A Comparative Study on Crystallisation for Virgin and Recycled Polyethylene Terephthalate (PET): Multiscale Effects on Physico-Mechanical Properties.

Poly(Ethylene Terephthalate) (PET) is one of the most used polymers for packaging applications. Modifications induced by service conditions and the means to make this matter circular have to be understood to really close the loop (from bottle to bottle for example). Physico-chemical properties, crystalline organisation, and mechanical behaviour of virgin PET (vPET) are compared with those of recycled PET (rPET). Using different combined experimental methods (Calorimetry, Small Angle X-ray Scattering [SAXS], Atomic Force Microscopy [AFM], Dynamic Mechanical Analysis [DMA], and uniaxial tensile test), it has been proven that even if there is no change in the crystallinity of PET, the crystallisation process shows some differences (size and number of spherulites). The potential impact of these differences on local mechanical characterisation is explored and tends to demonstrate the development of a homogeneous microstructure, leading to well-controlled and relevant local mechanical property characterisation. The main contribution of the present study is a better understanding of crystallisation of PET and recycled PET during forming processes such as thermoforming or Injection Stretch Blow Moulding (ISBM), during which elongation at the point of breaking can depend on the microstructure conditioned by the crystallisation process.

Compressive and Flexural Strengths of Mortars Containing ABS and WEEE Based Plastic Aggregates.

The incorporation of plastic aggregates as a partial replacement of natural aggregates in cementitious materials is interesting in several ways. From a mechanical point of view, the partial substitution of sand with plastic aggregates could improve some properties (e.g., ductility, thermal insulation). This paper deals with the mechanical strength of mortars containing plastic aggregates as a partial replacement of sand. Part of the volume of sand in cement mortars is substituted with plastic aggregates which originate from WEEE (Waste from Electrical and Electronic Equipment) and consist of a mix of ABS (acrylonitrile-butadiene styrene), HIPS (high impact polystyrene) and PP (Polypropylene), or of monomaterial ABS from WEEE sorting. Three rates of replacement (by volume of sand) were tested: 10%, 15% and 30%. Mechanical tests were performed according to European standard EN196-1. The results show that compressive and flexural strength decrease with rate of replacement, but remain satisfactory for structural purposes. In addition, the density of mortar is reduced with the incorporation of plastic aggregates. The decrease of mechanical strength is mainly due to the weak bond between cement paste and plastic aggregates leading to the increase of porosity. Furthermore, it appears that mortars containing plastic aggregates could present a ductile rupture.

Characterization of Optimized Ternary PLA/PHB/Organoclay Composites Processed through Fused Filament Fabrication and Injection Molding.

The aim of this study was to investigate the structure-properties relationship of ternary blends of polylactide/polyhydroxybutyrate (PLA/PHB)/organo-modified layered silicate (OMLS). Morphological, thermal, rheological, and mechanical characterizations were performed to understand the influence of OMLS on PLA/PHB (70/30 wt%) formulations optimized through modifications with an epoxy-based chain extender, the use of a plasticizer, as well as the influence of the type of processing route: injection molding or fused filament fabrication. The addition of OMLS allowed the blend compatibility to be improved, with the appearance of a single melting peak on DSC thermograms at 146 °C, as well as the reduction in the size of the nodules for the injected molded specimens. Concerning the printed samples, AFM analysis revealed a coalescence of the PHB minor phase due to its degradation. This phenomenon was dramatically enhanced in the presence of OMLS and has been ascribed to the degradation of both the organo-modifier and the PHB minor phase in the blend. Rheological and mechanical tests (17% decrease in Young's modulus and 13% decrease in elongation at break) confirmed this degradation that would have occurred during the manufacturing of the filaments and the printing of specimens due to additional thermal and cooling steps.

Chemical Recycling of Vacuum-Infused Thermoplastic Acrylate-Based Composites Reinforced by Basalt Fabrics.

The objective of this work was to compare the material recovered from different chemical recycling methodologies for thermoplastic acrylate-based composites reinforced by basalt fabrics and manufactured by vacuum infusion. Recycling was done via chemical dissolution with a preselected adapted solvent. The main goal of the study was to recover undamaged basalt fabrics in order to reuse them as reinforcements for "second-generation" composites. Two protocols were compared. The first one is based on an ultrasound technique, the second one on mechanical stirring. Dissolution kinetics as well as residual resin percentages were evaluated. Several parameters such as dissolution duration, dissolution temperature, and solvent/composite ratio were also studied. Recycled fabrics were characterized through SEM observations. Mechanical and thermomechanical properties of second-generation composites were determined and compared to those of virgin composites (called "first-generation" composites). The results show that the dissolution protocol using a mechanical stirring is more adapted to recover undamaged fabrics with no residual resin on their surface. Moreover, corresponding second-generation composites display equivalent mechanical properties than first generation ones.

