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Investigation of natural dyes and ancient textiles from korea using TOF-SIMS
Applied Surface Science 255 (2008) 1033–1036
Contents lists available at ScienceDirect
Applied Surface Science journal homepage: www.elsevier.com/locate/apsusc
Investigation of natural dyes and ancient textiles from korea using TOF-SIMS Yeonhee Lee a,*, Jihye Lee b, Youngsoo Kim b, Seokchan Choi c, Seung Wook Ham c, Kang-Jin Kim b a
Advanced Analysis Center, Korea Institute of Science & Technology, 39-1 Haweolgok Dong, Seoul 136-791, Republic of Korea Department of Chemistry, Korea University, Seoul 136-7131, Republic of Korea c Department of Chemistry, Chung-Ang University, Seoul 156-756, Republic of Korea b
A R T I C L E I N F O
A B S T R A C T
Article history:
The identification of the colorants used on ancient textiles provides a historical pathway to the understanding of the processes associated with one of the oldest of chemical technologies, namely textile dyeing. In this paper, time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to detect dyes on textiles avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. The plant dyes investigated belong to a variety of chemical groups, which include curcumin, crocin, carthamin, purpurin, alizarin, brazilin, shikonin, and indigo. Reference textile samples were prepared with dye extracts of plants and were characterized by TOF-SIMS. TOF-SIMS spectra for the dyed textiles showed element ions from metallic mordants, specific fragment ions, and molecular ions from organic dyes. Remnant dyes on excavated textiles have also been identified using TOF-SIMS. The ancient textile sample showed the presence of indigo clearly, although the fiber itself had degraded badly. From the results, it was concluded that most of plant dyes can be identified with TOF-SIMS and it is a very promising technique for the archaeology field. ß 2008 Elsevier B.V. All rights reserved.
Available online 13 May 2008 Keywords: Dyes Textiles Mordants TOF-SIMS Archaeology
1. Introduction The archaeological textile research involves chemical detective work to investigate and to identify the sources of the dyestuffs used in old textiles. These studies of the colorants used by ancient peoples include a multidisciplinary research that combines history, archaeology, religion, botany, and microanalytical chemistry [1–3]. Such an examination of the textiles of past cultures discover the development and technological advancement of textile dyeing through various archaeological periods. Today, researchers have a great benefit from the instrumental analyses of ancient artifacts. Dyestuffs have been analyzed with microchemical tests, thin layer chromatography, high-performance liquid chromatography, infrared spectroscopy, visible ultraviolet spectroscopy, X-ray fluorescence, and energy dispersive X-ray spectroscopy. Further, new surface analytical methods developed for the modern samples in semi-conductor, industrial quality control, and environmental areas may also be applicable to
* Corresponding author. Tel.: +82 2 958 5971; fax: +82 2 958 5969. E-mail address: [email protected] (Y. Lee). 0169-4332/$ – see front matter ß 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2008.05.097
the analyses of very small archaeological samples. Surface analytical techniques have been used to study ancient materials since the 1970s and provided the widest range of information with the minimal degree of damage to the object under investigation [4,5]. X-ray photoelectron spectroscopy (XPS) and AES applications to art and archaeology have been reviewed by Lambert et al. and Spoto and Ciliberto [6,7]. The static time-of-flight secondary ion mass spectrometry (TOF-SIMS) with cluster ions and high detection efficiency has expanded the application of SIMS to the study of a variety of organic, polymeric, and biological materials [8,9]. The research indicating the potential of TOF-SIMS in the scientific fields of archaeology and conservation is very limited in number, however, shows its own advantages for specific applications. The advantage of TOF-SIMS in investigating archaeological remains has been recently discussed by Kempson et al. [10]. Organic analysis of the ancient materials is very valuable to the study of archaeological artifacts, such as food residues and dyes. This paper presents the investigation of various dye components, textiles dyed with plant extracts, and ancient Korean textile samples by TOF-SIMS. This analytical approach describes how TOFSIMS contributes to investigating archaeological materials.
