Showing papers in "Journal of Polymers and The Environment in 2001"

A Literature Review of Poly(Lactic Acid)

Abstract: A literature review is presented regarding the synthesis, and physicochemical, chemical, and mechanical properties of poly(lactic acid)(PLA). Poly(lactic acid) exists as a polymeric helix, with an orthorhombic unit cell. The tensile properties of PLA can vary widely, depending on whether or not it is annealed or oriented or what its degree of crystallinity is. Also discussed are the effects of processing on PLA. Crystallization and crystallization kinetics of PLA are also investigated. Solution and melt rheology of PLA is also discussed. Four different power-law equations and 14 different Mark–Houwink equations are presented for PLA. Nuclear magnetic resonance, UV–VIS, and FTIR spectroscopy of PLA are briefly discussed. Finally, research conducted on starch–PLA composites is introduced.

Physical Properties and Fiber Morphology of Poly(lactic acid) Obtained from Continuous Two-Step Melt Spinning

Abstract: Fibers of poly(lactic acid) (PLA) produced by two-step melt-spinning are studied. The PLA resin used contains a 98:02 ratio of L:D stereochemical centers. A range of processing conditions is explored. The cold-draw ratio is varied from 1 to 8 under conditions of constant heating. In addition, three draw ratios are studied at three different heating rates. The thermal, mechanical, and morphological properties of the resultant fibers are determined. Properties can be widely manipulated through a combination of draw ratio and draw temperature. A maximum tensile strength and modulus of 0.38 GPa and 3.2 GPa, respectively, are obtainable. Using atomic force microscopy, the fiber morphology is found to be highly fibrillar; microfibril diameters are roughly 40 nm in diameter. Very high draw ratios cause the fiber to turn from shiny and translucent to dull and white; this transition is attributed to surface crazing. Significant molecular weight loss is observed upon processing (weight-average molecular weights drops between 27% and 43%).

Degradation of Polyethylene and Nylon-66 by the Laccase-Mediator System

Abstract: We investigated whether the laccase-mediator system (LMS) with 1-hydroxybenzotriazole (HBT) as a mediator could degrade high-molecular-weight polyethylene and nylon-66 membranes. The LMS markedly reduced the elongation and tensile strength of these membranes. After 3 days of treatment with the LMS, the M w of polyethylene decreased from 242,000 to 28,300, and that of nylon-66 from 79,300 to 14,700. The LMS also decreased the polydispersity (M w/M n) of polyethylene and nylon-66. Furthermore, these reductions in elongation, tensile strength, and molecular weight were accompanied by morphological disintegration of the polyethylene and nylon-66 membranes. These results strongly suggest that the LMS with HBT can effectively degrade polyethylene and nylon-66.

Fast and Living Ring-Opening Polymerization of l-Lactide Initiated with In-situ–Generated Calcium Alkoxides

Abstract: The ring-opening polymerization of l-lactide with calcium alkoxides generated in-situ from bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] and 2-propanol are presented. The polymerization in THF at room temperature proceeds rapidly and in a living manner, giving poly(l-lactide)s of controlled molecular weight, low polydispersity, and tailored end-functionalities. Kinetic studies show the absence of an induction period and a pseudo-first order rate constant of 6.41 L mol−1 min−1, which is significantly higher than for related Y5(μ-O)(O i Pr)13− or aluminum alkoxide-initiated polymerizations. The initiation involves a two-step process: (1) alcoholysis of bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] to give the corresponding calcium alkoxide and (2) ring-opening of l-lactide via acyl-oxygen cleavage and insertion into the calcium-alkoxide bond. In the presence of excess alcohol, fast and reversible exchange between free alcohol molecules and coordinated alkoxide ligands takes place. This allows tuning of the poly(l-lactide) molecular weight over a wide range.

Eco-Compatible Use of Olive Husk as Filler in Thermoplastic Composites

Abstract: A study on the possibility of recycling waste materials, such as olive husk, the solid phase derived from an olive oil mill, in blend with thermoplastic polymers to produce new materials for manufacturer of, for example, containers and formworks, has been carried out The present paper describes the methodology used for the preparation and the characterization of composite samples prepared by mixing various percentages of olive husk and polypropylene A screening on the chemical-physical characteristics of the olive husk is reported, as well as a set of tests applied to evaluate the mechanical properties of the manufactured products obtained

Polymer Barrier Films

Abstract: Many polymers such as polyolefins (polyethylene, polypropylene), poly(vinyl chloride), aliphatic polyamides, poly(ethylene terephthalate), polycarbonate, and others are used as protective barrier films against the mass transport of small molecules of gases, vapors, and liquids (known as diffusates, permeants) in different applications. The barrier properties depend on the polymer characteristics such as solubility, diffusion, permeability, and others, the nature of the fluid, temperature, and other factors. Mainly polymer barrier film application in packaging, construction, and agriculture are discussed.

