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Some Non-Destructive and Micro-Analytical Methods for the

Conservation on Textiles from Cultural Heritage

Recep KARADAG

Marmara University, Fine of Art Faculty, Natural Dyes Laboratory, Istanbul-Turkey.

Abstract: Since the history of mankind, put on or cover oneself is one of the basic needs. For this, various

fibres of textiles were used for examples linen, cotton, wool, silk, mohair, etc. In this present paper, non-

destructive and micro analytical methods were investigated for conservation of the historical and

archaeological textiles that they are received until recent years. Identification of an art object material of

cultural heritage had received significant attention, because of its importance for the development of

appropriate restoration and conservation strategies.

Keywords: Cultural heritage, conservation, HPLC-PDA, SEM-EDX, natural dyes.

Introduction

Since pre-historical times, mankind has searched for materials for colouring skin, painting and for dyeing

(CARDON, 2003). For dyeing purposes, organic dyes of vegetal and animal origin were employed through

human history (HOFENK DE GRAAFF, 2004). Before the 19th century, textiles were dyed with natural

dyestuffs that were largely of plant or insect origin (SUROWIEC et al., 2006).

Natural dyes are obtained from plants (buckthorn, weld, madder, hemp, etc.), insects (cochineal, Ararat

kermes, etc.), and molluscs Hexaplex trunculus (Murex trunculus), Murex brandaris (Bolinus brandaris), etc.)

(KARAPANAGIOTIS et al., 2006; ROSENBERG, 2008).

Throughout history, cochineal (Dactylopius coccus Costa) was used to obtain red colour (HOFENK DE

GRAAFF, 2004). The cochineal insect contains 10–12 % carminic acid, but it also contains traces of

kermesic acid, flavokermesic acid and an unknown component (KARADAG, 2007; MAGUREGUI et al.,

2007). This dyestuff is a natural colorant that can be obtained from the dried bodies of female scale insect

species, Dactylopius coccus Costa (DEVEOGLU et al., 2011; MIKROPOULOU et al., 2009). Weld (Reseda

luteola L.) was the main source of yellow dyestuff in Europe. The main flavonoid components are luteolin,

apigenin (DEVEOGLU et al., 2012; WOUTERS and ROSARIO-CHIRINOS, 1992) and a minor compound

chrysoeriol in Reseda luteola L. (PEGGIE et al., 2008). Weld and woad (Isatis tinctoria L.) were used in 1st

century Masada textiles, 3rd century Palmyra textiles, 13th century Seljuk carpets and 15th – 20th century

Ottoman textiles for yellow and green colours (KARADAG, 2007). The primary Ottoman source of blue colour

was indigo from Indigofera tinctoria L. (BECHTOLD and MUSSAK, 2009). The acorn caps of Quercus

ithaburensis Decaisne were used for obtaining the black dye in the Ottoman textiles (KARADAG, 2007). The

acorn caps of the plant contain tannin compounds up to 35% (DEVEOGLU et al., 2010).

Although historically, thin-layer chromatography (TLC) had been used (KARADAG and DOLEN, 2007;

KARADAG and DOLEN, 1997, KARAPANAGIOTIS et al., 2008), nowadays, it has been replaced almost

International Conference on Cultural Heritage and New Technologies | Vienna | 2014

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entirely by high performance liquid chromatography (HPLC) combined with spectrophotometric UV-Vis

detection (KARAPANAGIOTIS et al., 2008; KARADAG et al., 2010). In 2003, Trojanowicz et al. determined

natural dyes occurring in historical Coptic textiles by high-performance liquid chromatography with UV–Vis

and mass spectrometric detection (SZOSTEK et al., 2003). In the same year, Cristea et al. reported a study

on HPLC analysis of the main flavonoids present in Reseda luteola L. (CRISTEA et al., 2003). In 2005,

Karapanagiotis and Chryssoulakis identified red natural dyes used in historical objects by HPLC-DAD-MS

(KARAPANAGIOTIS and CHRYSSOULAKIS, 2006). In 2011, Yurdun et al. reported on the determination of

natural yellow, blue, green and black dyes in some 16th– 17th century Ottoman silk and wool textiles using

HPLC with diode array detection (YURDUN et al., 2011). Textiles decorated with metals have been known

for thousands of years (ABDEL-KAREEM and Al-SAAD, 2007).

