Recycling of crate material: Weatherability of stabilised recycled high density polyethylene

The uv stabilising effect of various stabilisers added to degraded, yellow-pigmented, high density polyethylene (HDPE) crate material originating from crates that have been in use for 10–13 years was investigated. For that purpose, outdoor and Xenotest-1200 exposure tests were carried out, and rates of oxygen absorption during photo-oxidation were determined. The uv stability of the degraded HDPE could be considerably improved—in particular, by the addition of a hindered amine type stabiliser (Tinuvin 770). The uv stability attainable is such that reuse of recycled crate material for the production of new crates is, after upgrading, a realistic possibility.A comparison of the results of outdoor and accelerated ageing showed that the acceleration factors strongly depend on the type of stabiliser applied. This can be attributed to the different mechanisms of stabilisation by which the various additives act.The uv stability of the recycled polymer appeared to be almost independent of the degree of degradation of the crates before recycling. This implies that it is not necessary to exclude from recycling heavily degraded crates which had failed due to brittle fracture.     

Contamination in food from packaging material

Packaging has become an indispensible element in the food manufacturing process, and different types of additives, such as antioxidants, stabilizers, lubricants, anti-static and anti-blocking agents, have also been developed to improve the performance of polymeric packaging materials. Recently the packaging has been found to represent a source of contamination itself through the migration of substances from the packaging into food. Various analytical methods have been developed to analyze the migrants in the foodstuff, and migration evaluation procedures based on theoretical prediction of migration from plastic food contact material were also introduced recently. In this paper, the regulatory control, analytical methodology, factors affecting the migration and migration evaluation are reviewed.     

Comparison of extraction methods for sampling of low molecular compounds in polymers degraded during recycling

The demand for mechanical recycling of plastic waste results in an increasing amount of recycled polymeric materials available for development of new products. In order for recycled materials to find their way into the material market, high quality is demanded. Thereby, a complete and closed loop of polymeric materials can be achieved successfully. The concept of high quality for recycled plastics imply that besides a pure fraction of e.g. polyethylene (PE) or polypropylene (PP), containing only minor trace amount of foreign plastics, knowledge is required about the type and amount of low molecular weight (LMW) compounds. During long-term use (service-life), products made of polymeric materials will undergo an often very slow degradation where a series of degradation products are formed, in parallel, additives incorporated in the matrix may also degrade. These compounds migrate at various rates to the surrounding environment. The release rate of LMW products from plastics depends on the initiation time of degradation and the degradation mechanisms. For polymers the formation of degradation products may be initiated already during processing, and subsequent use will add products coming from the surrounding environment, e.g. fragrance and aroma compounds from packaging. During recycling of plastics, emissions which contain a series of different LMW compounds may reach the environment leading to unwanted exposure to additives and their degradation residues as well as degradation products of polymers.Several extraction techniques are available for sampling of LMW compounds in polymers before chromatographic analysis. This paper reviews and compares polymer dissolution, accelerated solvent extraction (ASE), microwave assisted extraction (MAE), ultrasound assisted extraction (UAE), super critical fluid extraction (SFE), soxhlet extraction, head-space extraction (HS), head-space solid phase micro extraction (HS-SPME), and head-space stir bar sorptive extraction (HSSE) as appropriate sampling methods for LMW compounds in recycled polymers. Appropriate internal standards useful for these kinds of matrices were selected, which improved the possibility for later quantification. Based on the review of extraction methods, the most promising techniques were tested with industrially recycled samples of HDPE and PP and virgin HDPE and PP for method comparison.     

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.     

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.     

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.     

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.     

Analytical tools for identification of non-intentionally added substances (NIAS) coming from polyurethane adhesives in multilayer packaging materials and their migration into food simulants