Y. Lee et al. / Applied Surface Science 255 (2008) 1033–1036
1034
2. Experimental 2.1. Materials and dyeing methods Main components of dyes such as curcumin, crocin, carthamin, purpurin, alizarin, brazilin, shikonin, and indigo were purchased from Tokyo Chemical Industry (TCI) Co. Ltd., Tokyo, Japan. The natural dyes were extracted from a total of seven plants. Turmeric and sapanwood were imported from India, Burma, and the Philippines, whilst gardenia, safflower, madder, gromwell, and indigo were all readily available in Korea. The majority of the natural plant dyes were extracted in water either by soaking at room temperature or by heating. The textile samples were dyed usually at 40 8C for 30 or 60 min. A detailed description of dyeing methods is presented elsewhere [11]. Table 1 shows empirical formula, molecular weight, and properties of major components of plant dyes selected for this work. 2.2. Instrumental evaluation For the TOF-SIMS study, a Physical Electronics model PHI 7200 TOF-SIMS/SALI instrument was used with Cs+ ion gun operated at 8 keV, at an ion current of 1 nA, and the operating spot size was 50 mm in diameter. The ion pulses have a typical pulse length of 1 ns. Secondary ions generated by a primary ion pulse on the target surface are extracted and accelerated to the energy of 3.3 keV. In the following flight path, lens and reflectron optics are integrated for focusing the secondary ion beam and for energy compensation, respectively. An electron gun was operated in pulsed mode at low electron energy with a target current 1 mA for charge compensation. 3. Results and discussion Eight pure dye components were purchased from manufacturer and their TOF-SIMS spectra were obtained from thin layer films cast from solutions of dyes in methanol on a silver substrate. Table 1 presents the results from positive ion TOF-SIMS analysis of dyes. TOF-SIMS spectra of pure dyes such as curcumin, purpurin, alizarin, brazilin, shikonin, and indigo show the presence of
molecular ions, M+H and specific fragment ions. However, the spectra of crocin and carthamin with the large molecular weight have not yielded molecular ion peaks. Some characteristic fragments were observed. The analysis of dyed textile means the study of one complex mixture in another. In order to determine whether ions in TOFSIMS spectra of dyes are due to the dyes or to the textile, it is necessary to obtain a background spectrum of the silk textile. The textile used in this work gives aliphatic and aromatic hydrocarbon ions below m/z 300, as well as nitrogen containing ions. Textile samples were dyed with various dye extracts of plants and representative TOF-SIMS spectra of textile samples dyed with madder, gromwell, indigo, and safflower are shown in Fig. 1. In the case of textiles with madder, gromwell, and indigo, molecular ion and specific peaks of the major components in dyes were observed with the background from the minor components and textiles. Some informative peaks were also used to identify the individual dyes such as safflower and gardenia. The process of textile dyeing involves the fixing of a colorant into the textile by physical or chemical methods in order to produce a direct or indirect bond between the dye and the fiber. Many of the natural dyes did not have a strong chemical affinity for the textile fibers. Therefore, a mordant or fixing agent was used in the dyeing process. TOF-SIMS spectra of textiles used with natural dyes and mordants are shown in Fig. 2. Abundant ions from metal mordants such as copper, tin, aluminium, and iron were easily observed in the mass range of m/z 1–150. TOF-SIMS spectra provide the characteristic ions from most mordant elements and dye molecules, and therefore can be used to distinguish dyestuffs. After textile samples dyed with plant dye extracts are analyzed for reference compilation, remnant dye on excavated textile has also been identified using TOF-SIMS technique on a scale far below that which is possible by extractive techniques. TOF-SIMS analysis provided information on both element including isotope discrimination and molecular species present on the surface of the archaeological textile coming from individual tomb in Korea. Two ancient textiles of 16th and 17th century were analyzed and compared with the previous reference data. Fig. 3(a) shows the TOF-SIMS spectrum obtained from the thread taken from the
