Rendering Bio-Inert Low Density Polyethylene Amenable For Biodegradation Via Fast High Throughput Reactive Extrusion Assisted Oxidation

An energy efficient high throughput pre-treatment of low density polyethylene (LDPE) using a fast reactive extrusion (REX) assisted oxidation technique followed by bacterial attachment as an indicator for bio-amenability was studied. Silicon dioxide (SiO2) was selected as a model oxidizing and catalytic reagent with the REX process demonstrated to be effective both in the presence and absence of the catalyst. Optimized 5-minute duration pretreatment conditions were determined using Box-Behnken design (BBD) with respect to screws speed, operating temperature, and concentration of SiO2. The crystallinity index, carbonyl index and weight loss (%) of LDPE were used as the studied responses for BDD. FTIR and DSC spectra of the residual LDPE obtained after pretreatment with the REX assisted oxidation technique showed a significant increase in residual LDPE carbonyl index from 0 to 1.04 and a decrease of LDPE crystallinity index from 29% to 18%. Up to 5-fold molecular weight reductions were also demonstrated using GPC. Optimum LDPE pretreatment with a duration of 5 minutes was obtained at low screw speed (50 rpm), operating temperature of 380-390⁰C and variable concentration of SiO2 (0 and 2% (w/w)) indicating that effective pretreatment can occur under noncatalytic and catalysed conditions. Biofilms were successfully formed on pretreated LDPE samples after 14 days of incubation.Furthermore, the technique proposed in this study is expected to provide a high throughput approach for pretreatment of pervasive recalcitrant PE based plastics to reduce their bio inertness.

Combined use of Bacillus strains and Miscanthus for accelerating biodegradation of poly(lactic acid) and poly(ethylene terephthalate)

Background The aim of this study was to verify whether the presence of Bacillus strains and of miscanthus influence biodegradation and formed of biofilm of poly(lactic acid) (PLA) and poly(ethylene terephthalate) (PET). Methods The experiment conducted in compost soil showed that strains Bacillus subtilis and Bacillus cereus isolated from heavy metal contaminated environment have biochemical activity and accelerate biodegradation of both plastic materials. Results For PLA film it was found that the carbonyl index dropped by over 15% in the presence of B. subtilis, while the film tensile strength decreased by 35% and the oxygen to carbon O/C ratio was higher by 3% in the presence of B. cereus, and the presence of miscanthus resulted in a loss of weight. For PET film, a decrease in the carbonyl index by 16% was observed following inoculation with B. cereus. The metabolic activity of this strain contributed to the reduction of the film’s tensile strength by 17% and to the increase in the permeability to O2 and CO2. The most intense degradation of PET film was observed in the presence of bacteria and plants. B. subtilis strain combined with miscanthus plantings may be a promising method for accelerating PLA and PET degradation in compost soil.

Photocatalytic Degradation of Polyamide 66; Evaluating the Feasibility of Photocatalysis as a Microfibre-Targeting Technology

Wastewater treatment plants (WWTPs) have been identified as main contributors to releasing microfibres into the environment, however, WWTPs do not have microfibre-targeting technologies. In this study, photocatalysis is evaluated as a potential technology to treat microfibres in WWTPs by studying the degradation of polyamide 66 (PA66) microfibres using ultraviolet (UV) and titanium dioxide (TiO2). PA66 microfibres suspended in deionised water were exposed to different combinations of UV and TiO2. The degradation of the PA66 microfibres was monitored by changes in mass, carbonyl index and morphology using microbalance, infrared spectroscopy, and scanning electron microscopy. The formation of by-products from the degradation of the fibres was evaluated by measuring the chemical oxygen demand (COD) of the treated water. The degradation efficiency was optimised under UVC with a dose of 100 mg TiO2/L. Under these conditions, the PA66 microfibres presented a 97% mass loss within 48 h. The photocatalytic conditions applied generated a relatively low level of by-products (<10 mg/L of COD). Therefore, photocatalysis with TiO2 an UVC could potentially be a feasible technology to treat microfibres in WWTPs, although more investigation is required to establish if this treatment leads to the formation of nanofibres. Further work is needed to translate the present optimised conditions to WWTPs.

Application of Earth Pigments in Cycloolefin Copolymer: Protection against Combustion and Accelerated Aging in the Full Sunlight Spectrum

In this paper, we assess various natural earth pigments as potential colorants and stabilizers for ethylene–norbornene copolymer composites. Several cycloolefin copolymer (COC) composites colored with 2 wt% of a selected pigment were prepared using a two-step mixing method. The aging resistance of the polymer composites was investigated in terms of changes to their mechanical properties, following accelerated aging in the full sunlight spectrum (100, 200, 300, 400, and 500 h). Fourier-transform infrared spectroscopy (FTIR), surface energy measurements, and spectrophotometry were used to assess the color changes, surface defects, and morphology of the composites. Thermogravimetric analysis (TGA) was used to study their thermal stability. The combustion characteristics of the prepared COC composites were evaluated based on the microcombustion calorimetry test (MCC). The application of earth pigments resulted in interesting color changes and a significant improvement in the aging resistance of the COC-filled samples, as evidenced by higher aging factor values and lower carbonyl index parameters compared to the reference (COC). The best results were observed for hematite (HM), gold ochre (GO), and red ochre (RO). In addition, the application of earth pigments, especially iron ochre (IO) and red ochre (RO), in COC contributed to a significant reduction in the heat release rate (HRR) values, indicating improved flame retardancy. This research opens the possibility of producing colorful COC composites with enhanced photostability and reduced flammability for use in polymer applications.

