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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
How to study in situ natural dyestuffs ?
Eu-ARTECH
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)
I. Non invasive portable equipments: x-ray fluorescence
Eu-ARTECH
The
X-ray
fluorescence
portable
equipment for in situ measurements, is
made up by:
1. open beam X-ray generator (W target,
excitation energy Lb=9.671 keV);
2. non-cryogenic silicon drift detector SDD
having resolution of 130 eV at 5.9 keV.
I. Non invasive portable equipments: fiber optic mid-FTIR
Eu-ARTECH
portable JASCO VIR 9500 spectophotometer:
Midac Illuminator IR radiation source
Michelson interferometer
liquid nitrogen cooled MCT
it is easily portable:
weight ~35 Kg
volume 50x50x50 cm3
Remspec mid-IR fiber optic sampling probe:
best S/N from 900 to 2000 cm–1
abs of Se-H between 2050 and 2250 cm-1
optical layout:
0°/0° geometry
2.4
2.2
absorbance (a.u.)
spectral range: 900-4000 cm-1
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
500
probe surface distance 2-5 mm
2180 cm
19 chalcogenide glass fibers
-1
2.6
1000
1500
2000
2500
3000
-1
wavenumber (cm )
3500
4000
I. Non invasive portable equipments: UV-vis fluorescence
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 2nd
order scatter and stray light.
Eu-ARTECH
1. weld lakes
XRF: the mordant
Eu-ARTECH
Weld 1
Weld 2
Weld 3
Ca (K)
2000
1500
Counts
Counts
Argon
1000
Ca
K
Ca (Kb)
500
Argon
Channels
0
Channels
W1: Ca, W2: Ca, W3: Ca & K
mid FTIR: the mordant
Eu-ARTECH
Weld 1
allum
carbonate
2.0
Log 1/R
1.5
1.0
0.5
0.0
1000
2000
3000
4000
5000
-1
wavenumber ( cm )
6000
mid FTIR: the mordant
Eu-ARTECH
Weld 2
allum
carbonate
2.0
Log 1/R
1.5
1.0
0.5
0.0
1000
2000
3000
4000
5000
-1
wavenumber ( cm )
6000
mid FTIR: the mordant
Eu-ARTECH
Weld 3
1.0
5160
Log 1/R
OH comb. band
0.5
0.0
1000
2000
3000
4000
5000
-1
wavenumber ( cm )
6000
UV-vis absorption: the colour
Eu-ARTECH
420
0.8
0.6
Weld 1
Weld 2
Weld 3
290
411
655
Absorbance / a.u.
Absorbance / a.u.
1.0
668
0.4
0.2
500
550
600
650
 / nm
0.0
200
300
400
500
 / nm
600
700
800
700
750
800
Eu-ARTECH
UV-vis fluorescence: the lake
Lake type 1 (Int / 1)
Lake type 2 (Int / 1.2)
Lake type 3 (Int / 3.4)
Emission Intensity / a.u.
525 550
663
450
500
550
600
650
675
700
750
800
 / nm
Normalized emission spectra of weld lakes (exc:366 nm)
Eu-ARTECH
3D UV-vis fluorescence: the lake
Exc. 250-400 nm
3D UV-vis fluorescence: the lake
545.07 , 173.539
Eu-ARTECH
1 6 7 .1 1
3 7 5 .0 0
550
150
1 5 4 .3 1
1 4 1 .5 0
1 2 8 .7 0
1 1 5 .8 9
100
3 9 0
Intensity (a.u.)
3 5 0 .0 0
1 0 3 .0 9
3 2 5 .0 0
9 0 .2 9
7 7 .4 8
3 0 0 .0 0
50
6 4 .6 8
5 1 .8 7
3 9 .0 7
2 7 5 .0 0
2 5 0 .0 0
500
4 5 0 .0 0
5 0 0 .0 0
5 5 0 .0 0
800
3 9 0
600
6 0 0 Wavelength
.0 0
6 5 0 . 0 0(nm)
W a v e le n g t h ( n m )
8000 . 6 6
700
7 0 0 .0 0
7 5 0 .0 0
8 0 0 .0 0
51 63 26 . 71 69
525
3 7 5 .0 0
Intensity (a.u.)
Intensity (a.u.)
1 3 .4 6
524.02 , 584.351
1000
150
547.01 , 141.344
2 6 .2 7
0
3 5 0 .0 0
51 12 95 . 79 80
41 71 65 . 76 91
41 30 35 . 83 02
100
600
39 95 0. 0. 83 1
38 4 7. 7. 84 3
3 2 5 .0 0
37 04 4. 4. 85 4
3 0 0 .0 0
400
50
26 64 1. 1. 86 5
25 13 8. 8. 86 6
14 73 5. 5. 87 8
200
13 3 2. 2. 8 9
2 7 5 .0 0
82 92 . 9 09
0
2 5 0 .0 0
weld1
41 62 . 97 20
0
500
500
4 5 0 .0 0
5 0 0 .0 0
5 5 0 .0 0
600
600
6 0 0 . 0Wavelength
0
6 5 0 . 0 0 (nm)
Wavelength
(nm) 7 0 0 . 0 0
W a v e le n g t h ( n m )
80032 . 94 31
700
700
7 5 0 .0 0
8 0 0 .0 0
weld2
weld3
Eu-ARTECH
UV-vis fluorescence: the lake
Excitation spectra of weld lake 1 and 3 (Varian)
666
lake 1 em= 720 nm
lake 3 em= 720 nm
Emission Intensity / a.u.
200
0
400
500
600
 / nm
700
Eu-ARTECH
Summary
mordant
Weld lake 1 CO3-KAl(SO4)2
Weld lake 2 KAl(SO4)2
CO3-Weld lake 3 Ca & K
Complex luteolin:Al
max abs
max fluo
420 (655)
550 (663)
411 (668)
550 (675)
411
525
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
Eu-ARTECH
1. textiles
Eu-ARTECH
XRF: the mordant
Sulphur
Untreated silk
Potassium