Table 1 Details of the dyes extracted from the plants and specific ions obtained from their TOF-SIMS spectra Name of plant botanical (English)
Part employed for dyeing
Major dye component
MW
Form and solubilitya
Peak mass for positive ion (m/z) Molecular ion, M+ +
Fragment ion
Curcuma longa L. (turmeric)
Rhizome
Curcumin
C21H20O6 368.38
Orange-yellow crystal pow. w i, eth i, al s, aa s
(M+H) , 369
Gardenia jasmoides Ellis (gardenia)
Ripe fruits
Crocin
C44H64O24 976.96
Brownish red needles hot w s, al s, eth s
–
Carthamus tinctorius L. (safflower)
Flowers
Safflor yellow carthamin
C43H42O22 910.79
Dark red powder, dil alkali solution s, eth s
–
Rubia cordifolia L. Rubia akane nakai (madder) Caesalpinia sappon L. (sapponwood) Lithospermum erythror-hizon Shieb. et zucc. (gromwell) Indigofera tinctoria L. (Indigo)
Root
Purpurin Alizarin
Wood
Brazilin
C14H8O5 256.21 C14H8O4 240.21 C16H14O5 286.27
(M+H)+, 257 (M+H)+, 241 (M+H)+, 287
Root
Shikonin
C16H16O5 288.29
Long orange needles hot w s, al s(red),eth s(int. yellow) Yellow crystals, turn orange in air and light, w s, al s, eth s Dark purple powder, w s, organic sol s
(M+H)+, 289
C16H15O4 (271), C10H5O4 (189)
Leaves or whole plant
Indigotin or indigo
C16H10N2O2 262.26
Dark blue powder, w, al, eth, dil acid i
(M+H)+, 263
C16H11N2O (247), C15H11N2O (235)
a
w, water; eth, ether; al, alcohol; aa, acetic acid; s, soluble; I, insoluble; int, intense.
C20H19O5 (339), C 19H17O4 (309), C10H9O3 (177) C12H22O10 (326), C12H22O9 (310), C11H20O9 (296) C37H37O21 (817), C31H26O16 (654), C22H21O11 (461), C21H22O11 (450), C12H13O8 (285), C12H13O7 (269) C14H8O4 (240) C13H9O4 (229) C16H13O4 (269)
Y. Lee et al. / Applied Surface Science 255 (2008) 1033–1036
1035
Fig. 1. Positive ion TOF-SIMS spectra of textiles dyed with (a) madder, (b) gromwell, (c) indigo and (d) safflower.
Fig. 2. Positive ion TOF-SIMS spectra of textiles dyed with (a) sapponwood and CuSO4, (b) turmeric and SnCl4, (c) turmeric and KAl(SO4)2, and (d) safflower and FeSO4 as a mordant.
Fig. 3. Positive ion TOF-SIMS spectra of antique textiles known as (a) Kim-Wak and (b) Gurye Sonssi.
official uniform (Kim-Wak) dated 17th century. As shown in the figure, the specific fragment ions are observed at m/z 235 and m/z 247, as well as molecular ion at m/z 263. The other ancient sample is a small piece taken from a man’s Korean clothes dated 16th century (Gurye Sonssi). Although the fiber itself had degraded, the presence of indigo is clearly shown in the TOF-SIMS spectrum (Fig. 3(b)). However, mordant-related peaks were not found in the ancient textiles that were dyed with indigo. Indigo has a strong affinity for the textile fibers so that it was hardly used with the mordant (the vat dyes). That is the reason why we cannot find
mordant peak in the spectra of ancient textiles. TOF-SIMS technique is a valuable analytical tool to distinguish the ancient dyed textiles. 4. Conclusions High resolution TOF-SIMS is a powerful technique for structural characterization of dyes. TOF-SIMS spectra of textiles dyed with various plant extracts were obtained in the mass range m/z 0– 1000. Molecular ions and fragment ions from the organic
1036
Y. Lee et al. / Applied Surface Science 255 (2008) 1033–1036
component of dyes were observed as well as elemental ions from the mordants. And two ancient textiles were also analyzed and their results showed the presence of indigo. TOF-SIMS is a useful analytical technique for archaeological research. Minimal sample size and preparation make it ideal for the analysis of small and precious samples. And the applications made in this work have clearly demonstrated the advantages that this technique can provide in the study of our past. Acknowledgment This work was supported by the National Research Institute of Cultural Heritage R&D Program.
