Korona

RADICAL GENERATION AND POLYMER SURFACE
FUNCTIONALIZATION IN FLOWING ATMOSPHERIC

PRESSURE PULSED DISCHARGES*
Ananth N. Bhoja) and Mark J. Kushnerb)

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
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
Iowa State University

ICOPS_2006_Ananth_2 Optical and Discharge Physics
APPLICATIONS OF POLYMERS
Polymers are used in variety of applications from textile apparel to
packaging to biomedical materials.
Packaging material Textiles Biomedical filtration

The specific polymeric material is chosen not only for its bulk
properties but also for surface characteristics such as wettability,
adhesion and surface reactivity.

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

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.
(b)
(a) Chemical groups are incorporated onto
(c) 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 Iowa State University

PLASMA TREATMENT IMPROVES ADHESIVE BONDING
Adhesion strength of PE
Peel Strength (MPa)
improves by a factor of 2-3

within a few seconds of
treatment in an air plasma.
No Treatment Adhesion shows some
atmospheric degradation
indicating long term
reactivity.
Time (mins)
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)

INDUSTRIAL SURFACE MODIFICATION OF POLYMERS
Pulsed atmospheric filamentary discharges (coronas) are routinely

used to web treat commodity polymers like polypropylene (PP) and
polyethylene (PE).
TYPICAL CONDITIONS
kVs at few kHz
t ~ few ms
Web speed few m/s
Gap : few mm
Filamentary Plasma 10s 200 mm

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.
COMMERCIAL CORONA PLASMA EQUIPMENT
Sigma, Inc.
Tantec, Inc.
Advantages: Disadvantages:
No vacuum equipment required. Lack of specificity - mix of
functional groups are produced.
Suitable for high throughput and
continuous operation. Higher probability of surface
contamination.
Economical.
Most commonly treated polymer is
polypropylene (PP).
STRUCTURE OF POLYPROPYLENE
Polypropylene (PP) is a saturated hydrocarbon polymer containing
alternating methyl (-CH3) 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 HT > HS > HP.
The surface site density of PP is about 1015/cm2 C-atoms.

TREATMENT OF PP IN CORONA DISCHARGES
PP undergoes surface oxidation in O2 containing discharges such

as in air.
Coverage of O-containing groups is near 2.5% (2 x 1013 cm-2) for high

energy density treatment and < 1% (<1013 cm-2) at lower energies.
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.
Micropatterned cell growth on
amino-functionalized polystyrene
in NH3 and H2 plasmas
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.
Ref: K. Schroeder et al, Plasmas

and Polymers 7,103-125 (2002) Iowa State University
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?

MODEL ELECTROSTATICS, CHARGED PARTICLE TRANSPORT
Fully implicit solution of Poissons equation.

t - s (t ) qi N i (t )
i
Continuity: Multi-fluid charged species equations using modified
Scharfetter-Gummel fluxes.
N i ni 1 ni exp(x)
Si i 1/ 2 D
t 1 exp(x)
q i 1 i
m
q x 2v

D
Surface charge on dielectric surfaces.
S
t

qii 1 i jE
i
2-d unstructured mesh.

ELECTRON TRANSPORT AND REACTION KINETICS
Electron energy transport:

3 5
ne kTe / t S Te LTe kTe Te Te
2 2
Reaction Kinetics include sources due to electron impact and heavy

particle reactions, photoionization and contributions from
secondary emission.

r r 3
N i (r ) ij N j (r ) exp d r

S Pi (r )
2
4 r r

S Si j , j ij j
j

FLUID MODULE : NEUTRAL PARTICLE TRANSPORT
Fluid averaged values of mass density, mass momentum and
thermal energy density obtained in using unsteady algorithms.

Continuity : ( v ) ( inlets , pumps )
t

v

Momentum: NkT v v m qi N i Ei
t i
c pT
T v c pT Pi v Ri H i ji E

Energy :
t i i
Individual neutral species densities are updated.

