Processing and properties of engineering plastics recycled from waste electrical and electronic equipment (WEEE)

The characteristics of engineering plastics used in the preparation of electrical and electronic equipment were studied. More specifically, their thermal response was recorded by DSC experiments, the rheological properties were investigated via MFI tests and the mechanical properties were evaluated with tensile tests. The aim was to establish a procedure for recycling the same engineering plastics deriving from waste of electrical and electronic equipment (WEEE), which offers the additional advantage of using the as-received waste stream as a recyclable mixture, i.e. without sorting and classification of its components.The experimental results showed that blends of PC with ABS or ABS/HIPS can be prepared by direct mixing and this, would allow easy handling of the engineering plastics coming from WEEE, i.e. blending without the need of sorting. These mixtures can be easily processed and display acceptable mechanical properties with reasonable cost. Therefore, the processing characteristics and properties of the systems studied in this work could be the key for the design of an interesting approach for handling solid plastic waste from electrical and electronic devices.     

Improvement in toughness of poly(l-lactide) (PLLA) through reactive blending with acrylonitrile-butadiene-styrene copolymer (ABS): Morphology and properties

Poly(l-lactide) (PLLA) was melt-blended with acrylonitrile-butadiene-styrene copolymer (ABS) with the aim of enhancing impact strength and elongation at break of PLLA, but not sacrificing its modulus and stiffness significantly. However, PLLA and ABS were found to be thermodynamically immiscible by simply melt blending and the formed blends show deteriorated mechanical properties. The reactive styrene/acrylonitrile/glycidyl methacrylate copolymer (SAN-GMA) by incorporating with ethyltriphenyl phosphonium bromide (ETPB) as the catalyst was used as the in situ compatibilizer for PLLA/ABS blends to improve the compatibility between PLLA and ABS. The reactive process during melt blending was investigated by Fourier transformed infra-red (FTIR). It showed that the epoxide group of SAN-GMA reacted with PLLA end groups under the mixing conditions and that the addition of ETPB accelerated the reaction. Phase structure and physical properties of the compatibilized blends were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), tensile tests and impact property measurements. It was found that the size of ABS domains in PLLA matrix is significantly decreased by addition of the reactive compatibilizer. The dynamic mechanical analysis revealed markedly shifted glass transition temperatures for both PLLA and ABS, indicating the improved compatibility between PLLA and ABS. The mechanical tests showed the compatibilized PLLA/ABS blends had a very nice stiffness-toughness balance, i.e., the improved impact strength and the elongation at break with a slightly loss in the modulus.     

Detection of degradation of ABS materials via DSC

ABS is a well-known and widely-used rigid engineering polymer. The mechanical properties of ABS are critical to its proper functioning in a given application, such as a medical device. It is therefore important to retain those properties during processing, fabrication, and use. To that end, thermal analysis and mechanical testing were employed to understand the origin of observed mechanical property losses. Oxidation onset temperature (OOT) testing and differential scanning calorimetry (DSC) analysis indicated a slightly lower onset temperature and a higher glass transition temperature, respectively, for parts which demonstrated a reduction in mechanical properties. It is also demonstrated that degradation of the butadiene-phase of the ABS is responsible for the mechanical property reduction, and that this degradation only proceeds at an appreciable rate at elevated temperatures in the presence of oxygen.     

Effect of residual contaminants and of different types of extrusion processes on the rheological properties of the post-consumer polypropylene

Rheological measurements were conducted to verify the influence of different mechanical recycling processes and the presence of contaminants on the degradation of post-consumer polypropylene. Firstly, polypropylene (PP) was contaminated to simulate a post-consumer material, following the protocol recommended by the FDA. PP was subsequently recovered (washed and dried) and the samples were submitted to different extrusion processes. The rheological data demonstrated that the different types of processing applied and the presence of contaminants altered the molecular structure of the samples. The contaminants acted as agents that accelerated the polymer degradation. The contaminated samples submitted to higher shear rates exhibited greater decrease in their molar mass and a slight narrowing in the molar mass distribution. Also, it was observed that the most degraded samples showed decrease in their molar mass, in the viscosity and in the level of their molecular entanglements. These samples also exhibited a more Newtonian behavior and their molar mass distribution showed a slight narrowing. By calculating the ratio of the molar mass it was possible to quantify the degree of degradation of PP samples, confirming the results obtained.     

