Emission of Volatiles from Polymers — A New Approach for Understanding Polymer Degradation

Emission of low molar mass compounds from different polymeric materials was determined and the results from the volatile analysis were applied to predict the degree of degradation and long-term properties, to determine degradation rates and mechanisms, to differentiate between biotic and abiotic degradation and for quality control work. Solid-phase microextraction and solid-phase extraction together with GC-MS were applied to identify and quantify the low molar mass compounds. Volatiles were released and monitored at early stages of degradation before any matrix changes were observed by e.g. SEC, DSC and tensile testing. The analysis of volatiles can thus also be applied to detect small differences between polymeric materials and their susceptibility to degradation. The formation of certain degradation products correlated with the changes taking place in the polymer matrix, these indicator products could, thus, be analysed to rapidly predict the degree of degradation in the polymer matrix and further to predict the long-term properties and remaining lifetime of the product.     

链霉菌(Streptomyces sp.)对吡啶的降解特性

从焦化废水的活性污泥中分离出对溶液中吡啶具有降解效果的链霉菌（Streptomyces sp．）,考察了吡啶初始质量浓度、初始pH、降解温度、振荡速度等对吡啶降解效果的影响,初步探讨了该菌降解吡啶的动力学与机理。实验结果表明,该菌对吡啶有很强的耐受力,能以吡啶为惟一碳源和氮源生长。链霉菌在初始pH=8、降解温度30℃、振荡速度100r／min的条件下培养7d后,吡啶的质量浓度从250mg/L降至6．6mg/L,吡啶降解率达97．4％。该菌对吡啶的降解反应符合一级动力学方程,初始质量浓度为100mg／L时的吡啶降解速率常数为0．4011d^-1。紫外一可见光谱分析表明,吡啶经该菌降解后的特征环被破坏。     

Degradation of Phenolic Resin by Tremetes versicolor

A phenolic resin that is used as syntan in leather manufacturing was degraded using Tremetes versicolor. On degradation of this resin for eight days, the reduction in biochemical oxygen demand (BOD), chemical oxygen demand (COD) and total organic carbon (TOC) were 65.11, 76.66 and 72.94% respectively. It was found from the infra red (IR) spectra of the samples that up to seven days the aromaticity was not perturbed however there were reductions in BOD and COD. Addition of co-substrate starch, brought about reduction in BOD, COD and TOC by 85.36, 91.93 and 89.98% respectively. After eight days, there observed a disturbance in the aromatic ring. The enzyme was extracted and assayed for polyphenol oxidase and laccase. Polyphenol oxidase activity and laccase activity of the crude enzyme were found to be 31.4 and 1.67 U/mL. On ammonium sulfate precipitation and dialysis, the polyphenol oxidase activity and laccase activity were enhanced by 1.5- and 3.2-folds respectively.     

CoFe2O4@Methylcelloluse as a New Magnetic Nano Biocomposite for Sonocatalytic Degradation of Reactive Blue 19

Journal of Polymers and the Environment - Reactive Blue 19 (RB19) removal from synthetic textile wastewater was investigated by using a CoFe2O4@methylcellulose (MC) activated with peroxymonosulfate...     

Analysis of Products Generated from the Thermal and Catalytic Degradation of Pure and Waste Polyolefins using Py-GC/MS

The possibility of transforming waste plastics into valuable hydrocarbons via catalytic cracking and reforming is attracting increasing interest. Pyrolysis coupled with Gas Chromatographic separation and Mass Spectrometry detection (Py-GC/MS) has been used in this work to study the product selectivity of various catalysts in the conversion of pure and residual polyethylene samples into hydrocarbon products. Five acid solids of comparable aluminium contents but different textural and acid properties were tested as catalysts, including three zeolites (standard ZSM-5, nanocrystalline n-ZSM-5 and Beta) and two mesostructured solids (Al-MCM-41 and Al-SBA-15). Thermal cracking of the pure and residual polymers generated a similar range of products to each other, with a high proportion of linear paraffins and olefins of varying lengths. The presence of zeolitic materials resulted in complete elimination of heavy linear products, an increase in the light hydrocarbon fraction and a marked selectivity towards the formation of single-ring aromatic species, particularly benzene, toluene and xylene. Aromatic formation was particularly notable with the small crystal size n-ZSM-5 (aromatic selectivity up to 53.9%) and less marked in the case of standard ZSM-5 (up to 36.4%) and Beta zeolite (up to 35.0%). Mesostructured catalysts like Al-MCM-41 and Al-SBA-15 favoured the production of light C₂–C₅ hydrocarbons (up to 57.9%) while the formation of aromatic products was significantly lower than with zeolitic materials. The paper examines the extent and the causes for this product selectivity and discusses its connection with the acid and textural properties of each catalyst. It was also observed that, under the experimental conditions employed, the products generated were not significantly affected by the nature and origin of the polymers employed.     

