Melt Strength and Rheological Properties of Biodegradable Poly(Lactic Aacid) Modified via Alkyl Radical-Based Reactive Extrusion Processes

Poly(lactic acid) (PLA) has been modified using twin-screw reactive extrusion to improve its melt properties and crystallinity. In this work lauroyl peroxide was used as an alkyl free radical source, abstracting hydrogen atoms from the PLA backbone leading to branching and chain extension reactions. Once the linear viscoelastic region was determined for these polymers, changes in dynamic rheology (dynamic viscosity real and loss modulus) were measured. Gel permeation chromatography showed that the molecular weight and polydispersity increased to a maximum with the addition of 1.00 and 0.50?wt% peroxide, respectively. Low temperature ?? transitions in dynamical mechanical thermal traces gave further evidence that branching had also occurred. G?ttfert Rheotens measurements showed a three fold increase in melt strength due to both increased chain length and branching. Thermal analysis showed the level of crystallisation had decreased also possibly due to branching. Reductions in crystallinity and improved melt strength are known to be critical for film and foam formation.     

Reactive Blending of Biodegradable Polymers: PLA and Starch

Poly(lactic acid) (PLA) and starch are important biodegradable polymers. Mechanical properties of blends of PLA and starch using conventional processes were very poor because of incompatibility. In this study, PLA and starch were blended with a reactive agent during the extrusion process. The affects of the reactive blending were investigated and significant improvements were confirmed by measuring the tensile strength and elongation at break, IR spectra, and DSC.     

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.     

Thermal, Mechanical and Rheological Behavior of Poly(lactic acid)/Talc Composites

In the present study, influence of talc on thermal, mechanical and rheological behavior of PLA is investigated and the structure?Cproperty correlation for the PLA/talc composites is established. Poly(lactic acid)/talc composites are prepared by melt mixing of PLA with talc in twin screw extruder followed by blown film processing. Various characterizations techniques are used to evaluate thermal, morphological, mechanical and rheological behavior of PLA/talc composites and its blown film. DSC analysis showed that degree of crystallinity of PLA/talc composites was higher than that of neat PLA because of nucleating ability of talc. Spherulite morphology of PLA/talc composites showed that talc has increased nucleation density of spherulite having smaller radius than that of neat PLA. Talc is effective in enhancing tensile modulus and storage modulus of PLA due to reinforcing ability of talc particles.     

Degradation and Stabilization of Poly(Butylene Adipate-co-Terephthalate)/Polyhydroxyalkanoate Biodegradable Mulch Films Under Different Aging Tests

Journal of Polymers and the Environment - The degradation and stability of biodegradable films determine the service length of mulch films in actual use. Most biodegradable polymers degrade too...     

Thermal,Rheological, Mechanical and Morphological Behavior of High Density Polyethylene and Carboxymethyl Cellulose Blend

In this study water soluble sodium carboxymethyl cellulose (CMC) was blended with high density polyethylene (HDPE) by peroxide-initiated melt compounding technique. The compatibility of the blended polymers were carried out by silane crosslinking agent. A series of blends were prepared by varying the CMC contents up to a maximum of 50 phr. The physical properties of non-crosslinked and crosslinked blends were investigated in detail. FTIR analysis of crosslinked blend confirmed the presence of Si–O–Si and Si–O–C absorption peaks at 1050 and 1159 cm^?1. Thermal stability of crosslinked blends improved as compared to its non-crosslinked congener. Rheological study of crosslinked blends illustrated high complex viscosity and dynamic shear storage modulus. The tensile strength of virgin polyethylene was 8.1 MPa whereas the maximum tensile strength of 19.6 MPa was observed in crosslinked blend. Similarly lower deformation was observed in crosslinked blends under static load. Scanning electron microscopy of crosslinked formulations also showed strong adhesion between the polymers interface. The compatibility of HDPE and CMC is attributed to both free radical and condensation reactions.     

Geophysical and Hydrologic Monitoring of Air Sparging Flow Behavior: Comparison of Two Extreme Sites

The distribution of air around injection wells is an important determinant of the effectiveness, design, and cost of air sparging remediation systems. High-level air sparging field tests were conducted at two sites for the purpose of determining the pattern of airflow under widely different subsurface conditions. One site consisted of relatively homogeneous dune sand (Site A). The other consisted of highly heterogeneous glacial till (Site B). At both sites, cross-borehole electrical resistance tomography (ERT) was used to image the principal region of airflow in the saturated zone. The response of conventional monitoring data was compared with the ERT results. At Site A, the principal region of airflow was approximately symmetric about the sparge well and only 2.4 m in radius. At Site B, the pattern of airflow was much more complex and had a major horizontal component. In both site studies, conventional monitoring data provided a much more ambiguous indication of the region of airflow in the saturated zone than did ERT. The investigations at these two sites demonstrate that, while the exact distribution of injected air is not readily discernible by conventional monitoring, the character of the airflow pattern can be recognized when appropriate physical response data are collected. Such response data can be used to evaluate site suitability for air sparging and to improve the system design and operation.     

Critical Review of Norms and Standards for Biodegradable Agricultural Plastics Part II: Composting

The critical review of norms and standards and corresponding tests to determine the compostability of biodegradable plastics, possibly applicable also to biodegradable agricultural plastics, shows that many norms concerning testing and labelling of compostable plastics have been established at the international level. Some of them are about plastic materials, some others are about products like packaging. The media and conditions of testing cover mainly the conditions designed for industrial composting facilities, and only a few concern home composting conditions. Considering that the end of life management of biodegradable agricultural plastic products will be done at the farm to reduce the management of the waste and also its cost, only a few of these norms are considered to be suitable for adaptation to cover also biodegradable agricultural plastic products. The biodegradability validation criteria under composting conditions, such as the threshold percentage of biodegradation and disintegration, the time and temperature, and the ecotoxicity, are presented for the main norms and standard testing methods. Based on these different norms and their content, a list of specs and technical requirements that could be adapted to meet farm composting conditions for agricultural compostable plastics is proposed. These requirements may be used as criteria for the establishment of a new integrative norm for agricultural compostable plastics.     

