Renewable Cellulose Derived Carbon Nanospheres as Nucleating Agents for Polylactide and Polypropylene

Nucleation of polylactide and polypropylene using novel renewable resource biobased carbon nanospheres (CNS) is investigated using differential scanning calorimetry and polarized optical microscopy. Isothermal studies near the optimal crystallization temperature demonstrate at least a five-fold increase in crystallization rate in PP but only a 1.4 times faster crystallization in PLA. Non-isothermal studies reveal an asymptotic relationship of the maximum crystallization temperature with increasing CNS weight loading in PP and no relationship in PLA. Microscopy indicates some aggregation in the solution blended samples and that average spherulite size is reduced 10-fold due to faster nucleation in the composites as compared to the neat polymer. The fractional crystallinity achieved during non-isothermal crystallization increases by about 7% with addition of a small amount of CNS and decreases with weight loading higher than 1%. The crystallization rates obtained in polypropylene are competitive with widely used mineral talc nucleating agents.     

Evaluation of the Biodegradation of Starch and Cellulose Under Controlled Composting Conditions

In order to verify the response of the controlled composting test method (i.e., the ISO/DIS 14855:1997, the ASTM D 5338-92, or the CEN counterpart) to starch at different concentrations, the maximum amount prescribed by the test method (100 g) and lower amounts (60 and 30 g), as if starch were a coingredient in a blend, were tested. After 44 days of incubation (at a constant temperature of 58°C) the biodegradation curves were in a plateau phase, displaying the following final values (referred to a nominal starch initial amount of 100 g): starch 100 g, 97.5%; starch 60 g, 63.7%; and starch 30 g, 32.5%. The data show a CO₂ evolution roughly equal, in each case, to the theoretical maximum, indicating a complete starch mineralization. We cannot discern whether the deviations found at lower concentrations are caused by a priming effect. In any case, the extent of the deviations is not high and is acceptable in biodegradation studies. The average biodegradation of cellulose, obtained gathering four independent experiments with 11 biodegradation curves, turned out to be 96.8 ± 6.7% (SD) after 47 ± 1 days. The data indicate that the controlled composting is a reliable test method also for starch and cellulose and, consequently, for starch-based and cellulose-based materials.     

Sustainable Bio-Composites from Renewable Resources: Opportunities and Challenges in the Green Materials World

Sustainability, industrial ecology, eco-efficiency, and green chemistry are guiding the development of the next generation of materials, products, and processes. Biodegradable plastics and bio-based polymer products based on annually renewable agricultural and biomass feedstock can form the basis for a portfolio of sustainable, eco-efficient products that can compete and capture markets currently dominated by products based exclusively on petroleum feedstock. Natural/Biofiber composites (Bio-Composites) are emerging as a viable alternative to glass fiber reinforced composites especially in automotive and building product applications. The combination of biofibers such as kenaf, hemp, flax, jute, henequen, pineapple leaf fiber, and sisal with polymer matrices from both nonrenewable and renewable resources to produce composite materials that are competitive with synthetic composites requires special attention, i.e., biofiber–matrix interface and novel processing. Natural fiber–reinforced polypropylene composites have attained commercial attraction in automotive industries. Natural fiber—polypropylene or natural fiber—polyester composites are not sufficiently eco-friendly because of the petroleum-based source and the nonbiodegradable nature of the polymer matrix. Using natural fibers with polymers based on renewable resources will allow many environmental issues to be solved. By embedding biofibers with renewable resource–based biopolymers such as cellulosic plastics; polylactides; starch plastics; polyhydroxyalkanoates (bacterial polyesters); and soy-based plastics, the so-called green bio-composites are continuously being developed.     

Chain-Length Shortening of Methyl Ethyl Hydroxyethyl Cellulose: An Evaluation of the Material Properties and Effect on Foaming Ability

During the past century, plastics have become a natural element in our every-day life. Lately however, an awareness about the fossil origin and often non-degradable nature of many plastics is rising. This has resulted in the emergence of some bio-based and/or biodegradable plastics, often produced from renewable resources. One possible candidate for bioplastics production could be found in cellulose. This paper aims at contributing information regarding a cellulose derivative, which could possibly be used in foamed plastics applications. Therefore, the reduction of the chain-length of a methyl ethyl hydroxyethyl cellulose (MEHEC), assessed by size exclusion chromatography, and the effect of chain-length on the foaming behaviour were studied. The foaming was accomplished with a hot-mould technique using aqueous polymer solutions. The generated steam was here used as the blowing agent and important parameters were polymer concentration and solution viscosity. The density of the produced foams was assessed and was in some cases comparable to that of commodity foams. It was found that reducing the chain-length enabled an increase of the initial polymer concentration for the foaming process. This is believed to be beneficial for creating more structurally stable foams of this type.     