几种金属氧化物催化臭氧氧化降解p-CBA

选择Al₂O₃,TiO₂,MnO₂,Fe₃O₄ 4种金属氧化物对溶液中的对氯苯甲酸（p-CBA）进行催化臭氧氧化降解。催化剂的表征结果显示：TiO₂具有最大的比表面积,为93.84 m²/g,Al₂O₃的比表面积最低,仅为10.28 m²/g;MnO₂和Fe₃O₄表面含有大量强酸性位,故其等电点较低,分别为1.45和1.82。4种催化剂对p-CBA的吸附能力与其比表面积相关,而催化臭氧氧化活性高低却与其等电点的高低顺序一致。Al₂O₃具有最高的等电点（6.92）,也表现出相对较强的催化臭氧氧化活性。在臭氧通量6 mg/min、p-CBA初始质量浓度40 mg/L、Al₂O₃投加量0.5 g/L、反应时间40 min的条件下,p-CBA去除率达到58.6%,远高于单独臭氧化和吸附过程的去除率。     

A New Approach for the Flocculation Mechanism of Chitosan

A peak III/I ratio (_peak) in pyrene-fluorescence spectrum was used to measure the polarity of microenvironment of chitosan adsorbing pyrene molecules. The authors detected the pyrene-fluorescence spectrum of chitosan with different degrees of deacetylation (DD) and determined the relationship between the flocculation of bentonite colloid and the _peak of chitosan with a different molecular weight (MW) and DD. It can be concluded that MW rather than DD plays a key role in the flocculation and that bond bridging rather than charge neutralization dominates the flocculation with chitosan from a microenvironmental structure of view.     

Rapid and Low-Cost Method for Evaluation of Nutrient Release from Controlled-Release Fertilizers Using Electrical Conductivity

Methods to determine nutrient release rates of coated fertilizers usually rely on chemical analyses, which often are time-consuming and/or expensive. Our goal was to develop an innovative and rapid low-cost method to evaluate nutrient release from polymer coated MAP or urea using conductometry. The release in water is determined by measuring the electric conductivity (EC) over time, with intervals dependent on release rates. In the case of soluble salt fertilizers, EC can be immediately determined and converted to a concentration using a calibration curve. In the case of urea, an additional step is needed to convert the neutral urea into ammonium. The release rates in water were assessed for a range of commercial and laboratory-coated fertilizers. A validation test demonstrated strong agreement with the release determined using analytical techniques. The EC method hence offers an easy way to quickly evaluate the time course of release of nutrients from controlled-release fertilizers.     

TiO2/AC复合催化剂光催化降解布洛芬

以钛酸丁酯为钛源、粉末活性炭为载体,采用溶胶-凝胶法制备了活性炭负载型二氧化钛（TiO₂/AC）复合催化剂,并运用XRD和FE-SEM技术对其进行了表征。在紫外光条件下,研究了TiO₂/AC光催化降解布洛芬的影响因素。研究结果表明：布洛芬质量浓度为40 mg/L时,在室温、焙烧温度500 ℃、TiO₂/AC催化剂加入量2.0 g/L、溶液pH 3.0的最佳条件下,光催化降解180 min时布洛芬的降解率达85.6%;阴离子Cl^-和NO₃^-对布洛芬的降解有强烈的抑制作用;阳离子Fe²⁺和Cu²⁺及氧化性物种H₂O₂对布洛芬的降解均呈现两面性,随物种浓度的增加,布洛芬的降解率先增大后减小;该催化剂具有良好的稳定性,可多次重复使用而不失活。     

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Evaluation of Poly(ethylene-terephthalate) Products of Chemical Recycling by Differential Scanning Calorimetry

Poly (ethylene-terephthalate), (PET) bottles waste was chemically recycled by glycolysis and hydrolysis. The depolymerization processes were carried out in different time intervals from 5 to 360 min, in two different molar ratios of PET/EG, 1:5 and 1:18 and at different temperatures. The PET glycolysis leads to formation of bis(2-hydroxy-ethyl)terephthalate (BHET) monomer and PET oligomers with hydroxyl and carboxyl end groups while PET hydrolysis is followed by formation of monomers terephthalic acid (TPA) and ethylene glycol (EG). Fractions of monomers and oligomers were further characterized by FTIR spectroscopy and by differential scanning calorimetry (DSC). The results show that DSC is successful method to describe the different structures of oligomers formed during chemical recycling of PET.     

A New Approach of BioCO2 Fixation by Thermoplastic Processing of Microalgae

Effective sequestration of carbon dioxide (CO₂) by algae reduces greenhouse gases effect on global warming. Algae biomass or residual such as biomeal from algae biofuel processing can be judiciously used for industrial applications such as fertilizer, animal feed, and plastics. Conversion of algae into useful plastic materials can be accomplished by extrusion technology. During algal plastic manufacturing, up to 20% thermoplastic algal blends can be fixated into or encapsulated by a non-biodegradable polymer such as polyolefin, which is known to be resistant to abiotic or biotic degradation. As a result, CO₂ that is captured by algae through photosynthesis is permanently stored in a form of biomass and will not be released back into the atmosphere. The extrusion of microalgae reported in this article is a novel process to sequester CO₂ and at the same time it makes a good use of the algae biomass in plastic manufacturing. Mechanical properties of the thin plastic films containing microalgae are comparable to the neat polyurethane or polyethylene films. Injection molded articles containing microalgae are dimensionally stable. However, a lower tensile strength, especially elongation at break, is observed in comparison to the neat polypropylene.     

