Debromination of flame-retarded TV housing plastic waste

The thermal stability and degradation kinetics of TV housing plastic and brominated flame retardants were studied by means of thermogravimetry. The effects of the treatment temperature on the removal rate of Br were investigated using a tube furnace reactor under isothermal and vacuum conditions. The results showed that the weight loss of TV housing plastic was divided into two stages: the thermal degradation of brominated flame retardants mainly occurred at 290°–350°C, and the degradation of the high-impact polystyrene resin mainly occurred at 350°–455°C. Nearly 90% of Br can be removed from TV housing plastic when the treatment temperature exceeds 280°C.     

Degradable polymers: The role of the degradation environment

The degradability of several degradable polymers was examined using three types of degradation environments. These include exposure in a laboratory-scale composting test system containing material representative of the organic fraction of municipal solid waste (MSW), exposure in a thermal hydrolytic environment consisting of water at 60‡C, and exposure in a thermal-oxidative, dry oven environment of 60‡C. The results of the investigation clearly indicate that, in addition to chemical and biological activity which can lead to polymer degradation, physical restructuring and reorganization of the macromolecular structure may also occur at temperatures typically found in a compost environment, resulting in changes in the mechanical properties of the polymer films. In the case of the polyethylene-modified polymers evaluated in this study, all behaved similarly, but differently from the other polymer types. The polyethylene-based films appeared to be susceptible to oxidative degradation and should degrade in a composting environment providing that there is sufficient air in contact with the film for a sufficient period of time. However, when exposed in a laboratory composter, it appears that although ideal temperature-time curves may be obtained, the test time period was insufficient in comparison to the induction period required to achieve the desired thermal oxidative degradation. Issued as NRCC No. 37620.     

Biodegradation behavior and material properties of aliphatic/aromatic polyesters of commercial importance

Copolyesters of aliphatic monomers with a defined amount of terephthalic acid recently have been shown to be biodegradable. This group of plastic materials exhibits very interesting material properties with regard to their technical application potential. A tensile strength of 25 N/mm² combined with elongations at break up to 1500% was achieved for BTA materials. Melting points varied from 80 to 140‡C. Biodegradation rate under compositing conditions were determined, showing typical erosion rates of films, in the range of 5 to 10 Μm/week. The material properties and the degradation rate as well can be adjusted by the copolymer composition. Stretching of the polymer in the cold state leads to 10-fold higher mechanical strength of the material. The polyester chain can be extended to high molar masses, resulting in melt viscosities suitable, e.g., for melt below extrusion.     

Effect of Solvent Composition on Porosity,Surface Morphology and Thermal Behavior of Metal Alginate Prepared from Algae (<Emphasis Type="Italic">Undaria pinnatifida</Emphasis>)

Alginates, extracted from algae are linear unbranched polymers containing β-(1→4)-linked d-mannuronic acid (M) and α-(1→4)-linked l-guluronic acid (G) residues. The conversion of alginic acid into the metal alginate is confirmed using FTIR spectroscopy. Asymmetric and symmetric stretching of free carboxyl group present in metal alginate occurs almost at the same position in various solvent compositions. Total intrusion volume of metal alginate prepared in propanol (0.0742 mL/g) is greater compared to those in ethanol (0.0648 mL/g) and methanol (0.0393 mL/g) as solvent. Surface morphology as well as porosity and pore size distribution of metal alginate are greatly influenced by solvent. It can be seen from thermal analysis results that calcium alginate prepared using different solvent compositions started decomposing at 100 °C, but rapid degradation started around 200 °C. The results showed a stepwise weight loss during thermal sweep, indicating different types of reactions during degradation. First and second step of rapid degradation was situated around 200–300 and 300–550 °C, respectively; whereas the final step is situated around 550–650 °C. The trend of degradation was similar for all the solvents, although the amount of final residue varied from one solvent to another. At the same time, lower thermal stability was also observed with higher heating rates. Additionally, a kinetic analysis was performed to fit with TGA data, where the entire degradation process has been considered as three consecutive first order reactions.     

