Study of Aging Characteristics of Ternary Blends of Polyethylenes—II

Six film samples of low-density polypropylene (LDPE)/linear LDPE (LLDPE)/high-density polypropylene (HDPE) with varying ratios of LDPE (20–45 ... wt%) and LLDPE (25–50 wt%) having a fixed amount of HDPE at 30 wt% were prepared by blown film extrusion technique. The samples were aged at four different temperatures, 55°, 70°, 85°, and 100°C, for four different time periods in the interval of between 150 hours and up to 600 hours. The change in the structure of various constituents and the formation of various oxygenated (peroxy and hydroperoxy) and unsaturated groups during thermo-oxidative degradation was discussed by infrared spectroscopy. The visiosity-average molecular weight was found to have decreased slowly in the initial aging hours and temperatures, whereas it decreased by 10% with its previous value tensile strength that is, 100°C when aged for 600 hours. The tensile strength of the sample first increased by 67% at 55°C and 89% at 70°C up to 450 hours, whereas the values increased by 52.5% at 85°C and 33.9% at 100°C when aged for 150 hours and then decreased. The percentage elongation at break increased by 2.7% at 55°C and 10.7% at 70°C for 150 and 300 hours of aging, respectively, whereas the percentage decreased when aged at 85°C and 100°C for up to 600 hours of aging. The values of gel content (percent) increased and initial degradation temperature decreased with aging time and temperature.     

Utilization of Sunflower Stalk in Manufacture of Thermoplastic Composite

Dimensional stability and mechanical performance of polypropylene thermoplastic composites filled with sunflower stalk (SS) flour at 30, 40, 50, and 60 wt% contents of the SS flour were investigated. The thickness swelling and water absorption of the specimens increased with increasing SS flour content. The modulus in the flexural and tensile improved with increasing SS flour content while the tensile and flexural strengths of the specimens decreased. The use of maleic anhydride polypropylene (3 wt%) had a positive effect on the dimensional stability and mechanical properties of the polypropylene thermoplastic composites filled with SS flour. The melting temperature of polypropylene decreased with increasing content of the SS flour. The degree of crystallinity of filled polypropylene composites between fibre loading of 0–30 % by weight was higher than that of unfilled polypropylene composites. However, further increment in the filler content decreased the degree of crystallinity. The obtained results showed that SS flour could be potentially suitable raw material in the manufacture of polypropylene composites.     

Mechanical Recycling of PLA Filled with a High Level of Cellulose Fibres

Composites consisting of 30 vol% PLA and 70 vol% cellulose fibres were prepared with compression moulding. In the first part of the study, the recyclability of this composite material was investigated by grinding the material and using the recyclate obtained as a filler for PLA. Thus, the recyclate was compounded with PLA in loadings ranging from 20 to 50 wt%. The composites obtained were characterised by tensile tests, Charpy impact tests, DMTA, and SEM. Tests showed that the recyclate had a relatively good reinforcing effect. Stress at break increased from about 50 to 77 MPa and the modulus increased from 3.6 to 8.5 GPa. In the second part of the study, the ability to mechanically recycle the composites obtained was evaluated by repeated processing. Composite with two loadings of the recyclate (20 wt% and 50 %) was injection moulded repeatedly, six times. Tests showed that the composite material with 20 wt% recyclate could withstand six cycles relatively well, while the composite with the higher load degraded much more quickly. For the composites with 50 wt% recyclate, signs of polymer degradation could be seen already after reprocessing the composite once.     

An analysis of the composition and metal contamination of plastics from waste electrical and electronic equipment (WEEE)

