Recent Research and Prospect of Deacidifying Materials for Paper and Paper-based Cultural Relics

doi:10.6023/A22110475

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (3): 309-318.DOI: 10.6023/A22110475 Previous Articles

Review

纸张与纸质文物脱酸材料近期研究与展望

金姗姗^a, 王思浓^a^,^b^,^*()

a 复旦大学图书馆中华古籍保护研究院上海 200433
b 齐鲁工业大学制浆造纸科学与技术教育部重点实验室齐鲁工业大学(山东省科学院) 济南 250353

投稿日期:2022-11-26 发布日期:2023-02-10
作者简介:
金姗姗, 复旦大学图书馆, 中华古籍保护研究院, 在读博士研究生. 目前主要研究方向为纤维素降解动力学, 预期纸寿的评估, 以及多功能保护材料的合成.
王思浓, 复旦大学图书馆, 中华古籍保护研究院, 副研究馆员, 主要从事功能性纳米材料与纸质文物保护研究.
基金资助:
制浆造纸科学与技术教育部重点实验室开放基金资助(KF201921); 复旦大学中华古籍保护研究院研究生科学研究基金资助

Recent Research and Prospect of Deacidifying Materials for Paper and Paper-based Cultural Relics

Shanshan Jin^a, Sinong Wang^a^,^b()

a Institute for Preservation and Conservation of Chinese Ancient Books, Fudan University Library, Fudan University, Shanghai 200433, China
b Key Laboratory of Pulp and Paper Science & Technology of Ministry of Education, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250353

Received:2022-11-26 Published:2023-02-10
Contact: *E-mail: wangsn@fudan.edu.cn
Supported by:
Foundation of Key Laboratory of Pulp and Paper Science and Technology of Ministry of Education of China(KF201921); Graduate Scientific Research Fund of the Institute for Preservation and Conservation of Chinese Ancient Books, Fudan University

Paper and paper-based cultural relics are of great value as the main carriers for writing and preserving information. Acid-catalyzed hydrolysis is one of the most fatal reactions for paper degradation, and deacidification would effectively slow down the rate of its degradation and prolong the life time of paper. Therefore, the design and application of deacidifying materials with safety and effectiveness is the indispensable requirement for the protection of paper and paper-based cultural relics. Generally, alkaline materials, such as amino/amine compounds, magnesium/calcium hydroxides, oxides, carbonates are the mostly used deacidifying materials for their good paper compatibility, suitable alkalinity, low cost and low toxicity, which exhibit considerable paper deacidification performance. In this review, the recent research progresses of deacidifying materials on liquid phase deacidification process were reviewed, including the categories of deacidifying materials, preparation methods and the relationship between paper deacidification performance and structures of deacidifying materials, finally, the challenges and development of deacidifying materials were also discussed. For classification purpose according to chemical structure, deacidifying materials can be divided into four categories: ionic form, molecular form, micro/nano-scale form and composite form. The deacidifying materials with molecular form can significantly improve the mechanical properties of paper and show a certain deacidification effect, it is necessary to control the improvement of mechanical properties within reasonable ranges while considering the effective deacidification performance. Micro/nano-scale materials with large surface area, good penetration and high efficiency are the widely used deacidifying materials, which can achieve better deacidification effects at lower concentrations. The controlled alkalinity, high dispersion and suspension stability in solvents and uniform distribution in paper fibers of micro/nano-scale materials are highly demanded. Additionally, ionic form materials can interact with paper fibers more evenly through homogeneous deacidification process, but their alkaline reserve is relatively insufficient. And more insight is demanded into the co-existence stability of composite deacidifying materials and its contribution to paper protection.

Key words: paper, acid degradation, deacidifying materials, protection of paper-based cultural relics

Cite this article

Shanshan Jin, Sinong Wang. Recent Research and Prospect of Deacidifying Materials for Paper and Paper-based Cultural Relics[J]. Acta Chimica Sinica, 2023, 81(3): 309-318.

