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民国纸币印刷颜料的光老化性能初探

  • 裔传臻1,2

    机 构：

    1. 上海博物馆,上海 200003

    2. 馆藏文物保存环境研究国家文物局重点科研基地(上海博物馆),上海 200231

    ×
  • ， 徐文娟1,2

    机 构：

    1. 上海博物馆,上海 200003

    2. 馆藏文物保存环境研究国家文物局重点科研基地(上海博物馆),上海 200231

    ×
  • ， 吴旦敏1

    机 构：

    1. 上海博物馆,上海 200003

    ×
  • ， 王恩元1,2

    机 构：

    1. 上海博物馆,上海 200003

    2. 馆藏文物保存环境研究国家文物局重点科研基地(上海博物馆),上海 200231

    ×

1. 上海博物馆,上海 200003；
2. 馆藏文物保存环境研究国家文物局重点科研基地(上海博物馆),上海 200231；

A preliminary study on the photo-degradation of printing pigments on banknotes issued during the period of the Republic of China

  • YI Chuanzhen1,2

    Affiliation：

    1. Shanghai Museum, Shanghai 200003 , China

    2. Key Scientific Research Base of Museum Environment (Shanghai Museum), National Cultural Heritage Administration, Shanghai 200231 , China

    ×
  • ， XU Wenjuan1,2

    Affiliation：

    1. Shanghai Museum, Shanghai 200003 , China

    2. Key Scientific Research Base of Museum Environment (Shanghai Museum), National Cultural Heritage Administration, Shanghai 200231 , China

    ×
  • ， WU Danmin1

    Affiliation：

    1. Shanghai Museum, Shanghai 200003 , China

    ×
  • ， WANG Enyuan1,2

    Affiliation：

    1. Shanghai Museum, Shanghai 200003 , China

    2. Key Scientific Research Base of Museum Environment (Shanghai Museum), National Cultural Heritage Administration, Shanghai 200231 , China

    ×

1. Shanghai Museum, Shanghai 200003 , China；
2. Key Scientific Research Base of Museum Environment (Shanghai Museum), National Cultural Heritage Administration, Shanghai 200231 , China；

作者简介:

裔传臻(1991—),女,2015年硕士毕业于复旦大学,馆员,研究方向为纸质文物保护,E-mail:yichuanzhen1991@163.com

中图分类号:K876.9

文献标识码:A

文章编号:1005-1538(2023)03-0087-07

DOI:10.16334/j.cnki.cn31-1652/k.20221202777

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目录contents

    摘要

    为了初步评价光照对民国纸币的影响,为博物馆纸币文物的展陈照明和保存提供建议,本研究选取了八枚纸币分别进行LED灯和自然光老化实验,并通过拉曼光谱仪和X射线荧光光谱仪确定了纸币样品颜料的主要成分——合成有机颜料红49:1、普鲁士蓝、铬酸铅和炭黑。通过老化前后的色差分析可知,纸币红色颜料变化最大,其他颜色变化相对较小。因此,对于民国纸币类文物,尤其是含有红色合成有机颜料的纸币文物,需要控制其光照条件以防止老化变色。

    Abstract

    In order to do a preliminarily evaluation of the influences of light on banknotes issued during the period of the Republic of China and to provide suggestions for their exhibition and preservation in museums, eight banknotes were selected for light aging tests with LED light and natural light. The main pigments of the banknotes were determined using Raman spectrometry and X-ray fluorescence spectrometry. The results indicate that PR49:1, Prussian blue, lead chromate and carbon black were used. The red pigment (PR49:1) on banknotes faded fastest, while the other pigments had relatively smaller color changes. Therefore, it is necessary to control lighting to prevent the photo-degradation of banknotes, especially those containing synthetic organic red pigments.

