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                    <text>Study on Corrosion Factors of Iron Artifacts Recovered from the Middle West Sea
Kim Taek-joon¹, Yoo Dae-young² and Lee Hyeon-ji²
¹Curator, Natural Research Institute of Maritime Cultural Heritage
²Reseacher, National Research Institute of Maritime Cultural Heritage
ABSTRACT
This study investigates corrosion process through analysis of corrosion products and desalination solution as a
precedent study to present proper conservation treatment methods for iron artifacts collected from the middle
West Sea. Depending on the environment where the iron artifacts were buried underwater, the corrosion patterns
may be different. In order to treat the heritage stably and effectively for conservation, the major corrosion factors
and information to remove or control the factors should be obtained. The underwater environment is rich in
water, oxygen and salt, and it is very easy for iron artifacts to be corroded. In an environment where oxygen
supply is little like seabed mud, anaerobic corrosion may occur. The iron artifacts in the seabed may be deeply
buried in the mud or exposed on the surface of the seabed. This study intends to obtain information on the
corrosion pattern of iron artifacts collected from the seabed surface of middle West Sea. In addition to those
deeply buried in dense silt, there are also cases of recovering those exposed on the seabed or shallowly buried in
the surface layer. In this study, we obtained information on the corrosion patterns of iron artifacts recovered from
the seabed layer in the central West Sea.The samples used in the study were corrosion products from iron
artifacts excavated from waters of Mado, Taean and of Seomeopbeol, Ongjin and desalination solution and the
major components of corrosion products and anions of desalination solution were analyzed using Scanning
Electron Microscope-Energy Dispersive Spectroscope (SEM-EDS) and X-ray Diffraction (XRD), Ion
Chromatography (IC). The analysis result shows that major components including P, S and Mackiwanite (FeS)
were identified as compounds related to it. In the desalination solution, high concentration of Cl- and SO42- was
measured. It is expected that this study result can be utilized as essential data for establishing methods for
effective and systematic conservation of iron artifacts excavated from underwater and it is intended to continue
additional studies such as analysis on corrosion product of iron artifacts recovered from various waters and
corrosion reproduction experiment through collaboration with various fields.
Keywords: middle West Sea, iron artifacts, corrosion factor, corrosion product
List of Tabless
Table 1. Results of analysis on corrosion product of iron pot recovered from Mado (EDS, XRD)
Table 2. Results of analysis of corrosion product of iron pot recovered from Seomeopbeol sea area (EDS, XRD)
Table 3. Results of analyzing desalination solution of iron pot excavated from Mado (IC)
Table 4. Results of analyzing desalination solution of iron pot excavated from Seomeopbeol (IC)

INTRODUCTION
Middle West Sea is a place where underwater cultural heritage is buried. Along the Taean coast
Goryeo celadon was net-caught while fishing octopus by Ongjingun Seomeopbeol, Ansansi Daebudo
and Hwaseongsi Jebudo in Korea. In particular, five shipwrecks from Goreyo and Joseon dynasties
were discovered and surveyed in the Taean offshore of Chungcheongnam-do for eight years from 2007
to 2015 and historic ships from early and mid-eighth century was discovered in the waters of
Seomeopbeol in Incheon in 2013. Iron pots, which were used as kitchenware by crew or carried as
cargo, were lifted.
Underwater environment is rich in water, oxygen and salt where iron artifacts are easily corroded. In
addition, in an environment where oxygen supply is low like in the mud, anaerobic corrosion may
occur by sulfate reducing bacteria. Therefore, the corrosion patterns of iron artifacts may be different
in the underwater environment depending on each condition or various factors. In order to conserve
damaged iron artifacts effectively and stably, information on how to remove or control major factors
that influence corrosion should be obtained.

1

�CORROSION OF IRON ARTIFACTS IN UNDERWATER ENVIRONMENT
Cl- and SO42- are dissolved in seawater at about 19 gr and 2.6 gr per 1 L (1 gr = 0.0684 g), and their
high electrical conductivity promotes corrosion of iron artifacts (Baek Young-Nam and Yeo
Woon-Hwan 1980, 673). Deposits formed on the surface of iron artifacts are removed by the high flow
rate of the environment, and corrosion can be accelerated (Japanese Standards Association 1984, 33).
Due to these various factors, iron artifacts are actively corroded in the seabed environment, concretion,
a very hard foreign substance is formed on the surface. According to previous studies, the main
component of concretion is CaCO3, and iron artifacts are corroded and it is the clump of organisms
and shells and surrounding mud. Concretion is densely formed and corrods independently from the
external environment and the process is as follows (North and MacLeod 1987, 76-78):
1. Reduction reaction occurs with the formation of cathode in an isolated water in the concretion.
2. An anode is formed on the surface of iron artifacts, releasing Fe2+ and Fe3+ with oxidation
reaction, resulting in creation of acidic solution at pH 4-5.
3. Hydrolysis of Fe2+ + H2O → Fe (OH)+ + H+ by acidic solution.
4. FeCO3 is formed as part of Ca2+ in CaCO3 of concretion is interchanged with Fe2+.
5. Part of CaCO3 is dissolved by Ca (HCO3)2 that includes H+, increasing pH concentration of the
surrounding environment.
6. As the pH concentration rises, oxides, hydroxides and hydroxide chlorides such as Fe2+and
Fe3+ are gradually eluted.
7. During steps one to six, CaCO3 condensate is gradually dissolved and hard iron cementing is
formed.
In addition, anaerobic corrosion can occur in places where oxygen is scarce, such as deep in the mud
of the seabed environment. The typical example of anaerobic corrosion of iron artifacts is corrosion by
sulfide reduced by sulfate reducing bacteria (4Fe + SO42-+ H+→ 3Fe2++FeS + H2O). The resulting
corrosion forms black iron sulfide, which is oxidized in red when exposed to the atmosphere (Fujii
2009, 50-51).
METHODOLOGY
In this study, desalination solution (Sodium Sesquicarbonate 0.1M aqueous solution) used during the
conservation treatment of iron pots collected from Mado, Taean, Chungcheongnamdo and waters of
Seomeopbeol, Ongjin, Incheon and corrosion products removed from the surface, were used as
samples. The iron pots from the Mado were discovered through visual exploration of the sea bottom
and part of the surface layer of the sea bottom by divers during wide-area exploration in 2011
(NRIMCH 2017, 27). Iron pots collected from Seomeopbeol were recovered from the sand and shell
layer identified during the southeast Shingoji probe survey in the first underwater excavation survey in
2012 (NRIMCH 2014, 33-34).
The components of corrosion product samples were analyzed using Scanning Electron
Microscope-Energy Dispersive Spectroscope (SEM-EDS) and the external characteristics of the point
where certain components (P, S) were detected were observed. Then they were powdered and the
compound was identified through X-ray Diffraction (XRD) analysis. Concentration of desalination
solution was measured using Ion Chromatography (IC) to measure concentration of anions (F-, Cl-,
SO42, NO3-, PO43-) to identify the relationship between SEM-EDS and XRD analysis result.
The number of corrosion product analysis samples was 16 in total (eight from Mado and the others
from Seomeopbeo) and the points (55 points in Mado and 41 points in Seomeopbeol, 96 points in
total) subjected to SEM-EDS analysis were selected with 40x magnification of stereoscopic
microscope images were recorded using digital recording device attached. Conditions of SEM-EDS
analysis include voltage of 15-20 kV, WD 10 mm, spot size 25, measurement time of 60 seconds and
magnification up to 9,000 times. Conditions of XRD analysis for 16 powdered samples after

