U.
S.
Environmental
Protection
Agency
June
20,
2003
Draft
Agenda
Fluoropolymer
Technical
ECA
Workgroup
Meeting
Monday,
June
23,
2003
9:
00­
12:
00
PM
Mission
Statement:
The
Fluoropolymer
Workgroup
will
develop
ECA
proposal(
s)
for
data
needs
identified
in
items
2,
7,
8,
9
and
11
of
Table
II
in
the
EPA
Preliminary
Framework
document,
specifically
addressing:
(
a)
the
physical/
chemical
(
p­
chem)
properties
of
the
fluoropolymers;
(
b)
the
presence
of
PFOA
emitted
from
fluoropolymer­
treated
products
and
articles
as
they
age
during
use
for
those
products
and
articles
not
included
in
the
Letter
of
Intent
(
LOI)
commitments;
(
c)
determining
the
incineration
byproducts
of
fluoropolymers
and
fluoropolymer­
treated
articles
and
determining
the
p­
chem,
fate,
and
transport
properties
of
those
byproducts;
and
(
d)
product
stewardship
information.

Meeting
Objective:
Scoping
meeting
to:
1.
Identify,
with
respect
to
each
of
the
data
needs
enumerated
above
in
the
EPA
Preliminary
Framework,
what
specific
portions
of
the
work
are
included
in
the
LOI,
to
allow
all
workgroup
participants
to
understand
fully
what
is
included,
how
many
and
what
chemicals/
types
of
chemicals
are
covered,
what
tests
will
be
conducted,
what
protocols
will
be
used,
when
information
will
be
reported,
etc.
2.
Identify
and
discuss
activities
within
the
EPA
Preliminary
Framework
beyond
the
scope
of
the
LOI
which
may
be
appropriate
for
consideration
in
the
ECA
process;
3.
Identify
workgroup
next
steps
and
assignments
Workgroup
Participants:
3M;
Bennett
&
Williams;
CPSC;
EPA;
EWG;
FMG
Order
of
Meeting:

°
Introductions:
Chair,
Phil
Oshida,
Director,
Chemical
Control
Division,
U.
S.
EPA
EPA
Technical
Lead:
John
Blouin,
Economics,
Exposure
&
Technology
Division
°
Presentation
on
scope
of
LOI
commitments
(
OPPT­
2003­
0012­
0012)
by
industry
°
Discussion
of
activities
beyond
the
LOI
commitments
for
consideration
by
ECA
process
°
Identification
of
workgroup
next
steps;
determination
of
workgroup
assignments
for
workgroup
and
plenary
meetings
on
July
9
and
10,
2003
PFOA
ECA
Fluoropolymer
Technical
Workgroup
Meeting
June
23,
2003
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ECA
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June
23,
2003
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ECA
Fluoropolymer
Technical
Workgroup
Meeting
June
23,
2003
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Fluoropolymer
Technical
ECA
Workshop
Agenda
°
Product
Stewardship
°
Physical/
Chemical
properties
of
Fluoropolymers
°
Articles
of
Commerce
Testing
°
Incineration
FMG
­
Product
Stewardship
June
23rd,
2003
EPA
ECA
Framework
Objective
Improved
understanding
on
industry's
product
stewardship
efforts
with
respect
to
the
products
and
issues
for
which
PFOA
is
a
concern
FMG
LOI
Commitment
°
The
fluoropolymer
manufacturers
have,
and
will
continue
to
follow
principles
of
product
stewardship
similar
to
those
described
by
ACC
or
SOCMA
Responsible
Care
®
programs.

°
The
FMG
is
committed
under
the
LOI
to
providing
appropriate
product
stewardship
information
to
fluoropolymer
processors.
FMG
­
Product
Stewardship
(
PS)

Efforts
°
Leadership,
accountability
and
performance
measurements
and
resource
commitment:

 
Each
company
maintains
written
policies
developed
and
approved
by
senior
management
around
product
stewardship
and
incorporates
PS
in
business
planning
and
individual
performance
planning.

 
Companies
commit
resources
to
industry
efforts
to
provide
best
collective
knowledge
of
product
health
and
safety
information.
Information
is
published
in
industry
documents.
FMG
­
Product
Stewardship
(
PS)

Efforts
°
Safety,
Health,
and
Environmental
information:

 
Industry
members
individually
and
collectively
work
through
trade
organizations
e.
g
SPI/
APME
to
maintain
and
share
latest
SHE
information
 
Examples:

°
MSDS
sheets
for
all
products
sold
°
Guide
for
Safe
Handling
of
Fluoropolymer
Resins
°
Guide
for
Safe
Handling
of
Fluoropolymer
Dispersions
°
Technical
literature
 
LOI
commitment
°
share
technology
for
recycle
and
destroy
or
use
°
emission
reduction
program
°
update
safe
handling
guide
FMG
­
Product
Stewardship
(
PS)

Efforts
°
Product
risk
characterization,
management,

design
and
improvement.

 
Industry
works
through
APME's
Toxicology
group
to
fund
relevant
toxicology
and
environmental
fate
research
to
better
understanding.

 
LOI
commitment
°
10
studies
funded
for
completion
in
2003
FMG
­
Product
Stewardship
(
PS)

Efforts
°
Employee
education
and
product
use
including
contract
manufacturers,
and
distributors.

 
FMG
companies
have
and
continue
to
be
committed
to
the
education
of
their
employees,
contract
manufacturers
and
distributors
with
training
through
product
literature
and
safe
handling
guides
 
LOI
commitment:
share
specific
safety,
health
and
environmental
compliance
programs
with
EPA.
FMG
­
Product
Stewardship
(
PS)

Efforts
°
Customers
and
direct
receivers
of
products
 
Information
provided
through
individual
company
MSDS,
product
literature,
processing
technical
guides.

 
Industry
documents
e.
g.
Safe
Handling
Guides
 
Training
at
customer
sites
and
trade
association
meetings
°
PFOA
reviews
at
SPI
Fluoropolymer
Division
semi­
annual
meetings
held
Oct.
2000,
March
2001,
October
2001,
March
2002,
October
2002,
and
April
2003
 
Technical
support
to
processors
to
enable
to
meet
statutory
obligations.
FMG
­
Product
Stewardship
(
PS)

Efforts
°
Customers
and
direct
receivers
of
products
(
cont'd)

 
LOI
commitments:

°
Develop
representative
material
balance
for
fate
of
PFOA
at
fluoropolymer
dispersion
users'
sites.

°
Develop
representative
articles
of
commerce
testing
°
Define
appropriate
product
stewardship
elements
to
address
findings.

°
Continue
to
provide
updated
information
as
developed
to
maintain
occupational
and
safety
standards
current.
Product
Stewardship
Summary
°
Industry
has
had
comprehensive
PS
programs
over
the
years
following
accepted
principles
°
LOI
commitment:

 
Fund
additional
toxicology
and
fate
studies
 
Update
information
materials
with
new
information
 
Continue
to
conduct
training
and
offer
technical
support
to
processors
 
Fund
study
to
understand
material
fate
at
users
of
dispersion
fluoropolymers.