    关键词

    民国纸币 ； 光老化 ； 合成颜料 ； 拉曼光谱 ； XRF

  • 0 引言

  • 我国是世界上最早发明和使用纸币的国家，纸币萌芽于唐末飞钱，产生于北宋交子[1]。纸币的发明对日常生活和经济社会发展都起到了积极的推动作用[2]，历代纸币文物也是研究中国历史、政治经济、文化交流、贸易和生产技术的重要资料。

  • 纸币文物主要由纸张和印刷颜料构成，不同年代的纸币颜料和纸张成分都有所不同，其中颜料种类多样，既有早期的无机颜料，也有近现代的合成颜料。施继龙等利用拉曼光谱分析发现两枚清末和民国票贴使用了朱砂和群青颜料[3]。季金鑫等利用拉曼光谱仪、视频显微镜和扫描电子显微镜能谱仪，发现光绪三十二年（1906年）天津德胜源银号票据、中华民国二十年（1931年）公行票据和1945年中华民国银行支票分别使用了朱砂、普鲁士蓝、雌黄、雄黄等无机颜料，也有颜料红146和颜料红53:1两种合成有机颜料[4-5]。甘清分析的清末和民国三个版别蟠龙邮票使用了朱砂、铅丹、群青、普鲁士蓝、铬酸铅等天然和合成无机颜料[6]。李涛研究发现大明通行宝钞“一贯”版使用了红色铅丹和黑色炭黑颜料，纸张为桑皮; 大清宝钞和户部官票使用了朱砂、普鲁士蓝和炭黑颜料，纸张纤维分别为麻类和桑皮; 民国纸币和当票使用了普鲁士蓝和群青，纸张纤维分别是树皮针叶木混合纤维和树皮类纤维[7]。裔传臻利用拉曼光谱研究了11枚1945年民国法币，发现普遍使用了颜料红49:1、普鲁士蓝和铅铬黄等颜料[8]。

  • 由于部分纸币文物色彩丰富，容易受到光学辐射损害而发生老化褪色和变色，根据GB/T23863—2009《博物馆照明设计规范》，对光特别敏感的展品其展平面的照度应≤50 lx，年曝光量≤50 000 lx·h[9]。国内已有不少针对纺织品染料、书画颜料进行的不同光源下模拟光老化的研究:如贺冰等研究了卤素灯、荧光灯和LED灯对黄檗和槐米等黄色植物染料染色的丝绸样品的褪色影响[10]; 徐方圆等从光谱角度研究了不同照明光源对7种植物染料染色丝绸样品的褪色影响[11]; 党睿等研究了白光LED、卤钨灯、金卤灯光源对部分中国书画矿物颜料和植物颜料的损伤情况[12-13]; 冯荟等采用常规光老化方法分析了黄檗、槐米、苏木、紫草和茜草这五种常见植物染料在卤素灯及LED光源下的褪色速率[14]; 谭慧娇和党睿通过色差和拉曼光谱评估不同窄带光对丝质文物的色彩损伤[15]。然而目前对于有机颜料和纸币老化的研究相对较少:康文烈等对比了PY.151、PR.254和PV.23等合成有机颜料在紫外加速老化、氙弧灯和户外暴晒下的颜色变化[16]; Anghelone等研究了含有酞蓝和酞绿的丙烯酸颜料光老化和降解过程[17]; Sabatini等对四种含有曙红的色淀颜料进行了光老化研究[18]; Micheluz等研究了使用有机颜料红48:2和53:1着色的红色聚乙烯物体的变色以及降解[19]。

  • 本研究选取了八枚不同颜色的民国纸币，使用拉曼光谱仪和X射线荧光光谱仪对其主要颜料进行成分分析，并利用LED光源和自然光对其进行光老化实验和色差测定，以便对民国纸币文物的光老化性能开展研究。

  • 1 样品与方法

  • 1.1 纸币样品

  • 选取主要颜色为红色、橙色、紫色、蓝色和绿色的民国纸币作为老化样品（样品自购，分别由中央印制厂、英美钞票公司、德纳罗印钞公司等不同印刷机构承印，面额各异）。纸币样品的详细信息见表1。

  • 表1 纸币样品信息

  • Table1 Information of banknote samples

  • 1.2 光照老化实验及分析方法

  • 将纸币样品分为两组，每张样品都用宣纸遮盖一半，分别进行人工光照老化和自然光照老化实验。

  • 人工光照老化实验在图1所示的老化箱内进行，光源为德国欧克照明有限公司的LED轨道射灯，色温3 000 K。将轨道射灯直接置于老化箱顶部的挂杆上，调节灯具位置使得试验台上光照尽量均匀。调整后，样品台上平均照度为759.9 lx，照度均匀度为94.75%。将第一组纸币样品放置于老化箱样品台上，进行连续光照老化实验，定期进行色差测定并轮换样品位置。目前人工光照老化实验已进行了237 d，按照博物馆每天累积光照8 h、照度不超过50 lx且年曝光量不超过50 000 lx·h计算，相当于在博物馆展出了86.5年。

