Metal Plate Connectors and Iron Nails on the Tripitaka Koreana

Chapter 16

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Metal Plate Connectors and Iron Nails on the Tripitaka Koreana Printing Woodblocks Choon Ho Do,*,1 Chong-Hong Pyun,2 Byung-Yong Yu,2 and Jung Hyun Bae3 1Division

of Fisheries System Eng., National Fisheries R&D Institute, 216 Gijanghaean-ro, Kijang-eup, Kijang-gun, Busan 619-705, Korea 2Korea Institute of Science & Technology, Hwarangno 14-gil 5, Seongbuk-gu, Seoul 136-791, Korea 3Joongang Conservation Center for Cultural Heritage, 782-34 Bangbaebon-dong, Seocho-gu, Seoul 137-829, Korea *E-mail: [email protected]

The compositions of the metal plate connectors and nails that make up the Korean Buddhist Tripitaka (Canon) Printing Woodblocks, carved between AD 1236 and 1251 were determined using X-ray fluorescence spectroscopy (XRF), electron probe micro-analyzer (EPMA) and scanning electron microscopy. Copper was the main component of the metal plate connectors, as determined by XRF analysis. The composition of the nails used to connect the end pieces and the main printing wooden plate was mainly iron according to EPMA results. The iron nails were made through hand-forging of sponge iron.

Introduction History The Korean Buddhist Tripitaka (Canon) printing woodblocks, of which there are more than 81,000, were carved during the Mongolian invasion of Korea in the period AD 1236-1251. ‘Tripitaka’ is a Sanskrit word meaning three baskets. ‘Tripitaka’ is used as a term for the Buddhist canons because the Tripitaka contains three categories, sermons, precepts and commentaries. These woodblocks are a second edition. The first ones carved during AD 1011–1087 using the text of Chinese Northern Song (960-1127) burned by another previous © 2013 American Chemical Society In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Mongolian invasion in 1231. Today, the woodblocks are stored at the Haein-sa Temple, in Hapchun, Kyungsangnam-do, Korea. These objects are Korean cultural treasures, and the temple where they reside was designated as a UNESCO World Heritage Site in 1995 (1) and documentary heritage in 2007 by UNESCO (2). The woodblocks are stored in two buildings at the temple site, where they sit on shelves in sequence like books in a library (Figure 1). The text of the second edition was employed as a main text for the Japanese version, the Taishō Tripitaka printed using metal types during 1924-1934. In this paper, we examined the composition and structures of the metal plate connectors and iron nails used to assemble the woodblocks by optical microscopy, X-ray fluorescence spectroscopy (XRF) and scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). The metal plate connectors and nails fixed the main body plate to the end pieces of the woodblocks. We have previously reported studies on the iron nails found in the woodblocks (3). Since the metal plate connector sample employed for the elemental analysis in one of our previous studies was a part of a recent repair, our previous study was incorrect, unfortunately. Because the woodblocks have much significance as part of our shared national and world heritage, there is much interest in the scientific reasons for the excellent state of preservation of these objects. There are several possible reasons for their preservation including (1) the natural environment and climate in which the woodblocks are stored; (2) the remote location and protection during wartime; (3) the dedication of many concerned people, especially the Buddhist monks to whom their care was entrusted; (4) the unique design and preparation of the woodblocks, in particular the Japanese lacquer coatings that are present; and (5) the anti-microbial properties of copper and its compounds. Studies of the surface coatings of these artifacts were presented at the ACS National Meeting in 1996 (4), and further reports on that work were featured in C&E News later that same year (5). We will further elaborate on the anti-microbial properties of copper later in this paper.

Figure 1. (a) Two storage houses for the woodblocks are shown in parallel; (b) The wood blocks stored on shelves in sequence. 278 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Structure of the Canon Woodblocks and the Printing Method Used


The woodblock is composed of three parts (6, 7): two side handles (end pieces) and a main block, as shown in Figure 2. The end pieces are connected to the main block using wooden pegs (holes in Figure 2a), and the four corners are connected using metal plate connectors to reinforce the connections.. The woodblocks are found in two widths, 68 cm and 78 cm. Each is 24 cm high and on average 3 cm thick in the main body. The area on which the carved Buddhist Canon is located is 51 cm x 23 cm.