Calcium

Mordanted silk
Dyed silk - 1
Dyed silk - 2



Eu-ARTECH
XRF: the mordant
Sulphur
Untreated wool

Washed wool

Mordanted wool

Dyed wool - 1

Dyed wool - 2

Potassium
Calcium






mid FTIR: the textile
Eu-ARTECH
2.0
1.8
silk
wool
1.6
log(1/R)
1.4
1.2
1.0
0.8
0.6
0.4
0
1000
2000
3000
4000
5000
-1
wavenumber (cm )
6000
7000
UV-vis absorption: the colour
Eu-ARTECH
Absorption spectra of silk
1.2
373
408
1: untreated silk
4: mordanted silk
8: dyed silk (bath 3)
9: dyed silk (bath 4)
332
Absorbance / a.u.
1.0
0.8
0.6
0.4
666
0.2
0.0
200
300
400
500
 / nm
600
700
800
UV-vis absorption: the colour
Eu-ARTECH
Absorption spectra of wool samples
1.6
385
1.4
430
2: untreated wool
3: washed wool
5: mortanted wool
6: dyed wool (dye bath 1)
7: dyed wool (dye bath 2)
Absorbance / a.u.
1.2
1.0
0.8
0.6
665
0.4
0.2
0.0
200
300
400
500
 / nm
600
700
800
UV-vis
Eu-ARTECH
fluorescence: wavelenght effect (bath 4)
Normalized emission spectra of dyed silk (sample 8)
at different excitation wavelenghth
1.4
1.2
exc: 280 nm
675
exc: 390 nm
519 536
intensity
1.0
0.8
0.6
720
0.4
0.2
0.0
400
500
600
700
-1
wavenumber (cm )
800
Eu-ARTECHUV-vis
fluorescence: dyed Silk bath effect
Emission spectra of dyed silk ( exc: 390 nm)
1.6
675
bath 3
bath 4
1.4
intensity (a.u.)
1.2
507
1.0
535
0.8
0.6
720
0.4
0.2
0.0
450
500
550
600
650
wavelenght (nm)
700
750
800
3D UV-vis fluorescence: dyed Silk
Eu-ARTECH
3 8 7 .2 0
3 3 8 .8 0
T
3 9 0
3 6 3 .0 0
3 1 4 .6 0
2 9 0 .4 0
140
120
140
150
140
120
140
150
100
120
100
120
120
100
120
120
100
100
100
80
100
80
100
80
100
100
80
100
80
80
80
60
80
60
60
60
60
60
60
40
40
40
50
40
40
40
1 6 2 .3 2
1 5 0 .1 7
1 3 8 .0 1
1 2 5 .8 5
1 1 3 .6 9
1 0 1 .5 3
8 9 .3 7
7 7 .2 1
Bath 3
6 5 .0 5
5 2 .8 9
4 0 .7 3
20
20
20
2 8 .5 8
1 6 .4 2
2 6 6 .2 0
500
4 3 8 .6 4 0
4 6 6 .0 5 5
4 9 3 .4 7 0
5 2 0 .8 8 5
5 4 8 .3 0 0
5 7 5 .7 1 5
600
Wavelength (nm)
6 0 3 .1 3 0
6 3 0 .5 4 5
6 5 7 .9 6 0
8004 . 2 6
700
6 8 5 .3 7 5
7 1 2 .7 9 0
7 4 0 .2 0 5
7 6 7 .6 2 0
7 9 5 .0 3 5
W a v e le n g t h ( n m )
3 9 0 .0 0
3 8 0 .0 0
3 7 0 .0 0
3 5 0 .0 0
3 4 0 .0 0
3 9 0
Intensity (a.u.)
Intensity (a.u.)
3 6 0 .0 0
3 3 0 .0 0
3 2 0 .0 0
3 1 0 .0 0
3 0 0 .0 0
2 9 0 .0 0
2 8 0 .0 0
2 7 0 .0 0
70
80
70
100
70
70
140
70
60
70
60
60
60
60
60
120
60
80
60
50
60