N i t t
N i t t N i t v Di NT SV S S

N T
SURFACE KINETICS MODULE
To predict surface compositions, a surface kinetics module is
incorporated into the plasma dynamics model.
Fluxes
Plasma Surface Surface

Dynamics Kinetics Model densities of
Model functional
groups
Sticking
coefficients Surface reaction
mechanism
Module predicts densities of surface resident groups using

fluxes from the plasma and a user-provided 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.
CORONA DISCHARGE GEOMETRY
2 mm
Not to scale
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.

GAS PHASE CHEMISTRY: He/O2/H2O
Treatment in O2 containing plasmas is known to effectively
incorporate O atoms into the surface.
Process is initiated by electron impact dissociation of O2 and H2O

into radicals such as O and OH.
DYNAMICS OF THE FIRST PULSE: Te, SOURCES
Te peaks at the
ionization front
initiated near the
electrode and
propagates toward
Te 0-9 eV the PP surface.
Electron sources by
electron impact
ionization track the
maximum in Te.
Electron Source
5x1020-5x1023 cm-3s-1
Animation Slide-GIF
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 02 ns, no flow

ICOPS_2006_Ananth_19
MIN MAX Optical and Discharge Physics
log scale
PLASMA DYNAMICS OF THE FIRST PULSE
[e] 1011 1014 cm-3 OH 1011 1014 cm-3 O 1011 1015 cm-3
Electron density of 1013-1014 cm-3 is produced behind the front.

O and OH are produced predominantly by electron impact reactions
of O2 and H2O respectively.
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 02 ns, no flow. Animation Slide-GIF

log scale
END OF FIRST PULSE AFTERGLOW: RADICALS
[O] 1011 1013 cm-3 [OH] 1011 1013 cm-3 [O3] 5x1012-5 x 1014 cm-3
The density of O decreases to 1012 cm-3 in the interpulse period as it

is consumed in 3-body reactions with O2 to form O3 (1014 cm-3).
The density of OH decreases to 1012 as it reacts with both O and O3.
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 100 ms, no flow

log scale
RADICALS AND GROUPS AT CARBON CENTERS ON PP
Polypropylene structure
Different radicals and functional groups are created at the carbon

atoms when treated in O2 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:
t = 1 - 10 ms
Alkyl radicals (R*) formed by H abstraction by OH and O.
Propagation and saturation:
t = 10-100 ms
Peroxy (R-O-O*) formed by the addition of O2 to alkyl (R*) sites.

SURFACE REACTION MECHANISM: PROPAGATION
Propagation:
t = 10-100 ms
Alkoxy (R-O*) formed by reaction of O3 and O with alkyl (R*) sites.

Surface surface reactions:
t = 10-50 ms
Alkoxy (R-O*) radicals abstract H from surrounding sites to form
alcohol (R-OH) groups.

SURFACE REACTION MECHANISM: CHAIN SCISSION
Carbonyl (R-C=O) groups are formed by chain scission.
t = 50 - 100 ms
Abstraction from carbonyl groups (R-C*=O) may lead to further

chain degradation evolving CO2 into the gas phase.
t = 100 - 1000 ms

SURFACE REACTION MECHANISM: TERMINATION
Termination
t = 100 - 1000 ms
Addition of OH produces carboxylic acid groups.
H and OH also add to alkyl radicals (R*) in termination steps.

PP TREATMENT WITH A SINGLE PULSE
RH + O, OH R* + OH, H2O R* + O, O3 R - O* + O2
R* + O2 R - OO*
R*
R-OO*
R-O*
Alkyl (R*) radicals are formed within 10 ms.

Alkoxy (R-O*) and peroxy (R-OO*) are
formed as alkyl (R*) sites react over 10s ms .
0.5 cm
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 0 100 ms Iowa State University

DYNAMICS WITH REPETITIVE PULSING (NO FLOW)
10 cm
[e]
OH
O and OH are generated in each pulse and consumed between pulses

in reactions with O2 and O3 respectively.
O3
O3 is relatively unreactive and so accumulates pulse-to-pulse.

