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Chemical Conservation of Paper-Based Cultural Heritage

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A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (30 September 2024) | Viewed by 17113

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Special Issue Editors

Dr. Yueer Yan

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Guest Editor

Institute for Preservation and Conservation of Chinese Ancient Books, Fudan University, Shanghai 200433, China
Interests: paper cultural heritage; nondestructive testing; chemical degradation; preventive conservation

Prof. Dr. Yi Tang

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Guest Editor

Department of Chemistry, Fudan University, Shanghai 200433, China
Interests: zeolite catalysis and nanomaterials for energy conversion and fine chemicals production
Special Issues, Collections and Topics in MDPI journals

Prof. Dr. Yuliang Yang

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Guest Editor

Department of Macromolecular Science, Fudan University, Shanghai 200433, China
Interests: macromolecular material; polymer physics; polymer chemical application

Special Issue Information

Dear Colleagues,

For millennia, paper has been the ultimate messenger of human wisdom, delivering information on the zeitgeist of each era across the boundary of time. However, paper undergoes severe deterioration along its lengthy life course, hence requiring intensive care to protect it. Chemists can play crucial roles in this mission, considering the interdisciplinary nature of the field of chemistry. The relationship between heritage science and applied chemistry is particularly close when facing a system as complex as paper heritage, where intrinsic and extrinsic factors are entangled to form convoluted degradation mechanisms. Currently, as the public’s awareness of cultural heritage protection increases, an ever-growing effort has been devoted to the preservation and conservation of paper-based historical heritage. Studies on aging mechanisms and lifetime evaluation have emerged, and a kaleidoscope of preventive/remedial conservation techniques has thrived on the basis of multiple functionalized materials. Nevertheless, there are always blanks to fill in, regarding finding suitable monitoring tools, specifying conservational environment parameters, and determining more feasible protection methods.

Therefore, this Special Issue aims to provide updates on the latest development in analysis and characterization techniques, new insight into degradation mechanisms, and freshly proposed conservation methods on the topic of paper-based cultural heritage chemistry.

Dr. Yueer Yan
Prof. Dr. Yi Tang
Prof. Dr. Yuliang Yang
Guest Editors

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Keywords

paper-based cultural heritages
analysis techniques
degradation mechanisms
conservation methods

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Published Papers (11 papers)

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Editorial

Jump to: Research

6 pages, 143 KiB

Open AccessEditorial

Chemical Conservation of Paper-Based Cultural Heritage

by Yueer Yan, Yi Tang and Yuliang Yang

Molecules 2025, 30(1), 122; https://doi.org/10.3390/molecules30010122 - 31 Dec 2024

Viewed by 942

Abstract

Paper-based cultural heritages, represented by ancient books, archives, calligraphy, and paintings, recorded the development of human civilization [...] Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

Research

Jump to: Editorial

18 pages, 6297 KiB

Open AccessArticle

Research on the Structure and Properties of Traditional Handmade Bamboo Paper During the Aging Process

by Zirui Zhu, Kai Zhang, Yu Xue, Zhongming Liu, Yujie Wang, Yanli Zhang, Peng Liu and Xingxiang Ji

Molecules 2024, 29(23), 5741; https://doi.org/10.3390/molecules29235741 - 5 Dec 2024

