Molecular Modification and Compatibilization of Collected Polyethylene

The increasing use of plastics in packaging materials leads to growing amounts of plastic waste. Recycling material is generally regarded as advantageous. But in fact very few products are made from plastic waste, partly this can be explained by that little is known about the recycling process and the properties of collected materials. There is a need for injection moulding grades of recycled polyethylene, while large amounts of extrusion grades are available from packaging waste. A controlled way of de-branching or partly degrading PE would be desirable. Peroxides are commonly used to crosslink polyolefins, but under certain conditions a chain scission reaction occur. Another problem encountered with recycling of polyethylene are the poor miscibility of low amounts contaminations, i. e. polypropylene. A compatibilizer can improve properties of such polymer blends, in this work EPDM is used as compatibilzer. Studies of mechanical properties and viscosity measurements show that it is possible to partly degrade PE with peroxide exposing it to high temperature and oxygen. The properties of PE/PP blends were improved with EPDM as compatibilizer.     

Reactive Compatibilization of Biobased Polyurethane Prepolymer Toughening Polylactide Prepared by Melt Blending

Polylactide (PLA) is a major biodegradable polymer, which has received extensive interests over the past decades and holds great potential to replace several petroleum-based polymeric materials. Nevertheless, the inherent brittleness and low impact strength have restricted its invasion to niche markets. In this paper, the authors demonstrate that the entirely bio-sourced blends, namely PLA and castor oil-based polyurethane prepolymer (COPUP), were first melt-compounded in an effort to prepare novel biodegradable materials with an excellent balance of properties. NCO-terminated COPUP was successfully synthesized and subsequently mixed with variable concentration of PLA matrix using melt-compounded by twin-screw extrusion technique. The miscibility, phase morphology, mechanical properties, and thermal resistance of the blends were investigated. During FTIR analysis, it suggests that the interfacial compatibilization between COPUP and PLA phase occurred by the reaction of –NCO group of MDI with terminal hydroxyl group of PLA. DMA analysis showed that COPUP and PLA showed some limited miscibility with shifted glass transition temperature. The morphologies of fracture surface showed a brittle-to-ductile transition owing by the addition of COPUP. The crystallization behavior was studied by differential scanning calorimeter (DSC). The strain at break and notched impact strength of PLA/COPUP blends were increased more than 112–15.4 times elegant of neat PLA; the increase is superior to previous toughening effect by using petroleum-based tougheners. Furthermore, the thermal resistances and melt flow properties of the materials were also examined by analysis of the melt flow index and heat deflection temperature use in the work. With enhanced toughness, the PLA/COPUP blends could be used as replacements for some traditional petroleum-based polymeric materials.     

Physical Characterization and Pre-assessment of Recycled High-Density Polyethylene as 3D Printing Material

3D printing has received lots of attention due to its limitless potential and advantages in comparison to traditional manufacturing processes. This study focuses on the most popular type of home 3D printers, namely fused filament fabrication (FFF) printers, which use plastic filaments as the feedstock. The rather high material cost and large amount of plastic waste generated by FFF 3D printers have driven the need for plastic filaments produced from recycled plastic waste. This study evaluates, in terms of physical characterization, the feasibility of using recycled high-density polyethylene (HDPE), one of the most commonly used plastics, as the feedstock for 3D printers, in comparison with the common acrylonitrile butadiene styrene plastic pellets. In-house extrusion using recycled HDPE pellets and flakes is possible. The diameter consistency and extrusion rate results, along with other physical characterization results, including differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, Raman spectroscopy, and water absorption, suggest that making filaments from recycled HDPE pellets is a viable option, as the obtained filament has favorable water rejection and comparable extrusion rate and thermal stability. Existing methods for overcoming the warping and adhesion problems in 3D printing with HDPE were also reviewed. In order to increase the market competitiveness of waste-derived filaments, optimization of the extrusion process, studies on the mechanical and aging properties, and development of a standard characterization methodology and database are crucial.     

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

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.     

Mechanism of Depolymerization Reaction of Polyethylene Terephthalate: Experimental and Theoretical Studies

The depolymerization reaction of polyethylene terephthalate (PET) was analyzed on the basis of both experimental data and numerical data obtained from quantum chemistry calculations. Various alcohols were used as solvents in the search for the reaction mechanism. The activation energy obtained from the optimized structures of the ground state and the transitional state was compared with our experimental data. Based on these comparisons, it was found that the formation of rings from alkoxyl groups and carbonyl carbon atoms at the transitional state is highly important when the ester bonds of PET are broken. Moreover, the most appropriate alcohol was suggested for the depolymerization reaction.     

