Effect of atmospheric pressure on ozone cracking of rubber

Ozone chamber testing of rubbers occupies a prominent place in the field of polymeric degradation testing. In such testing the rate of ozone cracking of rubber vulcanizates is a function of the rate of collision of ozone molecules with the rubber surface, all other factors constant. However, the conventional mode of expression of the ozone concentration in chamber testing is on a volume O₃ per volume air basis, i.e. parts O₃ per hundred million (10⁸) air by volume, abbreviated by pphm.In this paper we show that at equal ozone concentrations expressed as pphm, cracking rate is a function of the ambient atmospheric pressure (in the chamber). Thus variations in ozone test results may occur in intra- or inter-laboratory testing if ambient atmospheric pressure at the time or place of test is sufficiently different. A mode of expression that avoids this is recommended, i.e. the partial pressure of O₃ in mPa.     

Radiation-Chemical Formation of Ozone in an Oxygen-Containing Gas Atmosphere

The process of ozone formation in an oxygen-containing gas atmosphere by the action of ionizing radiation was studied. A kinetic model of the process was constructed for the O₂–N₂ system. The effects of the main parameters of radiolysis on the O₃ formation rate were analyzed. The atmospheric emission of ozone from industrial-scale power units that employ electron-beam flue gas cleaning of harmful impurities was evaluated from the standpoint of its conceivable favorable effect on the Earth ozone layer.     

Surface degradation of poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene) terpolymer by ozone in water

Saturated olefinic rubbers have been widely used as materials for not only municipal waterworks, but also for household uses. As a sanitizing agent for water, chlorine will be replaced by ozone in the near future from an environmental point of view. However, the ozone treatment in water seriously damages saturated olefinic rubbers, which are necessary for the infrastructure of daily life. Here, we report the surface degradation of cross-linked poly(ethylene-co-propylene-co-5-ethylidene-2-norbornene) terpolymer (EPDM) by ozone treatment, both in water and air. We also discuss how the presence of water impacts the ozone oxidation of EPDM, resulting in macroscopic damage to EPDM.     

Oxidation profiles of thermally aged nitrile rubber

The thermal degradation of a commercial, stabilized, unfilled nitrile (Buna-N) rubber material was investigated at temperatures in the range 85–140 °C. The resulting heterogeneous oxidation, due to diffusion limitations in oxygen availability, was studied using infrared microscopy and modulus profiling. Degradation-related spectral changes were observed primarily in the hydroxyl, carbonyl and ester regions; quantitative analysis revealed identical oxidation profiles for these chromophores. These chemical oxidation profiles (carbonyl formation) were correlated with mechanical modulus (hardness) profiles. Degradation of the sample proceeds via a linear increase in the carbonyl concentration, but an exponential increase in the modulus with time. It is concluded that the profile development and aging behavior can be described by a diffusion-limited autoxidation mechanism which can be modeled computationally. The results are compared to those of a previously studied carbon-black-filled material.     

Ionizing-Radiation Ignition of a Hydrogen–Air Mixture

The behavior of a hydrogen–air mixture under the action of ionizing radiation was studied. A kinetic model for radiation-chemical processes in the H₂–O₂–N₂ system was constructed, and the effects of the main parameters of radiolysis on shifting its flammability limits were analyzed. It was found that, under normal conditions (p = 0.1 MPa, T ₀ = 300 K), the ignition of the stoichiometric mixture began at a radiation intensity of about 0.1 kGy/s. The induction period of the chain H₂ oxidation reaction shortened with increasing radiation dose rate and pressure.     

Investigation on the effects of beta and gamma irradiation on conducting polymers for sensor applications

Two conductive polymers were evaluated to be the active materials in a sensor device for the detection of beta radiation. This was accomplished by characterizing the changes in conductivity of electrically conducting polymer films caused by exposure to tritium gas for varying lengths of time. The behavior of these materials when exposed to gamma radiation was also studied to gain further insight into the mechanism of conductivity degradation by ionizing radiation. Two types of conductive polymer, polyaniline (PANi) and poly(3,4-ethylenedioxythiophene) (PEDOT), were chosen as candidate materials for their widespread commercial use. The change of surface resistance (conductivity) of PANi and PEDOT films when exposed to gamma radiation in both air and deuterium environments was evaluated as well as tritium exposures in 10⁴ and 10⁵ Pa gas. Raman and absorbance spectra of gamma irradiated samples were obtained to determine the mechanism of conductivity degradation in both polymers. Post-irradiation gas analysis of the samples contained in deuterium revealed very little (or no) hydrogen in the containment vessel, indicating that hydrogen–deuterium isotopic exchange was not responsible for the decrease in surface conductivity due to gamma exposure. The effects of irradiation-induced oxidation were also studied for both conductive polymers during gamma irradiation. It was concluded that chain scission via free radical formation and chain cross-linking are most likely the two dominant mechanisms for conductivity change and not de-protonation of the polymer.     

