increase, compared to control. Differential scanning calorimetry data for the blends showed single T_m and T_g values of an intermediate value between those of zein and PVP control samples. Field emission scanning electron microscopy images show no obvious inhomogeneities, and confocal fluorescence microscopy showed no decreased uniformity in the PVP/zein films compared to control. Electrospun fibers of the zein/PVP blends were also obtained. These findings suggest that zein and polyvinylpyrrolidone combine to form a compatible blend, the first such blend of zein with a synthetic polymer.     

From Natural Oils to Epoxy Resins: A New Paradigm in Renewable Performance Materials

The direct conversion of natural products to useful engineering materials is desirable from both economic and environmental considerations. We describe the synthesis and properties of 100?% oil-based epoxy resins generated from three epoxidized oils. The catalyst, tris(pentafluorophenyl)borane (B(C₆F₅)₃) in toluene, allowed for controlled cationic polymerization at a very low concentration. Epoxidized oils (derived from triolein, soybean, and linseed oil) had varying epoxy content, rendering resins of different cross-link density. The polymerization was carried out at room temperature followed by post-curing at elevated temperature to speed up conversion. Epoxy resins were amorphous transparent glasses below glass transitions and hard rubbers above. Despite their high cross-link density, these materials show relatively low T_g’s reflecting the aliphatic nature of fatty acids and the presence of plasticizing “dangling” chains. The structure of the triglyceride starting oils influenced the properties of the resulting materials: the more regular structure of triolein compared to the very heterogeneous structures of soybean and linseed oils seemed to have enhanced some properties of the polymer networks. These epoxy polymers are potentially useful as encapsulating and potting compounds for electronic applications.

     

Photodegradation of Poly(lactic acid) Stereocomplex by UV-Irradiation

Neat poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) films and PLLA/PDLA blend films were prepared by solution casting, and their photodegradation by UV-irradiation was investigated using wide-angle X-ray scattering (WAXS), gel permeation chromatography, differential scanning calorimetry, tensile testing, and polarized optical microscopy. The PLLA/PDLA blend film was more photodegradation-resistant than the neat PLLA and PDLA films when photodegradation was monitored by molecular weight, melting temperature, and WAXS crystalline peak positions. This indicates that the chains in both amorphous and crystalline regions of the PLLA/PDLA blend film were photo-cleavage-resistant compared to those of the neat PLLA and PDLA films. The changes in melting temperature and WAXS crystalline peak positions before and after photodegradation respectively indicated the increased crystalline lattice disorder and the decreased crystalline lattice sizes of the neat PLLA and PDLA films, whereas these changes were insignificant for the blend films. Photodegradation caused no significant change in tensile properties, with the exception of significant decreases in the tensile strength and elongation at break of PLLA/PDLA blend film. However, the tensile strength and elongation at break of the PLLA/PDLA blend film retained higher values compared to those of the neat PLLA and PDLA films during photodegradation. In spite of the slower photodegradation of the PLLA/PDLA blend film traced by M _n, T _m, and WAXS crystalline peak positions than that of neat PLLA and PDLA films, the rapid decrease in tensile strength and elongation at break of the former than that of the latter should be due to the highly-ordered structural difference between them, i.e., the three dimensional dry gel of the former and the spherulites of the latter.     

Effects of compost biocovers on gas flow and methane oxidation in a landfill cover

Previous publications described the performance of biocovers constructed with a compost layer placed on select areas of a landfill surface characterized by high emissions from March 2004 to April 2005. The biocovers reduced CH₄ emissions 10-fold by hydration of underlying clay soils, thus reducing the overall amount of CH₄ entering them from below, and by oxidation of a greater portion of that CH₄. This paper examines in detail the field observations made on a control cell and a biocover cell from January 1, 2005 to December 31, 2005. Field observations were coupled to a numerical model to contrast the transport and attenuation of CH₄ emissions from these two cells. The model partitioned the biocover’s attenuation of CH₄ emission into blockage of landfill gas flow from the underlying waste and from biological oxidation of CH₄. Model inputs were daily water content and temperature collected at different depths using thermocouples and calibrated TDR probes. Simulations of CH₄ transport through the two soil columns depicted lower CH₄ emissions from the biocover relative to the control. Simulated CH₄ emissions averaged 0.0 g m^?2 d^?1 in the biocover and 10.25 g m^?2 d^?1 in the control, while measured values averaged 0.04 g m^?2 d^?1 in the biocover and 14 g m^?2 d^?1 in the control. The simulated influx of CH₄ into the biocover (2.7 g m^?2 d^?1) was lower than the simulated value passing into the control cell (29.4 g m^?2 d^?1), confirming that lower emissions from the biocover were caused by blockage of the gas stream. The simulated average rate of biological oxidation predicted by the model was 19.2 g m^?2 d^?1 for the control cell as compared to 2.7 g m^?2 d^?1 biocover. Even though its V_max was significantly greater, the biocover oxidized less CH₄ than the control cell because less CH₄ was supplied to it.     

