On-line detection of heavy metals and brominated flame retardants in technical polymers with laser-induced breakdown spectrometry

The use of laser-induced breakdown spectrometry (LIBS) for the analysis of heavy metals and brominated flame retardants in end-of-life waste electric and electronic equipment (EOL-WEEE) pieces is investigated. Single- and double-pulse plasma excitation as well as the influence of detection parameters is studied to yield a parameter field with improved sensitivity and limits of detection. A LIBS analyzer was set up as an on-line measuring unit to detect heavy metals and brominated flame retardants in moving EOL-WEEE pieces in an automatic sorting line. An autofocusing unit with an adjustment range of 50 mm was incorporated to permit measurements of objects that pass by a LIBS analyzer with their surfaces at various distances from it. Tests with EOL-WEEE monitor housings on the conveyor belt of a pilot sorting system successfully demonstrated the capability of the LIBS analyzer to quantify the concentration of hazardous elements in real waste EOL-WEEE pieces.     

Substantive intumescent flame retardants for functional fibrous polymers

This paper discusses the potential for developing substantive intumescent, flame retardant fibres. It also reviews very recent work in the authors' laboratories that has demonstrated the successful reaction of char-promoting polyol phosphoryl chlorides with fibres containing active hydrogens such as cellulose flame retarded cellulose, wool and polyamide. Results show that satisfactory char enhancement occurs with evidence that intumescent character exists in some of these and that the chemical treatments are resistant to boiling in water. Using this chemistry, there is the potential, therefore, of creating the first generation of substantive intumescent fibres that will provide a cost-effective range of textiles with significantly enhanced fire resistant properties.     

Simulated solar UV-irradiation of endocrine disrupting chemical octylphenol

The photolysis of octylphenol (OP) was investigated using a solar simulator in the absence/presence of dissolved natural organic matter (DNOM), HCO(3)(-), NO(3)(-) and Fe(III) ions. The effects of different parameters such as initial pH, initial concentration of substrate, temperature, and the effect of hydrogen peroxide concentration on photodegradation of octylphenol in aqueous solution have been assessed. The results indicate that the oxidation rate increases in the presence of H(2)O(2), nitrate and DNOM. Phenol, 1,4-dihydroxylbenzene and 1,4-benzoquinone were identified as intermediate products of photodegradation of octylphenol, through an HPLC method. In addition, the disappearance of the estrogenic activity of octylphenol during irradiation using YES test was investigated. Based upon the YES test results, there was a strong decrease of estrogenic activity of octylphenol after 8h irradiation in the presence of hydrogen peroxide.     

改性蒙脱土硅橡胶阻燃复合材料的制备

研究了分别采用十六烷基三甲基溴化铵(CTAB)和磷酸三丁酯作为插层剂改性的有机蒙脱土(OMMT)的阻燃效果及抑制熔滴物产生的效果,发现单独添加OMMT的硅橡胶阻燃复合材料都有抑制熔滴物产生,减少烟和灰尘生成的作用,但是不具备阻燃的效果;将OMMT与100份Al(OH)3和40份Fe2O3进行复配,发现只需添加3份的有机蒙脱土一(OMMT-1)或5份有机蒙脱土二(OMMT-2)即可达到垂直燃烧FV-0级别;热重分析表明,OMMT的热稳定性能比蒙脱土原土好,OMMT-1的比OMMT-2的好。     

均三嗪系列膨胀型阻燃剂的合成及应用

均三嗪系列膨胀型阻燃剂具有抑烟、低毒、无腐蚀、阻燃效果佳等优点,在无卤膨胀阻燃高聚物领域具有很好的应用潜力。综述了均三嗪系列膨胀型阻燃剂的合成及应用,以三聚氰胺或三聚氯氰为基,通过化学反应重建或复配等方法可以得到一系列无卤膨胀阻燃剂,同时介绍了上述阻燃剂对高聚物的阻燃情况,最后提出了均三嗪系列阻燃剂未来的发展方向。     

