13 Corona

RADICAL GENERATION AND POLYMER SURFACE
FUNCTIONALIZATION IN FLOWING ATMOSPHERIC

PRESSURE PULSED DISCHARGES*

Ananth N. Bhoj
a)
and Mark J. Kushner
b)

a)
Department of Chemical and Biomolecular Engineering,
University of Illinois, Urbana, IL. bhoj@uiuc.edu
b)
Department of Electrical and Computer Engineering,
Iowa State University, Ames, IA. mjk@iastate.edu

Website: http://uigelz.ece.iastate.edu

33
rd
IEEE International Conference on Plasma Science
Traverse City, MI
June 4 8, 2006

*Supported by the NSF and 3M, Inc.
ICOPS_2006
Iowa State University
Optical and Discharge Physics
AGENDA
ICOPS_2006_Ananth_2
- Plasma Surface Modification of Polymers
- Description of the Model
- Atmospheric Pressure He/O
2
/H
2
O Corona Discharges for
Polypropylene Treatment
- Gas flow
- Pulsing frequency
- Web speed
- Concluding remarks

- Polymers are used in variety of applications from textile apparel to
packaging to biomedical materials.

- The specific polymeric material is chosen not only for its bulk
properties but also for surface characteristics such as wettability,
adhesion and surface reactivity.
APPLICATIONS OF POLYMERS
ICOPS_2006_Ananth_3
- Biomedical filtration - Packaging material - Textiles
- The poor wettability and adhesion properties of hydrocarbon
polymers is due to their low surface energy and limits use.
- Ideally, the surface energy should exceed the liquid by 2-10 mN/m.

- Plasma treatment is an effective dry process alternative to liquid
chemical processes used to functionalize or activate the surface.
ICOPS_2006_Ananth_4
-Poor wettability-low
surface energy
SURFACE PROPERTIES OF POLYMERS
Electrical Discharge

An electrical discharge is the passage of electrical current through a material
which normally does not conduct electricity. Consider, for example, a simple
experiment which we have all experienced. If we hold two wires a few
millimeters apart, and connect each to one pole of a battery, no perceptible
electrical current flows through the air, because the air is insulating. However if
these wire were connected to a high voltage source of several thousand volts,
sparks will fly. The normally insulating air was transformed into a conductor, a
process called electrical breakdown, and the sparks which we would see are a
form of an electrical discharge.
Normally air consists of neutral molecules of nitrogen, oxygen, and other
gases, in which electrons are tightly bound to atomic nuclei. During the
breakdown process, some of the negatively charged electrons are separated
from their host atoms, leaving them with a positive charge. The negatively
charged electrons, and the positively charged atoms (known as positive ions)
are then free to move separately under the influence of the applied voltage.
Their movement constitutes an electrical current.
The collection of ions and electrons is known as a plasma, and one of its more
important properties is that a plasma can conduct electrical current.
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.
Theory of Corona Treating

OXIDATION: Basically, this theory states that the energy of the
corona breaks the molecular bonds on the surface of the non-polar
substrate. The broken bonds then recombine with the free radicals
in the corona environment to form additional polar groups on the film
surface. These polar groups have a strong chemical affinity to the
polar inks and adhesives, which results in improved adhesion.
Similarly, the polar surface results in an increased surface energy
which correlates with improved wettability.
MICROPITTING: The micropitting theory states that the surface of
the material being treated is pittted, increasing the surface area and
giving it a better surface for the coating or lamination to grab onto.
THE ELECTRET EFFECT: The electret theory describes a process
within the corona where the polar chain of the polymer being treated
is carbonized giving it a chemically reactive surface for the coating
or lamination to bond to.
FUNCTIONALIZATION OF POLYMER SURFACES
- Functionalization occurs by the chemical interaction of plasma
produced species - ions, radicals and photons with the surface.
- Chemical groups are incorporated onto
the surface which change surface
properties.
- Process usually only treats the top mono-
layers not affecting the bulk.
Wettability on PE film with 3 zones of treatment:
a)untreated b)slightly treated c) strongly treated.
Courtesy: http://www.polymer-surface.com
ICOPS_2006_Ananth_5
(a)
(b)
(c)
PLASMA TREATMENT IMPROVES ADHESIVE BONDING
ICOPS_2006_Ananth_6
- Peel strength of Polyethylene (PE)
downstream of an atmospheric pressure air
non-equilibrium discharge.