Animation Slide-GIF
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 1 kHz, 0.005 s
1010 1014
ICOPS_2006_Ananth_28 cm-3, log scale Optical and Discharge Physics
PP TREATMENT WITH REPETITIVE PULSE (NO FLOW)
RH + O, OH R* + OH, H2O R* + O2 R-O-O*
Alkyls (R*) are regenerated every

pulse by O and OH, and consumed.
2 cm Peroxy (R-O-O*) accumulate pulse-to-
pulse
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 1 kHz, 0.05 s Iowa State University
PULSED DISCHARGES WITH GAS FLOW
Axial gas flow varied from negligible to a few slpm (t = 10s ms)
How does gas flow aid in treatment downstream?

- 5 kV, 1 atm, He/O2/H2O=89/10/1, few slpm ( | v | = 10s 100s cm/s)

EFFECT OF GAS FLOW ON RADICALS: [O]
no flow
10 slpm
30 slpm
O is highly reactive with O2 to form ozone (O3).

Although some O is convectively transported downstream, local
reaction kinetics dominate. Nearly all O reacts prior to the next pulse.
Animation Slide-GIF
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 0 0.005 s, 1 kHz, static surface
1010 1014 Iowa State University

cm-3, log scale Optical and Discharge Physics
EFFECT OF GAS FLOW ON RADICALS: [O3]
no flow
10 slpm
30 slpm
With gas flow, the accumulating O3 is convected downstream.
Animation Slide-GIF

EFFECT OF GAS FLOW ON PP TREATMENT
R* + O2 R-O-O*
R* + O3 R - O* R-OH 10 cm
R-OH R-OO*
Alkoxy (R-O*) and alcohol (R-OH) decrease under the electrode.

Peroxy (R-O-O*) increases downstream as alkyl sites are saturated.

WEB TREATMENT OF POLYMER SURFACES
Polymer surfaces are

continuously treated at web
speeds of a few m/s.
Model addresses web
treatment by translate the
surface properties on the
Moving surface grid at a few m/s.
TYPICAL CONDITIONS
t ~ few ms
Gap : few mm

CONTINUOUS TREATMENT
R-O*
Moving surface
10 cm
R-OH
Moving surface
R*
Moving surface
Surface has active sites which react

downstream of the plasma zone.
Moving surface
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 0-0.025s, 1
kHz, web speed = 4 m/s, no flow
R* + O2 R-O-O*
R* + O3 R - O* R-OH
CONTINUOUS TREATMENT: GAS FLOW
Moving surface
R* + O2 R-O-O*
R* + O3 R - O* R-OH 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 O3.
- 5 kV, 1 atm, He/O2/H2O=89/10/1, 0.05 s, Iowa State University
1 kHz, film spd = 4 m/s Optical and Discharge Physics
CONTINUOUS TREATMENT: SURFACE RESIDENCE TIME
R* + O2 R-O-O* Moving surface

R* + O3 R - O* R-OH 10 cm
R-OH R-OO*
Moving surface Moving surface
Lower web speeds improves uniformity by averaging out pulse-to-

pulse modulation.
- 5 kV, 1 atm, He/O2/H2O=89/10/1,
0 0.05 s, 1 kHz
USE OF REACTIVE GAS MIXTURES
Use of reactive gases (such as NH3) in room-air environments

require sophisticated gas injection and confinement.
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/O2 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]
He/O2
Peak electron densities
Air
(1014 cm-3) are
generated adjacent to
the momentary
cathode.
Evidence of sparking
at edge of electrode.
[e]
1010 1014 cm-3
Animation Slide-GIF
-15 kV, 1 atm, He/O2=90/10, 0 0.005 s, 1 kHz, 10 slpm

