Use of nanoclay as an environmentally friendly flame retardant synergist in polyamide-6

Due to their very high levels of flame retardancy, chlorinated and brominated flame retardants had been the most widely used flame retardant additives in plastics industry. However, these flame retardants lead to formation of very toxic volatiles and by-products during fire. Therefore, the recent trend is to replace all of them with non-halogenated flame retardants. In this respect, the use of nanoclays as a synergist flame retardant is becoming more and more important. Thus, the main aim of this work was to investigate the synergistic flame retardant effect of nanoclays with phosphorous compounds in polyamide-6 composites. For this purpose, exfoliated clay nanocomposites of flame retarded/glass fiber reinforced polyamide-6 were prepared by melt compounding. A flame retardant based on phosphorus compounds was used at various levels in glass fiber reinforced polyamide-6 and nanocomposites. Flammability and fire behaviors were evaluated by limiting oxygen index, UL94 and cone calorimeter tests. Substitution of a certain fraction of the flame retardant with nanoclays was found to significantly reduce the peak heat release rate and delay the ignition in cone calorimeter. Moreover, remarkable improvements were obtained in limiting oxygen index along with maintained UL94 ratings.     

Brominated and organophosphate flame retardants in selected consumer products on the Japanese market in 2008

The concentrations of traditional brominated flame retardants (BFRs) and organophosphate flame retardants (OPFRs) in new consumer products, including electronic equipment, curtains, wallpaper, and building materials, on the Japanese market in 2008 were investigated. Although some components of the electronic equipment contained bromine at concentrations on the order of percent by weight, as indicated by X-ray fluorescence analysis, the bromine content could not be fully accounted for by the BFRs analyzed in this study, which included polybrominated diphenylethers, decabromodiphenyl ethane, tetrabromobisphenol A, polybromophenols, and hexabromocyclododecanes. These results suggest the use of alternative BFRs such as newly developed formulations derived from tribromophenol, tetrabromobisphenol A, or both. Among the 11 OPFRs analyzed, triphenylphosphate was present at the highest concentrations in all the products investigated, which suggests the use of condensed-type OPFRs as alternative flame retardants, because they contain triphenylphosphate as an impurity. Tripropylphosphate was not detected in any samples; and trimethylphosphate, tributyl tris(2-butoxyethyl)phosphate, and tris(1,3-dichloro-2-propyl)phosphate were detected in only some components and at low concentrations. Note that all the consumer products evaluated in this study also contained traditional BFRs in amounts that were inadequate to impart flame retardancy, which implies the incorporation of recycled plastic materials containing BFRs that are of global concern.     

Determination of solid waste sorption capacity for selected heavy metals in landfills

The adsorption process is largely a surface-action phenomenon. In this study, sorption capacities for heavy metals on a solid waste matrix were investigated. Five heavy metals (iron, copper, zinc, nickel and cadmium) were chosen because of their availability in any landfill site. The conditions during all the experimental runs were pH 7.0, temperature 32 degrees C and suppressed microbial degradation. For adsorption isotherm (Freundlich and Langmuir) calculations, fixed quantities of heavy metal ions were mixed with variable quantities of solid waste. The ratio of mass of adsorbate per unit mass of adsorbent was changed five times, by changing only the adsorbent amount. The results showed that the time required to reach equilibrium varied from metal to metal but all reached equilibrium within the first 32 h. The relative potential of sorption of the individual metals and mixed metals on the solid waste matrix is Fe > Zn > Cu > Ni > Cd. The sorption capacity of domestic solid waste matrix for heavy metals is quite significant and this property might prove helpful for the in situ removal of heavy metals in landfill operation.     