2

�SEM-EDS and one additional sample (corrosion product of iron pot from Mado shipwreck no. 4) were
voltage of 40 kV, current of 30 mA, and target Cu.
For desalination solution analysis, 16 samples (eight from Mado, the others from Seomeopbeol) were
prepared and anion concentration was measured using IC. As Cl- concentration of the desalination
solution sample was expected to be very high, it was diluted with ultrapure water 100 times and
cellulose filter was used to remove impurities in the sample and then anion analysis was conducted.
STUDY RESULTS
Analysis of corrosion product
When sulfate reducing bacteria is involved in the corrosion process, the high content of phosphorus
and sulfur may be detected in the corrosion products (Lee Yong-deuk et al. 1996, 256), SEM-EDS
analysis was conducted to check whether these two components are detected and their content. The
results of analyzing corrosion products showed that sulfur was detected in 15 samples except for one
sample from Mado (MD6). The maximum sulfur level was 63.61 wt per cent (MD8) in samples from
Mado and 25.13 wt per cent (SE7) in samples from Seomeopbeol sea area and other samples contained
0.64~23.02 wt per cent. Among them MD8 is characterized by maximum sulfur content of 11.51 wt
per cent and phosphorus content of 12.17 wt per cent. This result can be interpreted that sulfate
reducing bacteria influenced the corrosion process of iron pots collected from Mado and
Seomeopbeol. However, these compounds were identified with the identification of mackinawite (FeS)
in MD1 and other samples identified iron oxides such as siderite (FeCO3) or goethite (FeOOH) formed
by the influence of concretion.
Table 1. Results of analysis on corrosion product of iron pot recovered from Mado (EDS, XRD)

Sample

Maximum content of major ingredient
(wt per cent)

Compound Name
(Chemical Formula)

P

S

Ca

MD1

-

11.85

10.12

Magnetite (Fe3O4) calcite (CaCO3) mackinawite (FeS)

MD.2

-

1.40

0.51

Magnetite (Fe3O4) siderite (FeCO3)

MD3

-

2.53

-

Siderite (FeCO3)

MD4

-

6.65

-

Siderite (FeCO3)

MD5

-

1.54

-

Magnetite (Fe3O4) quartz (SiO2)

MD6

-

-

-

Magnetite (Fe3O4) siderite (FeCO3)

MD7

-

63.61

-

Siderite (FeCO3)

MD8

12.17

11.51

-

Magnetite (Fe3O4)

Table 2. Results of analysis of corrosion product of iron pot recovered from water Seomeopbeol sea area (EDS, XRD)

Sample

Maximum content of major ingredient
(wt per cent)

Compound Name
(Chemical Formula)

P

S

Ca

SE1

-

0.64

1.36

Siderite (FeCO3) magnetite (Fe3O4) goethite (FeOOH)

SE2

0.27

1.11

3.63

Siderite (FeCO3)

SE3

-

2.96

0.48

Siderite (FeCO3) magnetite (Fe3O4)

SE4

-

0.87

1.51

Siderite (FeCO3) goethite (FeOOH)

SE5

-

8.48

4.09

Magnetite (Fe3O4) goethite (FeOOH)

SE6

0.17

4.04

-

Goethite (FeOOH)

SE7

-

25.13

37.80

Siderite (FeCO3) magnetite (Fe3O4)

SE8

-

23.02

31.61

Siderite (FeCO3) magnetite (Fe3O4) goethite (FeOOH)

3

�Iron sulfide such as Mackinawite or pyrite (FeS2) are formed together with oxides such as FeOOH,
serving as the evidence to show corrosion by sulfate reducing bacteria (Lee Jae-ik and Seo Myeong-po
1992, 63), but this study did not obtain results with unique characteristics. However, according to
previous studies, iron sulfide in a honeycomb structure, which is easily oxidized to calcium sulfate in
the form of iron crystals, was observed in European old ships using iron nails (Kim Yong-han 1987,
151-152), SEM observation confirmed similar type of corrosion products in SE5 and SE7. In addition,
samples from Seomeopbeol contain large amounts of Calcium and SE7 and SE8 showed high
concentration of sulfur so it is considered to be the result of oxidation of iron sulfide. However, in the
XRD analysis, the identification of relevant compounds (CaSO4, etc.) was not done and SEM
observation did not confirm unique characteristics, requiring further research on this matter.
Analysis of desalination solution
Sixteen samples were collected from desalination solution from six pots, three from each area
including MT64 and SE405 where corrosion product analysis sample was collected (red square in
Table 3 and 4) to conduct anion analysis. The analysis results showed that Table 3 and 4 Cl- and SO42concentration was higher overwhelmingly than other anions and EDS ingredient analysis showed 20
ppm or higher PO43- in the MT64 sample where phosphorus was detected. PO43- was measured in the
sample from primary desalination solution of YDS1 and YDS on December 4, 2013 once respectively
but it was not identified in samples after that.
Table 3. Results of analyzing desalination solution of iron pot excavated from Mado (IC)

Sample (date)
M3S262 (‘12.3.15)
M3S262 (‘12.5.24)
M3S262 (‘12.6.28)
MS76 (’12.4.25)
MS76 (’12.6.7)
MS76 (‘12.7.12)
MT64 (’12.3.22)
MT64 (’12.5.16)

Anion concentration (ppm)
FClSO420.18
60.74
241.41
0.16
48.11
104.80
0.14
30.24
72.29
0.20
14.54
41.83
0.37
13.96
40.22

NO33.49
-

PO43-

0.28

14.33

29.56

-

-

0.28
0.25

223.83
109.66

271.22
194.79

-

25.44
22.64

Table 4. Results of analyzing desalination solution of iron pot excavated from Seomeopbeol (IC)

Anion concentration (ppm)
FCl-

SO42-

NO3-

PO43-

SE403 (‘14.1.7)

0.12

41.05

100.64

-

-

SE403 (‘14.3.5)
SE403 (‘14.5.13)
YDS1 (‘13.12.4)
YDS1 (‘14.8.5)
YDS1 (‘15.4.7)
YDS4 (‘13.12.4)
YDS4 (‘14.4.17)

0.27
0.07
0.77
0.01
0.01
0.46
0.05

13.62
10.79
1530.31
172.80
110.51
439.99
55.61

17.19
7.66
84.31
27.17
54.32
48.19
10.04

6.00
3.97
7.19

16.27
15.68
-

Sample (date)

As presented in Table 3 and 4, SO42- was clearly detected in the desalination solution from the two
sites. Generally, Cl- dissolution is the focus in the process of stabilization considering the impact of sea
water containing large amounts of salt for iron artifacts excavated from underwater but as shown in the
result, whether SO42- remains or not should be checked mandatorily.

4

�CONCLUSIONS
This study was conducted to obtain information on effective methods of conservation treatment by
analyzing corrosion products of iron artifacts collected from the Middle West Sea and desalination
solution. The iron artifacts recovered from waters included artifacts lifted by removing strong and
dense mud layers and artifacts buried near the surface layer or exposed on the seabed surface. In order
to find out the pattern of corrosion of iron artifacts, wide area exploration of waters of Mado, Taean
and excavation survey in waters of Seomeopbeol, Ongjin were conducted and the corrosion product of
iron pots lifted and desalination solution were used as samples for research. In the iron corrosion
process, when sulfate reducing bacteria is involved, significant amounts of sulfur and phosphorus can
be detected. Therefore, in this study, SEM-EDS analysis was conducted for the components of iron pot
corrosion products from Mado and Seomupbeol.
Previous studies on iron test piece corrosion by seawater, mud (collected from Mado) and Na2S water
solution, ingredients such as Sulfur or Phosphorus were not detected at all (Kim Taek-joon 2013,
47-50).
In our SEM-EDS analysis on corrosion products, a large amount of sulfur was detected in most
samples and one sample from Mado contained 12.17 wt per cent of phosphorus. Sulfate reducing
bacteria is confirmed in the process of iron pot from Mado and Seomupbeol. However, in the XRD
analysis, there were no clear results except for the identification of mackinawite (FeS) in one sample.
In the anion analysis of desalination solution, highly concentrated Cl- and SO42- were measured and it is
considered to be related to the identification of sulfur as the main ingredient of corrosion products.
Sulfur and SO42- were major factors that influence the corrosion of iron artifacts collected from the
Middle West Sea. However, it was not possible to obtain specific information on how these factors are
involved in corrosion of iron artifacts. Follow-up research will involve sulfate reducing bacteria and
further analysis of corrosion products of iron artifacts collected from various sea areas.
Acknowledgements
I would like to thank people from the Conservation Science Lab of NRIMCH for helping with the analysis of samples.
Bibliography
Fujii, Tetsuo. Countermeasures against Corrosion of Metal Materials. Tokyo: Nikkan Industrial Newspaper, 2009 (In
Japanese).
Kim, Taek-joon. “Study of Corrosion Characteristics of Iron Objects Excavated from Taean Mado Waters.” Master’s thesis,
Hanseo University, 2013 (In Korean).
Kim, Yonghan, “Conservation and Restoration of the Shipwreck.” Conservation Studies 8 (1987): 123-148 (In Korean).
Lee, Jae-ik. and Seo, Myeongpo. “Corrosion of metals by microorganisms.” Journal of Corrosion Science 21, no. 1 (1992):
50-66 (In Korean).
Lee, Yong-deuk. Ryu, Seung-ki. and Kim, Youngho. “Microbially Influenced Corrosion of Stainless Steels.” Journal of
Corrosion Science 25, no. 2 (1996): 249-259 (In Korean).
Noboru, Masko. Anticorrosion Technique Manual. Tokyo: Sanbi Printing, 1984 (In Japanese).
North, Neil A. MacLeod, Ian D. “Corrosion of Metals.” In Corrosion of Marine Archaeological Objects, edited by Colin
Pearson, 68-98. London: Butterworths, 1987.
NRIMCH. Waters off Taean-Mado Underwater Excavation, Series of Research Report of NRIMCH 62. Taean: NRIMCH,
2017 (In Korean).
NRIMCH. Incheon Ongingun Yeongheungdo Shipwreck Underwater Excavation, Series of Research Report of NRIMCH 35.
Mokpo: NRIMCH, 2014 (In Korean).
Paik, Yeongnam. and Yeo, Woonkwan. “A Study of Marine Corrosion Phenomena of Metals.” Theses Collection of Kyung
Hee University 10 (1980): 673 (In Korean).

