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18° International Symposium on Plasma Chemistry – Kyoto, Japan
Improving of surface properties of PET
with environmental friendly Atmospheric Pressure Plasma
treatments
Domenico D’Angelo Environment Park S.p.A.
22nd INTERNATIONAL IFATCC CONGRESS – Friday, May 7, 2010 - Stresa
Ionisation degree.
Plasma
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Ionisation degree = 1
Termonuclear plasma
Ionisation degree = 10-7 -10-4
Conventional plasma chemical
systems
Completly ionised plasma Weakly ionised plasma
Plasma and plasma chemistry
Plasma
Thermal plasma Non thermal plasma
Pressure range
T0 = Te
T0 « Te
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Thermodynamic equilibrium
Plasma and plasma chemistry
Gas pressure Strengths Disadvantage Low
(~ 0.01 kPa) Uniformity Batch process
Expensive equipment Subatmospheric
(~ 1 kPa) Uniformity Batch process
Expensive equipment
Atmospheric
(~ 100 kPa) In-line
speed Only in some plant
uniformity
Typical pressure ranges
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Plasma System: Atmospheric Plasma Pressure Glow Dielectric Barrier Discharge
• Two planar modular stainless steel electrodes • Self plasma-impedance adapting glow discharge • Lab scale version of production-size unit • Roll to roll system:10m/min max velocity • Max Power 2500W • 4 indipendent gas lines • 2 independent monomer lines • 1 micro-droplets dispenser • pre-heating system
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
• Vertical electrodes configuration suitable for textiles and polymeric rolls. (natural and polymeric fibers, PP,PE,PET etc)
• Horizontal electrodes configuration:possibility to treat rigid plane surfaces (wood laminates, polymeric sheets,cellulose
APP-DBD PLASMA SYSTEM: CHANGEABLE ELECTRODES CONFIGURATION
Why plasma technologies?
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Intrinsic properties
Additional functionalities
Traditional finishing Plasma processing
Flexibility
Strenght
“Hand” or touch
Low specific Weight
Require the use of large amount of chemicals, water, and energy
Comparison of plasma treatment vs. traditional processes
Parameter Plasma Traditional Solvent None (gas phase) Water Energy Electricity Heat
Type of reaction Complex Simple Deepness of the
Treatment Very thin layer Bulk of the fibers
New treatments High potentialities Very rare Water and energy
consumption Low High
Pollution Very low High
Equipment Totally new Slow evolution
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Textile processing
Wet washed polyester fabric
Application of the finish
Drying Plasma treatment
Polymerization
Finished polyester
Drying
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Dyeing
HO CH2CH2OC COO CH2CH2OHn
OO
Dye
Dye
DyeDye
Dye
Dye
1 2 3
The dyeing process is industrially performed above the glass transition temperature
Polyester/natural blends
HO CH2CH2OC COO CH2CH2n
OO
OC
O
COCH2CH2OC
O O
SO3H
HO CH2CH2OC COO CH2CH2n
OO
OC
O
COCH2CH2OC
O O
N
HO CH2CH2OC COO CH2CH2n
OO
OC
O
COCH2CH2OC
O
CH2CH2CH2CH2CH2CH2
O
Dyeing
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
HO CH2CH2OC COO CH2CH2OHn
OO
All these modifications lead to a variation of the bulk properties of the textile
Plasma and plasma chemistry
PLASMA
electrons gas
Ionisations Dissociations Excitation
Positive ions Negative ions Radicals Molecules Light
Etching Grafting Deposition Activation NH2
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Plasma surface interaction
Ka
Kb
Kc
KdKe
KfKg
KhKi
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Parameter used in APP-GDBD treatments
POWER
TIME
SCCM PRECURSOR