Water transport in polylactic acid (PLA), PLA/ polycaprolactone copolymers, and PLA/polyethylene glycol blends

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester, and water vapor permeability may have a significant influence on the rate of degradation. A method is devised to use bags prepared from PLA films and filled with molecular sieves to determine the water vapor permeability in the polymer, its copolymers with caprolactone, and blends with polyethylene glycol. The “solution-diffusion” model is used to determine the permeability parameters. These include the solubility coefficient,S, a measure of the equilibrium water concentration available for hydrolysis and the diffusion coefficient,D, which characterizes the rate of water vapor diffusion into the film under specific conditions. Values ofS andD at 50‡C and 90% relative humidity ranged from 400 × 10^-6 to 1000 × 10^-6 cm³ (STP)/(cm³ Pa) and 0.20 × 10^-6 to 1.0 × 10^-6 cm²/s, respectively. TheS andD coefficients were also measured at 20 and 40‡C and compared to those of other polymers. The degree of crystallinity was found to have little influence on the measured permeability parameters. The heat of sorption, δH_S, and the activation energy of diffusion, E_D, were used to show that the permeability process is best described by the “water cluster” model for hydrophobic polymers. Finally, the diffusion coefficient is used to compare the rate of water diffusion to the rate of water consumption by ester hydrolysis. Results indicate that hydrolytic degradation of PLA is reaction-controlled.     

Effect of Decalin Solvent on the Thermal Degradation of HDPE

The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C₅–C₃₂ yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, α-olefins and α,ω-dienes were detected. Increasing the decalin/plastic ratio led to enhanced α-olefin and n-paraffins yields, but the increase was more significant in the case of α-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical β-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.     

Effects of Electron-Beam Irradiation and Ultraviolet Light (365 nm) on Polylactic Acid Plastic Films

Strips of Ca-I [polylactic acid (PLA) monolayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN] cut in the machine and nonmachine directions were irradiated with an electron beam using a CIRCLE III Linear Accelerator (MeV Industries S.A., Jouy-en-Josas, Cedex, France). The effects of 33-kGy irradiation on the physical properties of the Ca-I strips were studied. In addition, the effects of ultraviolet (UV) light (365-nm) illumination on the degradation of three PLA plastic films, Ch-I (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC), MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC) were analyzed by a modified ASTM D5208-91 method. Results showed that irradiation had decreased the weight-average molecular weight (M _w), stress at break, percentage of elongation, and strain energy of Ca-I by 35.5, 26.7, 32.3, and 44.8%, respectively (P < 0.01). The shelf life of the irradiated Ca-I strips at 5°C and <20 ± 5% RH was about 6 months. The degradation rate of Ch-I, GII, and Ca-I with no UV light treatment at 55°C and 10% RH was 2512, 5618, and 3785 M _w/week, respectively. Under the UV light illumination (365 nm), the degradation rate of Ch-I, GII, and Ca-I, was 2982, 8722, and 7467 M _w/week, respectively. Hence, the degradation rate of GII and Ca-I was increased 55 and 97% by UV light (P < 0.008), respectively. This trend was not observed in Ch-I because its starting M _w (78,000 g/mol) was close to the tensile strength lost range (50,000 to 75,000 g/mol) of PLA films. To our knowledge, this is the first study to demonstrate that UV light does further enhance the degradation of PLA films.     

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

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.     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Microtox assay to determine the toxicity of degradation products from degradable plastics

Six types of starch-polyethylene degradable plastics were evaluated for the release of water-soluble toxic compounds under accelerated degradation conditions. A plastic strip (2.5×15.2 cm) was placed in a 250-ml Erlenmeyer flask with 100 ml of ASTM type I water with or without trace element solutions and shaken at 65°C and 110 rpm for 20 weeks in replicates of two. High temperature was used to accelerate the oxidative degradation of polyethylene. Plastic degradation was measured by loss of tensile strength, percentage elongation, strain energy, and weight-average molecular weight. The most rapid period of polyethylene thermal degradation was complete for most materials by day 28. Ten-milliliter aqueous samples were removed from each flask at days 1, 7, 28, 56, 84, and 140 (water volumes were maintained at 100 ml with fresh type I water), filtered through glass filters, then evaluated by using the Microtox Toxicity Analyzer (Microbics Corporation, Carlsbad, CA). No water-soluble toxic compounds were detected during the period of rapid film degradation. Toxicity was observed at day 28 for one film and at day 84 for all films, which could possibly correlate with the release of small oxidative compounds such as formaldehyde and acetaldehyde. Because of the sensitivity of this assay, positive results must be confirmed by otherin vitro studies.Journal Paper No. J-14851 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Projects No. 2889 and 0178.     