5

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West Sea. Depending on the environment where the iron artifacts were buried underwater, the corrosion patterns&#13;
may be different. In order to treat the heritage stably and effectively for conservation, the major corrosion factors&#13;
and information to remove or control the factors should be obtained. The underwater environment is rich in&#13;
water, oxygen and salt, and it is very easy for iron artifacts to be corroded. In an environment where oxygen&#13;
supply is little like seabed mud, anaerobic corrosion may occur. The iron artifacts in the seabed may be deeply&#13;
buried in the mud or exposed on the surface of the seabed. This study intends to obtain information on the&#13;
corrosion pattern of iron artifacts collected from the seabed surface of middle West Sea. In addition to those&#13;
deeply buried in dense silt, there are also cases of recovering those exposed on the seabed or shallowly buried in&#13;
the surface layer. In this study, we obtained information on the corrosion patterns of iron artifacts recovered from&#13;
the seabed layer in the central West Sea.The samples used in the study were corrosion products from iron&#13;
artifacts excavated from waters of Mado, Taean and of Seomeopbeol, Ongjin and desalination solution and the&#13;
major components of corrosion products and anions of desalination solution were analyzed using Scanning&#13;
Electron Microscope-Energy Dispersive Spectroscope (SEM-EDS) and X-ray Diffraction (XRD), Ion&#13;
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were identified as compounds related to it. In the desalination solution, high concentration of Cl&#13;
- and SO4&#13;
2- was&#13;
measured. It is expected that this study result can be utilized as essential data for establishing methods for&#13;
effective and systematic conservation of iron artifacts excavated from underwater and it is intended to continue&#13;
additional studies such as analysis on corrosion product of iron artifacts recovered from various waters and&#13;
corrosion reproduction experiment through collaboration with various fields.&#13;
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                    <text>Development and State of Research on Conservation Treatment of Underwater Cultural
Heritage in Korea
Bo-hyun Lee (Conservation Science Research Curator, National Research Institute of
Maritime Cultural Heritage)
ABSTRACT
Conservation treatment of large waterlogged wooden historic ships improved gradually as historic ships were
excavated one after another. After 40 years, exhibition halls and conservation treatment centers have been
established and in operation in Mokpo and Taean. Taean is equipped with Asia's largest vacuum freezer and
Mokpo conservation treatment place with a long history is being transformed into a new conservation treatment
center. In addition, the National Research Institute of Maritime Cultural Heritage, which has Korea's only
underwater cultural heritage conservation and treatment facility, has been publishing treatment reports and
guidelines for many years. However, as the acidic aging was discovered on the Sinan shipwreck like the Vasa
and Mary Rose, it has become an issue and various studies were conducted to identify the cause and treatment
method accordingly. It is unreasonable to apply the results of test pieces in the laboratory directly to the entire
Sinan shipwreck, which was restored and displayed at the exhibition hall. Therefore, it is planned to conduct a
partial test gradually to find a method that can handle exhibition and treatment at the same time.
Keywords: underwater cultural heritage, conservation treatment, research status, challenges
List of Tables
Table 1. State of conservation treatment of historic ships recovered from underwater (as of May 2023)
Table 2. List of publications on conservation of underwater cultural heritage

INTRODUCTION
This study deals with overall matters related to the conservation treatment of underwater cultural
heritage (UCH) in Korea which started in 1976.
The research was partially addressed in Conservation Treatment of Historic Ships Collected from the
Sea published by the National Research Institute of Maritime Cultural Heritage (NRIMCH) in 2021.
This study intends to deal with the current state of research on conservation science of UCH in Korea
in detail from more various perspectives. In addition, this study intends to highlight the current
research projects and future tasks.
We will examine the process of development before touching upon the current state of conservation
science of UCH in Korea.
DEVELOPMENT OF CONSERVATION TREATMENT OF UNDERWATER CULTURAL
HERITAGE IN KOREA
Conservation treatment of UCH in Korea began with the excavation of the Sinan shipwreck in 1976.
However, excavation of the Sinan shipwreck which started in the sea, a special environment, presented
many challenges from the beginning. There was no infrastructure to speak of such as professionals,
budget and treatment facility and there was a big problem of how to treat super-large wooden historic
ships. At that time conservation treatment technology of Japan was more advanced than that of Korea
but the conservation treatment technology for wooden historic ships in East Asia was not comparable
to that of Europe. Accordingly, Korea started direct exchanges with museums in many parts of Europe
including Switzerland, Germany, Denmark, Sweden and the UK in order to learn Europe’s historic
ship conservation treatment method and restoration technology in 1983. Korea dispatched domestic
experts to international courses for wooden cultural heritage conservation sponsored by UNESCO and
ICCROM and started forming academic exchanges. Thanks to this, the current state of wooden

1

�historic ships in Europe and various treatment methods became widely known in Korea. In the 1990s,
the waterlogged wooden conservation treatment area took its root firmly in Korea’s cultural heritage
conservation science.
In addition, PEG-2 step treatment method was applied to the Sinan shipwreck through joint basic
experiment and research conducted together with the German Maritime Museum. PEG-2 step is a
method of impregnating a low-molecular PEG400 solution at a low concentration, and then heating the
high-molecular solid PEG4000 at 40-45 °C and impregnating it to a high concentration (Kim Ik-joo
2004, 68-69). This method still works for submerged shipwrecks.
Table 1. State of conservation treatment of historic ships recovered from underwater (as of May 2023)
No.

Name

Size (length x
width (m)) /
No. of pieces

Treatment
method

Date of treatment
period

Treatment
status

Location

1

Sinan shipwreck

34 x 11 /
1, 729 pieces

1981-2004

Exhibition

Mokpo
Museum

2

Wando shipwreck

9 x 3.5 /
1, 81 pieces

1984-1998

Exhibition

Mokpo
Museum

3

Dalido shipwreck

10.5 x 2.7 /
1, 33 pieces

Jul. 1995- Dec. 2009

Exhibition

Mokpo
Museum

4

Sipyidongpado
shipwreck

7 x 2.5 /
1, 14 pieces

2004-2016

Exhibition

Mokpo
Museum

5

Jindo shipwreck

16.8 x 2.3 /
1, 2 pieces

Jun. 1992-present

Dried

Mokpo
Conservation
Center

6

Anjwado
shipwreck

14.7 x 4.5 /
1, 39 pieces

Aug. 2005-present

Dried

Mokpo
Conservation
Center

7

Daebudo
shipwreck

6.6 x 1.4 /
1, 7 pieces

Dec. 2006-present

Dried

Mokpo
Conservation
Center

8

Taean shipwreck

8.2 x 1.5 /
1, 7 pieces

May 2008-present

Reinforced
(70%)

Taean
Conservation
Center

9

Mado
no. 1

shipwreck

10.8 x 3.7 /
1, 40 pieces

Oct. 2009-present

Reinforced
(70%)

