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Migration of Volatile Compounds from Paper Stacks During Accelerated Migration of Volatile Compounds from Paper Stacks during Accelerated Ageing A thesis submitted to the Department of Art In conformity with the requirements for the Degree of Master in Art Conservation Queen's University Kingston, Ontario, Canada September, 1999 Copyright O Anna Elisabeth Bülow National Library Bibliothèque nationale ($1 of Canada du Canada Acquisitions and Acquisitions et Bibliographic Services services bibliographiques 395 Wellington Street 395. rue Wellington Ottawa ON KI A ON4 Ottawa ON K! A ON4 Canada Canada The author has granted a non- L'auteur a accordé une licence non exclusive licence allowing the exclusive permettant à la National Library of Canada to Bibliothèque nationale du Canada de reproduce, loan, distnbute or sel1 reproduire, prêter, distribuer ou copies of this thesis in microform, vendre des copies de cette thèse sous paper or electronic formats. la forme de microfiche/film, de reproduction sur papier ou sur format électronique. The author retains ownership of the L'auteur conserve la propriété du copyright in th~sthesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial extracts fiom it Ni la thèse ni des extraits substantiels may be p~tedor otherwise de celle-ci ne doivent être imprimés reproduced without the author's ou autrement reproduits sans son permission. autorisation. Abstract In order to develop improved artificial ageing methods for paper, several research projects conducted by different laboratories throughout North America have shown that paper sheets, aged in an enclosed environment or arranged in stacks, deteriorate faster than single sheets aged under the same conditions. This was found to be especially true for acidic paper. The objectives of this project are: to investigate the changes in paper properties from the top of the stack (open to environment) to the centre. to determine if they are effected by possible migration of volatile products from the paper. and to find out whether or not the diffusion of acidic compounds have the same effect on the stability of therrnally aged paper and naturally aged paper. An alurn- rosin sized fully bleached kraft paper was aged in stacks, at three different temperature and humidity conditions and four different intervals. The stacks were open at the top to allow diffusion of volatile products to occur. Test methods included grammage, moisture content, brightness, yellowness, L*a*b*, zero-span tensile strength, pH and the degree of polymerization. These tests showed a decrease in paper properties from the top of the stack to the centre. This indicates a diffusion effect where volatile compounds escape from the paper at the top of the stack, but remain trapped towards the centre, where more severe degradation occurs. It is not entirely clear if this diffusion effect is the same at ambient conditions as it is at the elevated temperatures used in this study. The research project was carried out in collaboration with the Canadian Conservation Institute. .. III Acknowledgements I would like to thank: Paul Bégin, Canadian Conservation lnstitute (CCI), Ottawa, Ontario, Canada, for his invaluable advice. assistance and guidance during my research project. In addition. I would like to thank Paul Bégin and Joe lraci from CC1 West for the "Pizza-Lunches". Thea Burns, Art Conservation Program. Department of Art at Queen's University, Kingston, Ontario. Canada, for her supervision. advice and interest throughout the project. The Canadian Conservation Institute, for providing laboratory equiprnent and Elizabeth Kaminska for proofreading and assisting with the occasions I rescuing of samples during the determination of the degree of polymerization. Also1, l would like to thank Season Tse for her support. Dr. David Grattan, Manager of Conservation Processes and Materials Research at CC1 for his advice and support during this research work. The School of Graduate Studies and Research, Queen's University, for its financial support of this thesis. Contents A bstract II ., . Acknowledgements III Contents iv List of Figures List of Tables vii 1 Introduction 2 Historical Ovetview 2.1 Important Developrnents in Paperrnakinç 2.2 Permanence of Paper 3 Current Research in Accelerated Ageing Procedures 4 Experirnental 4.1 Samples 4.2 Accelerated Ageing 4.3 Test Methods 5 Results 6 Discussion 7 Conclusion References Appendix 1 (Figures) Appendix 2 (Tables) Appendix 3 (Materials and Equiprnent) Vita List of Figures Figure 1 Distribution of Test Specimens Figure 2 Brightness vs. Page Figure 3 Yellowness vs. Page Figure 4 b' vs. Page Figure 5 Stightness ILS. ogeiq Tirne, pages #i and ?