CN115261161B - 一种基于壳聚糖的锈蚀青铜器温和除锈凝胶 - Google Patents
一种基于壳聚糖的锈蚀青铜器温和除锈凝胶 Download PDFInfo
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Abstract
本发明涉及一种基于壳聚糖的锈蚀青铜器温和除锈凝胶的制备方法,其将壳聚糖水溶液与PVA水溶液混匀,然后加入硝酸银水溶液,混匀获得均相溶液,即得。本发明凝胶能与具有复杂形状锈蚀青铜文物充分接触,对锈蚀成分为吸附量大,除锈效率高;吸附锈蚀成分后得凝胶可完整剥离,在处理面残留量极低;凝胶与器物结合方式为物理吸附,脱除为无损脱除,对锈蚀层较厚的器物,可实现多次除锈,不损伤器物。
Description
技术领域
本发明属于文物保护、材料学技术领域,具体涉及一种基于壳聚糖的锈蚀青铜器温和除锈凝胶。
背景技术
由于埋藏环境及文物自身特点,青铜文物在出土后的存放过程会发生不同程度的锈蚀,其中危害最大的是被称为“青铜器癌症”的粉状锈,其组分中的氯离子通过典型的小孔加速腐蚀方式导致青铜器短时间内局部粉化甚至穿孔,发生严重损毁,导致不可挽回的损失。因此,遵循文物保护“修旧如旧,去害存利”的原则,在不改变青铜器外观、色泽、不损伤基体的前提下,阻断腐蚀的演进,防止馆藏青铜器的继续锈蚀劣化已是文保领域亟待解决的世界性难题。
国内外常用机械法、化学清洗法、氯化银转化法、电解还原法等处理粉状锈。“机械法”法中的手工除锈,易导致器物表面产生划痕;超声清洗除锈效率高,但易使器物表面产生微小针孔,或损伤铭文;激光清洗除锈效果好、精度高,对青铜器基体损伤小,但难以处理复杂曲面,控制不当会导致局部过热,改变器物表面颜色甚至其组成结构;同时以上方法均难以根除“粉状锈”的诱发因素,不适用于锈蚀严重的脆弱青铜文物;氯化银转化法、电解还原法则会不同程度的改变器物原貌;“化学法”除锈效率较高,对基体损伤小,但清洗剂残留渗入青铜基体,将对青铜基体的再次腐蚀留下隐患。
常用的水凝胶除锈法,清洗剂被包覆在水凝胶的交联网络中,渗透效果差,而且易于在器物表面形成凝胶残留,不能完全剥离造成二次污染。同时,多数凝胶只有在模量较大时才有可能自剥离脱离器物表面,这样高交联度的胶凝过程将会导致器物表面产生应力开裂,尤其是脆弱青铜器,锈蚀面积大,基体强度低,难以用以上方法除锈。
发明内容
本发明目的在于克服现有技术缺陷,提供一种基于壳聚糖的锈蚀青铜器温和除锈凝胶。该凝胶能与复杂形状的锈蚀青铜文物充分接触,对锈蚀成分吸附量大,除锈效率高;吸附锈蚀成分后的凝胶可完整剥离,且不损伤器物。
为实现上述目的,本发明采用如下技术方案:
一种基于壳聚糖的锈蚀青铜器温和除锈凝胶的制备方法,其是将壳聚糖水溶液与PVA水溶液混匀,然后加入硝酸银水溶液,混匀获得均相溶液,即得。
上述基于壳聚糖的锈蚀青铜器温和除锈凝胶的制备方法,进一步的,是将20-40%(w/v)的壳聚糖水溶液与20-30ml、2-6%(w/v)的聚乙烯醇PVA水溶液按体积比1-4:1混匀,然后加入1-4ml浓度0.05-0.3M的硝酸银水溶液。
本发明提供了采用上述方法制备得到的基于壳聚糖的锈蚀青铜器温和除锈凝胶。
本发明还提供了上述凝胶在锈蚀青铜器除锈中的应用。
具体的,上述凝胶在锈蚀青铜器除锈中的应用,可以将凝胶静置陈化5-7天,用浇筑法浇筑在待除锈的锈蚀青铜器表面。
进一步的,上述凝胶在锈蚀青铜器除锈中的应用,优选在浇筑后室温干燥24±6h,然后直接从锈蚀青铜器表面将已吸附锈蚀成分的凝胶层移除。
本发明凝胶利用壳聚糖对铜锈的吸附效应,以及壳聚糖@Ag配位网络与聚乙烯醇凝胶的双网络作用产生的弱黏附实现对锈层的吸附与温和脱除,和现有技术相比,本发明具有如下有益效果:
本发明凝胶能与具有复杂形状锈蚀青铜文物充分接触,对锈蚀成分为吸附量大,除锈效率高;吸附锈蚀成分后得凝胶可完整剥离,在处理面残留量极低;凝胶与器物结合方式为物理吸附,脱除为无损脱除,对锈蚀层较厚的器物,可实现多次除锈,不损伤器物。
附图说明