Taean
Conservation
Center

10

Mado
no. 2

shipwreck

12.8 x 5 /
1, 41 pieces

-

Oct. 2010-present

Desalinated

Taean
Conservation
Center

11

Mado
no. 3

shipwreck

12 x 8 /
1, 21 pieces

-

-

Conserved
on site

-

12

Yeongheungdo
shipwreck

6 x 1.5 /
1, 3 pieces

-

Jul. 2013-present

Desalinated

Mokpo
Conservation
Center

13

Mado
no. 4

12 x 5 /
1, 22 pieces

-

-

Conserved
on site

-

14

Daebudo
shipwreck no. 2

9.2 x 2.9 /
1, 50 pieces

-

Jul. 2015-present

Desalinated

Mokpo
Conservation
Center

15

Jebudo shipwreck
no. 1

9.2 x 2.9

-

-

Conserved
on site

-

16

Jebudo shipwreck
no. 2

9.2 x 2.9

-

-

Conserved
on site

-

shipwreck

PEG
2-Step
method
(400/4000)

2

�The Sinan shipwreck was unveiled in 2004 after 18 years of conservation treatment and 10 years of
hull restoration.
After excavation of Sinan shipwreck, historic ships were discovered one after another in the West Sea
of Korea, including Wando shipwreck (1984), Jindo Pyokpari Tongnamu Pae (1992), Dalido
shipwreck (1995), Sipyidongpado shipwreck (2004), Anjwado shipwreck (2005), Daebudo shipwreck
(2006), Taean shipwreck (2008), Mado shipwreck no. 1 (2009), Mado shipwreck no. 2 (2010), Mado
shipwreck no. 3 (2011), Yeongheungdo shipwreck (2013), Mado shipwreck no. 4 (2014), Daebudo
shipwreck no. 2 (2015), Jebudo shipwreck no. 1 (2016) and Jebudo shipwreck no. 2 (2016). Table 1
summarizes where these ships have been treated for conservation or in the process of conservation
treatment, while some are conserved on site.
As historic ships have been excavated continuously, Korea’s underwater archeology and conservation
treatment technology of historic ships have grown remarkably. The conservation treatment
infrastructure, organization and budget have become one of the top in Asia.
The NRIMCH, which started in Mokpo Conservation Center in 1982, is now operating museums in
Mokpo (Jeollanam-do) and Taean (Chungcheongnam-do) respectively and has its own conservation
treatment facility. Mokpo conservation center, which started with two employees about 42 years ago,
has now ten employees in Mokpo and five in Taean. Taean conservation center has installed and run
test operation of Asia's largest vacuum freezer.
CURRENT STATE OF CONSERVATION SCIENCE FOR UCH IN KOREA
Cultural heritage excavated from water is very diverse in materials such as metal, ceramics, wood, and
stone. Various kinds of artifacts are excavated from ships as ships are a carrier of transport goods,
which contains living space on the ship. Therefore, conservation methods should be applied differently
depending on materials.
Korea has already prepared guidelines on conservation treatment by material with dividing artifacts
into those excavated from land and those from underwater and has treated them by referring to these
guidelines.
Recovered Artifacts so far are mainly made of wood (hull components, etc.) and ceramics (transport
goods), so the proportion of conservation treatment for historic ships and ceramics is high.
Out of 50,762 artifacts excavated, 47,036 pieces are ceramics, accounting for more than 93 per cent. In
addition, all five pieces which are nationally designated cultural property and in possession are
ceramics.
Natural scientific analysis of ceramics excavated from the sea began in earnest in the early 2000s.
Depending on the excavation site and function, various analyzes have been conducted, such as the
base soil, firing temperature, minor components, and estimation of the production site. Starting from
this year, research is being conducted to scientifically reveal the relationship between the production
and the consumption areas, and the correlation between the times and materials based on the existing
research results.

3

�Table 2. List of publications on conservation of UCH
Major content

No
.

Title

Date

1

Guideline on
Conservation
Treatment of
Artifacts
Excavated from
Underwater

2013

A guideline on conservation treatment of
artifacts excavated from underwater including
treatment cases.

2

Conservation
Manual of
Maritime
Archaeological
Objects in Korea

2014

English version of the guideline on conservation
treatment of artifacts excavated from
underwater, introducing how to treat wooden
artifacts, ceramics and metal artifacts.

3

Conservation
Treatment of
Ceramics
Excavated from
Underwater

2020

Classifying pottery which was excavated the
largest in volume into pottery, celadon and white
porcelain and reporting treatment methods and
cases.

4

Conservation
Treatment of
historic Ships
Excavated from
Underwater

2021

Containing the process of conservation
treatment for Sinan shipwreck, Wando
shipwreck, Jindo shipwreck, Dalido shipwreck
and Sipyidongpado shipwreck and natural
scientific analysis details.

5 Comprehensive
Report on Sinan
Ship
Conservation
Project

2022

Summarizing the research on analysis on aging
of Sinan shipwreck and conservation treatment
method comprehensively.

Cover

ISSUES REGARDING CONSERVATION SCIENCE OF UCH IN KOREA
Korea's historic ship conservation treatment can be divided into two fields. First, conservation
treatment of waterlogged wood using PEG and infrastructure. Second, neutralization treatment of
acidic aging that occurs in historic ships treated with PEG.
First, the conservation of waterlogged wood with PEG is to treat the wood using PEG-2 step method
as mentioned earlier. Reinforcement treatment is done with PEG 400-PEG 4000 and not vacuum
lyophilization but control drying is done for conservation. Taean conservation treatment room is
equipped with the latest vacuum lyophilizer that can treat 10 m. The Mokpo Conservation Center
needs facility replacement as it was established in 1981.
Conservation treatment of waterlogged wood using PEG and infrastructure
The hull varies in length from about 2 m to 10 m for each member and a specially designed tank is
required for reinforcement treatment. The tank should be made of stainless steel with strong corrosion
resistance, and a heat source (boiler hot water and electric coil) and temperature sensor should be
attached to maintain a constant temperature. In addition, in order to mix the high molecular weight

4

�PEG well, a solution circulation pump facility that can exchange the upper and lower solutions is
required. Moreover, boiler, expansion tank, and hot water pipe facilities should be in place in the boiler
room upon heating treatment using boiler hot water.
Assuming that the hull members are 5-6 m long, 0.1 m thick, and 0.5 m wide, the weight usually
reaches 300 kg. Hoists, cranes, and lifts that can lift and move these members safely and easily are
essential. Therefore, in order to conserve and treat large-sized timbers such as hulls, a large-scale
processing facility should be established.
The NRIMCH started seismic construction of PEG reinforcement treatment in 2022, and planned PEG
reinforcement treatment internal construction (water drainage, piping, electricity, etc.) and tank (10 m
x 1 m x 1 m * 1 unit, 6 m x 1 m x 1 m * 6 units), desalination treatment room improvement in 2025
and drying treatment room improvement in 2026.
Acidic aging of historic ships treated with PEG
Acidic aging is caused by the presence of iron compounds in wood and prolonged exposure, and the
same phenomenon has already appeared in foreign ships such as Vasa, Mary Rose, and Batavia, and
efforts have been made to solve this problem.
The Sinan shipwreck experienced acidic aging since 2010 and various methods were tried inside and
outside the laboratory to solve the problem. Constant temperature and humidity monitoring has been
conducted to secure raw data and the aging condition of the hull has been recorded with 3D scanning
using 3D digital methods. After that, surface contaminants were removed through dry cleaning, and a
deterioration map was also prepared to compare changes in surface conditions. Integrated Pest
Management is being implemented to prevent harmful organisms in exhibition halls and storage areas
and to establish a stable conservation environment. Various acidic aging treatment experiments were
conducted in the laboratory and the Comprehensive Report on Sinan Ship Conservation Project that
contains the results of experiments was recently released. This experiment is the result of the
experiment on a test piece carried out in the laboratory, but it is difficult to practically apply chemical
treatment to the 924 m2 exhibition room. Therefore, the Heritage Science Team of the NRIMCH plans
to expand the treatment area in the future, starting with a direct spot test on the Sinan shipwreck,
which was exhibited from this year. Our future task will be how to open the exhibition site to the
audience safely as the conservation treatment is underway in the exhibition hall.