References [1] H. Schweppe, Practical Hints on Dyeing with Natural Dyes, Smithsonian Institution, Washington, DC, 1986. [2] J. Wouter, A. Verhecken, J. Soc. Dyers Color. 107 (1991) 266. [3] B. Guineau, Stud. Conserv. 34 (1989) 38. [4] J.B. Lambert, C.D. McLaughlin, Archaeometry 18 (1976) 169. [5] L.J. Cline Love, L. Soto, B.T. Reagor, Appl. Spectrosc. 34 (1980) 131. [6] J.B. Lambert, C.D. McLaughlin, C.E. Shawl, L. Xue, Anal. Chem. 4 (1999) 614A. [7] G. Spoto, E. Ciliberto (Eds.), Mordern Analytical Methods in Art and Archaeology, Wiley, New York, 2000, pp. 363–404. [8] L. Van Vaeck, A. Adriaens, R. Gijbels, Mass Spectrosc. Rev. 18 (1999) 1. [9] B. Hagenhoff, Mikrochim. Acta 132 (2000) 259. [10] I.M. Kempson, W.M. Skinner, P.K. Kirkbride, A.J. Nelson, R.R. Martin, Eur. J. Mass Spectrom. 9 (2003) 589. [11] C.K. Koh Choo, Y.E. Lee, Color. Technol. 118 (2002) 35.
Contents lists available at ScienceDirect
Applied Surface Science journal homepage: www.elsevier.com/locate/apsusc
Investigation of natural dyes and ancient textiles from korea using TOF-SIMS Yeonhee Lee a,*, Jihye Lee b, Youngsoo Kim b, Seokchan Choi c, Seung Wook Ham c, Kang-Jin Kim b a
Advanced Analysis Center, Korea Institute of Science & Technology, 39-1 Haweolgok Dong, Seoul 136-791, Republic of Korea Department of Chemistry, Korea University, Seoul 136-7131, Republic of Korea c Department of Chemistry, Chung-Ang University, Seoul 156-756, Republic of Korea b
A R T I C L E I N F O
A B S T R A C T
Article history:
The identification of the colorants used on ancient textiles provides a historical pathway to the understanding of the processes associated with one of the oldest of chemical technologies, namely textile dyeing. In this paper, time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to detect dyes on textiles avoiding the time-consuming and destructive extraction procedures necessary for the spectrophotometric and chromatographic methods previously used. The plant dyes investigated belong to a variety of chemical groups, which include curcumin, crocin, carthamin, purpurin, alizarin, brazilin, shikonin, and indigo. Reference textile samples were prepared with dye extracts of plants and were characterized by TOF-SIMS. TOF-SIMS spectra for the dyed textiles showed element ions from metallic mordants, specific fragment ions, and molecular ions from organic dyes. Remnant dyes on excavated textiles have also been identified using TOF-SIMS. The ancient textile sample showed the presence of indigo clearly, although the fiber itself had degraded badly. From the results, it was concluded that most of plant dyes can be identified with TOF-SIMS and it is a very promising technique for the archaeology field. ß 2008 Elsevier B.V. All rights reserved.
