Screening the Impact of Surfactants and Reaction Conditions on the De-Inkability of Different Printing Ink Systems for Plastic Packaging.

One of the major applications (40% in Europe) of plastic is packaging, which is often printed to display required information and to deliver an attractive aesthetic for marketing purposes. However, printing ink can cause contamination in the mechanical recycling process. To mitigate this issue, the use of surfactants in an alkaline washing process, known as de-inking, has been employed to remove printing ink and improve the quality of recyclates. Despite the existence of this technology, there are currently no data linking the de-inking efficiency with typical printing ink compositions. Additionally, it is necessary to investigate the de-inking process under the process parameters of existing recycling plants, including temperature, NaOH concentration, and retention time. This study aims to evaluate the performance of commonly used printing inks with different compositions under various washing scenarios for plastic recycling in conjunction with different de-inking detergents containing surfactants or mixtures of surfactants. The results indicate that the pigments applied to the ink have no significant effect on the de-inking process, except for carbon black (PBk 7). Nitrocellulose (NC) binder systems exhibit high de-inkability (over 95%) under the condition of 55 °C and 1 wt.% NaOH. However, crosslinked binder systems can impede the de-inking effect, whether used as a binder system or as an overprint varnish (OPV). The de-inking process requires heating to 55 °C with 1 wt.% NaOH to achieve a substantial effect. Based on the findings in this work, breaking the Van der Waals forces, hydrogen bonds, and covalent bonds between the printing ink and plastic film is an essential step to achieve the de-inking effect. Further research is needed to understand the interaction between surfactants and printing inks, enabling the development of de-inkable printing inks and high-performance surfactants that allow for de-inking with less energy consumption. The surfactant and NaOH have a synergistic effect in cleaning the printing ink. NaOH provides a negative surface charge for the adsorption of the cationic head of the surfactant and can hydrolyze the covalent bonds at higher concentrations (>2 wt.%).

Lab-scale and full-scale industrial composting of biodegradable plastic blends for packaging.

Background: The acceptance of compostable plastic packaging in industrial composting plants is not universal despite available certification due to the persistence of plastic residues after composting. To better understand this discrepancy, this study compared the disintegration rates of two blends designed for rigid packaging (polylactic acid based) and soft packaging (polybutylene succinate based) in lab-scale composting tests and in an industrial composting plant. Methods: A lab-scale composting test was conducted in triplicates according to ISO 20200 for 4, 8 and 12 weeks to check the disintegration potential of the blends. Duplicate test material were then exposed in the compost pile of an industrial composting plant for a duration of 3 weeks and compared with a supplementary lab-scale test of the same duration. Results: The rigid packaging samples (1 mm thickness) retained on average 76.4%, 59.0% and 55.7% of its mass after 4, 8 and 12 weeks respectively in the lab-scale. In the plant, the average remaining mass was 98.3%, much higher compared to the average of 68.9% after 3 weeks in the supplementary lab-scale test. The soft packaging samples (109±9 µm sample thickness) retained on average 45.4%, 10.9% and 0.3% of its mass after 4, 8 and 12 weeks respectively in the lab-scale. In the plant, a high average remaining mass was also observed (93.9%). The supplementary lab-scale test showed similar remaining mass but higher fragmentation after 3 weeks. Conclusions: The results show that the samples achieved significant disintegration in the lab-scale but not in the plant. The difference between the tests that might further contribute to the differing degradation rates is the composition and heterogeneity of the composting substrate. Therefore, the substrate composition and thermophilic composting duration of individual plants are important considerations to determine the suitability of treating compostable plastic in real-world conditions.

There is resistance from industrial composting plants to the treatment of compostable biodegradable plastics. This study aims to compare the disintegration rates of two new biodegradable plastic blends developed for rigid and soft packaging applications in controlled industrial composting conditions in the lab as well as under actual industrial composting conditions in a composting plant. Results show significant disintegration of the material in the lab-scale up to 12 weeks. However, there were notable differences in the degree of disintegration of the samples in the lab compared to real-world conditions after 3 weeks. The 1 mm thick polylactic acid-based blend for rigid packaging experienced much higher disintegration in the lab with 68.9% remaining mass after 3 weeks compared to 97.2% remaining mass in the industrial composting plant. The 109 µm thick polybutylene succinate-based blend for soft packaging had similar remaining masses comparing the lab and full-scale tests. However, the lab-test showed higher fragmentation after 3 weeks. The characteristics of the organic waste inputs are potential causes of the lower disintegration rates. The study highlights the need to better understand the real-world industrial composting conditions and their variations when evaluating composting as a treatment method for biodegradable plastics.

Assessment of Supercritical CO2 Extraction as a Method for Plastic Waste Decontamination.

