基于羟基磷灰石材料的风化脆弱骨质文物加固保护研究

doi:10.15541/jim20220729

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1345-1354.DOI: 10.15541/jim20220729

基于羟基磷灰石材料的风化脆弱骨质文物加固保护研究

刘妍¹^,²^,³(), 张宇帆¹^,²^,³, 王茜蔓¹^,²^,³, 李婷¹^,²^,³, 马文婷¹^,²^,³, 杨富巍¹^,²^,³(), 陈靓¹^,²^,³, 赵东月¹^,²^,³, 严小琴¹^,²^,³

1.西北大学中国-中亚人类与环境“一带一路”联合实验室, 西安 710127
2.西北大学文化遗产研究与保护技术教育部重点实验室, 西安 710127
3.西北大学文化遗产学院, 西安 710127

收稿日期:2022-11-03 修回日期:2023-06-01 出版日期:2023-06-02 网络出版日期:2023-06-02
通讯作者: 杨富巍, 男, 教授. E-mail: yangfuwei@nwu.edu.cn
作者简介:刘妍 (1977-), 女, 教授. E-mail: liuyan@nwu.edu.cn
基金资助:
国家自然科学基金(B050121975202);国家自然科学基金(52108031);国家哲学社会科学基金(20BKG038);国家哲学社会科学基金(18CKG027);国家大学生创新创业训练计划(S202110697043);陕西省哲学社会科学重点研究基地项目(17JZ072);陕西省自然科学基金(2023-JC-2024-YB-097);2022年西北大学学术繁荣计划开放课题(2023-JC-YB-097);国家重点研发计划(2022YFF0903800)

Consolidation of Fragile Weathered Bone Relics Using Hydroxyapatite Material as Consolidant

LIU Yan¹^,²^,³(), ZHANG Yufan¹^,²^,³, WANG Ximan¹^,²^,³, LI Ting¹^,²^,³, MA Wenting¹^,²^,³, YANG Fuwei¹^,²^,³(), CHEN Liang¹^,²^,³, ZHAO Dongyue¹^,²^,³, YAN Xiaoqin¹^,²^,³

1. China-Central Asia “the Belt and Road” Joint Laboratory on Human and Environment Research, Northwest University, Xi’an 710127, China
2. Key Laboratory of Cultural Heritage Research and Conservation, Northwest University, Xi’an 710127, China
3. School of Culture Heritage, Northwest University, Xi’an 710127, China

Received:2022-11-03 Revised:2023-06-01 Published:2023-06-02 Online:2023-06-02
Contact: YANG Fuwei, male, professor. E-mail: yangfuwei@nwu.edu.cn
About author:LIU Yan (1977-), female, professor. E-mail: liuyan@nwu.edu.cn
Supported by:
National Natural Science Foundation of China(B050121975202);National Natural Science Foundation of China(52108031);National Social Science Foundation of China(20BKG038);National Social Science Foundation of China(18CKG027);National College Student Innovation and Entrepreneurship Training Program(S202110697043);Key Research Base Project of the Social Science Foundation of Shanxi Province(17JZ072);Natural Science Foundation of Shanxi Province(2023-JC-2024-YB-097);Open Project of the Academic Prosperity Program of Archaeology of Northwestern University in 2022(2023-JC-YB-097);National Key Research and Development(2022YFF0903800)