Available online 13 May 2008 Keywords: Dyes Textiles Mordants TOF-SIMS Archaeology
1. Introduction The archaeological textile research involves chemical detective work to investigate and to identify the sources of the dyestuffs used in old textiles. These studies of the colorants used by ancient peoples include a multidisciplinary research that combines history, archaeology, religion, botany, and microanalytical chemistry [1–3]. Such an examination of the textiles of past cultures discover the development and technological advancement of textile dyeing through various archaeological periods. Today, researchers have a great benefit from the instrumental analyses of ancient artifacts. Dyestuffs have been analyzed with microchemical tests, thin layer chromatography, high-performance liquid chromatography, infrared spectroscopy, visible ultraviolet spectroscopy, X-ray fluorescence, and energy dispersive X-ray spectroscopy. Further, new surface analytical methods developed for the modern samples in semi-conductor, industrial quality control, and environmental areas may also be applicable to
* Corresponding author. Tel.: +82 2 958 5971; fax: +82 2 958 5969. E-mail address: [email protected] (Y. Lee). 0169-4332/$ – see front matter ß 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2008.05.097
the analyses of very small archaeological samples. Surface analytical techniques have been used to study ancient materials since the 1970s and provided the widest range of information with the minimal degree of damage to the object under investigation [4,5]. X-ray photoelectron spectroscopy (XPS) and AES applications to art and archaeology have been reviewed by Lambert et al. and Spoto and Ciliberto [6,7]. The static time-of-flight secondary ion mass spectrometry (TOF-SIMS) with cluster ions and high detection efficiency has expanded the application of SIMS to the study of a variety of organic, polymeric, and biological materials [8,9]. The research indicating the potential of TOF-SIMS in the scientific fields of archaeology and conservation is very limited in number, however, shows its own advantages for specific applications. The advantage of TOF-SIMS in investigating archaeological remains has been recently discussed by Kempson et al. [10]. Organic analysis of the ancient materials is very valuable to the study of archaeological artifacts, such as food residues and dyes. This paper presents the investigation of various dye components, textiles dyed with plant extracts, and ancient Korean textile samples by TOF-SIMS. This analytical approach describes how TOFSIMS contributes to investigating archaeological materials.
Y. Lee et al. / Applied Surface Science 255 (2008) 1033–1036
1034
2. Experimental 2.1. Materials and dyeing methods Main components of dyes such as curcumin, crocin, carthamin, purpurin, alizarin, brazilin, shikonin, and indigo were purchased from Tokyo Chemical Industry (TCI) Co. Ltd., Tokyo, Japan. The natural dyes were extracted from a total of seven plants. Turmeric and sapanwood were imported from India, Burma, and the Philippines, whilst gardenia, safflower, madder, gromwell, and indigo were all readily available in Korea. The majority of the natural plant dyes were extracted in water either by soaking at room temperature or by heating. The textile samples were dyed usually at 40 8C for 30 or 60 min. A detailed description of dyeing methods is presented elsewhere [11]. Table 1 shows empirical formula, molecular weight, and properties of major components of plant dyes selected for this work. 2.2. Instrumental evaluation For the TOF-SIMS study, a Physical Electronics model PHI 7200 TOF-SIMS/SALI instrument was used with Cs+ ion gun operated at 8 keV, at an ion current of 1 nA, and the operating spot size was 50 mm in diameter. The ion pulses have a typical pulse length of 1 ns. Secondary ions generated by a primary ion pulse on the target surface are extracted and accelerated to the energy of 3.3 keV. In the following flight path, lens and reflectron optics are integrated for focusing the secondary ion beam and for energy compensation, respectively. An electron gun was operated in pulsed mode at low electron energy with a target current 1 mA for charge compensation. 3. Results and discussion Eight pure dye components were purchased from manufacturer and their TOF-SIMS spectra were obtained from thin layer films cast from solutions of dyes in methanol on a silver substrate. Table 1 presents the results from positive ion TOF-SIMS analysis of dyes. TOF-SIMS spectra of pure dyes such as curcumin, purpurin, alizarin, brazilin, shikonin, and indigo show the presence of
