Rapid Screening Method for Brominated Flame Retardants and Hexavalent Chromium by Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)

J. Naka, N. Hirano, H. Kurokawa, J. Kobayashi, Y. Kawashima
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Abstract

By Directive on RoHS, the use of six hazardous substances is restricted to new electrical and electronic equipment put on the market in Europe from 1 July 2006. The estimation of the type and the content of brominated flame retardants is necessary in plastics of the equipment and the parts. The new technique by using time-of-flight secondary ion mass spectrometry (TOF-SIMS) is proposed for rapid screening test of these substances. We named this technique one droplet extraction method. The sampling method of brominated flame retardants in plastic materials with toluene on silver substrate was investigated for analysis of trace organic compounds by TOF-SIMS. High impact polystyrene (PS) and polypropylene (PP) plates were prepared as evaluation samples containing decabromodiphenylether (DeBDE) of 0.01-10 wt%. Evaluation time that includes sample pretreatment time and measurement time was about 1 hour. The positive quasi-molecular ion (DeBDE+Ag)+ (DeBDE cationized with Ag) was suitable for estimation of DeBDE. It was proved that content and spectral intensity had the clear magnitude correlation within 0.01-10 wt% content of DeBDE. It was found that the quick decision of whether the brominated flame retardants in the plastics is the substance restricted or not by Directive on RoHS is possible by this method. We can screen the substances in wide range of content of 0.01-10 wt%. Also it was found that the quick decision of whether hexavalent chromium is present in metals is possible by an application of this method. It was confirmed that one droplet extraction method using TOF-SIMS is a very powerful technique for the rapid screening test of brominated flame retardants and Cr (VI). It can be expected that hazardous substance management that concerns Directive on RoHS becomes more reliable
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飞行时间二次离子质谱法快速筛选溴化阻燃剂和六价铬
根据RoHS指令,由2006年7月1日起,在欧洲投放市场的新电器及电子设备不得使用六种有害物质。对设备和部件塑料中溴化阻燃剂的种类和含量进行估算是必要的。提出了利用飞行时间二次离子质谱法(TOF-SIMS)对这些物质进行快速筛选的新技术。我们将此技术命名为“一滴萃取法”。用TOF-SIMS法研究了塑料材料中溴化阻燃剂在银基体上的取样方法,并对痕量有机化合物进行了分析。制备了高冲击聚苯乙烯(PS)和聚丙烯(PP)板作为评价样品,其中十溴二苯醚(DeBDE)含量为0.01-10 wt%。评估时间包括样品预处理时间和测量时间约为1小时。正准分子离子(DeBDE+Ag)+ (DeBDE被Ag阳离子化)适合用于DeBDE的估计。结果表明,在DeBDE含量0.01 ~ 10 wt%范围内,其含量与光谱强度具有明显的幅度相关性。结果表明,该方法可以快速判断塑料中溴化阻燃剂是否为RoHS指令限制物质。我们可以筛选含量在0.01- 10wt %范围内的物质。还发现,应用该方法可以快速确定金属中是否存在六价铬。验证了TOF-SIMS单滴萃取法是一种非常有效的溴化阻燃剂和Cr (VI)快速筛选试验技术,可以预见RoHS指令相关有害物质管理将变得更加可靠
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