史前黄铜器及其冶炼工艺
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摘要
迄今为止,世界范围内共发现了公元前5千纪至公元前2千纪早期的黄铜制品约40余件,分布在爱琴海、两河流域、波斯湾、伊朗、中亚和中国等地。将这些黄铜制品的检测结果及其冶炼工艺进行系统梳理和总结后,得出以下推论:(1)黄铜与砷铜一样,是人类最早使用的一种重要合金;(2)这些黄铜制品中,除少量制品仅含铜、锌元素外,大多数制品还不同程度地含有铅、锡、镍、铁、砷和银等元素中的一种或几种,且元素含量分布范围较广,这一现象与冶炼所用矿石和冶炼条件有紧密的联系;(3)史前黄铜应由铜锌共生矿或混合矿(铜氧化矿和锌氧化矿)冶炼获得,且最初采用的是固体还原工艺,经简单加工成型。共生矿或混合矿冶炼是人类早期认识与利用金属时获得合金的一种主要方式。
This paper presents a review of over forty prehistoric brass objects(5th–early 2nd millenium BC) found around the Aegean Sea, the Mesopotamia, Central Asia, China, Iran and the Persian Gulf. Based on detection and analysis of the metallurgical process of these objects, it is concluded that: 1) brass is one of the earliest alloys as important as arsenical copper; 2) some of the objects under discussion contain copper and zinc only, while most objects contain lead, tin, nickel, iron, arsenic, silver and other elements, probably as a result of minerals in use and smelting conditions; 3) these prehistoric brass objects probably came from ores containing zinc and copper or mixture of copper and zinc ores and were manufactured using the solid-state reduction technique in the initial stage. The smelting of mineral intergrowth or mixed ores was an early and important way of producing alloy.
This paper presents a review of over forty prehistoric brass objects(5th–early 2nd millenium BC) found around the Aegean Sea, the Mesopotamia, Central Asia, China, Iran and the Persian Gulf. Based on detection and analysis of the metallurgical process of these objects, it is concluded that: 1) brass is one of the earliest alloys as important as arsenical copper; 2) some of the objects under discussion contain copper and zinc only, while most objects contain lead, tin, nickel, iron, arsenic, silver and other elements, probably as a result of minerals in use and smelting conditions; 3) these prehistoric brass objects probably came from ores containing zinc and copper or mixture of copper and zinc ores and were manufactured using the solid-state reduction technique in the initial stage. The smelting of mineral intergrowth or mixed ores was an early and important way of producing alloy.
引文
[1][6]半坡博物馆、陕西省考古研究所、临潼县博物馆:《姜寨--新石器时代遗址发掘报告》,文物出版社,1988年,第148、544-548页。
[2][3]A.M.Pollard,C.Heron,Archaeological Chemistry.Cambridge:Royal Society of Chemistry,1996,pp.196-204;P.T.Craddock,ed.,2000 Years of Zinc and Brass,London:British Museum Press,1998.
[4]R.J.Forbes,Studies in Ancient Technology(Volume VIII),Leiden:E.J.Brill,1964,pp.265-275.
[5]安志敏:《中国早期铜器的几个问题》,《考古学报》1981年第3期;安志敏:《试论中国的早期铜器》,《考古》1993年第12期。
[7]韩汝玢、柯俊主编《中国科学技术史·矿冶卷》,科学出版社,2007年,第177、182-183页。
[8]中国社会科学院考古研究所编著《胶县三里河》,文物出版社,1988年,第8、21、196-199页。
[9]王建平、王力之:《山西周家庄遗址出土龙山时期铜片的初步研究》,《中国国家博物馆馆刊》2013年第3期。
[10][11][12][13][14][15][16][17][18][19][20]C.P.Thornton,“Of Brass and Bronze in Prehistoric Southwest Asia”,in S.La Niece,D.Hook,and P.T.Craddock,eds.,Metals and mines:Studies in Archaeometallurgy,London:Archetype Publications,2007,pp.123-135.
[21]东北工学院有色重金属冶炼教研室等编著《锌冶金》,冶金工业出版社,1978年,第114-122页。
[22]东北工学院有色重金属冶炼教研室等编著《锌冶金》,冶金工业出版社,1978年,第114-122页;何堂坤:《关于〈天工开物〉所记炼锌技术之管见》,《化学通报》1984第7期。
[23][25]Justine Bayley,“The Production of Brass in Antiquity with Particular Reference to Roman Britain”,in P.T.Craddock,eds.,2000 Years of Zinc and Brass,pp.7-26.
[24]R.J.Forbes,Studies in Ancient Technology(Volume VIII),Leiden:E.J.Brill,1964,pp.265-275;苏荣誉:《原始黄铜初探》,《青铜文化研究》第7辑,黄山书社,2011年,第148-158页。
[26][27]北京钢铁学院冶金史组:《中国早期铜器的初步研究》,《考古学报》1981年第3期。
[28]W.Ro s t o c k e a n d J.R.D v o r a k,“S o m e Experiments with Co-Smelting to Copper Alloys”,Archeomaterials,no.5,1991,pp.5-20.
[29]凡小盼、黄洁、赵瑞廷等:《中国早期黄铜混合矿冶炼工艺的模拟探索》,《南方文物》2010年4期。
[30]P.T.Craddock,“The Composition of the Copper Alloys Used by the Greek,Etruscan and Roman Civilisations 3:the Origins of Early Use of Brass”,Journal of Archeological Science,vol.5,no.1,1978,pp.1-16.