 
Share
technology
to
reduce
environmental
emissions
Product
Stewardship
Summary
°
FMG
believes
that
Product
Stewardship
needs
are
included
in
LOI
°
FMG
member
companies
are
willing
to
provide
additional
information
on
their
programs
as
needed
Physical/
Chemical
Properties
°
Document
prepared
to
address
Item
2
of
the
framework
document
(
Document
also
addresses
item
3)

°
Recommendation:
interested
parties
review
document
and
discuss
any
additional
needs
at
the
July
9
technical
meeting.
Articles
of
Commerce
Testing
LOI
Summary
°
Intent
of
study:
evaluate
the
potential
for
articles
of
commerce
to
contribute
to
APFO
exposure
°
Commits
to
analysis
for
APFO
in
articles
made
with:

 
Dry
fluoropolymer
resins
 
Liquid
dispersions
°
Articles
selected
based
on:

 
Widespread
consumer
use
 
Sample
of
industrial
and
commercial
products
Articles
of
Commerce
Testing
°
Selection
Criteria
 
Consumer
applications
­
applications
where
the
general
public
may
routinely
comes
in
contact
with
articles
containing
a
fluoropolymer
 
Industrial
applications
­
applications
that
are
used
in
an
industrial
or
commercial
setting
 
High
heat
processing
­
applications
where
the
article
during
manufacture
receives
thermal
exposure
(
time
and
temperature)
above
where
APFO
is
expected
to
be
driven
off
or
destroyed
 
Low
heat
processing
­
applications
where
the
article
during
manufacture
may
not
receive
such
thermal
exposure
Articles
of
Commerce
Testing
°
Prioritization
criteria
based
on
potential
exposure
routes
 
Consumer
applications
 
Low
heat
applications
 
Higher
Volume
industrial
applications
°
Test
Protocol
 
New
articles
°
FDA
Test
21
CFR
175.300
°
Extraction
with
appropriate
simulated
food
solvents
°
Targeted
completion
by
end
of
2003
 
Aged
articles
°
FDA
Test
­
Guidance
for
Industry,
dated
April,
2002
°
Extraction
with
appropriate
solvents
for
240
hours
Articles
of
Commerce
Testing
°
Next
Steps
 
New
Articles
°
FMG
will
review
articles
for
testing
covered
in
the
LOI
on
July
9
°
Develop
and
Finalize
study
plan
°
Validate
analytical
methods
°
Identify
3rd
parties
for
testing
°
Complete
timeline
 
Aged
Articles
°
Based
on
results
above,
select
appropriate
articles
for
testing
Incineration
of
Fluoropolymers
°
Intent:
determine
if
incineration
results
in
emissions
of
PFOA
 
Fluoropolymers
 
Fluoropolymer
containing
articles
°
Protocol
 
Model
incineration
using
Univ
of
Dayton
lab
scale
thermal
degradation
test
°
Municipal
and
Hazardous
Waste
incineration
Incineration
of
Fluoropolymers
°
Choose
representative
fluoropolymers
and
articles
°
Adapt
existing
protocol
to
fluoropolymers,

 
Use
3M
study
as
basis
 
Set
up
detection
system
capable
of
capturing
and
quantifying
PFOA
in
exhaust
stream
 
Review
protocol
with
EPA
prior
to
starting
test
BASIC
FLUOROPOLYMER
DATA
(
23
June
2003)

Fluoropolymers
Manufacturing
Group
(
FMG)
Society
of
the
Plastics
Industry,
Inc.
(
SPI)
1801
KStreetNW
Washington,
D.
C.

Table
of
Contents
Introduction
Item
2.
P­
chem
properties
to
inform
fate
testing
Item
2.1
Polytetrafluoroethylene,
PTFE
Item
2.1.1
Polymerization
Item
2.1.2
Properties
Item
2.1.2.1
Molecular
Structure
Item
2.1.2.2
Molecular
Weight
and
Crystallinity
Item
2.1.2.3
Transitions
Item
2.1.2.4
Chemical
Resistance
2.1.2.5
Oxygen
Compatibility
ofPTFE
Item
2.2
Perfluoroalkoxy
Polymer,
PFA
Item
2.1.1
Polymerization
Item
2.1.2
Properties
Item
2.1.2.1
Molecular
Structure
liem
2.1.2.2
Molecular
Weight
and
Crystallinity
Item
2.1.2.3
Transitions
Item
2.1.2.4
Chemical
Resistance
Item
2.3
Perfluorinated
Ethylene­
Propylene
Copolymer,
FEP
Item
2.1.1
Polymerization
Item
2.1.2
Properties
Item
2.1.2.1
Molecular
Structure
Item
2.1.2.2
Molecular
Weight
and
Crystallinity
Item
2.1.2.3
Transitions
Item
2.1.2.4
Chemical
Resistance
Item
2.4
Optical
Spectral
Properties
and
Weathering
Resistance
of
Fluoropolymers
Item
2.5
Effect
of
Ozone
on
Fluoropolymers
Item
3.
Elucidation
of
degradation
pathways
and
identification
of
degradation
products
­
2­
FLUOROPOLYMER
DATA
NEEDS
Introduction
Commercial
fluoropolymers
based
on
TFE
include
homopolymers
and
copolymers.
Homopolymers
contain
99%
or
more
by
weight
TFE
and
1%
or
less
by
weight
of
another
monomer
according
to
the
convention
by
American
Societyfor
Testing
Materials
(
ASTM).
The
comonomers
may
or
may
not
be
fully
fluorinated.
Commercially
significant
examples
of
the
minor
comonomers
(
also
called
modifiers)
include
perfluoromethyl
vinyl
ether
(
PMVE),
perfluoroethyl
vinyl
ether
(
PEVE),
perfluoropropyl
vinyl
ether
(
PPVE),
hexafluoropropylene
(
HFP),
chlorotrifluoroethylene
(
CTFE)
and
perfluorobutyl
ethylene
(
PFBE).
Ofthese,
CTFE
and
PFBE
are
not
perfluorinated.

Copolymers
of
TFE
(
according
to
the
ASTM
definition)
contain
1%
or
more
by
weight
of
one
or
more
comonomers.
Commercially
significant
examples
of
these
comonomers
include
PMVE,
PEVE,
PPVE,
HFP
and
combinations
thereof.

In
this
paper,
ASTM
definition
of
homopolymer
and
copolymer
is
observed
for
clarity.
Furthermore,
separate
discussion/
data
are
presented
for
homopolymer
and
copolymers
where
ease
of
understanding
and
clarity
of
discussion
are
enhanced
by
such
division.
It
is
noteworthy
to
realize
that
generally
all
perfluoropolymers
are
available
in
pellet,
fine
powder
and
dispersion
forms.

Item
2.
P­
chem
properties
to
inform
fate
testing
"
P­
chem
properties"
is
the
abbreviation
for
the
physico­
chemical
properties
of
fluoropolymers.
The
intent
of
this
Item
is
to
explore
physical­
chemical
properties
that
provide
information
("
inform")
about
the
destiny
("
fate")
of
fluoropolymers
after
they
have
been
produced,
be
it
in
application
or
other
manners
ofpresence.

Item
2.1
Polytetrafluoroethylene,
PTFE
[
CAS
number
9002­
84­
0]

Item
2.1.1
Polymerization
This
plastic
is
a
perfluorinated
straight­
chain
polymer
with
very
high
molecular
weight.
It
is
produced
by
free­
radical
polymerization
mechanism
in
an
aqueous
media
via
addition
polymerization
of
tetrafluoroethylene
(
CF2=
CF2,
molecular
weight
100.02,
CAS
number
116­
14­
3).
Contrary
to
condensation
polymerization,
no
molecule
has
to
be
removed
to
allow
the
addition
polymerization
to
occur.
The
initiator
for
the
polymerization
is
usually
awater­
soluble
peroxide
such
as
ammonium
persulfate
or
disuccinic
peroxide.
Aredox
catalyst
is
used
when
low
temperature
polymerization
is
desired.
PTFE
can
be
produced
by
suspension
(
orslurry)
polymerization
in
the
absence
of
a
surfactant
to
obtain
granular
resins
or
in
the
presence
of
a
perfluorinated
surfactant
(
emulsion
polymerization)
to
produce
fine
powder
and
dispersion
products.

There
also
low
molecular
weight
grades
of
PTFE,
called
micropowders,
micronized
powder
andfluoroadditives,
that
are
produced
by
either
direct
polymerization
or
radiochemical/
thermal
degradation
of
high
molecular
PTFE.
These
powders
are
usually
used
as
a
minor
ingredient
to
impart
fluoropolymer­
like
properties
to
a
host
system,
such
as
thermoplastics
or
printing
inks.

Basic
Fluoropolymer
Data
(
23
June
2003).
­
3­
Item
2.1.2
Properties
PTFE
has
unique
properties
such
as
chemical
inertness,
heat
resistance
(
both
high
and
low),
electrical
insulation
properties,
low
coefficient
of
friction
and
non­
stick
property
over
a
wide
temperature
range.
It
has
a
density
in
the
range
of
2.1­
2.3
g/
cm3
and
melt
viscosity
in
the
range
of
1­
10
GPa.
s
[
1].
PTFE
melt
does
not
flow
because
of
its
high
molecular
weight,
thus
requiring
non­
conventional
fabrication
techniques
similar
to
those
employed
for
metal
powder
(
granular
PTFE),
ceramic
paste
(
fine
powder
PTFE)
and
latex
(
dispersion
PTFE)
processing.
Three
ASTM
methods
and
ISO
standards
govern
the
classification
of
various
forms
of
PTFE.
These
methods
include
ASTM
D4894­
98
(
granular),
ASTM
D4895
(
fine
powder),
ASTM
D4441­
98
(
dispersion)
and
ASTM
D5675­
98
(
micropowders,
except
dispersions
D4441­
98).
ISO
Standards
12086­
1
and
12086­
2
specify
all
forms
of
PTFE.

