The application of organophosphorus flame‐retardants in epoxy resin

The influence of two novel aryl phosphate mixtures on fire retardancy and the thermal stability of epoxy resin were studied. Combustion behavior, decomposition pathway, and thermal and thermo‐oxidative degradation of the epoxy resin were examined by using the limiting oxygen index, vertical burning test (UL‐94), cone calorimeter test, thermogravimetric analysis, and thermogravimetry coupled with Fourier‐transform infrared spectroscopy. The morphology of the residues from the degradation of flame‐retarded epoxy resins was investigated by using scanning electron microscopy. Data from the cone calorimeter test demonstrated that the total heat evolved, heat release rate, and peak heat release rate decreased significantly when the epoxy resin contained these retardants. Moreover, a 20 wt% of both phosphate mixtures in the epoxy resin allowed for a satisfactory oxygen index (30–33%) and for UL‐94 V2 to be achieved. The condensed‐phase and gas‐phase actions of these aryl phosphate flame‐retardants are proposed as the mode of flame‐retardancy in epoxy resins. J. VINYL ADDIT. TECHNOL., 23:142–151, 2017. © 2015 Society of Plastics Engineers     

Physicochemical,Antioxidative, and Sensory Properties of Refined Rapeseed Oils

Physicochemical characteristics, antioxidant capacity (AC), and sensory quality of rapeseed oils available on the Polish market were analyzed and compared. The fatty acid composition (saturated fatty acids = 6.91–7.58%, monounsaturated fatty acids = 64.14–66.14%, and polyunsaturated fatty acids = 27.22–30.17%), color (T420 = 54.5–83.8%), amounts of free fatty acids (0.02–0.07%), primary (PV = 0.04–2.04 meq O₂ kg⁻¹) and secondary (AV = 1.02–3.21) oxidation products, phosphorus (0.38–1.62 mg kg⁻¹), chlorophyll (0.002–0.068 mg kg⁻¹), and polycyclic aromatic hydrocarbons (Σ4PAH = 0.00–2.50 μg kg⁻¹) in the commercial rapeseed oils meet the requirements of the European Food Regulation and Codex Alimentarius standards. Moreover, total phenolic content (TPC = 40.3–467.9 mg SA kg⁻¹) in the studied oils significantly differs from each other. However, the AC of rapeseed oils was analyzed using the novel iron oxide nanoparticle-based (IONP = 5552.1 − 18,510.2 μmol TE/100 g) method and the modified ferric reducing antioxidant power (FRAP = 55.7–280.3 μmol TE/100 g), cupric reducing AC (CUPRAC = 79.6–784.0 μmol TE/100 g), 2,2-diphenyl-1-picrylhydrazyl (DPPH = 185.7–516.7 μmol TE/100 g), and 2,2′-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS = 465.6–2142.6 μmol TE/100 g) assays. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied for discrimination of the refined rapeseed oils based on fatty acid composition, physicochemical parameters, AC, and sensory properties.     

Ultrastructural and developmental toxicity of potato and tomato leaf extracts to beet armyworm,Spodoptera exigua (lepidoptera: noctuidae)

Beet Armyworm, Spodoptera exigua is a herbivorous moth and a serious pest of many economically important plants, which are used as food sources. Because of rigorous standards of food quality, usage of synthetic insecticides in crop protection, against pests, is limited. Solanaceae plant extracts may be a relatively cheap source of efficient natural insecticides that can limit usage of synthetic substances. Their biological activity is not fully known. In particular, ultrastructural studies, using transmission electron microscopy, are not usual. In the present article we describe the effects of sublethal concentrations of tomato and potato leaf extracts against S. exigua. Acute lethal effects were not observed. Both extracts exerted similar effects within midgut and fat body cells. Midgut cells were not significantly altered while fat body cells showed prominent swelling of nuclear envelope and endoplasmic reticulum, vacuolization of mitochondria and fusion of fat droplets. These changes were much more intensive within groups exposed to potato than tomato extracts at highest concentration at least. Light microscopy was used to observe and document developmental alterations of S. exigua exposed to potato and tomato leaf extracts. Potato leaf extracts significantly decreased hatching success and caused morphological malformations of imagoes. Among them, malformations of wings were the most prominent. Interestingly, these effects were not observed within populations exposed to tomato extracts at highest concentration at least.     

2-azaallylic rearrangement in homogeneous systems

In this work we present mechanism of the base-catalyzed 2-azaallylic rearrangement in homogeneous media. Detailed 2-azaallylic rearrangement studies have shown that tautomerism of derivatives of benzylidenebenzhydrylamines and N-fluorenylidenebenzylamines is not adequately encomposed by the Hammet equation and the equilibrium constant in the case of studied derivatives depends on the electronic as well as steric factors of the azaallylic system substituents. The presence of steric interactions which influence the equilibrium state has been additionally confirmed by means of crystallographic and molecular mechanics data as well as NOE studies. This revised version was published online in August 2006 with corrections to the Cover Date.     