The compositions of three WEEE plastic batches of different origin were investigated using infrared spectroscopy, and the metal content was determined with inductively coupled plasma. The composition analysis of the plastics was based mainly on 14 samples collected from a real waste stream, and showed that the major constituents were high impact polystyrene (42 wt%), acrylonitrile–butadiene–styrene copolymer (38 wt%) and polypropylene (10 wt%). Their respective standard deviations were 21.4%, 16.5% and 60.7%, indicating a considerable variation even within a single batch. The level of metal particle contamination was found to be low in all samples, whereas wood contamination and rubber contamination were found to be about 1 wt% each in most samples. In the metal content analysis, iron was detected at levels up to 700 ppm in the recyclable waste plastics fraction, which is of concern due to its potential to catalyse redox reactions during melt processing and thus accelerate the degradation of plastics during recycling. Toxic metals were found only at very low concentrations, with the exception of lead and cadmium which could be detected at 200 ppm and 70 ppm levels, respectively, but these values are below the current threshold limits of 1000 ppm and 100 ppm set by the Restriction of Hazardous Substances directive.     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

The Effects of Additives on the Biodegradation of Polycaprolactone Composites

Because environmental pollution caused by plastic waste is a major problem investigations concerning biodegradable packaging are important and required. In this study, the biodegradation of PCL composite films with organic (glycerol monooleate and oleic acid) and inorganic additives (organo nano clay) was investigated to understand which additive and the amount of additive was more effective for biodegradation. The relationship between the degree of crystallinity and the effect of additives on the biodegradability of polycaprolactone (PCL) was examined. PCL composite films were prepared using organo nano clay (0.1–0.4–1–3 wt%) and oleic acid (1–3–5 wt%) or GMO (1–3–5 wt%). The 35 films prepared with PCL (P), clay (C), oleic acid (O), or glycerol monooleate (G) are coded as P_C#wt%_O (or G)#wt%. The composite films, P_C0.4_O5 contains 0.4 wt% clay and 5 wt% oleic acid and the P_C3_G1 contains 3 wt% clay and 1 wt% glycerol monooleate. The biodegradation of PCL films in simulated soil was studied for 36 months. The films were periodically removed from the simulated soil and film thicknesses, weight losses, visual changes, crystal structures, and a functional group analyses were performed. PCL composite films are separated into three groups, depending on degradation time, (1) films that degraded before 8 months (fast degradation), (2) films that degraded around 24 months (similar to neat PCL), and (3) films that take longer to degrade (slow degradation). The films in the first group are PCL films with 1 and 3 wt% clay additive and they begin to biodegrade at the 5th month. However, a composite film of PCL with only 0.4 wt% clay and 5 wt% GMO addition has the shortest degradation time and degraded in 5 months. The films in the last group are; P_G3, P_G5, P_C0.1, P_C0.1_O1, and P_C0.1_O5 and they took around 30 months for biodegradation. It was observed that increasing the organo nanoclay additive increases the biodegradability by disrupting the crystal structure and causing a defective crystal formation. The addition of GMO with organo nano clay also accelerates biodegradation. The addition of organo nano clay in an amount as small as 0.1 wt% acts as the nucleating agent, increases the degree of crystallinity of the PCL composites, and slows the biodegradation period by increasing the time.     

Effects of fly ash addition on physical properties of porous clay-fly ash composites via polymeric replica technique

The porous composites of clay and fly ash have the potential to be used in many fields, such as catalyst support and gas adsorbents. In this study, various ratios of fly ash (1–2) with different percentage of suspension (50–70 wt%) were applied to produce porous clay-fly ash composites via polymeric replica technique. Fabrication process starts by mixing clay and fly ash in distilled water to form slurry. The process is followed by fully immersing polymer sponge in slurry. The excess slurry is then removed through squeezing. Finally, the sponge coated with slurry is sintered at 500 and 1250 °C for 1 h. It is found that the compressive strength of porous composites improves significantly (0.178–1.28 MPa) when the amount of clay-fly ash suspension mixture (50–70 wt%) increases. The compressive strength of porous composites is mainly attributed to the mullite, quartz and amorphous phase formations. These results are supported by X-ray diffraction analysis. On the other hand, increase in the amount of suspension reduces the apparent density (from 2.44 to 2.32 g/cm³) and porosity (from 97 to 85 %). The reduction in apparent density is believed to be caused by the presence of high fly ash content in porous composites. The melted fly ash cenospheres have closed the internal pores and increased density of samples. Higher suspension level not only reduces porosity, but also increases close pores of the porous composites. The results are justified through the observation from the structures of porous clay-fly ash composites.     