Improving the Rheological and Mechanical Properties of Recycled PET Modified by Macromolecular Chain Extenders Synthesized by Controlled Radical Polymerization

In this work, a series of reactive copolymers of glycidyl methacrylate (G), styrene (S) and acrylonitrile (AN), were synthesized through reversible addition-fragmentation chain transfer polymerization and evaluated as macromolecular chain extenders in reactive extrusion of recycled poly(ethylene terephthalate) (rPET). The results obtained indicate that the addition of the reactive copolymers as chain extenders modifies the chain conformation in rPET causing low crystallization rate and low crystallinity. The physical and rheological properties (melt flow and intrinsic viscosity) of chain-extended rPET improved, rendering better processability. rPET modified with polymeric chain extenders shows improved rheological properties (complex viscosity, storage and loss modulus) and also displays higher elongation at break and impact properties as the GMA content in the chain extenders increase.     

Cellulose acetate biodegradability upon exposure to simulated aerobic composting and anaerobic bioreactor environments

Cellulose acetate (CA) films with degree of substitution (d.s.) values of 1.7 and 2.5 were exposed to biologically active in-laboratory composting test vessels maintained at approximately 53 °C. The CA 1.7- and 2.5-d.s. films (thickness values of 0.5–1.0 and 2.0 mil, respectively) had completely disappeared by the end of 7- and 18-day exposure time periods in the biologically active bioreactors, respectively. The relatively small CA film weight loss observed in the poisoned control test vessels allows the conclusion that CA film erosion during the composting exposures resulted, at least in part, from biologically mediated processes. Under strictly anaerobic conditions, an active methanogenic inoculum was developed by acclimation of a sewage sludge to a synthetic municipal solid waste (SMSW) mixture at 42°C. The CA 1.7-d.s. film samples (0.5- to 1.0-mil thickness) were exposed in anaerobic serum bottles containing a 25% solids loading of SMSW in which methanogenic activity was rapidly established after introducing of the developed inoculum. For exposures of 30 days only small visually distinguishable fragments of the CA 1.7-d.s. films were recovered. In contrast, exposure of the CA 1.7-d.s. film to a poisoned control test vessel resulted in negligible weight loss. Therefore, degradation of the CA 1.7-d.s. films upon exposure to the anaerobic bioreactors was due, at least in part, to biologically mediated processes.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Renewable Resources and Enzymatic Processes to Create Functional Polymers: Adapting Materials and Reactions from Food Processing

We are exploiting materials and concepts from food science to create functionalized, environmentally friendly derivatives of the biopolymer chitosan, a byproduct of seafood processing. Functional groups are grafted onto chitosan using tyrosinase, the enzyme responsible for food browning. The functionalizing groups studied include low-molecular-weight phenols derived from natural sources and high-molecular-weight proteins. The approach of using low-molecular-weight phenols to functionalize chitosan is illustrated with arbutin, a natural phenol found in pears. Results demonstrate that tyrosinase initiates reactions that lead to the conversion of arbutin–chitosan solutions into gels. These gels can be rapidly broken by treatment with the chitosan-hydrolyzing enzyme chitosanase, demonstrating that the chitosan derivatives remain biodegradable. We briefly review other studies in which low-molecular-weight natural phenols are enzymatically grafted onto chitosan to confer functional properties. The creation of co-polymers is illustrated by results in which tyrosinase is used to couple gelatin onto chitosan. Gelatin is a proteinaceous byproduct of meat production. The tyrosinase-generated gelatin–chitosan conjugates have been observed to offer interesting rheological and thermal properties. These results demonstrate the potential for using renewable resources and enzymatic processing to create environmentally friendly polymers with useful functional properties.     

