Mg0.5NixZn0.5-xFe2O4 spinel as a sustainable magnetic nano-photocatalyst with dopant driven band shifting and reduced recombination for visible and solar degradation of Reactive Blue-19

Focussing on visible light active ferrites for high performance removal of noxious pollutants, we report the synthesis of Mg_0.5Ni_xZn_0.5-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, & 0.5) ferrite nanoparticle for degradation of reactive blue-19 (RB-19). Lattice parameters calculated using intense X-ray diffraction (XRD) peaks and Nelson-Riley plots (N-R plot) are in well agreement with each other. The sample Mg_0.5Ni_0.4Zn_0.1Fe₂O₄ (M5N4) exhibits best performance with 99.5% RB-19 degradation in 90 min under visible light. Photoluminescence (PL) results confirm that recombination of charge carriers is highly reduced in the photocatalyst. Scavenging experiments suggest that O₂⁻ radicals were the dominant species responsible for photocatalytic performance. The photocatalytic mechanism was explained in terms of dopant driven shifting of conduction bands and valence bands (calculated by Mott-Schottky plots). The thermodynamic probability of radical generation along with role of redox cycles of metal ions has been discussed in the mechanism. The dye degradation was ascertained by detection of intermediates via mass spectrometry analysis and a possible degradation route was also predicted. The findings in this work provide intriguing opportunities to modify the electronic band structure of spinel ferrites for visible and solar light photocatalytic activity for environmental detoxification.     

Environmental factors and kinetics of microbial degradation of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) in an aqueous medium

Environmental factors such as oxygen, temperature, and microbial species may have significant effects on decomposition of biodegradable polymers. A representative biodegradable, thermoplastic polymer, poly(3‐hydroxybutyrate‐co‐hydroxyvalerate) (PHBV), was decomposed in an aqueous medium under controlled laboratory conditions by soil microbes for the intrinsic degradation kinetics and the effects of the environmental factors on polymer biodegradation. The amount of proteins, including the PHBV depolymerases, that attached to the polymer surfaces was quite constant during the period of significant mass loss of the polymer specimens. The microbial polymer degradation followed a zero‐order rate model, so the residual mass fraction of PHBV films declined linearly with time. The mixed aerobic microbial organisms from fertile soil showed a higher activity of polymer degradation than an aerobic PHBV‐producing bacterium and the mixed anaerobes in the same soil. The mixed anaerobic microorganisms from barren soil decomposed the polymer at a slower rate than the anaerobes from fertile soil, and this was attributed to fewer microbial cells in the barren soil instead of the difference in the microbial species. The temperature effect on PHBV degradation can be described with an Arrhenius equation, and the activation energy is around 16 kcal/mol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 205–213, 2003     

Bi12TiO20 synthesized directly from bismuth (III) nitrate pentahydrate and titanium glycolate and its activity

Pure phase of sillenite structure, Bi₁₂TiO₂₀, was directly synthesized using stoichiometric bismuth (III) nitrate pentahydrate and titanium glycolate by co-precipitation. The influence of pH on the structure of Bi₁₂TiO₂₀ was studied in the pH range of 3–10. The sillenite structure was characterized using XRD and FTIR. The photo-degradation reaction of 4-nitrophenol (4-NP) was used to study photocatalytic activity of Bi₁₂TiO₂₀ as a function of the preparation pH. The rate of decomposition was followed by UV-vis and TOC. The beginning concentration of 4-NP, 44 ppm, decreased to less than 1 ppm within 30 min for all prepared catalysts. It was found that the decomposition rate constant of Bi₁₂TiO₂₀ is six times higher than those of either TiO₂ or Bi₂O₃ under the same conditions.     

