CN105237040B - 一种石质文物及石材表面石膏风化层的选择性清除方法 - Google Patents
一种石质文物及石材表面石膏风化层的选择性清除方法 Download PDFInfo
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Abstract
本发明提供了一种石质文物及石材表面石膏风化层的选择性清除方法。其做法是在水溶液中利用助溶剂将石质文物及石材表面有害的石膏风化层溶解、转化，并最终以难溶盐形式留在助溶剂中。该方法清除石膏风化层彻底、无化学物质残留且具有选择性，石膏清除完毕后溶解及转化反应即可自动终止，不损伤石材基底。
Description
技术领域
本发明属于材料腐蚀及防护技术领域，具体涉及一种石质文物及石材表面石膏风化层的选择性清除方法。
背景技术
石膏是常见于石质文物或石材表面的一类有害风化产物，它能造成石质文物及石材的表面溶蚀、龟裂和剥落等病害。目前有三种此类石膏风化层的清理技术，即化学清洗法、离子交换法清洗法和粒子喷射清洗法[赵林娟. 几种常用清洗方法的清洗效果对比讨论. 中国文物科学研究, 2014, 3: 85-87]。化学清洗法中清洗剂的主要成分为碳酸铵、氨水、尿素、磷酸盐、EDTA。这些方法清洗效果好, 但也有相当的风险性。如清洗完成后，部分碳酸铵、氨水、尿素、磷酸盐等物质会滞留于石质文物或石材中的微孔隙中，造成藻类、真菌和地衣等生物的滋生，加速文物或石材的风化[石美风等. 石质文物保护中的化学清洗技术. 文物保护与考古科学, 2011, 23: 89-96.]。EDTA 则会使石灰岩石材表面的碳酸钙重结晶而改变其粗糙度、质感和颜色等外观[Toreno． Study of the action oftetrasodium EDTA on calcium， copper，and iron compounds present in calcareousmaterials．OPD restauro: rivista dell'Opificio delle pietre dure e laboratoriodirestauro di Firenze, 2004，16: 114-121.]。离子交换树脂清洗法是利用离子交换树脂的活性化学基团与石膏风化层中钙离子和硫酸根离子的交换吸附作用将石膏风化层溶解而除去。该方法成本相对较高［Tabasso M L．石质品的保护处理．文物保护与考古科学，1996，8: 55-62．］且没有选择性，石膏层清理结束后如不及时撤出交换树脂，石质文物及石材的基材也有可能溶解而造成损伤。粒子喷射法[张治国等. 海洋出水石质文物表面凝结物的清洗技术研究.石材，2013,12:38-42]是一种物理干洗方法。它是靠气流驱动的磨料和待处理表面之间的物理摩擦达到清洗的目的。粒子喷射技术的最大优势是可用于清除大面积的不溶性硬垢层。不过，和交换树脂法一样，粒子喷射技术也不具有选择性，处理时间控制不当也会损伤到石质文物或石材的基材。
发明内容
本发明所要解决的技术问题是针对现有技术中的缺点而提供了一种石质文物及石材表面石膏风化层的选择性清除方法。
为解决本发明的技术问题采用如下技术方案：
一种石质文物及石材表面石膏风化层的选择性清除方法，使用助溶剂的水溶液对石质文物或石材表面的石膏风化层进行溶解、转化处理。
所述助溶剂为碳酸钡、草酸钡或草酸锶。
所述助溶剂的用量为1.55-3.50g/cm2（以待处理石膏风化层单位面积所需助溶剂的质量计算）。
助溶剂水溶液作用下，利用敷贴法（将浸有助溶剂水溶液的脱脂棉等吸水材料敷贴在待处理石质文物或石材表面）或溶液浸泡法（将待处理石质文物或石材浸泡于添加了助溶剂的水溶液中）对石质文物或石材表面的石膏风化层进行溶解、转化处理12-48小时。
本发明提供了一种全新的石质文物及石材表面石膏风化层的清除方法。其做法是在水溶液中利用助溶剂将石质文物及石材表面有害的石膏风化层溶解、转化，并最终以难溶盐形式留在助溶剂中。本发明可将石质文物及石材表面有害的石膏风化层完全清除，无化学物质残留且具有选择性，石膏清除完毕后溶解及转化反应即可自动终止，不损伤石材基底。以碳酸钡为例，其机理如下：
。
具体实施方式
下面结合具体实例对本发明做详细说明：
实施例1以草酸钡为助溶剂
