Study of sequential abiotic and biotic degradation of styrene butadiene rubber.

Styrene butadiene rubber is one of the main constituents of tire tread. During tire life, the tread material undergoes different stresses that impact its structure and chemical composition. Wear particles are then released into the environment as weathered material. To understand their fate, it is important to start with a better characterization of abiotic and biotic degradation of the elastomer material. A multi-disciplinary approach was implemented to study the photo- and thermo- degradation of non-vulcanized SBR films containing 15 w% styrene as well as their potential biodegradation by Rhodoccocus ruber and Gordonia polyisoprenivorans bacterial strains. Each ageing process leads to crosslinking reactions, much surface oxidation of the films and the production of hundreds of short chain compounds. These degradation products present a high level of unsaturation and oxidation and can be released into water to become potential substrates for microorganisms. Both strains were able to degrade from 0.2 to 1.2 % (% ThOD) of the aged SBR film after 30-day incubation while no biodegradation was observed on the pristine material. A 25-75 % decrease in the signal intensity of water extractable compounds was observed, suggesting that biomass production was linked to the consumption of low-molecular-weight degradation products. These results evidence the positive impact of abiotic degradation on the biodegradation process of styrene butadiene rubber.

Characteristics, fate, and impact of marine plastic debris exposed to sunlight: A review.

The increase of plastic production from the middle of the twentieth century was inevitably followed by an increase in the amount of plastic dumped in the natural environment. There, the plastic debris are exposed to sunlight, temperature, humidity, and physical stress. This can induce photo-oxidative and thermal degradation. This review discusses the mechanism of plastics UV weathering and its characteristics. Comparison of the photodegradation rate and physico-chemical properties are made according to the weathering mode (natural/accelerated) and medium (air/water). Since the photodegradation can lead to plastics fragmentation, this phenomenon is described along with the methodologies used in literature to evaluate the fragmentation. The impact of the photodegraded plastic debris on the marine environment is also presented in term of (i) photodegradation products and stabilizers leakage, (ii) organic pollutants accumulation, transfer, and leakage, and (iii) toxicity on marine organisms.

New insights into the mechanism of photodegradation of chitosan.

Chitosan films were subjected to accelerated artificial weathering at λ>300 nm and 60 °C in the presence of O2. The resulting variations in the chemical structure were characterized by IR spectroscopy and UV-vis spectroscopy, and a photooxidation mechanism was proposed based on the identified oxidation photoproducts. The formation of gluconolactone derivatives leading to chain scissions was shown. In addition, low molecular weight photoproducts, which accounted for chitosan deacetylation, were detected. Furthermore, crosslinking reactions occurred, as revealed by gel fraction characterization. Variations in the mechanical and surface properties were characterized by AFM, and the reduction in macroscopic properties was correlated with the structural changes observed at the molecular scale by a multiscale approach.

Experimental evidence of plastic particles transfer at the water-air interface through bubble bursting.

Plastic debris in the marine environment are the subject of an extensive literature. According to studies dedicated to the determination of plastic litter abundance and to the characterisation of degradation and fragmentation processes, models were used to estimate the global plastic debris abundance and to simulate their transfer and distribution. Despite these efforts, there is still missing plastic in the models used as areas exist where plastic abundance is less than that estimated. In parallel, microplastics presence in the atmosphere and in remote areas was confirmed suggesting long range atmospheric transport. Potentially addressing both these issues, recent literature suggests that microplastics (MPs) and nanoplastics (NPs) can be transferred from the marine environment to the atmosphere via the bursting of air bubbles at the sea surface. Nevertheless, to date there is no direct evidence of this transfer. In this study, we evaluate plastic particles transfer as a function of MPs/NPs characteristics and water composition by simulating the bubble bursting phenomenon in a laboratory reactor. Size distribution of transferred particles were recorded, and their plastic nature was confirmed using electron microscopy. Results show that under tested conditions, the transfer is possible but limited to particles smaller than 1 µm. The influence of the presence of proxies of components of the sea surface microlayer in the water was evaluated showing a higher particle transfer rate in the presence of a surfactant (sodium dodecyl sulfate) and no significant effect of polysaccharides (xanthan gum and dextran). The surface state of the particles can alter their behaviour in the aqueous phase and thus their transfer to the atmosphere. The effect of bubble size was also evaluated showing a higher transfer rate with the smaller bubble size. In addition, experiments performed with grounded polyethylene (PE) samples showed higher transfer for UV-aged PE than for pristine PE.