Item
2.1.2.1
Molecular
Structure
Figure
2.1
shows
a
schematic
of
a
segment
of
a
PTFE
molecule,
which
is,
in
reality,
appears
as
a
helix
with
13
carbons
atoms
required
for
a
180
°
turn
at
temperature
<
19
°
C.
At
temperatures
>
19
°
C,
15
carbon
atoms
are
necessary
for
a
180
°
turn.
Recent
Atomic
Force
Microscopy
research
at
NASA
has
actually
revealed
the
helical
structure
of
PTFE
(
Figure
2.2).

r
F
F
F
F
Figure
2.1
A
Segment
ofPolytetrafluoroethylene
Molecule
The
backbone
of
the
molecule
is
formed
of
carbon­
carbon
bonds,
where
each
carbon
is
bonded
to
two
fluorine
atoms.
Both
are
extremely
strong
bonds
(
C­
C,
607
kJ/
mole
and
C­
F,
552
kJ/
mole.).
The
basic
properties
of
PTFE
stem
from
these
two
very
strong
chemical
bonds.
The
size
of
the
fluorine
atom
allows
the
formation
of
a
uniform
and
continuous
covering
around
the
carbon­
carbon
bonds
and
protects
them
from
attack,
thus
imparting
chemical
resistance
and
stability
to
the
molecule.
PTFE
is
rated
for
continuous
use
up
to
260
°
C.
PTFE
does
not
dissolve
in
any
common
organic
or
inorganic
solvent.
In
fact,
no
common
commercial
chemical
is
known
to
chemically
attack
PTFE.
The
fluorine
sheath
is
also
responsible
for
the
low
surface
energy
(
18
dynes/
cm)
and
low
coefficient
of
friction
(
0.05­
0.8,
static)
of
PTFE.
Another
attribute
of
the
uniform
fluorine
sheath
is
the
electrical
inertness
(
or
non­
polarity)
of
the
PTFE
molecule.
Electrical
fields
impart
only
slight
polarization
in
this
molecule,
so
volume
and
surface
resistivity
are
high.

Basic
Fluoropolymer
Data
(
23
June
2003)
­
4­

Depth
Figure
2.2
Fourier­
filtering
Mode
of
Image
Obtained
by
Atomic
Force
Microscopy­
the
bright
white
spots
show
individual
fluorine
atoms
along
the
PTFE
Chain
[
2]

Item
2.1.2.2
Molecular
Weight
and
Crystallinity
Apractical
consequence
of
chemical
inertness
of
PTFE
is
that
primary
methods
such
as
Osmotic
pressure
and
intrinsic
viscosity
or
secondary
methods
such
as
gel
permeation
chromatography
and
fractional
precipitation
can
not
measure
its
molecular
weight.
Instead
an
indirect
indication
is
used
to
judge
molecular
weight.
Standard
specific
gravity
(
SSG)
consists
of
(
perASTMMethods
D4894
or
D4895)
measurement
of
the
specific
gravity
of
a
chip
prepared
according
to
standardized
compression
molding,
heating
(
sintering)
and
cooling
rate
cycles.
The
underlying
principle
is
that
lower
molecular
weight
PTFE
crystallizes
more
extensively,
thus
yielding
higher
SSG
values
[
3].
The
operating
assumption
is
an
absence
of
voids
in
the
PTFE
chip,
although
there
are
methods
to
correct
for
the
voids
[
4].

SSG
has
been
correlated
with
molecular
weight
in
a
study
in
which
the
end
groups
were
marked
by
using
an
initiator
containing
a
radioactive
sulfur
[
5].
Commercial
polymers
were
found
to
have
number­
average
molecular
weights
in
the
range
of
one
to
10
million.
A
correlation
(
Eq.
2.1)
has
been
developed
[
6]
to
calculate
a
number­
average
molecular
weight
using
measured
SSG
values.
Table
2.1
shows
examples
ofM~
values
calculated
from
equation
M~
O.
597[
log
0.157
]
x106
(
2.1)
2.306
 
SSG
A
Basic
Fluoropolymer
Data
(
23
June
2003)
­
5­

Table
2.1
Calculated
Values
ofMolecular
Weight
(
Eq.
2.1)
SSG
M~
x1116
2.16
18.9
2.20
9.6
2.25
3.5
2.30
0.4
Melting
and
crystallization
of
PTFE
has
been
studied
by
Differential
Scanning
Calorimetry
(
DSC)
and
a
correlation
has
been
found
between
the
heat
of
crystallization
and
the
number­
average
molecular
weight
[
7].
This
correlation
(
Eq.
2.2)
is
independent
of
cooling
rate
in
the
range
of
4­
32
°
C/
mm.
In
this
equation
DeltaH~
is
the
heat
of
crystallization
in
J/
g.
For
example
a
heat
of
crystallization
of
26
J/
g
yields
aM~
of
1
.7x1
06.

 
10
 
5.16
M~=
2.1x10(
Deltaj­
j~)
(
2.2)

PTFE
that
has
not
been
previously
melted
has
a
ciystallinity
of
92­
98%,
indicating
a
linear
and
non­
branched
molecular
structure.
Upon
reaching
342
°
C,
it
melts
changing
from
a
chalky
white
color
into
a
transparent
amorphous
gel.
The
second
melting
point
of
PTFE
is
327
°
Cbecause
it
never
re­
crystallizes
to
the
same
extent
as
prior
to
its
first
melting.
Melting
point
of
PTFE
increases
with
pressure.

It
is
difficult
to
determine
the
molecular
weight
distribution
of
PTFE
because
of
absence
ofMW
measurement.
An
indication
of
the
MW
distribution
is
the
width
of
the
DSC
thermogram
at
half
the
height
atthe
peak
melt
point.
Basically,
the
wider
the
thermogram,
the
broader
the
MW
distribution
(
line
segment
AB
in
Figure
2.3).

Heat
Flow
A
B
TemDerature
Figure
2.3
Schematic
ofDSC
Thermogram
Basic
Fluoropolymer
Data
(
23
June
2003)
­
6­

Item
2.1.2.3
Transitions
Anumber
of
first
and
second
order
transitions
have
been
reported
for
PTFE
as
summarized
in
Table
2.2.
Those
transitions
that
are
close
to
room
temperature
are
of
practical
interest
because
of
their
impact
on
processing
of
the
material.
Below
19
°
Cthe
crystalline
system
of
PTFE
is
anearly
perfect
triclinic.
Above
19
°
C,
the
unit
cell
changes
to
hexagonal.
In
the
range
of
19
 
30
°
C,
the
chain
segments
become
increasing
disorderly
and
the
preferred
crystallographic
direction
disappears.
Between
19
°
Cand
3
0
°
C,
there
is
a
large
expansion
in
the
specific
volume
of
PTFE
approaching
1.8%
[
8]
which
must
be
considered
in
measuring
the
dimensions
of
articles
made
from
this
plastics.

Item
2.1.2.4
Chemical
Resistance
Polytetrafluoroethylene
is
by
far
the
most
chemically
resistant
polymer
among
thermoplastics.
Few
substances
chemically
interact
with
PTFE.
The
exceptions
among
those
commercially
encountered
include
molten
alkali
metals,
gaseous
fluorine
at
high
temperatures
and
pressures,
and
few
organic
halogenated
compounds
such
as
chlorine
trifluo.
ride(
CJF3
)
and
oxygen
difluoride
(
OF2).
The
inertness
of
PTFE
arises
from
its
molecular
structure.
Afew
other
chemicals
have
been
reported
to
attack
PTFE
at
or
near
its
upper
service
temperature
(
260
°
C).
PTFE
reacts
with
80%
sodium
or
potassium
hydroxide.
It
also
reacts
with
some
strong
Lewis
bases
including
metal
hydrides
such
as
boranes
Table
2.2
Transitions
of
Polytetrafluoroethylene
[
9]

31J
St
1
Order
,

€
rvsialline
.