Impact of PP Impurities on ABS Tensile Properties: Computational Mechanical Modelling Aspects.

Recycling of plastics is hindered by their important variety and strong incompatibility. However, sorting technologies bear costs and meet limits. Very high purities (<2 wt%) are difficult to reach. Yet, such rates may be detrimental to functional properties. In this work, an ABS matrix (major plastic in Waste of Electrical and Electronic Equipments) was filled with 4 wt% of PP to mimic impurities in ABS after recycling. PP-g-MA was introduced in the blend to improve the compatibility. A finite element model was developed from the mechanical behavior of each component. ABS and PP were individually characterized from tensile tests instrumented with photomechanics and their behaviors were modelled through a set of numerical parameters (elasto-visco-plasticity with a Gurson's criterion behavior). Comparison between the determinist model results and the experimental data (strength, volumetric variation) shows that this type of modelling could be a predictive tool in order to anticipate composite mechanical properties and to understand micromechanisms of deformation (damage, cavitation). The main result is that PP introduced at 4 wt% into ABS does not alter the static mechanical properties despite polymers incompatibility. The addition of PP-g-MA modifies the local properties and possibly conduct to a premature breakage of the polymer blend.

Degradation of Styrenic Plastics during Recycling: Accommodation of PP within ABS after WEEE Plastics Imperfect Sorting.

With the development of dark polymers for industrial sorting technologies, economically profitable recycling of plastics from Waste Electrical and Electronical Equipment (WEEE) can be envisaged even in the presence of residual impurities. In ABS extracted from WEEE, PP is expected to be the more detrimental because of its important lack of compatibility. Hence, PP was incorporated to ABS at different rates (2 to 8 wt%) with a twin-screw extruder. PP was shown to exhibit a nodular morphology with an average diameter around 1-2 µm. Tensile properties were importantly diminished beyond 4 wt% but impact resistance was decreased even at 2 wt%. Both properties were strongly reduced as function of the contamination rate. Various potential compatibilizers for the ABS + 4 wt% PP system were evaluated: PPH-g-MA, PPC-g-MA, ABS-g-MA, TPE-g-MA, SEBS and PP-g-SAN. SEBS was found the most promising, leading to diminution of nodule sizes and also acting as an impact modifier. Finally, a Design Of Experiments using the Response Surface Methodology (DOE-RSM) was applied to visualize the impacts and interactions of extrusion temperature and screw speed on impact resistance of compatibilized and uncompatibilized ABS + 4 wt% PP systems. Resilience improvements were obtained for the uncompatibilized system and interactions between extrusion parameters and compatibilizers were noticed.

MIR spectral characterization of plastic to enable discrimination in an industrial recycling context: III. Anticipating impacts of ageing on identification.

Ageing of polymers entails important structural changes and degrades their functional properties, particularly their aspect. Since sorting is a primordial step in recycling to achieve acceptable mechanical properties, the use of promising technologies such as MIR-HSI (Mid-Infrared Hyperspectral Imagery), which could overcome black plastics sorting issue, has to take into account the influence of ageing on identification. As ageing strongly impacts spectra, it can create confusion between materials, especially in an automatized scheme. Based on laboratory FTIR-ATR (Fourier-Transform Infrared Attenuated Total Reflection), this work investigates spectral evolutions of natural and accelerated photodegradation of Waste of Electric and Electrical Equipment plastics (WEEE) as PE, PP, HIPS, ABS and PC to help identifying a polymer despite its ageing degree. Oxidation marks were described and retrieved within a stock of about one hundred of real waste samples, then differentiated from other sources of spectral alteration as formulation. Laboratory ageing data were found to be consistent and often more extreme than real waste samples values. Generally, styrenics showed stronger spectral alteration than polyolefins despite their respective aspects. No significant spectral alteration of PC was obtained here or observed in the waste stock. As an important oxidation marker, the carbonyl peak was also found to often enable fast identification through its wavenumber. If well taken in account, ageing should not induce confusion with other polymers, even formulated, as characteristic signals are different. Finally, the different industrial sub-ranges within MIR are not affected at the same degree, possibly influencing a technological choice for industrial sorting.

MIR spectral characterization of plastic to enable discrimination in an industrial recycling context: II. Specific case of polyolefins.

