CN116330419B - 一种用于饱水木质文物冷冻干燥的前处理方法 - Google Patents
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Abstract
本发明提供一种用于饱水木质文物冷冻干燥的前处理方法，包括如下步骤：将饱水木质文物浸泡于0.5％‑2wt％的氢键抑制剂溶液中，并调节氢键抑制剂溶液的pH值近中性范围，浸泡温度20‑50℃，固液体积比为1:5‑1:20，浸泡渗透时间为1天或以上；浸泡后，吸水纸将饱水木质文物表面水分吸去，于‑30℃至‑10℃预冻结。本发明用针对木材组分氢键重组导致收缩的问题，采用氢键抑制剂溶液浸泡的方法，形成苯硼酸‑纤维素氢键复合物、苯硼酸‑木质素氢键复合物等结构，抑制饱水木质文物中纤维素等木材组分中的氢键在干燥过程中发生重组及相应的收缩，改善常规冷冻干燥法的不足，进一步提高饱水木质文物的脱水定形效果。
Description
技术领域
本发明属于文物保护技术领域，具体涉及一种用于饱水木质文物冷冻干燥的前处理方法。
背景技术
木质文物是考古出土的重要文物类型，其中以饱水木质文物最为常见。在水浸环境中，化学及生物腐蚀作用导致木材逐渐腐朽，饱水木质文物中的木材结构、化学组成和物理性质均发生不同程度的劣化。为了长期保存，饱水木质文物必须合理的脱水定形，但未采取保护措施的饱水木质文物在脱水过程中将发生严重收缩、变形以致外观的损毁，故须采取有效的脱水定形措施。现有饱水木质文物脱水定形方法包括冷冻干燥法、超临界流体干燥法、溶剂置换法等，这些方法主要通过消除或减小液体的表面张力减少文物干燥时的收缩。另外，也可使用天然树脂加固法、聚乙二醇加固法、单体聚合加固法等加固方法提升文物的强度以抵抗干燥时的收缩应力，减少收缩。CN105509192B专利公开了一种用于含水文物冷冻干燥保存的除湿空调系统及方法，CN113551326A专利公开了一种含水文物冷冻干燥除湿空调系统，可用于饱水木质文物脱水定形；CN115401757A专利公开了一种利用聚乙烯亚胺和1,4-丁二醇二缩水甘油醚缩聚对饱水木质文物完成脱水加固定形的方法；CN115446937A专利公开了一种原子转移自由基聚加固木质文物的方法，可提升木质文物的尺寸稳定性，抑制干燥收缩；CN106985237B专利提供了一种木质文物脱水定型加固剂的制备方法。这些方法中，饱水木质文物的脱水定形方法仍难以满足当前的保护工作实际需求，主要体现在干燥收缩、文物及人员的安全性和工艺便捷三个方面难以兼顾。以广泛应用的几种方法为例，冷冻干燥法可消除液体表面张力导致的收缩，但无法抑制氢键重组导致的收缩，因此脱水定形的效果并不理想；各类加固方法通常使用大量有机溶剂或加固试剂，工艺相对复杂，对操作人员和环境不利，且加固作用对于干燥收缩的抑制相对有限。因此，急需一种工艺便捷、进一步提高饱水木质文物脱水定形效果的方法以改进现有的脱水定形工艺。
发明内容
本发明的目的之一在于一种用于饱水木质文物冷冻干燥的前处理方法，进一步减少该类文物冷冻干燥后的收缩变形。该方法用针对木材组分氢键重组导致收缩的问题，采用氢键抑制剂溶液浸泡的方法，形成苯硼酸-纤维素氢键复合物、苯硼酸-木质素氢键复合物等结构，抑制饱水木质文物中纤维素等木材组分中的氢键在干燥过程中发生重组及相应的收缩，改善常规冷冻干燥法的不足，进一步提高饱水木质文物的脱水定形效果。
本发明采用的技术方案如下
一种用于饱水木质文物冷冻干燥的前处理方法，包括如下步骤：
将饱水木质文物浸泡于0.5％-2wt％的氢键抑制剂溶液中，并调节氢键抑制剂溶液的pH值保持在适宜文物的近中性范围，浸泡温度20-50℃，固液体积比为1:5-1:20，且保证完全浸没木质文物，浸泡渗透时间为1天或以上；浸泡后，吸水纸将饱水木质文物表面水分吸去，于-30℃至-10℃预冻结；
所述氢键抑制剂为苯硼酸、烷基硼酸及其衍生物。