In Europe, metal threads or metallic yarns had been used for the textiles. Initially, thin wires of solid gold,

silver, or gilt silver were used (MUROS et al., 2007). The metal threads can inhibit microbial growth if they

contain heavy metals and especially if they contain copper (KAVKLER et al., 2011). Metal strips wound

around a silk or cotton core constitute the typical structure of metal threads. Metal strips can be made of pure

gold, gold alloyed with silver, gilded or gild-silvered copper and gold-like copper alloys (ENGUITA et al.,

2002). Relevant studies were published on the morphology of degraded archaeological textiles,

characterised by means of scanning electron microscopy (SEM) equipped with an energy dispersive X-ray

spectrometer (EDS) (GOLDSTEIN et al., 2008).

The scientific examination of textile materials contains a number of stages: first, the structure of the textile

itself; second, the structure of the yarns that make up the textile; third, the nature of the fibres that were used

for the yarns; and, fourth, the dyestuffs or pigments that may have been used as colorants, as well as the

mordant used with the dyestuffs. The first two stages require similar equipment and techniques; the third and

fourth stages require different equipment and procedures, necessitate other specialists, and depend for their

success at least partially on the availability of comparative material (KING, 1978). Characterization of metal

threads on historical textile materials is important for preservation of valuable cultural heritage. Corrosion is

one of the most important detrimental effects of air pollutants on cultural heritages (FERM et al., 2006).

The CIEL*a*b* (1976)-system was introduced to describe colour as a result of these three factors. This

system is a three-dimensional space, with coordinate axes L*, a* and b*. L* denotes the brightness of the

colour (L*=0: black, L*=100: white), a* represents the green-red axis (a* negative: green, a* positive: red)

and b* represents the blue-yellow axis (b* negative: blue, b* positive: yellow). Each colour can be

represented as a set of values for L*, a* and b*, and consequently as a point in this colour space (KRIKKEN,

2008).

In this study, some non-desctructive and micro analytical methods will be investigated for conservation of the

historical and archaeological textiles.

Material and Methods

Reagents

All the chemicals were of HPLC gradient from Merck (Darmstadt, Germany). Ultrapure water from

Elga/Purelab Option-Q7BP system with conductivity of 18 MΩ/cm was used in all experiments. Acetonitrile,

Karadag – Some Non-Destructive and Micro-Analytical Methods

3

trifluoro asetic acid, hydrochloric acid, methanol and dimethyl sulfoxide (DMSO) were obtained from Merck

(Darmstadt, Germany). Standard solutions were prepared in methanol from luteolin, genistein, carminic acid

and flavokermesic acid.

HPLC Analysis

HPLC Instrumentation

Chromatographic measurements were carried out using an Agilent 1200 series system (Agilent

Technologies, Hewlett-Packard, Germany) including G1322A Degasser, G1311A Quat pump, G1329A

autosample, G13166 TCC, and G1315D Diode Array Detector. PDA detection is performed by scanning from

191 to 799 nm with a resolution of 2 nm, and the chromatographic peaks were monitored at 255, 268, 276,

350, 491, 520, 580 and 620 nm. Column: A Nova Pak C18 analytical column (39×150 mm, 4 µm, Part No

WAT 086344, Waters) was used. Analytical and guard columns were maintained at 30°C and data station

was the Agilent Chemstation. Two solvents were utilized for chromatographic separations of the hydrolysed

samples. Solvent A: H2O- 0.1% TFA and solvent B: CH3CN- 0.1 % TFA. The flow rate was 0.5 ml/min. and

following elution program was applied in Table 1.

Time (min.) Flow rate (ml/min.) H2O- 0.1% TFA (v/v) CH3CN- 0.1 % TFA (v/v)

0.0 0.5 95 5 1.0 0.5 95 5 20 0.5 70 30 25 0.5 40 60 28 0.5 40 60 33 0.5 5 95 35 0.5 5 95 40 0.5 95 5 45 0.5 95 5

Tab. 1 – HPLC analysis is performed using the following gradient elution.

Extraction Procedure for HPLC Analysis of Historical and Archaeological Textiles

The extraction of historical and archaeological textiles samples were performed with a solution mixture of

%37HCl:MeOH:H2O; 2:1:1; v/v/v) for 8 minutes at 100 oC in open small tubes to extract dyestuffs. After

cooling under running cold tap water, the solution was evaporated just to dryness in a water bath at 65 oC

under a gently stream of nitrogen. The dry residue was dissolved in 200 µl of the mixture of MeOH:H2O (2:1;

v/v) or 200 µl DMSO and was centrifuged at 4000 rpm for 10 min. 50 to 100 µl supernatant was injected into

the HPLC apparatus. In this work, samples belong to two different art object were analysed by HPLC-PDA

(Figs. 4,5).