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Fig. & Tab. 7

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序号	纸张		成分	方法	脱酸材料		脱酸材料结构	溶剂
a^[19]	自然老化旧书			浸泡	3-氨基丙基三甲氧基硅烷	ATMS		乙醇
					3-氨基-2,2-二甲基丙基三甲氧基硅烷	AMTMS
					3-氨丙基三乙氧基硅烷	ATES
					3-氨丙基甲基二乙氧基硅烷	AMDES
					3-(N,N-二甲基氨基)丙基三甲氧基硅烷	DMATMS
b^[20]	P1	>95% CL SWP		浸泡	3-氨丙基甲基二乙氧基硅烷	AMDES		HMDSO
	P2	75% WP 25% SWP
	自然老化B1928
c^[26]	P3		CL (>95%)	浸泡	3-(N,N-二甲基氨基)丙基甲基二乙氧基硅烷	DMAPDES		HMDSO
d^[21]	P4		>95% CL SWP	浸泡	3-氨丙基甲基二乙氧基硅烷	AMDES		HMDSO
d^[21]	P4		>95% CL SWP	浸泡喷涂	3-氨丙基三乙氧基硅烷	APTES		HMDSO
序号	纸张		成分	方法	脱酸材料		脱酸材料结构	溶剂
				浸泡喷涂	APTES-AMDES 共聚物	APTES-AMDES		HMDSO/ 无溶剂
e^[27]	宣纸			浸泡	N-氨乙基-3-氨丙基- 三乙氧基硅烷	AETAPTES		乙醇
f^[28]	打印纸			浸泡	γ-缩水甘油醚氧丙基三甲氧基硅烷	KH560		乙醇
g^[23]	S1 (1986) WP			浸泡	甲基硅酸钾	PMS		水
	BDP
	宣纸		SWP>75% CL
h^[24]	滤纸			浸泡	水溶性聚酰胺	PAAOH		水
i^[29]	色谱纸			浸泡	硼烷叔丁胺络合物	TBAB
					硼烷氨络合物	AB
					硼烷N,N-二异丙基乙胺络合物	DIPEAB
					硼烷二甲胺络合物	DMAB
					硼烷吗啡络合物	MB
					硼烷三乙胺络合物	TEAB
					硼烷三甲胺络合物	TMAB

序号	纸张		成分	方法	脱酸材料		脱酸材料结构	溶剂
a^[19]	自然老化旧书			浸泡	3-氨基丙基三甲氧基硅烷	ATMS		乙醇
					3-氨基-2,2-二甲基丙基三甲氧基硅烷	AMTMS
					3-氨丙基三乙氧基硅烷	ATES
					3-氨丙基甲基二乙氧基硅烷	AMDES
					3-(N,N-二甲基氨基)丙基三甲氧基硅烷	DMATMS
b^[20]	P1	>95% CL SWP		浸泡	3-氨丙基甲基二乙氧基硅烷	AMDES		HMDSO
	P2	75% WP 25% SWP
	自然老化B1928
c^[26]	P3		CL (>95%)	浸泡	3-(N,N-二甲基氨基)丙基甲基二乙氧基硅烷	DMAPDES		HMDSO
d^[21]	P4		>95% CL SWP	浸泡	3-氨丙基甲基二乙氧基硅烷	AMDES		HMDSO
d^[21]	P4		>95% CL SWP	浸泡喷涂	3-氨丙基三乙氧基硅烷	APTES		HMDSO
序号	纸张		成分	方法	脱酸材料		脱酸材料结构	溶剂
				浸泡喷涂	APTES-AMDES 共聚物	APTES-AMDES		HMDSO/ 无溶剂
e^[27]	宣纸			浸泡	N-氨乙基-3-氨丙基- 三乙氧基硅烷	AETAPTES		乙醇
f^[28]	打印纸			浸泡	γ-缩水甘油醚氧丙基三甲氧基硅烷	KH560		乙醇
g^[23]	S1 (1986) WP			浸泡	甲基硅酸钾	PMS		水
	BDP
	宣纸		SWP>75% CL
h^[24]	滤纸			浸泡	水溶性聚酰胺	PAAOH		水
i^[29]	色谱纸			浸泡	硼烷叔丁胺络合物	TBAB
					硼烷氨络合物	AB
					硼烷N,N-二异丙基乙胺络合物	DIPEAB
					硼烷二甲胺络合物	DMAB
					硼烷吗啡络合物	MB
					硼烷三乙胺络合物	TEAB
					硼烷三甲胺络合物	TMAB

序号	纸张	成分	方法	脱酸剂	溶剂
a^[47]	S1	BSP	浸泡	Ca(OH)₂	水
b^[48]	Whatman paper		浸泡喷涂涂刷	Mg(OH)₂	异丙醇
c^[49]	韦托法		涂刷	CH₃OMgOCOOCH₃	水
d^[48]	Whatman paper		浸泡喷涂涂刷	Nano-Mg(OH)₂	异丙醇
e^[40]	《马克思恩格斯选集第二卷》1972 年出版		超声雾化	Ca(OH)₂	水
f^[37]	杂志		浸泡超临界CO₂	Ca(OH)₂	水/乙醇
g^[41]	BP		浸泡	Nano-Mg(OH)₂-SDS	水
h^[35]	S2	70% HWBP 30% SWBP 20% PFAK	喷洒	Nano-Ca(OH)₂	环己烷
i^[36]	文件		浸泡	Nano-Ca(OH)₂	水/异丙醇
j^[34]	油画纸			Nano-Ca(OH)₂	乙醇/正丙醇
k^[46]	P1	90% GW 10% SWBP 20% KLAS	浸泡	Nano-Ca(OH)₂	乙醇
k^[46]	P2	75% GW 25% SWBP 20% KLAS	浸泡	Nano-Ca(OH)₂	异丙醇
l^[39]	MWP-1920/1940		亚临界	Nano-Ca(OH)₂	R134a (超临界)
l^[39]	Newspaper in 1962		亚临界	Nano-Ca(OH)₂	R134a (超临界)
m^[43]	宣纸新闻纸机制纸		浸泡	MgO oleic acid-modified	环己烷
n^[44]	纸张(种类未知)		浸泡	MgO-Hal	羟丙基纤维素水溶液
o^[46]	P1	90% GW 10% SWBP 20% KLAS	浸泡	Nano-CaCO₃	乙醇
o^[46]	P2	75% GW 25% SWBP 20% KLAS	浸泡	Nano-CaCO₃	异丙醇
p^[45]	含有酸性油墨的纸		涂刷	Nano-Ca(C₂H₅COO)₂	乙醇
q^[37]	Standard paper		浸泡超临界CO₂	Mg(CH₃COO)₂	水/乙醇
r^[32]	手稿(1350; 1712; 1576)		浸泡	Ca(HCO₃)₂ Mg(HCO₃)₂	水
s^[50]	古籍修复时拆下的护页纸		浸泡	NaHCO₃	水
t^[51]	报纸		超临界	Na₂B₄O₇•10H₂O	水/乙醇、超临界CO₂