Biodegradable Polymers from 5-Hydroxylevulinic Acid: 1. Synthesis and Characterization of Poly(5-hydroxylevulinic acid)

As an attempt to synthesize new biodegradable polymers from renewable cellulose resources, melt polycondensation of 5-hydroxylevulinic acid (5-HLA) was reported for the first time. The resulting product, poly(5-hydroxylevulinic acid) (PHLA), was synthesized and characterized with GPC, FTIR, ¹H NMR and DSC. The in vitro degradation behaviors in phosphate-buffered saline (PBS) and in deionized water (DW) were also examined. The molecular weight of PHLA is not high (several 1,000s), but it possesses unordinary high glass transition temperature (as high as 120 °C). This is very different from existing aliphatic polyesters that usually have T _gs lower than 60 °C. The high T _g is attributed to the formation of inter- and/or intramolecular hydrogen bonds due to a characteristic keto–enol tautomerism equilibrium in the polymer structure. PHLA readily degraded hydrolytically in aqueous media.     

Water Absorption Kinetics and Hygrothermal Aging of Poly(lactic acid) Containing Halloysite Nanoclay and Maleated Rubber

Poly(lactic acid)/halloysite nanoclay composites (PLA/HNC) containing maleic anhydride grafted styrene-ethylene/butylene-styrene (SEBS-g-MAH) were produced using melt compounding followed by compression molding. The effects of hygrothermal aging on the thermal properties and functional groups changes of the HNC reinforced PLA (with and without SEBS-g-MAH) at three different temperatures (i.e., 30, 40 and 50 °C) were analyzed using differential scanning calorimetry and Fourier transform infrared spectroscopy techniques. The diffusion coefficient (D) of PLA was decreased by the incorporation of HNC and SEBS-g-MAH. The activation energy of water diffusion (E _a ) of PLA/HNC/SEBS-g-MAH nanocomposites was higher than that of pure PLA. The glass transition temperature (T _g ), cold-crystallization temperature (T _cc ) and melting temperature (T _m ) of the PLA sample were shifted to lower temperature and the effect was more pronounced at 50 °C. The carbonyl index values of all PLA samples increased after immersed in 40 and 50 °C, which is due to the formation of higher amount of carboxyl groups during the hydrolysis process.     

Arsenic Removal from Dilute Solutions by High Surface Area Mesoporous Iron Oxyhydroxide

Mesostructured iron oxyhydroxide (FeO _x ) and iron oxyhydroxide–phosphate (FeO _x P) composites were organized using dodecylsulfate surfactant as a template. X-ray diffraction studies depicted a lamellar structure of the product. Ion exchange and solvent extraction methods were employed for the removal of the surfactant. Carboxylate ions exchanged lamellar type mesostructured material reorganized to a wormhole-like mesoporous material when heated under N₂ atmosphere. Surfactant was completely removed by carboxylate ions as observed by the Fourier transform infrared spectra. High surface area acetate-exchanged FeO _x (230 m² g^?1) was obtained after the surfactant removal from the composite (2.8 m² g^?1). Surface area of acetate-exchanged FeO _x P was the highest (240 m²g^?1) after the removal of the surfactant. Local structure of iron species of FeO _x was investigated by X-ray absorption fine structure spectroscopy. Further, Fe···Fe bond appeared at 3.21–3.25 Å with coordination number 2–3, showing a high degree of un-saturation of Fe···Fe bonds. As compared with bulk iron oxyhydroxide and iron-intercalated montmorillonite, the mesoporous iron materials were highly effective for arsenic removal from low concentrations of aqueous solutions. Furthermore, mesoporous iron materials were stable in aqueous phase.     

