Eu-ARTECH Spectroscopic Techniques for in situ non invasive Study of Natural Dyestuffs Costanza Miliani Centre of Excellence SMAArt University of Perugia, Italy CNR – ISTM (Institute of Molecular Sciences and Technologies)

Eu-ARTECH Catia Clementi, PhD student Brenda Doherty, PhD student Alessandro Sassolini, fellowship

Eu-ARTECH How to study in situ natural dyestuffs ? 1.XRF : elemental analysis of mordents and chelation ions 2.FTIR : molecular analysis of mordents and chelant 3.UV-vis abs : color characterization 4.UV-vis fluo : dye characterization MOLAB equipments and lab spectrofluorimeter (Varian)

Eu-ARTECH I. Non invasive portable equipments: x-ray fluorescence The X-ray fluorescence portable equipment for in situ measurements, is made up by: 1. open beam X-ray generator (W target, excitation energy L  =9.671 keV); 2. non-cryogenic silicon drift detector SDD having resolution of 130 eV at 5.9 keV.

Eu-ARTECH I. Non invasive portable equipments: fiber optic mid-FTIR it is easily portable: weight ~35 Kg volume 50x50x50 cm 3 portable JASCO VIR 9500 spectophotometer: Midac Illuminator IR radiation source Michelson interferometer liquid nitrogen cooled MCT Remspec mid-IR fiber optic sampling probe: 19 chalcogenide glass fibers spectral range: cm -1 best S/N from 900 to 2000 cm –1 abs of Se-H between 2050 and 2250 cm -1 optical layout: 0°/0° geometry probe surface distance 2-5 mm

Eu-ARTECH A. Exciting light source: 175 W Xenon lamp, nm emission. B. H-10 Jobin Yvon UV monochromator for selecting the excitation wavelength. C. Quartz fibre-optic Y cable D. CCD spectrometer Avantes AvaSpec-2048 pixels ( nm) of high sensitivity (86 photons/counting). E. Optical filters (interference and cut-on filter) are used to cut-off 2 nd order scatter and stray light. I. Non invasive portable equipments: UV-vis fluorescence

Eu-ARTECH 1. weld lakes

Eu-ARTECH W1: Ca, W2: Ca, W3: Ca & K XRF: the mordant

Eu-ARTECH mid FTIR: the mordant

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Eu-ARTECH 5160 mid FTIR: the mordant OH comb. band

Eu-ARTECH UV-vis absorption: the colour

Eu-ARTECH Normalized emission spectra of weld lakes (exc:366 nm) UV-vis fluorescence: the lake

Eu-ARTECH 3D UV-vis fluorescence: the lake Exc nm

Eu-ARTECH weld1 weld2 weld D UV-vis fluorescence: the lake

Eu-ARTECH UV-vis fluorescence: the lake

Eu-ARTECH mordant max abs max fluo Weld lake 1CO 3 -- KAl(SO 4 ) (655)550 (663) Weld lake 2KAl(SO 4 ) 2 CO (668)550 (675) Weld lake 3Ca & K Complex luteolin:Al max fluo = 540 nm Complex apigenin:Al max fluo = 523 nm Complex luteolin:Mg max fluo = 520 nm O.S. Wolfbeis et al. Z. Naturforsc 39b, , 1983 Summary

Eu-ARTECH 1. textiles

Eu-ARTECH SulphurPotassiumCalcium Untreated silk  Mordanted silk Dyed silk - 1  Dyed silk - 2  XRF: the mordant

Eu-ARTECH SulphurPotassiumCalcium Untreated wool  Washed wool  Mordanted wool  Dyed wool - 1  Dyed wool - 2  XRF: the mordant

Eu-ARTECH mid FTIR: the textile

Eu-ARTECH UV-vis absorption: the colour

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Eu-ARTECH UV-vis fluorescence: wavelenght effect (bath 4)

Eu-ARTECH UV-vis fluorescence: dyed Silk bath effect

Eu-ARTECH 3D UV-vis fluorescence: dyed Silk Bath 3 Bath 4

Eu-ARTECH UV-vis fluorescence: dyed wool bath 1

Eu-ARTECH dyed wool Bath 1 Exc Exc

Eu-ARTECH UV-vis fluorescence: dyed wool bath 2

Eu-ARTECH dyed wool bath 2 Exc Exc

Eu-ARTECH mordant max abs max fluo wool 1Ca & K 430 (665)550 (675) wool 2Ca (675) silk 3Ca & K 408 (666)(536) 675 (720) silk4Ca 373(507) 675 (720) Summary

Eu-ARTECH UV-vis fluorescence: the lake

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