M.J. Shenton et al, J. Phys D. 34, 2754 (2001)
P
e
e
l

S
t
r
e
n
g
t
h

(
M
P
a
)

Time (mins)
No Treatment
- Adhesion strength of PE
improves by a factor of 2-3
within a few seconds of
treatment in an air plasma.
- Adhesion shows some
atmospheric degradation
indicating long term
reactivity.
- Pulsed atmospheric filamentary discharges (coronas) are routinely
used to web treat commodity polymers like polypropylene (PP) and
polyethylene (PE).
INDUSTRIAL SURFACE MODIFICATION OF POLYMERS
ICOPS_2006_Ananth_7
TYPICAL CONDITIONS
- kVs at few kHz
- t ~ few ms
- Web speed few m/s
- Gap : few mm
- Filamentary Plasma 10s 200 m

Corona- Basic Concept
A corona treatment system in its simplest form can be thought of as a capacitor.
Voltage is applied to the top plate which, in the case of corona treatment, would be
the electrode. The dielectric portion of the capacitor would be made up of some
type of roll covering, air and the substrate (film or sheet). The final component, or
bottom plate, would take the form of an electrically grounded roll. In the corona
treatment system the voltage build-up ionises the air in the air gap creating a
corona, which modifies the surface and increases the surface energy of the
substrate passing over the electrically grounded roll. The level of treatment is
controlled by the energy of the discharge and the air gap. For health and safety
reasons, the ozone generated in the corona must be removed from the working
environment.
Covered Roll
Covered roll stations have the dielectric covering on the ground roll and the
high voltage electrode is bare metal.
Advantages: 1.Designed to treat non-conductive surfaces. It is a more efficient system
than bare roll.
2.Must be used for substrates that are difficult to treat (i.e., high slip
polypropylene, high slip polyethylene).
3.Easy to adjust treat width and to "lane" treat specific areas which leave
other areas untreated.
4.Can use a variety of dielectric coverings to accommodate customer
preference for cost, durability, size and quality.
5.Can treat any width material.
Disadvantages: 1.Dielectric failures can be cumbersome to repair as the roll must be
removed from the station.
2.Stations are typically larger than comparable bare roll stations.
3.Cannot treat metallized substrates.
Bare Roll
Bare roll stations have the dielectric covering on the high voltage electrode and the
ground electrode is bare metal.
Advantages:
1. Can treat metallized substrates.
2. More compact than covered roll treater stations.
3. Easy to repair dielectric failures on electrodes.
Disadvantages: 1. Less efficient than covered roll.
2. Cannot easily adjust treat width or lane treat (Pillar is introducing
a new product that eliminates this disadvantage).
3. Limited to maximum 120 inch treat width.
4. Will not treat certain substrates.
5. Requires large volumes of makeup air, as air is needed to cool
the electrodes.
- Advantages:
- No vacuum equipment required.
- Suitable for high throughput and
continuous operation.
- Economical.
COMMERCIAL CORONA PLASMA EQUIPMENT
ICOPS_2006_Ananth_8
- Sigma, Inc.
- Disadvantages:
- Lack of specificity - mix of
functional groups are produced.
- Higher probability of surface
contamination.
- Most commonly treated polymer is
polypropylene (PP).
- Tantec, Inc.
STRUCTURE OF POLYPROPYLENE
ICOPS_2006_Ananth_9
- Polypropylene (PP) is a saturated hydrocarbon polymer containing
alternating methyl (-CH
3
) and H at the carbon centers on the
backbone.

- A Carbon atom can be attached to 3 H atoms (primary Carbon), 2 H
atoms (secondary Carbon) or 1 H atom (tertiary Carbon).
- The reactivity of the H depends on the C to which it is bonded,
scaling as H
T
> H
S
> H
P
.
- The surface site density of PP is about 10
15
/cm
2
C-atoms.

- PP undergoes surface oxidation in O
2
containing discharges such
as in air.

- Coverage of O-containing groups is near 2.5% (2 x 10
13
cm
-2
) for high
energy density treatment and < 1% (<10
13
cm
-2
) at lower energies.
TREATMENT OF PP IN CORONA DISCHARGES
ICOPS_2006_Ananth_10
- Ref: OHare et al, Surf. Interface Anal. 33, 335342 (2002)
PROCESSING HIGH-VALUE PRODUCTS
- Biomedical materials are treated in
(expensive) low pressure plasmas to
selectively enhance cell adhesion or
chemical reactivity to a reagent.
- The drawback in using atmospheric
pressure discharges is the lack of
functional group specificity.
- Improved control over incorporation of functional groups onto
surfaces would enable use of commodity polymer processing
techniques for high-value products with significant cost-savings.
- Micropatterned cell growth on
amino-functionalized polystyrene
in NH
3
and H
2
plasmas

- Ref: K. Schroeder et al, Plasmas
and Polymers 7,103-125 (2002)
GOALS OF THIS INVESTIGATION
- Results from 2-d modeling investigation of plasma and surface
processes for polymer treatment will discuss degree and
uniformity of surface functionalization.
- Spatial dynamics of repetitively pulsed discharges.
- Interplay between radical generation, transport and surface
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?
- Fully implicit solution of Poissons equation.