Rheological Investigation of Wood-Polypropylene Composites in Rotational Plate Rheometer

In this research work, the rheological properties of Wood-Plastic Composites (WPC) with some selected compositions are investigated. WPC is being recognized as a green composite that, in the past 20?years, has emerged to a commercial product. A study on rheological properties of these materials can give insight into the proper selection of composition and processing condition. Two grades of polypropylene (PP) with two different melt flow indexes (MFI) were selected to prepare WPCs with three different wood contents (50, 60 and 70?% wt.). Four types of rheological experiments were performed utilizing a rotational plate rheometer: (1) strain sweep, (2) frequency sweep, (3) temperature sweep and (4) steady shear rate sweep. The independent variables were chosen as wood content, MFI of polymer (two types), melt temperature, frequency or shear rate, the gap between the plates, and strain percentage. The strain sweep tests specified the linear and non-linear viscoelastic zones of each experiment. The results of frequency sweep experiments indicated that increasing the wood content and frequency and also decreasing the strain percentage and the gap distance, lead to an increase in the storage modulus. Regarding the loss modulus, wood percentage and the gap distance presented positive effects and strain percentage showed a negative effect. The behavior of complex viscosity was almost similar to that of the storage modulus but increasing the frequency caused a decrease in the complex viscosity. In case of temperature sweep experiments, it was observed that the rheological properties exhibit a rapid change near to a temperature of 160?°C. The results also showed that beyond this point, increasing the wood content and also MFI of polypropylene caused an increase in the storage modulus. The results of steady shear rate sweep experiments specified that increasing wood content and also decreasing the MFI of PP, the gap distance and shear rate lead to an increase in both viscosity and shear stress.     

Performance of Cow Dung Reinforced Biodegradable Poly(Lactic Acid) Biocomposites for Structural Applications

In this work, performance of cow dung (CD) reinforced poly(lactic acid) (PLA) biocomposites was investigated for the potential use in load bearing application. CD of average 4 mm size was blended with PLA at different CD ratios (0–50 wt%) and their effects on the biocomposite properties were studied. The results showed an improvement in the flexural properties, while the tensile and impact strength dropped by 20 and 28% with the addition of 50% CD. The decline in the tensile and impact strength was due to micro-cracking and voids formation at higher CD content. Also, the incorporation of CD slightly decreased the thermal stability of the biocomposite. However, dynamic mechanical properties of the biocomposites generally improved. SEM analysis of tensile and impact fractured surfaces indicated that the CD had a reasonable adhesion with matrix. Moreover, the SEM micrographs of soil burial studies showed an accelerated degradation of higher CD wt% biocomposites.     

Biodegradation of Bloodmeal-Based Thermoplastics in Green-Waste Composting

Polymers that are compostable and manufactured from renewable resources have gained significant importance in recent years. The objective of this work was to assess the biodegradability of bloodmeal-based thermoplastics in a commercial green-waste composting situation. Materials plasticised with tri-ethylene–glycol lost about 45% of their original mass after 12 weeks composting while unplasticised samples lost 35%. Degradation appeared to have been in two phases; an initial loss of soluble, low molecular compounds in the mesophilic phase followed by degradation of high molecular compounds as the temperature exceeded about 40 °C in the thermophilic phase. It was found that as degradation proceeded materials became more soluble. In addition, plasticised and unplasticized samples contained about 60 wt% moisture after 4 weeks of composting conditioning at 50% relative humidity resulted in approximately 8–10 wt% moisture, unaffected by the extent of degradation. FTIR revealed that proteins underwent hydrolytic cleavage resulting in the formation of primary amines. A significant reduction in combustion temperature was observed, indicative of a reduction in covalent bonding, likely due to shorter chains lengths or less cross-linking.     

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.     