Characterization of the liquid product recovered through pyrolysis of PMMA-ABS waste

Thermal decomposition of waste polymethylmethacrylate-acrylonitrile-butadiene-styrene (PMMA-ABS) blend has been carried out using analytical and lab-scale pyrolysis methods in order to identify the substantial components appearing in the liquid product. Additionally decomposition characteristics of the blend have been investigated regarding the possible interrelation between the two components during the pyrolysis. The interactions between PMMA and ABS seem to modify the decomposition characteristics of the ABS, resulting in a lower degradation temperature than that of pure ABS. Moreover the simultaneous decomposition results in recombination of the products yielding new volatile compounds. During batch pyrolysis relatively high amount of gas production was observed, that is in contradiction with the results obtained by analytical pyrolysis and the data found in the literature where pyrolysis of the PMMA as well as the ABS was reported to yield low amount of gas products. The liquid product retrieved from thermal decomposition has been analyzed with respect to the possible utilization as a propellant. Hence aside from the investigation of contained elements and compounds, determination of density, viscosity, research octane number (RON), calorific value, and gaseous emissions has been carried out as well. The relatively high yield (65 wt%), and outstanding compression tolerance (RON = 110.2) observed at the pyrolysis oil make it a feasible fuel admixture.     

The role of additives in the recycling of polymers

The main problems in post-consumer plastics recycling are due to the degradation undergone by the polymers during processing steps and by the products during their lifetime and, for heterogeneous recycling, to the incompatibility of different polymers. To reduce the negative effects of the recycling steps, two main ways can be adopted for homogeneous materials: restabilization during the recycling to avoid or at least to slow the degradation and addition of fillers and modifiers capable of improving the performance of thermoplastic polymers without increasing the final cost of the secondary material. In the case of mixed plastics, compatibilization is the necessary step to obtain secondary materials with acceptable properties.     

TG-FTIR study of the thermal degradation of polyoxymethylene (POM)/thermoplastic polyurethane (TPU) blends

A series of blends of polyoxymethylene (POM)/thermoplastic polyesterurethane (TPU) has been obtained by mechanical processing using a double screw extruder. The thermal stability and the thermal degradation profiles of POM/TPU blends were investigated by thermogravimetric analysis (TG) coupled on-line with Fourier transform infrared spectroscopy (FTIR). It was found that incorporation of TPU into POM matrix resulted in increase of thermal stability of blends in comparison with pristine materials. The thermal degradation of TPU in inert gas atmosphere proceeds in two steps while the thermal degradation of POM is basically a one step process with a substage in a higher temperature range. The most abundant volatile products of the thermal degradation were identified; the possibly routes of their formation have been presented. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mechanical properties and molecular structures of virgin and recycled HDPE polymers used in gravity sewer systems

The widespread use of plastics in the conditioning, packaging and building material sectors generates an enormous amount of industrial waste which could be recycled for wastewater pipes and fittings. Nevertheless, current manufacturing standards in the piping industry recommend against the use of post-consumer recycled materials—a policy based on inadequate understanding of the properties and long-term mechanical performance of recycled materials. The present study compared the material characteristics of virgin and recycled high-density polyethylene (HDPE) plastics commonly found in the piping industry. Mechanical testing, oxidative induction time (OIT), melt flow index (MFI) and thermal analysis were used in conjunction with X-ray fluorescence (μ-XRF), size exclusion chromatography and ¹³C solid-state NMR to evaluate mechanical behavior and molecular structure as well as contaminant or filler contents. This study provides evidence for the degradation processes impact that can occur when post-industrial and post-consumer polymers are recycled. However, the study identified two measures to improve the material qualities of post-consumer recycled HDPE: 1) reducing the amount of contaminants or, alternatively, improving their compatibility with HDPE resins, and 2) improving current sorting and recycling processes to increase the amount of tie molecules in HDPE materials.     