50
50
50
50
100
50
50
40
60
40
40
40
80
40
40
40
30
30
30
60
30
40
1 4 8 .7 5
1 3 7 .6 5
1 2 6 .5 5
1 1 5 .4 5
1 0 4 .3 6
9 3 .2 6
8 2 .1 6
7 1 .0 6
5 9 .9 6
40
20
20
20
20
20
10
4 8 .8 6
3 7 .7 7
2 6 .6 7
1 5 .5 7
2 6 0 .0 0
500
4 5 0 .0 0
5 0 0 .0 0
600
5 5 0 .0 0
6 0 0 Wavelength
.0 0
6 5 0 . 0 0(nm)
W a v e le n g t h ( n m )
8004 . 4 7
700
7 0 0 .0 0
7 5 0 .0 0
8 0 0 .0 0
Bath 4
Eu-ARTECH
UV-vis fluorescence: dyed wool bath 1
Normalized emission spectra of dyed wool (sample 6)
at different excitation wavelenghth
550
1.0
560
exc: 280 nm
Emission Intensity / a.u.
exc: 366 nm
exc: 390 nm
0.8
0.6
675
0.4
0.2
0.0
400
500
600
 / nm
700
800
dyed wool Bath 1
Eu-ARTECH
3 3 8 .8 0
3 9 0
Intensity (a.u.)
Intensity (a.u.)
3 6 3 .0 0
3 1 4 .6 0
2 9 0 .4 0
60
60
50
120
120
120
100
120
80
50
40
60
100
40
100
100
80
40
60
80
30
80
30
80
40
60
30
60
60
60
40
20
20
40
20
40
40
20
20
10
10
20
10
20
20
1 3 2 .7 1
1 2 2 .5 4
1 1 2 .3 7
1 0 2 .2 0
9 2 .0 3
8 1 .8 6
7 1 .6 9
6 1 .5 2
5 1 .3 5
4 1 .1 8
3 1 .0 1
2 0 .8 4
2 6 6 .2 0
Exc. 250-390
500
4 3 8 .6 4 0
4 6 6 .0 5 5
4 9 3 .4 7 0
5 2 0 .8 8 5
5 4 8 .3 0 0
5 7 5 .7 1 5
675.00 , 212.811
3 8 7 .2 0
1 0 .6 7
600
Wavelength (nm)
6 0 3 .1 3 0
6 3 0 .5 4 5
6 5 7 .9 6 0
6 8 5 .3 7 5
8000 . 5 0
700
7 1 2 .7 9 0
7 4 0 .2 0 5
7 6 7 .6 2 0
7 9 5 .0 3 5
W a v e le n g t h ( n m )
5 5 6 .6 0
5 3 2 .4 0
4 8 4 .0 0
5 5 0
Intensity (a.u.)
Intensity (a.u.)
5 0 8 .2 0
4 5 9 .8 0
4 3 5 .6 0
4 1 1 .4 0
3 8 7 .2 0
Exc. 450-560
140
100
200
120
100
150
200
100
200
150
120
200
80
80
100
80
150
80
150
150
80
100
150
150
80
100
150
60
60
100
80
60
100
100
60
100
100
60
40
40
40
40
50
50
40
50
50
50
20
20
20
20
2 2 5 .4 6
2 0 8 .2 4
1 9 1 .0 1
1 7 3 .7 9
1 5 6 .5 6
1 3 9 .3 4
1 2 2 .1 1
1 0 4 .8 9
8 7 .6 6
7 0 .4 3
5 3 .2 1
3 5 .9 8
3 6 3 .0 0
1 8 .7 6
600
6 0 3 .1 3 0
650
6 3 0 .5 4 5
6 5 7 .9 6 0
700
6 8 5 . 3 7 5 Wavelength
7 1 2 .7 9 0
W a v e le n g t h ( n m )
8001 . 5 3
750
(nm)7 4 0 . 2 0 5
7 6 7 .6 2 0
7 9 5 .0 3 5
UV-vis fluorescence: dyed wool bath 2
Normalized emission spectra of dyed wool (sample 7)
at different excitation wavelenghth
515
1.0
Emission Intensity / a.u.
Eu-ARTECH
exc: 280 nm
exc: 366 nm
0.8
exc: 390 nm
0.6
0.4
0.2
0.0
300
400
500
600
 / nm
700
800
dyed wool bath 2
3 9 0 .0 0
Eu-ARTECH
3 8 0 .0 0
