Spatial resolution of degradation in stabilized polystyrene and polypropylene plaques exposed to accelerated photodegradation or heat aging

Spatial resolution of photo and thermooxidation processes in polypropylene (PP) and polystyrene (PS) plaques was studied by electron spin resonance imaging (ESRI) and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR FTIR). Polymer plaques made of PP and PS stabilized with various systems based on hindered amine stabilizers (HAS) were exposed to accelerated photodegradation and to heat aging in air atmosphere. Concentration profiles of nitroxides generated during the degradation process in the plaques were measured by ESRI, carbonyl and hydroxy groups were identified by ATR FTIR, transparency of the plaques in the actinic part of solar radiation, including a part of UV-B (295-315 nm), full range of UV-A (315-400 nm) and visible radiation was measured by optical techniques. A mechanism of the degradation consistent with all experimental data is suggested.     

Development of positron annihilation spectroscopy to test accelerated weathering of protective polymer coatings

A variable mono-energetic positron beam with a computer-controlled system has recently been constructed at the University of Missouri–Kansas City for weathering studies of polymeric coatings. The beam is designed to measure the S-parameter from Doppler-broadening energy spectra and the sub-nanometer defect properties from positron annihilation lifetimes (PAL). Significant variations of S-parameter and ortho-positronium intensity in coatings, as obtained from the newly built beam and from the Electrotechnical Laboratory’s beam, respectively, are observed as a function of depth and exposure time due to the Xe-light irradiation. A high sensitivity of positron annihilation signal response to the early stage of degradation is observed. Development of positron annihilation spectroscopy to test accelerated weathering of polymeric coatings is discussed.     

GC/MS studies on revealing products and reaction mechanism of photodegradation of pesticides

The photolytic degradation of frequently applied s-triazine type pesticides was investigated. A special, immersible UV-light source was applied in order to carry out photodegradation. The degradation processes were followed by TLC, GC and GC/MS techniques. Following the irradiation of the sample, the degradation products were isolated by SPE column chromatography. EI mass spectrometry was used to identify the degradation species.All four of the different s-triazine type pesticides studied underwent photolytic decomposition. The kinetic aspect of photodegradation of prometryn, terbutryn, simazine and atrazine was revealed completely, while in case of prometryn and terbutryn a detailed mechanism of photolytic transformation was established. Four degradation species were detected, as a consequence of two parallel ways of degradation. Both pesticides suffered the loss of thio-methyl groups prior to cleavage of the alkyl groups. Deamination did not occur under the conditions applied. The kinetic behaviour with respect to photodegradation displayed significant differences when comparing the decomposition of s-triazine type pesticides: prometryn decomposed 10 times faster than terbutryn.     

Studies on photostability of butyrylated, milled wood lignin using spectroscopic analyses

Photo-stabilisation of butyrylated milled wood lignin (MWL) was investigated in this study. Chemical changes were confirmed by NMR and FT-IR spectra after butyrylation. Improvements in the photostability of MWL by butyrylation were evaluated by spectral analyses including ESR, FT-IR and UV-VIS spectra. From ESR analyses, butyrylation reduces the amount of phenoxyl free radicals of MWL after UV irradiation, which results in inhibiting the photo-oxidation of lignin followed by a significant decrease in the formation of colored chromophores. The carbonyl, carboxyl and quinonoid structures were less detected in the butyrylated MWL after UV irradiation than those of untreated MWL, and the content of degraded water-soluble materials from the photo-degradation of MWL was also reduced upon butyrylation.     

The efficacy of photostabilizers on the color change of wood filled plastic composites

In this study, we compared the performance of different hindered amine light stabilizers and ultraviolet absorbers as photostabilizers of wood plastic composites (WPC). We showed how their functional groups and molecular weights influence the photostabilization of WPC subjected to natural weathering for 2000 h. The changes were followed using color measurements and FTIR spectroscopy which provided insight into the photodegradation mechanism of weathered WPC.The results indicate that weathering causes color fading and changes in yellowing. We propose that WPC undergo two competing redox reactions upon UV exposure. The first is the oxidation of lignin which leads to the formation of paraquinone chromophoric structures which is dominant in the first 250 h of exposure. The second is the reduction of the paraquinone structures to hydroquinones which leads to photobleaching.High molecular weight diester HALS were found to be the most effective in controlling long term fading and yellowing changes. Furthermore, the addition of a benzotriazole ultraviolet absorber shows great synergism in controlling fading when added to a diester HALS.     