Radiolysis of alkyl benzene sulfonat (ABS) in aqueous solution

Degradation of alkyl benzene sulfonate (ABS) in aerated aqueous solution irradiated with gamma radiation with doses up to 1.8 kGy were studied. The degree of degradation, pH change, the effect of pH on the degradation, COD values and the degradation products were determined. The degradation of ABS increases with the increase of doses and decreases with the increase of ABS concentration. The degradation was somewhat more efficient in slightly acidic and neutral solutions than at basic pH oxalic acid was detected by HPLC as degradation product.     

Chromatographic pattern in recycled high-impact polystyrene (HIPS) - Occurrence of low molecular weight compounds during the life cycle

The analysis of the chromatographic pattern of virgin, reprocessed, thermo-oxidised, and recycled high-impact polystyrene (HIPS) proves to be a suitable and sensitive tool to assess the degree of degradation of HIPS during its first life and subsequent recycling. Different low molecular weight compounds, such as residues of polymerisation, degradation products, and additives have been identified and relatively quantified in HIPS, using microwave-assisted extraction and further analysis by gas chromatography-mass spectrometry (GC-MS). The release of residues of polymerisation has been proven to occur during reprocessing, thermo-oxidation, and in recycled samples, which may show the emissions of volatile and semi-volatile organic compounds during the life cycle of HIPS. A wide range of oxidised degradation products are formed during reprocessing and thermo-oxidation; these products can be identified as oxidised fragments of polystyrene (PS), oxidised fragments from polybutadiene (PB) phase, and oxidised fragments from the grafting points between the PS and PB phase. Real recycled HIPS samples may also contain contaminations and fragments from additives included in their original formulations; the presence of brominated fragments from flame retardants in electronic waste is here observed.     

Thermomechanical degradation of filled polypropylene

The main problem in post-consumer plastics recycling is due to the thermomechanical stress acting on the melt during the reprocessing operations. The macromolecules break because of the temperature and of the mechanical stress. The extent of degradation is then correlated to the level of mechanical stress which, in turn, is proportional to the viscosity of the melt. The presence of fillers increases the viscosity of the polymers and then it is expected that the level of thermomechanical degradation of these systems is larger than that of the unfilled material. In this work the thermomechanical degradation kinetic of a polypropylene sample is investigated as a function of the calcium carbonate content. It is shown that the decrease of viscosity, that is the decrease of molecular weight, is directly related to the increase of viscosity due to the filler content. The worsening of the mechanical properties are consistent with the change of viscosity.     

Physical properties of virgin-recycled ABS blends: Effect of post-consumer content and of reprocessing cycles

Virgin/post-consumer ABS (pc-ABS) blends were re-processed and re-formed up to three times. The effect of pc-ABS content and of reprocessing cycles on the physical properties of the prepared blends was evaluated by mechanical tests (tensile, flexural and impact tests) and by rheological and thermo-mechanical measurements. The processability of pc-ABS blends was not substantially different by that of virgin ABS up to two recycling steps even if the third one induced a slightly decrease of viscosity, more remarkable on increasing the pc-ABS content. The mechanical and thermo-mechanical properties of the samples worsened on increasing the level of pc-ABS and after each reprocessing operation even if the most relevant decreases were observed after the first recycling.     

Study of the isothermal degradation of poly(vinyl chloride) by direct inlet mass spectrometry

Films of poly(vinyl chloride) (PVC) were degraded isothermally at 160, 180, 200, 220, 240 and 280°C for 30 min in the ion source of a mass spectrometer and the volatile products of degradation were monitored by direct inlet mass spectrometry, which has the advantage of monitoring several degradation products at the same time. Both the evolution rate of the volatile products and their composition were recorded during the isothermal degradation of PVC. A technique was developed for the preparation of samples that improves the repeatability of the method.     