Physico-Chemical Properties of Cobalt–Ruthenium (10% Co–0.5% Ru) Catalysts Supported on Binary Oxides 8.5%ZrO<Subscript>2</Subscript>/Support (SiO<Subscript>2</Subscript>, Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, TiO<Subscript>2</Subscript>) for Fischer-Tropsch Synthesis

The promotion of Fischer-Tropsch catalysts 10%Co/Al₂O₃, 10%Co/SiO₂, 10%Co/TiO₂ by 0.5% Ru and the modification of supports by 8.5 wt% ZrO₂ have been studied. The following properties: catalyst specific surface area as well as reducibility and dispersion of metallic phase were studied by different techniques: BET, TPR, and H₂ chemisorption. The modification of supports by non-reducible ZrO₂, results in a decrease of cobalt oxide reduction on Al₂O₃ and TiO₂ but not on SiO₂ supports. Additionally the enhancement of cobalt dispersion was found for all catalysts with ZrO₂ modified supports. The impact of Ru promotion is likely due to the stabilization of applied supports, prevention or blockage of interaction between surface Co species and support and an increase in cobalt oxide reducibility to the catalytically active metallic cobalt phase.     

The influence of ageing of epoxy coatings on adhesion of polyurethane topcoats and protective properties of coating systems

The dependence of adhesion and protective properties of coating systems on surface properties of epoxy intermediate coatings, aged and non-aged before an application of polyurethane topcoats, were examined. The intermediate coatings were aged 500 h in UV chamber. The surface free energy and polar groups were estimated after ageing. After applying polyurethane topcoats on aged and non-aged epoxy coatings, resistance to salt spray and thermal shocks were tested as well as internal stresses were measured before and after corrosion tests.The results showed that adhesion in coating systems with polyurethane topcoats applied on aged epoxy coatings depends strongly on the degradation degree of epoxy intermediate coatings and the value of generated internal stresses. Coatings with good adhesion retention in corrosion environments have good protective properties even when temporary blistering has occurred.     

Antioxidant activity and free radical‐scavenging capacity of ethanolic extracts of thyme,oregano, and marjoram

Phenolic compounds were extracted from thyme (Thymus vulgaris L.), oregano (Origanum vulgare L.) and marjoram (Origanum majorana L.) with 95% ethanol. A number of antioxidant and radical‐scavenging capacity tests were performed on the prepared extracts using colorimetric assays and model system studies. Specifically, these included determining the content of total phenolics, antioxidant efficacy in a linoleic acid‐ferric thiocyanate model system, reducing power, scavenging effect on 2,2'‐diphenyl‐1‐picrylhydrazyl radical, and hydroxyl radical‐scavenging activity by electron paramagnetic resonance spectroscopy. Moreover, the efficacies of the prepared herb extracts were investigated in a real‐life food product: the stabilization of butter against oxidation.     

The importance of electrode material in environmental electrochemistry: Formation and reactivity of free hydroxyl radicals on boron-doped diamond electrodes

A model describing the hydroxyl radical (HO) concentration profile at the boron-doped diamond (BDD) electrode, in the presence and absence of organic compounds, is presented. It is shown that this profile depends strongly on the reaction rate constant between the HO and the organic compound. Furthermore, it is shown that the presence of organics affects the current-potential (I-V) curves. In fact, the higher the reaction rate between organics and HO, the higher is the shift of the I-V curves toward lower potential with respect to oxygen evolution. Supposing that water discharge to free hydroxyl radicals on BDD is governed by Nernst equation, this shift of the I-V curves toward lower potentials has been calculated and compared with the experimental data obtained on BDD using two model compounds: methanol and formic acid.     

Thermal stability of expanded perlite modified by mullite

Results of the thermal stability of expanded perlite modified by mullite are presented. Mullite was formed from alumino-silicate gel by sol–gel method. This method allowed us to obtain very homogenous and reactive gel and phase formation of mullite took place at relatively low temperatures. Expanded perlite modified with alumino-silicate gel after firing above the temperature of mullite formation had better thermal stability and durability during heating. The thermal stability of this material was examined up to 1400 °C.     

Hydrogenation of 2-Butyn-1,4-diol in the Presence of Functional Crosslinked Resin Supported Pd Catalyst. The Role of Polymer Properties in Activity/Selectivity Pattern

Functional gel type resins of various crosslinking degrees (3–20%) with C=O and carboxylic groups were used as the supports for Pd catalysts (0.5–2 wt% Pd). The role of polymer properties was studied in the hydrogenation of 2-Butyne-1,4-diol (B3-D) to alkene (B2-D) and alkane (B1-D). Hydrogenation was studied at atmospheric pressure of hydrogen using THF, H₂O and THF + H₂O mixtures as the solvents. Systematic studies were carried out to determine the role of the type of solvent, crosslinking degree of polymer, the content of Pd in catalysts, initial B3-D concentration and the procedure of catalyst reduction in activity/selectivity behaviour of catalysts. Swelling degree of polymer matrix under the catalytic run exhibits crucial role in the activity and selectivity to alkene, B2-D. In the presence of highly expanded catalyst (THF solvent, 3% crosslinking degree, 1 wt% Pd) the alkyne, B3-D, is hydrogenated to alkene, B2-D, with selectivity ca. 85% up to high B3-D conversion (90%). The suppression of alkene to alkane hydrogenation in the stage of B3-D is ascribed to high ability of Pd centres in the Pd/OFP catalysts to strong adsorption of alkyne substrate. It may also be related to steric hindrances of polymer in the vicinity of active Pd centres. At small content of added water (5% by vol.) to THF the catalysts offer very attractive performance in terms of activity and 98% selectivity to alkene. Water facilitates interactions of B3-D with functional groups of polymer that leads to better expansion of polymer matrix and more effective suppression of alkene hydrogenation in the alkyne stage.