Photodegradation of polyglycidol in aqueous solutions exposed to UV irradiation

The photodegradation of polyglycidol in aqueous solution with UV wavelength of 254 nm was investigated. The experiments were carried out in air at a constant temperature and the photodegradation of polyglycidol (PGl) was compared to that of poly(ethylene oxide) (PEO), the most widely studied polyether. Size exclusion chromatography with multiangle light scattering detection (SEC-MALLS) was used to measure the changes in the molar masses and molar mass dispersities of polymers during degradation. The molar mass of PGl decreased dramatically during the first period of UV irradiation and then gradually approached a limiting value of 17,000 g/mol, regardless of the initial polymer concentration. PEO was less sensitive to UV irradiation than polyglycidol however, both polymers degrade mainly via chain scission. The degradation of PGl and PEO leads to acidification of their water solution. The photooxidation products were analyzed by FTIR and NMR spectroscopy and the spectrophotometric results revealed that the irradiation of the polymers led to the formation of carbonyl groups in the macromolecular chains. A mechanism accounting for the main routes of PGl photooxidation is proposed.     

Correlations between structure and accelerated artificial ageing of XLPE

The elucidation of the structural and morphological changes that occur during the crosslinking of polyethylene and the correlation of these changes with the physical, chemical and ageing resistance is very important to forecast the properties and the performance of the final material.The accelerated ageing of XLPE samples with various degrees of crosslinking has been carried out using two types of artificial weathering equipments, with UV or Xenon light bulbs with different cycles of temperature and humidity, varying time of exposition for both systems. The changes in the properties of the materials have been analyzed by Tensile Tests, Scanning Electron Microscopy (SEM), Dynamic-Mechanical Analysis (DMA), X-Ray Diffraction (XRD). The main degradation effects for each level of crosslinking is presented for the pristine XLPE.     

Factors influencing the photostability of reactive dyes in polymers

This paper examines several important factors that are believed to affect the photostability of reactive dyes in polymer substrates. The light stability of the dye-polymer covalent bond was found to be influenced by several factors such as the nature of the dyeing process, the nature of the polymer and humidity. In the former the presence of residual washing powder played and important role, whereas in the latter two, although photohydrolysis occurred to a greater extent in nylon 6,6 than in cellulose, humidity had an important influence only in a cellulose environment. In agreement with these findings the presence of a hydroxy radical trap, potassium thiocyanate, inhibited photohydrolysis in cellulose, whereas the presence of an electron trap, cadmium sulphate, inhibited photohydrolysis in nylon 6,6.On the other hand, the influence of the covalent bond on photofading of the dyes was found to be variable. However, the presence of the reactive triazinyl group appeared to stabilise the dye.     

Gas chromatographic method for studying the rate of photodegradation of some nitrogen-containing pesticides

Summary The photodegradation behaviour of 12 nitrogen-containing herbicides (atrazine, cyanazine, terbuthylazine, terbutryn, EPTC, buthylate, molinate, cycloate, vernolate, fenuron, chloroxuron, and methabenzthiazuron) has been examined. The compounds were degraded completely when exposed to a mercury-vapour lamp; the degradation process was followed by consecutive GC measurements. All the compounds studied had measurable photochemical activity, although actual and average degradation rates varied significantly. All the compounds except terbutryn furnished more than one major degradation product, in different ratios. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Separation and Identification of Photolysis Products of Clothianidin by Ultra-Performance Liquid Tandem Mass Spectrometry

Photolysis of clothianidin by Xenon lamp was investigated by Ultra-Performance Liquid Chromatography Electrospray Ionization tandem mass spectrometry (UPLC-ESI/MS/MS). Quantitative study on the photodegradation of clothianidin found that the photodegradation obeyed first order kinetics (C = 9.9917e – 0.187^t, R² = 0.994). The half-life was about 3.6 hours. Qualitative study on photolysis products of clothianidin were taken by checking all total ion spectra of different sample time. A total of eight products was found in this study. The structure of each product was determined by the total ion spectrometry spectrum and daughter-scan spectrum. The mechanism of photodegradation of this pesticide included radical denitration, nucleophilic substitution, and rearrangement, ring-open, and ring-close. Through the analysis of the change of every product and the mass information, the photolysis pathway was drawn. From this study, products of V, VI, and VII seemed more stable than clothianidin.     

Comparison of two accelerated Nafion™ degradation experiments

This work describes a systematic investigation of the degradation of Nafion™ 112 membranes using a Fenton's accelerated aging experiment. Two variations of the experiment were compared: a solution method where iron ions and peroxide exist together in solution prior to the addition of Nafion™, and an exchange method where Nafion™ in the Fe²⁺ form is exposed to hydrogen peroxide. Accelerated aging experiments were conducted over 3-5 days. Weight loss, fluoride ion release, ion exchange capacity, intrinsic viscosity, morphological characteristics, and dimensional changes were measured. FTIR spectra, mechanical properties and membrane barrier properties were also investigated.     