进一步的，所述氢键抑制剂为苯硼酸、4-三氟甲基苯硼酸或甲基硼酸。
进一步的，使用氢氧化钠、氢氧化钾、碳酸钠或碳酸氢钠调节氢键抑制剂溶液的pH值为6.3-8.0。
进一步的，氢键抑制剂溶液的浓度为1wt％。
进一步的，浸泡温度为20℃。
进一步的，固液体积比为1:5-10。
进一步的，浸泡渗透时间为1-7天。
进一步的，于-20℃预冻结。
本发明的目的之二是提供了采用上述前处理步骤的饱水木质文物冷冻干燥，将预冻结后的饱水木质文物置于冷冻干燥设备内，干燥温度为-30℃至-5℃，干燥至文物重量基本不再变化。
进一步的，采用风冷冷冻干燥设备或真空冷冻干燥设备进行冷冻干燥。
进一步的，干燥时间为14天以上。
本发明具备以下有益效果：
采用便捷的前处理步骤，无需使用大量有机溶剂或加固材料，仅需使用低浓度的含有硼酸根离子或硼酸活性基团的水溶液浸泡渗透，即可减少饱水木质文物冷冻干燥时的收缩，提高脱水定型效果，同时基本不明显改变文物的化学结构。
附图说明
图1是本发明反应机理示意图；
图2是实施例1中马尾松船板前处理后的红外光谱图；
图3是实施例1中乌桕隔板前处理后的红外光谱图；
图4是实施例1中红外光谱O-H伸缩振动区域差谱；
图5是实施例2中样品冷冻干燥后体积收缩率示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明确，以下结合实例对其进行具体描述。有必要指出的是，以下实例仅用于本发明进行解释和说明，并不用于限定本发明。本领域技术人员根据上述发明内容所做的一些非本质的改进和调整，仍属于本发明的保护范围。
以下实施例采用的处理方法为：
(1)氢键抑制剂溶液浸泡(冷冻干燥前处理)
将饱水木质文物浸泡于0.5％-2％的氢键抑制剂溶液，可使用氢氧化钠调节pH值在适宜文物的近中性范围6.3-8.0，其中未调节pH值的氢键抑制剂溶液pH约为6.3，浸泡温度20-50℃。固液体积比为1:5-1:20，且保证完全浸没木质文物。浸泡渗透时间根据文物体量而定，可选取1-7天或以上。浸泡后，吸水纸将饱水木质文物表面水分吸去，于-30℃至-10℃预冻结。
(2)冷冻干燥
将预冻结后的饱水木质文物置于冷冻干燥设备内，可选用风冷冷冻干燥设备或真空冷冻干燥设备等，根据文物体量和保存状态选用适宜的除湿速率或真空度，干燥温度可选-30℃至-5℃，干燥时间依文物体量而定，直至重量基本不再变化，时间通常为2周以上。
实施例1
对南海I号出水的绝对含水率为507％的南宋船板样品(松科松属马尾松)和绝对含水率为863％的隔板样品(大戟科乌桕属)实施本方法所述前处理方法，具体为：将饱水木质文物浸泡于1％的苯硼酸水溶液，使用氢氧化钠调节pH值在适宜文物的近中性范围6.3-8.0，浸泡温度20℃。固液体积比为1:10，且保证完全浸没木质文物。浸泡渗透时间根据文物体量而定，可选取1天或以上。浸泡后，将饱水木质文物表面水分吸去，于-20℃预冻结。采用风冷冷冻干燥，期间控制相对湿度为60-90％，温度为-10℃，直至文物重量不再变化。
利用衰减全反射-傅里叶变换红外光谱分析其化学结构，结果如图2、图3所示，其中：(a)代表仅冷冻干燥；(b)代表pH 6.3，20℃苯硼酸前处理后冷冻干燥；(c)代表pH 8.0，20℃苯硼酸前处理后冷冻干燥；(d)代表所用试剂苯硼酸。苯硼酸主要吸收峰位于1345cm-1处的B-O不对称伸缩振动、693cm-1处的苯环C-C面外变形振动和635cm-1处的O-B-O面外变形振动吸收峰。饱水木质文物实施前处理步骤并冷冻干燥后，上述苯硼酸收吸收峰在饱水木质文物的红外光谱中发生明显偏移，分别位于1316cm-1、701cm-1和645cm-1，表明部分苯硼酸在饱水木质文物中的化学环境发生明显改变。