Analytical protocol to study the food safety of (multiple-)recycled high-density polyethylene (HDPE) and polypropylene (PP) crates: Influence of recycling on the migration and formation of degradation products

An analytical protocol was set up and successfully applied to study the food safety of recycled HDPE and PP crates. A worst-case scenario was applied that focused not only on overall migration and specific migration of accepted starting materials but also on migratable degradation products of polymers and additives that may be formed during mechanical recycling.The analytical protocol was set up to cover a wide variety of possible migrants. Identification and semi-quantification were possible for almost all migrants that increased significantly with increasing mechanical recycling steps for both the HDPE and PP crates.It was concluded that the analytical protocol was suitable to study the influence of (multiple) recycling on the food safety of plastic materials. The protocol can be applied to other plastic food contact materials and provides valuable information on the food safety of the recycling process and the resulting recycled food contact materials in addition to challenge testing.     

Quality Assessments of Recycled Plastics by Spectroscopy and Chromatography

Quality assessments will be important for improved use of recycled polymeric materials. Ongoing preparation of new standards in the area of recycled polymers needs an overview of which properties and thus which polymer characterisation methods that will be important for that purpose. We suggest three polymeric properties as important for this work; these are degree of mixing (composition), degree of degradation and number and amount of low molecular weight compounds (e.g. degradation products, additives, flavour compounds). DSC showed increased degradation as multi modality for LDPE materials obtained from three different sites in a recycling plant. IR demonstrated that the carbonyl index increased during the various steps going from collected material to new product. GC chromatograms obtained for collected film flakes, processed granules and ready-made bags were quite complex with a series of hydrocarbons among other compounds. The recycling process seems, however, to remove some of the low molecular weight compounds found in the incoming dirty material.     

Pretreatment of Plastic Waste: Removal of Colorants from HDPE Using Biosolvents

Plastics recycling remains a challenge due to the relatively low quality of the recycled material, since most of the developed recycling processes cannot deal with the additives present in the plastic matrix, so the recycled products end up in lower-grade applications. The application of volatile organic solvents for additives removal is the preferred choice. In this study, pretreatment of plastic packaging waste to remove additives using biosolvents was investigated. The plastic waste used was high-density polyethylene (HDPE) with blue and orange colorants (pigment and/or dye). The first step was to identify the type of colorants present in the HDPE, and we found that both plastics presented only one colorant that was actually a pigment. Then, limonene, a renewable solvent, was used to solubilize HDPE. After HDPE dissolution, a wide range of alcohols (mono-, di-, and tri-alcohols) was evaluated as antisolvents in order to selectively precipitate the polymer and maximize its purity. The use of limonene as solvent for plastic dissolution, in combination with poly-alcohols with an intermediate alkyl chain length and a large number of hydroxyl (OH) groups, was found to work best as an antisolvent (1,2,3-propanetriol and 1,2,4-butanetriol), leading to a removal of up to 94% and 100% of the blue and orange pigments, respectively. Finally, three cycles of extraction were carried out, proving the capability of the solvent and antisolvent to be recovered and reused, ensuring the economic viability and sustainability of the process. This pretreatment provides a secondary source of raw materials and revenue for the recycling process, which may lead to an increase in the quality of recycled polymers, contributing to the development of an economical and sustainable recycling process.     

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.     

Analytical strategies for the quality assessment of recycled high-impact polystyrene: a combination of thermal analysis, vibrational spectroscopy, and chromatography