  • 第二组纸币样品直接置于室内窗边，进行自然光照老化实验。经测定，室内白天照度最高可达50 000 lx，紫外线相对含量达70 μW/cm2。目前自然光照老化实验已进行了353 d。

  • 图1 光照老化箱示意图

  • Fig.1 Schematic diagram of the experimental chamber for light aging

  • 1.3 色差测定

  • 使用柯尼卡美能达CM-700d色差仪测定纸币样品的颜色变化。由于仪器测试孔直径大小为6 mm，为了防止测试区域存在多种颜色影响色度值，选取纸币上颜色较为集中的主色调区域和纸币纸张区域进行色差测定，每个区域选取2~3个点测定取其平均值。本实验使用CIE1976L*a*b*色空间度量颜色变化，所对应的色差公式为:

  • ΔE*=ΔL*2+Δa*2+Δb*2
    (1)

  • 式中，ΔE*表示色差; ΔL*表示颜色的亮度差异; Δa*正值表示红色差异，负值表示绿色差异; Δb*正值表示黄色差异，负值表示蓝色差异。

  • 1.4 纸币颜料测定

  • 使用Renishaw inVia Reflex显微共聚焦激光拉曼光谱仪，将纸币样品直接置于样品台上对纸币主要颜色成分进行原位测定。拉曼光谱测试范围为100~3 000 cm-1，物镜倍数×50，激光光源波长为785 nm，光栅刻线1 200 gr/mm。为避免损伤样品，样品表面激光功率控制在0.25~0.5 mW。曝光时间根据样品信号强弱从10~60 s不等，累加10次。

  • 使用德国Bruker公司Tracer 5i型便携式X射线荧光光谱仪（XRF）对纸币颜料进行元素检测。Rh靶，测试电压40 kV，电流20 mA，测试时间60 s。

  • 2 结果与讨论

  • 图2a和图2b分别为样品1-4红色颜料和样品1-3蓝色颜料的拉曼光谱。红色颜料处的拉曼特征峰为120、150、224、314、343、389、549、722、827、1 210、1 232、1 263，1 352、1 416、1 429、1 472、1 488、1 515、1 563、1 606和1 621 cm-1，蓝色颜料处的拉曼特征峰为270、529、2 097和2 157 cm-1。根据相关文献以及颜料拉曼数据库[8，20-23]，样品1-4的红色颜料中120、150、224、314、389和549 cm-1为铅丹的特征峰，其余为颜料红49:1（C.I.Pigment Red 49:1，C20H13N2O4S0.5Ba）的特征峰，XRF的检测结果也显示该样品含有铅和钡元素。样品1-3的蓝色颜料主要为普鲁士蓝。样品1-1绿色颜料和样品1-2紫色颜料的拉曼光谱与样品1-3的相似，主要为普鲁士蓝。

  • 图2c和图2d分别为样品2-1红色颜料和样品2-3橙色颜料的拉曼光谱。红色颜料的拉曼特征峰与第一组样品中红色颜料的相似——为颜料红49:1。橙色颜料的拉曼特征峰为142、359、841、1 344和1 595 cm-1，前四个特征峰属于铬酸铅（PbCrO4·PbO），后两个属于炭黑，XRF测试结果也显示该样品含有铅和铬元素。样品2-2绿色颜料和样品2-4蓝色颜料的拉曼光谱与样品1-3的相似，主要为普鲁士蓝。

  • 颜料红49:1，俗称立索尔红，是一种合成有机颜料，1899年由P.Julius发现[24]，主要用于印墨着色，尤其是用于出版凹印墨。1895年出现的对位红是出现最早的有机颜料，此后立索尔红、色淀红、银朱R、酞菁颜料等被陆续发明，如今市面上的有机颜料已达679种之余[25]。

  • 图2 部分颜料的拉曼光谱

  • Fig.2 Raman spectra of some pigments

  • 铬酸铅颜料着色力高，遮盖力强，如今仍被应用于部分涂料、塑料与油墨产品。随着国际社会对铅暴露问题的密切关注，联合国环境规划署和世卫组织协调成立含铅涂料全球联盟，建立含铅涂料全球各国监管框架以彻底淘汰含铅涂料[26]。