[31]赵匡华、张惠珍:《中国古代炼丹术中诸药金、药银的考释与模拟实验》,《自然科学史研究》1987年第6期。
[32]Brain D.Newbury,Michael R.Notis and Dale E.Newbury,“Revisiting the Zinc Composition Limit of Cementation Brass”,Historical Metallurgy,vol.39,no.2,2005,pp.75-81.
[33]凡小盼、王昌燧、周卫荣等:《中国早期黄铜冶炼工艺模拟实验研究》,《中国钱币》2011年第3期。
[34][38]Benjamin W.Roberts,Christopher P.Thornton and Vincent C.Pigott,“Development of Metallurgy in Eurasia”,Antiquity,vol.83,no.322,2009,pp.1012-1022.
[35]Benjamin W.Roberts and Christopher P.T h or n ton,Archaeometallurg y in Global Perspective,New York:Springer Science Business Media,2014,p.36,p.687.
[36]Xiaopan Fan,Garman Harbottle,Changsui Wang et al.,“Brass before Bronze?Early Copperalloy Metallurgy in China”,Journal of Analytical Atomic Spectrometry,vol.27,no.5,2012,pp.821-826.
[37]H.Lechtman,and S.Klein,“The Production of Copper-Arsenic Alloys(Arsenic Bronze)by Cosmelting:Modern Experiment,Ancient Practice”,Journal of Archaeological Science,vol.26,no.5,1999,pp.497-526.
[2][3]A.M.Pollard,C.Heron,Archaeological Chemistry.Cambridge:Royal Society of Chemistry,1996,pp.196-204;P.T.Craddock,ed.,2000 Years of Zinc and Brass,London:British Museum Press,1998.
[4]R.J.Forbes,Studies in Ancient Technology(Volume VIII),Leiden:E.J.Brill,1964,pp.265-275.
[5]安志敏:《中国早期铜器的几个问题》,《考古学报》1981年第3期;安志敏:《试论中国的早期铜器》,《考古》1993年第12期。
[7]韩汝玢、柯俊主编《中国科学技术史·矿冶卷》,科学出版社,2007年,第177、182-183页。
[8]中国社会科学院考古研究所编著《胶县三里河》,文物出版社,1988年,第8、21、196-199页。
[9]王建平、王力之:《山西周家庄遗址出土龙山时期铜片的初步研究》,《中国国家博物馆馆刊》2013年第3期。
[10][11][12][13][14][15][16][17][18][19][20]C.P.Thornton,“Of Brass and Bronze in Prehistoric Southwest Asia”,in S.La Niece,D.Hook,and P.T.Craddock,eds.,Metals and mines:Studies in Archaeometallurgy,London:Archetype Publications,2007,pp.123-135.
[21]东北工学院有色重金属冶炼教研室等编著《锌冶金》,冶金工业出版社,1978年,第114-122页。
[22]东北工学院有色重金属冶炼教研室等编著《锌冶金》,冶金工业出版社,1978年,第114-122页;何堂坤:《关于〈天工开物〉所记炼锌技术之管见》,《化学通报》1984第7期。
[23][25]Justine Bayley,“The Production of Brass in Antiquity with Particular Reference to Roman Britain”,in P.T.Craddock,eds.,2000 Years of Zinc and Brass,pp.7-26.
[24]R.J.Forbes,Studies in Ancient Technology(Volume VIII),Leiden:E.J.Brill,1964,pp.265-275;苏荣誉:《原始黄铜初探》,《青铜文化研究》第7辑,黄山书社,2011年,第148-158页。
[26][27]北京钢铁学院冶金史组:《中国早期铜器的初步研究》,《考古学报》1981年第3期。
[28]W.Ro s t o c k e a n d J.R.D v o r a k,“S o m e Experiments with Co-Smelting to Copper Alloys”,Archeomaterials,no.5,1991,pp.5-20.
[29]凡小盼、黄洁、赵瑞廷等:《中国早期黄铜混合矿冶炼工艺的模拟探索》,《南方文物》2010年4期。
[30]P.T.Craddock,“The Composition of the Copper Alloys Used by the Greek,Etruscan and Roman Civilisations 3:the Origins of Early Use of Brass”,Journal of Archeological Science,vol.5,no.1,1978,pp.1-16.
[31]赵匡华、张惠珍:《中国古代炼丹术中诸药金、药银的考释与模拟实验》,《自然科学史研究》1987年第6期。
[32]Brain D.Newbury,Michael R.Notis and Dale E.Newbury,“Revisiting the Zinc Composition Limit of Cementation Brass”,Historical Metallurgy,vol.39,no.2,2005,pp.75-81.
[33]凡小盼、王昌燧、周卫荣等:《中国早期黄铜冶炼工艺模拟实验研究》,《中国钱币》2011年第3期。
[34][38]Benjamin W.Roberts,Christopher P.Thornton and Vincent C.Pigott,“Development of Metallurgy in Eurasia”,Antiquity,vol.83,no.322,2009,pp.1012-1022.
[35]Benjamin W.Roberts and Christopher P.T h or n ton,Archaeometallurg y in Global Perspective,New York:Springer Science Business Media,2014,p.36,p.687.
[36]Xiaopan Fan,Garman Harbottle,Changsui Wang et al.,“Brass before Bronze?Early Copperalloy Metallurgy in China”,Journal of Analytical Atomic Spectrometry,vol.27,no.5,2012,pp.821-826.
[37]H.Lechtman,and S.Klein,“The Production of Copper-Arsenic Alloys(Arsenic Bronze)by Cosmelting:Modern Experiment,Ancient Practice”,Journal of Archaeological Science,vol.26,no.5,1999,pp.497-526.