Synthesis and Extraction Study of Calix[4]arene Dinitrile Derivatives Incorporated in a Polymeric Backbone with Bisphenol-A

Abstract: Two new copolymers containing pendant calix[4]arene units with nitrile functionalities at their lower rim have been synthesized via nucleophilic substitution reactions involving 5,11,17,23-tetra-tert-butyl-25,27-bis(cyanomethoxy)-26,28-dihydroxy-calix[4]arene (3) or 25,27-bis(cyanometh oxy)-26,28-dihydroxy-calix[4]arene (4) with 1,5-dibromopentane and bisphenol-A. The phase transfer studies were performed by using liquid–liquid extraction procedures. It has been deduced from the observations that both copolymers show a good phase transfer affinity toward selected alkali, alkaline earth, and transition metal cations, unlike their precursor (3).

Outdoor Weathering Evaluation of Carbon-Black-Filled, Biodegradable Copolyester as Substitute for Traditionally Used, Carbon-Black-Filled, Nonbiodegradable, High-Density Polyethylene Mulch Films

Abstract: Carbon-black-filled, biodegradable, copolyester mulch film (Eastar®, or EA, Tennessee Eastman, Kingsport, TN) and commercial carbon-black-filled, high-density polyethylene (HDPE) mulch film were exposed for 12 weeks to commercial vegetable crop growing conditions by being placed directly on irrigated soil in the field of the University of Tennessee Alcoa Highway State Agriculture Experiment Station (Knoxville, TN) and by being placed on a plywood exposure rack as described by the American Society of Testing and Materials (ASTM) Standard Test Method 1435: Outdoor Weathering of Plastics. Mechanical properties and weather information were collected in order to evaluate the feasibility of using the newly developed biodegradable EA mulch film to replace the nonbiodegradable HDPE mulch film. Results indicate that the EA mulch film exhibited favorable tensile strength and elongation-at-break during outdoor exposure rack testing and outdoor, in-field, placed directly on the soil, exposure testing, suggesting biodegradable EA could be a substitute for the HDPE nonbiodegradable material.

Bioabsorbable Soy Protein Plastic Composites: Effect of Polyphosphate Fillers on Biodegradability

Abstract: The use of biodegradable polymers made from renewable agricultural products such as soy protein isolate has been limited by the tendency of these materials to absorb moisture. A straightforward approach for controlling the inherent water absorbency of the biodegradable polymers involves blending special bioabsorbable polyphosphate fillers, biodegradable soy protein isolate, plasticizer, and adhesion promoter in a high-shear mixer followed by compression molding. The procedure yields a relatively water-resistant, biodegradable soy protein polymer composite, as previously reported. The aim of the present study is to determine the biodegradability of the new polyphosphate filler/soy protein plastic composites by monitoring the carbon dioxide released over a period of 120 days. The results suggest that the composites biodegrade satisfactorily, with the fillers having no significant effect on the depolymerization and mineralization of the soy protein plastic, processes that would otherwise result in nonbiodegradable composites. Further, the results indicate that the biodegradation and useful service life of these biocomposites may be controlled by changing the filler concentration, making the biocomposites useful in applications in which the control of water resistance and biodegradation is critical.

The Effect of UV-B Irradiation on the Biodegradability of Poly-β-Hydroxybutyrate (PHB) and Poly-ɛ-Caprolactone (PCL)

Abstract: The biodegradability of poly-β-hydroxybutyrate and poly-ɛ-caprolactone in soil compostage before and after irradiation of the polymers for 192, 425, and 600 h in a Weather-Ometer was examined. The biodegradability tests were done in soil compostage at pH 7.0, 9.0, and 11.0 to assess the influence of this parameter on degradation. The rate of degradation was directly proportional to the soil alkalinity. Poly-β-hydroxybutyrate showed the greatest weight loss and aging in a Weather-Ometer did not significantly increase the biodegradation, except when the polymer was aged for 425 h and buried in soil compostage of pH 11.0.