In Situ flushing of contaminated soils from a refinery: Organic compounds and metal removals

This article demonstrates the applicability of in situ flushing for the remediation of soil contaminated with petroleum hydrocarbons at a Mexican refinery. The initial average total petroleum hydrocarbon (TPH) concentration for the demonstration field test was 55,156 g/kg. After six weeks of in situ flushing with alternate periods of water and water/surfactant, an average concentration of 1,407 mg/kg was reached, achieving a total removal efficiency of 98 percent. At the end of the process, no hydrocarbons such as diesel; gasoline; benzene, toluene, ethyl benzene, and xylene (BTEX); or petroleum aromatic hydrocarbons (PAHs) were found. Iron washing achieved a removal efficiency of 70 percent, and for vanadium, the removal efficiency was 94.4 percent. The volume of soil treated was 41.6 m³ (38 m²), equivalent to 69.5 tons of soil. A rough calculation of the process costs estimated a total cost of $104.20/m³ ($114.00/m²). Our research indicates that there are a few studies demonstrating in situ flushing experiences under field conditions where both organic (TPH, diesel, gasoline, PAHs, BTEX) and metal (iron and vanadium) removals are reported. © 2004 Wiley Periodicals, Inc.     

Intrinsic and Stimulated In Situ Biodegradation of Hexachlorocyclohexane (HCH)

The feasibility of the biodegradation of HCH and its intermediates has been investigated. A recent characterisation of two sites in The Netherlands has shown intrinsic biodegradation of HCH. At one site, breakdown products (monochlorobenzene, benzene and chlorophenol) were found in the core of the HCH-plume, whereas the HCH-concentration decreased over time and space. Characterisation of a second, industrial site indicated less intrinsic biodegradation and the need to stimulate biodegradation. In the laboratory, enhanced HCH degradation was tested with soil and groundwater material from both sites, and the required conversion to the intermediates benzene and monochlorobenzene was demonstrated. Furthermore, the biodegradation of these intermediates could be initiated by adding low amounts of oxygen (<5%). Adding nitrate enhanced this degradation. We hypothesise that this occurs through anaerobic nitrate reducing conversion of oxidised intermediates.At the non-industrial other site, intrinsic degradation took place, as shown in the laboratory experiments. Interpretation of the field data with computer codes Modflow and RT3D was performed. As a result of the modelling study, it has been proposed to monitor natural attenuation for several years before designing the final approach.At the industrial site, the results of the batch experiments are applied. Anaerobic HCH degradation to monochlorobenzene and benzene is stimulated via the addition of an electron donor.Infiltration facilities have been installed at the site to create an anaerobic infiltration zone in which HCH will be degraded, and these facilities are combined with the redevelopment of the site.     

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with Carbokalk, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H₂S completely. Thus, some H₂S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.     

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

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.     

Environmental and Cost Assessment of a Polypropylene Nanocomposite

This paper describes a study on the use of a polypropylene (PP)/layered silicate nanocomposite as packaging film, agricultural film, and automotive panels. The study’s main question was “Are the environmental impacts and costs throughout the life cycle of nanocomposite products lower than those of products manufactured from conventional materials?” The conventional (benchmark) materials studied were pure polypropylene as packaging film, pure polyethylene as agricultural film, and glass fiber-reinforced polypropylene as automotive panels. In all three cases, the use of the PP nanocomposite resulted in a reduction of the amount of material used, while ensuring the same functionality. Material reduction was estimated using Ashby’s material indices and amounted to ?9% for packaging film, ?36.5% for agricultural film, and ?1.25% for automotive panels. It goes without saying that a product’s impact on the environment will decrease when less material is used. The production and incorporation of nanoparticles, however, may have additional impacts. We found clear environmental benefits throughout the entire life cycle when the PP nanocomposite is used in the manufacture of agricultural film. We noted some cost benefits when the nanocomposite is used in the production of agricultural film and automotive panels. If the price of nanoclay is at most €5,000 tonne then the cost of nanocomposite packaging film is also lower than that of the conventionally produced product.     

Wood Polypropylene (PP) Composites Manufactured by Mango Wood Waste with Virgin or Recycled PP: Mechanical,Morphology, Melt Flow Index and Crystalline Behaviour

Compositions of wood-polypropylene composites (WPCs) are prepared through melt compounding followed by injection moulding. WPCs are formulated for eight compositions with a different weight ratio of wood, virgin or recycled polypropylene and coupling agent. WPCs compositions are compared in terms of Melt Flow Index, Tensile, FESEM images, Flexural and crystallinity index for same operating variable conditions. From the results, recycled polypropylene based WPCs are superior in comparison to virgin polypropylene based WPCs. With the addition of 5 % coupling agent in recycled polypropylene-based composites for 45:50 composition, tensile and flexural values of WPCs are higher in comparison to all composition and neat virgin or recycled polypropylene. This work stands for the utilization of waste wood with recycled plastic for replacement of wood and virgin plastic.     