Various analytical techniques (thermal analysis, vibrational spectroscopy, and chromatographic analysis) were used in order to monitor the changes in polymeric properties of recycled high-impact polystyrene (HIPS) throughout mechanical recycling processes. Three key quality properties were defined and analysed; these were the degree of mixing (composition), the degree of degradation, and the presence of low molecular weight compounds. Polymeric contaminations of polyethylene (PE) and polypropylene (PP) were detected in some samples using differential scanning calorimetry (DSC). Vibrational spectroscopy showed the presence of oxidised parts of the polymeric chain and gave also an assessment of the microstructure of the polybutadiene phase in HIPS. The presence of low molecular weight compounds in the HIPS samples was demonstrated using microwave-assisted extraction followed by gas chromatography-mass spectrometry (GC-MS). Several volatile organic compounds (VOCs), residues from the polymerisation, additives, and contaminations were detected in the polymeric materials. Styrene was identified already in virgin HIPS; in addition, benzaldehyde, α-methylbenzenaldehyde, and acetophenone were detected in recycled HIPS. The presence of oxygenated derivates of styrene may be attributed to the oxidation of polystyrene (PS). Several styrene dimers were found in virgin and recycled HIPS; these are produced during polymerisation of styrene and retained in the polymeric matrix as polymerisation residues. The amount of these dimers was highest in virgin HIPS, which indicated that emission of these compounds may have occurred during the first life-time of the products. This paper demonstrates that a combination of different analytical strategies is necessary to obtain a detailed understanding of the quality of recycled HIPS.     

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.     

Degradation of polyolefines during various recovery processes

The purpose of the presented research was the investigation of the stability and differences of degradation of polyolefines during various recycling processes. In modeling the recycling process during melting, extrusion with a one-screw extruder was used. Recycling through selective dissolution was modulated by two different solvents (xylene and a definite mixture of n-alkanes). Materials used for the investigations were polypropylene (PP), low-density polyethylene (LDPE) and high-density polyethylene (HDPE) (Ziegeler-Natta technology with vanadium catalyst). Changes in the chemical structure of polymers were measured with infrared spectroscopy and differential scanning calorimetry (DSC). Flow properties were characterized by melt flow index, and mechanical characteristics by tension. Experimental results show that for PP and HDPE, utilizing all investigated recycling technologies, chain scission prevailed over branching. For the LDPE chain branching was obtained. By the same token, differences in crystallinity (and as follows, in molecular mass) between the same materials, recycled by extrusion and selective dissolution, was obtained. During selective dissolution changes of properties and morphology in dependence of the solvent used were observed with the trend being that the amount of the admixture of n-alkane used in this investigation was more considerable with regard to the amount of material destruction as compared to xylene. Any reduction of the mechanical properties of any of the investigated polymers as a result of the various methods used was comparable.     

Identification and segregation of materials in mixed waste

A great amount of plastics are present in waste material, a high percentage of which stem from the family of so-called “commodities”. Bearing this in mind, it is essential to develop a recycling system in order to avoid the environmental deterioration their presence causes and to reuse materials whose composition enables their recovery. The first problem this paper deals with is the separation of individual polymers before recycling in order to obtain regenerated products of high quality with consequently greater value. The work involves an attempt to use chemical additives as tracers in commonly occurring plastics such as PE, PVC, PP, etc. The tracers must be non-toxic and must not alter the physical or transformation properties of the plastics. They should be identifiable by simple spectroscopic methods so as to enable physical separation of different polymers prior to recyclying.     

Recycling technology of poly(ethylene terephthalate) materials

Poly(ethylene terephthalate) (PET) has become one of major post consumer plastics wastes, in addition to polyethylene (PE), polypropylene (PP), polystyrene (PS) and poly(vinyl chloride) (PVC). The challenge to large-volume plastics companies is to learn how to collect, separate, reprocess and market their low-cost products and make a profit, too. The effort of PET recycling, however, is the most successful story in the plastic recycling technology, including both reclaim and upgrade of PET waste. Beverage bottles made of PET are recycled more than 20% of the total production. The technology of today can reclaim the post-consumer PET bottles to produce high-quality granulated PET with better than 99% purity. A practical reclaim process for recycling PET bottles (including bottle, HDPE base cup, aluminum cap, liner, label and adhesive) is available by the Center for Plastics Recycling Research in USA. PET recycling process, like for other plastics, can be divided into three categories: incineration, physical recycling, and chemical recycling. To make the plastic recycling business pay requires more than simple recovery and marketing. Greatest profit potential is in upgraded and value-added reclaim products. Upgrading involves compounding with additives to make material more processable, adding reinforcement, or producing extrusions or finished parts from reclaim resins. For instance, a modified injection-moldable resin made from PET bottle scrap is claimed to provide high impact and processability at less cost than competitive materials. It is foreseen that chemical recycling of waste PET bottle becomes feasible if the price of raw material goes up. Three economical processes are involved in this technology: pyrolysis, hydrocracking, and hydrolysis. The hydrolysis process is presently employed to recover the raw material for unsaturated polyester resin manufacture or polyols for the production of polyurethane resin. It is reported in this presentation that polymer concrete could be a huge potential market for chemical reclaim of PET materials, especially for green or mixed-color PET, which are priced lower than colorless PET reclaim materials.     

