project: life12 env/it/352 «bionad» > > davide pellegrini iccom-cnr, pisa 6 months progress...
TRANSCRIPT
PROJECT: LIFE12 ENV/IT/352 «BIONAD»
<<Naturalised dyes replacing commercial colorants for environmentally friendly leather dyeing and water recycle>>
DAVIDE PELLEGRINI ICCOM-CNR,
Pisa6 Months Progress Meeting – BIOKIMICA premises, Santa Croce sull’Arno (PI),
June 13th 2014
Actions
B.1 BIOKIMICA, INESCOP, ICCOM-CNR(0-6 months)
Demonstration of the use of traditional chemical acid dyes in leather dyeing
B.2 BIOKIMICA, INESCOP, (ICCOM-CNR)(0-6 months)
Demonstration of the quality features of dyed leather with acid dyes
B.4 BIOKIMICA, (ICCOM-CNR)(3-9 months)
Demonstration of naturalised dyes in leather dyeing at laboratory level
DO30
DR202DY42
DB27
Naturalised dyes
LACTOSE
Commercial acid dyes
NN
NH2
OCH3
CH3
SO3Na
N
N
CH3
O
N
NH
SO3Na
NaO3S
NH
N N
N
O
CH3
O37 Y49
R249B113
Leather dyeing procedure
0.2 g 4 mg/2 mL2% (dye/leather)
Magnetic stirring at 20°C for 1 h
Heating at 55°C
400 µL MilliQ + 4 mg formic acid
Magnetic stirring for 0.5 h
Washing with 4 mL MilliQfor 3 times
1. Formic acid at 55°C
B.1, B.4
Leather dyeing procedure
Magnetic stirring at 20°C for 1 h
Neutralization with 50µL K2CO3 (pH = 7-8)
Magnetic stirring for 10 min
2. Neutralization
Washing with 4 mL MilliQfor 3 times
0.2 g
B.1, B.4
4 mg/2 mL2% (dye/leather)
Heating at 55°C
400 µL MilliQ + 4 mg formic acid
Magnetic stirring for 0.5 h
Dyes characterizationUV-Vis
Naturalised dyes
Commercial acid dyes
1 Dyeing bath2 Washing 13 Washing 24 Washing 3
B.1, B.2, B.4
FORMIC ACIDPROCEDURE
Naturalised dyes
Commercial acid dyes
1 Dyeing bath2 Washing 13 Washing 24 Washing 3
B.1, B.2, B.4
Dyes characterizationUV-VisNEUTRALIZATIO
NPROCEDURE
B.1, B.2, B.4
Dyes characterizationUV-Vis
200 250 300 350 400 450 500 550 600 650 700 750 800
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
Wavelength [nm]
Abs
orb
anc
e
DO30 dyeing bathDO30 washing 1DO30 washing 2DO30 washing 3
0.0
0.5
Washing water 3
Washing water 2
Washing water 1
A
Tanning solution
-61%-79%
-83%
442
Dyed leather characterization
Naturalised dyes
Commercial acid dyes
2%
5%
10%
15%
B.1, B.2, B.4
Naturalised dyes
Commercial acid dyes
Formic acid
Neutralization
B.1, B.2, B.4
Dyed leather characterization
Dyed leather characterization
Colorimetry
B.1, B.2, B.4
CM2600d KONICA MINOLTA
360-740 nmα = 10°
D65d. 5 mm
SAMPLESCI SCE
L a b L a bDR202 acid 48.11 39.65 13.66 48.08 39.59 13.64DY42 acid 81.47 -7.6 25.79 81.35 -7.56 25.75DB27 acid 53.56 -13.29 -22.35 53.4 -13.29 -22.39DO30 acid 62.92 25.73 39.27 62.9 25.65 39.22Red acid 52.46 48.56 11.48 52.33 48.62 11.56
Yellow acid 78.02 -10.69 57.24 77.85 -10.62 57.18Blue acid 32.12 3.76 -22.11 31.96 3.79 22.21