Degradation of Polylactic Acid (PLA) Plastic in Costa Rican Soil and Iowa State University Compost Rows

In this study the degradation of polylactic acid (PLA) plastic films in Costa Rican soil and in a leaf composting environment was investigated. Three types of PLA films were used: Ch-I, (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC). The average soil temperature and moisture content in Costa Rica were 27°C and 80%, respectively. The average degradation rate of PLA plastic films in the soil of the banana field was 7675 M _w/week. Two compost rows were set up at the Iowa State University (ISU) (Ames) compost site. Temperature and relative humidity of the compost rows were kept at 55 ± 5°C and 50 ± 10% RH, respectively. The degradation rates of GII and Ca-I in the compost rows were 113,290 and 71,283 M _w/week, respectively. Therefore, it was estimated that in Costa Rican soil and in compost rows, PLA would be visibly degraded in 6 months and in 3 weeks, respectively.     

Behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes

We investigated the thermal properties and behavior of bromine on the thermal decomposition of paper-based phenolic laminate wastes containing polybrominated flame retardants. The thermal properties of the phenolic laminate wastes were measured with a thermogravimeter and a conduction-type scanning calorimeter (TG-CSC). The weight loss of the wastes on thermal decomposition was mainly in three phases between 40°C and 600°C. The enthalpy (ΔH) of the thermal decomposition was 104 cal/g. The material balance of the decomposition components was measured with batch-type thermal decomposition equipment. The ratios of carbon residue, liquid, and gas on decomposition at 800°C in a vacuum were 37 wt. %, 48 wt. %, and 15 wt. %, respectively. The bromine contents in the carbon residue and liquid were less than 0.02 wt. % and 10 wt. %, respectively. These results are useful both in the carbonization process of these wastes and in the application of carbon residue as carbon materials. Received: August 11, 2000 / Accepted: March 7, 2001     

Solid phase microextraction (SPME) as an effective means to isolate degradation products in polymers

A new sample preparation technique, solid phase microextraction (SPME), was compared with direct headspace-GC-MS with respect to the type and amount of identified compounds. Three types of LDPE films containing photosensitising additives according to the Scott-Gilead patents and pure LDPE were used as model substances. The polyethylene films were thermally aged at 80‡C after the induction period was surpassed by subjecting the materials to 100 h of UV radiation. The new SPME method was developed using nonpolar poly(dimethylsiloxane) and polar carbowax fibers to extract the low molecular weight products formed in the polyethylene films during aging. Many more products were identified after SPME followed by GC-MS than after direct headspace-GC-MS of the samples. The SPME method allowed the identification of homologous series of carboxylic acids, ketones, and furanones, while direct headspace-GC-MS identified only a few carboxylic acids (C1-C6) and small amounts of some ketones and furanones. In general, SPME was more effective in extracting less volatile products, and in particular, the polar carbowax fiber identified also C7-C12 carboxylic acids and 4-oxopentanoic acid. By SEC and FTIR we confirmed that the number and amount of former degradation products correlated well with the decrease in molecular weights and the amount of formed carbonyl compounds.     

The Effect of Masterbatch Addition on the Mechanical, Thermal, Optical and Surface Properties of Poly(lactic acid)

There has been considerable interest in the use of the biodegradable polymer poly(lactic acid) (PLA) as a replacement for petroleum derived polymers due to ease of processability and its high mechanical strength. Other material properties have however limited its wider application. These include its brittle properties, low impact strength and yellow tint. In an attempt to overcome these drawbacks, PLA was blended with four commercially available additives, commonly known as masterbatches. The effect of the addition of 1.5 wt% of the four masterbatches on the mechanical, thermal, optical and surface properties of the polymer was evaluated. All four masterbatches had a slight negative effect on the tensile strength of PLA (3–5% reduction). There was a four fold increase in impact resistance however with the addition of one of the masterbatches. Differential scanning calorimetry demonstrated that this increase corresponded to a decrease in the polymer crystallinity. However there was an associated increase in polymer haze with the addition of this masterbatch. The clarity of PLA was improved through the addition of an optical brightener masterbatch, but the impact resistance remained low. The glass transition and melting temperatures of PLA were not affected by the addition of the masterbatches, and no change was observed in surface energy. Some delay in PLA degradation, in a PBS degradation medium at 50 °C, was observed due to blending with these masterbatches.     