Figure 2. The shape and dimension of a typical Buddhist Cannon printing woodblock.

The method by which the printing blocks were used took four steps. First, the woodblock was placed on the printing table, as shown in Figure 3, and a watersoluble black ink was coated onto the surface of the block. Second, a sheet of rice paper was carefully placed evenly on top of the inked block. Third, the surface of the paper was then gently pressed to transfer the ink to the paper, and finally the paper was removed to yield the final printed page. 279 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 3. Printing woodblock sitting on a print table. Description of the Metal Plate Connectors Metal plates connect the main body and end pieces (or handles) of the woodblocks. Seven different types of these metal connectors have been observed; photos of two of these are shown in detail in Figure 4. Figure 5 shows all of the different connectors and their dimensions. White dots in Figure 5 depict iron nails. The majority of the metal plate connectors are of Types a-e. The number of Type f connectors is small. Type g connectors are made of steel and believed to be recent repairs and occur only rarely. Based on their color, Types a-f appear to be copper. Types a and b are one-piece connectors and type c is composed of two metal strips although their exterior views are very similar each other. The thickness of the connectors is approximately 1 mm. Several different types of the metal connectors indicate that these metal connectors might be fastened at different periods.

Figure 4. Two types of metal plate connectors used four corners to combine end pieces and main body. 280 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 5. Shapes and dimensions of the metal plate connectors. The dimension of the numbers is centimeter. Experimental A piece of the metal plate connector (probably Type d or Type e) was obtained from a staffer of the Conservation Division, the Haein-sa Temple. Modern copper and brass plates were employed for comparison with the woodblock plate connectors. Nails have fallen out of many of the woodblocks due to rusting. Figure 6 shows holes due to missing nails. It also shows the types of the metal plate connectors. These loose nails were collected from the floor of the storage areas using a magnet. Nails were cross-sectioned longitudinally, then cured in epoxy resin prior to polishing for scanning electron microscopy (SEM) and electron probe micro-analyzer (EPMA) analyses. Nital solution, 2% was used for 30 seconds to etch the surface of the nail for surface analysis.

Figure 6. Missing nails – Two holes are shown in the figure. 281 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

The metal plate connectors were examined by optical microscopy on a Zeiss Axioscope. Wavelength dispersive XRF analysis was done using a Rigaku model ZSX Primus II. The nails were examined by FEI Corporation SEM (Inspect F50 model) with Ametek EDAX for electron microscopy and EPMA analysis. Because EDAX with Pegasus software performs ZAF correction, it is unnecessary to calibrate the data.

Results and Discussion


Composition of the Metal Plate Connectors Anyone who is familiar with the blue-green color of an architectural copperclad dome will recognize the same color in the metal plate connectors. The front and back surfaces of the metal plate connector were examined with WDS-XRF and compared to a modern copper plate (Figure 7). Because we found from Figure 8 that XRF spectrum of the metal plate connector was different from one of known brass plate and didn’t contain zinc, we examined the metal plate connector with the known copper plate connector for later study. The elemental analyses by XRF are listed in Table I. These results show that the metal plate connector is composed of 98% copper. Because neither zinc nor tin are observed, the metal plate connector is not made of either brass or bronze. The metal plate connector contained about 1% silver, indicative that it is not of modern manufacture, as modern copper plate is usually obtained through electrorefining, where noble metals such as silver and gold are separated as anode slime (8). The modern copper standard did not show any evidence of silver. The composition of the surface of the metal plate connector was compared with the oxidation layer intact, and with it removed through polishing, as shown in Figure 9. The oxidized surface shows more silicon and aluminum, as well as several other elements. This indicates that the surface was also contaminated with dust in addition to oxidation.

Figure 7. Examined (a) metal plate connector and (b) modern copper plate. 282 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 8. Comparison of XRF spectrum of metal plate connector with brass plate.