Cited by 1 | Viewed by 1557

Abstract

Handmade papers, as carriers of paper-based cultural relics, have played a crucial role in the development of human culture, knowledge, and civilization. Understanding the intricate relationship between the structural properties and degradation mechanisms of handmade papers is essential for the conservation of historical documents. In this work, an artificial dry-heat-accelerated aging method was used to investigate the interplay among the mechanical properties of paper, the degree of polymerization (DP) of cellulose, the chemical composition, the hydrogen bond strength, the crystallinity, and the degree of hornification for paper fibers. The results demonstrated for the first time that the mechanical properties of handmade bamboo paper exhibited an initial plateau region, a rapid decline region, and sometimes a second plateau region as it undergoes a dry-heat aging process. The changes in cellulose, hemicellulose, and lignin content were tracked throughout these three stages. The lignin content was relatively stable, while the cellulose and hemicellulose content decreased, which was consistent with the observed decline in mechanical properties. When the DP of cellulose decreased to the range of 600–400, there was a critical point in the mechanical properties of the paper, marking a transition from the initial stable region to a rapid decline region. The fiber embrittlement caused by cellulose chain breakage resulting from the decrease in DP was counteracted by the enhancement of intermolecular hydrogen bonds and the hornification process. A second stable region appeared when the DP was less than 400, marking a transition from a balanced or slightly decreasing trend in the initial plateau region to a sharp decline. This study also discussed for the first time that the formation of the second plateau region may be due to the presence of hemicellulose and lignin, which hinder the further aggregation of cellulose and maintain the structural stability of the fiber cell. The findings of this study can provide guidance for improving ancient book preservation strategies. On the one hand, understanding how these components affect the durability of paper can help us better predict and slow down the aging of ancient books. On the other hand, specific chemical treatment methods can be designed to stabilize these components and reduce their degradation rate under adverse environmental conditions. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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16 pages, 5493 KiB

Open AccessArticle

Influence of Relative Humidity on the Mechanical Properties of Palm Leaf Manuscripts: Short-Term Effects and Long-Term Aging

by Wenjie Zhang, Shan Wang and Hong Guo

Molecules 2024, 29(23), 5644; https://doi.org/10.3390/molecules29235644 - 28 Nov 2024

Cited by 2 | Viewed by 662

Abstract

Palm leaf manuscripts are a valuable part of world cultural heritage. Studying the mechanical properties of palm leaf manuscripts and their changes due to environmental influences is of great significance for understanding the material characteristics, aging mechanisms, and preventive conservation of these manuscripts. This study used dynamic vapor sorption (DVS) and a thermomechanical analyzer (TMA) to investigate the changes to the mechanical properties of palm leaf manuscripts in response to different relative humidity conditions and different time periods. The short-term study results show that exposure to varying relative humidities leads to changes in the equilibrium moisture content (EMC) of palm leaf manuscripts, causing the bending strength of the samples to decrease significantly with increasing humidity. The bending modulus initially increases and then decreases as the humidity increases. Moreover, the greater the desorption hysteresis of the samples, the more pronounced the changes to the mechanical properties. Therefore, a stable environment in terms of humidity can prevent changes in the mechanical properties of palm leaf manuscripts, thereby preventing the onset of degradation. The results of the long-term aging studies indicate that prolonged exposure to either very dry or very humid conditions greatly affects the mechanical properties of palm leaf manuscripts, which is detrimental to their preservation. The samples kept at 50% RH did not exhibit significant signs of deterioration, with no notable changes in their mechanical properties or chemical structure. This suggests that 50% RH is a relatively optimal humidity condition for the preservation of palm leaf manuscripts. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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14 pages, 8273 KiB

Open AccessArticle

Facile Synthesis of Low-Dimensional and Mild-Alkaline Magnesium Carbonate Hydrate for Safe Multiple Protection of Paper Relics

by Yi Wang, Zirui Zhu, Jinhua Wang, Peng Liu, Xingxiang Ji, Hongbin Zhang and Yi Tang

Molecules 2024, 29(20), 4921; https://doi.org/10.3390/molecules29204921 - 17 Oct 2024

Viewed by 1011

Abstract

Paper-based cultural relics inevitably face a variety of diseases such as acidification, yellowing, and strength loss during long-term preservation, where weakly alkaline inorganic materials play an important role in their deacidification treatments. In this work, by simply adjusting the supersaturation of crystal growing solution without the use of any organic additives, one-dimensional (1D) and two-dimensional (2D) weakly alkaline materials—magnesium carbonate hydrates (MCHs)—were controllably synthesized. It is worth noting that the coatings of 1D/2D MCHs not only cause little change in chromatic aberration and water wettability, but also ensure their safety for alkali-sensitive pigments. Meanwhile, the deacidification, anti-aging, strength-enhancing, and flame-retardant effects of these materials have been tested on ancient book papers, all of which achieved good protective effects. In contrast, 1D MCH materials brought about significant enhancement in both mechanical strengths and flame-retardant effects, and the related effects were investigated. Based on this facile micromorphology control strategy, more low-dimensional nanomaterials are expected to be synthesized by design for the protection of paper-based relics, which will expand our knowledge on functional deacidification and protection mechanisms. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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14 pages, 4852 KiB