Corrigendum: Dispersion and Stabilization of Exfoliated Graphene in Ionic Liquids.

[This corrects the article DOI: 10.3389/fchem.2019.00223.].

Dispersion and Stabilization of Exfoliated Graphene in Ionic Liquids.

The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. Because ionic liquids can be easily obtained with chosen molecular structures and tuneable physicochemical properties, they can be use as media to optimize the exfoliation of graphite. The understanding of the interactions involved between graphite and various chemical functions in the solvent ions will be helpful to find liquids capable of dissociating and stabilizing important quantities of large graphene layers. After a step of sonication, as a mechanical precursor, samples of suspended exfoliated graphene in different ionic liquids have been characterized experimentally in terms of flake size, number of layers, total concentration and purity of the exfoliated material. Nine different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate anions have been tested. UV-vis, Raman and X-ray photoelectron in addition to high resolution transmission electron and atomic force microscopy have been selected to characterize suspended exfoliated graphene in ionic liquids. The number of layers in the flakes exfoliated, the size and concentration depend of the structure of the ionic liquid selected. In order to obtain large flake sizes, ionic liquids with bis(trifluoromethylsulfonyl)imide anions and a cation with an alkyl chain of medium length should be selected. Smaller cation and anion favors the exfoliation of graphene. The exfoliation caused the formation of C-H bonds and the oxidation of the graphitic surface.

Thin bacteria/Layered Double Hydroxide films using a layer-by-layer approach.

This paper reports the design of thin bacteria/Layered Double Hydroxides (LDH) films in which bacterial cells of Pseudomonas sp. strain ADP were assembled alternatively with Mg2Al-NO3 LDH nanosheets by a layer-by-layer deposition method. The UV-Vis spectroscopy was used to monitor the assembly process, showing a progressive increase in immobilized bacteria amount upon deposited cycles. The {ADP/LDH}n film was characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy and atomic force microscopy. The metabolic activity of immobilized bacteria was determined using chronoamperometry by measuring the biochemical oxygen demand in presence of glucose using an artificial electron acceptor (Fe(CN)6(3-)) at 0.5V/Ag-AgCl. A steady current of 0.250µAcm(-2) was reached in about 30s after the addition of 5mM glucose.

Water as a morphological probe to study polymer-filler interfaces: an original application of thermoporosimetry.

This paper is devoted to the characterization of polymer-filler interfaces by thermoporosimetry using water as a probe. Composites of EVA filled with aluminium hydroxide with high filler content for the required fire retardant properties have been studied. After water sorption at 90 °C, the composites have been analyzed by thermoporosimetry using water as a morphological probe. This technique first allowed studying the influence of the filler content and the specific surface area on the water uptake. The study with drying steps and two molecular probes (water and cyclohexane) has highlighted that water is confined at the interface and thus thermoporosimetry is a powerful tool to characterize interfaces in EVA-ATH composites.

Photooxidation of cellulose nitrate: new insights into degradation mechanisms.

Cellulose nitrate (or nitrocellulose) has received considerable interest due to its uses in various applications, such as paints, photographic films and propellants. However, it is considered as one of the primary pollutants in the energetic material industries because it can be degraded to form polluting chemical species. In this work, the UV light degradation of cellulose nitrate films was studied under conditions of artificially accelerated photooxidation. To eliminate the reactivity of nitro groups, the degradation of ethylcellulose was also investigated. Infrared spectroscopy analyses of the chemical modifications caused by the photooxidation of cellulose nitrate films and the resulting formation of volatile products revealed the occurrence of de-nitration and the formation of oxidation photoproducts exhibiting lactone and anhydride functions. The impact of these chemical modifications on the mechanical and thermal properties of cellulose nitrate films includes embrittlement and lower temperatures of ignition when used as a propellant.

Photochemical behavior of polylactide/ZnO nanocomposite films.