Heavy metal vaporization and abatement during thermal treatment of modified wastes

This study examines the vaporization percentage and partitioning of heavy metals Cd, Pb and Zn during thermal treatment of wastes with added PVC, heavy metals or phosphate, and the efficiency of sorbents for removal of these metallic compounds in flue gas of an industrial solid waste incinerator. Firstly, vaporization experiments were carried out to determine the behavior of heavy metals during combustion under various conditions (type of waste, temperature, presence of chloride or phosphate ...). The experimental results show relatively high vaporization percentage of metallic compounds within fly ash and limestone matrix while heavy metals within sediments treated with phosphoric acid are less volatile. Vaporization of metals increases with increasing temperature and with chloride addition. The thermal behavior of the selected heavy metals and their removal by sorbents (sodium bicarbonate, activated carbon) was also studied in an industrial solid waste incinerator. These pilot scale experiments confirm that heavy metals are concentrated in fly ashes and cyclone residues, thus effectively controlling their release to the atmosphere.     

Effect of Amino alcohol functionalized polyethylene as compatibilizer for LDPE/EVA/clay/flame-retardant nanocomposites

The synergistic effect of organo-modified montmorillonite (Nanomer I28E and Cloisite 20A) and metal hydroxides (magnesium hydroxide MH and alumina trihydrate ATH) as flame retardants in LDPE/EVA nanocomposites compatibilized with amino alcohol grafted polyethylene (PEgDMAE) was studied. Morphological characterization of nanocomposites was carried out by means of X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM). Flame-retardant properties of nanocomposites were evaluated by the UL-94 horizontal burning and cone calorimeter tests and limiting oxygen index (LOI). Thermal degradation behavior was analyzed with a Fourier transform infrared coupled with the thermogravimetric analyzer (TG-FTIR). The XRD analysis showed a displacement of the d₀₀₁ plane characteristic peak of clay to lower angles, which indicates an intercalated–exfoliated morphology. From STEM images it was observed a good dispersion of flame retardants (MH and ATH) throughout the polymer matrix which was reflected in flame-retardant properties. TG-FTIR showed a better thermal stability of nanocomposites and the gases evolved during combustion showed an important reduction. Based on thermal stability and thermal degradation results, the flame-retardant mechanism of LDPE/PEgDMAE/EVA/Clay/MH nanocomposites was proposed.     

Geiger photodiode array for compact, lightweight laser-induced breakdown spectroscopy instrumentation

The development of a unique spectrometer based on an array of Geiger photodiodes has been shown to enhance the performance of laser-induced breakdown spectroscopy (LIBS) instrumentation. These compact, silicon-based detectors eliminate the need for postamplification electronics, allow for the detection of single photons at room temperature, and do not require complex gating-timing circuitry. The detectors have dark-count rates of <500 Hz at room temperature and a good response from the UV to the near IR. Their high sensitivity makes them candidates for standoff analysis as part of a LIBS spectrum analyzer.     

Adsorption of heavy metals from wastewater with waste activated sludge

Abstract

The purpose of this study is the investigation of the adsorption of heavy metals from wastewater with waste activated sludge (WAS) so as to increase the operational flexibility of activated sludge processes for the shock loading problems of heavy metals. By contacting the raw wastewater with WAS, before it entered the activated sludge process unit, some heavy metals in the wastewater were removed, and the pH value of the acidic wastewater rose. Five metals, Cu, Zn, Ni, Cd and Pb, were studied, some factors which affected this biosorption phenomena were investigated, and expressions of the adsorption isotherms were discussed. A semi‐empirical mass transfer‐adsorption model was developed to describe the kinetic experimental data.     

Application of laser-induced breakdown spectroscopy for total carbon quantification in soil samples

The increase of greenhouse gas (i.e., CO(2)) levels in the atmosphere has caused noticeable climate change. Many nations are currently looking into methods of permanent underground storage for CO(2) in an attempt to mitigate this problem. The goal of this work is to develop a process for studying the total carbon content in soils before, during, and after CO(2) injection to ensure that no leakage is occurring or to determine how much is leaking if it is occurring and what effect it will have on the ecosystem between the injection formation and the atmosphere. In this study, we quantitatively determine the total carbon concentration in soil using laser-induced breakdown spectroscopy (LIBS). A soil sample from Starkville, Mississippi, USA was mixed with different amounts of carbon powder, which was used as a calibration for additional carbon in soil. Test samples were prepared by adding different but known amounts of carbon powder to a soil sample and then mixing with polyvinyl alcohol binder before being pressed into pellets. LIBS spectra of the test samples were collected and analyzed to obtain optimized conditions for the measurement of total carbon in soil with LIBS. The total carbon content in the samples was also measured by a carbon analyzer, and the data (average of triplicates) were used as a reference in developing calibration curves for a modified version of the single linear regression model and the multiple linear regression model. The calibration data were then used to determine the total carbon concentration of an unknown sample. This work is intended to be used in the initial development of a miniaturized, field-portable LIBS analyzer for CO(2) leak detection.     