Open AccessArticle

Multi-Functional Repair and Long-Term Preservation of Paper Relics by Nano-MgO with Aminosilaned Bacterial Cellulose

by Hongyan Mou, Ting Wu, Xingxiang Ji, Hongjie Zhang, Xiao Wu and Huiming Fan

Molecules 2024, 29(16), 3959; https://doi.org/10.3390/molecules29163959 - 22 Aug 2024

Cited by 2 | Viewed by 1237

Abstract

Paper relics, as carrieres of historical civilization’s records and inheritance, could be severely acidic and brittle over time. In this study, the multi-functional dispersion of nanometer magnesium oxide (MgO) carried by 3-aminopropyl triethoxysilane-modified bacterial cellulose (KH550-BC) was applied in the impregnation process to repair aged paper, aiming at solving the key problems of anti-acid and strength recovery in the protection of ancient books. The KH550-BC/MgO treatment demonstrated enhanced functional efficacy in repairing aged paper, attributed to the homogeneous and stable distribution of MgO within the nanofibers of BC networks, with minimal impact on the paper’s wettability and color. Furthermore, the treatment facilitated the formation of adequate alkali reserves and hydrogen bonding, resulting in superior anti-aging properties in the treated paper during prolonged preservation. Even after 30 days of hygrothermal aging tests, the paper repaired by KH550-BC/MgO was still in a gently alkaline environment (pH was about 7.56), alongside a 32.18% elevation compared to the untreated paper regarding the tear index. The results of this work indicate that KH550-BC/MgO is an effective reinforcement material for improving the long-term restoration of ancient books. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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16 pages, 4792 KiB

Open AccessArticle

Anti-Cracking TEOS-Based Hybrid Materials as Reinforcement Agents for Paper Relics

by Mengruo Wu, Le Mu, Zhiyue Zhang, Xiangna Han, Hong Guo and Liuyang Han

Molecules 2024, 29(8), 1834; https://doi.org/10.3390/molecules29081834 - 17 Apr 2024

Cited by 4 | Viewed by 1487

Abstract

Tetraethoxysilane (TEOS) is the most commonly used silicon-based reinforcement agent for conserving art relics due to its cost-effectiveness and commercial maturity. However, the resulting silica gel phase is prone to developing cracks as the gel shrinks during the sol–gel process, potentially causing severe damage to the objects being treated. In this study, dodecyltrimethoxysilane (DTMS) was introduced into TEOS to minimize this shrinkage by adding elastic long chains to weaken the capillary forces. The gel formed from the DTMS/TEOS hybrid material was transparent and crack-free, featuring a dense microstructure without mesopores or micropores. It exhibited excellent thermal stability, with a glass transition temperature of up to 109.64 °C. Evaluation experiments were conducted on artificially aged, handmade bamboo paper. The TEOS-based hybrid material effectively combined with the paper fibers through the sol–gel process, polymerizing into a network structure that enveloped the paper surface or penetrated between the fibers. The surface of the treated paper displayed excellent hydrophobic properties, with no significant changes in appearance, color, or air permeability. The mechanical properties of the treated bamboo paper improved significantly, with longitudinal and transverse tensile strengths increasing by up to 36.63% and 44.25%, respectively. These research findings demonstrate the promising potential for the application of DTMS/TEOS hybrid materials in reinforcing paper relics. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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13 pages, 6457 KiB

Open AccessArticle

Study on the Properties of FEVE Modified with Ag₂O/OH-MWCNTS Nanocomposites for Use as Adhesives for Wooden Heritage Objects

by Gele Teri, Cong Cheng, Kezhu Han, Dan Huang, Jing Li, Yujia Luo, Peng Fu and Yuhu Li

Molecules 2024, 29(6), 1365; https://doi.org/10.3390/molecules29061365 - 19 Mar 2024