Radiation-chemical treatment of flue gases from thermal power stations for the removal of mercury vapor

The efficiency of radiation-chemical treatment of flue gases from thermal power stations for removing nitrogen and sulfur oxides was examined as applied to the removal of mercury vapor from the gases. A kinetic scheme of the process was developed. It involves the liquid-phase oxidation of Hg by O₃ molecules formed under the action of ionizing radiation on the gas macrocomponents followed by adsorption of the oxidation products at soot particles. It was found that almost complete removal of mercury vapor is attained at typical radiation doses and soot concentrations in the flue gases.     

Corona Above Water Reactor for Systematic Study of Aqueous Phenol Degradation

A small batch reactor is developed to study the removal of phenol from a thin layer of water by creating pulsed corona discharges above the water. Pulses of up to 40 kV are applied with a duration of ~50 ns and an energy of ~60 mJ. In this CAW (Corona Above Water) reactor an ozone yield of upto 90 g/kWh is obtained in ambient air. The phenol degradation is 48 g/kWh, using a 1 mM initial concentration in demineralized water. The degradation yield increases to almost 100 g/kWh by adding to the water either H₂O₂ or Fe₂SO₄ or NaOH. The first two additions are considered to increase to amount of OH radicals. In the case of NaOH addition it is observed that much more ozone dissolves in the water. The addition of the OH scavenger t-butanol shows that in most cases the main oxidation route of phenol in the CAW reactor is direct ozone attack.     

Effect of degradation on electronic properties of polymer solar cells

We present here the effect of degradation on electronic properties of polymer solar cells. Investigations were performed on two types of solar cells based on the bulk‐heterojunction network of poly(3‐hexylthiophene) and phenyl [6,6] C₆₁ butyric acid methyl ester, one with slow degradation whereas other with faster degradation. Samples were prepared in identical conditions with controlled atmosphere, but for faster degradation, one of the samples was exposed to ambient air (rich in O₂ and H₂O molecules) before deposition of top metal electrode. The sample with slow degradation showed linear degradation in short circuit current density (J_sc), whereas the sample with faster degradation exhibited exponential degradation in J_sc. Linear degradation happens due to degradation in the active layer only whereas the exponential degradation is because of through degradation of the solar cell. The effect of degradation is investigated on different diode parameters. Because of different degradation processes in the two samples, the variations in diode parameters with time are different. Copyright © 2013 John Wiley & Sons, Ltd.     

Thermal degradation of poly(acrylic acid) containing metal nitrates and the formation of YBa2Cu3O7−x

The use of polymers containing metal salts as ceramic high‐temperature superconductor (HTSC) precursors may provide a relatively simple and rapid method for producing materials that can take advantage of advanced polymer processing and then be pyrolyzed to HTSCs. The mechanisms of thermal degradation in these precursors, which have not been characterized, can be used to optimize the pyrolysis conditions for HTSC production. This article describes the degradation of a precursor based on poly(acrylic acid) (PAAc) containing yttrium, barium, and copper nitrates in the proportions needed for the formation of the HTSC YBa₂Cu₃O_7?x (YBCO). This article also describes the effects of the pyrolysis process on the resulting materials. The degradation of the precursor is a complex, multistage process. The presence of the metal ions and HNO₃ reduces the thermal stability of PAAc and increases the degradation rate. The results indicate that the initial stages of the pyrolysis should be conducted in argon or nitrogen to inhibit BaCO₃ formation and that the final stages should be conducted in air/oxygen to enhance oxidation. Optimization of the pyrolysis conditions produces a YBCO film with minimal contamination. © 2005 Wiley Periodicals, Inc. J PolymSci Part B: Polym Phys 43: 1168–1176, 2005     

Study on catalytic mechanisms of Fe3O4-rGOx in three typical advanced oxidation processes for tetracycline hydrochloride degradation