纸泥/环氧酚醛树脂复合物与环氧酚醛树脂的阻燃性研究

将含各类阻燃剂加入到环氧酚醛树脂和纸泥/环氧酚醛聚合物中,用UL-94等级燃烧测试法测定体系的燃烧等级,结果表明:TCEP和无机阻燃剂对环氧酚醛树脂有阻燃作用,但卤化和磷酸化的阻燃剂能增强纸浆/环氧酚醛复合材料的阻燃性.用热重分析仪和差示扫描量热仪对复合材料进行热分析研究阻燃机理,结果显示环氧酚醛树脂材料和纸泥/环氧酚醛复合材料的阻燃性取决于本身的热容和热分解行为.     

Mechanical properties and flammability of sisal/PP composites: Effect of flame retardant type and content

In this research, magnesium hydroxide (Mg(OH)₂) and zinc borate, as flame retardants, were incorporated into sisal/PP composites. Maleic anhydride grafted polypropylene was also used as a compatibilizer. Adding flame retardants into sisal/PP composites reduced burning rate and increased thermal stability of the composites. No synergistic effect was observed when both magnesium hydroxide and zinc borate were incorporated in the sisal/PP composites. In addition, the sisal/PP composites exhibited insignificant difference of shear viscosity at high shear rate indicating that types of flame retardants used in this study had no impact on the processability of the composites. Good distribution of flame retardants and sisal fiber in PP matrix was also observed. All PP composites had lower impact strength than the neat PP. However, the sisal/PP composites with the addition of Mg(OH)₂ and zinc borate exhibited comparable tensile and flexural properties to the sisal/PP composites without adding those flame retardants. Therefore, the addition of Mg(OH)₂ and zinc borate enhanced flame retardancy of sisal/PP composites without sacrificing their mechanical properties.     

On-line monitoring of remediation process of chromium polluted soil using LIBS

Due to large growth in leather and textile industries to cater for the needs of a growing world population, contamination of soil and water resources by chromium has become a great threat for humans and animals. In this work, Laser Induced Breakdown Spectroscopy (LIBS) was applied to monitor the remediation process of soil contaminated with Chromium metal. This study was conducted at a laboratory scale by setting up an experiment in a container holding soil contaminated with chromium. This setup represents actual field conditions where remediation process could be applied and monitored for the removal of toxic metals like Cr. For generation of LIBS spectrum, the plasma was produced by focusing a pulsed Nd: YAG laser at 1064 nm on the soil contaminated with chromium under remediation process. The evaluation of the potential and capabilities of LIBS as a rapid tool for remediation process of contaminated sites is discussed in detail. Optimal experimental conditions were evaluated for improving the sensitivity of our LIBS system for monitoring of remediation process through parametric dependence study. The minimum detection limit of our spectrometer for chromium in soil matrix was 2 mg Kg(-1).     

微波萃取-GC-MS法测定软包装材料中有机磷酸酯

目的建立有效的阻燃剂使用规范和监管制度,利用微波萃取-GC-MS法测定软包装材料中5种有机磷酸酯阻燃剂的含量。方法以软包装材料为研究对象,样品经微波萃取,采用DB-5色谱柱分离,利用GC-MS进行测定。结果在0.2~50.0 mg/kg范围内,线性相关系数均大于0.9994,线性关系良好;检出限在0.05~0.10 mg/kg之间,定量限在0.2~0.5 mg/kg之间;加标回收率在85.6%~104.7%之间,相对标准偏差为1.3%~2.5%。结论文中方法简便、快速,能够满足软包装材料中对5种有机磷酸酯阻燃剂检测的要求。     