Natural Weathering of Polypropylene and Waste Tire Dust (PP/WTD) Blends

Three series of polypropylene and waste tire dust (PP/WTD) blends using three different WTD sizes were prepared, compression-molded and cut into dumbbells. The specimens were exposed to natural weathering in the northern part of Malaysia for a period of 6 months. The results show that at the same blend composition, blends with fine WTD size exhibit higher mechanical properties than that of blends with coarse WTD after exposure to natural weathering. Regardless of WTD size, the retention of tensile strength and elongation at break, E_b increases with the increase in WTD content. From the exposed surface morphology, it is apparent that the blends with fine WTD and WTD-rich blends were able to withstand weathering better than blends with coarse WTD and PP-rich blends. The DSC thermograms suggest that the overall drop in melting temperature (T_m) of the exposed blends decreases as the WTD content increases.     

Effect of Nanoscale SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> as the Fillers on the Mechanical Properties and Aging Behavior of Linear Low-Density Polyethylene/Low-Density Polyethylene Blends

Linear low-density polyethylene (LLDPE) was blended with low-density polyethylene (LDPE) at a fixed ratio (80 wt LLDPE and 20 wt %LDPE) and filled with nanoparticles of SiO₂ and TiO₂ at a ratio up to wt 5%, so as to develop the polymeric composites suitable to preparing the agricultural micro-irrigation pipes having good environmental adaptability. These compounds were blended using calcium stearate, polyethylene wax, and titanate coupling agent as the auxiliary dispersants, and ethylene-vinyl acetate copolymer (EVA) as the toughness improver. The LLDPE/LDPE composites filled with the nanoparticles were extruded and injected to prepare the composites specimens for the performance evaluations and micro-irrigation pipe field test. The mechanical properties, thermostability, and processibility of the injected composites were investigated. The effect of heating in an oven and irradiating by ultraviolet on the mechanical properties of the composites was explored. The environmental adaptability of the micro-irrigation pipes made of the filled LLDPE/LDPE composites was evaluated making use of long-term outdoor field test in northwest China where the arid and harsh natural conditions are of great concerns. It was found that the LLDPE/LDPE blend with the LLDPE mass fraction fixed as 80% showed balanced mechanical and thermal properties and flexibility, and was suitable to be used as the basic resin matrix. The incorporation of nano-TiO₂ contributed to effectively improving the resistance to heating and ultraviolet irradiation of the composites. The composite made from 91% basic resin matrix, 6% EVA, and 3% mixed nano-SiO₂ and TiO₂, showed balanced comprehensive properties. The micro-irrigation pipes made of this filled LLDPE/LDPE composite had good environmental adaptability and service behavior in a three-year field test and were suitable to be used in arid area.     

Characterization and Properties of Hydrophilic Cellulose Acetate Propionate Derivative

The chemical modification of Acrylamidomethyl Cellulose Acetate Propionate (AMCAP) was carried out by radical addition of acrylic acid. The structural modification was confirmed with the aid of FTIR, MS and NMR techniques. Thermal properties of hydrophilic cellulose derivative (AMCAP–H₂O₂) such as glass transition (T_g 153 °C) and thermal stability (372.7 °C) were determined by DSC and TGA techniques, respectively. These thermal properties confirmed the introduction of carboxylic groups into AMCAP structure, which causes an impact in their properties. The AMCAP–H₂O₂ shows minor contact angle compared to AMCAP, giving a more hydrophilic characteristic, due to acrylic acid addition into the side chains of AMCAP polymer.     

Effect of Lignosulfonate on the Thermal and Morphological Behavior of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The effect of lignosulfonate on poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, was studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The PHBV/lignosulfonate samples were prepared by melt mixing in an internal mixer. SEM showed that PHBV/lignosulfonate samples present a cracked surface that is more intense in mixtures with high lignosulfonate proportions. According to DSC, melting and glass transition temperatures of the PHBV matrix decrease with lignosulfonate addition. The same effect was observed for melting enthalpies (ΔH_m), which indicates a decrease of crystallinity. TGA showed that thermal stability of PHBV/lignosulfonate samples was shifted to lower temperatures, which indicates the existence of an interaction between the thermal decomposition processes of PHBV and lignosulfonate.     