Advances and approaches for chemical recycling of plastic waste

The global production and consumption of plastics has increased at an alarming rate over the last few decades. The accumulation of pervasive and persistent waste plastic has concomitantly increased in landfills and the environment. The societal, ecological, and economic problems of plastic waste/pollution demand immediate and decisive action. In 2015, only 9% of plastic waste was successfully recycled in the United States. The major current recycling processes focus on the mechanical recycling of plastic waste; however, even this process is limited by the sorting/pretreatment of plastic waste and degradation of plastics during the process. An alternative to mechanical processes is chemical recycling of plastic waste. Efficient chemical recycling would allow for the production of feedstocks for various uses including fuels and chemical feedstocks to replace petrochemicals. This review focuses on the most recent advances for the chemical recycling of three major polymers found in plastic waste: PET, PE, and PP. Commercial processes for recycling hydrolysable polymers like polyesters or polyamides, polyolefins, or mixed waste streams are also discussed.     

Effects of reprocessing of oxobiodegradable and non-degradable polyethylene on the durability of recycled materials

The use of plastics is steadily increasing in our daily lives, and plastics are the fastest-growing component of the waste stream. Although the efficiency of plastic recycling is increasing, plastics are often seen as a permanent environmental problem because of littering. The introduction of oxobiodegradable polyolefins (OBDs), containing prodegradant additives, is considered to be a way to reduce this problem by enabling the fast degradation of plastics in the environment. The prodegradant additives form radicals that attack the polymer chains, causing chain scissions and generation of low molecular mass oxidation products that can be consumed by microorganisms. There is, however, a concern that the prodegradant additives will present a problem if OBD materials end up in the conventional plastic recycling streams. The present study therefore highlights the impact of mixing OBD materials with conventional polyolefins to evaluate the impact on the remaining service life of the recyclates.The study included the use of two different OBDs, mixed in different proportions (10% and 20%) in a conventional polyethylene. The remaining service life of the mixtures was evaluated by monitoring the reduction in tensile strain after exposure to thermo-oxidative degradation at 70 °C, compared with a pure polyethylene. The impact of stabilizer content in the mixtures was also evaluated together with the effect of mixing partially degraded OBDs into the recyclate.The results show that the incorporation of minor fractions of OBD materials in the existing recycling streams will not create a severe effect on the service life of the recyclates as long as the polymer mixture possesses a reasonable degree of stabilization.     

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.     

Oxidative degradation products analysis of polymer materials by pyrolysis gas chromatography–mass spectrometry

Pyrolysis gas chromatography–mass spectroscopy (PGC–MS) has been proved to be a powerful method to analyze both the volatile additives and the macromolecular structure of polymer materials. In this paper, flash evaporation technique was used to analyze the volatile degradation products of polymer materials during natural and artificial aging. In high density polyethylene (HDPE) composites, mainly n-alkanes with carbon number from 14 to 29 were detected after natural aging, while no oxidative product was found. Different composites have different n-alkane distributions. In contrast, various oxidative products including ketones, alcohols, esters and unsaturated species could be found in aged polypropylene (PP) nanocomposites. Nanoparticles accelerated the chain scission of PP and increased the formation of oxidative products significantly. During thermal oxidation of nitrile rubber (NBR) seal rubbers, heat/oxidation-induced extra crosslinking predominated and no volatile degradation products was detected. The main change happened in the volatiles is the decrease of additives, especially paraffins, antioxidant RD and hindered phenol. This resulted in the hardening of the rubber and the weakening of the protection from oxidation. Furthermore, the additive distribution along the depth was investigated, showing different migration speeds of different additives. From the additive levels remained in the NBR rubber, it is possible to predict the degradation status. In summary, PGC–MS can supply abundant information of polymer degradation and is helpful for mechanism research.     