Orange acid 55.68 32.81 40.07 55.56 32.87 40.19DR202 neutr 45.11 40.08 14.81 45.04 40.06 14.81DY42 neutr 80.83 -7.45 30.18 80.72 -7.41 30.14DB27 neutr 51.54 -13.61 -21.97 51.39 -13.61 -22.02DO30 neutr 60.93 27.44 40.41 60.92 27.37 40.35Red neutr 54.3 48.46 -11.38 54.19 48.52 -11.45
Yellow neutr 80.71 -11.06 47.98 80.6 -10.94 47.58Blue neutr 35.82 3.48 -23.8 35.73 3.54 -23.84
Orange neutr 64.6 2.14 38.04 64.5 24.12 38.03
FT-IR CHARACTERIZATION
05001000150020002500300035000
0.02
0.04
0.06
0.08
0.1
0.12
Wavenumbers [1/cm]
Abs
orb
anc
e
AMIDE IC=O ν
~1650 cm-1
AMIDE IICN ν, NH δ
~1550 cm-1
ATR spectrum128 scans
Untreated leather
COOH ν~1730 cm-1
B.1, B.2, B.4
FT-IR CHARACTERIZATION
05001000150020002500300035000
0.02
0.04
0.06
0.08
0.1
0.12
Wavenumbers [1/cm]
Abs
orb
anc
e
AMIDE IICN ν, NH δ
~1550 cm-1
ATR spectrum128 scans
Untreated leather
COOH ν~1730 cm-1
AMIDE I1~1654 cm-1
AMIDE I2~1636 cm-1
AMIDE IC=O ν
~1650 cm-1
B.1, B.2, B.4
162016251630163516401645165016551660
Wavenumbers [1/cm]
0.954
0.96
0.966
0.972
0.978
0.984
0.99
0.996
1.002
1.008
1.014
1.02
Abs
orba
nce
BLANKDO30-HCl
DY42-HClDR202-HClDB27-HCl
1654 cm-1 1650 cm-1 1634 cm-1 1637 cm-1
Naturalised dyes
FT-IR CHARACTERIZATION
B.1, B.2, B.4
162016251630163516401645165016551660166516700.965
0.97
0.975
0.98
0.985
0.99
0.995
1
1.005
1.01
Wavenumbers [1/cm]
Abs
orba
nce
BLANKORANGE
37YELLOW 49RED 249
BLUE 113
FT-IR CHARACTERIZATIONCommercial dyes
B.1, B.2, B.4
FT-IR CHARACTERIZATION
Principal Component Analysis
05001000150020002500300035000
0.02
0.04
0.06
0.08
0.1
0.12
Wavenumbers [1/cm]
Abs
orb
anc
e
AMIDE I1~1654 cm-1
AMIDE I2~1636 cm-1
VARIABLES
Peak heights of
AI1/AIIAI2/AII
COOH/AII
B.1, B.2, B.4
AMIDE IICN ν, NH δ
~1550 cm-1
COOH ν~1730 cm-1
AMIDE IC=O ν
~1650 cm-1
FT-IR CHARACTERIZATION
Principal Component Analysis
-2 0 2 4
-1.5
0.0
1.5
DO30-HCl DO30-HCl
Yellow
Orange
Red
Blue
Yellow
Orange
Red
Blue
DY42-HCl
DR202-HCl
DB27-HCl
DY42-HCl
DR202-HCl
DB27-HCl
PC1 (69%)
PC
2 (
29
%)
Leather
Blank
Blank
-1 0 1
-1
0
1
AI1/AII
AI2/AII
PC1
PC
2
COOH/AII
PCA
Variables: AI1/AII, AI2/AII, COOH/AII
Var. tot. = 98%Matrix: covariance
Score plot
Loading plotFormic acid procedure
Neutralization procedure
B.1, B.2, B.4
FT-IR CHARACTERIZATION
Principal Component Analysis
-2 0 2 4
-1.5
0.0
1.5
DO30-HCl DO30-HCl
Yellow
Orange
Red
Blue
Yellow
Orange
Red
Blue
DY42-HCl
DR202-HCl
DB27-HCl
DY42-HCl
DR202-HCl
DB27-HCl
PC1 (69%)
PC
2 (
29
%)
Leather
Blank
Blank
-1 0 1
-1
0
1
AI1/AII
AI2/AII
PC1
PC
2
COOH/AII
PCA
Variables: AI1/AII, AI2/AII, COOH/AII
Var. tot. = 98%Matrix: covariance
Score plot
Loading plot1 2
Formic acid procedure
Neutralization procedure
B.1, B.2, B.4
FT-IR CHARACTERIZATION
Principal Component Analysis
-2 0 2 4
-1.5
0.0
1.5
DO30-HCl DO30-HCl
Yellow
Orange
Red
Yellow
Orange
Blue
DY42-HCl
DR202-HCl
DY42-HCl
DR202-HCl
DB27-HCl
PC1 (69%)
PC
2 (
29
%)
Leather
Blank
Blank
-1 0 1
-1
0
1
AI1/AII
AI2/AII
PC1
PC
2
COOH/AII
PCA
Variables: AI1/AII, AI2/AII, COOH/AII
Var. tot. = 98%Matrix: covariance