Acknowledgements
I would like to thank organizers and committee members for making a decision for Korea to host APConf 2023. I would also
like to express my gratitude to my seniors and colleagues who have worked hard for conservation science at the NRIMCH.
Bibliography
Kim, Ik-Joo. “Conservation of Waterlogged Ancient Ship in Korea.” The Conservation and Restoration of Shinan Ship, the
20 Years History (2004): 58-71 (In Korean).
NRIMCH. Conservation Manual of Maritime Archaeological Objects in Korea, Series of Research Report of NRIMCH 31.
Mokpo: NRIMCH, 2013 (In Korean).
NRIMCH. The Conservation of Ceramics Excavated from Underwater, Series of Research Report of NRIMCH 61. Mokpo:
NRIMCH, 2020 (In Korean).
NRIMCH. The Conservation of Shipwrecks Excavated from Underwater, Series of Research Report of NRIMCH 63. Mokpo:
NRIMCH, 2021 (In Korean).
NRIMCH. The Comprehensive Report on Conservation Project of Sinan Shipwreck, Series of Research Report of NRIMCH
74. Mokpo: NRIMCH, 2022 (In Korean).

5

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                    <text>Antimicrobial hydrogel patches for deacidification and conservation of waterlogged
archaeological wood
Xiaohang Suna, Junjie Chena, Xuanwei Zhangb, Qiang Chena*
a

School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai Campus,
Zhuhai, Guangdong Province, China 519082
b

Marinetime Silk Road Museum of Guangdong, HVFF+3H3, Jiangcheng District, Yangjiang,
Guangdong Province, China, 529536
*E-mail: chenqiang3@mail.sysu.edu.cn

ABSTRACT
The Nanhai No. 1 hull, a Chinese merchant ship sank during the Southern Song dynasty and excavated from the
South China Sea, is an example of underwater cultural heritage waterlogged wood that has been preserved in
situ for centuries. Although the overall structure of the wooden artifacts is still intact they are severely degraded
and acidified. It is now urgent to explore effective approaches for its conservation, we explore the feasibility of
antimicrobial hydrogel patches. Antimicrobial hydrogel patches dispersed with antibacterial and deacidification
nanoparticles simultaneously deacidify, moisturize, and reinforce both antibacterial and mechanical aspects of
waterlogged wood. In the construction of the antimicrobial hydrogel patches, the double network hydrogel was
used to prepare the hydrogel substrate with stretch and mechanical strength. We have successfully applied the
antimicrobial hydrogel patches to the waterlogged wood from Nanhai No. 1, with the support of the Maritime
Silk Road Museum of Guangdong. We demonstrate here the advantages of hydrogel patches to protect
waterlogged wood with testing in deacidification, compression and antimicrobial.
KEYWORDS: Underwater cultural heritage waterlogged wood; Antibacterial (preserve); Nanhai No. 1;
Deacidification; Antimicrobial (preventative); Mechanical support (protect against the harsh external conditions)

INTRODUCTION
In 2007, the 800-year-old Nanhai No.1 shipwreck hull was raised from the seabed and moved to the
Marine Silk Road Museum, where it was conserved (Z. Liu et al. 2018). Early studies of the wood at
the museum showed that the structural damage of the underwater cultural heritage (henceforth UCH)
waterlogged wood, composed of softwoods, was severe to not withstand long-term spray
deacidification and moisture retention (Huang et al. 2021; R. Li et al. 2022; Z. Liu et al. 2018; Yin et
al. 2019). As the archaeological excavation continues on the Nanhai No. 1, like other conservation
efforts the severe acidification and salt deposition on the surface is an important challenge for the
protection of the UCH (Amornkitbamrung et al. 2015; Babiński et al. 2017; Baglioni and Giorgi 2006;
Cavallaro et al. 2017; Chelazzi, Giorgi, and Baglioni 2006; Dong et al. 2010; Durán et al. 2016;
Eriksen, Gregory, and Matthiesen 2017; Giorgi, Chelazzi, and Baglioni 2005; Giorgi et al. 2002; L.
Liu et al. 2019; Mahltig et al. 2008; Majka, Babiński, and Olek 2017; Piotrowska and Konieczny
2015; Poggi et al. 2016; Sandström, Fors, and Persson 2003; Sandström et al. 2002; Schofield et al.
2011; Walsh-Korb 2022; Walsh-Korbs and Avérous 2019; Y. Li et al. 2022; Zelinka 2014; Zhou,
Wang, and Hu 2021). Temperature, salinity, fungi, and bacteria are the cause of the severe cell wall
decay (Capretti et al. 2008; Colombini et al. 2009; Hoffmann and Jones 1989. To neutralize the
sulfuric acid and add antimicrobial protection for UCH waterlogged wood we prepared and applied an
antimicrobial hydrogel patch. Antimicrobial hydrogel patches dispersed with antibacterial and
deacidification nanoparticles simultaneously deacidify, moisturize, and reinforce both antibacterial
and mechanical aspects of waterlogged wood (Gong 2014; Gong et al. 2003). This antimicrobial
hydrogel patch served as mechanical support, deacidification, and antibacterial functions, during
post-excavation conservation and prior to the addition of consolidates (Bai et al. 2019). We conducted
1

�a thorough literature review of shipwreck conservation of waterlogged woods; here we demonstrate in
collaboration with the Maritime Silk Road Museum of Guangdong the advantages of antimicrobial
hydrogel patches to protect waterlogged wood on the Nanhai No. 1 hull with testing in
deacidification, compression, and antimicrobial.
EXPERIMENTS
Materials
The UCH waterlogged wood from the Nanhai No. 1 shipwreck was generously provided by the
Maritime Silk Road Museum of Guangdong with a maximum moisture content of around 529%. The
UCH waterlogged wood was stored in 0.5wt% isothiazolinone solution and washed with excess
amount of water three times prior to conservation. The following chemicals were purchased:
Acrylamide (AR, 99.0%) and sodium citrate (98%) from Aladdin; Potassium persulfate (GR, 99.9%),
potassium bicarbonate (AR, 99.5%), and N,N,N',N'-Tetramethylethylenediamine (99%) from
Macklin; N,N-methylenebisacrylamide (MBAA,98%) from Maya Reagent; Silver nitrate (99%) from
Alfa Aesar; Calcium Sulfate (97%) from Rhawn; and sodium alginate (AR, 98%) from RYON. All
chemicals were used directly without additional purification.
Method
We prepared the antimicrobial hydrogel patches and performed three tests: deacidification,
compression and antimicrobial.
Preparation of antimicrobial hydrogel patches
12.44grams (g) of acrylamide and 1.56g of sodium alginate were dissolved in deionized water to form
an acrylamide solution with a water content of 60-80 per cent by weight (wt%). After degassing the
solution for one day, we added 0.0018g and 0.0036g of silver nitrate and 0.2g sodium citrate. Then we
added 0.5g potassium persulfate, 0.0074g MBAA, 0.031g tetramethylethylenediamine and potassium
bicarbonate (KHCO3) at 1.5g, 2.5g, and 3.5g. The solution was transferred to a transparent mold and
exposed to UV light (254nanometers (nm), 8 watts (W) power output) for one hour. The resulting
hydrogel was carefully removed from the molded and immersed in calcium sulfate solution for 20-40
minutes.
Deacidification test
The Nanhai No. 1 UCH waterlogged wood was wrapped for three hours with the antimicrobial
hydrogel patch (see recipe above). The pH of the UCH waterlogged wood was measured by soaking
1g in 30g of deionized water for 30 minutes and measuring the pH of the soaking water (Mettler
Toledo, FE28). The pH meter was calibrated with a standard solution before use.
Compression test
A compression test was conducted using a universal tensile tester (Haida Instrument, HD-A513). The
displacement as a function of force was measured for the synthesized hydrogels with the KHCO3
concentration at 1.5g, 2.5g, and 3.5g and compression speed of 116 millimeters per minute (mm/min).
Antimicrobial test
The antimicrobial performance of the hydrogels was measured via disk diffusion test based on Oxford
cup method. Briefly, the prepared agar medium was sterilized at 121°C for 15 minutes, and cooled to
about 55-50°C before pouring into a petri dish to form the bottom layer of agar gel. Then, E. coli
culture grown in sterilized lysogeny broth (LB) media was applied on the surface of the agar media.
2

�After one day when the E. coli culture completely covers the agar media, the prepared hydrogel was
grinded into a flowable state and added dropwise into an Oxford cup. With 37°C and one day
incubation, the antimicrobial performance was evaluated based on the zone of inhibition around the
Oxford cup.
RESULTS AND DISCUSSION
In this paper, an antimicrobial hydrogel patch used in the early stages of UCH waterlogged wood
conservation was prepared using weak alkaline compounds. Fig. 1a shows a sample of the
waterlogged wood. Water was sprayed routinely to maintain the water content of the waterlogged
wood. Waterlogged wood, on the hull of Nanhai No.1 shipwreck, in some areas show heavy
precipitation and bacterial decomposition (Fig. 1b 1c and 1d).