- Continuity: Multi-fluid charged species equations using modified
Scharfetter-Gummel fluxes.

- Surface charge on dielectric surfaces.

- 2-d unstructured mesh.

MODEL ELECTROSTATICS, CHARGED PARTICLE TRANSPORT
( ) |
.
|
\
|
+ = u V V

i
i i s
t N q t - t ) ( ) ( c
i
i
S
t
N
+ V =
c
c
|
( ) ( ) ( ) ( )
+ u V V + V =
c
c
i
E i i i
S
j q
t

o |
1
|
|
.
|
\
|
A
A
=
+
+
) exp( 1
) exp(
1
2 / 1
x
x n n
D
i i
i
o
o
o |
D
v
x q
q
i i

2
1
|
.
|
\
|
A
u u
|
|
.
|
\
|
=
+
o
ELECTRON TRANSPORT AND REACTION KINETICS
- Electron energy transport:

- Reaction Kinetics include sources due to electron impact and heavy
particle reactions, photoionization and contributions from
secondary emission.
( ) ( ) ( )
|
.
|
\
|
V u V = c
|
.
|
\
|
c
e e e e e e e
T T kT T L T S t kT n k
2
5
/
2
3
(
(
(
]
(
'
'
|
|
.
|
\
| '
'
=
2
3
4
exp ) ( ) (
) (
r r
r d
r r
r N r N
r S
j ij i
Pi

t

o
= V =
j
j ij Si
j j S | ,
- Fluid averaged values of mass density, mass momentum and
thermal energy density obtained in using unsteady algorithms.

Continuity :

Momentum:

Energy :

- Individual neutral species densities are updated.

) pumps , inlets ( ) v (
t
+ V =

c
c
( )
( ) ( )

+ V V V =
i
i i i
E N q v v NkT
t
v

c
c
( )
( )

+ A V + + V V =
i i
i i i i p
p
E j H R v P T c v T
t
T c

k
c
c
( ) ( )
( )
S V
T
i
T i i i
S S
N
t t N
N D v t N t t N + +
|
|
.
|
\
|
|
|
.
|
\
|
A +
V V = A +

FLUID MODULE : NEUTRAL PARTICLE TRANSPORT
SURFACE KINETICS MODULE
- To predict surface compositions, a surface kinetics module is
incorporated into the plasma dynamics model.

- Module predicts densities of surface resident groups using
fluxes from the plasma and a user-provided mechanism.
Plasma
Dynamics
Model
Fluxes
Surface
densities of
functional
groups
Sticking
coefficients
Surface
Kinetics Model
Surface reaction
mechanism
Components of Corona Treating
Systems
Power Source
The power source generally consists of a high frequency
generator and a high voltage output transformer. In very general
terms, the purpose of the power source is to raise the incoming
electricity (typically 50/60 Hz, 230/460 V) to a higher frequency
(10-35 kHz) and higher voltage (10 kV). The power source is
commonly referred to as a power supply or a generator.
Typically, power supplies are rated in kilowatts (kW) and can
range from 500 W to 30 kW, depending on the application.
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.
- Electrode embedded in dielectric with tip exposed to the
processing gas with a gap of 2 mm to the PP surface.
- Atmospheric pressure
- Applied voltage (10 ns pulses) at up to 10s kV, 0.1 10 kHz.

CORONA DISCHARGE GEOMETRY
Not to scale
2

m
m

GAS PHASE CHEMISTRY: He/O
2
/H
2
O
- Treatment in O
2
containing plasmas is known to effectively
incorporate O atoms into the surface.

- Process is initiated by electron impact dissociation of O
2
and H
2
O
into radicals such as O and OH.
DYNAMICS OF THE FIRST PULSE: T
e
, SOURCES
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 02 ns, no flow
Animation Slide-GIF
MIN

MAX
log scale
- T
e

0-9 eV
- Electron Source
5x10
20
-5x10
23
cm
-3
s
-1
- T
e
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 T
e
.

- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 02 ns, no flow.
- O 10
11
10
15
cm
-3
- OH 10
11
10
14
cm
-3
PLASMA DYNAMICS OF THE FIRST PULSE
- Electron density of 10
13
-10
14
cm
-3
is produced behind the front.
- O and OH are produced predominantly by electron impact reactions
of O
2
and H
2
O respectively.
Animation Slide-GIF
- [e] 10
11
10
14
cm
-3
MIN

MAX
log scale
END OF FIRST PULSE AFTERGLOW: RADICALS
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 100 s, no flow
- The density of O decreases to 10
12
cm
-3
in the interpulse period as it
is consumed in 3-body reactions with O
2
to form O
3

(10
14
cm
-3
).
- The density of OH decreases to 10
12
as it reacts with both O and O
3
.
MIN

MAX
log scale
- [O
3
] 5x10
12
-5 x 10
14
cm
-3
- [OH] 10
11
10
13
cm
-3
- [O] 10
11
10
13
cm
-3
RADICALS AND GROUPS AT CARBON CENTERS ON PP
- Polypropylene structure

- Different radicals and functional groups are created at the carbon
atoms when treated in O
2

containing plasmas:
Alkyl Alkoxy Carbonyl Alcohol Peroxy Acid

R* R O* R = O R OH R O O* O = R OH
SURFACE REACTION MECHANISM: INITIATION
- Initiation by H abstraction:

Alkyl radicals (R*) formed by H abstraction by OH and O.

- Propagation and saturation:

Peroxy (R-O-O*) formed by the addition of O
2
to alkyl (R*) sites.
t = 1 - 10 s
t = 10-100 s
- Propagation:

Alkoxy (R-O*) formed by reaction of O
3
and O with alkyl (R*) sites.
- Surface surface reactions:

Alkoxy (R-O*) radicals abstract H from surrounding sites to form
alcohol (R-OH) groups.
SURFACE REACTION MECHANISM: PROPAGATION
t = 10-100 s
t = 10-50 ms
SURFACE REACTION MECHANISM: CHAIN SCISSION
- Carbonyl (R-C=O) groups are formed by chain scission.

- Abstraction from carbonyl groups (R-C*=O) may lead to further
chain degradation evolving CO
2
into the gas phase.
t = 50 - 100 ms
t = 100 - 1000 ms
- Termination

Addition of OH produces carboxylic acid groups.

H and OH also add to alkyl radicals (R*) in termination steps.
SURFACE REACTION MECHANISM: TERMINATION
t = 100 - 1000 ms
R* + O, O
3
R - O* + O
2
R* + O
2
R - OO*

PP TREATMENT WITH A SINGLE PULSE
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 0 100 s
- Alkyl (R*) radicals are formed within 10 s.
- Alkoxy (R-O*) and peroxy (R-OO*) are
formed as alkyl (R*) sites react over 10s s .
R-OO*
R-O*
0.5 cm
R*
RH + O, OH R* + OH, H
2
O

- O and OH are generated in each pulse and consumed between pulses
in reactions with O
2
and O
3
respectively.

- O
3
is relatively unreactive and so accumulates pulse-to-pulse.
DYNAMICS WITH REPETITIVE PULSING (NO FLOW)
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 1 kHz, 0.005 s
- OH
- O
3

- O
-[e]
10 cm
Animation Slide-GIF
10
10
10
14

cm
-3
, log scale
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 1 kHz, 0.05 s
PP TREATMENT WITH REPETITIVE PULSE (NO FLOW)
2 cm
RH + O, OH R* + OH, H
2
O
- Alkyls (R*) are regenerated every
pulse by O and OH, and consumed.
- Peroxy (R-O-O*) accumulate pulse-to-
pulse
R* + O
2
R-O-O*
PULSED DISCHARGES WITH GAS FLOW

- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, few slpm ( | | = 10s 100s cm/s)
- Axial gas flow varied from negligible to a few slpm (t = 10s ms)
- How does gas flow aid in treatment downstream?
v

EFFECT OF GAS FLOW ON RADICALS: [O]

- no flow
- 10 slpm
- 30 slpm
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 0 0.005 s, 1 kHz, static surface
- O is highly reactive with O
2
to form ozone (O
3
).
- Although some O is convectively transported downstream, local
reaction kinetics dominate. Nearly all O reacts prior to the next pulse.
10
10
10
14

cm
-3
, log scale
Animation Slide-GIF
EFFECT OF GAS FLOW ON RADICALS: [O
3
]