Score plot
Loading plot1 2
1 High AI1/AII, AI2/AII
Formic Acid procedure(and RED
neutralization)2 Low AI1/AII, AI2/AII
Neutralization procedure
(and DB27-HCl and blue formic acid
procedure)
Formic acid procedure
Neutralization procedure
B.1, B.2, B.4
Blue
Red
DB27-HCl
FT-IR CHARACTERIZATION
Principal Component Analysis
1000110012001300140015001600170018001900
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
Wavenumbers [1/cm]
Abs
orba
nce
DY42-HCl Formic
acidDY42-HCl
Neutralization
AMIDE II INCREASES
B.1, B.2, B.4
COLLAGEN CROSS-LINKING
FT-IR
~1654 cm-1/~1690 cm-1
Collagen cross-linking type
Pyridinoline (Pyr)
Dehydro-dihydroxy-norleucine (deH-
DHLNL)
B.1, B.2, B.4
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.516
54cm
-1/1
690c
m-1
Collagen cross-linking
Blank
Leather
Commercial
Naturalised
Naturalised dyes
Rich in Pyr type cross-
linking
COLLAGEN CROSS-LINKING
FT-IR
B.1, B.2, B.4
Naturalised dyes 5%, 10%,
15%
Same behavior of commercial dyes
2% 0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
1654
cm-1
/169
0cm
-1
Collagen cross-linking
COLLAGEN CROSS-LINKING
FT-IR
B.1, B.2, B.4
COLLAGEN CROSS-LINKING
TGA
100 200 300 400 500 60010
20
30
40
50
60
70
80
90
100
T (°C)
TG
%0
50
100
150
200
250
300
350
DT
G (
ug/m
in)
Gas: N2 200 mL/minHeating: 30-700°C, 10 °C/min
B.1, B.2, B.4
COLLAGEN CROSS-LINKING
TGA
100 200 300 400 500 60010
20
30
40
50
60
70
80
90
100
T (°C)
TG
%
0
50
100
150
200
250
300
350
DT
G (
ug/m
in)
T01
T02
Tonset
% fin
SAMPLE
T01 Tonset T0
2 % fin
Leather 77.4 302.2 334.3 22.2892BLANK 72.7 299.9 338 20.2782
DB27 2% 70.6 300.6 339.5 20.9291DO30 2% 76.6 298.2 337 21.5649DY42 2% 74 297.7 337.6 20.2527DR202
2%74.1 299.1 339 21.639
Blue 76.1 299.2 335.4 22.3998Orange 75.4 302 335.2 22.1174Yellow 71.9 300.6 333.5 20.4022Red 73 299.1 336 21.37
DB27 15%
72.7 299.3 330.9 22.6931
DO30 15%
77.7 297.4 334.6 22.4728
DR202 15%
79 299.9 330.6 22.1285
DY42 15%
76.5 299.5 331.5 22.5689
B.1, B.2, B.4
COLLAGEN CROSS-LINKING
TGA
B.1, B.2, B.4
326.0
328.0
330.0
332.0
334.0
336.0
338.0
340.0
342.0
.T 02
100 200 300 400 500 60010
20
30
40
50
60
70
80
90
100
T (°C)
TG
%
0
50
100
150
200
250
300
350
DT
G (
ug/m
in)
T01
T02
Tonset
% fin
Naturalised2%
Commercial2%
Naturalised
15%
FUTURE ACTIONS
B.1 BIOKIMICA, INESCOP, ICCOM-CNR(0-6 months)
Demonstration of the use of traditional chemical acid dyes in leather dyeing
HPLC-DAD characterization of dyes bath and washing solutions
GC-MS characterization of the volatile fraction of the dyed leather
C.1 ICCOM-CNR, UNIFI, INESCOP, BIOKIMICA(0-12 months)
Monitoring on the enviromental impact of acid dyes within leather manufacture
Atomic spectroscopy determination of the metal content of dyeing wastewaters (Cr, Co, Cu, Fe)
BIONAD PEOPLE @ ICCOM-CNR, PISA
Emilia BramantiAlessandro D’Ulivo
Massimo Onor
Manuela Cempini
Davide Pellegrini
Emanuela Pitzalis