Crystal
Disorder
`)
fl
I
}
rder
Crystalline
~
LX)
2uid
Order
Amorphous
On­
set
ot
rotaticoial
motion
around
C­
C
bond
­
31)
Order
Amorphous
1
30
2'~(
irder
Amorphous
(
B2H6),
aluminum
chloride,
ammonia,
and
some
amines
(
R­
NH2)
and
imines
(
R=
NH).
Slow
oxidative
attack
may
take
place
by
70%
nitric
acid
at
250
°
Cunder
pressure.
It
is
important
to
test
the
effect
of
these
reagents
on
PTFE
under
the
specific
application
temperature
to
determine
the
material
limitations.

Tables
2.3
through
2.6
show
actual
results
of
chemical
compatibility
testing
for
a
large
number
of
chemicals
from
various
classes
of
compounds.
Based
on
the
chemical
resistance
of
PTFE,
one
can
conclude
that
there
is
no
possibility
of
hydrolysis
of
PTFE.
Water
alone
has
no
effect
on
PTFE
or
any
other
perfluoropolymer.

Other
properties
of
PTFE
can
be
found
in
Table
2.7.
19
1
Ot
icr
crystalline
Anrular
Displacement
Basic
Fluoropolymer
Data
(
23
June
2003)
7­

Table
2.3
Chemical
Resistance
of
PTFE
to
Common
Solvents
[
10]

20
SI)
70
0,3
0,4
0
Table
2.4
Chemical
Compatibility
ofPTFE
with
Halogenated
Solvents
[
11]

chemw~
i1
Ch.
lorofomi
Elfect
on
PTFE
Saniple
Wets,
insoluble
at
boi:
Ling
point
Ethylene
Bromide
0.3%
weight'
gain
after
24
hr.
at
l00~
C
Fhioiinatnd
Hydrocarbons
Wets,
s~
veflingoccurs
in
bailing
solvent
Fluoro­
naphthàlene
iusokthle
at
boiling
çcilnt,
same
swelling
FlLloiomtmbenzene
Insolub:
le
at
boiling
~
xiaL
some
sweiing
Pen
tachIorobenzamide
insoluble
PerfiL:
Ioioxyleue
insoluble
at
bailing
point,
slight
sweilling
Tetmbron'ioethane
hisoluble
at
boiling
point
Tetmc1iioro~
h.
yieiie
Wets,
sonic
s~
eiiingafter
2
hr
at
I20~
C
Trirhioroacetic
Acid
hisollubie
at
bailing
point
Trickloroethvlene
:
L1iSOlUbiB
at
boilling
point
after
1
hr.
Acetone
12
ma
12
me.
2
wk,

Beniene
75
96
hr
05
100
$
hr
200
S
hr
1.0
Carbon
Tetrachloride
25
i2mo,
0.6
50
12
mo.
1.6
70
2
wk.
1.9
100
$
hr
2.5
200
8
hr
3.7
Ethanol
(
95W)

.
25
121110.
0
50
12
ma
(
1
~
70
2
wk,
0
100
Shr
0,1
200
S
hr
0.3
Ethyl
A~
etate
25
l2ino,
0,5
50
121110,
0.7
70
2
wk.
0,7
Tolnene
25
121110,
0.3
50
12
mc.
0.6
70
2
wk.
0.6
Basic
Fluoropolymer
Data
(
23
June
2003)
­
8­

Table
2.5
Chemical
Compatibility
of
PTFE
with
Common
Acids
[
12]

Reagent
E'wosure
Eiposure
Thee
%~~
uI
Gain,
%
Temperature,
C
Hydrochloric
Acid
lU%
25
12
.
i.
no.
0
10%
50
12
mo
0
llJ%
70
12
ma
U
20%
100
Shr
U
209~,
200
Shr
U
Nitric
Arid
10%
10%
25
12
mc.
70
l2mo.
U
0.1
Sulfuric
Acid
30%
30%
30%
30%
25
12
ma
70
l2mo,
100
S
hr
2:
00
.
Sin
0
0
0
(
LI
Sodium
HydroxIde
10%
10%
50%
50%
25
l2mo,
70
12.
ina
100
Shr
200
Sin
0
0.1
0
0
Ainmoniurn
Hydroxide
10%
10%
25
12am.
70
12
mo.
0
0.1
2.1.2.5
Oxygen
Compatibility
ofPTFE
Oxygen
is
singled
out
due
to
its
propensity
to
facilitate
auto­
ignition
of
organic
material
including
plastics.
Fluoropolymers
are
extensively
used
for
oxygen
services
because
of
their
low
flammability.
Oxygen
does
not
interact
with
polytetrafluoroethylene
under
most
circumstances.

Limiting
oxygen
index
(
LOI)
of
PTFE
is
greater
than
95%
under
ambient
conditions.
This
means
that
PTFE
does
not
burn
without
an
ignition
source
in
an
atmosphere
containing
less
than
95%
oxygen.
LOI
is
not
a
complete
predictor
of
all
practical
conditions
in
which
oxygen
and
PTFE
may
interact.
Anumber
of
considerations
apply.

Basic
Fluoropolymer
Data(
23
June
2003)
­
9­
Table
2.6
Chemical
Compatibility
of
PTFE
with
Common
Acids
[
13]

.~
~
g~
q
~.
~

oLiiL~
at
bDilingpciivL
Abrn~
icl
A~
ethA~
id
..

Ap1i~
ane
Ti~
1ub1a­
02~
wenght
gain
aFb~
r24k~
it
15
FFC
AT
MiEydtht~
.

°.
Nc~
I2FThct
at
E~
1~

°
ADyl.
Aøeietc:

AUyl~
M~
ihat~
ryiidc..
.
:.,:.

Aiiunnchkinde
.
:°
1fftat~
n~
p~
hLfti
,~::
:
N~~
F1~
ctittii~
ui
tnmp~
ahL1~

lusahLhk
in
rdthcm
~
inlJi~`
aC1,
l­
5~
anEyd~
nius~
A1CJ~
.
..
~.
..

°
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tte~
Am~
iiiiiu.
C1iim~
d~
.
.
2
~
nwhu1iiaat
ngp~
int
;.
Ai~
iLiue
I~
lubJc­
OJ%
~
iigkt
gait
aFter24
hr.
~
t
15
~
C
Bma~.
°
Na
~

.
uhi}
ibe
,
tt
b
p~
iai:.
.
&
ma
Ai~
it
°

BUti~
1A~
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yiMit1iac~
y1abe
°
°
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..
I~
iilil~
a~
boiling
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int~
°
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°

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afT~
tnti~
ai~

Cakium
Chloride
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Na
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.
.
.
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°
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..:~.:.
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WuL~~
lxYI~
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melting
1x]
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Naphthiii~
me
°
°,:
°~
°°,
°

°
NUro1urnze~
ne
.
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Nb~
2~
ra­
Ththriol
,:
°
No
affe~
t
.
°.

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Nib
­
2­~
Móthy1.
Pn~
pan~'
J
n­
Oct~
iui~
ylAka1rnI
.
.
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cffãt
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°
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°

°
Pbrnml
tnr~
riIulil,
iat
lrnilingpciint
ph
b~
llk~
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ia
.
.
­
10­

Table
2.7
Various
Properties
of
Fluoropolymers
[
14,15,16]

Property
PTFE
FEP
ETFE
PFA
Specific
Gravity
2.15
2.15
1.70
2.15
Melting
Point
(
2nd),
°
C
327
260
270
310
Tensile
Strength,
MPa
20
20
40
28
Elongation,
%
300
300
200
300
Flexural
Modulus,
MPa
560
650
1,100
650
Temperature
Rating,
°
C
260
200
150
260
Dielectric
Constant
2.1
2.1
2.6
2.1
Coefficient
ofFriction
0.1
0.2
0.4
0.2
Cut­
Through,
kg
4.5
4.5
18
4.5
Chemical
Resistance
Excellent
Excellent
Very
good
Excellent
Item
2.2
Perfluoroalkoxy
Polymer,
PFA
[
CAS
number
26655­
00­
5]

Item
2.2.1
Polymerization
PFA
is
a
copolymer
of
TFE
and
aperfluoroalkyl
vinyl
ether
such
as
perfluoropropyl
vinyl
etherPPVE
(
CF2CF­
O­
C3F7,
molecularweight
266,
CAS
number
1623­
05­
8)),
which
can
be
produced,
in
an
aqueous
and
non­
aqueous
media.
Terpolymers
of
this
class
contain
other
monomers
such
as
hexafluoropropylene
HFP
(
CF2CF­
CF3,
molecular
weight
150.02,
CAS
number
116­
15­
4)
Commercially,
it
is
polymerized
by
free­
radical
polymerization
mechanism
usually
in
an
aqueous
media
via
addition
polymerization
of
TFE
and
perfluoropropyl
vinyl
ether.
The
initiator
for
the
polymerization
is
usually
a
water­
soluble
peroxide
such
as
ammonium
persulfate.
In
general,
the
polymerization
regime
resembles
that
used
to
produce
PTFE
by
emulsion
polymerization.