Use of Oxidation Onset Temperature Measurements for Evaluating the Oxidative Degradation of Isotatic Polypropylene

The widespread use of polymeric materials in many applications requires polymers that are weather resistant. The aim of this study is to examine the usefulness of oxidation onset temperature measurements as a tool for evaluating oxidative degradation of isotatic polypropylene. Differential scanning calorimetry was used to measure the oxidation onset temperature in formulations of isotatic polypropylene containing different concentrations of light and thermal stabilizers after aging in a Weather-Ometer. Oxidation onset temperature gave better results than oxidation induction time for evaluating the degradation of isotatic polypropylene during aging in a Weather-Ometer. However, both tests showed a poor correlation with the appearance of cracks seen by optical microscopy.     

Polyhydroxybutyrate-Based Nanocomposites with Cellulose Nanocrystals and Bacterial Cellulose

Polyhydroxybutyrate (PHB) films nanoreinforced with hydrolyzed cellulose nanocrystals (CNC) and bacterial cellulose (BC) were prepared by solvent casting. The influence of different cellulose nanoparticles content (2, 4 and 6 wt% of CNC and 2 wt% of BC) on the PHB properties was studied. CNC nanocomposites presented good dispersion of the nanocrystals, improving transparency, mechanical and barrier properties of the PHB films. On the other hand, reduced thermal stability and mechanical properties were yielded by BC addition due to the intrinsic lower degradation temperature and higher length of the BC nanofibrils compared to CNC. Nanocomposites performance variation is mainly caused by the marked difference in nanoparticles structure. It was demonstrated that PHB–CNC films exhibited higher performance enhancement without detrimental effect of the pristine PHB properties.     

Hydrometallurgical processing of Nd–Fe–B magnets for Nd purification

An evaluation of various metal purification processes subsequent to the leaching processing of the neodymium (Nd) product from neodymium–iron–boron (Nd–Fe–B) magnets has been conducted. These post-leaching purification processes included precipitation; replacement and electrolysis were studied in order to check the purity of the recovered neodymium. A hydrometallurgical investigation was adopted to digest the metal content of the scrap Nd–Fe–B magnets for the recovery of valuable Nd metal and other metals such as Fe, B, Co and Ni. The effect of leaching conditions such as solid-to-liquid ratio and temperature were optimized and 100 % Nd, 100 % Fe, 100 % B and 85.87 % Co leaching efficiencies were achieved under these conditions. The coating material of the magnet, Ni, achieved 50 % impregnation after increasing the reaction temperature to 70 °C. The metals present in the optimal leaching solution were recovered 99 % by pH adjustment. However, the replacement had the highest separation efficiency for the recovery of Nd metal. Further, the optimal leaching Nd–Fe–B solution was subjected to the electrolysis processes in order to verify the recovery efficiency for all metals.     

Phosphogypsum Waste Used as Reinforcing Fillers in Polypropylene Based Composites: Structural,Mechanical and Thermal Properties

The industrial production of wet phosphoric acid in Morocco led to controversial stockpiling of waste phosphogypsum by-products resulting in the release of significant amounts of toxic impurities in salt marshes. In the framework of fighting against global climate change and efforts to reduce toxic industrial wastes (phosphate industry), this work presents a new polymer composite based on phosphogypsum (PhG) and polypropylene (PP).The compounds were produced by twin-screw extrusion and injection molding. The morphological results show that good affinity between PhG and PP led to good particle dispersion/distribution in the polymer matrix. Thermal characterizations showed that PhG particles improved the thermal stability of PP with a 50 °C increase at 40 wt%. The optimum tensile modulus was also obtained at 40 wt% with a 74 % increase over neat PP. Dynamical mechanical analysis showed that PhG addition can improve the viscoelastic properties of PP for potential applications under dynamic stress. Overall, it can be concluded that PhG is potential reinforcing filler for the production of PP composites and represents a promising avenue for the valorization of this waste as a new raw material while resolving some environmental issues.     