有机磷阻燃剂插层钙基蒙脱土纳米复合物的制备和表征EI北大核心CSCD

采用一种简单直接、绿色无溶剂的制备方法,将三种有机磷小分子阻燃剂(9,10-二氢-9-氧杂-10-膦菲-10-氧杂(DOPO)、磷酸三苯酯(TPP)、季戊四醇磷酸酯(PEPA))分别插层进入到钙基蒙脱土(CaMMT)的片层中,制备了三种有机磷阻燃剂的蒙脱土纳米复合物(DOPO-CaMMT,TPP-CaMMT和PEPA-CaMMT)。X射线衍射(XRD)表明三种含磷小分子成功插层进入了蒙脱土的片层中,透射电子显微镜(TEM)验证了三种蒙脱土纳米复合物中蒙脱土的层间距表现出不同程度的增加,热重分析(TGA)表征了纳米复合物热稳定性的变化。对三种纳米复合物的形成机理进行研究。结果表明,TPP和PEPA均以一步插入到蒙脱土片层中;DOPO按照两步插层蒙脱土,且层间距更大。三种有机磷阻燃剂在插层进入蒙脱土层间形成的纳米复合物,实现了蒙脱土在聚合物中更好的分散性及磷硅协同的阻燃效应。     

阻燃剂对双酚F型环氧树脂液氧相容性影响

为研究环氧树脂阻燃改性对其液氧相容性的影响,本文通过添加六溴环十二烷和三氧化二锑对双酚F型环氧树脂进行阻燃改性,并通过对阻燃改性树脂进行液氧相容性测试来研究其液氧相容性.实验结果表明:添加质量分数4.8%的三氧化二锑可改善树脂的液氧相容性;添加质量分数6.8%六溴环十二烷和2.2%三氧化二锑的双酚F型环氧树脂表现出更好的液氧相容性.仅添加质量分数9.0%六溴环十二烷的双酚F型环氧树脂表现出非常好的液氧相容性,在20次液氧冲击实验中未表现出敏感性反应.为了更清楚地分析液氧相容性机理,对冲击前后的试样表面进行扫描电镜(SEM)和X射线光电子能谱(XPS)分析.结果表明:六溴环十二烷和三氧化二锑在冲击过程中抑制环氧树脂与液氧反应,提高了环氧树脂与液氧的相容性.     

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.     

Synergistic flame retardancy effect of graphene nanosheets and traditional retardants on epoxy resin

Novel non-toxic halogen-free flame retardants are replacing traditional flame retardants in polymer and polymer matrix composite structures. In this study, graphene nanosheet (GNS) is investigated in combination with traditional layered double hydroxide (LDH), layered rare-earth hydroxide (LRH), and phosphorus-based flame retardant (DOPO) to enhance the flame retardancy of epoxy resin. A synergistic flame retardancy effect is achieved in GNS/LDH and GNS/DOPO systems where combined GNS and LDH increased the viscosity of the epoxy melt, and limited the flame propagation through inhibition of dripping. The limiting oxygen index of epoxy increased from 15.9 to 23.6 with addition of 0.5 wt.% each of GNS and LDH. With the addition of 2.5 wt.% of both GNS and LDH, the total heat release of epoxy resin also reduced from 33.4 MJ/m² to 24.6 MJ/m². The synergistic effect of GNS and DOPO adopted a different mechanism. The addition of 2.5 wt.% of GNS and DOPO reduced the peak heat release rate from 1194 kW/m² to 396 kW/m², and the total heat release rate from 72.5 MJ/m² to 48.1 MJ/m². The synergistic mechanisms of the flame retardants were closely analyzed and correlated with the flame retardant properties.     

A framework for an alternatives assessment dashboard for evaluating chemical alternatives applied to flame retardants for electronic applications

The goal of alternatives assessment (AA) is to facilitate a comparison of alternatives to a chemical of concern, resulting in the identification of safer alternatives. A two-stage methodology for comparing chemical alternatives was developed. In the first stage, alternatives are compared using a variety of human health effects, ecotoxicity, and physicochemical properties. Hazard profiles are completed using a variety of online sources and quantitative structure–activity relationship models. In the second stage, alternatives are evaluated utilizing an exposure/risk assessment over the entire life cycle. Exposure values are calculated using screening-level near-field and far-field exposure models. The second stage allows one to more accurately compare potential exposure to each alternative and consider additional factors that may not be obvious from separate binned persistence, bioaccumulation, and toxicity scores. The methodology was utilized to compare phosphate-based alternatives for decabromodiphenyl ether (decaBDE) in electronic applications.     