molecular ions, M+H and specific fragment ions. However, the spectra of crocin and carthamin with the large molecular weight have not yielded molecular ion peaks. Some characteristic fragments were observed. The analysis of dyed textile means the study of one complex mixture in another. In order to determine whether ions in TOFSIMS spectra of dyes are due to the dyes or to the textile, it is necessary to obtain a background spectrum of the silk textile. The textile used in this work gives aliphatic and aromatic hydrocarbon ions below m/z 300, as well as nitrogen containing ions. Textile samples were dyed with various dye extracts of plants and representative TOF-SIMS spectra of textile samples dyed with madder, gromwell, indigo, and safflower are shown in Fig. 1. In the case of textiles with madder, gromwell, and indigo, molecular ion and specific peaks of the major components in dyes were observed with the background from the minor components and textiles. Some informative peaks were also used to identify the individual dyes such as safflower and gardenia. The process of textile dyeing involves the fixing of a colorant into the textile by physical or chemical methods in order to produce a direct or indirect bond between the dye and the fiber. Many of the natural dyes did not have a strong chemical affinity for the textile fibers. Therefore, a mordant or fixing agent was used in the dyeing process. TOF-SIMS spectra of textiles used with natural dyes and mordants are shown in Fig. 2. Abundant ions from metal mordants such as copper, tin, aluminium, and iron were easily observed in the mass range of m/z 1–150. TOF-SIMS spectra provide the characteristic ions from most mordant elements and dye molecules, and therefore can be used to distinguish dyestuffs. After textile samples dyed with plant dye extracts are analyzed for reference compilation, remnant dye on excavated textile has also been identified using TOF-SIMS technique on a scale far below that which is possible by extractive techniques. TOF-SIMS analysis provided information on both element including isotope discrimination and molecular species present on the surface of the archaeological textile coming from individual tomb in Korea. Two ancient textiles of 16th and 17th century were analyzed and compared with the previous reference data. Fig. 3(a) shows the TOF-SIMS spectrum obtained from the thread taken from the
Table 1 Details of the dyes extracted from the plants and specific ions obtained from their TOF-SIMS spectra Name of plant botanical (English)
Part employed for dyeing
Major dye component
MW
Form and solubilitya
Peak mass for positive ion (m/z) Molecular ion, M+ +
Fragment ion
Curcuma longa L. (turmeric)
Rhizome
Curcumin
C21H20O6 368.38
Orange-yellow crystal pow. w i, eth i, al s, aa s
(M+H) , 369
Gardenia jasmoides Ellis (gardenia)
Ripe fruits
Crocin
C44H64O24 976.96
Brownish red needles hot w s, al s, eth s
–
Carthamus tinctorius L. (safflower)
Flowers
Safflor yellow carthamin
C43H42O22 910.79
Dark red powder, dil alkali solution s, eth s
–
Rubia cordifolia L. Rubia akane nakai (madder) Caesalpinia sappon L. (sapponwood) Lithospermum erythror-hizon Shieb. et zucc. (gromwell) Indigofera tinctoria L. (Indigo)
Root
Purpurin Alizarin
Wood
Brazilin
C14H8O5 256.21 C14H8O4 240.21 C16H14O5 286.27
(M+H)+, 257 (M+H)+, 241 (M+H)+, 287
Root
Shikonin
C16H16O5 288.29
Long orange needles hot w s, al s(red),eth s(int. yellow) Yellow crystals, turn orange in air and light, w s, al s, eth s Dark purple powder, w s, organic sol s
(M+H)+, 289
C16H15O4 (271), C10H5O4 (189)
Leaves or whole plant
Indigotin or indigo
C16H10N2O2 262.26
Dark blue powder, w, al, eth, dil acid i
(M+H)+, 263
C16H11N2O (247), C15H11N2O (235)
a
w, water; eth, ether; al, alcohol; aa, acetic acid; s, soluble; I, insoluble; int, intense.