Figure 1 waterlogged wood (a) with precipitation cleaned; (b) on the hull of Nanhai No.1 shipwreck; (c) and (d) with
severe bacterial decomposition.

Another advantage of the hydrogel deacidification material is that it is soft and easily stretches to
change shape. The tensile and compression properties were measured. Fig. 2a and 2b are photographs
of released and stretched hydrogel, respectively. More than 1000% elongation was achieved with the
polyacrylamide/alginate hydrogel with silver nanoparticles dispersed.

3

�Figure 2 polyacrylamide/alginate hydrogel (a) at rest; (b) tensioned and elongated; (c) graph of compression with
different KHCO3 concentrations.

The hydrogels with 0.5% and 2.5% KHCO3 are close in Young’s modulus, while the hydrogel with
2.5% KHCO3 has higher Young’s modulus (Fig 2c), which might be caused by the difference in ionic
crosslinking of silver and potassium ions. The hydrogel with potassium percarbonate was used to
wrap the waterlogged wood (Fig. 3a-c). The weak alkaline KHCO3 neutralized the sulfuric acid in the
waterlogged wood, which resulted in a pH increase from 4.0 to 7.2 (Fig 3d). It was also confirmed
that above 0.5% KHCO3 concentration, the increase in KHCO3 did not contribute to the pH increase
remarkably. Gentle adhesion of the hydrogel to the wood neutralization occurs immediately, which
lead to fast and significant pH increase. We suspect this is due to the large water content of the
hydrogel, while also performing the adhesion underwater, is homogeneous.

Figure 3 antimicrobial hydrogel (a) patch (b) patch and waterlogged wood (c) wrapped around waterlogged wood;
(d) bar graph of pH test with different KHCO3 concentrations.

The results of hydrogel antibacterial experiments proved it can protect waterlogged wood from
bacterial degradation. When 30 μg/mL silver nitrate in the hydrogel was converted to silver
nanoparticles, the antimicrobial properties of the hydrogels became sufficient to prevent bacterial
degradation. Comparing Fig 4b and 4c, we see the increase of the silver nanoparticles from 30 μg/mL
4

�silver nitrate converted to silver nanoparticles to 60 μg/mL silver nitrate converted to silver
nanoparticles had less effect on the increase in antimicrobial properties.

Figure 4 antimicrobial hydrogel with silver nitrate converted to silver nanoparticles (a) control sample without;(b)
zones of inhibition caused by 30 μg/mL; (c) zones of inhibition caused by 60 μg/mL.

CONCLUSIONS
In this paper, we explore the feasibility of using antimicrobial hydrogel patches with excellent
mechanical strength for conservation of waterlogged wood. We focused our testing on antimicrobial
hydrogels deacidification and antibacterial properties. We noted the prepared hydrogel patches match
well with weak alkaline and high water content properties to carry out ion exchange to reduce the
acidity. Double network polymer structure was utilized to increase the stretch of the hydrogel, which
provides mechanical support to the highly decayed softwood. These antimicrobial hydrogel patches
can perform targeted restoration and preservation as indicated by our research and testing of UCH
waterlogged wood from Nanhai No.1 with the help of the Maritime Silk Road Museum of
Guangdong.
AUTHOR INFORMATION
Mailing address: School of Chemical Engineering and Technology, Sun Yat-sen University Zhuhai, Guangdong Province
519082 China; Email: chenqiang3@mail.sysu.edu.cn
Xiaohang Sun, Junjie Chen, Xuanwei Zhang, Qiang Chen* contributed equally to this work. All authors have given approval
to the final version of the manuscript.

ACKNOWLEDGMENT
This work was supported by the National Natural Science Foundation of China (51972264).

5

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7

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situ for centuries. Although the overall structure of the wooden artifacts is still intact they are severely degraded&#13;
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antimicrobial hydrogel patches. Antimicrobial hydrogel patches dispersed with antibacterial and deacidification&#13;
nanoparticles simultaneously deacidify, moisturize, and reinforce both antibacterial and mechanical aspects of&#13;
waterlogged wood. In the construction of the antimicrobial hydrogel patches, the double network hydrogel was&#13;
used to prepare the hydrogel substrate with stretch and mechanical strength. We have successfully applied the&#13;
antimicrobial hydrogel patches to the waterlogged wood from Nanhai No. 1, with the support of the Maritime&#13;
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                <text>Sun, Xiaohang , Junjie Chena, Xuanwei Zhangb, and Qiang Chena. 2023. “Antimicrobial hydrogel patches for deacidification and conservation of waterlogged archaeological wood.” Edited by Jennifer Craig, Jay Mok and T. Kurt Knoerl. In Proceedings of Fifth Asia Pacific Regional Conference on Underwater Cultural Heritage: Gwangju, The Republic of Korea, November 13-18 2023. The Museum of Underwater Archaeology. URL: https://apconf.omeka.net/exhibits/show/apconfproceedings/item/1909 </text>
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                    <text>Conserving Ropes from the Phanom-Surin Shipwreck in Thailand: Case Study on
Storage and Exhibition at the National Museum of Thailand
Natchaya Pattanasuttirata , Kunthida Chimmab , Puangporn Srisomboon, and Monchalus
Pitisinchoochai
Conservation Science Division, Office of National Museum, The Fine Arts Department,
Ministry of Culture, Thailand
a
Natchaya.peary@gmail.com, bChimma.kun@hotmail.com
ABSTRACT
There are several important factors to consider when studying appropriate conservation methods for fibers in
museum exhibitions or storage. This research focused on investigating the potential of using Trehalose and
polyethylene glycol 4000 (PEG4000) as treatments for shipwreck rope fibers in Thailand's museums. The
efficacy of these treatments was evaluated by using a twisted fiber thread to tie the torpedo jar. The initial
desalinated fibers were subjected to three groups: untreated rope was dried at room temperature, ropes conserved
with Trehalose, and ropes conserved with PEG4000. Identical concentrations of both the Trehalose and
PEG4000 solutions started at a concentration of 25 percent brix then increased progressively to 40 percent and
60 percent brix.
We employed four different analyses. We used scanning electron microscopy to study morphological properties.
Prior to treatment and after treatment we compared numerical evaluation of the colour change using ΔE* values
(CIE L*a*b* system). We recorded reflectance using wavelengths of white light ranges (380-780 nm). We used
differential scanning calorimetry technique for thermal properties.
The results indicate the Trehalose fibers had a melting temperature of 192.8°C and exhibited less change in
colour and reflectance compared to the others. The PEG4000 fibers had a melting temperature at 59.3°C.
Trehalose had higher thermal properties compared to PEG4000. Thus, Trehalose is an appropriate conservation
material for ropes and other fiber-based materials that are stored or displayed in environments with high
humidity and temperature, such as the case in Thailand.
Keywords Phanom-Surin Shipwreck, conservation of rope (fiber), Trehalose, PEG4000
List of Figure
Figure 1 The twisted fiber used for tie Torpedo jars
Figure 2. Untreated fiber. a) Cross-sectional, b) Cross-sectional lumen, c) Longitudinal
Figure 3. PEG4000 fiber. (a) Cross-sectional, (b) Cross-sectional lumen, (c) Longitudinal
Figure 4. Trehalose fiber. (a) Cross-sectional, (b) Cross-sectional lumen, (c) Longitudinal
Figure 5. Fresh sugar palm fiber. (a) Cross-sectional, (b) Cross-sectional lumen, (c) Longitudinal
Figure 6. Twisted rope. (a) Untreated rope, (b) Trehalose-treated rope, (c) PEG4000-treated rope
Figure 7. Graph of reflectance comparison results between untreated fiber, Trehalose fiber, and PEG4000 fiber.
Figure 8. DSC thermogram of untreated fibers (a), pure Trehalose (b), pure PEG4000 (c), Trehalose fibers (d), and
PEG4000 fibers (e): 1st Heating.