Item
2.2.2
Properties
ofPFA
PFA
polymers
are
fully
fluorinated
and
melt
processible.
They
have
chemical
resistance
and
thermal
stability
comparable
to
polytetrafluoroethylerre
(
PTFE).
Meltviscosity
of
PFA
is
more
than
one
million
times
lower
than
PTFE
(<
10~
Pa.
s).
Specific
gravity
of
perfluoroalkoxy
resins
is
in
the
range
of
2.12­
2.17.
Perfluoroalkoxy
polymers
melt
and
flow
and
can
be
processed
by
typical
thermoplastic
techniques
such
as
extrusion,
injection
molding
and
rotational
molding.
PFA
resins
are
specified
by
ASTM
Method
D3307,
which
also
provides
procedures
or
references
to
other
ASTM
methods
for
the
measurement
of
resin
properties.
Figure
2.4
illustrates
a
segment
of
PFA
molecule.

Item
2.2.2.1
Molecular
Structure
Perfluoroalkoxy
polymers
have
a
similar
structure
to
PTFE
except
that
randomly
after
every
few
TFE
monomer
units
a
comonomer
(
e.
g.,
PPVE)
appears
in
the
molecule,
as
shown
in
the
Figure
2.4.
For
example
for
a
copolymer
containing
3.5%
by
weight
of
PPVE,
the
ratio
of
Basic
Fluoropolymer
Data
(
23
June
2003)
 
11
 
TFE
to
PPVE
is
about
99
to
1.
Of
course
this
ratio
is
an
average
value
and
the
actual
number
of
TFE
units
occurring
between
consecutive
PPVE
groups
may
be
more
or
less
than
99.
The
comonomer
pendent
groups
reduce
the
extent
of
crystallization
as
well
as
the
size
of
individual
crystallites.

liem
2.2.2.2
Molecular
Weight
and
Crystaiinity
Crystallinity
and
specific
gravity
of
PFA
parts
decrease
when
the
cooling
rate
of
the
molten
polymer
is
increased.
The
lowest
crystallinity
obtained
by
quenching
molten
PFA
in
ice
was
48%
(
specific
gravity
2.123).

 
c
 
c
 
C
 
c
 
c
 
c­
 
I
1
I
I
I
I
F
F
F
F
F
Figure
2.4
A
Segment
of
Perfluoroalkoxy
Polymer
(
PFA)
Molecule
(
Rf
=
C3F7,
C2F5
or
CF3)
Similar
to
PTFE,
molecular
weight
of
PFA
can
not
be
measured
by
conventional
techniques.
An
indirect
factor
called
meltflow
rate
(
MFR)
also
called
meltflow
index
(
MFI)
is
used
which
is
the
amount
of
polymer
melt
that
would
flow
through
a
capillary
rheometer
at
a
given
temperature
under
a
defined
load
(
Figure
2.5).
For
PFA
and
FEP,
MFR
is
defined
as
the
Load
(~
M+
Astm=~
D.
ff/
o)

 
Piston
Theimcumter
(
D=
a4742n~
i)

0rPRF
(~
o.
1'
c,

,.­
Bairel
u­'
(
D=
555O4mr~

Taiiper~
ure
ContrxI
(
±
02C)

)
N
(
D~
2Ll9~
rTnl
L~
8OOOrmj
Figure
2.5
Schematic
Diagram
ofMFR
(
MFI)
Capillary
Rheometer
number
of
grams
of
polymer
in
10
minutes.
MFR
is
inversely
proportional
to
viscosity;
viscosity
is
directly
proportional
to
molecular
weight
of
the
polymer.
The
higher
the
MFR,
the
lower
the
molecular
weight.

Molecular
weight
distribution
is
determined
by
measuring
the
dynamic
moduli
of
the
polymer
melt
using
rheological
analyses.
Figure
2.6
shows
the
viscosity­
shear
rate
plot
for
two
Basic
Fluoropolymer
Data(
23
June
2003)
12­
hypothetical
polymers
with
different
MW
distributions.
Crystallinity
of
virgin
(
unmelted)
PFA
is
65­
75%.
DSC
can
be
used
to
study
melt
and
crystallization
of
PFA.

I
0
>

Item
2.2.2.3
Transitions
PFA
exhibits
one
first
order
transition
at
­
5
°
Cin
contrast
to
two
temperatures
for
PTFE
at
19
and
30
°
C.
It
has
three
second
order
transitions
at
­
100,
­
30
and
90
°
C[
18].

Item
2.2.2.4
Chemical
Resistance
Chemical
properties
of
PFA
are
just
as
good
as
those
of
PTFE
because
of
stable
perfluorinated
structure
of
the
former.
See
section
2.1.2.4
for
additional
information.
Table
2.8
and
Figure
2.8
show
actual
test
data
for
the
effect
of
chemical
exposure
on
the
mechanical
properties
of
PFA
and
MFA.
MFA
refers
to
a
perfluoroalkoxy
polymer
made
with
PMVE
(
perfluoromethyl
vinyl
ether,
CAS
number
1187­
93­
5)
`
Broad
MWD
Narrow
.
MWD
S1~
earRate
(
k,
g
scale)

Figure
2.6
Viscosity­
shear
Rate
Plot
of
two
Polymers
[
17]

Basic
Fluoropolymer
Data
(
23
June
2003)
­
13­

Table
2.8
Effect
of
Immersion
in
Organic
Chemical
for
168
hours
on
PFA
[
19]

1Iydnxnrtons:
lsxuclmie
Muçblbn
Mineral
Oil
Thlnene
99
1W
190
110
94
91
57
511
1W
1W
95
1W
02
0.5
0
0.7
Artunalic:
aCr~
I
obeawie
191
210
92
50
96
1W
02
02
Akthal:
Bennl
AkxuhDI
205
93
99
03
Ether
Thtmh}
t1r~
1funun
iS6
911
1W
0.7
Amine:

Aniline
n­
Ritftmine
F

li}
lalcdinrm'me
1115
79
1
Li
94
96
96
1W
97
1W
03
0.4
0]

AlLidrycle:

Iansuiddhyde
lIP
50
99
0.5
Kelonc
Cydoliextame
MoIh~
1Ethyl
Kekine
Azerrçilieuone
156
80
202
92
50
50
1W
1W
1W
04
0.4
0.15
E~
1ara:
Umctliylplithalik
w­
1kitftcetaie
7'
rS~­
Puty1
Phoaphato
220
125
2W
98
93
91
1W
1W
1W
03
0.5
2.0
Chir&
u
tact
Mod1)
lena
Chloiik
Pchkirceth~
1ene
.