C20H19O5 (339), C 19H17O4 (309), C10H9O3 (177) C12H22O10 (326), C12H22O9 (310), C11H20O9 (296) C37H37O21 (817), C31H26O16 (654), C22H21O11 (461), C21H22O11 (450), C12H13O8 (285), C12H13O7 (269) C14H8O4 (240) C13H9O4 (229) C16H13O4 (269)
Y. Lee et al. / Applied Surface Science 255 (2008) 1033–1036
1035
Fig. 1. Positive ion TOF-SIMS spectra of textiles dyed with (a) madder, (b) gromwell, (c) indigo and (d) safflower.
Fig. 2. Positive ion TOF-SIMS spectra of textiles dyed with (a) sapponwood and CuSO4, (b) turmeric and SnCl4, (c) turmeric and KAl(SO4)2, and (d) safflower and FeSO4 as a mordant.
Fig. 3. Positive ion TOF-SIMS spectra of antique textiles known as (a) Kim-Wak and (b) Gurye Sonssi.
official uniform (Kim-Wak) dated 17th century. As shown in the figure, the specific fragment ions are observed at m/z 235 and m/z 247, as well as molecular ion at m/z 263. The other ancient sample is a small piece taken from a man’s Korean clothes dated 16th century (Gurye Sonssi). Although the fiber itself had degraded, the presence of indigo is clearly shown in the TOF-SIMS spectrum (Fig. 3(b)). However, mordant-related peaks were not found in the ancient textiles that were dyed with indigo. Indigo has a strong affinity for the textile fibers so that it was hardly used with the mordant (the vat dyes). That is the reason why we cannot find
mordant peak in the spectra of ancient textiles. TOF-SIMS technique is a valuable analytical tool to distinguish the ancient dyed textiles. 4. Conclusions High resolution TOF-SIMS is a powerful technique for structural characterization of dyes. TOF-SIMS spectra of textiles dyed with various plant extracts were obtained in the mass range m/z 0– 1000. Molecular ions and fragment ions from the organic
1036
Y. Lee et al. / Applied Surface Science 255 (2008) 1033–1036
component of dyes were observed as well as elemental ions from the mordants. And two ancient textiles were also analyzed and their results showed the presence of indigo. TOF-SIMS is a useful analytical technique for archaeological research. Minimal sample size and preparation make it ideal for the analysis of small and precious samples. And the applications made in this work have clearly demonstrated the advantages that this technique can provide in the study of our past. Acknowledgment This work was supported by the National Research Institute of Cultural Heritage R&D Program.
References [1] H. Schweppe, Practical Hints on Dyeing with Natural Dyes, Smithsonian Institution, Washington, DC, 1986. [2] J. Wouter, A. Verhecken, J. Soc. Dyers Color. 107 (1991) 266. [3] B. Guineau, Stud. Conserv. 34 (1989) 38. [4] J.B. Lambert, C.D. McLaughlin, Archaeometry 18 (1976) 169. [5] L.J. Cline Love, L. Soto, B.T. Reagor, Appl. Spectrosc. 34 (1980) 131. [6] J.B. Lambert, C.D. McLaughlin, C.E. Shawl, L. Xue, Anal. Chem. 4 (1999) 614A. [7] G. Spoto, E. Ciliberto (Eds.), Mordern Analytical Methods in Art and Archaeology, Wiley, New York, 2000, pp. 363–404. [8] L. Van Vaeck, A. Adriaens, R. Gijbels, Mass Spectrosc. Rev. 18 (1999) 1. [9] B. Hagenhoff, Mikrochim. Acta 132 (2000) 259. [10] I.M. Kempson, W.M. Skinner, P.K. Kirkbride, A.J. Nelson, R.R. Martin, Eur. J. Mass Spectrom. 9 (2003) 589. [11] C.K. Koh Choo, Y.E. Lee, Color. Technol. 118 (2002) 35.