序号	纸张	成分	方法	脱酸剂	溶剂
a^[47]	S1	BSP	浸泡	Ca(OH)₂	水
b^[48]	Whatman paper		浸泡喷涂涂刷	Mg(OH)₂	异丙醇
c^[49]	韦托法		涂刷	CH₃OMgOCOOCH₃	水
d^[48]	Whatman paper		浸泡喷涂涂刷	Nano-Mg(OH)₂	异丙醇
e^[40]	《马克思恩格斯选集第二卷》1972 年出版		超声雾化	Ca(OH)₂	水
f^[37]	杂志		浸泡超临界CO₂	Ca(OH)₂	水/乙醇
g^[41]	BP		浸泡	Nano-Mg(OH)₂-SDS	水
h^[35]	S2	70% HWBP 30% SWBP 20% PFAK	喷洒	Nano-Ca(OH)₂	环己烷
i^[36]	文件		浸泡	Nano-Ca(OH)₂	水/异丙醇
j^[34]	油画纸			Nano-Ca(OH)₂	乙醇/正丙醇
k^[46]	P1	90% GW 10% SWBP 20% KLAS	浸泡	Nano-Ca(OH)₂	乙醇
k^[46]	P2	75% GW 25% SWBP 20% KLAS	浸泡	Nano-Ca(OH)₂	异丙醇
l^[39]	MWP-1920/1940		亚临界	Nano-Ca(OH)₂	R134a (超临界)
l^[39]	Newspaper in 1962		亚临界	Nano-Ca(OH)₂	R134a (超临界)
m^[43]	宣纸新闻纸机制纸		浸泡	MgO oleic acid-modified	环己烷
n^[44]	纸张(种类未知)		浸泡	MgO-Hal	羟丙基纤维素水溶液
o^[46]	P1	90% GW 10% SWBP 20% KLAS	浸泡	Nano-CaCO₃	乙醇
o^[46]	P2	75% GW 25% SWBP 20% KLAS	浸泡	Nano-CaCO₃	异丙醇
p^[45]	含有酸性油墨的纸		涂刷	Nano-Ca(C₂H₅COO)₂	乙醇
q^[37]	Standard paper		浸泡超临界CO₂	Mg(CH₃COO)₂	水/乙醇
r^[32]	手稿(1350; 1712; 1576)		浸泡	Ca(HCO₃)₂ Mg(HCO₃)₂	水
s^[50]	古籍修复时拆下的护页纸		浸泡	NaHCO₃	水
t^[51]	报纸		超临界	Na₂B₄O₇•10H₂O	水/乙醇、超临界CO₂

序号	纸张	纸浆	方式	脱酸剂	溶剂
a^[52]	中性纸酸性纸	BSP	浸泡涂刷	MC/Ca(OH)₂	水
b^[54]	滤纸	100%纤维素	浸泡	TMSC/Mg(OH)₂	HMDSO
b^[54]	德国木浆纸	50% WP＋50% CP	浸泡	TMSC/Mg(OH)₂	HMDSO
c^[55]	模拟宣纸/WP		涂刷	EC/Mg(OH)₂	乙醇
d^[56]	纸张		浸泡喷洒	MgO/Ca(OH)₂/ETA	HMDSO
e^[53]	模拟老化纸		雾化	NaCO₃/Ca(C₃H₅O₂)₂/纤维素纳米晶体	水
f^[57]	报纸		涂刷	羧甲基纤维素/小麦淀粉浆糊/Ca(OH)₂	水

纸张与纸质文物脱酸材料近期研究与展望

Recent Research and Prospect of Deacidifying Materials for Paper and Paper-based Cultural Relics

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