摘要/Abstract

摘要：

考古发掘出土的风化骨质文物通常疏松多孔、力学强度低、质地脆弱, 易出现翘曲、开裂、酥粉化等现象,亟需探索脆弱骨质文物加固保护的新方法。本研究采用羟基磷灰石前驱材料氧化钙-磷酸氢钙的醇分散液渗入脆弱骨质内部, 再用蒸馏水渗入引发氧化钙与磷酸氢钙反应而生成羟基磷灰石连续相。该连续相能填充脆弱骨内部的孔隙和裂缝, 并通过桥连黏接而加固骨质。利用电镜、能谱、XRD、色差、质量、孔隙率、密度和断面强度等研究考察了悬浮分散液中氧化钙与磷酸氢钙的质量配比(1 : 1、1 : 3、1 : 4、1 : 5、1 : 6、1 : 7)和施加方式(刷涂、滴渗和浸泡)对加固效果的影响，结果表明, 悬浮分散液中氧化钙和磷酸氢钙的质量配比为1 : 3, 且施加方式为刷涂时, 加固处理效果最佳。经加固处理后, 脆弱骨的孔隙率下降了17.3%, 质量、密度和表面强度分别提高了38.39%、34.49%和16.32%, 且其色差∆E也小于3.0, 符合文物保护要求。本研究为脆弱骨质文物的加固保护提供了新的有效方法。

关键词: 脆弱考古骨, 加固保护, 加固剂, 加固方式, 羟基磷灰石

Abstract:

Archaeological weathered bones are usually porous and fragile, easily to warp, crack and crumble. To avoid these relic damages, consolidation technology is badly needed. Here, we explored a new consolidation method for weak bone relics using hydroxyapatite as protectant. Briefly, dispersion of calcium oxide mixed with calcium hydrophosphate in alcohol was used firstly to permeate into the fragile bones as precursor of hydroxyapatite consolidant. Then pure water was used to trigger the reaction between calcium oxide and calcium hydrophosphate, which leads to formation of a continuous phase of hydroxyapatite consolidant. By filling and bridging the pores or fissure inside the fragile bones, hydroxyapatite consolidant can act as a reinforcement material. Effects of the mass ratio of calcium oxide to calcium hydrophosphate (1 : 1, 1 : 3, 1 : 4, 1 : 5, 1 : 6, 1 : 7) and the application ways (brushing, drip infiltration and soaking) on the protective performance were investigated by scanning electron microscope (SEM), energy dispersive spectroscope (EDS), X-ray diffraction (XRD) and characterizations of color difference, weight increment, porosity, density and cohesive strength determination. The results showed that the best consolidation performance could be obtained when the mass ratio of 1 : 3 and the brushing consolidation method were adopted. In this case, porosity of the fragile bones decreased by 17.3%. Mass, density and cohesive strength of the fragile bones increased by 38.39%, 34.49% and 16.32%, respectively. Moreover, the color difference of bones is less than 3.0, which is allowable in the field of heritage conservation.

Key words: fragile archaeological bone, consolidation, consolidant, consolidation way, hydroxyapatite

中图分类号:

刘妍, 张宇帆, 王茜蔓, 李婷, 马文婷, 杨富巍, 陈靓, 赵东月, 严小琴. 基于羟基磷灰石材料的风化脆弱骨质文物加固保护研究[J]. 无机材料学报, 2023, 38(11): 1345-1354.

LIU Yan, ZHANG Yufan, WANG Ximan, LI Ting, MA Wenting, YANG Fuwei, CHEN Liang, ZHAO Dongyue, YAN Xiaoqin. Consolidation of Fragile Weathered Bone Relics Using Hydroxyapatite Material as Consolidant[J]. Journal of Inorganic Materials, 2023, 38(11): 1345-1354.

图/表 18

图1 25%悬浮浓度的氧化钙-磷酸氢钙乙醇分散液

Fig. 1 Calcium oxide-calcium hydrogen phosphate dispersion in alcohol at concentration of 25%

表1 实验分组方案

Table 1 Experimental groups of different mass ratios

Group	Mass ratio
Group	1 : 1	1 : 3	1 : 4	1 : 5	1 : 6	1 : 7
Brushing	1	2	3	4	5	6
Soaking	7	8	9	10	11	12
Dripping	13	14	15	16	17	18

图2 基于氧化钙-磷酸氢钙乙醇分散液的风化脆弱骨样品加固机理示意图

Fig. 2 Consolidation mechanism of weathered bones using calcium oxide-calcium hydrogen phosphate dispersion in alcohol as consolidant

图3 脆弱骨样品加固处理前后色差

Fig. 3 Color difference of fragile bone samples after consolidation treatment Samples 1 to 19 are introduced in Table 1, respectively