Sample Gas and precursors Power (W) Time (sec)
K/S Untreated - - - 0.32
B He 100% 1000 60 0.52 C N2 75% 1000 60 0.58
A1 O2 75% 1000 60 0.71 A2 O2 55% 1000 60 0.67 A3 O2 35% 1000 60 0.69 A4 O2 15% 1000 60 0.61
D Activation with O2 75% 1000 60 0.71
NH3 15% 1000 60
E Activation with O2 75% 1000 60 0.93
HEMA/NH3 mixture 350 60
0,0
1,0
2,0
3,0
4,0
5,0
6,0
1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6
Energy input W/F [W/sccm]
Depo
sitio
n ra
te [n
m/m
in]
TEXTILE STRUCTURE
Structure
O
O
O
O
O
O
O
O
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Acid Blue (127:1)
Dyeing procedure
Basic Red 18
RRSK2
)1(/2−
=K = absorption coefficient
S = scattering coefficient
R = reflection factor
OES analysis
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
EXCITED SPECIES WAVELENGTHS He* 447.1 nm He* 501.7 nm H* 486.1 nm H* 656.3 nm O* 777.4 nm O* 844.6 nm CO 519.8 nm CO 561.0 nm
Hem + O2 à He + O* + O+ + e
He+ + O2 à He+ + O + O*
He+ + O2 à He + O+ + O*
Penning reaction:
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
XPS analysis
HO CH2CH2OC COO CH2CH2OHn
OOO1s 1
O1s 2 C1s 1 C1s 3
C1s 2
D
C
B
A4
A3
A2
A1
0.140.544.833.4561.76PET O2/NH3
0.090.543.1034.3062.59PET N2
0.030.581.9436.0162.06PET He
0.020.521.3233.8364.86PET He/O2
0.020.581.1236.4562.47PET He/O2
0.010.560.9335.8863.25PET He/O2
0.010.690.7640.5458.69PET He/O2
-0.445-30.8269.18PET untreated
-0.4-28.671.4PET theorical
N/CO/CN %O %C %
D
C
B
A4
A3
A2
A1
0.140.544.833.4561.76PET O2/NH3
0.090.543.1034.3062.59PET N2
0.030.581.9436.0162.06PET He
0.020.521.3233.8364.86PET He/O2
0.020.581.1236.4562.47PET He/O2
0.010.560.9335.8863.25PET He/O2
0.010.690.7640.5458.69PET He/O2
-0.445-30.8269.18PET untreated
-0.4-28.671.4PET theorical
N/CO/CN %O %C %
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Non treated APP treated
HO CH2CH2OC COO CH2CH2OHn
OOO1s 1
O1s 2 C1s 1 C1s 3
C1s 2
XPS analysis
The deconvolution of the O1s electron peak shows the change in the relative proportions of oxygen singly and doubly bonded to carbon.
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Two competitive processes
COOCH2CH2OCO
COOCH2CH2OCO 2H
COOCH2CH2OCO COOCH2CH2OCO
In the sample B there is a strong crosslinking, depending on the high percentage of helium and low percentage of oxygen.
Conclusion
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
The treated PET showed significant improvement in the water absorbance and the dyeability An increase in color depth upon dyeing was obtained after treating PET fabrics with the two types of plasma treatment performed in this work The introduction of hydrophilic groups increases the affinity of PET fibers for dyes The reinforced crosslinked layer that stabilized the surface is formed under the action of the He active species, while the oxigen species induce the formation of an oxidized polymeric structure The presence of O2 in excess induces a depopulation of the excited levels of He, particularly the metastable ones, a fact which is reflected by a considerable decrease of the stability of the surface properties of the treated polymer The results proved the suitability of plasma treatment in textile industry especially in PET dyeing and processing by enhancing the wettability of the polyester fibers
Thanks for your attention !!!
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
22nd International IFATCC Congress – Friday, May 7, 2010 Stresa - Dr. Domenico D’Angelo
Department of General Chemistry and Organic Chemistry and NIS, Interdepartmental Center of Excellence, University of Torino
Foundation Bruno Kessler, Trento
GRINP s.r.l., Torino
Dr. Guy Buyle, Centexbel, Belgium
Acknowledgements
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