Colour Measurements of Historical Textiles and Reproduced Silk Brocades

L*, a* and b* values for historical and archaeological textiles were measured with Konica Minolta CM-2300d

Software Spectra Magic NX (6500 K, 45o). CIELAB colour difference, between any two colours in CIE

space, is the distance between the colour locations. This distance can be expressed as delta E (∆E*). ∆L* =

the liqhtness difference, ∆a* = the red/green difference and ∆b* = the yellow/blue difference.


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2*2*2** )()()( baLE ∆+∆+∆=∆

CIELAB graphs and L*, a*, b* values belong to samples were shown in Figs. 8.

SEM-EDX Analysis

Characterization of metal threads on historical textiles is important for preservation of valuable cultural

heritage. The SEM with EDS analysis is non-destructive and capable of offering precise elemental

composition information towards the characterization of metal samples in the historical textiles (Table 2). The

analysis of the composition is mainly aiming to identify the techniques involved in their manufacture. In this

work the samples were investigated using a TESCAN VEGA3 EasyProbe Scanning Electron Microscope

(SEM) equipped with Energy Dispersion Spectroscopy (EDX with detector Bruker 410-M, software: Esprit

1.9). The electron microscope image was shown in Fig. 6.

Technical Analysis

Optical microscope is used for yarn or fibre characterization of historical and archaeological textiles. In this

study the historical samples were investigated using a OLYMPUS SZ61 (SZ2-ILST, camera C18U). Weft

and warp density, yarn spinning twist and technical of weaving were detected of the historical textiles for

restoration and conservation. The microscope images were shown in Fig. 7.

Result

Historical textiles in museums are exposed to many challenges such as humidity, changing temperature,

effect of light, effect of air pollution, non-standard storage and display methods.

Identifying the weaving structure, color value, twist and spinning of yarns, chemical compositions of metal

threads, dyestuffs and dye resources of the art objects need to know for accurate and non-destructive

restoration, conservation and cleaning methods.

In this work, HPLC-PDA is used for dyestuff analysis in the historical and archaeological textiles that is the

most widely used and preferred analytical method. The most important dyestuffs were detected natural dyes

luteolin, genistein, carminic acid, flavokermesic acid, etc. dyes which are found in historical textiles (Figure

4,5). One of the most useful procedures for fast and simple determination of specific metals of interest is

scanning electron microscopy (SEM) equipped with an EDX detector. This is a simple method which

provides information on chemical composition of sample surfaces and chemical analysis of metals threads

(Table 2). Colour values (L*, a* and b*) of textile art objects are measured using the CIEL*a*b* system

(Figure 8). Optical microscope is used for yarn or fibre characterization of historical textiles. It is very

important that the historical textile was weaved which kind of yarn (Fig. 7).

In this paper, samples from historical textile objects (Figure 1-3) were provided from Topkapi Palace

Museum collection.


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Fig. 1 – Printed silk caftan-Inventory Number 13/198 (#ltop overview, #bottom detail).


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Fig. 2 –Velvet ceremonial caftan-Inventory Number 13/264 (#top overview, #bottom detail).


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Fig. 3 – Silk brocade caftan-Inventory Number 13/266 (#top overview, #bottom detail).


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Fig. 4 – (a) HPLC chromatograms of velvet yellow sample in the historical art object (Inventory number 13/264). (b) spectra of sample

together with luteolin standard. (c) spectra of sample together with genistein standard.

Fig. 5 – (d) HPLC chromatograms of red sample in the historical art object (Inventory number 13/266). (e) spectra of sample together

with carminic acid standard. (f) spectra of sample together with flav stokermesic acid standard.


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Fig. 6 – The SEM- EDX image of metal thread sample (Inventory number 13/198).

Tab. 2 – The elemental analysis results of metal thread sample (Inventory number 13/198).

Fig. 7 – The microscope images of historical textile (Inventory number 13/266).

Identified Elements Wt%

C 6.11

O 3.28

Mg 1.16

Cl 5.33

Ca 0.10

Ag 76.84

Au 7.18


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(1)

(2)

(3)

Fig. 8 – The CIEL*a*b graphs of historical art objects (1-13/198, 2-13/264, 3-13/266).