Table I. Elemental Analyses of the metal plate connector and modern copper plate (wt%) Metal plate connector (inside)

Metal plate connector (outside)

Modern copper plate

Na

0.908

Mg

1.1

0.0151

Al

0.0135

6.1

0.0321

Si

0.0708

10.2

0.068

P

0.0223

0.601

0.0586

S

0.0214

0.935

0.0757

Cl

0.475

0.762

0.038

K

-

0.91

0.0107

Ca

-

2.017

0.009

Fe

0.0695

0.867

0.0313

Cu

97.9

74.2

99.4

Ag

0.957

0.699

-

283 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 9. Original oxidized surface and cleaned surface of metal plate connector.

The surface of the metal plate connector was compared to that of the modern copper plate by optical microscopy. Images of the surfaces are shown in Figure 10. The surface of the metal plate connector (Figure 10a) shows a typical “blistered” surface formed during production of copper directly from copper ores. The modern copper plate (Figure 10b) shows streaks formed by rolling the copper flat.

Figure 10. Comparison of the surfaces of (a) metal plate connector and (b) modern copper plate, observed by optical microscope (x50).

Copper is produced by the following method. Copper ore, usually chalcopyrite (CuFeS2) was heated with silica to remove iron as a slag (Equation 1). The resulting copper matte consisting of Cu2S was then roasted to convert it to copper oxide. Copper oxide is converted to “blister” copper due to the gases evolved during cooling, as shown in Equations 2 and 3. 284 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Effects of Copper Metal Plates The structural role of the metal plate connectors was to connect the main woodblock body to the end pieces and fix them firmly in place. We assume that the metal plate connectors also had a protective role, inhibiting the growth of fungi. Copper and copper compounds are known to have anti-microbial properties (9–11). Because the metal plates are made of nearly pure copper, we believe that this, in combination with the Japanese lacquer coating, has helped to preserve the Koryo Buddhist Cannon Woodblocks from decomposition.

Special Patterns on the Surfaces of the Metal Plate Connectors A few metal plate connectors have been observed with arabesque patterns depicting lotuses (Figure 11). These patterns appear to have been inscribed manually, as the patterns differ slightly from each other. The metal plate connectors with lotus patterns are rare amongst the collection of woodblocks. We do not yet know why these patterned metal plate connectors are present on some of the woodblocks, but we continue searching for clues, as this may provide additional information about the history of these unique artifacts.

Figure 11. Arabesque patterns of lotus on the some metal connectors are shown.


Composition of the Iron Nails


Iron nails were used to firmly fix the main body of the woodblocks to the end pieces. The nails examined in this study are shown in Figure 12; on average, the nails are approximately 3 cm long. The shapes observed with the naked eye exhibit the typical pattern of nails hand-wrought by hammering. The nails were examined further by SEM-EPMA.

Figure 12. Iron nails used for the woodblocks.

In ancient times, nails were produced form iron ores by the following general process. Iron is produced by reducing iron ore with either charcoal or coal directly, as shown in Equation 4. Because the temperature reached only below 1,000 °C in this process, sponge iron is produced. Sponge iron must then be heated and hammered manually to form the nails. Slag present in the sponge is squeezed out of the porous iron, and in the process of hammering, the iron becomes more dense (12, 13).

We examined the compositions and structures of the cross-sections and longitudinal-sections of the nails by SEM-EPMA. Nails were cut and the surfaces were polished, as shown in Figure 13. Figure 14 shows the SEM image of the cross-section of nail a from Figure 13. The composition of the flat surface away from the crack (shown in Figure 14a) was approximately 1% carbon and 99% iron, indicative of steel. The roughly “S” shaped crack in Figure 14a indicates that two pieces of metal were folded together in the manufacture of the nail, a sign of forging. These hand-forging (-wrought) iron nails are different from cut nails and modern wire nails (14, 15). The other areas shown in Figure 14b-d were the subject of further SEM-EPMA analysis. 286 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 13. Nails were cut cross section and longitudinal direction.