3
5
5
5
6
6
6
8

List of Table
Table 1 shows the results of the L*a*b* colour space data for untreated rope, rope treated with Trehalose, and rope treated
with PEG4000
7

1

�1. INTRODUCTION
The Phanom-Surin shipwreck was discovered at Samut Sakhon, Thailand in September 2013. The
shipwreck is dated to the 9th century CE (1stROFAD 2016). We narrow our discussion to the excavated
rope fibers. Our literature review on rope fiber or “Tao” fibers identified them as Arenga pinnata,
commonly known as the sugar palm or Arenga palm (Mahaphol 2013). For centuries sugar palm fibers
were used as ropes for ships due to their exceptional strength, durability, and resistance to saltwater
(Ishak et al. 2012, 700). Our study expands from this literature review to focus on the conservation of
twisted rope/fiber, used to tie Torpedo jars (Figure 2), with a specific emphasis on museum exhibition
and storage purposes.
In this study, we compared conservation of fresh sugar palm fibers in PEG4000 and Trehalose, which
demonstrated superior properties compared to the non-treated fibers. We examined moisture
absorption, which the fibers treated with Trehalose (henceforth Trehalose fiber) showed lower
moisture absorption than the fibers treated with PEG4000 (henceforth PEG4000 fiber). We compare
the physical characteristics of the fibers that underwent conservation treatment (in either PEG4000 or
Trehalose) by the changes in reflectance, colour and heat resistance. Our results are intended for use to
design a conservation plan for the appropriate environment for museum display, storage, and
conservation.

Figure 1 The twisted fiber used to tie Torpedo jars

2. MATERIALS AND METHODS
2.1 Materials
On the Phanom-Surin shipwreck ropes were used to tie Torpedo jars. PEG4000 (M w ≈ 3500 - 4000)
was purchased from Loba ChemieTM, India. Trehalose (TREHA®) was purchased from Hayashibara
Co.Ltd., Japan.
2.2

Samples preparation

We prepared the fiber samples by flushing with deionized water until the electrical conductivity (EC)
of the solution was below 100 μS. The fibers were divided into three groups, dry at room temperature,
soaked with Trehalose or PEG4000. We tightly covered the fibers while soaking to prevent water
evaporation.
i.
ii.

Untreated - The untreated fibers were dried at room temperature.
Soaked with Trehalose - The fibers were immersed in Trehalose starting with 20
percent brix at room temperature (34°C). The solution was heated, while the Trehalose
concentration increased from 40 percent to 60 percent brix. The controlled temperature
did not exceed 80°C, and the fibers were immersed for 24 hours. Once the fibers
reached the (20, 40, 60) percent brix constants the fibers were dried with an electric-fan
until completely dried. The fibers were cleaned with warm water to remove any
residual Trehalose and dried until a constant weight is obtained.

2

�iii.

2.3

Soaked with PEG4000 - The immersion process in PEG4000 follows the same
procedure as immersion in the Trehalose solution, but the fibers were left to dry at room
temperature.
Scanning electron microscopy (SEM)

After sample preparation (see above for details) all fibers were immersed in liquid nitrogen, broken up
and stored in a desiccator to absorb moisture for one day. Each were coated with gold (Au-Coating)
through an auto fine coater (Smart Coater, DII-29030SCTR) for 4 minutes. Analysis was conducted
with a benchtop scanning electron microscope (JCM-7000, JEOL) at 5 kilovolts (kV).
2.4

Differential Scanning Calorimetry (DSC)

After sample preparation and SEM all fibers underwent thermal analysis with the Differential
Scanning Calorimetry (DSC) technique (Mettler Toledo brand). Five milligrams (mg) of sample were
sealed hermetically in the aluminium crucible. Nitrogen gas was purged at a flow rate of 20 millilitres
per minute (mL/min). At a heating rate of 10 °C/min across a range from -20 to 200°C to 50 to 230°C.
2.5

Spectroradiometer

After sample preparation, SEM and DSC all fibers underwent spectroradiometer (Konica Minolta CS2000), with wavelengths from 380 to 780 nanometers (nm) range. The samples were prepared by
twining and thickening the ropes, three random points were selected for spectroradiometer at a 0.2
aperture in the (CIELAB) (Commission Internationale de l´Eclairage, L*, a* and b* represent each of
the three values the CIELAB color space uses to measure objective color and calculate color
differences. L* represents lightness from black to white on a scale of zero to 100, while a* and b*
represent chromaticity with no specific numeric limits. Negative a* corresponds with green, positive
a* corresponds with red, negative b* corresponds with blue and positive b* corresponds with yellow).
Under the International Commission on Illumination (CIE) commonly used D65 - D series of
illuminants portray standard illumination conditions at open-air in different parts of the world measurements were taken and the reflectance values were averaged. The data was then analyzed for
colour variability.

3. RESULTS AND DISCUSSION
Our study focuses on the conservation of waterlogged fiber in Trehalose and PEG4000 that was used
to tie Torpedo jars in the Phanom-Surin shipwreck (Figure 2), for the purpose of museum exhibition
and storage.
3.1

Scanning Electron Microscopy

Microscopic examinations of fibers treated with Trehalose and PEG4000 show structural differences
compared to untreated rope samples. Untreated rope displayed severe degradation, collapse of cells,
and the longitudinal section had a hole where the silica had come off (Figure 4-c). Fresh sugar palm
fibers retain silica (Figure 7-c). Cross-sections of PEG4000-treated and Trehalose-treated ropes
appeared similar to each other. PEG4000-treated rope had a smoother longitudinal surface (Figure 5c), while Trehalose-treated rope exhibited an orthorhombic crystal form (Figure 6-c). These
differences indicate distinct effects of the different immersive treatments of conserved fibers.
Trehalose and PEG4000 conserved fibers of twisted rope show surface cracks due to SEM sample
preparation. The micrograph of these twisted fibers (Figure 8) show reduced bend and twist resistance.
Specifically, Trehalose exhibits lower twist resistance than PEG4000. In previous research the
conserved fibers improved tensile strength (Mahaphol 2013). Trehalose, with its rigid crystalline
structure, demonstrates higher tensile strength than PEG4000 and untreated rope.

3

�Silica Body

(a)

(b)

Hole of Silica Body

(c)

Figure 2. Untreated fiber. a) Cross-sectional, b) Cross-sectional lumen, c) Longitudinal

(a)

(b)

(c)

Figure 3. PEG4000 fiber. (a) Cross-sectional, (b) Cross-sectional lumen, (c) Longitudinal

(a)

(b)

(c)

Figure 4. Trehalose fiber. (a) Cross-sectional, (b) Cross-sectional lumen, (c) Longitudinal

Silica Body

(a)

(b)

(c)

Figure 5. Fresh sugar palm fiber. (a) Cross-sectional, (b) Cross-sectional lumen, (c) Longitudinal

(a)

(b)

(c)

Figure 6. Twisted rope. (a) Untreated rope, (b) Trehalose-treated rope, (c) PEG4000-treated rope

4

�3.2

Reflectance (percent)

Figure 7. Graph of reflectance comparison results between untreated fiber,
Trehalose fiber, and PEG4000 fiber.

