Hanji paper, the paper material traditionally used in Korea, is in the focus of the present aging and mechanistic study. As raw materials and historic recipes for paper making are still available for Hanji today, specimen resembling historical material at the point of production can be prepared. While from that starting point, historical material had taken the path of natural aging, newly prepared samples-prepared according to both historic and current recipes-were artificially aged, and both aging modes can be compared. For the first time, an in-depth chemical and mathematical analysis of the aging processes for Hanji is presented. The aging of Hanji paper, resulting in hydrolysis and oxidation processes, was addressed by means of selective fluorescene labeling of oxidized groups in combination with gel permeation chromatography, providing profiles of carbonyl and carboxyl groups relative to the molar mass distribution. Starting Hanji showed the highest molecular weight ([1,400 kDa) ever reported for paper. We have defined two critical parameters for comparison of the paper samples: half-life DP (the time until every chain is split once on average) and life expectancy (the time until an average DP of failure is reached and no further mechanical stress can be tolerated). The two values were determined to be approximately 500 and 4,000 years, respectively, for the Hanji samples, provided there is no UV radiation. The rate of cellulose chain scission under accelerated aging (80°C, RH 65 %), was about 600 times faster than under natural conditions. In addition, cellulose degradation of Hanji paper under accelerated aging condition was about 2-3 times slower than that of historical rag paper as those used in medieval Europe.
The Annals of Joseon Dynasty, which recorded governmental affairs for 472 years (AD 1392-1863) during the Joseon dynasty is an representative paper cultural heritage in Korea. Being recognised their authenticity and values they were designated as the No 151 national treasure of Korea in 1973 and registered as 'The Memories of the World' by UNESCO in 1997.Unusually, some volumes of the Annals were treated by beeswax for the permanent preservation. However, the examinations on the deterioration of the beeswax-treated volumes had been exposed the serious damage than the untreated volumes. In particular, the larger amount of beeswax were worst in deterioration condition.In order to solve these problems, NRICH(National Research Institute of Cultural Heritage) of Korea launched the investigation study for the conservation of beeswax-treated volumes of the Annals. Now then, the five study areas have been set up; 1) to understand the damaged condition of the Annals; 2) to analyse the raw materials and production techniques; 3) to test the degradation degree using the duplication samples for understanding the aging factors and mechanism; 4) to develop the conservation techniques through dewaxing and thereafter strengthening the base paper of Hanji; 5) to develop the long-term storage technique using inert gases. On the basis of outcomes from this study, NRICH will plan to establish the systematic conservation and management plan for the beeswax-treated volumes of the Annals in future.
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The optimum dewaxing ratio in dewaxing treatment by the heat and pressure method was investigated by considering aging stability of dewaxed Hanji. Commercial Hanji was coated with beeswax and thermally aged at 150 o C for 24 hours. Then it was dewaxed using the laboratory sheet press equipped with hot plates on both top and bottom sides. Dewaxing ratio was controlled by pressing temperature and time. Four type of dewaxed Hanji samples with different dewaxing ratio were prepared and thermally aged at 150 o C. Then the aging stability of dewaxed Hanji samples was evaluated in terms of optical and strength properties. It was found that the aging stability of dewaxed Hanji was superior with higher dewaxing ratio. The result concluded that, in the aspect of aging stability, the coated beeswax in beeswax-treated Hanji shall be completely removed if the coated wax would be dewaxed.
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