Selectivity of Nano Zerovalent Iron in In Situ Chemical Reduction: Challenges and Improvements

Nano zerovalent iron (nZVI) is a promising remediation technology utilizing in situ chemical reduction (ISCR) to clean up contaminated groundwater at hazardous waste sites. The small particle size and large surface area of nZVI result in high reactivity and rapid destruction of contaminants. Over the past 20 years, a great deal of research has advanced the nZVI technology from bench‐scale tests to field‐scale applications. However, to date, the overall number of well‐characterized nZVI field deployments is still small compared to other alternative remedies that are more widely applied. Apart from the relatively high material cost of nZVI and questions regarding possible nanotoxicological side effects, one of the major obstacles to the widespread utilization of nZVI in the field is its short persistence in the environment due to natural reductant demand (NRD). The NRD for nZVI is predominantly due to reduction of water, but other reactions with naturally present oxidants (e.g., oxygen) occur, resulting in situ conditions that are reducing (high in ferrous iron phases and H₂) but with little or no Fe(0). This article reviews the main biogeochemical processes that determine the selectivity and longevity of nZVI, summarizes data from prior (laboratory and field) studies on the longevity of various common types of nZVI, and describes modifications of nZVI that could improve its selectivity and longevity for full‐scale applications of ISCR. © 2016 Wiley Periodicals, Inc.     

Experimental Investigation of Cellulose/Silver Nanocomposites Using In Situ Generation Method

Cellulose gel films were prepared by regeneration process using pre-cooled aq.(8 wt% LiOH + 15 wt% urea) mixture as solvent and ethyl alcohol as non solvent. The Terminus cattapa leaf extract diffused wet cellulose films were then dipped in 1–5 mM aq.AgNO₃ solutions to allow in situ generation of silver nanoparticles (AgNPs). Besides the in situ generation, some AgNPs were also formed outside the wet films in the solution. The AgNPs formed outside the films were observed under transmission electron microscope and scanning electron microscope. The nanocomposite films were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis and tensile test. The thermal stability of the composite films was lower than that of the matrix up to a temperature of ~300 °C and afterwards showed a reverse trend. The tensile strength of the nanocomposite films was found to be higher than the matrix but decreased with increasing concentration of aq.AgNO₃. The cellulose/AgNPs composite films showed good antibacterial activity against E. coli (gram positive) and Bacillus sp. (gram negative). Based on the aforementioned properties, the cellulose/AgNPs composite films can be considered for antibacterial packaging and medical applications.     

Microbially Mediated In Situ Desorption Accelerates Remediation of Large Gasoline Product Plume

Remediation of a large separate‐phase hydrocarbon product and associated dissolved‐phase gasoline plume was accelerated by coupling multiphase extraction with in situ microbial stimulation. At the beginning of remediation activities, the separate‐phase hydrocarbon plume extended an estimated seven acres with product thickness measuring up to 2.1 feet thick. Within 18 months after beginning extraction, reduction of gasoline constituents in groundwater became asymptotic and measureable product disappeared from the upgradient source area. At that time, the remediation team initiated a program of limited in situ anaerobic bioremediation with the goal of stimulating production of natural surfactants from native microbes to release petroleum from the soil matrix. Groundwater concentrations of gasoline constituents increased gradually over the next three years, improving recovery without biofouling the pump‐and‐treat infrastructure. Using this approach, the groundwater component of the remedy was completed in less than five years, substantially less than the 10 years to 15 years predicted by modeling. This strategy demonstrated a more sustainable approach to remediation, reducing electrical usage by an estimated 800 megawatt hours, reducing infrastructure requirements, and preserving an estimated 150 million gallons of groundwater for this arid agricultural area. © 2014 Wiley Periodicals, Inc.     

Combined thermal and zero‐valent iron In Situ soil mixing remediation technology

Thermal remediation of contaminated soils and groundwater by injection of hot air and steam using large‐diameter auger in situ soil mixing effectively remediates volatile and semivolatile organic compounds. This technology removes large amounts of contamination during the early treatment stages, but extended treatment times are needed to achieve high removal percentages. Combining thermal treatment with another technology that can be injected and mixed into the soil, and that continues to operate after removal of the drilling equipment, improves removal efficiency, and reduces cost. Using field‐determined pseudo first‐order removal rates, the cost of the combined remediation of chlorinated volatile organic compounds (CVOCs) by thermal treatment followed by reductive dechlorination by iron powder has been estimated as 57 percent of the cost of thermal treatment alone. This analysis was applied to a case‐study remediation of 48,455 cubic yards, which confirmed the cost estimate of the combined approach and showed over 99.8 percent removal of trichloroethene and other chlorinated VOCs. © 2010 Wiley Periodicals, Inc.     