  • 普鲁士蓝{Fe4[Fe（CN）6]3}是1704年由德国人狄斯巴赫偶然间发现合成，是第一个现代意义上的人工合成颜料。根据李涛的研究，至迟在1759年，普鲁士蓝就已经通过海运被输入到中国（广州很可能是最早的登陆地点），1775—1778年，普鲁士蓝在中国的输入量已经十分可观[7]。目前国内各类文物上都有发现普鲁士蓝的存在[27-31]。

  • 2.2 纸币颜色变化

  • 表2为老化前后纸币样品的L*、a*和b*值。

  • 表2 纸币样品老化前后L*、a*和b*值

  • Table2 Values of L*, a* and b* before and after photo-degradation

  • 1）LED光源老化结果。图3a和图3b为第一组纸币颜料和纸张在LED光源照射老化下的色差变化图，其中样品1-4红色颜料的颜色变化最大，色差值达7.17，蓝色、紫色和绿色颜料的颜色变化在4左右，故色牢度等级秩序为绿色＞紫色＞蓝色＞红色。

  • 样品1-1、1-2和1-3的纸币纸张色差值分别为7.71、4.13和11.02。纸币样品在进行人工光照老化前，已有纸张变黄现象（b*值分别为16.54、11.70和21.48），老化前后的颜色变化主要由黄色褪色变白造成。

  • 2）自然光老化结果。图4为样品2-1在自然光照射老化前和老化353 d后的对比照片，纸币上的红色颜料几乎完全褪去，色差已高达49.10，L*值由54.41增长至85.28，a*值由38.98减至1.20，b*值由15.34减至9.90。图3c和图3d为第二组纸币颜料和纸张老化后的色差变化图，各颜料的色牢度等级秩序为:绿色＞蓝色＞浅绿色＞橙色＞浅黄色＞红色。纸币纸张和第一组样品一样，表现为黄色褪色后纸张变白。

  • 根据拉曼和XRF检测结果，两枚纸币样品的红色颜料为合成有机颜料红49:1，而其他纸币样品上的绿色、蓝色和紫色颜料中主要含有普鲁士蓝，为合成无机颜料。相对而言，合成无机颜料的耐候性、耐光性等性能较有机颜料更好，而有机颜料的色相更为丰富。Ghelardi等利用气相色谱-质谱联用仪和红外光谱仪，对几种合成颜料的光老化产物进行了研究，发现部分颜料老化后其芳香环有脱硫和羟基化的现象[32]。而光辐射主要由光化学反应和光的热效应引发或加速文物的老化，根据倒易定律，光损伤是一种光能累积的结果，与光照时间和照度的乘积即累积照度成正比。因此，对于主要颜色为红色或者以合成有机颜料呈色的纸币样品，应当对其陈列和保存时的光照予以降低和关注。对纸币所使用的纸张材料和老化性能将在之后进行研究。

  • 图3 样品的颜料色差值和纸张色差值

  • Fig.3 Changes of color difference of the pigments and paper of the samples

  • 图4 样品2-1自然光老化353天后的变化

  • Fig.4 Sample2-1 after 353 days of aging under natural light

  • 3 结论

  • 光照是文物老化变色的重要因素之一，对光敏感的文物需要控制其光照时间和强度。本研究中的纸币文物颜料主要包括合成有机颜料红49:1、合成无机颜料普鲁士蓝以及铅丹、铬酸铅和碳黑。在3 000 K色温的LED光源和自然光老化实验中，红色颜料变化最大，其色差值分别达7.17和49.10，在自然光下老化353 d的红色纸币已几乎完全褪色。绿色、蓝色、紫色和橙色等纸币颜色变化相对较小。因此，对于民国纸币文物，尤其是含有红色合成有机颜料的纸币文物，需要控制其光照条件以防止老化变色。

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  • 基本信息

    中图分类号: K876.9
    文献标识码: A
    DOI: 10.16334/j.cnki.cn31-1652/k.20221202777
    文章编号: 1005-1538(2023)03-0087-07

    基金信息

    国家重点研发计划项目(2020YFC1522500)资助；

    引用信息

    稿件历史

    收稿日期: 2022-12-14

  • 参考文献

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