古代锡青铜器中铅夹杂物的锡含量:随时间变化的过程?

IF 8.3 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY
G. Artioli, A. Fontanari, I. Angelini, Chiara Lucarelli, M. Etter, Henrik Jeppesen, S. Shilstein, S. Shalev
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引用次数: 0

摘要

在古代,铅是生产大型青铜器(尤其是大型雕像)时添加的一种常见元素,以增强铸造过程的流动性。由于铅不与纯铜或锡铜合金相形成固溶体,因此在铜锡铅三元熔体冷却过程中,铅通常以球状液滴的形式出现在金属基体中,嵌入锡青铜晶体(通常为 α 相)内部或其间隙位置,成为最后的结晶相。最近,有人建议将铅液滴中的非平衡锡含量作为检测现代材料的可行参数[Shilstein、Berner、Feldman、Shalev & Rosenberg (2019)。STAR Sci.考古。5, 29-35]。该应用假设了一个随时间变化的过程,其时间尺度为数百年,根据几微米长度的锡在铅中的扩散系数估算 [Oberschmidt, Kim & Gupta (1982). J. Appl. Phys. 53, 5672-5677]。因此,近代锡青铜器中的含铅夹杂物实际上是含 ∼ 3% 锡原子的铅锡蜕变固溶体。与此相反,在古代器物中,由于发生了不混合过程,以及锡从微纳米包体中扩散到基体中,导致铅包体中的锡含量大大降低,甚至可以忽略不计。铅夹杂物中的锡含量取决于对铅锡固溶体中相的晶格参数的精确测量,因为对于低锡值来说,它与 Vegard 定律密切相关。本文介绍并讨论了对现代和古代样品进行的几项新测量,以验证该方法是否适用于检测现代伪装成古代的艺术品。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
The tin content of lead inclusions in ancient tin-bronze artifacts: a time-dependent process?
In antiquity, Pb was a common element added in the production of large bronze artifacts, especially large statues, to impart fluidity to the casting process. As Pb does not form a solid solution with pure Cu or with the Sn–Cu alloy phases, it is normally observed in the metal matrix as globular droplets embedded within or in interstitial positions among the crystals of Sn-bronze (normally the α phase) as the last crystallizing phase during the cooling process of the Cu–Sn–Pb ternary melt. The disequilibrium Sn content of the Pb droplets has recently been suggested as a viable parameter to detect modern materials [Shilstein, Berner, Feldman, Shalev & Rosenberg (2019). STAR Sci. Tech. Archaeol. Res. 5, 29–35]. The application assumes a time-dependent process, with a timescale of hundreds of years, estimated on the basis of the diffusion coefficient of Sn in Pb over a length of a few micrometres [Oberschmidt, Kim & Gupta (1982). J. Appl. Phys. 53, 5672–5677]. Therefore, Pb inclusions in recent Sn-bronze artifacts are actually a metastable solid solution of Pb–Sn containing ∼3% atomic Sn. In contrast, in ancient artifacts, unmixing processes and diffusion of Sn from the micro- and nano-inclusions of Pb to the matrix occur, resulting in the Pb inclusions containing a substantially lower or negligible amount of Sn. The Sn content in the Pb inclusions relies on accurate measurement of the lattice parameter of the phase in the Pb–Sn solid solution, since for low Sn values it closely follows Vegard's law. Here, several new measurements on modern and ancient samples are presented and discussed in order to verify the applicability of the method to the detection of modern artwork pretending to be ancient.
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来源期刊
ACS Applied Materials & Interfaces
ACS Applied Materials & Interfaces 工程技术-材料科学:综合
CiteScore
16.00
自引率
6.30%
发文量
4978
审稿时长
1.8 months
期刊介绍: ACS Applied Materials & Interfaces is a leading interdisciplinary journal that brings together chemists, engineers, physicists, and biologists to explore the development and utilization of newly-discovered materials and interfacial processes for specific applications. Our journal has experienced remarkable growth since its establishment in 2009, both in terms of the number of articles published and the impact of the research showcased. We are proud to foster a truly global community, with the majority of published articles originating from outside the United States, reflecting the rapid growth of applied research worldwide.
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