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     

Biodegradable Polyester-Based Blend Reinforced with Curauá Fiber: Thermal,Mechanical and Biodegradation Behaviour

Biodegradable composites can be produced by the combination of biodegradable polymers (BP) as matrix and vegetal fibers as reinforcement. Composites of a commercial biodegradable polymer blend and curauá fibers (loaded at 5, 15 and 20 wt%) were prepared by melt mixing in a twin-screw extruder. Chemical treatments such as alkali treatment of the fiber and addition of maleic anhydride grafted polypropylene (MA-g-PP) as coupling agent were performed to promote polymer/fiber interfacial adhesion so that mechanical performance can be improved. The resulting composites were evaluated through hardness, melt flow index and tensile, flexural and impact strengths as well as water absorption. Thermal analysis and Fourier transform infrared spectroscopy were also employed to characterize the composites. The polymer/fiber interface was investigated through scanning electron microscopy analysis. The biodegradability of composites was evaluated by compost-soil burial test. The addition of curauá fiber promoted an increase in the mechanical strengths and composites treated with 2 wt% MA-g-PP with 20 wt% curauá fiber showed an increase of nearly 75% in tensile and 56% in flexural strengths besides an improvement in impact strength with respect to neat polymer blend. Nevertheless, treated composites showed an increase in water absorption and biodegradation tests showed that the addition of fiber retards degradation time. The retained mass of BP/20 wt% fiber composite with MA-g-PP and neat BP was 68 and 26%, respectively, after 210 days of degradation test.     

Renewable Resource-Based Composites of Acorn Powder and Polylactide Bio-Plastic: Preparation and Properties Evaluation

Renewable resource-based composites were prepared with acorn powder and Thermoplastic resin poly(lactic acid) (PLA) by twin-screw extrusion followed by injection molding processing or hot-compression molding processing. The study of the composites microstructure showed poor adhesion between acorn powder and PLA matrix. The hygroscopicity, mechanical properties and melt flow property of composites were promising even though the composites had a 70 wt% content of acorn powder. Silane coupling agent, 4,4′-Methylenebis (phenyl isocyanate) and PLA grafted with maleic anhydride did not show obvious effect on mechanical properties of composites. The impact resistance strength of reinforced composites with steel fiber webs were improved greatly in comparison with those having no steel fiber webs. Thermal properties results of DSC and DMA showed that the presence of acorn powder significantly affected the crystallinity, crystallization temperature (T_c), glass transition temperature (T_g) and melting temperature (T_m) of PLA matrix. The study results proved that composites had superior mechanical properties, enough to partially replace the conventional thermoplastic plastics.     

The behaviors of H2, CH4, C2H4 and C3H6 from the decomposition of polypropylene by NiO/Si–Al catalyst

The purpose of this study was to investigate the possibility of light gases produced from polypropylene, specifically hydrogen. In particular, we examined the effect of operating conditions on gaseous product and compositions in the catalytic cracking of polypropylene. We also characterized the gaseous product generated from polypropylene cracking. The feedstock (2.0 g) mixed with NiO/SiO₂–Al₂O₃ (Si–Al) was used, under non-isothermal conditions at low temperature range between 380 and 500 °C. Argon gas was used to carry the pyrolyzed gas, and the gas collected in a tedlar bag was analyzed for its behavior. We observed the behavior of major gases (H₂, CH₄, C₂H₄ and C₃H₆, etc.) according to reaction time and temperature. Finally, the effect of reaction conditions on evolved gases from catalytic cracking of polypropylene was analyzed.     

Effect of heating rate on the pyrolysis of high-impact polystyrene containing brominated flame retardants: fate of brominated flame retardants

In the case of plastics containing brominated flame retardants, various brominated organic compounds, including polybrominated dibenzodioxins and dibenzofurans, are yielded when they are degraded. In order to reduce the hazard that might be generated during after-live treatment, the behaviour of flame retarded high-impact polystyrene containing decabromo diphenylether and antimony oxide (Sb₂O₃), was investigated using several heating programs. It was found that the separation of the thermal process into two steps divided at 330?°C makes it possible to obtain an oil fraction rich in brominated compounds at low temperatures and an oil fraction depleted in brominated compounds at high temperatures. The low temperature oil contained a high concentration of SbBr₃ and dibromodibenzofurans. Various brominated compounds with a low volatility and 1-bromo-1-phenylethane from the reaction of HBr with styrene were among the substances in the high temperature oil. The concentration of brominated compounds was reduced from 6?wt% for degradation in a single step to below 1?wt% in the high temperature oil in the two step process.