#5 Figure 6-1 b* vs. Ageing Time, 70°C 1 61% RH Figure 6-2 b* vs. Ageing Time, 80°C 1 65% RH Figure 6-3 b* vs. Ageing Time, 90°C 169% RH Figure 7-1 Yellowness vs. Ageing Time, 70°C 1 61 O/O RH Figure 7-2 Yellowness vs. Ageing Time, 80°C 1 65% RH Figure 7-3 Yellowness vs. Ageing Time, 90°C 169% RH Figure 8 pH vs. Page Figure 9-1 pH vs. Ageing Time, 70°C / 61% RH Figure 9-2 pH vs. Ageing Time, 80°C 1 65% RH Figure 9-3 pH vs. Ageing Time, 90°C 1 69% RH Figure 10 Zero-span Breaking Length vs. Page Figure 11 Degree of Polymerization vs. Ageing Tirne Figure 12 b* vs. Ageing Time, Pages #Il#3 and #15 Figure 13 pH vs. Ageing Time, incl. single sheet and stack sheet 70 Figure 14 Rate of Degradation (Zero-span) 71 Figure 15 Rate of Degradation (DP) 72 Figure 16 Zero-span vs. Number of Broken Bonds 73 vii List of Tables Table 1 Differences in the Amoun! of Ageing Table 2 Grammage Table 3 Moisture Content Table 4 Brightness Table 5 ve!lowness Table 6 L' Table 7 a* Table 8 b* Table 9 PH Table 10 Zero-span Tensile Strength Table 11 Degree of Polymerization 1 Introduction Over the last decades there has been an increasing awareness of the problem of paper deterioration on the part of both the public and sc~entistsinvolved either in paper manufacture or in its preservation. This in turn has led to many different research studies concerning this issue. The following project was carried out in the context of extensive research studies currently being perforrned at the Canadian Conservation Institute, Ottawa. These studies focus on the development of an improved ageing method in order to predict the permanence of paper (Bégin et al. 1998 and 1999). Their results suggest that generally more attention should be paid not only to the ageing conditions thernselves, but also to the arrangement of paper in the ageing chamber during artificial ageing. Based on these experiments, it was found that volatile products, inherent in paper, are able to escape from free hung sheets, whereas they remain trapped if the paper sheets are arranged as a stack, when aged at elevated temperatures. Furthermore, it was shown that paper sheets aged in an open stack age to a different extent, depending on their placement in the stack (Carter 1996). The present study, therefore, focuses on the determination of the extent to which diffusion influences the ageing properties of paper in an open stack. lt also examines the extent to which this diffusion influences the properties of paper at different ageing conditions. The results of this study could help elucidate the question of whether or not artificial ageing methods are able to reproduce the same ageing mechanisms as natural ageing. In order to better understand issues involved in paper permanence, it is necessary to investigate the history of paper permanence from an historical point of view. The main focus, therefore, will not be the deterioration itself but the perception of paper permanence and the growiiig awareness of its importance now and in the future. The most important changes in papermaking will be outlined in the first half of this section. The second half will focus cn the causes of deterioration and their detection during the last hundred years as well as the development of artificial ageing procedures. The background section will explain recent developrnents in accelerated ageing studies, which indicate a difference in the results of ageing between free hung sheets and sheets aged as a stack. The outline and objectives of the project will be presented. The choice of sarnples, ageing conditions and test methods used, are illustrated in the first part of the experimental section. Following this, the test methods will be further explained. Results and discussion are presented separately in order to keep actual data and their interpretation apart. Conclusion and recommendations for future research will be given in the last section. Historical Overview The history of paper has been described many times. However, it seems necessary to recall the most important changes in papermaking in order to understand the history of paper-related science. The principal of papermaking as it was invented in China has undergone only little change. Its history has been thoroughly described, e.g. by Hunter (1978). Therefore. this ovewiew only focuses on issues relating to paper stability and permanence. The following section briefly outlines the historical developments in papermaking since the beginning of paper manufacture in Europe in the Middle Ages. The history of the science concerned with paper deterioration is focused on in part two of this section. 2.1 lmoortant Developments in Paoermakinq Early Papermaking Processes Paper is defined as a web consisting mainly of vegetable fibres, traditionally produced by dipping a mould into a fibre suspension. In addition, paper may be sized to prevent the feathering of ink, and contain fillers and colouring matters. It is commonly recognized that the art of papermaking was invented in China about two thousand years ago. Paper, as it was manufactured in Europe since the rniddle of the 121h century, consisted of fibres derived from rags, whose principal constituent is cellulose.
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