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Nano Meets the Sheet: Adhesive-Free Application of Nanocellulosic

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Nano Meets the Sheet: Adhesive-Free Application of Nanocellulosic Völkel et al. Herit Sci (2017) 5:23 DOI 10.1186/s40494-017-0134-5 RESEARCH ARTICLE Open Access Nano meets the sheet: adhesive‑free application of nanocellulosic suspensions in paper conservation L. Völkel1, K. Ahn2, U. Hähner3, W. Gindl‑Altmutter4 and A. Potthast2* Abstract Historical papers are often locally damaged by exogenous infuences and/or have endogenously degraded paper areas. The stabilization of such papers is very important because further use of the object can cause additional damage. Diferent types of nanocellulose are interesting as a novel stabilizing materials for paper due to their close structural relation to the paper matrix. Therefore, the present study investigated whether the treatment of historical papers with nanocellulose suspensions is a novel method for paper stabilization. Two diferent types of nanocellu‑ loses, bacterial cellulose and a mechanically nanofbrillated cellulose based on wood pulp, were tested with regard to their performance in stabilizing fragile papers. Concerning material handling and application in conservation steps, diferent ways to modify the suspensions were tested. The resulting suspensions were applied to historical papers from several centuries with diferent extents of damage. The paper-nanocellulose composites were characterized with regard to their optical and microscopic integrity and by physical and chemical analyses. The treatment of mechani‑ cal damage and the consolidation of weakened paper areas could be realized by the application of a nanocellulose suspension without an additional adhesive. The results of the treatment depend on the type of nanocellulose, on the paper material, on processing and application techniques. The paper discusses the applicability and stability of the diferently prepared nanocellulose suspensions, also with regard to their mode of application and long-term perfor‑ mance. Advantages and limitations are addressed in detail. Keywords: Bacterial cellulose, Nanofbrillated cellulose, Paper stabilization, Gel Permeation Chromatography (GPC), Mechanical testing, Aging Background quality and/or endogenous cellulose degradation—as in Mechanical damage in form of cracks, cuts, fractures, modern papers from the nineteenth and twentieth cen- losses, creases, and deformations very often occur to turies—as well as cellulose damage by biodeterioration documents in archives, libraries, and museums. Difer- reduce the strength characteristics of papers and worsen ent types of damage are caused by local and/or external mechanical damage when using those papers. Addition- forces acting on single items. Terefore, damage is most ally, most of the dangers in connection with reduced often present around the edges. Besides the direct infu- strength properties and prior damage result from the ence, sheet borders are exposed to atmospheric infu- reuse of the items that can cause new damage or inten- ences that could have a negative efect on the strength sify already existing defects [1]. Because mechanical properties close to the edge of papers. Poor material damage afects a great number of paper items in col- lections, stocks, and estates, its treatment is one of the basic and important challenges in restoration work [2]. *Correspondence: [email protected] As far as the treatment of mechanical damage is con- 2 Division of Chemistry of Renewables, Department of Chemistry, University of Natural Resources and Life Sciences (BOKU), cerned, the objective is to stabilize weakened papers and Konrad‑Lorenz‑Strasse 24, 3430 Tulln, Austria rehabilitate extremely damaged areas by adding Japanese Full list of author information is available at the end of the article paper. At the same time, the substance and quality of © The Author(s) 2017. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/ publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated. Völkel et al. Herit Sci (2017) 5:23 Page 2 of 17 papers should be preserved in case of further mechani- an interesting methodical approach. Tey allow for eas- cal stress. Tis should allow for lower risk when handling ier processing of the very thin Japanese tissue papers, a papers (Fig. 1). standardization of the adhesive quantity, and the mini- Te treatment of papers demands that can be gath- mization of the infuence of moisture or better humidity ered from physical, chemical, and optical aspects. Te control during the paper stabilization phase [7, 8]. For treatment should provide sufcient