This study explored the catalytic mechanism and performance impacted by the materials ratio of Fe₃O₄-GO_x composites in three typical advanced oxidation processes (AOPs) of O₃, peroxodisulfate (PDS) and photo-Fenton processes for tetracycline hydrochloride (TCH) degradation. The ratio of GO in the Fe₃O₄-GO_x composites exhibited different trends of degradation capacity in each AOPs based on different mechanisms. Fe₃O₄-rGO_20wt% exhibited the optimum catalytic performance which enhanced the ozone decomposition efficiency from 33.48% (ozone alone) to 51.83% with the major reactive oxygen species (ROS) of O₂^??. In PDS and photo-Fenton processes, Fe₃O₄-rGO_5wt% had the highest catalytic performance in PDS and H₂O₂ decomposition for SO₄^??, and ^?OH generation, respectively. Compared with using PDS alone, PDS decomposition rate and TCH degradation rate could be increased by 5.97 and 1.73 times under Fe₃O₄-rGO_5wt% catalysis. In the photo-Fenton system, Fe₃O₄-rGO_5wt% with the best catalyst performance in H₂O₂ decomposition, and TCH degradation rate increased by 2.02 times compared with blank group. Meantime, the catalytic mechanisms in those systems of that the ROS produced by conversion between Fe²⁺/Fe³⁺ were also analyzed.     

Effects of ultraviolet radiation on aqueous polyelectrolyte solutions

The effects of ultraviolet radiation on dilute aqueous solutions of poly(acrylic acid) and of other polyelectrolytes were studied by viscosity measurements in connection with the effects of ionizing radiation. It was found that ultraviolet light of wavelength below about 2300 Å brought about degradation of polymer chains mainly by indirect action via water, while light of wavelength above 2300 Å caused degradation by direct action in some polymers. It was deduced from the experiments that the protective effect of NaCl could be largely attributed to a decrease in the indirect action. It was also found that a low concentration of methanol was effective in preventing degradation by direct action, although methanol promoted degradation when present in high concentration. Since the promotive effect was not observed when light of wavelength below 3700 Å was eliminated by a filter, this effect was attributed to active products of the irradiation of methanol.     

Direct Evidence for a Peroxide Intermediate and a Reactive Enzyme–Substrate–Dioxygen Configuration in a Cofactor‐free Oxidase

Cofactor‐free oxidases and oxygenases promote and control the reactivity of O₂ with limited chemical tools at their disposal. Their mechanism of action is not completely understood and structural information is not available for any of the reaction intermediates. Near‐atomic resolution crystallography supported by in crystallo Raman spectroscopy and QM/MM calculations showed unambiguously that the archetypical cofactor‐free uricase catalyzes uric acid degradation via a C5(S)‐(hydro)peroxide intermediate. Low X‐ray doses break specifically the intermediate C5? OO(H) bond at 100 K, thus releasing O₂ in situ, which is trapped above the substrate radical. The dose‐dependent rate of bond rupture followed by combined crystallographic and Raman analysis indicates that ionizing radiation kick‐starts both peroxide decomposition and its regeneration. Peroxidation can be explained by a mechanism in which the substrate radical recombines with superoxide transiently produced in the active site.     

Radiation degradation susceptibility of vinyl polymers: Nitriles and anhydrides

The effect of γ irradiation on a series of vinyl polymers, which included polymethacrylonitrile, poly(α-chloroacrylonitrile), poly(dimethyl itaconate), poly(acrylic anhydride), and poly(methacrylic anhydride), was studied as part of a program to develop improved positive lithographic resists. Radiation-induced degradation was observed for polymethacrylonitrile, poly(α-chloroacrylonitrile), and poly(methacrylic anhydride). Molecular weight degradation as a function of dose was monitored by membrane osmometry or GPC techniques. For γ-irradiated poly(dimethyl itaconate) and poly(acrylic anhydride) crosslinking was found to predominate over chain scission. [G(s)–G(x)] values, calculated from molecular weight inverse versus dose curves, indicate that both nitrile polymers degraded more efficiently than a poly(methyl methacrylate) reference standard on the basis of M _n changes. The radiation behavior of the first three polymers confirms earlier findings than vinyl polymers with quaternary carbons predominantly degrade when subjected to ionizing radiation.     