Viewed by 1437

Abstract

The durability of wooden heritage objects and sites can be affected by external environmental factors, leading to decay, cracking, and other forms of deterioration, which might ultimately result in significant and irreversible loss. In this study, a FEVE resin was modified with Ag₂O/OH-MWCNTS (MA), denoted as MAF, where three concentrations were prepared using in situ precipitation, and the resulting composite adhesive was characterized by a high viscosity and effective bacteriostatic properties, demonstrating a better viscosity and thermal stability, as well as antibacterial properties, than pure FEVE resin. The results show that MAF adhesives present good thermal stability, as evidenced by a lower mass loss rate following treatment at 800 °C compared to the pure FEVE resin. At a consistent shear rate, the viscosity of MAF demonstrates a notable increase with the proportion of MA, which is better than that of FEVE. This suggests that the nano-Ag₂O particles in MA act as physical crosslinking agents in FEVE, improving the viscosity of the composite adhesive MAF. The adhesion strength between MAF and wood exhibits a similar trend, with wooden samples showing higher shear strengths as the proportion of MA increases in comparison to FEVE. Simultaneously, the antibacterial effects of the MAF adhesive exceeded 1 mm for Trichoderma, Aspergillus niger, and white rot fungi. The antibacterial activity of the MAF adhesive exhibited a direct correlation with the concentration of Ag₂O/OH-MWCNTS, with the most pronounced inhibitory effect observed on Trichoderma. The MAF adhesive demonstrates promising prospects as an adhesive for wooden heritage artifacts, offering a novel approach for the rapid, environmentally friendly, and efficient development of composite adhesives with superior adhesive properties. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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16 pages, 6872 KiB

Open AccessArticle

Ionic Liquids as Reconditioning Agents for Paper Artifacts

by Catalin Croitoru and Ionut Claudiu Roata

Molecules 2024, 29(5), 963; https://doi.org/10.3390/molecules29050963 - 22 Feb 2024

Cited by 3 | Viewed by 1494

Abstract

This research explores the potential of ionic liquids (ILs) in restoring paper artifacts, particularly an aged book sample. Three distinct ILs—1-ethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, 1-methyl-3-pentylimidazolium bis(trifluoromethylsulfonyl)imide, and 1-methyl-3-heptylimidazolium bis(trifluoromethylsulfonyl)imide —both in their pure form and isopropanol mixtures, were examined for their specific consumption in conjunction with paper, with 1-ethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide displaying the highest absorption. Notably, the methyl-3-heptylimidazolium ionic liquid displayed pronounced deacidification capabilities, elevating the paper pH close to a neutral 7. The treated paper exhibited significant color enhancements, particularly with 1-heptyl-3-methylimidazolium and 1-pentyl-3-methylimidazolium ILs, as evidenced by CIE-Lab* parameters. An exploration of ILs as potential UV stabilizers for paper unveiled promising outcomes, with 1-heptyl-3-methylimidazolium IL demonstrating minimal yellowing post-UV irradiation. FTIR spectra elucidated structural alterations, underscoring the efficacy of ILs in removing small-molecular additives and macromolecules. The study also addressed the preservation of inked artifacts during cleaning, showcasing ILs’ ability to solubilize iron gall ink, particularly the one with the 1-ethyl-3-propylimidazolium cation. While exercising caution for prolonged use on inked supports is still recommended, ILs are shown here to be valuable for cleaning ink-stained surfaces, establishing their effectiveness in paper restoration and cultural heritage preservation. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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13 pages, 1708 KiB

Open AccessArticle

Effect of Hemicellulose on the Wet Tensile Strength of Kozo Paper

by Zhiyou Han, Keiko Kida, Kyoko Saito Katsumata, Masaki Handa and Masamitsu Inaba

Molecules 2023, 28(19), 6996; https://doi.org/10.3390/molecules28196996 - 9 Oct 2023