Conclusion

Until the second half of the 19th century, archaeological and historical textiles were dyed with natural dye

sources. Historical textiles used for clothing were made silk, velvet, cotton and linen. Textiles were crafted

either with gold, silver threads or with both gold and silver threads. These textiles often represent the highest

form of cultural, artistic and socio-economic discoveries of their time periods. For this reason, conservation

and restoration of textiles are very important in the pass on to future generations. Characterization of textiles

ground blue

orange

13/198 Graph of L*, a*, b*

Ground cream colour

Green

13/264 Graph of L*,a*,b*

red

Metal thread yellow

green

13/266 Graph of L*, a*, b*


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(colour, dyestuff, yarn, metal threads) on historical textile materials is important for preservation of valuable

cultural heritage. Obtained results dictate decisions on cleaning, conservation and restoration steps.

The most important part of characterization is chemical analysis of originally applied materials, since this

enables understanding the nature of chemical and physical degradation and helps to determine the proper

cleaning methods.

Archaeological and historical textiles in museums are exposed to many challenges such as humidity,

changing temperature, effect of light, effect of air pollution, non- standard storage and display methods. All

these factors cause damage and decay in both fibres and threads which results in stain, dust and weakness

in separate parts. In this work many different yarn fibres and metal strips were characterized with different

techniques.

Accurate identification of materials in historical textiles (brocades, carpet, kilim, velvet, etc.) is necessary for

proper restoration and preservation of textile material culture, and for good restoration of old textiles.

Acknowledgements

Turkish Cultural Foundation (TCF) and Armaggan company are gratefully acknowledged

(www.turkishculturalfoundation.org ; www.tcfdatu.org ; www.armaggan.com ).

References ABDEL-KAREEM, O., AL-SAAD, Z., (2007), Conservation Strategy of Metal Embroidery Threads in Textile Objects in Museum of

Jordanian Heritage, the CSSIM / ICOM-LIC Meeting, Cairo 23.

BECHTOLD, T., MUSSAK, R., (2009). Handbook of Natural Colorants, John Wiley & Sons Ltd.

BORGES, M.E., TEJERA , R.L., DÍAZ, L., ESPARZA, P., IBÁÑEZ, E., (2011). Natural dyes extraction from cochineal (Dactylopius

coccus). New extraction methods, J Food Chem.

CARDON, D. (2003), Le Monde des Teintures Naturelles (Paris: Editeur).

CRİSTEA, D., BAREAU, I., VİLAREM, G., (2003). Identification and quantitative HPLC analysis of the main flavonoids present in weld

(Reseda luteola L.), Dyes Pigments 57, 267-272.

DEVEOGLU, O., TORGAN, E. & KARADAG, R. (2010), “ Identification of dyestuffs in the natural pigments produced with Al3+, Fe2+

and Sn2+ mordant metals from cochineal (Dactylopius coccus Costa) and walloon oak (Quercus ithaburensis Decaisne) by HPLC-

DAD”, Asian Journal of Chemistry , vol. 22, no. 9, pp. 7021-7030.

DEVEOGLU, O., KARADAG, R., YURDUN, T., (2011). Qualitative Hplc Determination of Main Anthraquinone and Lake Pigment

Contents from Dactylopius Coccus Dye Insect, Chem Nat Compd+ 47, 103-104.

DEVEOGLU, O., CAKMAKCI, E., TASKOPRU, T., TORGAN, E. AND KARADAG, R. (2012), “Identification by RP-HPLC-DAD, FTIR,

TGA and FESEM-EDAX of natural pigments prepared from Datisca cannabina L.”, Dyes Pigm., Vol. 94 No. 3, pp. 437-442.

ENGUİTA, O., CLİMENT-FONT, A., GARCİA, G., MONTERO, I., FEDİ, M.E., CHİARİ, M., LUCARELLİ, F., (2002). Characterization of

metal threads using differential PIXE analysis, Nucl Instrum Meth B 189, 328-333.

FERM, M., WATT, J., O'HANLON, S., DE SANTİS, F., VAROTSOS, C., (2006). Deposition measurement of particulate matter in

connection with corrosion studies, Anal Bioanal Chem 384, 1320-1330.

GOLDSTEİN, J.I. NEWBURY, D.E. JOY, D.C. LYMAN, C.E. ECHLİN, P. LİFSHİP, L.C.E. SAWYER AND J.R. MİCHAEL, (2003).

Scanning Electron Microscopy and X- ray Microanalysis, 3rd Edn, Kluwer Academic / Plenum, New York.


12

HOFENK DE GRAAFF, J.H., (2004). The colourful past : the origins, chemistry and identification of natural dyestuffs.