Tctmchlonde
121
77
96
97
1W
1W
1W
Oil
2fl
23
Lblnr&
1vents
Dm&
iylforninmicle
flmc{
L~'
lsilrwcide
flaccane
154
1119
101
96
95
92
1W
1W
1W
02
0.1
0.6
Miul&
AnlTyuIride%:

Glacial
J~
eIicAcid
11$
95
1W
0.4
AceuicAnhydrkle
139
91
99
03
TdchlxrtxiceuicMid
196
50
1W
22
Basic
Fluoropolymer
Data(
23
June
2003)
­
14­

 
~
~
MIowM~
R
A
B:

C:

0:

E:

F:

C:

H:

I:

J:

K:

Item
2.3
Perfluorinated
Ethylene­
Propylene
Copolymer,
FEP
[
CAS
number
25067­
11­
2J
Item
2.3.1
Polymerization
FEP
is
a
copolymer
of
TFE
and
a
hexafluoropropylene
(
HFP)
which
can
be
produced,
in
an
aqueous
and
a
non­
aqueous
media.
Terpolymers
of
this
class
contain
other
monomers
such
as
perfluoroalkyl
vinyl
ether
(
e.
g.,
PPVE)
to
improve
stress
crack
resistance.
Commercially,
it
is
polymerized
by
free­
radical
polymerization
mechanism
usually
in
an
aqueous
media
via
addition
polymerization
of
TFE
and
hexafluoropropylene.
The
initiatorfor
the
polymerization
is
usually
water­
soluble
peroxide
such
as
potassium
persulfate.
In
general,
the
polymerization
regime
resembles
that
used
to
produce
PTFE
by
emulsion
polymerization.
2C
1~~
iiieDr~
In

1:
£
LA~
flC
MO~
ULU~

...
L
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J_
L.
J_
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iiiari
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ith~
c~
rI~
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L
J
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L
L
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J~
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or~
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J.
 
 
 
 
 
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a
 
 
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aiy~
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enone~

Tduen&
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110
°
C
Carbon
tetredilc~
idej~
77CC
C~
meth~
fforrnamide
~
40CC
Methylene
chloride
~
4(
1
°
C
Fuming
nitric
acid
~
2~
3~'
C
Fuming
~
ulflirioead
~
23C
Pho~
p~
ric
e~*
J~.
S%~

Hydrogen
peroxide
~
0~(
I
.~
23CC
ZncthoriJe2S%~
1~
O~
C
Elhj'lene
diemine
©
11
?`~
C
Sodium
hydroxkie
~
120
°
C
A
~
CD
E
F
G
4
j
1~
L
~

Figure
2.8
Effect
of
Chemical
exposure
on
the
Mechanical
Properties
of
Perfluoroalkoxy
Polymer
[
20]

Basic
Fluoropolymer
Data(
23
June
2003)
­
15­
Item
2.3.2
Properties
Perfluorinated
ethylene­
propylene
copolymer
polymers
are
fully
fluorinated
and
melt
processible.
They
have
excellent
chemical
resistance
and
thermal
stability.
Melt
viscosity
of
FEP
is
more
than
one
million
times
lower
than
PTFE
(<
1
~
Pa.
s).
Specific
gravity
of
FEP
resins
is
in
the
range
of
2.13­
2.15.
FEP
polymers
melt
and
flow
and
can
be
processed
by
typical
thermoplastic
techniques
such
as
extrusion,
injection
molding
and
rotational
molding.
FEP
resins
are
specified
by
ASTM
Method
D2
116,
which
also
provides
procedures
or
references
to
other
ASTM
methods
for
the
measurement
of
resin
properties.
Figure
2.9
illustrates
a
segment
of
FEP
molecule.

F
F
F
F
F
F
I
I
I
I
 
c
 
c
 
C
 
c
 
c
 
c
 
I
I
I
I
F
F
F
F
F
F~'
 
f~­
F
F
Figure
2.9
A
Segment
of
Perfluorinated
Ethylene­
propylene
copolymer
Molecule
Item2.3.2.1
Molecular
Structure
FEP
polymers
have
a
similar
structure
to
PFA
except
that
randomly
after
every
few
TFE
monomer
units
a
comonomer
(
e.
g.,
HFP)
appears
in
the
molecule,
as
shown
in
the
Figure
2.9.
For
example
for
a
copolymer
containing
13%
by
weight
of
PPVE,
the
ratio
of
TFE
to
PPVE
is
about
10
to
1.
Ofcourse
this
ratio
is
an
average
value
and
the
actual
number
of
TFE
units
occurring
between
consecutive
HFP
groups
may
be
more
or
less
than
8.
The
perfluoromethyl
pendent
groups
reduce
the
extent
of
crystallization
as
well
as
the
size
of
individual
crystallites.

liem
2.3.2.2
Molecular
Weight
and
Crys/
allinity
Similar
to
PTFE,
molecular
weight
of
FEP
can
not
be
measured
by
conventional
techniques.
Similar
to
PFA,
MFR
is
used
to
characterize
molecular
weight
of
FEP.
The
higher
the
MFR,
the
lower
the
molecular
weight.
See
section
Item
2.2.2.2
for
more
information.
Molecular
weight
distribution
is
determined
by
measuring
the
dynamic
moduli
of
the
polymer
melt
using
rheological
analyses.
Figure
2.6
shows
the
viscosity­
shear
rate
plot
for
two
hypothetical
polymers
with
different
MW
distributions.
Crystallinity
of
virgin
(
unmelted)
FEP
is
65­
75%.
DSC
can
be
used
to
study
melt
and
crystallization
of
FEP.

item
2.3.2.3
Transitions
FEP
exhibits
a
single
first
order
transition
that
is
its
melting
point.
Similarly
to
PTFE,
FEP's
melting
point
increases
with
pressure
(
Table
2.9).
The
presence
of
the
pendent
group
causes
a
lowering
of
melting
point
relative
to
PTFE.
Melting
of
commercial
FEP
results
in
an
8%
increase
in
volume.
Crystallinity
of
parts
after
processing
(
i.
e.,
melting)
depends
on
the
cooling
rate
of
the
melt.
Relaxation
temperature
of
FEP
increases
with
hexafluoropropylene
content
ofthe
copolymer.
FEP
has
a
dielectric
transition
at
­
150
°
Cwhich
is
unaffected
by
the
monomer
composition
or
crystallinity
(
specific
gravity)
[
21].
Relaxation
temperatures
of
FEP
are
shown
in
Table
2.10.

Basic
Fluoropolymer
Data(
23
June
2003)
­
16­
Table
2.9
Effect
of
Pressnre
on
FEP
Melting
Point
[
22]

a
157
­
5
to
20
Item
2.3.2.4
Chemical
Resistance
Chemical
properties
of
FEP
are
just
as
good
as
those
of
PTFE
because
of
stable
perfluorinated
structure
of
the
former.
See
Section
2.1.2.4
for
additional
information.
Tables
2.11­
2.13
show
actual
test
data
forthe
effect
of
chemical
exposure
on
the
mechanical
properties
of
FEP.

Table
2.11
Chemical
Compatibility
of
FEP
with
Halogenated
Solvents
[
25]

qip~
i
I~/
J
Chloroform
Wets,
insoluble
at
bailing
point
Ethylene
Bromide
113%
weight
gain
alter
24
hrat
100
°
C
Fluoiinated
Hdrocatbons
Wets,
swelling
oOzU.
N
in
boiling
solvent
Flnon>
naphthatene
Iliallubte
atbailing
paint
some
swelling
Biwio:
nitixThmzeno
Insoluble
atbailing
paint,
some
swelling
Pentaclilorobennainide
Insoluble
Perfluoroxytsne
Insoluble
at
bailing
paint,
slight
swelling
Tettebrnoethane
Insoluble
at
bailing
point
TetmSklornabylene
Wets,
some
swelling
alter
2
hrat
120CC
Trichloruacthc
Acid
Insoluble
at
bailing
point
Trichhoroethylcue
Insoluble
at
bailing
pointafter
t
hr
Table
2.10
Transitions
Temperatures
of
FEP
Melting
[
22]

Basic
Fluoropolymer
Data
(
23
June
2003)
­
17­

Table
2.12
Chemical
Resistance
of
FEP
to
Common
Solvents
[
24]

Seiteist
Lipesera
Expoiusre
rime
WsEs2bt
Gate,
%

Temperatere,
r
21J
12
no
13
Arotoso
SO
12
inc
114
10
2;
sk
U
Ileuzene
lb
100
200
96
hr
&
br
bhr
0.5
0.6
i.
0
Cathon
Terachloride
25
50
10
100
200
12am
l2ino
2
wk~