Photodegradation study of some triazine-type herbicides

Triazines are amongst the most widely used herbicides. Since triazines can be found in many environmental compartments, their fate in ecosystems and the characterization of their degradation pathways in the environment are to be determined. In this paper we report on a study intended to investigate the photodegradation of some triazine-type herbicides: atrazine, cyanazine, terbuthylazine and terbutryn. The rate of photodegradation process was determined, and degradation schemes were outlined for the compounds studied. Moreover, experiments with different degrading energies were carried out in order to gain information about the effect of total degrading energy on the photodegradation process. The most significant processes of photodegradation of triazines are the partial or complete loss of side-chains, or rather the substitution of the heteroatom-containing side-chain to hydroxyl-group. Besides consecutive processes, loss of the different side-chains takes place parallely also, thus, different metabolites will be formed having mixed side-chains, until the cyanuric acid and 2-amino-4,6-dihydroxy-1,3,5-s-triazine are formed by losing all the side-chains. The presence of the dimer products could be detected during the degradation of all triazines. This proves the radical character of processes occurring during the photodegradation. Increasing the degradation energy (15 to 125 W) has raised the degradation rate by 2-5, and the chlorine containing metabolite—which was still present in the completely degraded mixture during the low-energy experiments—has completely disappeared from the mixture, thus, the increased degrading energy is favorable to the formation of less dangerous, nature identical metabolites.     

Toward developing accelerated stress tests for proton exchange membrane electrolyzers

Proton exchange membrane water electrolysis is technically the most suitable technology for the production of green hydrogen on a large scale. Although it is still more expensive than hydrogen produced from fossil sources, it has already been commercialized. Novel components with cost-effective materials and efficient manufacturing processes are being rapidly developed. However, these components must endure durability tests that can guarantee a lifetime of at least 50,000 operation hours. Consequently, there is an urgent need to develop accelerated stress test protocols based on a deep understanding of degradation mechanisms of stack components. Recent reports show that the main degradation mechanisms are associated to anode catalyst dissolution, membrane chemical decomposition, and formation of semiconducting oxides on the metal components. These mechanisms can be accelerated by stressors such as high current density, dynamic operation, and shutdown modes. On the basis of these reports and knowledge of the operational requirements for large-scale proton exchange membrane water electrolysis, we propose an accelerated stress test protocol for the fast evaluation of newly developed cost efficient and durable components.     

Investigation of polymer degradation by addition of magnesium

The effect of alkali metal magnesium on polymer degradation of physico-mechanical properties of radiation-vulcanized natural rubber latex (RVNRL) films was investigated. RVNRL films were prepared by the addition of Mg of different concentrations (0–30 ppm) to natural rubber latex and irradiation with various radiation doses (0–20 kGy). The radiation doses were optimized (12 kGy), and the adverse effect of Mg was studied against a reference film prepared without metal. Tensile strength, tear strength, and cross-linking density of the irradiated rubber films were decreased with increasing metal ion concentrations and decreasing radiation doses. The mechanical properties of the films were reduced by nearly 10% for 30 ppm Mg ions and at the optimum dose. In contrast, elongation at break, permanent set, and swelling ratio of the films were increased at the same conditions. The maximum tensile and tear strengths of irradiated rubber films without additive were 29.33 MPa and 47.95 N/mm, respectively, at a radiation dose of 12 kGy, and these values were about six times higher than those of blank samples. With the addition of Mg, the corresponding values decrease continuously, and the minimum values were found to be 26.35 MPa and 42.675 N/mm, respectively. The effect of divalent alkali metal on polymer chain scission can be explained by the classical electron concept reported in this article.     

Graphene quantum dot-phthalocyanine polystyrene conjugate embedded in asymmetric polymer membranes for photocatalytic oxidation of 4-chlorophenol

The feasibility of using π–π stacking as a means of fixing unsubstituted Zn phthalocyanine (ZnPc) to a support prior to formation of photoactive polymer asymmetric membranes was explored. Stable ZnPc–graphene quantum dot-polystyrene conjugates (6.15 μmol/g ZnPc loading) were synthesized and embedded in polystyrene membranes which proved to be photoactive with a singlet oxygen quantum yield of 0.43 in ethanol and 0.37 in water. The membranes also proved to be active in the photocatalytic oxidation of 4-chlorophenol in water where the reaction followed second-order kinetics. At 3.24 × 10^?4 mol L^?1, the photo-oxidation of 4-chlorophenol was observed with a k_obs of 35.9 L mol^?1 min^?1 and a half-life of 86 min.     