图4 加固方式和加固剂配比对脆弱骨样品质量增长率的影响

Fig. 4 Effects of consolidation way and consolidant ratio on the bone weight increment (The rectangle is Interquartile Range (IQR), which is used to mark data outliers) (a) Consolidation way; (b) Consolidant ratio

图5 加固方式和加固剂配比对脆弱骨样品孔隙率的影响

Fig. 5 Effects of consolidation way and consolidant ratio on the bone porosity (a) Consolidation way; (b) Consolidant ratio

图6 加固处理方式和加固剂配比对脆弱骨样品密度的影响

Fig. 6 Effects of consolidation way and consolidant ratio on the bone density (a) Consolidation way; (b) Consolidant ratio

图7 加固处理方式和加固剂配比对脆弱骨样品表面强度的影响

Fig. 7 Effects of consolidation method and consolidant ratio on surface strength of the bones (a) Consolidation way; (b) Consolidant ratio

图8 加固前脆弱骨样品的显微形貌

Fig. 8 Morphology of fragile bone sample before consolidation treatment The areas in red-framed indicate the fractures

图9 加固处理后脆弱骨样品显微形貌

Fig. 9 Morphologies of fragile bone samples after consolidation treatments with mass ratios of calcium oxide to calcium hydrogen phosphate at 1 : 1 (a), 1 : 3 (b), 1 : 4 (c), 1 : 5 (d), 1 : 6 (e) and 1 : 7 (f), respectively

图10 加固处理前后脆弱骨样品EDS元素面分布结果

Fig. 10 EDS analysis results of fragile bone samples before and after consolidation treatment (a, d) Ca; (b, e) P; (c, f) C, corresponding to Fig. 8 and Fig. 9(b)

表2 加固前后脆弱骨EDS元素分析结果

Table. 2 EDS analysis results of frgile bone before and after consolidation treatment

Element	Weight ratio before consolidation/%	Weight ratio after consolidation/%
C	0	5.62
O	56.93	56.32
Na	9.57	2.56
Mg	0.91	1.12
P	12.04	13.23
Ca	20.55	21.15
Total	100.00	100.00

图11 加固处理前后脆弱骨样品的截面形貌

Fig. 11 Cross-sectional topographies of fragile bone samples before and after consolidation treatments (a) Untreated; (b-d) Treated by brushing, soaking and dripping, respectively

图12 不同配比的加固剂对脆弱骨加固处理后的样品截面形貌

Fig. 12 Cross-sectional topographies of fragile bone samples treated by different mass ratios of calcium oxide to calcium hydrogen phosphate (a) 1 : 1; (b) 1 : 3; (c) 1 : 4; (d) 1 : 5; (e) 1 : 6; (f) 1 : 7

图13 脆弱骨样品加固处理前(a)后(b)的XRD图谱

Fig. 13 XRD results of bones before (a) and after (b) consolidation treatment

图14 加固剂质量配比对产物成分的影响

Fig. 14 Effect of consolidant ratio on final product Ratios of calcium oxide to calcium hydrogen phosphate in line(a-f) are 1 : 1, 1 : 3, 1 : 4, 1 : 5, 1 : 6 and 1 : 7, respectively

表3 各配比下的物相比例

Table 3 Phases of produts under different consolidant ratios

Ratio of CaO : CaHPO₄	Ca(OH)₂	CaHPO₄	Ca₅(PO)₄OH
1 : 1	+++	-	++
1 : 3	-	-	++++
1 : 4	-	++	+++
1 : 5	-	+++	++
1 : 6	-	+++	+
1 : 7	-	++++	+

图15 考古发掘出土脆弱骨片加固处理前(a)后(b)的照片

Fig. 15 Photos of archaeological bone before (a) and after (b) consolidation treatment

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基于羟基磷灰石材料的风化脆弱骨质文物加固保护研究

Consolidation of Fragile Weathered Bone Relics Using Hydroxyapatite Material as Consolidant

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