1. 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)

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

3. 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)

4. 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.

5. 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: 900-4000 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

6. Eu-ARTECH A. Exciting light source: 175 W Xenon lamp, 240-650 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 (200-1100 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

7. Eu-ARTECH 1. weld lakes

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

9. Eu-ARTECH mid FTIR: the mordant

10. Eu-ARTECH

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

12. Eu-ARTECH UV-vis absorption: the colour

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

14. Eu-ARTECH 3D UV-vis fluorescence: the lake Exc. 250-400 nm

15. Eu-ARTECH weld1 weld2 weld3 550 525 3D UV-vis fluorescence: the lake

16. Eu-ARTECH UV-vis fluorescence: the lake

17. Eu-ARTECH mordant max abs max fluo Weld lake 1CO 3 -- KAl(SO 4 ) 2 420 (655)550 (663) Weld lake 2KAl(SO 4 ) 2 CO 3 -- 411 (668)550 (675) Weld lake 3Ca & K411525 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, 231-237, 1983 Summary

18. Eu-ARTECH 1. textiles

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

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

21. Eu-ARTECH mid FTIR: the textile

22. Eu-ARTECH UV-vis absorption: the colour

23. Eu-ARTECH

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

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

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

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

28. Eu-ARTECH dyed wool Bath 1 Exc. 250-390 Exc. 450-560

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

30. Eu-ARTECH dyed wool bath 2 Exc. 250-390 Exc. 450-560

31. Eu-ARTECH mordant max abs max fluo wool 1Ca & K 430 (665)550 (675) wool 2Ca 385512 (675) silk 3Ca & K 408 (666)(536) 675 (720) silk4Ca 373(507) 675 (720) Summary

32. Eu-ARTECH UV-vis fluorescence: the lake

33. Eu-ARTECH