Sorting at industrial scale is required to perform mechanical recycling of plastics in order to obtain properties that could be competitive with virgin polymers. As a matter of fact, the most part of the various types of plastic waste are not miscible and even compatible. Mid-Infrared (MIR) HyperSpectral Imagery (HSI) is viewed as one of the solutions to the problem of black plastic sorting. Many Waste of Electrical and Electronic Equipment (WEEE) plastics are black. Nowadays, these materials are difficult to sort at an industrial scale because the main used pigment to produce this color, carbon black, masks the Near-Infrared (NIR) spectra of polymers, the currently most used technology for acute sorting in industrial conditions. In this study, laboratory Fourier-Transform Infrared (FTIR) in Attenuated Total Reflection mode (ATR) has been used as a theoretical toolbox based on physical chemistry to help building an automated HSI discrimination despite its limited conditions, especially shorter wavelengths ranges. Weaker resolution and very short acquisition times are other HSI limitations. Helping fast and exhaustive laboratory characterizations of polymeric waste stocks is the other goal of this study. This study focusses on polyolefins as they represent the second biggest fraction of WEEE plastics (WEEP) after styrenics and since little quantities mixed to styrenics during mechanical recycling can lead to important decrease in mechanical properties. Twelve references were thus evaluated and compared between each other and with real waste samples to highlight spectral elements, which can enable differentiation. Charts compiling the signals of discussed polymers were built aiming to the same objective.

MIR spectral characterization of plastic to enable discrimination in an industrial recycling context: I. Specific case of styrenic polymers.

One of the major limitations in polymer recycling is their sorting as they are collected in mixes. The majority of polymers are highly incompatible without compatibilizers. For sorting of polymers, high-speed online Near-Infrared (NIR) spectroscopy is nowadays relatively widespread. It is however limited by the use of carbon black as a pigment and UV-stabilizer, which strongly absorbs near-infrared signals. Mid-Infrared (MIR) hyperspectral cameras were recently put on the market. However, their wavelength ranges are smaller and their resolutions are poorer, in comparison with laboratory equipment based on Fourier-Transform Infrared (FTIR). The identification of specific signals of end-of-life polymers for recycling purposes is becoming an important stake since they are very diverse, highly formulated, and more and more used in copolymers and blends, leading to complex waste stocks mainly as WEEE (Waste Electrical and Electronic Equipment). Dark colored plastics are the major part of WEEE, which also contains mainly styrenics (ABS, HIPS and their blends). In addition, styrenics are especially concerned by the need of identification. In this framework, spectral characterizations of ten types of polymers were scrutinized through about eighty pristine and real waste samples. Polymer characteristic signals were aggregated in charts to help rapid and automatized distinction through specific signals, even in limited resolution and frequency ranges.

How to manage biocomposites wastes end of life? A life cycle assessment approach (LCA) focused on polypropylene (PP)/wood flour and polylactic acid (PLA)/flax fibres biocomposites.

Biocomposites has gained increasing attention in recent years. The environmental impacts of end-of-life (EoL) treatments of those emerging materials should be evaluated before they are produced and installed commercially, to ensure a minimal impact of these products all along their life cycle. Life cycle assessment (LCA) was carried out to evaluate environmental impacts of the EoL treatments of wood flour (WF) reinforced polypropylene (PP/WF) and flax fibers reinforced polylactic acid (PLA/Fl). The aim was to evaluate which EoL was the most environmental friendly to manage those emerging wastes in France and to help stakeholders of the waste sectors in their decisions. The attributional LCA was realized using the methodological framework of the international standard ISO 14040:2006. The study only focuses on the EoL of the biocomposites with four scenarios: incineration, landfill, composting and recycling. Mid-point indicators were evaluated thanks to the Recipe method. Results were also normalized to the annual mean environmental impact of a European inhabitant. For both biocomposites, recycling EoL scenario presents the lowest environmental impacts except for the freshwater eutrophication impact of the PP/WF EoL. Models should be completed in the future when new data will be available. Results obtained for both biocomposites are in agreement with the European waste hierarchy. If recycling of plastic is difficult to implement, incineration would be the preferable option for the PP/WF composite, while composting would be the other choice for PLA/Fl material.

Influence of impurities on the performances of HIPS recycled from Waste Electric and Electronic Equipment (WEEE).

In order to produce a high quality recycled material from real deposits of electric and electronic equipment, the rate of impurities in different blended grades of reclaimed materials has to be reduced. Setting up industrial recycling procedures requires to deal with the main types of polymers presents in WEEE (Waste Electric and Electronic Equipment), particularly High Impact Polystyrene (HIPS) as well as other styrenic polymers such as Acrylonitrile-Butadiene-Styrene (ABS), Polystyrene (PS) but also polyolefin which are present into WEEE deposit as Polypropylene (PP). The production of a substantial quantity of recycled materials implies to improve and master the compatibility of different HIPS grades. The influence of polymeric impurities has to be studied since automatic sorting techniques are not able to remove completely these fractions. Investigation of the influence of minor ABS, PS and PP polymer fractions as impurities has been done on microstructure and mechanical properties of HIPS using environmental scanning electron microscopy (ESEM) in order to determine the maximum tolerated rate for each of them into HIPS after sorting and recycling operations.