Due to the lack of advanced methods to clean plastic waste from organic contaminants, this study aimed at evaluating supercritical extraction as a decontamination method. Oil-adhesive high-density polyethylene (HD-PE) oil containers were subjected to supercritical extraction using supercritical carbon dioxide. The extraction was conducted at 300 bar, applying various temperatures (i.e., 70, 80 and 90 °C). The study assessed the impact of temperature on the decontamination efficiency. The variation in the samples' quality was first analyzed using near infrared (NIR) spectroscopy. An analysis of the content of polycyclic aromatic hydrocarbons (PAHs) was followed. Samples treated at 70 and 80 °C showed higher extraction efficiencies, in spite of the lower extraction temperatures. The NIR analysis showed that the plastic specimens did not experience degradation by the supercritical decontamination method. Moreover, the NIR spectra of the extracted oil showed the presence of a wide range of compounds, some of which are hazardous. This has been confirmed by a GC-MS analysis of the extracted oil. Based on the provided assessment, the quality of the decontaminated HD-PE plastic samples-from a contamination point of view-is enhanced in comparison to untreated samples. The level of PAHs contamination decreased to be within the allowed limits defined by the REACH regulation, and also met the specifications of the German Product Safety Committee. This study proved the effectiveness of the supercritical extraction using CO2 in extracting organic contaminants from plastics, while maintaining their quality.

The degree and source of plastic recyclates contamination with polycyclic aromatic hydrocarbons.

In this research, the degree and source of recyclates contamination with polycyclic aromatic hydrocarbons (PAH) was studied in eight different polyolefin recyclate samples; four originating from post-consumer packaging waste and four originating from a mixed source (post-industrial, post-commercial, and post-consumer). The aim was to assess the applicability of these recyclates in the different products' categories. Furthermore, the impact of previous contamination with PAH was excluded by analysing pure plastics before and after undergoing simulated recycling processes. Polythene recyclates originating from post-consumer plastic packaging waste had lower concentrations of the 16-US-EPA PAH (922.15 ± 420.75 µg kg-1) in comparison to the ones of a mixed origin (2155.43 ± 991.85 µg kg-1), r = -0.35, p > 0.05. The degree of recyclates contamination with PAH was always within the REACH limits for consumer products (<1.0 mg kg-1). On the other hand, only polythene recyclate sample originating from post-commercial waste did not comply with the REACH limits for children articles (0.5 mg kg-1). Hence, the source of plastic waste defines the quality of recyclates. All in all, the results indicated that the contamination of polyolefin recyclates with PAH is attributed to the material's previous contamination, or the sorption of plastics to organic compounds from the surrounding environment. Exposing plastics containing PAH additives to heat during extrusion could result in further accumulation of PAH in plastics.

Decontamination and recycling of agrochemical plastic packaging waste.

Agrochemical containers shall undergo decontamination before being considered for recycling. This study provides an assessment on the feasibility of the triple-rinsing decontamination procedure, while evaluating the appropriateness of the material's quality for recycling. To achieve the objectives of the study, (1) the effectiveness of the decontamination procedure was investigated; (2) containers´ long storage times and changes on the polymer´s structure were assessed; and (3) the quality of the recycled material was tested. Results showed that the triple-rinsing procedure was ineffective for the container´s complete decontamination, yet a further washing step - performed during the simulation of the recycling process - allowed for an improved degree of decontamination for recycling. Photo-oxidation imposed significant changes on the chemical structure of the polymer, where the active ingredient could be detected by FTIR, even after the application of rinsing and extraction. The chemical structure of the bulk material has not changed, indicating that the pesticide mobilization was only confined to the surface. The mechanical tests showed material quality appropriateness, where tensile strength values were within the suggested ranges, providing a possibility for further utilization of this material when appropriate decontamination is applied.

Towards a high quality recycling of plastics from waste electrical and electronic equipment through separation of contaminated fractions.

The aim of this study is to provide an evaluation of the recyclability of plastics derived from electrical equipment from contamination standpoint. A database was created to find trends in potentially toxic elements (PTEs) and bromine concentrations; in relation to unit's application, color, polymer type, and production date. For this study, 142 kg of plastics derived from waste electrical and electronic equipment, from the collection group 5, were analyzed. Less than 1.5 % of the analyzed material indicated hazardous characteristics due to their PTEs concentrations (following RoHS and REACH). Regarding the bromine (Br) content, larger quantities of plastics showed recycling incompatibility; 71 parts with total weight of 11 kg (8 %-wt) contained Br concentrations >2000 mg kg-1. The highest average value of Pb, Cd, Hg and Cr combined falls under the application category 'tools', which was as well the trend in appliances from before 1990. The same trend was observed for Br and antimony (Sb) contents; high concentrations were found in appliances from the 'tools' category. This study concludes that plastics derived from colored appliances and appliances labeled as tools have to be evaluated before being sent for recycling, due to high contamination risks.

Classification of plastic waste originated from waste electric and electronic equipment based on the concentration of antimony.