对有关红外光谱的O-H伸缩振动吸收峰进行差谱分析，如图4所示，其中：(a)代表pH 6.3，20℃苯硼酸前处理的马尾松样品差减仅冷冻干燥马尾松样品红外光谱；(b)代表pH 8.0，20℃苯硼酸前处理马尾松样品差减仅冷冻干燥马尾松样品红外光谱(c)代表pH 6.3，20℃苯硼酸前处理的乌桕样品差减仅冷冻干燥乌桕样品红外光谱；(d)代表pH 8.0，20℃苯硼酸前处理的乌桕样品差减仅冷冻干燥乌桕样品红外光谱；(e)代表苯硼酸O-H伸缩振动吸收峰位置。由图4可知马尾松船板样品前处理并冷冻干燥后3240cm-1附近吸收峰强度下降，3590cm-1附近吸收峰强度增加；乌桕隔板样品前处理并冷冻干燥后3458cm-1附近吸收峰强度下降，3620cm-1附近吸收峰强度增加。所有前处理后的样品红外光谱O-H伸缩振动吸收峰区域均向高波数移动，且不同于苯硼酸自身的O-H吸收峰位置，表明苯硼酸与木质文物间存在明显的氢键作用，改变了木质文物原本组分间的氢键缔合情况和振动频率。
上述结果表明苯硼酸与饱水木质文物组分间形成了苯硼酸-纤维素氢键复合物、苯硼酸-木质素氢键复合物等结构，可能形成了少量苯硼酸酯。此外，从图2、图3可知处理后，饱水木质文物原有的吸收峰未发生明显改变，表明该方法对该类文物影响较小。
实施例2
本实施例对实施例1中的马尾松船板和乌桕隔板的体积进行测定，参考国标GB/T1933-2009木材密度测定方法中的排水法法测定饱水状态和干燥后的体积，并计算体积收缩率为避免测定过程中木质文物迅速吸水影响测定结果，均使用凡士林表面封涂防水，结果如图5所示。结果表明未前处理、仅冷冻干燥的乌桕隔板体积收缩为8.9％，在pH6.3-8.0、温度在20-50℃条件下前处理后的各组乌桕隔板体积收缩率降低为平均-0.4％至0.9％；未前处理、仅冷冻干燥的马尾松船板体积收缩为10.9％，在pH6.3-8.0、温度在20-50℃前处理后的各组乌桕隔板体积收缩率降低为平均1.5％至2.7％。上述结果表明本方法可在pH6.3-8.0、温度在20-50℃的条件下，对绝对含水率507％的针叶材马尾松和863％的阔叶材乌桕饱水木质文物均可有效减少冷冻干燥后的体积收缩，改善脱水定形效果。
Claims (10)
1.一种用于饱水木质文物冷冻干燥的前处理方法，其特征在于，包括如下步骤：
将饱水木质文物浸泡于0.5%-2wt%的氢键抑制剂溶液中，并调节氢键抑制剂溶液的pH值保持在适宜文物的近中性范围，浸泡温度20-50℃，固液体积比为1:5-1:20，且保证完全浸没木质文物，浸泡渗透时间为1天或以上；浸泡后，吸水纸将饱水木质文物表面水分吸去，于-30℃至-10℃预冻结；
所述氢键抑制剂为苯硼酸、苯硼酸的衍生物、烷基硼酸或烷基硼酸的衍生物。
2.根据权利要求1所述的前处理方法，其特征在于，使用氢氧化钠、氢氧化钾、碳酸钠或碳酸氢钠调节氢键抑制剂溶液的pH值为6.3-8.0。
3.根据权利要求1所述的前处理方法，其特征在于，氢键抑制剂溶液的浓度为1wt%。
4.根据权利要求1所述的前处理方法，其特征在于，浸泡温度为20℃；浸泡渗透时间为1-7天。
5.根据权利要求1所述的前处理方法，其特征在于，固液体积比为1:5-10。
6.根据权利要求1所述的前处理方法，其特征在于，所述氢键抑制剂为苯硼酸、4-三氟甲基苯硼酸或甲基硼酸。
7.根据权利要求1所述的前处理方法，其特征在于，于-20℃预冻结。
8.一种用于饱水木质文物冷冻干燥的方法，其特征在于，包括如下步骤：
（1）采用权利要求1-7任一项所述的前处理方法对饱水木质文物进行前处理；
（2）将步骤（1）预冻结后的饱水木质文物置于冷冻干燥设备内，干燥温度为-30℃至-5℃，干燥至文物重量基本不再变化。
9.根据权利要求8所述的方法，其特征在于，采用风冷冷冻干燥设备或真空冷冻干燥设备进行冷冻干燥。
10.根据权利要求8所述的方法，其特征在于，干燥时间为14天以上。
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