Enhancement of cellulose acetate degradation under accelerated weathering by plasticization with eco-friendly plasticizers

Cellulose acetate (CA) with a degree of substitution (DS) of 2.5 has been plasticized using eco-friendly plasticizers such as triacetin, tripropionin, triethyl citrate, tributyl citrate, tributyl 2-acetyl citrate and poly(ethylene glycol) of low molecular weight. Thermo-mechanical properties and hydrophilicity of the modified CA have been measured and correlated with the content and nature of the plasticizer used and compared with unplasticized CA. The increase in toughening and the change in the hydrophilicity by the plasticization were evaluated in terms of aging and weathering stability under accelerated conditions. Samples were exposed to UV-degradation with water spray periods. The treated samples were removed periodically and characterized by several analytical techniques. The results are discussed with particular emphasis toward the effects of plasticization on enhancement of the degradation rate of CA. The plasticization of CA triggered an increase of the weight loss between 50 and 90%, where low molecular weight plasticizers were shown to be more effective. A right balance between hydrophilicity and plasticization efficiency (reduction of T_g) is needed to increase the degradation rate of CA.     

Mesoscopic simulations of accelerated polymer drift in microfluidic capillaries

We use a mesoscopic simulation technique to study the transport of polymers in dilute solution flowing through a cylindrical tube. The simulations use an explicit solvent model to include all the relevant hydrodynamic couplings and a coarse grained ideal chain model for the polymers (appropriate for systems near the theta temperature). For the interactions between the solvent and the tube wall we use a novel method that ensures continuity of the stress at the interface. We show that the results for the polymer drift velocity are independent of the degree of coarse graining. Further, for the case where the size of the chains is small but not negligible compared to the tube radius, our results are in excellent agreement with experiment. However, they also show that in this regime, the "accelerated" drift, relative to the average solvent flow velocity, is described by the steric effect of the tube wall excluding the polymer center of mass from sampling the full cross section of the tube. Hydrodynamic interactions have a negligible influence in this regime. Consequently, the agreement between experiment and theories that approximates the former but includes the latter is fortunate. When the undisturbed polymer radius approaches or exceeds the tube radius, the hydrodynamic interactions do have a significant effect. They reduce the drift velocity, in qualitative agreement with theoretical predictions. The accelerated drift still approaches the maximum value, one would expect based on a Poiseuille flow but more slowly than if one neglects hydrodynamics. Finally, we propose an empirical fit that accurately describes data in the intermediate regime.     

Controlling the quality of testing

 This article mainly focuses on the testing of products, materials, etc., but the general principles are applicable in a broader perspective. Quality of testing should be judged based on fitness for purpose. This judgement includes both objective and subjective elements. The possibility to make decisions and other professional judgements based on test results alone is discussed and compared with the decisions and judgements being made through the certification and inspection process. Quality, including the uncertainty of the test results, depends on many factors, and in order to make necessary improvements in the testing procedures based on the customers' needs, the right issues should be addressed. The question arises as to whether, in laboratories' quality systems and in the accreditation and certification process, attention is really paid to those factors that are crucial to obtaining reliable results.     

Influence of functional nanoparticles on the photostability of polymer materials: Recent progress and further applications

The photochemical behaviour of polymer–nanoparticles/nanocomposites has been studied depending on the geometry of the nanofiller and an overview of the studies reported in the last decade is tentatively given. Depending on their functionality, nanoparticles can impact the durability of the nanocomposite materials under light irradiation. The behaviour to UV-light exposure in presence of oxygen of various types of nanocomposites with clays, LDH and carbon nanotubes has been investigated and recent progress on the influence of functional nanoparticles on the polymer photodegradation is reported. The influence of photocatalytic (ZnO and TiO₂) nanoparticles and phosphors on the photooxidation of the polymeric matrix and the durability of the material properties are characterized. From a general point of view, the stabilization strategy of polymer nanocomposites must be adapted depending on the nanofiller.     

Sound transmission testing of polymer compounds

Acoustic properties of polymer compounds are an important consideration for many applications. Currently, there are standard test methods for the determination of these properties. There is, however, no standard for the equipment used in these tests, only a specification for the test conditions. The objective of this work was to evaluate the operation and performance of a bench top laboratory sound testing system for its potential as a simple cost effective method for the initial evaluation of materials that require specific acoustic properties. The work was limited to an investigation of the property of sound transmission loss (STL). A study of the effect of the mounting conditions for the samples on the STL was carried out. Following this, a series of polymer and polymer composite samples was tested. The results presented demonstrate the potential for the testing system as an effective standard test method for the acoustic properties of polymer composites and other materials.