3 7 0 .0 0
3 5 0 .0 0
3 4 0 .0 0
3 9 0
Intensity (a.u.)
3 6 0 .0 0
3 3 0 .0 0
3 2 0 .0 0
3 1 0 .0 0
3 0 0 .0 0
2 9 0 .0 0
2 8 0 .0 0
250
250
300
500
250
250
200
250
300
200
250
600
150
200
400
200
200
200
150
200
150
150
300
150
200
150
400
100
150
100
100
200
100
100
100
100
200
50
50
50
100
50
50
7 4 2 .8 4
6 8 5 .9 3
6 2 9 .0 1
5 7 2 .1 0
5 1 5 .1 8
4 5 8 .2 7
4 0 1 .3 5
3 4 4 .4 4
2 8 7 .5 2
2 3 0 .6 1
1 7 3 .6 9
1 1 6 .7 8
2 7 0 .0 0
Exc. 250-390
5 9 .8 7
2 6 0 .0 0
500
4 5 0 .0 0
5 5 0 .0 0
5 2 5 .0 0
4 7 5 .0 0
5 5 0
Intensity (a.u.)
Intensity (a.u.)
5 0 0 .0 0
4 5 0 .0 0
4 2 5 .0 0
4 0 0 .0 0
Exc. 450-560
3 7 5 .0 0
5 0 0 .0 0
600
5 5 0 .0 0
6 0 0 Wavelength
.0 0
6 5 0 . 0 0(nm)
W a v e le n g t h ( n m )
8002 . 9 5
700
7 0 0 .0 0
7 5 0 .0 0
8 0 0 .0 0
1000
300
600
800
200
400
140
400
120
120
500
400
800
250
500
800
120
100
600
100
150
300
400
300
100
200
400
300
600
80
80
80
300
300
150
400
100
200
200
60
200
400
60
200
200
100
40
40
200
50
100
200
100
100
50
20
20
9 6 3 .0 5
8 8 9 .1 4
8 1 5 .2 4
7 4 1 .3 4
6 6 7 .4 3
5 9 3 .5 3
5 1 9 .6 2
4 4 5 .7 2
3 7 1 .8 1
2 9 7 .9 1
2 2 4 .0 1
1 5 0 .1 0
7 6 .2 0
3 5 0 .0 0
6 0 0 .0 0
600
650
6 2 5 .0 0
6 5 0 .0 0
700
6 7 5 .0 0
7 0 0 .0 0
7 2 (nm)
5 .0 0
Wavelength
W a v e le n g t h ( n m )
8002 . 2 9
750
7 5 0 .0 0
7 7 5 .0 0
8 0 0 .0 0
Summary
Eu-ARTECH
mordant
wool 1
Ca & K
wool 2
Ca
silk 3
Ca & K
silk4
Ca
max abs
max fluo
430 (665)
550 (675)
385
512 (675)
408 (666)
(536) 675 (720)
373
(507) 675 (720)
UV-vis fluorescence: the lake
Eu-ARTECH
Emission spectra of weld lakes (exc:366 nm portable)
Lake type 1
Lake type 2
Lake type 3
2000
Normalized emission spectra of weld lakes ( exc:366 nm
Varian and portable)
1.0
0
400
500
600
 / nm
700
800
Emission Intensity / a.u.
Emission Intensity / a.u.
4000
Lake type 1
Lake type 2
Lake type 3
Lake type 1 p.
Lake type 2 p.
Lake type 3 p.
0.8
0.6
0.4
0.2
0.0
400
500
600
 / nm
700
800
Eu-ARTECH
Emission spectra of undyed wool ( exc= 366 nm portable)
448
2: untreated wool
3: washed wool
5: mordanted wool
0.8
0.6
Emission spectra of undyed silk (exc= 366 nm portable)
0.4
12000
Without cut
With cut
0.2
0.0
400
500
600
 / nm
700
Emission Intensity / a.u.
Emission Intensity / a.u.
1.0
10000
8000
6000
4000
2000
0
200
300
400
500
 / nm
600
700
800