Thermo-oxidative degradation of ultrahigh molecular weight poly(ethylene oxide) in volatile organic solvents

The degradation of ultrahigh molecular weight poly(ethylene oxide) (UHMWPEO) was investigated in three volatile organic solvents, methanol, chloroform, and tetrahydrofuran. Particularly, degradation rate was determined by means of Ubbelohde viscometry and degradation products were characterized by using electron spin resonance spectroscopy (ESR) and Fourier transform infrared spectroscopy (FTIR). The highest degradation rate was observed for UHMWPEO in tetrahydrofuran, with the lowest one in methanol. The ESR results showed that PEO-C• and •OH radicals were produced during the degradation process. Among these selected solvents, tetrahydrofuran was found to generate free radicals through an autoxidation mechanism. This would accelerate the degradation of UHMWPEO, resulting in the observed highest degradation rate in the UHMWPEO/tetrahydrofuran solution. Esters were also detected in the degradation products of these UHMWPEO solutions, while formates and formate ions were generated in the solutions of UHMWPEO/tetrahydrofuran and UHMWPEO/cloroform except for PEO/methanol. Furthermore, the degradation mechanism of UHMWPEO was deduced. This work enabled an in-depth understanding on the thermo-oxidative degradation mechanism of UHMWPEO in representative organic solvents, which would be instructive for developing optimal solution-based processing technique of UHMWPEO.     

Autoxidation of lipids in parchment

Historic parchment is a macromolecular material, which is complex due to its natural origin, inhomogeneity of the skin structure, unknown environmental history and potential localised degradation. Most research into its stability has so far focussed on thermal and structural methods of analyses.Using gas chromatographic analysis of the atmosphere surrounding parchment during oxidation, we provide the experimental evidence on the production of volatile aldehydes, which can be the products of lipid autoxidation. Oxidation of parchment with different aldehyde emissions was additionally followed in situ using chemiluminometry and the same techniques were used to evaluate the oxidation of differently delipidised parchment. It was shown that the production of peroxides and the emission of aldehydes from the material decrease with lower lipid content. Building on this evidence, we can conclude that the presence of lipids (either initially present in the skin or resulting from conservation intervention) leads to oxidative degradation of collagen and that the non-destructive analysis of the emission of volatiles could be used as a quick tool for evaluation of parchment stability.     

Analysis of flame retardant additives in polymer fractions of waste of electric and electronic equipment (WEEE) by means of HPLC-UV/MS and GPC-HPLC-UV

An HPLC-UV/MS method has been developed to identify and quantify flame retardants in post-consumer plastics from waste of electric and electronic equipment (WEEE). Atmospheric pressure chemical ionisation spectra of 15 brominated and phosphate-based flame retardants were recorded and interpreted. The method was applied to detect flame retardant additives in polymer extracts obtained from pressurised liquid extraction of solid polymers. In addition, a screening method was developed for soluble styrene polymers to isolate a flame retardant fraction through the application of gel permeation chromatography (GPC). This fraction was transferred to an online-coupled HPLC column and detected by UV spectroscopy, which allowed a reliable qualitative and quantitative analysis of brominated flame retardants in the polymer solutions.     

Thermal and photo-degradation of unstabilized ABS

Thermal- and photo-stabilities of unstabilized acrylonitrile-butadiene-styrene terpolymer, ABS, have been investigated by i.r. spectroscopy. Degradation of ABS samples is initiated by attack on the polybutadiene (PB) component; oxidation products containing hydroxyl and carbonyl groups are produced. The effect of prior thermal processing is to introduce into the polymer hydroperoxides arising from oxidative destruction of PB-unsaturation; these hydroperoxides act as catalysts during subsequent u.v. irradiation. The insolubility of degraded samples of ABS is associated with the formation of cross-linked structures and occurs mainly in the PB segment. It is concluded that the degradation characteristics of ABS are essentially those of the polybutadiene component.     