REPETITIVELY PULSED DISCHARGE DYNAMICS [O]
He/O2
Air Electron impact

dissociation of O2
produces delta function
sources of O.
In the interpulse period, O

is consumed in formation
of O3 while being
O
convected downstream.
1011 1015 cm-3
Animation Slide-GIF

REPETITIVELY PULSED DISCHARGE DYNAMICS [O3]
He/O2
Air
O3 is generated pulse to
pulse, accumulate in
discharge and is
convected downstream.
O3
1012 1016 cm-3
Animation Slide-GIF

CONTINUOUS PROCESSING OF PP
R* + O2 R-O-O*
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.
Moving surface
- 15 kV, 1 atm, He/O2/H2O=90/10,

0 0.05 s, 1 kHz, 10 slpm

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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RADICAL GENERATION AND POLYMER SURFACE

FUNCTIONALIZATION IN FLOWING ATMOSPHERIC

Ananth N. Bhoja) and Mark J. Kushnerb)

33rd IEEE International Conference on Plasma Science

*Supported by the NSF and 3M, Inc.

Plasma Surface Modification of Polymers

Description of the Model

Atmospheric Pressure He/O2/H2O Corona Discharges for

Iowa State University

Packaging material Textiles Biomedical filtration

Iowa State University

Iowa State University

Courtesy: http://www.polymer-surface.com Iowa State University

improves by a factor of 2-3

Peel strength of Polyethylene (PE)

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

Iowa State University

Pulsed atmospheric filamentary discharges (coronas) are routinely

Filamentary Plasma 10s 200 mm

Iowa State University

Advantages: 1.Designed to treat non-conductive surfaces. It is a more efficient system

Advantages: 1. Can treat metallized substrates.

Disadvantages: 1. Less efficient than covered roll.

A Carbon atom can be attached to 3 H atoms (primary Carbon), 2 H

Iowa State University

PP undergoes surface oxidation in O2 containing discharges such

Coverage of O-containing groups is near 2.5% (2 x 1013 cm-2) for high

Biomedical materials are treated in

Improved control over incorporation of functional groups onto

Ref: K. Schroeder et al, Plasmas

Iowa State University

2-d unstructured mesh.

Electron energy transport:

Reaction Kinetics include sources due to electron impact and heavy

Iowa State University

Individual neutral species densities are updated.

Plasma Surface Surface

Module predicts densities of surface resident groups using

Iowa State University

Electrode embedded in dielectric with tip exposed to the

Applied voltage (10 ns pulses) at up to 10s kV, 0.1 10 kHz.

Iowa State University

Process is initiated by electron impact dissociation of O2 and H2O

- 5 kV, 1 atm, He/O2/H2O=89/10/1, 02 ns, no flow

Electron density of 1013-1014 cm-3 is produced behind the front.

- 5 kV, 1 atm, He/O2/H2O=89/10/1, 02 ns, no flow. Animation Slide-GIF

Iowa State University

The density of O decreases to 1012 cm-3 in the interpulse period as it

- 5 kV, 1 atm, He/O2/H2O=89/10/1, 100 ms, no flow

Iowa State University

Different radicals and functional groups are created at the carbon

Iowa State University

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

Propagation and saturation:

Peroxy (R-O-O*) formed by the addition of O2 to alkyl (R*) sites.

Iowa State University

Alkoxy (R-O*) formed by reaction of O3 and O with alkyl (R*) sites.

Iowa State University

Abstraction from carbonyl groups (R-C*=O) may lead to further

Iowa State University

Addition of OH produces carboxylic acid groups.

H and OH also add to alkyl radicals (R*) in termination steps.

Alkyl (R*) radicals are formed within 10 ms.

Peroxy (R-O-O) formed by the addition of O2 to alkyl (R) sites.

Alkoxy (R-O) formed by reaction of O3 and O with alkyl (R) sites.