Combining stakeholder analysis and spatial multicriteria evaluation to select and rank inert landfill sites

This paper presents a method based on the combination of stakeholder analysis and spatial multicriteria evaluation (SMCE) to first design possible sites for an inert landfill, and then rank them according to their suitability. The method was tested for the siting of an inert landfill in the Sarca’s Plain, located in south-western Trentino, an alpine region in northern Italy. Firstly, stakeholder analysis was conducted to identify a set of criteria to be satisfied by new inert landfill sites. SMCE techniques were then applied to combine the criteria, and obtain a suitability map of the study region. Subsequently, the most suitable sites were extracted by taking into account also thresholds based on size and shape. These sites were then compared and ranked according to their visibility, accessibility and dust pollution. All these criteria were assessed through GIS modelling. Sensitivity analyses were performed on the results to assess the stability of the ranking with respect to variations in the input (criterion scores and weights). The study concluded that the three top-ranking sites are located close to each other, in the northernmost sector of the study area. A more general finding was that the use of different criteria in the different stages of the analysis allowed to better differentiate the suitability of the potential landfill sites.     

Reuse of Selected Lignocellulosic and Processed Biomasses as Sustainable Sources for the Fabrication of Nanocellulose via Ni(II)-Catalyzed Hydrolysis Approach: A Comparative Study

This study investigates for the first time the feasibility of isolating nanocellulose from several selected feedstocks via a novel Ni(II)-hydrolysis process, including lignocellulosic biomasses (oil palm trunk, banana peel and coconut husk) and processed biomasses (newspaper, tissue paper and cotton linter), with an obtained gravimetric yield ranging from 59.6 to 86.2%. The isolation of nanocellulose products from these selected feedstocks was verified by the successive removal of most of their non-cellulosic components (lignin and hemicellulose) and cellulose amorphous regions, the increase in the crystallinity index and the nanoscale of the individual crystals. Most importantly, the resultant nanocellulose products rendered better thermal stability than that of corresponding original sources, which are highly potential to be utilized as the new renewable sources of reinforcement materials with potential applications in bio-nanocomposites and thermoplastics. Therefore, this work proves the viability of direct production of nanocellulose from a variety of cellulosic sources by using Ni(II)-based transition metal salt catalyst. The results suggested that the concept of waste to wealth could be well executed from the obtained nanocellulose, which are greatly potential for various industrial applications.     

Assessment of Ball Milling as a Compounding Technique to Develop Nanocomposites of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate) and Bacterial Cellulose Nanowhiskers

The aim of this study was the assessment of high energy ball milling technique to develop poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanocomposites containing bacterial cellulose nanowhiskers (BCNW). Crystallization behaviour of PHBV/BCNW nanocomposites was studied under non-isothermal and isothermal conditions using differential scanning calorimetry. The changes in PHBV crystalline structure were also studied using X-ray diffraction. The results confirmed that BCNW acted as nucleating agents and, hence, favored the crystallization of the PHBV. The oxygen permeability of the nanocomposites was reduced by ~22 % when compared to that of the neat PHBV. This work provides a new insight into the development of polyhydroxyalkanoate composites by means of the high energy ball milling technique.     

Evaluation of a Slag and Portland Cement Mix to Simulate Treatment of Acidic Waste via Solidification/Stabilization in a Deep Soil Mix Application

Site investigations at an oil and gas facility identified a highly acidic waste referred to as residual acid tar that resulted in the transport of dissolved nickel toward the point of compliance at concentrations that exceeded site environmental screening levels. Solidification/stabilization (S/S) via deep soil mixing was selected as the remedial approach and a mixture of ground granulated blast furnace slag cement and Portland cement was subjected to treatability testing to evaluate the reagent mix's ability to achieve treatment objectives. Results from the treatability test showed a cement mix dose of 21 percent was sufficient to raise the pH above the target of 6.0 and reduce dissolved nickel concentrations to below site screening levels in leachate from treated samples of residual acid tar and material impacted by residual acid tar. Cement mix doses of 21 percent or greater were sufficient to achieve target strengths in the unimpacted shallow overburden. However, none of the doses tested were able to achieve target strengths in the residual acid tar or peaty material impacted by the residual acid tar. Results showed soil strengths increased significantly when the pH in leachate from the treated samples approached 12, suggesting the presence of organic acids related to the peaty soils may interfere with the cement set. Recommendations from the study include additional treatability testing to evaluate pre‐treatment with hydrated lime to satisfy acid neutralization requirements prior to dosing with the cement mix. ©2016 Wiley Periodicals, Inc.