Abrasion phenomena in twill tencel fabric

The abrasion characteristics of Tencel fabrics were evaluated by Martindale abrasion and laundering, and the breakdown mechanism of fibers was surveyed by scanning electron microscopy. The fabric was subjected to pad‐dry‐cure treatment with two different types of modified dimethyloldihydroxyethylene urea resins (Reaktant DH and Reaktant FC). Although the degree of dry abrasion varied with different resins, the damage exhibited by individual fibers differed little from untreated to resin‐treated; the major mechanism of abrasion was through friction, and the mechanism of fiber failure was multiple splitting and transverse cracking. In untreated Tencel, the characteristic feature of wet abrasion was massive fibrillation, and in crosslinked fabrics, the wet abrasion mechanism was through fiber slippage and slicing action, although in the Reaktant FC‐treated fabric, the wet abrasion mechanism was more through slicing than through fiber splitting. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1391–1398, 2006     

阳离子化多元醇防塌剂的研制

室内研究和现场应用表明,聚乙烯醇类防塌剂表现出较明显的增粘负效应,可引起钻井液粘度的急剧增加,严重影响其推广应用.通过金属盐催化降解和阳离子化反应,研制出了抑制性好且增粘负效应低的阳离子化改性多元醇防塌剂.考察了阳离子化试剂、反应温度、反应时间对取代度、反应效率和产品主要性能的影响,得出了阳离子化多元醇防塌剂最佳制备条件,即：PVA与阳离子化试剂物质的量比为1：1,反应温度为50℃,反应时间为4 h,阳离子度可达0.435.     

The radiation crosslinking and scission of ethylene-propylene copolymers studied by solid-state nuclear magnetic resonance

Methyl groups from chain scission and H-crosslinks have been identified by solid-state nuclear magnetic resonance in amorphous ethylene-propylene copolymers containing 23 and 36 mole % propylene after γ-irradiation to 10 MGy at 30°C. G (scission) and G (crosslink) values determined from the n.m.r. spectra and by extraction are in agreement, which suggests that the crosslinks are not clustered. This may differ from the situation in polyethylene where there is a substantial crystalline content. G(S). G(X) and the ratio G(S)/G(X) increase with increasing propylene content of the copolymers.     

Modelling thermal degradation of composite materials

A one–dimensional, transient thermal degradation heat transfer model for the response of composite materials when exposed to fire is presented. The model can handle layers of different materials. Material properties are functions of temperature. The reaction can be specified using Arrhenius‐type parameters or by inputting a density–temperature relationship determined by any experimental technique such as thermogravimetric analysis. The model is validated against the experimental data presented in Boyer's 1984 dissertation. Overall, the model provides excellent agreement with the experimental data. It is shown that very little difference is found between results arrived at by Arrhenius kinetics and results obtained by specifying the easier to measure density–temperature relationship. From this it is concluded that this technique is a viable alternative to Arrhenius‐type models. Copyright © 2006 John Wiley & Sons, Ltd.     

臭氧氧化-光催化降解水中的五氯酚

利用臭氧氧化-光催化技术降解水中的有机污染物五氯酚(PCP)。对比了紫外光照射、臭氧氧化、光催化、臭氧氧化-光催化4种方法降解PCP的情况。考察了臭氧氧化-光催化体系中臭氧流量、臭氧产量、PCP初始质量浓度、pH和CO23-等因素对PCP降解率的影响。实验结果表明,臭氧氧化-光催化法比单独使用紫外光照射、臭氧氧化、光催化法更能有效的去除PCP;增加臭氧流量和臭氧产量有利于提高PCP的降解率;降低PCP的初始浓度,PCP的降解率显著提高;pH对PCP的降解效果影响不明显;CO23-的存在显著降低了PCP的降解率。在臭氧氧化-光催化体系中,除臭氧直接氧化降解PCP外,臭氧与TiO2协同作用产生的.OH对PCP的降解也起到了重要作用。     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

XPS studies of directly fluorinated HDPE: problems and solutions

X-ray photoelectron spectroscopy (XPS) applied to the study of fluorinated polymer surfaces presents several problems related both to peak assignment and to degradation. In this work, we analyse extensively the question of XPS peak assignments in this kind of surfaces. We conclude that in this kind of surfaces using binding energy differences between fluorine and carbon is better than using absolute binding energies. Also a useful relation between fluorine photoelectron energy vs. polymer composition expressed through the atomic ratio fluorine/carbon (F/C) was found. A protocol for data treatment is proposed and applied to a XPS study of the degradation induced by X-ray on high-density polyethylene surfaces modified by direct fluorination. Results obtained for the degradation, namely the atomic ratio F/C obtained by two different methods, combined with angle resolved X-ray photoelectron spectroscopy (ARXPS) were used to study the fluorine concentration profile in depth, producing self-consistent results.