Recycling of waste from polymer materials: An overview of the recent works

Polymer recycling is a way to reduce environmental problems caused by polymeric waste accumulation generated from day-to-day applications of polymer materials such packaging and construction. The recycling of polymeric waste helps to conserve natural resource because the most of polymer materials are made from oil and gas. This paper reviews the recent progress on recycling of polymeric waste form some traditional polymers and their systems (blends and composites) such as polyethylene (PE), polypropylene (PP), and polystyrene (PS), and introduces the mechanical and chemical recycling concepts. In addition, the effect of mechanical recycling on properties including the mechanical, thermal, rheological and processing properties of the recycled materials is highlighted in the present paper.     

Degradability of linear polyolefins under natural weathering

High density polyethylene (HDPE), linear low density polyethylene (LLDPE), and isotactic polypropylene (PP) containing antioxidant additives at low or zero levels were extruded and blown moulded as films. An HDPE/LLDPE commercial blend containing a pro-oxidant additive (i.e., an oxo-biodegradable blend) was taken from the market as supermarket bag. These four polyolefin samples were exposed to natural weathering for one year during which their structure and thermal and mechanical properties were monitored. This study shows that the real durability of olefin polymers may be much shorter than centuries, as in less than one year the mechanical properties of all samples decreased virtually to zero, as a consequence of severe oxidative degradation, that resulted in substantial reduction in molar mass accompanied by a significant increase in content of carbonyl groups. PP and the oxo-bio HDPE/LLDPE blend degraded very rapidly, whereas HDPE and LLDPE degraded more slowly, but significantly in a few months. The main factors influencing the degradability were the frequency of tertiary carbon atoms in the chain and the presence of a pro-oxidant additive. The primary (sterically hindered phenol) and secondary (phosphite) antioxidant additives added to PP slowed but did not prevent rapid photo-oxidative degradation, and in HDPE and LLDPE the secondary antioxidant additive had little influence on the rate of abiotic degradation at the concentrations used here.     

Effect of ionizing radiation on physicochemical and mechanical properties of commercial monolayer and multilayer semirigid plastics packaging materials

Tensile testing, overall migration tests and sensory tests were used to evaluate the effects of gamma irradiation (5–60 kGy) on six commercial semirigid packaging materials. The monolayer and multilayer materials in sheet or bottle form were: polystyrene (PS), polypropylene (PP), polyvinyl chloride/high-density polyethylene (PVC/HDPE), polyethylene terepthalate (PET), HDPE/polyamide (HDPE/PA) and HDPE. In terms of mechanical strength, PET was the most radiation-resistant material, while the HDPE monolayer and multilayer showed some degradation after 60 kGy. PS was slightly affected after 30 kGy, whereas PP was severly degraded and became very brittle. Generally, there was no change in overall migration at lower doses; at higher doses migration from PP tended to increase, while migration from HDPE/PVC tended to decrease. Odor and taste transfer as well as discoloration were observed with most plastics, especially at higher doses, and it is concluded that these tests are a sensitive and important quality control tool for evaluating irradiated packaging materials.     