,%
hr
Sbr
0.6
1.6
1.9
2.5
3.1
Ethanbl
(
9595j
25
so
10
100
200
l2mo
l2nio
2
wk
bbr
bbr
0
0
0
0.1
0.3
Ethyl
Acolate
25
50
10
l2rno
i2
no
2wk
0.5
0.1
0.1
Tohiene
25
50
10
12mm
12
trio
2wk
0.3
0.6
0.6
Basic
Fluoropolymer
Data
(
23
June
2003)
­
18­

Table
2.13
Chemical
Compatibility
of
FEP
with
Common
Acids
and
Bases
[
26]

~
i:~
~
:
~

Hydr~
hIoricMid
10%
10%

10%

20%
20%
25
50
70
RX~
2O~
J
i2ina
l2ni~

l2itw
~
br
~,
hr
0
0
0
0
0
Nitric
Acid
10%

10%
25
70
l2mu
l2uio
0
0.1
Sulfuiic
Mid
30%
30%

30%
30%
25
70
L~
X)
2~
12
mo
12am
~
br
~
br
0
0
0
0.1
S~
xIimunHythc~
dd~
10%

10%

50%

50%
25
70
i~

2O~
12am
12am
8hr
&
Iir
0
0.1
0
0
AmaioriiuniHydm~
dd~
m
10%
10%
25
70
l2ino
12am
0
0.1
Item
2.4
Optical
Spectral
Properties
and
Weathering
Resistance
ofFluoropolymers
Tables
2.14
and
2.15
and
Figure
2.10
through
2.13
provide
optical
properties
including
refractive
index
and
transmission
spectrum
of
perfluoropolymers.
PTFE
and
other
fluoropolymers
are
virtually
transparent
to
ultraviolet
light
at
of
50
p.
m
or
less
thickness,
as
can
be
seen
from
the
data.
Figure
2.14
illustrates
the
stability
of
dielectric
constant
and
dissipation
factor
after
ten
years
of
outdoor
exposure
in
south
Florida.
In
contrast,
most
other
plastics
degrade
extensively
after
a
few
years
of
outdoor
exposure.
For
example,
acrylonitrile­
butadienestyrenepolymer
(
ABS)
completely
degrades
after
just
three
years
of
outdoor
exposure,
as
indicated
by
total
loss
of
elongation
of
exposed
samples
(
Figure
2.15).

Basic
Fluoropolymer
Data(
23
June
2003)
­
19­

Table
2.14
Refractive
Index
of
Perfluoropolymers
per
ASTM
D542
[
27]

C.)

E
U)

I..

I.­

Figure
2.10
Transmission
Spectrum
of
PTFE
(
Courtesy
DuPont
Fluoroproducts)

1~
00
90
TO
50
50
40
30
20
0
W~
gUt~
pm
Figure
2.11
Transmission
Spectrum
of
FEP
[
28]
100
~
 
1425micronT
.
ici
350
Wavelength,
nm
E
0.2
0.~
tO
1.4
1.82.2
3.0
7.0
9.0
12
15203050
Basic
Fluoropolymer
Data
(
23
June
2003)
100
­
20­

I
p
p
 
Refi~
ctiveIndex
ASTMD542­
50
(
at
0346
jim)
135
Haze~,%
ASSTM
D1003­
52
4
Light
Tmnsrriissb;
%

UV
(
a25­
o
.40
jim)

Vithle
(
t40­
0J0
Jim)

Infrared
(
0.70­
2~
40pm)
Spectmphotoxn
±
y
0J}
25mm
film
thiehiess
77­
91%

91­
96%
96­
98%
C)
C)

E
to
C
CC
I­
I­

250
350
450
550
650
Wavelength,
nm
100
Figure
2.12
Transmission
Spectrum
of
FEP
(
Courtesy
DuPont
Fluoroproducts)

60
443
20
200
300
400
500
600
700
800
900
WavoSngth
~
nm)

Figure
2.13
Transmission
Spectrum
of
FEP,
PFA
and
MFA
[
29]

Table
2.15
Optical
Properties
of
PFA
[
30]

Basic
Fluoropolymer
Data
(
23
June
2003)
­
21­

Table
2.17
Retention
of
Tensile
Properties
of
FEP
after
20
Years
Outdoor
Exposure
in
South
Florida
[
32]

~
0
1
2
3
4
8
~
7
0
9
10
Outdoor
Expoo~
im,
ysars
.011
.0O1~

.~

Figure
2.14
Retention
of
Dielectric
Constant
and
Dissipation
factor
after
10
years
Outdoor
Exposure
in
South
Florida
[
33]
Table
2.16
Tensile
Properties
of
PTFE
after
10
Years
Exposure
in
South
Florida
[
31]

a
2
I
F~.

D~
slectr1cOon~
1ant
~
U~
TJ11.
L
______

D~
tslpationFictcr
I
I
I
r
I
I
Basic
Fluoropolymer
Data
(
23
June
2003)
­
22­

Break
Elongation,
%
of
initial
retained
Outdoor
Exposure,
Years
Figure
2.15
Retention
of
Break
Elongation
of
ABS
after
3Years
Outdoor
Exposure
[
34]

Effect
of
Ozone
on
Fluoropolymers
(
Thefollowing
discussion
has
been
adopted
in
its
entirelyfrom
Section
13.2.1
of
Ebnesajjad,
S.,
Fluoroplastics,
Vol.
2:
Melt
Processible
Fluoroplastics,
William
Andrew
Inc.,
Norwich,
NY,
2002)
"
Ozone
is
considered
areactive
substance
against
plastics
due
t
~
its~
abilityto
readily
degrade
into
an
atom
and
a
molecule
of
oxygen.
The
atomic
oxygen
is
highly
reactive,
due
to
its
unpaired
electrons
in
its
last
orbital,
allowing
it
to
attack
and
etch
most
polymers.
Polytetrafluoroethylene
has
been
reported
to
be
very
resistant
to
etching
by
ozone
in
low
earth
orbit
environment,
where
atomic
oxygen
is
the
most
abundant
species
[
3
5,36].

03
~
O2+
O~

Resistance
of
polymers
to
ozone
attack
is
studied
in
space
environments
in
"
actual"
applications.
In
the
laboratory,
glow
discharge
or
plasma
etching
is
the
common
method
for
laboratory
study
of
ozone
effect.
Plasma
and
low
earth
orbit
environments
are
not
equivalent.
For
instance,
oxygen
plasma
contains
a
variety
of
other
particles
including
electrons
and
free
radicals
in
addition
to
atomic
oxygen.
In
contrast,
atomic
oxygen
is
the
dominant
constituent
of
low
earth
orbit.
0
0.5
1.0
1.5
2.0
2.5
3.0
`
I
3.5
Basic
Fluoropolymer
Data
(
23
June
2003)
­
23­
In
general,
oxygen
uptake
was
least
for
PTFE
and
most
for
polyethylene
in
experiments
in
which
a
series
of
fluorinated
polyolefins
were
exposed
to
ozone
"
out
of
glow."
This
means
that
plasma
or
glow
discharge
was
used
to
produce
atomic
oxygen
that
etched
the
sample
placed
outside
the
discharge
zone.
The
results
of
"
out
of
glow"
plasma
etching
and
low
earth
orbit,
by
and
large,
are
in
agreement
[
37].

Maximum
oxygen
uptake
decreases
with
an
increase
in
the
fluorine
content
of
the
polymers.
For
example,
polyvinylidene
fluoride
took
up
less
oxygen
as
a
result
of
03
exposure
than
polyethylene,
though
more
than
PTFE,
in
the
same
experiment
[
37].
The
exception
to
this
trend
is
polyvinyl
fluoride,
which
has
a
higher
etch
rate
than
polyethylene
(
Table
2.18).
Why
is
PVF
more
susceptible
to
ozone
attack
than
polyethylene?

Golub
[
38]]
has
proposed
an
explanation
attributing
the
high
etch
rate
of
PVF
to
the
ease
offluorine
formation
from
the
decomposition
ofthis
polymer.
Fluorine
promotes
degradation
of
molecular
oxygen
to
its
active
atomic
form
(
02
 
~
20)
or
by
further
reaction
with
PVF,
thus
enhancing
the
etch
rate.
Polyvinylidene
Fluoride
and
FEP
molecules
have
lower
etch
rates
due
to
the
higher
stability
of
CF2
group
to
oxygen
attack
than
CFH
in
PVF
or
CH2
in
polyethylene.
Both
polyvinylidene
Fluoride
and
copolymers
oftetrafluoroethylene
and
ethylene
(
ETFE)
have
low
etch
rates
due
to
the
protection
provided
to
the
CH2
groups
bonded
to
CF2
groups.
The
ultimate
stability
is
reached
in
the
linear
PTFE
chain,
which
consists
of
all
CF2
groups,
with
the
exception
of
the
few
end
groups."