Figure 14. (a) Cross section of nail a in Figure 13; (b) enlarged area 1; (c) enlarged area 2; (d) enlarged area 3. 287 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 15. Cross-section of the nail in Figure 14 after acid etching. (a) and (b) show two pieces were folded clearly; (c) grains and their boundaries are observed.

Figure 15 shows the cross-section of the nail in Figure 14 after acid etching using 2% nital. Figures 15a and 15b shows the cross-section of the nail is separated by two and shows that two pieces were folded and forged to form the nail. Figure 15c show the grain boundaries of ferrite, pure iron. Table II shows the elemental compositions observed for the nail cross-section shown in Figure 14. The crack area (denoted a-c in Table II) contains a high percentage of oxygen, indicative of the presence of oxides in that region. Of note is the large percentage of carbon observed at spot c, which is indicative of the presence of unreduced iron ore, carbon, and slag in that area. In the bulk area, spot d, no oxygen was detected, consistent with the composition of steel. The composition near the surface of the nail shows extensive oxidation, to a depth of 150 micrometers. Figure 16 shows photomicrographs of the longitudinal sections of a nail. An area near the top of the nail, containing both a crack similar to the one described previously, was enlarged (Figure 16c) and examined with EPMA. The elemental composition of the crack and the bulk of the nail are shown in Table III. The crack in the nail again contains slag, iron silicates, and the bulk composition is again consistent with that of steel. The composition of iron and oxygen elements and the round shapes of area a in Figure 16c indicate the formation of wustite, FeO in the region. 288 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Table II. Elemental analysis of the crack area in Figure 14 Wt% (a)

(b)

(c)

(d)

(e)

C

3.54

18.51

58.12

2.51

2.26

O

26.03

50.67

19.50

-

21.77

Fe

58.49

0.29

14.78

90.15

68.54

Na

3.96

0.29

-

-

-


4 Element

Figure 16. SEM of Longitudinal section of nail and its crack area. 289 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Table III. Elemental analysis of the crack area 2 of Figure 16b


Wt% Element

Area (a)

Area (b)

C

8.45

16.54

O

20.80

25.82

Fe

63.63

36.19

Al

0.47

3.24

Si

-

11.83

P

-

3.78

K

-

1.67

Ca

-

0.93

Conclusions We confirmed that the metal plate connectors of the Koryo Buddhist canon woodblocks were made from pure copper plate. We believe that the copper plate connectors have played a role in preservation of the woodblocks, acting as an anti-microbial agent in combination with the Japanese lacquer coating. The composition and structure of the iron nails show that they were formed through the hand-forging of sponge iron.

Acknowledgments We acknowledge the assistance from the Haein-sa Temple. We thank Dr. J. Doh and Mr. K. D. Choi of KIST for etching experiment, SEM and discussion and Prof. D. N. Lee of SNU for discussion.

References 1. 2.

3. 4. 5. 6.

Haeinsa Temple Janggyeong Panjeon, the Depositories for the Tripitaka Koreana Woodblocks. http://whc.unesco.org/en/list/737. Printing Woodblocks of the Tripitaka Koreana and Miscellaneous Buddhist Scriptures. Memory of the World. http://www.unesco.org/new/en/ communication-and-information/flagship-project-activities/memory-of-theworld/register/full-list-of-registered-heritage/registered-heritage-page-7/ printing-woodblocks-of-the-tripitaka-koreana-and-miscellaneous-buddhistscriptures/. Do, C. H.; Yi, T. –Y.; Pyun, C.-H.; Seo, J. M.; Kim, H. Lee, D. N.; Chang, S. K. Programme and Abstracts, 41st IUPAC Congress, 2007; p 62. Lee, T. Y.; Do, C. H. Polym. Prepr. 1996, 37 (2), 182. Stinson, S. C. Chem. Eng. News 1996, September 9, 34–36. Do, C. H.; Lee, T. Y. J. Conserv. Sci. 1999, 8, 33–39. 290 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

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Metal Plate Connectors and Iron Nails on the Tripitaka Koreana

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