In Situ Remediation of 1,4‐Dioxane Using Electrical Resistance Heating

Recent regulatory changes need more challenging treatment goals for 1,4‐dioxane. However, significant treatment limitations exist in part due to the high solubility and low Henry's law constant of 1,4‐dioxane. Two case studies are reported with substantial 1,4‐dioxane concentration reductions through in situ thermal remediation via electrical resistance heating (ERH). Concentration reductions greater than 99.8 percent of 1,4‐dioxane have been observed in the field using ERH. Concentrations of 1,4‐dioxane in air and steam extracted by an ERH vapor recovery system have also been evaluated. Laboratory studies were conducted to further understand the mechanisms that enable ERH remediation of 1,4‐dioxane. Vapor liquid equilibrium studies in water and soil were conducted and utilized to develop an ERH treatment cost model for 1,4‐dioxane. Existing field data were correlated to the 1,4‐dioxane treatment cost model. Field observations and laboratory testing indicate steam stripping that occurs through ERH remediation is an effective treatment method for 1,4‐dioxane. ©2015 Wiley Periodicals, Inc.     

In Situ treatment of PFAS‐impacted groundwater using colloidal activated Carbon

Poly‐ and perfluoroalkyl substances (PFASs) have been identified by many regulatory agencies as contaminants of concern within the environment. In recent years, regulatory authorities have established a number of health‐based regulatory and evaluation criteria with groundwater PFAS concentrations typically being less than 50 nanograms per liter (ng/L). Subsurface studies suggest that PFAS compounds are recalcitrant and widespread in the environment. Traditionally, impacted groundwater is extracted and treated on the surface using media such as activated carbon and exchange resins. These treatment technologies are generally expensive, inefficient, and can take decades to reach treatment objectives. The application of in situ remedial technologies is common for a wide variety of contaminants of concern such as petroleum hydrocarbons and volatile organic compounds; however, for PFASs, the technology is currently emerging. This study involved the application of colloidal activated carbon at a site in Canada where the PFASs perfluorooctanoate (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in groundwater at concentrations up to 3,260 ng/L and 1,450 ng/L, respectively. The shallow silty‐sand aquifer was anaerobic with an average linear groundwater velocity of approximately 2.6 meters per day. The colloidal activated carbon was applied using direct‐push technology and PFOA and PFOS concentrations below 30 ng/L were subsequently measured in groundwater samples over an 18‐month period. With the exception of perfluoroundecanoic acid, which was detected at 20 ng/L and perfluorooctanesulfonate which was detected at 40 ng/L after 18 months, all PFASs were below their respective method detection limits in all postinjection samples. Colloidal activated carbon was successfully distributed within the target zone of the impacted aquifer with the activated carbon being measured in cores up to 5 meters from the injection point. This case study suggests that colloidal activated carbon can be successfully applied to address low to moderate concentrations of PFASs within similar shallow anaerobic aquifers.     

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

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.     

Determination of In Situ Esterification Parameters of Citric Acid-Glycerol Based Polymers for Wood Impregnation

The development of wood treatments is of increasing industrial importance. A novel technique for improving the properties of lodgepole pine and white pine through modification of the microstructure is described. The present investigation is devoted to the synthesis and determination of in situ parameters of citric acid and glycerol based polymers for wood impregnation. This solvent free approach is environmentally friendly and achieved through an esterification condensation reaction under acidic conditions. Crude glycerol and citric acid reactants were cross-linked via a curing process at 160?°C creating a polymer with only water as the byproduct. The ester bonds and crosslinking levels were controlled using different catalysts and citric acid contents and related to the reaction time and temperature. The nature of bonding within the polymers and at the wood cell walls was determined by FT-IR analysis. The thermal properties such as glass transition temperature (T_g) were studied using TGA/DSC and the effect of citric acid content and catalyst type determined. Dimensional stability of impregnated wood samples improved above 50% for each sample with HCl and p-TSA catalysts compared to control samples. FTIR spectra were studied to show the presence of the ester linkages of the polymer in situ at the wood cell walls. Bonding between the polymer and wood macromolecules were observed by scanning electron microscopy and interpreted as evidence of chemical bonds at the wood cells. When prepared using a catalyst, the polymer was intimately incorporated into wood structure significantly improving the substrate dimensional stability. Enhanced stability makes this approach of particular interest for exterior wood products especially as a green renewable option for the wood industry.