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四种手枪在水环境中的腐蚀行为:腐蚀产物表征及其对沉积时间估算的影响。

Corrosion behaviour of four handguns in aqueous environments: corrosion product characterization and effects on estimating the time since deposition.

作者信息

Wogan Megan E, Webster-Hoffmeyer Katie S, Grgicak Catherine M

机构信息

Biomedical Forensic Sciences, Boston University School of Medicine, Boston MA 02118, USA.

出版信息

Sci Justice. 2013 Sep;53(3):363-70. doi: 10.1016/j.scijus.2013.04.010. Epub 2013 May 31.

Abstract

When a firearm has been disposed of in a body of water and becomes corroded, its appearance is altered and determining a time-since-immersion may be of import to the investigation. Therefore, in this study, the corrosion and mass loss of four handgun slides over a period of 180days were examined. Solid-state characterization of the metals and their corrosion products via SEM/EDX and powder X-ray Diffraction (pXRD) was performed. The pXRDs were analyzed against the NIST Powder Diffraction Database to determine the crystalline phases. Filings from the SS416 standard, Llama and Ruger handgun slide predominantly consisted of iron alloys. After 180-days in solution, pXRD indicated that the adherent corrosion products consisted of 1) γ-FeOOH and 2) iron oxide (Fe3O4 or Fe2O3). Additionally, pXRD analysis indicated that the adherent corrosion products of the SS416 standard also consisted of CrO3. Metal filings from the Raven and Jennings handgun slides were a mixture of iron-nickel-zinc and EDX and pXRD analyses of the corrosion products, when submersed in deionized water, indicated that the products consisted of: 1) γ-FeOOH, 2) iron oxide (Fe3O4 or Fe2O3), and 3) ZnFe2O4 or ZnO; where the Jennings adherent rust contained ZnFe2O4 and the Raven adherent rust contained ZnO. Further, pXRD of the corrosion products from these alloys, when submersed in 25 PSU (Practical Salinity Unit) solution, indicated that the products consisted of: 1) ZnO, 2) Zn(OH)2, 3) α-Ni(OH)2, and 4) NaCl. The data thus indicated that both metal composition and the presence of chloride ions had significant impacts on rates and products of corrosion and suggest that the presence of Cl(-) changes not only the rate of corrosion, but also the corroding species itself. While mechanisms and rates of the chloride driven corrosion processes offer explanations as to the different oxides and hydroxides observed between immersion conditions, they do not offer an explanation for the differences observed between handguns. Therefore, utilizing a general approach where surface area coverage of corrosion products is the sole consideration is not sufficient to determine time-since-immersion. Attempts to determine a time-since-immersion would require a priori knowledge of the mechanism of corrosion for a given metal mixture within a specified environment. The results described herein give indications as to the possible corrosion mechanism driving the process in high and low Cl(-) environments and show the necessity of including the metal composition, rust composition and ion concentration in any models that attempt to elucidate the time-since-immersion of handguns for forensic applications.

摘要

当一支枪支被丢弃在水体中并发生腐蚀时,其外观会发生改变,确定浸泡时间可能对调查很重要。因此,在本研究中,对四把手枪滑块在180天内的腐蚀和质量损失进行了检查。通过扫描电子显微镜/能谱仪(SEM/EDX)和粉末X射线衍射(pXRD)对金属及其腐蚀产物进行了固态表征。对照美国国家标准与技术研究院(NIST)粉末衍射数据库对pXRD图谱进行分析,以确定结晶相。SS416标准、羊驼牌和鲁格牌手枪滑块的锉屑主要由铁合金组成。在溶液中放置180天后,pXRD表明附着的腐蚀产物包括:1)γ-氢氧化铁(γ-FeOOH)和2)氧化铁(Fe3O4或Fe2O3)。此外,pXRD分析表明,SS416标准的附着腐蚀产物还包括三氧化铬(CrO3)。雷文牌和詹宁斯牌手枪滑块的金属锉屑是铁-镍-锌的混合物,对其浸没在去离子水中时的腐蚀产物进行的EDX和pXRD分析表明,产物包括:1)γ-氢氧化铁,2)氧化铁(Fe3O4或Fe2O3),以及3)铁酸锌(ZnFe2O4)或氧化锌(ZnO);其中詹宁斯牌附着锈中含有铁酸锌,雷文牌附着锈中含有氧化锌。此外,这些合金浸没在25实用盐度单位(PSU)溶液中的腐蚀产物的pXRD表明,产物包括:1)氧化锌,2)氢氧化锌(Zn(OH)2),3)α-氢氧化镍(α-Ni(OH)2),以及4)氯化钠(NaCl)。这些数据因此表明,金属成分和氯离子的存在对腐蚀速率和产物都有显著影响,并表明Cl(-)的存在不仅改变了腐蚀速率,还改变了腐蚀物种本身。虽然氯离子驱动的腐蚀过程的机制和速率可以解释在不同浸泡条件下观察到的不同氧化物和氢氧化物,但它们无法解释手枪之间观察到的差异。因此,仅以腐蚀产物的表面积覆盖率为唯一考虑因素的一般方法不足以确定浸泡时间。试图确定浸泡时间需要事先了解特定环境中给定金属混合物的腐蚀机制。本文所述结果表明了在高Cl(-)和低Cl(-)环境中驱动该过程的可能腐蚀机制,并表明在任何试图阐明手枪浸泡时间以供法医应用的模型中,都有必要纳入金属成分、锈成分和离子浓度。

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