Adhesives used in food packaging to glue different materials can provide several substances as potential migrants, and the identification of potential migrants and migration tests are required to assess safety in the use of adhesives. Solid-phase microextraction in headspace mode and gas chromatography coupled to mass spectrometry (HS-SPME-GC-MS) and ChemSpider and SciFinder databases were used as powerful tools to identify the potential migrants in the polyurethane (PU) adhesives and also in the individual plastic films (polyethylene terephthalate, polyamide, polypropylene, polyethylene, and polyethylene/ethyl vinyl alcohol). Migration tests were carried out by using Tenax(?) and isooctane as food simulants, and the migrants were analyzed by gas chromatography coupled to mass spectrometry. More than 63 volatile and semivolatile compounds considered as potential migrants were detected either in the adhesives or in the films. Migration tests showed two non-intentionally added substances (NIAS) coming from PU adhesives that migrated through the laminates into Tenax(?) and into isooctane. Identification of these NIAS was achieved through their mass spectra, and 1,6-dioxacyclododecane-7,12-dione and 1,4,7-trioxacyclotridecane-8,13-dione were confirmed. Caprolactam migrated into isooctane, and its origin was the external plastic film in the multilayer, demonstrating real diffusion through the multilayer structure. Comparison of the migration values between the simulants and conditions will be shown and discussed.     

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.     

Recycling of bioplastics,their blends and biocomposites: A review

This review presents scientific findings concerning the recycling of bioplastics, their blends and thermoplastic biocomposites, with special focus on mechanical recycling of bio-based materials. The paper does not include bio-based commodity plastics such as bio-derived polyolefins that are identical to their petroleum-based counterparts and that can be recycled in the same way. During the past few years, recycling of biopolymers and their blends has been studied using both mechanical and chemical methods, whereas in biocomposites, the focus has been on mechanical recycling. This review goes through the findings on the recyclability of various materials, the strengths and weaknesses of applied methods, as well as the potential strategies and opportunities for future improvements. There are still many blends that have not been investigated for their recyclability. Information about commercially available blends containing bioplastics is summarised in the Appendix because of the importance of their possible effects on the conventional plastic recycling streams.     

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.     

Thermally Robust yet Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)-Like Materials Based on Si−O Bonds

Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl- and olefin-related functional groups. Bifunctional silyl ethers (BSEs; SiR₂(OR′₂)) could expand the functional scope of PE mimics as they possess strong Si−O bonds and facile chemical tunability. Here, we report BSE-containing high-density polyethylene (HDPE)-like materials synthesized through a one-pot catalytic ring-opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si-substituents, providing handles to control thermomechanical properties. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid-catalyzed Si−O bond exchange with 1-propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain-growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step-growth Si−O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.     

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.     

Study and characterization of virgin and recycled LDPE/PP blends

Recycling of mixed plastic wastes composed of low-density polyethylene (LDPE) matrix and polypropylene (PP) was carried out by compounding using single-screw or twin-screw extruders. Blends of virgin polymers have been prepared to compare mechanical properties of both virgin and regenerated materials. First, a model composition of virgin LDPE/PP blend was prepared to study the effect of process parameters and that of different types of compatibilizers. Second, the results were applied to plastic wastes coming from industrial post-consumer plastic wastes. By adding compatibilizing agents such as ethylene-propylene-diene monomer, ethylene-propylene monomer, or PE-g-(2-methyl-1,3-butadiene) graft copolymer, elongation at break and impact strength were improved for all blends. The effect of these various copolymers is quite different and is in relation with their chemical structure. The recycled blends exhibit suitable properties leading to applications that require good mechanical properties.     

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.     

Development of methods for testing barriers in food packaging materials

In some countries recycled materials are not allowed to come into contact with food without a protective layer such as plastic or virgin fiber. The purpose of this kind of barrier is to reduce migration of substances form beyond the barrier to the food. Two methods for studying a functional barrier are described. Both utilize migration cells in which one surface of the test specimen (for example a paper plate) is exposed to the food simulant. The first method involves the addition of indidcatsor substances to the non-food contact layer. The second method is to measure the migration of substances originally present in the layers beyond the functional barrier layer. Several kinds of barrier used in commercial papaer plates were studied and differences between them were found.     