The aim of this research is a preliminary assessment of antimony concentration in plastic fractions deriving from different e-waste. We considered microwave ovens, desktop computers, laptops, mobile phones, a TV case, a PC monitor and LED lamps (63 items in total). The plastic fraction ranged from 8%-wt in computers and microwave ovens, up to 40%-wt in cell phones and 59%-wt in LED lamps. Specific polymers were identified through Near Infrared spectroscopy. The samples followed three parallel procedures: acid digestion with aqua regia; conversion into ashes at 600 °C then acid digestion with aqua regia; leaching according to UNI10802 reference procedure. Plastic components with significant amounts of antimony were the ones derived from desktop computers (25-1900 mg/kg) and from microwave ovens (830 mg/kg), yet their relative amount compared to the total weight of the item was limited. Items with larger plastic fractions showed lower concentrations of antimony (1-6 mg/kg in mobile phones cases and 160-640 mg/kg in plastic components of LED lamps). Leaching tests revealed that the analyzed plastic fractions could be mostly admitted in non-hazardous waste landfills. The analysis of ashed samples highlighted the need to further improve the acidic extraction procedure.

Assessment of plastic waste materials degradation through near infrared spectroscopy.

Plastic waste is a relevant challenge for waste management sector and further technological means have to be urgently researched. The evaluation of plastic waste quality through non-destructive, cost-effective and mature technologies could be without any doubt a key issue. This study is aimed at the assessment of Near Infrared (NIR) spectroscopy for the generation of global degradation-prediction models able to forecast plastic ageing. The degradation of Polyethylene terephthalate (PET), Acrylonitrile Butadiene Styrene (ABS), Polypropylene (PP) and Polyethylene (PE) was achieved by thermal ageing (at 85 °C, 105 °C and 120 °C and durations ranging from 4 to 504 h), to simulate environmental outdoor conditions. Experimental data obtained for each plastic material were elaborated through partial least square (PLS) regression to obtain empirical models. For all inspected plastic materials, a good correspondence between the variation in absorbance units and the change in chemical bonds vibrations was observed. The PLS models were afterwards calibrated (taking into account the different ageing conditions; first separately then including the ageing factors combined). A high accuracy (R2 equal to 0.85-1.00) was observed in predicting ageing for PET and ABS, while the correspondence showed a 30% decrease for PE and PP. This study proves that NIR spectroscopy can be recommended as an effective tool to investigate plastics degradation, with some limitations for specific polymers that need further investigations.

Wet fractionation of the succulent halophyte Salicornia sinus-persica, with the aim of low input (water saving) biorefining into bioethanol.

In this study Salicornia sinus-persica, a succulent halophyte was assessed for its potential to be used as a feedstock for bioethanol production. For such succulent, salty, green biomasses, direct fractionation and fermentation allow for water preservation in the process. Fresh biomass of S. sinus-persica was collected and split into two fractions by wet fractionation; liquid (juice) and solid (pulp). Sugar contents were found to be 1.0-1.5% for the juice fraction and 50% (w/w) for the fresh pulp. Direct fermentation of the juice using Saccharomyces cerevisiae showed no salt inhibition of the yeast and ethanol yields of ~70% were achieved. A pretreatment study was carried out for the pulp fraction applying mild hydrothermal pretreatment. Cellulose convertibility was found to be significantly higher for severity factors above 2.00, and the highest ethanol yield (76.91 ± 3.03%) was found at process severity of 3.06 (170 °C, 10 min).

Ordered mesoporous silica prepared by quiescent interfacial growth method - effects of reaction chemistry.

Acidic interfacial growth can provide a number of industrially important mesoporous silica morphologies including fibers, spheres, and other rich shapes. Studying the reaction chemistry under quiescent (no mixing) conditions is important for understanding and for the production of the desired shapes. The focus of this work is to understand the effect of a number of previously untested conditions: acid type (HCl, HNO3, and H2SO4), acid content, silica precursor type (TBOS and TEOS), and surfactant type (CTAB, Tween 20, and Tween 80) on the shape and structure of products formed under quiescent two-phase interfacial configuration. Results show that the quiescent growth is typically slow due to the absence of mixing. The whole process of product formation and pore structuring becomes limited by the slow interfacial diffusion of silica source. TBOS-CTAB-HCl was the typical combination to produce fibers with high order in the interfacial region. The use of other acids (HNO3 and H2SO4), a less hydrophobic silica source (TEOS), and/or a neutral surfactant (Tweens) facilitate diffusion and homogenous supply of silica source into the bulk phase and give spheres and gyroids with low mesoporous order. The results suggest two distinct regions for silica growth (interfacial region and bulk region) in which the rate of solvent evaporation and local concentration affect the speed and dimension of growth. A combined mechanism for the interfacial bulk growth of mesoporous silica under quiescent conditions is proposed.