Comparative Biodegradation Study of Starch- and Polylactic Acid-Based Materials

Abstract: The degradation of starch- and polylactic acid-based plastic films by microorganisms extracted from compost was studied in a liquid medium. The various degradation products produced were measured throughout the duration of the experiment, and total carbon balances were estimated. For an easily biodegradable material, the evolution of the way carbon repartitioned between different degradation products was quite similar whatever the experimental condition or the type of substrate. On the other hand, for a resistant material exposed to these microorganisms, the nature of the biodegradation depended strongly on the experimental conditions. In the latter case, a differential scanning calorimetry analysis confirmed the importance of the applied norm on the state of the residual material. The consequences for improved methods of estimation of biodegradability of these materials are discussed.

Radiation Crosslinking of Poly(Butylene Succinate) in the Presence of Inorganic Material and Its Biodegradability

Abstract: Three kinds of poly(butylene succinate)s (PBS) with different molecular weight were irradiated with electron beams in the presence of inorganic material. Fourteen kinds of inorganic materials were used in this work. The presence of inorganic material inside cross-linked PBS samples enhances the yield of gel formation. The heat stabilities of PBS samples were checked; it was found that silicon dioxide and carbon black significantly improve these properties. Enzymatic and soil burial tests were performed; the presence of these inorganic materials in cross-linked PBS accelerates the rate of biodegradation.

Thermal Degradation Mechanism of Low-Density Polyethylene Plastic Wastes in Cyclohexane

Abstract: The thermal LDPE degradation mechanism harnessing a high-pressure autoclave surrounded by a furnace was investigated in this work. Rates of formation of gas, liquid, and solid during degradation of PE plastic wastes in cyclohexane as solvent at 400 and 425°C have been experimentally determined. Four reaction mechanisms have been proposed and tested to estimates of gas, liquid, and solid. Proposed mechanisms are based on the assumption that the reactions are pseudo-first-order with respect to the reacting species. Pseudo-first-order rate constants for each of the indicated mechanistic steps have been calculated by nonlinear regression analysis. The best fit was obtained by model 2 (pure parallel reaction mechanism), and its activation energy was determined.

Effect of Pretreatment with UV Radiation on Physical and Mechanical Properties of Photocured Jute Yarn with 1,6-Hexanediol Diacrylate (HDDA)

Abstract: Jute yarns were grafted with a single impregnating monomer 1,6-hexanediol diacrylate (HDDA) in order to improve the physicomechanical properties. Jute yarns soaked for different soaking times (3, 5, 10, and 30 minutes) in HDDA+MeOH solutions at different proportions (1–10% HDDA in MeOH [v/v] along with photoinitiator Darocur-1664 [3%]) were cured under UV lamp at different UV radiation intensities (two, four, six, and eight passes). Concentration of monomer, soaking time, and intensity of UV radiation were optimized with extent of mechanical properties such as tensile strength, elongation at break, and modulus. Enhanced tensile strength (67%), modulus (108%), and polymer loading (11%) were achieved with 5% HDDA concentration, 5-minute soaking time, fourth pass of UV radiation. To further improve the mechanical properties, the jute yarns were pretreated with UV radiation (5, 10, 15, 30, and 50 passes) and treated with optimized monomer concentration (5%). UV-pretreated samples showed the enhanced properties. The tensile strength and modulus increase up to 84% and 132%, respectively, than that of virgin jute yarn. An experiment involving water absorption capacity shows that water uptake by treated samples was much lower than that of the untreated samples. During the weathering test, treated yarns exhibited less loss of mechanical properties than untreated yarns.