Effect of flame retardants on flame retardant,mechanical, and thermal properties of sisal fiber/polypropylene composites

A flame retardant efficiency of flame retardants; ammonium polyphosphate (APP), magnesium hydroxide (Mg(OH)₂), zinc borate (Zb), and combination of APP with Mg(OH)₂ and Zb in sisal fiber/polypropylene (PP) composites was investigated using a horizontal burning test and a vertical burning test. In addition, maleic anhydride grafted polypropylene (MAPP) was used as a compatibilizer to enhance the compatibility in the system; i.e. PP-fiber and PP-flame retardants. Thermal, mechanical, and morphological properties of the PP composites were also studied. Adding the flame retardants resulted in improved flame retardancy and thermal stability of the PP composites without deterioration of their mechanical properties. APP and combination of APP with Zb effectively enhanced flame retardancy of the PP composites. No synergistic effect was observed when APP was used in combination with Mg(OH)₂. SEM micrographs of PP composites revealed good distribution of flame retardants in PP matrix and good adhesion between sisal fiber and PP matrix.     

聚合型无卤阻燃剂研究进展

无卤、无毒聚合型阻燃剂已成为阻燃剂发展的一个新方向,其中磷系、氮系、磷-氮系聚合型阻燃剂是目前最常用的环保无卤阻燃剂。介绍了国内外磷系、氮系以及磷-氮、磷-硫、磷-硅聚合型阻燃剂的研究应用情况,并对不同聚合型阻燃剂的力学及热性能进行了详细介绍。     

无机阻燃剂的作用机理及研究现状

无机阻燃剂因无卤、低烟、无毒等特点已广泛应用于聚合物材料的阻燃.介绍了无机阻燃剂的阻燃机理,对各种无机阻燃剂及其复配协效体系的研究现状进行了详细阐述,并简要说明了目前无机阻燃剂的发展趋势.指出无机阻燃剂的多功能化,如抗菌、导电、防辐射等是近年来无机阻燃剂的重要发展方向之一.     

Policy options for the management of end of life computers in Mexico

End of life computers have raised public and government concern in Mexico because of several factors including the increase in the generation volumes, the presence of toxic chemicals such as polybrominated flame retardants and heavy metals (lead, mercury, hexavalent chromium, cadmium, and beryllium alloys), and the improper management of computers when they are disposed. This study was developed to evaluate the generation and management of end of life computers in Mexico to propose a policy option according to national conditions and existing infrastructure. The diagnosis identified that end of life computers are taken to three different management options: 7,087?tons are recycled, 5,154?tons are disposed in landfills/dumps and 38,332?tons are reused or remanufactured. From these numbers, three policy alternatives were evaluated and a policy is proposed based in extended responsibility for manufacturers/distributors, government and public.     

Optimal boiler control through real-time monitoring of unburned carbon in fly ash by laser-induced breakdown spectroscopy

A laser-induced breakdown spectroscopy (LIBS) technique has been applied for detection of unburned carbon in fly ash, and an automated LIBS unit has been developed and applied in a 1000-MW pulverized-coal-fired power plant for real-time measurement, specifically of unburned carbon in fly ash. Good agreement was found between measurement results from the LIBS method and those from the conventional method (Japanese Industrial Standard 8815), with a standard deviation of 0.27%. This result confirms that the measurement of unburned carbon in fly ash by use of LIBS is sufficiently accurate for boiler control. Measurements taken by this apparatus were also integrated into a boiler-control system with the objective of achieving optimal and stable combustion. By control of the rotating speed of a mill rotary separator relative to measured unburned-carbon content, it has been demonstrated that boiler control is possible in an optimized manner by use of the value of the unburned-carbon content of fly ash.     