Determination of the carbonyl index of polyethylene and polypropylene using specified area under band methodology with ATR-FTIR spectroscopy

The current measurement techniques described in the literature for the determination of the carbonyl index (CI) for polyolefins such as polyethylene and polypropylene were compared and contrasted. These were all found to be inconsistent or inaccurate and were not capable of differentiating significant changes in carbonyl peak evolution throughout accelerated ageing. As a consequence of these findings, a methodology, specified area under band (SAUB) is presented here to more accurately represent the CI as a general means of reporting. The increased precision in the methodology is explained and compared to other methodologies for determining CI. The SAUB method is also shown to be capable of elucidating the differences in relative extent and rates of CI for different polyolefins, exposed to the same conditions over the same time period.

Research on the Properties of Low Temperature and Anti-UV of Asphalt with Nano-ZnO/Nano-TiO2/Copolymer SBS Composite Modified in High-Altitude Areas

Strong ultraviolet light and low-temperature are the typical environmental characteristics in high-altitude areas. The performance of SBS-modified asphalt in the above environmental characteristics needs further study. To improve the resistance ultraviolet (UV) ageing and low-temperature performance of copolymer- (SBS-) modified asphalt, an SBS-modified asphalt containing nano-ZnO and nano-TiO2 is proposed. In this paper, nano-ZnO, nano-TiO2, and SBS were used as modifiers with the silane coupling agent (KH-560) as the nanomaterial surface modification. The orthogonal test table was used to analyse the effects of the three modifiers on the physical properties of modified asphalt at different dosages. On this basis, the physical properties, low-temperature properties, and ageing indices (carbonyl index and sulfoxide index) were studied for base asphalt, SBS-modified asphalt, nano-ZnO/SBS-modified asphalt, and nano-ZnO/nano-TiO2/SBS composite-modified asphalt before and after photoaging. The content changes of characteristic elements (Zn and Ti) in the nano-ZnO/nano-TiO2/SBS composite-modified asphalt before and after ageing were studied by scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS), and the UV ageing mechanism was revealed. The results indicate that two nanoparticles show the best compatibility with asphalt after surface modification and can improve the binding ability between SBS and base asphalt. The orthogonal test analysis shows that nano-ZnO has a highly significant effect on the low- and high-temperature performance of the nano-ZnO/nano-TiO2/SBS composite-modified asphalt, and nano-TiO2 has a significant effect on the high-temperature performance. Three optimal composite-modified systems for base asphalt including 4% nano-ZnO/1.5% nano-TiO2/3.2% SBS were proposed and had the best antiaging ability. Compared with the sulfoxide index, the carbonyl index changed most obviously before and after ageing. Additionally, the results reveal that nano-TiO2 has a good absorption effect at a wavelength of 365 nm (ultraviolet light), while nano-ZnO is liable to photolysis, and its activity decreases at this wavelength.

Influence of Oxygen Diffusion on Thermal Ageing of Cross-Linked Polyethylene Cable Insulation

Thermal ageing of cross-linked polyethylene (XLPE) cable insulation is an important issue threatening the safe operation of power cables. In this paper, thermal ageing of XLPE was carried out at 160 °C in air for 240 h. The influence of oxygen diffusion on thermal ageing of XLPE was investigated by Ultraviolet–visible spectrophotometer (UV–Vis), tensile testing, and Fourier transformed infrared spectroscopy (FTIR). It was observed that the degradation degree not only depended on ageing time but also on sample positions. The thermally aged samples were more oxidized in the surface region, presented a darker color, more carbon atoms appeared in the conjugate cluster, had smaller elongation at break and tensile strength, and a larger carbonyl index. As ageing time increased, the non-uniform oxidation of the XLPE samples became more prominent. The degree of non-uniform oxidation caused by oxygen diffusion was quantitatively studied by first order oxidation kinetic. The calculated results demonstrated that carbonyl index measured by FTIR was more sensitive to non-uniform oxidation with a shape parameter in the range of 1–2. The result shown in this paper is helpful for interpreting and predicting the non-uniform ageing behavior of high voltage XLPE cables.

Residues of Fluoroquinolone Antibiotics Induce Carbonylation and Reduce In Vitro Digestion of Sarcoplasmic and Myofibrillar Beef Proteins

Although the impact of oxidation on human health has been of growing interest, the oxidation of proteins, major component of meat, has received little attention. This paper describes the in vitro effect of five fluoroquinolones (FQs) on carbonylation of sarcoplasmic and myofibrillar proteins of beef when found at concentrations close to the maximum residue limit (MRL). Samples were treated individually with the FQs, determining in each protein fraction the carbonyl index, protein content and oxidized proteins identification, using 2,4-dinitrophenyhydrazine (DNPH) alkaline assay, Western blot and Bradford methods, and mass spectrometry, respectively. Besides, the in vitro effect of these residues on gastric and duodenal digestion of proteins was evaluated. The carbonylation induced by FQs affected both protein fractions being significant with respect to the blank in 73.3% of cases. This damage was correlated with loss of solubility and digestibility, with sarcoplasmic proteins the most affected. Danofloxacin and enrofloxacin were the FQs with greatest oxidant effects, especially affecting glycolysis and glycogen proteins. Our results suggest that these residues induce irreversible oxidative damage on the main beef proteins and could affect their nutritional value.