- - 5 kV, 1 atm, He/O
2
/H
2
- no flow
- 10 slpm
- 30 slpm
- With gas flow, the accumulating O
3
is convected downstream.
Animation Slide-GIF
10
10
10
14

cm
-3
, log scale
EFFECT OF GAS FLOW ON PP TREATMENT
- Alkoxy (R-O*) and alcohol (R-OH) decrease under the electrode.
- Peroxy (R-O-O*) increases downstream as alkyl sites are saturated.
10 cm
R-OH
R-OO*
R* + O
2
R-O-O*
R* + O
3
R - O* R-OH
- - 5 kV, 1 atm, He/O
2
/H
2
WEB TREATMENT OF POLYMER SURFACES
TYPICAL CONDITIONS
- t ~ few ms
- Gap : few mm
- Polymer surfaces are
continuously treated at web
speeds of a few m/s.
- Model addresses web
treatment by translate the
surface properties on the
grid at a few m/s.
Moving surface
CONTINUOUS TREATMENT
- Surface has active sites which react
downstream of the plasma zone.
- - 5 kV, 1 atm, He/O2/H2O=89/10/1, 0-0.025s, 1
kHz, web speed = 4 m/s, no flow
R-O*
Moving surface
10 cm
R-OH
Moving surface
Moving surface
R* + O
2
R-O-O*
R* + O
3
R - O* R-OH
R*
Moving surface
R*
Moving surface
CONTINUOUS TREATMENT: GAS FLOW
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1, 0.05 s,
1 kHz, film spd = 4 m/s
- 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
.
10 cm
Moving surface
R-OH
R-OO*
No flow
10 slpm
No flow
Moving surface Moving surface
R* + O
2
R-O-O*
R* + O
3
R - O* R-OH
CONTINUOUS TREATMENT: SURFACE RESIDENCE TIME
- - 5 kV, 1 atm, He/O
2
/H
2
O=89/10/1,
0 0.05 s, 1 kHz
- Lower web speeds improves uniformity by averaging out pulse-to-
pulse modulation.
R-OH
Moving surface
R-OO*
10 cm
Moving surface
Moving surface
R* + O
2
R-O-O*
R* + O
3
R - O* R-OH
- Use of reactive gases (such as NH
3
) in room-air environments
require sophisticated gas injection and confinement.
USE OF REACTIVE GAS MIXTURES
- F. Forster et al, Surf. Coatings Technol., 98, 1121 (1998).
- J. F. Behnke et al, Vacuum, 71, 417 (2003).
SHOE ELECTRODE CONFIGURATION
- Alternating positive and
negative 15 kV pulses.
- Gap = 2 mm.
- He/O
2
flow injected into an air
environment at a few slpm.
- Continuous processing with
moving web.
- Seed electrons randomly with
Gaussian distribution.

REPETITIVELY PULSED DISCHARGE DYNAMICS: [e]
- Peak electron densities
(10
14
cm
-3
) are
generated adjacent to
the momentary
cathode.
- Evidence of sparking
at edge of electrode.
- -15 kV, 1 atm, He/O
2
=90/10, 0 0.005 s, 1 kHz, 10 slpm
Animation Slide-GIF
- [e]

10
10
10
14
cm
-3
10
10
10
14

cm
-3
, log scale
Air

He/O
2
REPETITIVELY PULSED DISCHARGE DYNAMICS [O]
- Electron impact
dissociation of O
2

produces delta function
sources of O.

- In the interpulse period, O
is consumed in formation
of O
3
while being
convected downstream.
- -15 kV, 1 atm, He/O
2
=90/10, 0 0.005 s, 1 kHz, 10 slpm
Animation Slide-GIF
- O

10
11
10
15
cm
-3
10
11
10
15

cm
-3
, log scale
Air

He/O
2
- O
3
is generated pulse to
pulse, accumulate in
discharge and is
convected downstream.

REPETITIVELY PULSED DISCHARGE DYNAMICS [O
3
]
- -15 kV, 1 atm, He/O
2
=90/10, 0 0.005 s, 1 kHz, 10 slpm
Animation Slide-GIF
- O
3
10
12
10
16
cm
-3
Air

He/O
2
10
12
10
15

cm
-3
, log scale
CONTINUOUS PROCESSING OF PP
- The PP is functionalized by
successive pulses as it
moves through the
discharge.
- Peroxy (R-O-O*) coverage
increase towards the exit
due to cumulative
exposure.
- - 15 kV, 1 atm, He/O
2
/H
2
O=90/10,
0 0.05 s, 1 kHz, 10 slpm
Moving surface
R* + O
2
R-O-O*
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., O
3
) 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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RADICAL GENERATION AND POLYMER SURFACE

FUNCTIONALIZATION IN FLOWING ATMOSPHERIC

Iowa State University

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