Evaluation of carbonization as a thermal pretreatment method for landfilling by column leaching tests

To evaluate carbonization as a thermal pretreatment method for landfilling, the releasing characteristics of organic and inorganic constituents from carbonization residue derived from shredded residue of bulky waste was investigated by means of batch and column leaching tests. Shredded residue of bulky waste itself and its incineration ash were tested together to compare pretreatment methods. In batch leaching tests at a liquid/solid ratio of 10, the release of organic carbon from carbonization residue was at a remarkably low level. Besides, carbonization contributed to immobilize heavy metals such as chromium, cadmium, and lead within its residue. In column tests, the discharges of organic constituents were lowest from carbonization residue under aerobic conditions due to microbial activity. The leaching of Cd, Cr, Pb, and Cu from carbonization residue was suppressed under anaerobic conditions; however, this suppression effect tended to be weaker under aerobic conditions. From the results showing that the total releasing amounts of organic and inorganic constituents from carbonization residue are so low as to be comparable to that of incineration ash, carbonization can be considered as one of the thermal pretreatment methods of organic wastes.     

CeO_2/三维石墨烯催化臭氧氧化降解刚果红

采用原位氧化还原法制备了三维石墨烯负载型CeO_2催化剂(CeO_2/3D GN),采用XRD、FTIR、SEM、比表面积和零电荷点测定等方法对其进行了表征,并考察了CeO_2/3D GN非均相催化臭氧氧化降解水中刚果红染料的影响因素。表征结果显示:CeO_2/3D GN具有相互连通的三维网络结构;CeO_2纳米颗粒均匀地分散在石墨烯片层中;比表面积为190.89 m~2/g;零电荷点pH_(zpc)为7.36。实验结果表明:CeO_2/3D GN非均相催化臭氧氧化体系比单独臭氧氧化体系对刚果红溶液的脱色率提高了60.56百分点;连续5次重复利用CeO_2/3D GN,刚果红溶液脱色率为96.50%~98.00%;在臭氧流量为20 mg/min、催化剂投加量为1.5 g/L、初始溶液pH为7.00的最佳工艺条件下反应15 min,刚果红溶液脱色率可高达94.65%。     

锐钛矿-金红石混合晶型TiO2降解气相苯

用溶胶-凝胶法并通过控制煅烧温度合成不同晶相比的混合晶型纳米TiO_2,在紫外光光照下降解气相苯。考察了苯初始质量浓度、紫外灯光照强度和催化剂加入量对苯去除率的影响;探究了光催化降解气相苯的动力学特征。结果表明:450℃煅烧制备的催化剂降解苯效率最高,此催化剂金红石相质量分数为6.30%;在苯初始质量浓度为74.39 mg/m~3、催化剂加入量为7 g、光照强度为2.18 klux的最佳条件下反应84 min,苯去除率达99.73%;光催化降解率与光照强度之间符合0.5级动力学特征;当催化剂加入量为3 g时,单位时间单位质量催化剂降解苯的质量最多;苯的光催化降解反应均符合一级动力学方程。     

Degradation of Cellulosic Materials Under the Alkaline Conditions of a Cementitious Repository for Low- and Intermediate-Level Radioactive Waste. II. Degradation Kinetics

The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are - and -(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.     

Determination of Kinetic Parameters for the Degradation of Chitosan/Silica Hybrid Nano Composites

The thermal degradation behavior of chitosan (CS) and chitosan–silica (CS–Si) nanocomposites were studied using a differential kinetic model. The influence of the heating rate in the non-isothermal degradation kinetics of CS and CS–Si nanocomposites are presented. Kinetic parameters, such as the activation energy (E) and pre-exponential factor (A), and thermodynamic parameters, such as the Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS), were determined using the modified Arrhenius equation. It was shown that the rate constant for degradation (k), activation energy and pre-exponential factor depend on the heating rates. The order of reaction was found to be one. The isothermal stability of CS and CS–Si was determined from non-isothermal kinetics and was also found to be dependent on the heating rate. Thermogravimetric studies revealed that neat CS was less thermally stable than the CS–Si nanocomposites.     

微波紫外协同降解染料活性艳红X-3B研究

将微波激发的无极紫外灯应用于染料废水的处理研究,考察了反应过程中染料废水脱色率、TOC去除率、溶液pH以及反应前后染料废水高效液相色谱图的变化情况。染料活性艳红X-3B经无极紫外光处理110min后,脱色率达96％,TOC去除率达66％,降解效果明显好于单独使用微波或普通紫外灯的降解效果总和,溶液pH先降低后缓慢升高。