图1中,a)除锈前铜镜样品;b)浇筑除锈凝胶过程;c)经过一次除锈移除锈凝胶层后的铜镜样品;d)第一次除锈整体脱除的吸附锈蚀成分的凝胶层;e)第二次除锈处理后的铜镜试样;f)第二次除锈整体脱除的吸附锈蚀成分的凝胶层;
图2为无边框平面锈蚀试样的除锈过程:a)除锈前锈蚀铜片试样;b)浇筑凝胶等待凝胶;c)除锈后铜片试样。
具体实施方式
以下结合实施例对本发明的技术方案作进一步地详细介绍,但本发明的保护范围并不局限于此。
实施例1
一种基于壳聚糖的锈蚀青铜器温和除锈凝胶的制备方法,具体如下:
配制30%(w/v)壳寡糖水溶液,然后与25ml、4%(w/v)PVA水溶液按体积比2:1混合,搅拌均匀,再加入2毫升0.1M的硝酸银水溶液,继续搅拌混匀,制得均相溶液。
本发明还提供了上述凝胶在锈蚀青铜器除锈中的应用,用于除锈时,凝胶的使用方法如下:
将上述制备得到的均相溶液,静置陈化6天,用浇筑法(即流延成膜法,采用本领域常规技术即可,因不是本申请的创新之所在,故此不再赘述)浇筑在待除锈的青铜器样品表面,室温干燥24小时。因为凝胶干燥体积收缩,可直接从器物表面将吸附锈蚀成分的凝胶层移除(如图1a-c所示)。
图1分别给出了a)除锈前铜镜样品;b)浇筑除锈凝胶过程;c)经过一次除锈移除锈凝胶层后的铜镜样品;d)第一次除锈整体脱除的吸附锈蚀成分的凝胶层;e)第二次除锈处理后的铜镜试样;f)第二次除锈整体脱除的吸附锈蚀成分的凝胶层。如图1所示,使用本申请所制备除锈凝胶处理锈蚀铜镜样品的过程,图1中a为处理前铜镜,图1中b为凝胶浇筑于待处理铜镜样品后,凝胶固化前;将此样品室温干燥24小时后,由于干燥脱水,凝胶层体积收缩与铜镜自然分离,用镊子将吸附锈蚀成分的凝胶层整体移除,实现温和剥离。如图1中d所示,原本透明的凝胶吸附了锈层后呈现铜锈色。由图1中c可看出,铜镜边缘有部分顽固锈层在第一次除锈中未被去除,此时可重复图1 中b的浇筑、凝胶干燥过程,实现第二次除锈。图1中e为经过第二次除锈的铜镜,对比图1中c,可以看出,锈层明显减少,且基本去除。图1中f为二次除锈过程,吸附铜锈后干燥脱除的凝胶层。
除锈过程注意事项:
a)沿待处理青铜器物边缘出现的开裂部位,用镊子将凝胶取下,器物体积较小,或者器物有边框,可浇筑较厚凝胶层的情况,如图1所示,可实现“翻模”状凝胶整体脱除;
b)如待处理青铜器试样如图2所示,处理面为平面或凸面不能浇筑厚的凝胶层,可使用如图2中b所示方法,构建边框确保凝胶层的浇筑厚度(用聚四氟乙烯膜、锡纸、离型纸等沿着器物边缘包裹出具有一定高度约1cm的边框,使得凝胶可以在样品表面流延沉积出一定的厚度),以便整体脱除吸附锈蚀成分的凝胶层。
图2给出了无边框平面锈蚀试样的除锈过程:a)除锈前锈蚀铜片试样;b)浇筑凝胶等待凝胶;c)除锈后铜片试样。如图2中a所示为片状锈蚀青铜样品,图2中b为片材构建边框过程,为确保溶胶在片材表面沉积的厚度,用离型纸沿着试样边缘包裹,构建一个矩形围栏。图2中c为脱除锈层的片材试样,图中显示锈蚀已基本去除。
综上可以看出:本发明凝胶能与锈蚀青铜文物充分接触,对锈蚀成分为吸附量大,除锈效率高;吸附锈蚀成分后得凝胶可完整剥离;凝胶与器物结合方式为物理吸附,脱除为无损温和脱除,对锈蚀层较厚的器物,可实现多次除锈,且不损伤器物。
Claims (5)
1.一种基于壳聚糖的锈蚀青铜器温和除锈凝胶的制备方法,其特征在于,
将20-40%的壳聚糖水溶液与20-30ml、2-6%的PVA水溶液按体积比1-4:1混匀,然后加入1-4ml浓度0.05-0.3M的硝酸银水溶液,混匀获得均相溶液,即得。
2.一种基于壳聚糖的锈蚀青铜器温和除锈凝胶,其特征在于,采用权利要求1所述方法制备得到。
3.权利要求2所述凝胶在锈蚀青铜器除锈中的应用。
4.如权利要求3所述凝胶在锈蚀青铜器除锈中的应用,其特征在于,将凝胶静置陈化5-7天,用浇筑法浇筑在待除锈的锈蚀青铜器表面。
5.如权利要求4所述凝胶在锈蚀青铜器除锈中的应用,其特征在于,浇筑后室温干燥24±6h,直接从锈蚀青铜器表面将已吸附锈蚀成分的凝胶层移除。
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