strength and gen- this purpose, fabrication and processing technologies erate minimal material enforcement without produc- are helpful [7–9]. ing sharp edges; it should not provoke any endogenous Diferent types of nanocellulose can be interesting as changes or potential damage in the long term (like dis- a novel and innovative materials for paper stabilization locations at fbres), just to name a few examples [3]. Fur- due to their strong structural similarity to the paper thermore, stabilizing treatments are very often judged matrix (i.e., cellulose). In principle, the molecular struc- from an aesthetical viewpoint. During stabilizing treat- ture of the bacterial nanocellulose (BNC) and nanofbril- ment, there should not be any infuencing factors that lated cellulose (NFC) and that of conventional herbal/ lead to visual changes on the surface of the paper—this plant-based cellulose is identical. But there are consid- means low gloss, no colour changes, and no harming of erable diferences at the level of fber morphology. Te the lettering [3]. nanocelluloses of plant origin and of bacterial origin are Te traditional method of paper stabilization is to characterized by common specifc properties that are mend with Japanese paper [4–6]. Te adhesive is applied caused by their molecular construction and their struc- to Japanese paper or to the original item via brush appli- tures in the nanometre range. However, considerable cation. Both (the Japanese paper and the original item) diferences are mainly resulting from diferent produc- are subsequently glued together. As far as the process- tion processes. BNC, for example, has—compared with ing is concerned, there are some variations, but the NFC—a higher water retention capacity, a higher degree basic principle remains unchanged. Te selection of the of polymerization, and more uniform fbres (fbre diam- Japanese paper, the adhesive, and the method of treat- eter BNC: 20–100 nm, NFC: 5–100 nm; [10, 11]). An ment is determined by damage symptoms and object essential diference lies in the purity level of the nano- characteristics. In this context, and because of the fact celluloses. After a thorough cleaning, BNC can be pro- that in many cases local damage has to be treated, the duced with the highest degree of purity [12]. In contrast, development and the increased use of coated stabilizing in NFC, additional components (like hemicellulose, papers (remoistenable and heat-set tissues) represents lignin, and other substances) are contained, depending Fig. 1 Mechanical damage (cracks) at the edges of a letter. The scripture is compromised and threatened. (© Forschungsbibliothek Gotha der Universität Erfurt, Chart. A 496, p. 3) Völkel et al. Herit Sci (2017) 5:23 Page 3 of 17 on isolation and cleaning conditions during the produc- [25]. Because of the special surface characteristics, it is tion process. For both materials, the emerging nano- well-suited for transparent or coated papers, as well as dimensions require large fbre surfaces that, in turn, parchment, and can be used to stabilize or to fll losses cause strong interactions with substances of the environ- [25]. ment [11–13]. Te application of NFC has also been investigated, Bacterial nanocellulose has unique selling points in because the strength of paper can be improved by comparison to cellulose of plant origin due to the manu- coating or admixture [21]. A complete coating as a facturing process. It is synthesized by bacteria of the spe- new technique for strengthening acidic wood-based, cies Gluconacetobacter. During (in situ) or after (post) degraded paper was presented by Okayama et al. Te biosynthesis, the development of cellulose (i.e., form, strength of those papers were improved by the treat- structure, etc.) can be individually controlled. After less ment [26, 27]. Camargos et al. and Pereira used NFC or complex cleaning (cooking in sodium hydroxide solution CNC mixed with fllers, pigments, plasticizers, and siz- and washing) compared to the isolation of NFC, bacte- ing agents to fll paper losses in situ [28, 29]. Another rial products can be directly used. Moreover, BNC has a approach is the application of flms of microfbrillated very high molecular weight (species depending, around cellulose to mend cracks. In particular, the very good DP 8000), a high degree of crystallinity, and a distinct optical appearance and the positive mechanical char- mechanical strength [12, 14]. At the same time, it is also acteristics allowed the application for a special object believed that it has an exceptional level of chemical and group like “polyorama panoptique” (paper viewing thermal
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