Two-stage thermal gasification of polyolefins

Plastic pellets of polyethylene (PE), polypropylene (PP), and polystyrene (PS) were gasified in a two-stage thermal degradation process. The first stage is the conversion of polyolefins to distilled oils using a melting vessel. In the second stage, the oils from the first stage are gasified using a tubular reactor. The distilled oil yields of PE, PP, and PS in the first stage were 84, 89, 92 wt%, respectively, each at 470°C. The total gas yields of PE, PP, and PS in the second stage were 80, 74, and 6.2 wt%, respectively, each at 800°C. The main components of the product gas for PE and PP were methane and olefins such as ethene and propene. Some aromatic oils, including benzene, toluene, and xylene, were also produced as by-products. The amount of carbonaceous residue, or coke, was very low (less than 1 wt%). By dividing the process into two stages, the coking rate was considerably reduced compared with direct gasification of the polyolefins. Received: July 19, 2000 / Accepted: September 17, 2000     

Biodegradation of Polycaprolactone Powders Proposed as Reference Test Materials for International Standard of Biodegradation Evaluation Method

Polycaprolactone (PCL) powders were prepared from PCL pellets using a rotation mechanical mixer. PCL powders were separated by sieves with 60 and 120 meshes into four classes; 0–125 μm, 125–250 μm, 0–250 μm and 250–500 μm. Biodegradation tests of PCL powders and cellulose powders in an aqueous solution at 25°C were performed using the coulometer according to ISO 14851. Biodegradation tests of PCL powders and cellulose powders in controlled compost at 58°C were performed by the Mitsui Chemical Analysis and Consulting Service, Inc. according to ISO 14855-1 and by using the Microbial Oxidative Degradation Analyzer (MODA) instrument according to ISO/DIS 14855-2. PCL powders were faster biodegraded than cellulose powders. The reproducibility of biodegradation of PCL powders is excellent. Differences in the biodegradation of PCL powders with different class were not observed by the ISO 14851 and ISO/DIS 14855-2. An enzymatic degradation test of PCL powders with different class was studied using an enzyme of Amano Lipase PS. PCL with smaller particle size was faster degraded by the enzyme. PCL powders with regulated sizes from 125 μm to 250 μm are proposed as a reference material for the biodegradation test.     

Remediation of Soil and Ground Water Contaminated with PAH using Heat and Fe(II)-EDTA Catalyzed Persulfate Oxidation

The feasibility of degrading 16 USEPA priority polycyclic aromatic (PAH) hydrocarbons (PAHs) with heat and Fe(II)-EDTA catalyzed persulfate oxidation was investigated in the laboratory. The experiments were conducted to determine the effects of temperature (i.e. 20 ^∘C, 30 ^∘C and 40 ^∘ C) and iron-chelate levels (i.e., 250 mg/L-, 375 mg/L- and 500 mg/L-Fe(II)) on the degradation of dissolved PAHs in aqueous systems, using a series of amber glass jars as the reactors that were placed on a shaker inside an incubator for temperature control. Each experiment was run in duplicate and had two controls (i.e., no persulfate in systems). Samples were collected after a reaction period of 144 hrs and measured for PAHs, pH and sodium persulfate levels. The extent of degradation of PAHs was determined by comparing the data for samples with the controls. The experimental results showed that persulfate oxidation under each of the tested conditions effectively degraded the 16 target PAHs. All of the targeted PAHs were degraded to below the instrument detection limits (∼4 μ/L) from a range of initial concentration (i.e., 5 μ/L for benzo(a)pyrene to 57 μ/L for Phenanthrene) within 144 hrs with 5 g/L of sodium persulfate at 20 ^∘ C, 30 ^∘C and 40 ^∘C. The data indicated that the persulfate oxidation was effective in degrading the PAHs and that external heat and iron catalysts might not be needed for the degradation of PAHs. The Fe(II)-EDTA catalyzed persulfate also effectively degraded PAHs in the study. In addition, the data on the variation of persulfate concentrations during the experiments indicated that Fe(II)-EDTA accelerated the consumption of persulfate ions. The obtained degradation data cannot be used to evaluate the influence of temperature and Fe(II) levels on the PAH degradation because the PAHs under each of the tested conditions were degraded to below the instrument detection limit within the first sampling point. However, these experiments have demonstrated the feasibility of degrading PAHs in aqueous systems with persulfate oxidation. Additional tests are being conducted to evaluate the effectiveness of treating PAHs in soils and obtaining the rate of degradation of PAHs with persulfate oxidation. Two sets of laboratory experiments were conducted to evaluate the ability of sodium persulfate in oxidizing real world PAH-contaminated soils collected from a Superfund site in Connecticut. The first set of soil sample were treated only with persulfate and to the second batch, mixture of persulfate and Fe(II)-EDTA solutions were added. The results of the second test showed that within 24 hours, 75% to 100% of the initial concentrations of seven PAH compounds detected in the soil samples were degraded by sodium persulfate mixed with FE(II)-EDTA.     