Table
2.18
Relative
Mass
Loss
Rates
for
Polymer
Films
Exposed
to
Low
Earth
Orbit
[
37]

Polymer
~

Polyirnide
(
Kapton~)
Mass
Loss
Rate
I
Fluorine
to
Carbon
.

Ratio
0
Polyetherterphthalate
~
M~
lat~)

Polveth'qlene
(
low
densitv}
1
06
0
43
0
0
Polvethyletie
(
high
density)
0.~
0
0
Pol~~
inyl
Fluoride
(
TedIar~
j
116
0,5
Polyvinylideiie
Fluoride
(
KynarX)
.
1
PTFE
(
TefIon~)
­
0.03
2
Tetrafluoroeth
y
lcne/
ilexafluoropropylene
iTetlcinr_
FEP)
0.03
2
Basic
Fluoropolymer
Data
(
23
June
2003)
­
24­
Item
3
Thermal
Stability
(
Thefollowing
discussion
has
been
adopted
in
its
entiretyfrom
Section
13.4.1
of
Ebnesajjad,
S.,
Fluoroplastics,
Vol.
2:
Melt
Processible
Fluoroplastics,
William
Andrew
Inc.,
Norwich,
NY,
2002)
"
Fluoroplastics
are,
generally,
very
stable
at
or
below
their
specified
maximum
use
temperatures.
The
rate
of
degradation
of
these
plastics
at
higher
temperatures
is
a
function
of
their
chemical
structures
in
addition
to
temperature,
time
at
temperature,
and,
to
some
extent,
on
the
pressure
and
the
atmosphere
of
decomposition.
In
actual
processing,
degradation
is
tracked
by
indirect
measurement
of
molecular
weight.
Thermal
exposure
leads
to
a
reduction
in
the
molecular
weight,
which
can
be
quantified
by
an
increase
in
the
MFR,
heat
of
fusion
of
polymer,
and
specific
gravity
in
controlled
measurements.

Perfluoropolymers
are
more
thermally
stable
than
partially
fluorinated
resins.
Thermal
stability
usually
increases
with
the
fluorine
content,
as
do
other
basic
properties
of
fluoroplastics
like
chemical
resistance.
Figure
3.1
[
Figure
13.50
in
the
reference
text]
shows
a
comparison
of
degradation
rate
(
weight
percent
per
hour)
as
a
function
of
temperature
by
thermogravimetric
analysis
(
TGA).
It
can
be
seen
that
for
a
given
rate
of
degradation,
say
0.1%,
perfluoropolymers,
that
is
PTFE,
PFA,
and
FEP,
require
higher
temperatures
than
ETFE.
Among
the
perfluoropolymers,
PTFE
that
has
a
linear
unbranched
structure,
is
more
stable
than
PFA
and
FEP.
The
degradation
rates
of
specific
fluoropolymers
have
becirlisted
in
Table
3.1
[
Table
13.17
the
reference
text].

Degradation
is
usually
measured
and
characterized
by
weight
loss
using
TGA
techniques
while
degradation
products
are
identified
by
gas
chromatography,
infrared
spectroscopy,
and
mass
spectroscopy.
The
small
amount
of
degradation
requires
TGA
experiments
to
be
conducted
for
several
hours
to
allow
accurate
detection
of
weight
loss.
Table
3.2
[
Table
13.18
the
reference
text]
gives
a
comparison
of
the
composition
products
of
the
degradation
of
ETFE,
FEP,
and
PFA.
The
most
toxic
compounds
are
perfluoroisobutylene
(
PFIB)
and
carbonyi
fluoride
(
COF2)."

100
~,

A
.­
~,

~­~­­­
A'

I~­~
i:
iII
­
rn­­­~­­~­.­­­­~­
~­

.
 
~
.
..­.­..
A'

2~
L~
X
­
I
L~.
ETFE
J
PFA44OHP
U
FEP100
0
PFA34O
0
PTFE
7A
PTFE
6C
I
I
10
10.1
°
o.
oi
0.00
1
250
275
300
325
350
375
400
425
450
475
500
525
550
Degrees
Centigrade
Figure
3.1
Degradation
Rate
of
Fluoroplastics
in
Air
[
39]

Basic
Fluoropolymer
Data
(
23
June
2003)
­
25­

Table
3.1
Degradation
(
TGA)
Rates
of
Fluoroplastics
in
Air
as
a
Function
of
Time
and
Temperature
[
39]

%
1~
iLq~
1Lt
i.,]
Y~
J~
1Ir
J~
1in.
Irciip.'
C
1
IF
L~
I~
tflb~
l~
IuI
150
2~
0
0.31
DiMI
0.11
303
0.42
0.111'
0.14
325
0.
t~
7
350
FEP
205
~.
05
303
~
H.']
3
~
0.05
350
0.45
0.
L3
°
0.1~

375
0.~
7
4I~
XJ
3.2
PFA­
1
303
0.15
0.115
~
U.
05
0.117
350
0:
22
41~
0.55
PFA­
2
303
~
U.
03
<~
05
351.
J
0.12
~~
i.
03
0.115
4D3
02~

FiEk~
Pc~
th~
r
PTFE
41X1
~
n.
oo
425
0.15
42.5
11.04*

525
255**
~
s5.0
GnmuI~
r
PTFE
350
0.112
350
0.01)?

$~
X1
0.113
403
a.
oud~

425
,
0.116
425
H.
06~

*
E1t~
urlyraLulituuiin
11.5
b~
t
Jh~
rb~
jimin~.
run.

~
E3~
urlyrate
J'mrn
3.3
U~
i5.6
hc~
ir~
~
~
TUfl.

**
Odi~
ouipn~
iti~
riin
c~
n~
i
iu~
ur.
Initial
rni~
255%
p~
rh~
iiir.
Tlu~
rurn.
1t~
quilibriurn
Basic
Fluoropolymer
Data
(
23
June
2003)
­
26­

Table
3.2
Degradation
(
TGA)
Products
of
Fluoropolymers
in
Air
after
1
Hour
at
Temperature
[
39]

TEFZ&.,
200
351)
5.3
0.11'
S
PEP
1100
4011
2.5
0.1103
°­~
10'
S.
035
il.
i~

PFA
3411
400
0.4.3
PEA
4411
41311
0.2~

TtiFZ1iL.~.
200
Oil'S
°
FIFP
LOU
°
0.64
1.2
2.7~
l
11
L01~

PEA
340
PEA
4411
0.01
1.2
0.53
0.53
12.
123~

4&)~

l~~
e~
rfluDrabucIb~
n~

Arti:
1kc~
tii
this
~
n~
i1ytka1inr.
hniqu~~
x
vziiu~
L01Y~.~

r~
T1ii~~
cumin~
Lude~
i.
1!~
CO~
fairn
n~
c~
idaiian
d~
h~~
th'p{
c~
ne
uniL~

`
Endu~
k~
11.
19'
i'i~
nI~
CIf~
iCOE
Basic
Fluoropolymer
Data
(
23
June
2003)
­
27­

References
1.
Gangal,
S.
V.,
"
Polytetrafluoroethylene,
Homopolymers
of
Tetrafluoroethylene,"
in
Encyclopedia
ofPolymer
Science
and
Engineering,
2nd
ed.,
16:
577
 
600,
John
Wiley
&
Sons,
New
York,
1989.

2.
Lee,
J.
A.,
Observ.
of
Individual
Fluorine
Atoms
from
Highly
Oriented
Polytetrafluoroethylene
Film
by
Atomic
Force
Microsc.,
Marshall
Space
Flight
Ctr.,
Alabama.

3.
Sperati,
C.
A.,
and
Starkweather,
H.
W.,
Jr.,
Adv.
Polym..
Sci.,
2:
465,
1961.

4.
Moynihan,
R.
E.,
"
The
Structure
of
Perfluorocarbon
Polymers.
Infrared
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