Studies of the effects of copper, copper(II) oxide and copper(II) chloride on the thermal degradation of poly(vinyl chloride)

Investigations of the pyrolysis of poly(vinyl chloride) (PVC) in the presence of copper metal (Cu), copper(II) oxide (CuO) and copper(II) chloride (CuCl₂) are of potential importance because of the likelihood of the formation of these copper compounds during the thermal degradation of PVC-coated copper wires, a step in the recovery of copper from waste. The presence of Cu, CuO and CuCl₂ (i) retards the thermal degradation of PVC in air and in nitrogen and (ii) decreases the percentages of volatile products produced at both stages of the decomposition. These effects are greatest for PVC-CuO. The presence of copper, CuO or CuCl₂ in PVC has a major effect on the nature of the gaseous emissions of the thermal decomposition in air and in nitrogen. The concentrations of total chlorine, aliphatic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons and soot particulates are all affected relative to an equivalent amount of PVC. These changes are greatest for the PVC-CuO system for which total chlorine emissions in air and nitrogen are reduced by 40% in air and 20% in nitrogen, benzene emissions are reduced by greater than 90% in air and nitrogen, other aromatic and chloroaromatic emissions are reduced, and soot particulate emissions are reduced by more than 50% as the concentrations of aliphatic compounds are increased. These changes are consistent with the presence of copper or its compounds permitting more efficient combustion of the carbon content of the PVC and particularly in the case of PVC-CuO with the removal of chlorine during pyrolysis in the inorganic phase.     

The mechanical degradation of polystyrene

The catastrophic failure of a polymeric material is preceded by a number of complex, partially understood events occurring on the molecular level. These events range from the flow of ordered regions to the cleavage of primary bonds in the chain. In recent years, stress-induced bond cleavage in polymers has received increased attention, many authors nothing the presence of free radicals and/or volatile products released upon fracture; a free-radical decomposition mechanism involving up to 10³ molecules per chain rupture also has been postulated. A special tensile stress–strain and shear apparatus was developed and located inside the ion-source housing of a time-of-flight mass spectrometer to characterize the volatile products released during mechanical degradation of polystyrene. Volatile compounds evolved during stress and fracture of polystyrene were monitored either continuously or by z-axis modulated oscilloscopic display. The polystyrene was purified by two methods: vacuum outgassing and fractional reprecipitation. Large amounts of styrene evolved from both the as-received and outgassed samples; however, essentially none was observed from the reprecipitated samples. Previous reports on monomer evolution during mechanical stress of polystyrene may be the result of residual monomer and not mechanical degradation products. The product of the surface density of primary radicals and the chain length for unzipping is less than 3 × 10¹⁰ radicals/mm² indicating a maximum radical concentration of approximately 10¹⁰ radicals/mm².     

Effect of the additive level and of the processing temperature on the re-building of post-consumer pipes from polyethylene blends

One of the main shortcomings of the mechanical recycling is that the properties of the secondary materials are generally sensibly inferior with respect to the virgin ones. This feature implies, for sure, that they cannot be used for the same technological application but also other uses of the secondary material are impossible. The aim of this work is to study the re-building of recycled post-consumer pipes, made of a blend of different polyethylenes, by re-processing in the presence of a nitroxyl compound as radical generator. The processing temperature and the additive concentration have been varied in order to study the effect of these parameters on the final properties.The mechanical, rheological, solubility and thermal results indicate that low levels of additive and lower processing temperatures mostly cause long chain branching of the polyethylenes. On the contrary, at higher concentrations and temperatures cross-linked structures are formed. Dramatic variations of the melt viscosity are observed at low shear rates for the added materials, but in the window of the shear rates commonly used for processing, the viscosities are similar to the one of the as received material. Low processing temperatures and additive levels allow enhancing the ultimate properties, which approach the ones of the virgin materials. The elastic modulus is in any case lower than the one observed in the non-added material due to change in the molecular structure and in the crystallinity.The impact strength strongly increases in the presence of the additive. The presence of crosslinks that deviate the cracks and a local plastic deformation at the interface between the crosslinks and the matrix can be invoked to explain the results.