A New Test Method for Determining Biodegradation of Plastic Material Under Controlled Aerobic Conditions in a Soil-Simulation Solid Environment

Abstract: A new test method is described for assessing biodegradation of plastic material under simulated soil conditions An inert substrate can be activated with soil extract and nutrient and used in place of soil in biodegradation tests The biodegradation level is evaluated by determining the carbon dioxide (CO2) production released by the test reactors Effects of substrate nature, solution pH, nutrient composition, soil extract concentration, and activation duration on CO2 production were investigated, and the experimental conditions were optimized Results obtained with cellulose showed a biodegradation rate of 80% within 28 days Moreover, with this kind of substrate, reaction products and residues can be easily extracted and analysed

Starch-Based Polymers in Extrusion Coating

Abstract: The starch-based polymers exhibited shear thinning and elastic nature in rheological characterizations. Thin coatings with narrow neck-in could be produced at fairly high extrusion coating line speeds. Adhesion between the starch-based polymers and paperboard was typically weak. Water vapor barrier of starches was very poor. Soft starch grades had a good pinhole resistance and a good heat sealing performance. Brittle nature of starch caused cracking as the coated paperboards were creased.

LDPE/EPDM Multilayer Films Containing Recycled LDPE for Greenhouse Applications

Abstract: In this paper the reuse of recycled LDPE in combination with the incorporation of EPDM modifier in the production of greenhouse films has been investigated. A three-layer film (60-100-40 micron thickness) containing recycled LDPE in the middle layer and a high UV-stabilized 40-micron outer layer was developed and proven to be commercially successful. Films with 25% and 50% recycled material content were produced. The effect of natural weathering on the film properties over a period of 15 months has been observed. Changes in physical and mechanical property were determined. The addition of EPDM to the raw resin was found to improve the extrudability of the compound and improve the weather resistivity of the film. The EPDM-modified films containing 25% to 50% recycled material retained approximately 95% and 75%, respectively, of their original extensibility after 9 months' exposure to natural weathering. Optimization of EPDM and UV stabilizer concentration was carried out to develop a balanced film with excellent mechanical and physical properties and resistance to weathering conditions. The use of UV stabilizer concentrations slightly higher than commercial practice in the outer layer of the multilayer film can be justified by the cost reduction by the incorporation of recycled LDPE materials.

Melt Processing of a New Biodegradable Synthetic Polymer in High-Speed Spinning and Underpressure Spunbonding Process

Abstract: A new biodegradable synthetic polyesteramid (PEA) was characterized by means of thermogravimetry (TG) differential scanning calorimetry (DSC) and dynamic rheological measurements Two glass transition ranges at about −33 and 38°C and a melting enthalpy of 33 J/g were measured, indicating that PEA is an immiscible blend of two components with a small crystalline part The material was spun in a high-speed spinning process within the range of 2,000–6,000 M/min and an underpressure spunbonding process within the range of 3,600–7,700 M/min The textile physical properties of the fibers were 100 MPa tenacity at an elongation at break of 30%, and an E-modulus of 05 GPa The mass per unit area of the spunbonded nonwovens ranged from 70–159 g/M2 The strength of the spunbonded nonwovens was 28–51 N and 42–74 N in machine and cross direction, respectively The air permeability of the nonwovens decreased at high air velocities and more fineness of the filaments from 1240–380 l/M2 s

Effect of Poly(Vinyl Alcohol) and Polyethylene on the Growth of Red Pepper and Tomato

Abstract: Poly(vinyl alcohol) (PVA) and polyethylene (PE) were blended with a soil for cultivation, and their effects were investigated on the growth behavior of red pepper and tomato by examining the stems, the leaves, and the roots. PVA retarded the growth of red pepper significantly even at a concentration as low as 0.05%. The roots were depauperated more than the stems and the leaves. Tomato was also affected by PVA but to a lesser extent than red pepper. In contrast, the presence of both round pieces (10 mm diameter) of PE film and powdery PE influenced negligibly the growth of red pepper as well as that of tomato up to 35 wt% in soil.

Application of a Second-Order Kinetic Model to a Complex Melt Polymerization Reaction

Abstract: A novel copolymer system has been synthesized using methyl hydroquinone diacetate (MHQDA), 1,4 naphthalene dicarboxylic acid (1,4 NDCA), and polybutylene terephthalate (PBT) using the melt polymerization technique. The optimum kinetic parameters pertinent to this system are reported in this study. A simple second-order reaction sequence summarizes catalyzed and uncatalyzed reactions between MHQDA, 1,4 NDCA, and PBT. The kinetic parameters for the copolymerization reaction were determined using a new second-order model. This technique was used to compute the moles of acetic acid generated in the polymerization process. The model was compared to that of the experimentally determined data. Close comparison (percentage error of less than 5%) was obtained between the experimental and theoretical data. The kinetic data support block copolyester formation. The thermal data also supports formation of block polymers.