Post-fire flexural performance of epoxy-nanocomposite matrix glass fibre composites containing conventional flame retardants

This paper investigates the effect of varied nanoparticles (silicate nanoclays and double-walled carbon nanotubes) and micro-sized flame retardants (FRs) on the post heat/fire flexural performance of glass fibre-reinforced (GFR) epoxy composites. The fire reaction properties of GFR epoxy composites containing different combinations of nano- and micro-sized FRs were studied at varied incident heat fluxes (35–75 kW/m²). The flexural stiffness and modulus values of radiant heat-damaged GFR composites decreased rapidly with increasing incident heat flux. On another hand, the post-fire flexural properties of these specimens exposed for 30–90 s post-ignition at 50 kW/m² retained only 20% of their room temperature flexural properties. Despite significant improvements in the fire reaction properties, their post-fire flexural performance was least affected. This suggests that, while these flame retardants are effective in promoting char formation, the formed char networks are not consolidated enough to effectively constrain the fibre reinforcements.     

几种新型高含磷含氮聚磷酰胺阻燃剂的合成与表征

以螺环季戊四醇双磷酸酯二酰氯（SPDPC）和苯基二氯磷酸酯（PDCP）为酰氯单体,分别与哌嗪及乙二胺通过溶液缩聚合成了4种聚磷酰胺阻燃剂——聚哌嗪季戊四醇双磷酸酯（PPS）、聚乙二胺季戊四醇双磷酸酯（PES）、聚哌嗪苯基磷酸酯（PPP）及聚乙二胺苯基磷酸酯（PEP）。以IR、1H NMR,31 P NMR、元素分析、TGA表征其结构及热性能,以乌氏粘度计测定PPS与PES特性黏度,结果发现反应18h聚合度最大,分别为0.19和0.21dL/g。以激光解吸电离-飞行时间质谱仪（MALDI-TOF MS）表征PPP与PEP分子量及组成。结果表明聚合度均在7～8之间。     

Accident prediction models for urban roads

This paper describes some of the main findings from two separate studies on accident prediction models for urban junctions and urban road links described in [Uheldsmodel for bygader-Del1: Modeller for 3-og 4-benede kryds. Notat 22, The Danish Road Directorate, 1995; Uheldsmodel for bygader- Del2: Modeller for straekninger. Notat 59, The Danish Road Directorate, 1998] (Greibe and Hemdorff, 1995, 1988).The main objective for the studies was to establish simple, practicable accident models that can predict the expected number of accidents at urban junctions and road links as accurately as possible. The models can be used to identify factors affecting road safety and in relation to 'black spot' identification and network safety analysis undertaken by local road authorities.The accident prediction models are based on data from 1036 junctions and 142 km road links in urban areas. Generalised linear modelling techniques were used to relate accident frequencies to explanatory variables.The estimated accident prediction models for road links were capable of describing more than 60% of the systematic variation ('percentage-explained' value) while the models for junctions had lower values. This indicates that modelling accidents for road links is less complicated than for junctions, probably due to a more uniform accident pattern and a simpler traffic flow exposure or due to lack of adequate explanatory variables for junctions.Explanatory variables describing road design and road geometry proved to be significant for road link models but less important in junction models. The most powerful variable for all models was motor vehicle traffic flow.     

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.     

Preparation and properties of polystyrene nanocomposites with graphite oxide and graphene as flame retardants

In this study, graphite oxides (GOs) with different oxidation degrees and graphene nanosheets were prepared by a modified Hummers method and thermal exfoliation of the prepared GO, respectively. Polystyrene (PS)/GO and PS/graphene nanocomposites were prepared via melt blending. X-ray diffraction results showed that GOs and graphene were exfoliated in the PS composites. It could be observed from the scanning electron microscope images that GOs and graphene were well dispersed throughout the matrix without obvious aggregates. Dynamic mechanical thermal analysis suggested that the storage modulus for the PS/GO1 and PS/graphene nanocomposites was efficiently improved due to the low oxygen content of GO1 and the elimination of the oxygen groups from GO. The flammability of nanocomposites was evaluated by thermal gravimetric analysis and cone calorimetry. The results suggested that both the thermal stability and the reduction in peak heat release rate (PHRR) decreased with the increasing of the oxygen groups in GOs or graphene. The optimal flammability was obtained with the graphene (5 wt%), in which case the reduction in the PHRR is almost 50 % as compared to PS.