The influence of recycling on the properties of wood fibre — Plastic composites

The manufacture of composites offers the greatest flexibility to convert and utilize waste plastics, paper and wood into high-value products. This paper reports on two studies regarding the recycling of these materials. In one study, recycling was simulated by regrinding and injection-moulding composites of polypropylene (PP), polyethylene (PE) and old newsprint (ONP) eight times. The results indicated that reprocessing had only minor deleterious effect on the mechanical properties (tensile and flexural). The viscosity of neat PP decreased with repeated recycling indicating some thermo-oxidative degradation. The overall rheological character of PP composites did not change much. PE composites, on the other hand, showed increasing melt flow with reprocessing. The second study examined the effects of various coupling agents on the properties of multicomponent PP composites. Maleated polypropylene (MAPP) was the most effective coupling agent.     

The effect of Pb and other elements found in recycled polypropylene on the manufacturing of lead-acid battery cases

Polypropylene (PP) is one of the most common plastics used in the manufacturing of lead-acid battery cases, where the recycling of the material has become common practice, being both economically viable and environmentally friendly. During the recycling process, the various components of the spent battery are separated, where the crushed battery case is washed in order to remove any excess acid and lead-containing particles. The plastic components are subsequently melted and extruded into pellets that are then blended with virgin material to injection mold new battery cases and lids. This study showed that a significant amount of lead-containing particles in the form of lead dioxide and lead sulfate remain in the recycled plastic, and are evenly distributed throughout the polymer matrix. TEM studies showed that the particles are less than 1 μm in size and X-ray diffraction analysis of ashed recycled PP samples showed the presence, amongst others, of talc, calcium carbonate, rutile and iron oxide. These compounds come from a range of fillers, flame-retardants, colorants and impurities that originated from the various original battery cases that were recycled. The study showed that modern X-ray fluorescence (XRF) analysis is a quick and reliable method to quantify the amount of the elements found in the plastic and that the concentration of Pb in the plastic can be used as a type of “tracer” to determine the amount of recycled PP used in the manufacturing of a particular battery case. The study also showed that there is possible environmental contamination, in particular with Pb and Br contained in recycled PP during the injection molding process and the burning of the plastic. The Pb- and Br-containing particles are small enough to become air-borne during the burning process of the plastic, resulting in them being part of the soot and other hydrocarbon oils that are emitted. No Pb was observed in the gases emitted during simulated low-temperature injection molding conditions; however, a significant amount of Br was detected in the gases at the lower temperatures. Clear environmental waste classification of the battery case plastic should be done before its final incineration where the amount of trace metals present and its possible contamination to the environment should be considered. Care should also be taken for machine operators who work with the recycled plastic, that no excessive exposure to the halogenated compounds is experienced.     

What is the technical and environmental interest in reusing a recycled polypropylene-hemp fibre composite?

The integration of the environmental problem in the design of industrial products leads us to incorporate vegetal fibres and recycled polymers into composite materials. The aim of this work is to study the behaviour and the environmental interest of a recycled PP/hemp fibre after several injection cycles. The mechanical and rheological behaviour of recycled PP/hemp composite was first studied by using tensile, dynamical mechanic analysis and rheological measurements. Then, to better understand the influence of the recycling, a morphology study was carried out on composites by using optical and electron microscopy. Finally, we investigated the environmental advantages of our composite thanks to a simplified environmental assessment. Our results highlighted the environmental interest of using a recycled matrix to prepare composites reinforced with vegetal fibres and the interesting properties of this material after recycling.     

Supercritical Fluid Extraction (SFE) Optimization by Full-Factorial Design for the Determination of Irganox 1076, Irgafos 168, and Chimassorb 81 in Virgin and Recycled Polyolefins

The performance and feasibility of supercritical fluid extraction (SFE) applied to the extraction of some antioxidants (Irganox 1076, Irgafos 168) and one UV-stabilizer (Chimassorb 81) from both virgin and recycled low density polyethylene (LDPE), and virgin high density polyethylene (HDPE) are studied. Due to the high number of variables a full-factorial design has been applied to minimize the number of experiments required to reach the optimum extraction conditions. Further analysis has been carried out off-line by reversed-phase HPLC. Modification of the physical properties of the polymeric matrix and increased number of recycling cycles as well as the influence of physical properties on the efficiency of SFE are also discussed.