This study reports the effect of light on PLA/ZnO nanocomposites films produced by melt-extrusion. The attention focused on the discrimination between the photocatalytic degradation of PLA provoked by ZnO and the UV screening effect of the ZnO nanoparticles. The chemical modifications of PLA induced by UV light irradiation were analyzed using infrared spectroscopy and completed through the analysis of the low-molecular-weight photoproducts using IC and SPME and the characterization of chain scissions with SEC. A comprehensive mechanism for the photooxidation of PLA was then proposed. The results indicated that the photocatalytic activity of ZnO nanoparticles induces the oxidation of PLA. Because ZnO limits the penetration of light inside the samples, this effect mainly concerns the first micrometers at the surface of the exposed samples. Cross-sectional analysis using micro-IR and ATR-IR spectroscopies was performed to highlight the degradation profile in the PLA/ZnO nanocomposites.

Effect of ZnO nanofillers treated with triethoxy caprylylsilane on the isothermal and non-isothermal crystallization of poly(lactic acid).

The crystallization of PLA-silane surface-treated ZnO nanocomposites was investigated by DSC and compared to that of neat PLA. Several modes of crystallization were considered: isothermal and non-isothermal cold crystallization and also isothermal and non-isothermal melt crystallization. The kinetics of cold crystallization were studied using different methods, namely the Avrami and Ozawa-Flynn-Wall models, to calculate activation energies and kinetic constants. In contrast to what is typically observed when the foreign particles are added in a polymer matrix, the silane surface-treated ZnO delayed the crystallization of PLA and made it more difficult to start. The nucleation activity of the ZnO nanoparticles, ϕ, was calculated and found to be greater than 1 (ϕ = 1.7). This indicated that ZnO played an anti-nucleating role in the crystallization of PLA nanocomposites. This effect has been linked mainly to the interactions between the silane groups onto the surface of nanoparticles and PLA macromolecules. These interactions which reduce the mobility of polymer chains have been evidenced by rheological experiments.

Multiscale investigation of the poly(N-vinylcarbazole) photoageing mechanism.

During the past decade, the development of polymeric solar cells has received a great deal of attention from both academic and industrial laboratories. In order to enhance the device performances both in terms of power conversion efficiency stability in use conditions, Polycarbazole copolymers have attracted increasing attention. In this paper, the photodegradation of poly(N-vinylcarbazole) (PVK) was investigated from the molecular scale to the nanomechanical properties. It was shown irradiation provoked chain scissions, homolysis of the C-N bond and formation of new covalent bonds between the macromolecular chains. To fully understand the mechanism of the degradation of PVK provoked by exposure to UV radiation, mechanical analyses were performed. The consequences of the cross-linking reactions on the surface modifications were analyzed. Roughness and stiffness measurements were obtained through surface analysis and nanoindentation by atomic force microscopy (AFM), and depth-profiling experiments were also performed. The surface modifications and the shape of the profiles of the degradation photoproducts were explained in light of the chemical modifications of the PVK structure. Quantitative correlations were successfully obtained between the main relevant criteria of degradation, from the chemical structure to the mechanical properties. It was found that cross-linking reactions were prevalent.

Effect of low doses of 14 MeV neutrons on polymers.

The structural modifications of polymers irradiated with 14 MeV neutrons were studied. Two elastomers, a polypropylene-type polymer and poly(ethylene oxide) were exposed to low doses of fast neutrons in the range of 0.3-14 Gy. The radiation damages were observed at the molecular scale by infrared spectroscopy. The morphological changes were investigated by steric exclusion chromatography, insoluble fraction measurements, differential scanning calorimetry and X-ray diffraction. It was found that neutrons provoked oxidation processes accompanied by modifications in the polymer architecture, including chain scissions, crosslinking reactions and changes in the crystallinity. Moreover, the conventional antioxidants were shown to be inefficient in inhibiting the aging of the polymers. These results also suggest that the radiation damages could be used successfully for dosimetry applications using an easily implementable protocol.

Effect of a spreading adjuvant on mesotrione photolysis on wax films.

There is little information about pesticide photostability on plants, especially when considering the effects of the formulation. We evaluated the photostability of a herbicide, mesotrione, on wax films. These surfaces are good systems to mimic the outer layer of the leaf. Within the range of recommended agricultural rates, pure mesotrione half-life on cuticular wax films was between 100 and 160 min. Formulated, the phototransformation rate was multiplied by a factor of 4.8. We assume that the acceleration is mainly due to the surfactants, agents that allow a better spreading of the active ingredient at the leaf surface. Since mesotrione photolysis is a fast process on wax films, we can assume that this process would be significant in the field after treatment.