Beruflich Dokumente
Kultur Dokumente
a)
b)
Website: http://uigelz.ece.iastate.edu
33rd IEEE International Conference on Plasma Science
Traverse City, MI
June 4 8, 2006
*Supported by the NSF and 3M, Inc.
ICOPS_2006
AGENDA
Plasma Surface Modification of Polymers
Description of the Model
Atmospheric Pressure He/O2/H2O Corona Discharges for
Polypropylene Treatment
Gas flow
Pulsing frequency
Web speed
Concluding remarks
ICOPS_2006_Ananth_2
APPLICATIONS OF POLYMERS
Polymers are used in variety of applications from textile apparel to
Packaging
material
Textiles
Biomedical filtration
The specific polymeric material is chosen not only for its bulk
Electrical Discharge
Plasma
There are several types of electrical discharges:
The Corona is a 'partial' discharge occurring when a highly
inhomogeneous electric field is imposed. Typically, there is a
very high electric field adjacent to a sharp electrode, and a net
production of new electron-ion pairs occurs in this vicinity. The
Corona typically has a very low current, and very high voltage.
The Glow Discharge typically has a voltage of several hundred
volts, and currents up to 1 A. A small electron current is emitted
from the cathode by collisions of ions, excited atoms, and
photons, and then multiplied by successive electron impact
ionization collisions in the cathode fall region.
The Arc is a high current, low voltage discharge, where electron
emission from the cathode is from thermionic and/or field
emission. Electrical discharges can also by excited by RF,
microwave, or laser radiation, with or without electrodes.
(a)
(b)
Adhesion strength of PE
improves by a factor of 2-3
within a few seconds of
treatment in an air plasma.
No Treatment
Time (mins)
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Covered Roll
Covered roll stations have the dielectric covering on the ground roll and the
high voltage electrode is bare metal.
Advantages:
Disadvantages:
Bare Roll
Bare roll stations have the dielectric covering on the high voltage electrode and the
ground electrode is bare metal.
Advantages:
Disadvantages:
1.
2.
3.
1.
2.
3.
4.
5.
Sigma, Inc.
Tantec, Inc.
Advantages:
Disadvantages:
STRUCTURE OF POLYPROPYLENE
Polypropylene (PP) is a saturated hydrocarbon polymer containing
ICOPS_2006_Ananth_9
as in air.
treatment processes
Gas flow and composition
Web speed
Pulsing frequency
Applied voltage
How do process variables ultimately affect the relative abundance
of various surface functional groups?
ICOPS_2006_Ananth_12
t - s (t ) qi N i (t )
i
Scharfetter-Gummel fluxes.
N i
S i
t
ni 1 ni exp(x)
i 1/ 2 D
1 exp(x)
q i 1 i
2v
q
x
S
qii 1 i jE
t
i
ne kTe / t S Te L Te kTe Te Te
2
d r
N i (r ) ij N j (r ) exp
S Pi (r )
2
r
4
S Si j ,
j ij j
j
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( v ) ( inlets , pumps )
t
v
NkT v v qi N i Ei
t
i
c pT
T v c pT Pi v Ri H i ji E
:
t
i
i
N i t t
N i t t N i t v Di N T
NT
ICOPS_2006_Ananth_15
SV S S
Plasma
Dynamics
Model
Sticking
coefficients
Surface
densities of
functional
groups
Surface reaction
mechanism
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Treater Station
All treater stations have a high voltage electrode and a ground
electrode. A solid dielectric (insulating) material is needed to cover
one of the two electrodes in order to generate a corona
atmosphere, as opposed to a "lightening bolt" charge (the
dielectric covering (silicone, ceramic, epoxy, etc.) prevents the
voltage from arcing to the ground roll. Instead the air is broken
down and a corona (oxidised air) is generated). Heat, ozone and
NOX are formed.
2 mm
Not to scale
Electrode embedded in dielectric with tip exposed to the
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Te 0-9 eV
Te peaks at the
ionization front
initiated near the
electrode and
propagates toward
the PP surface.
Electron sources by
electron impact
ionization track the
maximum in Te.
Electron Source
5x1020-5x1023 cm-3s-1
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 02 ns, no flow
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MIN
log scale
MAX
Animation Slide-GIF
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MIN
log scale
MAX
Animation Slide-GIF
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MIN
log scale
MAX
Alkoxy
R*
R O*
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Carbonyl
R=O
Alcohol
Peroxy
R OH
R O O*
Acid
O = R OH
= 1 - 10 s
= 10-100 s
= 10-100 s
= 10-50 ms
= 50 - 100 ms
Abstraction from carbonyl groups (R-C*=O) may lead to further
= 100 - 1000 ms
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R* + O, O3 R - O* + O2
R* + O2 R - OO*
R*
R-OO*
R-O*
s.
[e]
O
OH
1014
Animation Slide-GIF
R* + O2 R-O-O*
Axial gas flow varied from negligible to a few slpm ( = 10s ms)
How does gas flow aid in treatment downstream?
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no flow
10 slpm
30 slpm
cm , log scale
-3
1014
no flow
10 slpm
30 slpm
With gas flow, the accumulating O3 is convected downstream.
Animation Slide-GIF
cm , log scale
-3
1014
R-OH
10 cm
R-OO*
Moving surface
TYPICAL CONDITIONS
~ few ms
Gap : few mm
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R-O*
CONTINUOUS TREATMENT
Moving surface
10 cm
R-OH
Moving surface
R*
Moving surface
Moving surface
R* + O2 R-O-O*
R* + O3 R - O* R-OH
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Moving surface
10 cm
R-OO*
R-OH
No flow
No flow
10 slpm
Moving surface
Moving surface
Gas flow reduces alkoxy (R-O*) and alcohol (R-OH) coverage and
increases peroxy (R-O-O*) by altering relative fluxes of O and O 3.
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 0.05 s, 1
kHz, film spd = 4 m/s
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Moving surface
R-OH
10 cm
R-OO*
Moving surface
Moving surface
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[e]
cm , log scale
-3
1014
Electron impact
dissociation of O2
produces delta function
sources of O.
In the interpulse period, O
is consumed in formation
of O3 while being
convected downstream.
Animation Slide-GIF
ICOPS_2006_Ananth_40
pulse, accumulate in
discharge and is
convected downstream.
O3
cm , log scale
-3
1015
CONTINUOUS PROCESSING OF PP
R* + O2 R-O-O*
The PP is functionalized by
successive pulses as it
moves through the
discharge.
Moving surface
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CONCLUDING REMARKS
Optimization of polymer treatment using commercial corona
equipment could lead to creating high value materials.
Control of process variables (eg., gas flow, mixture, web-speed) may
enable production of unique surface compositions.
In PP treatment, relative fluxes of reactive species is altered by gas
flow changing the abundance of alkoxy (R-O*) and peroxy (R-O-O*).
Ultimately, customization of surfaces must account for
Reactive radicals (e.g., O and OH) are regenerated each pulse;
longer lived (e.g., O3) accumulate over many pulses.
Gas flow transports long lived radicals over more surface area.
Moving speed mixes of two regimes.
Interplay between local rapid reactions and non-local slower
reactions may enable customization.
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