Morphological and Thermal Characterization of Linseed-Oil Based Polymers from Cationic and Thermal Polymerization

Linseed oil-based polymers have been synthesized via cationic and thermal polymerization and characterized through various techniques, such as SEM, DMA, DSC and TGA. The morphology of the polymer samples after extraction reveals the smooth structure of the polymer matrix. With an increase in oil content, the morphology is observed to be more loosely bound. With an increase in linseed oil content in the samples, the room temperature storage modulus (E′) varies from 10.4 × 10⁷ to 1.8 × 10⁷ Pa. The glass transition temperatures measured through DMA of the cationic samples ranges from 70 to −6 °C and the crosslink densities range from 18.4 × 10³ to 3.4 × 10³ mol/m³. The glass transition temperatures of the thermal samples range from 106 to −4 °C and the crosslink densities range from 7.7 × 10³ to 2.4 × 10³ mol/m³. The TGA results show three stages of degradation of the polymer samples and it is also revealed that these polymers are stable up to 200 °C, showing negligible decomposition.     

Thermal cracking of oils from waste plastics

Thermal cracking of decomposed waste plastic oil produces a good yield of olefins. The solvent extraction of such waste plastic oil seems to be efficient for increasing gas yields and recycling monomers. To assess the potential of monomer recovery from municipal waste plastics, the oils were cracked using a laboratory-scale quartz-tube reactor. The waste plastic oils were provided by two commercial plants of the Sapporo Plastic Recycle Co. and the Dohoh Recycle Center Co. in Japan. A model waste plastic oil made in a laboratory was also examined. Yields of ethene, propene, and other products were measured at different temperatures. Two-step pyrolysis reduces coking compared with the direct thermal degradation of plastics. The raffinates from waste plastic oils extracted by sulfolane were also cracked. The primary products were almost the same as those from nontreated oils. The maximum total gas yield was 78wt%–85wt% at 750°C, an increase of about 20wt% compared with that of nonextracted oil. Solvent extraction removes stable aromatic hydrocarbons such as styrene, which is more coked than cracked.     

High compressive strength of home waste and polyvinyl acetate composites containing silica nanoparticle filler

Simple mixing and hot pressing methods were used to make composites from home waste—in particular, paper and dry leaves—using polyvinyl acetate (PVAc) as an adhesive and silica nanoparticles as filler. The optimum composition for the strongest composites, in terms of compressive strength, had a mass ratio of silica nanoparticles/PVAc/(paper + dry leaves) of 3:80:280. With this mass ratio, a compressive strength of 68.50 MPa was obtained for samples prepared at a pressing temperature of 150°C, pressing pressure of 100 MPa, and pressing time of 20 min. The addition of silica nanoparticles increased the compressive strength by about 50%, compared with composites made without the addition of nanosilica (45.60 MPa). Higher compressive strength was obtained at a higher pressing pressure. At a pressing pressure of 120 MPa, pressing temperature of 150°C, and pressing time of 20 min, a compressive strength of 69.10 MPa was obtained. When the pressing time was increased to 45 min at a pressing pressure of 120 MPa, a compressive strength of 84.37 MPa was measured. A model was also proposed to explain the effects of pressing pressure and pressing time on compressive strength. The model predictions were in good agreement with the experimental data.