The Potential of Chicken Eggshell Waste as a Bio-filler Filled Epoxidized Natural Rubber (ENR) Composite and its Properties

Eggshell calcium carbonate (ECC) and eggshell calcium carbonate treated with high temperature (ECC-600) were prepared from chicken eggshell waste. ECC was obtained by crushing eggshell waste, eliminating membranes and followed by sieving. In the case of ECC-600, ECC powder was additionally heated at 600 °C for 2 h. Both were used to promote as fillers compared to that of commercial light-precipitated calcium carbonate (commercial CaCO₃) with various loading levels (i.e., 0, 25, 50 and 75 phr) in epoxidized natural rubber containing 25 mol% of epoxide group (ENR-25). Among the three types of fillers (i.e., ECC, ECC-600 and commercial CaCO₃), ECC filled materials showed superior vulcanization characteristics by the increasing of maximum torque (M_H) and cure rate index (CRI) with the reducing of cure time (t_c90) and scorch time (t_s2). The highest tensile properties as well as the lowest tension set value were also observed. Morphological property revealed that ECC was greater interfacial adhesion than those of others. In addition, dynamic mechanical properties of vulcanizates containing ECC, storage modulus (E′) was the highest and glass transition temperature (T _g ) shifted toward high temperature. Increasing of loading levels of any fillers affected the increase of M_H and CRI with reducing of t_c90 and t_s2. However, tensile properties decreased with increasing filler content but it did not affect T _g shifting except for a series of vulcanizates containing ECC.     

Synthesis of a block copolymer of poly(3-hydroxybutyrate) and poly(ethylene glycol) and its application to biodegradable polymer blends

A block copolymer {P[(R,S)-HB-b-EG]} of atactic poly[(R,S)-3-hydroxybutyrate] {P[(R,S)-HB]} and poly(ethylene glycol) (PEG) was prepared by the ring-opening polymerization of -butyrolactone in the presence of a macroinitiator (PEG/ZnEt₂/H₂O) which had been produced by the reaction of ,-dihydroxy PEG ( _n=3000) with ZnEt₂/H₂O (1/0.6) catalyst. The block copolymer ( _n=10,500, _w/ _n=1.2) was an A-B-A triblock copolymer comprising atactic P[(R,S)-HB] (A) and PEG (B) segments. The miscibility, physical properties, and biodegradability of binary blends of microbial poly[(R)-3-hydroxybutyrate] {P[(R)-HB]} with the block copolymer P[(R,S)-HB-b-EG] has been studied. The glass-transition temperature (T _g) data showed that the P[(R)-HB]/P[(R,S)-HB-b-EG] blend was miscible in the amorphous state. The P[(R)-HB] film became flexible and tough by means of blending with P[(R,S)-HB-b-EG] block copolymer. The enzymatic degradation of blend films was carried out at 37°C and pH 7.4 in a 0.1M phosphate solution of an extracellular PHB depolymerase fromAlcaligenes faecalis. The enzymatic degradation took place solely on the surface of the blend films.     

Biodegradability and Thermal Properties of Novel Natural Rubber/Linear Low Density Polyethylene/Thermoplastic Starch Ternary Blends

This work aimed to prepare biodegradable thermoplastic elastomers based on NR/LLDPE/TPS ternary simple blends to achieve some exclusive properties, i.e., good biodegradability in terms of water absorption and weight loss after burial, together with reasonable mechanical and thermal properties. A comparative study on biodegradability and other related properties of NR/LLDPE binary and NR/LLDPE/TPS ternary blends was performed. It was found that increasing the TPS proportion decreased storage modulus and complex viscosity. In addition, the size of dispersed TPS domains in the NR/LLDPE co-continuous matrix increased with TPS proportion, while the mechanical properties in terms of 100% moduli, tensile strength, elongation at break, and hardness decreased. This might be attributed to decreased interfacial adhesion with increasing size of TPS domains. Furthermore, increasing the TPS loading in the blend reduced the temperatures for 5 or 50% mass loss (T₅ or T₅₀) and the degradation temperature (T _d ). However, the biodegradability improved, in terms of increased water absorption and weight loss after burial in soil, with the loading level of TPS.