高效液相色谱法同时测定食品接触材料中抗氧化剂和紫外吸收剂的迁移量

采用高效液相色谱技术,建立了食品接触材料中多种抗氧化剂和紫外吸收剂迁移水平的检测方法。该方法测定的23种目标化合物具有较好的线性关系,相关系数（r²）≥ 0.9998,检出限和定量限分别在0.01到0.22 mg/L之间和0.03到0.85 mg/L之间。依据欧盟指令（EU）No. 10/2011,考察了5种食品模拟物30 g/L乙酸、10%（v/v）乙醇、20%（v/v）乙醇、50%（v/v）乙醇和油类模拟物（异辛烷）中抗氧化剂和紫外吸收剂的迁移量。该方法回收率在92.8%~117.7%之间,相对标准偏差在0.95%~9.72%之间。探讨了不同实验条件对抗氧化剂和紫外吸收剂回收率的影响。结果表明,该方法准确、稳定,完全满足欧盟指令（EU）No 10/2011和GB 9685-2008对食品接触材料及制品中抗氧化剂和紫外吸收剂特定迁移量（SML）的限量要求,并利用该方法测定了30批次食品接触材料中抗氧化剂和紫外吸收剂的迁移水平。     

Determination of partition behavior of organic surrogates between paperboard packaging materials and air

The suitability of recycled paperboard packaging materials for direct food contact applications is a major area of investigation. Chemical contaminants (surrogates) partitioning between recycled paper packaging and foods may affect the safety and health of the consumer. The partition behavior of all possible organic compounds between cardboards and individual foodstuffs is difficult and too time consuming for being fully investigated. Therefore it may be more efficient to determine these partition coefficients indirectly through experimental determination of the partitioning behavior between cardboard samples and air. In this work, the behavior of organic pollutants present in a set of two paper and board samples intended to be in contact with foods was studied. Adsorption isotherms have been plotted and partition coefficients between paper and air have been calculated as a basis for the estimation of their migration potential into food. Values of partition coefficients (Kpaper/air) from 47 to 1207 were obtained at different temperatures. For the less volatile surrogates such as dibutyl phthalate and methyl stearate higher Kpaper/air values were obtained. The adsorption curves showed that the more volatile substances are partitioning mainly in air phase and increasing the temperature from 70 to 100 degrees C their concentrations in air (Cair) have almost doubled. The analysis of surrogates was performed with a method based on solvent extraction and gas chromatographic-flame ionization detection (GC-FID) quantification.     

Interactions between poly(vinyl chloride) stabilised with epoxidised sunflower oil and food simulants

Commercial sunflower oil was epoxidised and used as organic co-stabiliser for rigid and plasticised poly(vinyl chloride) (PVC) containing Zn and Ca stearates as primary stabilisers and stearic acid as lubricant. For applications in the packaging of foodstuffs, migration testing must be performed. The detection and the quantification of contaminants migrating from the polymer into the food simulants are essential for the safety assessment of food contact plastic packaging materials. For that purpose, two food simulants were used: olive oil and 15% (v/v) aqueous ethanol. These represent fatty and moist food and beverages, respectively. The test conditions were 12 days at 40 °C. Circular samples of rigid PVC and PVC plasticised with dioctyl phthalate were immersed in a known volume of food simulant. A circular sample and 10 ml of food simulant were taken off every day to be analysed. Each sample was wiped and weighed. The rate of variation of the mass was determined as a function of time. The evolution of the peroxide index of olive oil with time was analysed. The specific migrations of the present additives were investigated by using two analytical methods (atomic absorption spectrometry and Fourier transform infrared spectroscopy). The influence of various parameters such as the nature of food simulant, the presence or the absence of the plasticiser, the agitation and time of contact was considered.     

超高效液相色谱/静电场轨道阱高分辨质谱法同时测定塑料食品接触材料中光稳定剂和抗氧化剂的特定迁移量

建立了超高效液相色谱/静电场轨道阱高分辨质谱同时测定塑料食品接触材料中多种光稳定剂和抗氧化剂特定迁移量的方法。采用30 g/L乙酸、体积分数分别为10%、20%、50%的乙醇和油类模拟物(异辛烷)这5种食品模拟物对塑料食品接触材料进行处理,对处理液进行超高效液相色谱/静电场轨道阱高分辨质谱分析,外标法定量。该方法测定的40种目标化合物在相应的范围内均具有良好的线性关系,相关系数均大于0.998,定量限为0.01~1.00μg/L。考察了上述5种食品模拟物中光稳定剂和抗氧化剂的特定迁移量,平均加标回收率为81.46%~94.53%,相对标准偏差为3.25%~9.99%。应用该方法对市售塑料食品接触材料进行了测定,结果在部分样品中检出了不同含量的光稳定剂和抗氧化剂。该方法灵敏度高,定量限低,满足塑料食品接触材料中光稳定剂和抗氧化剂特定迁移量的检测要求。