将表面石膏化大理石石材表面浸没于添加了助溶剂的水溶液中，其中助溶剂的水溶液是按照2.6g/cm2用量（以待处理石膏风化层单位面积所需助溶剂的质量计算）的助溶剂加入去离子水中，处理36小时后将大理石试块取出，蒸馏水冲洗、晾干后进行检测，得到结果见表1。
表1 清除效果
实施例2以草酸锶为助溶剂
将表面石膏化大理石石材表面浸没于添加了助溶剂的水溶液中，其中助溶剂的水溶液是按照1.55g/cm2用量（以待处理石膏风化层单位面积所需助溶剂的质量计算）的助溶剂加入去离子水中，处理48小时后将大理石试块取出，蒸馏水冲洗、晾干后进行检测，得到结果见表2。
表2 清除效果
实施例3以碳酸钡为助溶剂
按照3.5g/cm2用量（以待处理石膏风化层单位面积所需助溶剂的质量计算）的助溶剂加入去离子水中形成助溶剂的水溶液，将浸有助溶剂水溶液的脱脂棉均匀敷贴在表面石膏化石质文物表面，喷水淋湿后处理12小时，将脱脂棉除去，蒸馏水冲洗大理石，晾干后进行检测，得到结果见表3。
表3 清除效果
从结果上看，经所述方法处理后，石材表面的石膏风化层可被完全清除，石材的表面强度亦有了明显提高，且毛细水吸收和外观等固有性质基本不影响，结果令人满意。
注：表面石膏化的石质文物或石材的制备按文献方法[JL Prez Bernal, MABello. Modeling sulfur dioxide deposition on calcium carbonate, Ind. Eng.Chem. Res., 42 (2003) 1028-34.]进行，即将二氧化硫和空气混合后送入温、湿度可控的反应室，石质文物或石材在反应室中与二氧化硫及空气接触反应3天后取出，去离子水冲洗干净、自然晾干即可。
Claims (2)
1.一种石质文物及石材表面石膏风化层的选择性清除方法，其特征在于：使用助溶剂的水溶液对石质文物或石材表面的石膏风化层进行溶解、转化处理，所述助溶剂为碳酸钡、草酸钡或草酸锶，所述助溶剂的用量为1.55-3.50g/cm2。
2.根据权利要求1所述的一种石质文物及石材表面石膏风化层的选择性清除方法，其特征在于：在助溶剂水溶液作用下，利用敷贴法或溶液浸泡法对石质文物或石材表面的石膏风化层进行溶解、转化处理12-48小时。
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Citations (4)
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| JPH0948681A (ja) * | 1995-06-02 | 1997-02-18 | Mitsubishi Materials Corp | 石膏硬化体とその製造方法 |
| CN1772713A (zh) * | 2005-10-12 | 2006-05-17 | 浙江大学 | 石材和石质文物的表面仿生防护方法 |
| WO2014032167A1 (en) * | 2012-08-29 | 2014-03-06 | Protocol Environmental Solutions, Inc. | Gypsum remover |
| CN104478478A (zh) * | 2014-10-30 | 2015-04-01 | 杨富巍 | 一种风化骨质文物的加固保护方法 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0948681A (ja) * | 1995-06-02 | 1997-02-18 | Mitsubishi Materials Corp | 石膏硬化体とその製造方法 |
| CN1772713A (zh) * | 2005-10-12 | 2006-05-17 | 浙江大学 | 石材和石质文物的表面仿生防护方法 |
| WO2014032167A1 (en) * | 2012-08-29 | 2014-03-06 | Protocol Environmental Solutions, Inc. | Gypsum remover |
| CN104478478A (zh) * | 2014-10-30 | 2015-04-01 | 杨富巍 | 一种风化骨质文物的加固保护方法 |
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