Ecotoxicity Evaluation of the Biodegradable Polymers PLA,PBAT and its Blends Using <Emphasis Type="Italic">Allium cepa</Emphasis> as Test Organism

Biodegradable polymers are considered a feasible option to minimize the environment impacts of high disposal of solid waste. Nevertheless, environmental safety of these materials is a few explored issue. In this context, this study evaluated ecotoxicological effects in soil of the biodegradable materials poly(lactic acid)-PLA, poly(butylene adipate co-terephthalate)-PBAT and their blends compatibilized with a chain extender. The tool used for this analysis was the bioassay with Allium cepa as test organism. The studied materials were not phytotoxic, cytotoxic, genotoxic nor mutagenic for meristematic cells of A. cepa.     

Melt Flow Behavior and Processability of Polylactic Acid/Polystyrene (PLA/PS) Polymer Blends

The present investigation dealt with the flow behavior and processability of polylactic acid/polystyrene (PLA/PS) polymer blends using a capillary rheometer. For this purpose, PLA/PS blends with different ratios of the concentrations were prepared using a single screw extruder. The shear viscosity, shear stress, shear rate, power-law index, viscous activation energy at a constant shear stress, and elongational stress were determined. PLA/PS blends exhibited a typical shear-thinning behavior over the entire range of shear rates tested, and the viscosity values of the blends would tend to decrease with increasing amount of PLA. In addition, the polymer blend of 70 % PLA and 30 % PS was found to be relatively less sensitive to the processing temperature, implying that the extrusion process was more desirable for fabrication of PLA/PS polymer blend than the injection process.     

Thermal and Rheological Properties of Poly(lactic acid)/Low-Density Polyethylene Blends and Their Supercritical CO<Subscript>2</Subscript> Foaming Behavior

Low-density polyethylene (LDPE) was employed to improve the thermal and rheological properties as well as the supercritical CO₂ foaming behavior of poly(lactic acid) (PLA) through melt mixing and batch foaming method, due to its long branched chain structure, moderate crystallization capacity and good foamability. The differential scanning calorimetry and polarized optical microscope results showed that the introduction of LDPE had a slight effect for promoting the crystallization of PLA. An important synergistic effect on the rheological properties of PLA/LDPE blends was found through rotational rheometer. With the content of LDPE, the size of spherical LDPE dispersion phase became bigger gradually, which was observed by scanning electron microscope (SEM). A very interesting cellular morphology evolution from flower-like cellular structure to complex cellular structure and then to mono-porous cell structure was found in the SEM images of the PLA/LDPE blending foams with the foaming temperature at 95 °C. The effect of blending ratio and foaming temperature on the cellular morphology and foaming parameters was investigated.     

Biodegradability of a Selected Range of Polymers and Polymer Blends and Standard Methods for Assessment of Biodegradation

Synthetic polymers are important to the packaging industry but their use raises aesthetic and environmental concerns, particularly with regard to solid waste accumulation problems and the threat to wildlife. Some concerns are addressed by attention to problems associated with source reduction, incineration, recycling and landfill. Others are addressed by the development of new biodegradable polymers either alone or in blends. Materials used for biodegradable polymers include various forms of starch and products derived from it, biopolyesters and some synthetic polymers. Starch is rapidly metabolised and is an excellent base material for polymer blends or for infill of more environmentally inert polymers where it is metabolised to leave less residual polymer on biodegradation. This should help to improve the environmental impact of waste disposal. A number of standard methods have been developed to estimate the extent of biodegradability of polymers under various conditions and with a variety of organisms. They tend to be used mainly in the countries where they were developed but there is much overlap between the standards of different countries and wide scope for development of consistent and international standards.     

Effect of the Fe2O3/TiO2 Nanoparticles on the Structural,Mechanical, Electrical Properties and Antibacterial Activity of the Biodegradable Chitosan/Polyvinyl Alcohol Blend for Food Packaging

Journal of Polymers and the Environment - As the request for ready-made food grows, it’s more important than ever to develop effective antimicrobial food packaging materials to assure...     

Degradation of Cellulosic Materials Under the Alkaline Conditions of a Cementitious Repository for Low- and Intermediate-Level Radioactive Waste. II. Degradation Kinetics

The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are - and -(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.     

Citric Acid and Vitamin C as Coupling Agents for the Surface Coating of ZrO<Subscript>2</Subscript> Nanoparticles and Their Behavior on the Optical,Mechanical, and Thermal Properties of Poly(vinyl alcohol) Nanocomposite Films

A series of bio-nanocomposites (BNC)s were fabricated through solution casting method. At first, the surfaces of ZrO₂ NPs were functionalized with citric acid and Vitamin C as green modifier agents. Then, PVA as polymer matrix was embedded with different contents (4, 8 and 12 wt%) of modified ZrO₂ (m-ZrO₂) NPs with the aim of ultrasonic irradiation process. The resulting BNCs were studied by various techniques. Thermal stability of obtained BNCs was enhanced after NPs’ addition to the PVA matrix. Optical activity of these new BNCs makes them potential candidate for UV shielding material. Lastly, the tensile strengths of the BNCs were increased in comparison to the pure PVA.