The results of the reflectance (percent) measurements indicate that both PEG4000 and Trehalose
conserved fibers increased reflectance compared to the non-treated fiber. Pointedly, the PEG4000 fiber
exhibited higher reflectance percentage than the Trehalose fiber. This suggests that PEG4000
treatment may have more significant impact on enhancing the fiber's reflective properties. PEG4000
fiber (Figure 5-c) surfaces were coated with a layer of silica so the longitudinal surface reflection was
smoother and more uniform, which resulted in regular reflection of incident light. In contrast, the
Trehalose fiber (Figure 6-c) have rough surfaces with irregularly shaped rectangular features and
thickness varies, which leads to scattered reflection of incident light. The diffused light in multiple
directions is disordered and does not exhibit regular reflection. This causes a decrease in the detected
signal.
3.3

Colour measurement ΔE*

Table 1 shows the results of the L*a*b* colour space data for untreated fiber, Trehalose fiber, and PEG4000 fiber.
L* ± SD

a* ± SD

b* ± SD

ΔE*

No-treatment (PSF )

14.17±2.20

0.66±0.21

2.20±0.23

-

PSF/PEG4000

15.85±3.05

0.56±0.77

1.03±0.44

2.05

PSF/Trehalose

14.12±4.49

0.98±0.53

2.03±0.98

0.37

No-treatment (Currently)

23.53±4.59

1.89±0.60

7.33±0.45

10.74

Treatment
a

Note: a PSF refers to Phanom-Surin fiber

The untreated fiber has a low L* value of 14.17, indicating a relatively dark colour. The positive a*
value of 0.66 and positive b* value of 2.20 suggests the colour of the untreated fiber has a slightly
reddish-yellow hue. The PEG4000 fiber increased the L* value to 15.85, indicating a brighter colour.
The a* value decreased slightly to 0.56, indicating a slightly greener hue, while the b* value
decreased significantly to 1.03, indicating a more blueish hue. The Trehalose fiber resulted in a similar
L* value as the untreated fiber at 14.12, but a higher positive a* value of 0.98 and a higher positive b*
value of 2.03. This suggests that the Trehalose fiber colour has a more reddish-yellow hue than the
untreated fiber.
The CIE L*a*b* colour system allowed us to evaluate the colour change of the fiber. The colour
difference (ΔE*) was calculated by comparing the colour values of the treated and non-treated fibers.
ΔE* value greater than one was considered visually detectable.
5

�The results of the colour measurement ΔE* for PEG4000 fiber (2.05) and Trehalose fiber (0.37)
(non-treated fiber so there is no ΔE* value) indicate that the addition of PEG4000 to the fiber caused a
significant colour change, while Trehalose fiber minimally changed. These findings suggest that the
Trehalose treatment more effectively preserves the colour stability of the sugar palm fiber than
PEG4000. The cause of colour change requires further investigation.
3.4

Differential Scanning Calorimetry (DSC)

Figure 8. DSC thermogram of untreated fibers (a), pure Trehalose (b), pure PEG4000 (c),
Trehalose fibers (d), and PEG4000 fibers (e): 1st Heating.

We investigated the thermal properties of fibers following preservation with Trehalose and PEG4000
treatment, which resulted in changes in the thermogram characteristics of the fibers.
Figure 10 (a) and (d) show the relationship between Fiber and Fiber/Trehalose. DSC thermogram:
peaks at 96.11°C and 139.73°C for Fiber, and 92.27°C and 149.44°C for Fiber/Trehalose. The first
peak corresponds to water evaporation. Fiber/Trehalose has more easily evaporated water due to the
attributed hydroxyl groups in the cellulose structure, which make it difficult to bond with water. The
presence of a hydroxyl group of Trehalose in Fiber/Trehalose also binds to the cellulose of the fiber,
causing a decrease in the amount of bonding between water and cellulose. At 149.44°C, the melting
temperature (Tm) of Fiber or Fiber/Trehalose occurs. In fact, Trehalose's melting temperature is at
192.80°C, which causes the crystals of the Trehalose chain to fold into lamellae this absorbs heat
energy from surroundings and causes vibrations until the intermolecular attraction is overcome. As a
result, the crystals dissociate into randomly spaced Trehalose chain molecules. The second peak of
Fiber/Trehalose (Figure 10 (b)) covers Trehalose's melting peak and has a wide range. The
temperature transition from glassy state to rubbery state (T g) occurs at 106.50 °C, where Trehalose
chains in the amorphous region absorb heat energy, which increase distance between chains and free
up space for volume. Comparison of the DSC of Fiber and Fiber/Trehalose, Trehalose treatment raised
the second peak temperature, this indicates higher melting temperature and improved high-temperature
resistance.
Figure 10 (a) and (c) show the relationship between Fiber and Fiber/ PEG4000. From and (c), the first
peak observed at 54.36°C (Figure 10e) corresponds to the melting temperature (T m) of PEG4000. A
lower melting point than Trehalose. PEG4000 is composed of repeated units of ethylene glycol, which
6

�enable it to form hydrogen bonds with water molecules. In comparison, Trehalose is composed of a
cyclic glucose disaccharide that forms strong hydrogen bonds due to the two glucose molecules being
linked by an α,α-1,1-glycosidic bond. These structures when compared result in Trehalose’s higher
melting temperature than PEG4000.
Based on the thermal investigation, Trehalose-treated rope showed superior thermal stability and less
moisture absorption than PEG4000.
4. CONCLUSION
We demonstrated the use of Trehalose and PEG4000 in the conservation of twisted fiber used to tie the
torpedo jars on the Phanom-Surin shipwreck. The results showed the Trehalose fibers had less change
in colour, reflectance and higher thermal properties compared to the PEG4000 fibers. We conclude
Trehalose is an effective conservation material for fibers in high humidity and temperature
environments. The use of Trehalose as a conservation treatment for sugar palm fibers created a barrier
between the cellulose structure and water, which reduced the amount of water that can evaporate from
the fibers. The experiments in this study are informative and favour Trehalose as the preferred fiber
treatment for museum display and storage in high humidity and heat environments, such as Thailand.

Acknowledgements
The authors sincerely thank Mr.Sanae Mahaphol and Ms.Sopit Panyakhan, Scientists from conservation science division, and
The Fine Arts Department of Thailand for their help and constant encouragement. Thanks Ms.Sirin Yuanyaidee, Director of
Kanchanaphisek National Museum and staff. Thank you Assoc.Prof.Dr.Mantana Opaprakasit and Dr.Intatch
Hongrattanavichit from Faculty of Science Chulalongkorn University for their support with the analysis instruments and their
advice. Moreover, we’re grateful to the Sumitomo Foundation, Japan and Ms.Umaporn Kruekamwang, Director of Office of
National Science Museum Thailand for the support.

Bibliography
Ishak, M.R., S.M. Sapuan, Z. Leman, M.Z.A. Rahman, U.M.K Anwar, and J.P. Siregar. "Sugar palm (Arenga pinnata): Its
fibres, polymers and composites." ELSEVIER (2012): 700.
Mahaphol, Saneh. "The conservation of ropes from the Phanom-Surin Shipwreck Site, Thailand." Academia (2013): 1-16.
The 1st Regional Office of Fine Arts Department, Ratchaburi Fine Arts Department (1stROFRD). Study of Phanom-Surin
Shipwreck, Phanthai Norasing Sub-district, Meuang District, Samut Sakhon Province (2013-2015). Bangkok:
Bangkok in House, co., 2016.

7

�8

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                <text>There are several important factors to consider when studying appropriate conservation methods for fibers in&#13;
museum exhibitions or storage. This research focused on investigating the potential of using Trehalose and&#13;
polyethylene glycol 4000 (PEG4000) as treatments for shipwreck rope fibers in Thailand's museums. The&#13;
efficacy of these treatments was evaluated by using a twisted fiber thread to tie the torpedo jar. The initial&#13;
desalinated fibers were subjected to three groups: untreated rope was dried at room temperature, ropes conserved&#13;
with Trehalose, and ropes conserved with PEG4000. Identical concentrations of both the Trehalose and&#13;
PEG4000 solutions started at a concentration of 25 percent brix then increased progressively to 40 percent and&#13;
60 percent brix.&#13;
We employed four different analyses. We used scanning electron microscopy to study morphological properties.&#13;
Prior to treatment and after treatment we compared numerical evaluation of the colour change using ΔE* values&#13;
(CIE L*a*b* system). We recorded reflectance using wavelengths of white light ranges (380-780 nm). We used&#13;
differential scanning calorimetry technique for thermal properties.&#13;
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                <text>Pattanasuttirata, Natchaya, Kunthida Chimmab, Puangporn Srisomboon, and Monchalus Pitisinchoochai. 2023. “Conserving Ropes from the Phanom-Surin Shipwreck in Thailand: Case Study on Storage and Exhibition at the National Museum of Thailand.” Edited by Jennifer Craig, Jay Mok and T. Kurt Knoerl. In Proceedings of Fifth Asia Pacific Regional Conference on Underwater Cultural Heritage: Gwangju, The Republic of Korea, November 13-18 2023. The Museum of Underwater Archaeology. URL: https://apconf.omeka.net/exhibits/show/apconfproceedings/item/1908 </text>
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