Detection of chromium in wastewater from refuse incineration power plant near Poyang Lake by laser induced breakdown spectroscopy

A laser induced breakdown spectroscopy (LIBS) system was developed for determination of toxic metals Cr in wastewater collected from a refuse incineration power plant near Poyang Lake. The plasma was generated by focusing a pulsed Nd:YAG laser at 1064 nm on the surface of liquid. Experimental conditions were optimized for improving the sensitivity and repeatability of the LIBS system through a parametric dependence study in potassium bichromate (K(2)Cr(2)O(7)) aqueous solutions. Calibration curves for Cr I 425.43 and 357.87 nm lines are compared and the limit of detection is found to be 39 and 86 ppm, respectively. This calibration curve of Cr I 425.43 nm has been used for quantification of Cr in wastewater collected from a refuse incineration power plant near Poyang Lake where the concentration of Cr is found to be 97 ppm. The results between LIBS and standard analytical technique such as atomic absorption spectroscopy were compared, and the relative standard deviation was 8.5%.     

两种新型无机复合阻燃改性沥青的流变性能及其阻燃机制

针对目前沥青阻燃剂存在的毒性大、造价高及耐热性差等问题,制备了两种由金属氧化物和金属氢氧化物组成的新型无机复合阻燃剂.通过动态剪切流变试验、弯曲梁流变(BBR)试验和Brookfield旋转黏度试验,深入研究了两种新型阻燃改性沥青的高温流变性能、低温流变性能以及黏度特性.在此基础上,借助DSC试验探究了两种复合阻燃改性沥青的阻燃机制,并对比了两种无机复合阻燃剂与常用阻燃剂的经济效益.试验结果表明:两种无机复合阻燃剂阻燃的抑烟效果良好,可显著改善沥青的高温抗车辙性能,提高沥青胶浆的低温性能,增加沥青黏度;两种无机复合阻燃改性沥青的抗车辙因子与温度呈现良好的相关性; 将两种复合阻燃剂加入到沥青中,能使沥青相态变化需要更多能量,改性沥青在受热过程中更加稳定.     

Quantitative analysis of liquids from aerosols and microdrops using laser induced breakdown spectroscopy

Laser induced breakdown spectroscopy (LIBS) is shown to be capable of low volume (90 pL) quantitative elemental analysis of picogram amounts of dissolved metals in solutions. Single-pulse and collinear double-pulse LIBS were investigated using a 532 nm dual head laser coupled to a spectrometer with an intensified charge coupled device (CCD) detector. Aerosols were produced using a micronebulizer, conditioned inside a concentric spray chamber, and released through an injector tube with a diameter of 1 mm such that a LIBS plasma could be formed ~2 mm from the exit of the tube. The emissions from both the aerosols and a single microdrop were then collected with a broadband high resolution spectrometer. Multielement calibration solutions were prepared, and continuing calibration verification (CCV) standards were analyzed for both aerosol and microdrop systems to calculate the precision, accuracy, and limits of detection for each system. The calibration curves produced correlation coefficients with R(2) values > 0.99 for both systems. The precision, accuracy, and limit of detection (LOD) determined for aerosol LIBS were averaged and determined for the emission lines of Sr II (421.55 nm), Mg II (279.80 nm), Ba II (493.41 nm), and Ca II (396.84 nm) to be ~3.8% RSD, 3.1% bias, 0.7 μg/mL, respectively. A microdrop dispenser was used to deliver single drops containing 90 pL into the space where a LIBS plasma was generated with a focused laser pulse. In the single drop microdrop LIBS experiment, the analysis of a single drop, containing a total mass of 45 pg, resulted in a precision of 13% RSD and a bias of 1% for the Al I (394.40 nm) emission line. The absolute limits of detection of single drop microdrop LIBS for the emission lines Al I (394.40 nm) and Sr II (421.5 nm) were approximately 1 pg, and Ba II (493.41 nm) produced an absolute detection limit of approximately 3 pg. Overall, the precision, accuracy, and absolute LOD determined for single microdrop LIBS resulted in a typical performance of ~14% RSD, 6% bias, and 1 pg for the elements Sr II (421.55 nm), Al I(394.40 nm), Mg II (279.80), and Ba II(493.41 nm).