Cited by 1 | Viewed by 1417

Abstract

Kozo paper, usu-mino-gami, is frequently used as the first back lining paper of hanging scrolls in order to support the main paper with a painting or a work of calligraphy on it. To dye it an appropriate color, paper is often treated with an alkali mordant solution. However, current kozo paper products have received such comments from conservators that wet tensile strength is weak and hard to handle. Therefore, improving the wet tensile strength of kozo paper is required. In previous papers, the effect of the sheet forming method, cooking condition, and parenchyma cell content between fibers on the wet tensile strength of kozo paper has been investigated. In this paper, the effect of glucuronoxylan, the main component of hardwood hemicellulose on the wet tensile strength of kozo paper was investigated. The wet tensile strength of kozo paper, when made in different cooking conditions, was evaluated using the Finch device. Glucuronoxylan content in fiber was analyzed using GC-FID. According to the results, it has been proved that glucuronoxylan content (with a xylan to glucan molar ratio of 4.43% to 5.16%) itself contributes to the wet tensile strength of the kozo sheet. Therefore, to increase the wet tensile strength of kozo paper, it is recommended to cook under milder conditions, thus retaining a higher amount of glucuronoxylan in the pulp. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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15 pages, 3296 KiB

Open AccessArticle

An Investigation into the Performance and Mechanisms of Soymilk-Sized Handmade Xuan Paper at Different Concentrations of Soymilk

by Chunfang Wu, Yangyang Liu, Yanxiao Hu, Ming Ding, Xiang Cui, Yixin Liu, Peng Liu, Hongbin Zhang, Yuliang Yang and Hongdong Zhang

Molecules 2023, 28(19), 6791; https://doi.org/10.3390/molecules28196791 - 25 Sep 2023

Cited by 3 | Viewed by 1664

Abstract

Invaluable paper relics that embody a rich traditional culture have suffered damage, requiring urgent restoration. In this context, the utilization of soymilk as a sizing agent holds great significance and reverence. This study investigates the use of soymilk as a sizing agent for Xuan paper and evaluates its effects on various properties and the long-term behavior of the paper. The findings reveal that the application of soymilk as a sizing agent for Xuan paper imparts distinct properties, including hydrophobicity, improved mechanical properties, and unique chromaticity. These characteristics—arising from the papillae on the surface of the Xuan paper, the protein folding of the soy protein, and hydrogen-bonding interactions between the soy protein and paper fibers—play a crucial role in shaping the paper’s unique attributes. From a physicochemical perspective, the aging process leads to multiple changes in paper properties. These changes include acidification, which refers to a decrease in pH, as well as a decline in mechanical strength, an increase in chromaticity, and a decrease in the degree of polymerization (DP) of the paper. The Ekenstam equation is employed to predict the lifespan of the paper, showing longer lifespans for Sheng Xuan paper and a negative correlation between soymilk concentration and lifespan in soymilk-sized paper. Our work provides valuable insights for the preservation and maintenance of paper, highlighting the potential benefits and challenges of using soymilk for surface sizing. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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16 pages, 3930 KiB

Open AccessArticle

Thermal, Rheological, Structural and Adhesive Properties of Wheat Starch Gels with Different Potassium Alum Contents

by Haibo Zhao, Hongbin Zhang, Qiang Xu, Hongdong Zhang and Yuliang Yang

Molecules 2023, 28(18), 6670; https://doi.org/10.3390/molecules28186670 - 17 Sep 2023

Cited by 4 | Viewed by 2233

Abstract

Wheat starch (WS) is a common adhesive material used in mounting of calligraphy and paintings. Potassium alum (PA) has indeed been used for many centuries to modify the physicochemical properties of starch. Thermal analysis revealed that the presence of PA led to an increase in the gelatinization temperature and enthalpy of the starch gels. The leached amylose and the swelling power of the starch gels exhibited a maximum at the ratio of 100:6.0 (WS:PA, w/w). The rheological properties of starch gels were consistent with changes in the swelling power of starch granules. SEM observations confirmed that the gel structure became more regular, and the holes grew larger with the addition of PA below the ratio of 100:6.0 (WS:PA, w/w). The short-range molecular order in the starch gels was enhanced by the addition of PA, confirmed by FT-IR analysis. Mechanical experiments demonstrated that the binding strength of the starch gels increased with higher PA concentrations and decreased significantly after the aging process. TGA results revealed that PA promoted the acid degradation of starch molecules. This study provides a detailed guide for the preparation of starch-based adhesive and its applications in paper conservation. Full article

(This article belongs to the Special Issue Chemical Conservation of Paper-Based Cultural Heritage)

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