KARADAG, R. & DOLEN, E. (1997), “Examination of historical textiles with dyestuffs analyses by TLC and derivative spectrophometry”,

Turk J. Chem, vol.21, no.2, pp. 126-133.

KARADAG, R., (2007). Dogal Boyamacilik, , T.C. Kultur ve Turizm Bakanligi, Ankara.

KARADAG, R. & DOLEN, E. (2007), “Re-examination of Turkey red”, Ann. Chim., vol. 97, no. 7, pp. 583-589.

KARADAG, R., TORGAN, E. & YURDUN, T. (2010), “Formation and HPLC analysis of the natural lake pigment obtained from madder

(Rubia tinctorum L.)”, Rewiews in Analytical Chemistry, vol. 29, no. 1, pp. 1-12.

KARAPANAGİOTİS, I., CHRYSSOULAKİS, Y., ( 2006). Investigation of red natural dyes used in historical objects by HPLC-DAD-MS,

Ann Chim-Rome 96, 75-84.

KARAPANAGİOTİS, I., LAKKA, A., VALİANOU, L., CHRYSSOULAKİS, Y., (2008). High-performance liquid chromatographic

determination of colouring matters in historical garments from the Holy Mountain of Athos, Microchim Acta 160, 477-483.

KAVKLER, K., GUNDE-CİMERMAN, N., ZALAR, P., DEMŠAR, A., (2011). FTIR spectroscopy of biodegraded historical textiles,

Polymer Degradation and Stability 96, 574-580.

KRİKKEN, J.B., ZİJP, J.R. & HUYSMANS, M.C. (2008), “Monitoring dental erosion by colour measurement: an in vitro study”, Journal of

Dentistry, vol. 36, no. 9, pp. 731-735.

MAGUREGUİ, M.I., ALONSO, R.M., BARANDİARAN, M., JİMENEZ, R.M., GARCİA, N., (2007). Micellar electrokinetic chromatography

method for the determination of several natural red dyestuff and lake pigments used in art work, Journal of chromatography. A 1154,

429-436.

MIKROPOULOU, E., TSATSARONI, E., VARELLA, E.A., (2009). Revival of traditional European dyeing techniques yellow and red

colorants, J Cult Herit 10, 447-457.

MUROS, V., WÄRMLÄNDER, S.K.T.S., SCOTT, D.A., THEİLE, J.M., (2007). Characterization of 17th-19th Century Metal Threads from

the Colonial Andes, Journal of the American Institute for Conservation 46, 229-244.

PEGGİE, D.A., HULME A.N., MCNAB, H., QUYE A., (2008). Towards the identification of characteristic minor components from textiles

dyed with weld (Reseda luteola L.) and those dyed with Mexican cochineal (Dactylopius coccus Costa), Microchim Acta, 162: 371-380.

ROSENBERG, E. (2008). Anal. Bioanal. Chem., 391, 42.

SUROWİEC, I., QUYE, A. & TROJANOWİCZ, M. (2006), “Liquid chromatography determination of natural dyes in extracts from

historical Scottish textiles excavated from peat bogs”, Journal of Chromatography A, vol. 1112, no. 1-2, pp. 209-217.

SZOSTEK, B., ORSKA-GAWRYS, J., SUROWİEC, I., TROJANOWİCZ, M., (2003). Investigation of natural dyes occurring in historical

Coptic textiles by high-performance liquid chromatography with UV-Vis and mass spectrometric detection, Journal of chromatography. A

1012, 179-192.

WOUTERS, J., ROSARİO-CHİRİNOS, N., (1992). Dye Analysis of Pre-Columbian Peruvian Textiles with High-Performance Liquid

Chromatography and Diode-Array Detection, Journal of the American Institute for Conservation 31, 237-255.

YURDUN, T., KARADAG, R., DOLEN, E., MUBARAK, M.S., (2011). Identification of natural yellow, blue, green and black dyes in 15th -

17th centuries Ottoman silk and wool textiles by HPLC with diode array detection, Rev Anal Chem 30, 153-164.

Imprint:

Proceedings of the 19th International Conference on Cultural Heritage and New Technologies 2014 (CHNT 19, 2014)

Vienna 2015

http://www.chnt.at/proceedings-chnt-19/

ISBN 978-3-200-04167-7

Editor/Publisher: Museen der Stadt Wien – Stadtarchäologie

Editorial Team: Wolfgang Börner, Susanne Uhlirz

The editor’s office is not responsible for the linguistic correctness of the manuscripts.

Authors are responsible for the contents and copyrights of the illustrations/photographs.

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