Enzyme‐Inspired Room‐Temperature Lithium–Oxygen Chemistry via Reversible Cleavage and Formation of Dioxygen Bonds

Li‐O₂ batteries are promising energy storage systems due to their ultra‐high theoretical capacity. However, most Li‐O₂ batteries are based on the reduction/oxidation of Li₂O₂ and involve highly reactive superoxide and peroxide species that would cause serious degradation of cathodes, especially carbon‐based materials. It is important to explore lithium‐oxygen reactions and find new Li‐O₂ chemistry which can restrict or even avoid the negative influence of superoxide/peroxide species. Here, inspired by enzyme‐catalyzed oxygen reduction/oxidation reactions, we introduce a copper(I) complex 3 N‐Cu^I (3 N=1,4,7‐trimethyl‐1,4,7‐triazacyclononane) to Li‐O₂ batteries and successfully modulate the reaction pathway to a moderate one on reversible cleavage/formation of O?O bonds. This work demonstrates that the reaction pathways of Li‐O₂ batteries could be modulated by introducing an appropriate soluble catalyst, which is another powerful choice to construct better Li‐O₂ batteries.     

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO2 Capture from Air: Roles of Atmospheric Water

Direct air capture (DAC) processes for extraction of CO₂ from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al₂O₃, is explored in detail. By combining CO₂ adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with ¹⁸O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.     

Structure Selectivity of Alkaline Periodate Oxidation on Lignocellulose for Facile Isolation of Cellulose Nanocrystals

Reported here for the first time is the alkaline periodate oxidation of lignocelluloses for the selective isolation of cellulose nanocrystals (CNCs). With the high concentrations as a potassium salt at pH 10, periodate ions predominantly exist as dimeric orthoperiodate ions (H₂I₂O₁₀^4?). With reduced oxidizing activity in alkaline solutions, dimeric orthoperiodate ions preferentially oxidized non‐ordered cellulose regions. The alkaline surroundings promoted the degradation of these oxidized cellulose chains by β‐alkoxy fragmentation and generated CNCs. The obtained CNCs were uniform in size and generally contained carboxy groups. Furthermore, the reaction solution could be reused after regeneration of the periodate with ozone gas. This method allows direct production of CNCs from diverse sources, in particular lignocellulosic raw materials including sawdust (European beech and Scots pine), flax, and kenaf, in addition to microcrystalline cellulose and pulp.     

Synergetic effect of ozone and ultrasonic radiation on degradation of chitosan

Under conditions of continuous ozone gas application and constant ultrasonic radiation (UR), chitosan was effectively degraded. The existence of a synergetic effect of ozone and ultrasonic radiation on the degradation of chitosan was demonstrated by means of determination of viscosity-average molecular weight. The efficiency of the ozone and ultrasonic radiation treatment compared with acid hydrolysis on degradation of chitosan was investigated. In addition, the structure of the degraded chitosan was characterized by FT-IR and ¹³C NMR spectral analyses. The whole initial chitosan's monomer structure still existed in the resulting degraded chitosan with different low molecular weight. The pilot study of the chemical stability of the degraded chitosan was carried out. There was no significant change of the total degree of deacetylation (DD) of degraded chitosan compared with the initial chitosan. The combined O₃/UR technique is promisingly suitable for scale-up manufacture of low-molecular-weight chitosan.     

Degradation of poly(3-hydroxybutyrate) and its blends during treatment with UV light and water

The degradation of films of poly(3-hydroxybutyrate) and its blends with ethylene-propylene rubber during their treatment with water and UV radiation at 20 and 90°C is studied. Changes in the structural characteristics of both components during degradation are investigated via DSC, IR spectroscopy, and optical microscopy. It is shown that pure poly(3-hydroxybutyrate) features the highest weight loss during degradation in distilled water at 20°C. In the case of the blends, the most significant changes in the structures of the components are observed for the 50: 50 (wt %) sample.     

Oxidation of Acetylene in Atmospheric Pressure Pulsed Corona Discharge Cell Working in the Nanosecond Regime

Combined experimental and modeling studies of acetylene oxidation in pulsed corona discharges working in the nanosecond regime are presented. The corona cell was characterized in term of power deposition to provide input data for the model. The concentrations of ozone, CO, CO₂ and residual acetylene were systematically measured for model validation purposes. The model used allows describing the detailed chemistry in the discharge and the mass transfer between the microdischarges and the discharge free regions in the corona cell. Results showed that the model allows a satisfactory prediction of the acetylene residual fraction, CO and CO₂ yields and O₃ concentration for a wide range of conditions. They enabled a precise identification of the product distribution and confirmed the central role of O-atom in the oxidation process. They also revealed that ketene, H₂CCO, plays an important role in the oxidation mechanism and allowed drawing some conclusions on the optimization of the oxidation process.