17
PART I
1.1 Introduction
The era of fluoropolymers began with a small mis-
hap, which did not go unnoticed by the ingenious and
observant Dr. Roy Plunkett of DuPont Company.[1]
In 1938, he had been at DuPont for two years, con-
centrating mostly on the development of fluorinated
refrigerants. He was experimenting with tetrafluoro-
ethylene (TFE) for synthesis of a useful refrigerant
(CClF 2-CHF2).[2] The effort was spurred by the de-
sire to create safe, nonflammable, nontoxic, colorless,
and odorless refrigerants. On the morning of April 6,
1938, when Plunkett checked the pressure on a full
cylinder of TFE, he found none. However, the cylin-
der had not lost weight. Careful removal of the valve
and shaking the cylinder upside down yielded a few
grams of a waxy looking white powder—the first poly-
mer of tetrafluoroethylene.[2]
Plunkett analyzed the white powder, which was
conclusively proven to be polytetrafluoroethylene
(PTFE). The slippery PTFE could not be dissolved in
any solvent, acid, or base and upon melting formed a
stiff clear gel without flow.[3] Later, research led to
the discovery of processing techniques similar to those
used with metal powders. At the time, the Manhattan
Project was seeking new corrosion-resistant material
for gaskets, packings, and liners for UF6 handling.
Figure 1.1 Reenactment of the discovery of polytetra-
fluoroethylene (Teflon®) in 1938 by DuPont scientist Dr. Roy
Plunkett (right). (Courtesy DuPont.)
© Plastics Design Library
1 Fundamentals
PTFE provided the answer and was used in production.
The US government maintained a veil of secrecy
over the PTFE project until well after the end of World
War II.
Large-scale monomer synthesis and controlled po-
lymerization were technical impediments to be re-
solved. Intensive studies solved these problems and
small-scale production of Teflon® (trademark, 1944)
began in 1947. In 1950, DuPont scaled up the com-
mercial production of Teflon in the USA with the con-
struction of a new plant in Parkersburg, West Virginia.
In 1947, Imperial Chemical Industries built the first
PTFE plant outside the US, in Western Europe. Since
then, many more plants have been built around the
globe. Over the last six decades, many forms of PTFE
and copolymers of other monomers and TFE have
been developed and commercialized.
The words of Plunkett himself best summarize the
discovery of PTFE. He recounted the story of Teflon
in a speech to the American Chemical Society at its
April 1986 meeting in New York. “The discovery of
polytetrafluoroethylene (PTFE) has been variously de-
scribed as (i) an example of serendipity, (ii) a lucky
accident and (iii) a flash of genius. Perhaps all three
were involved. There is complete agreement, how-
ever, on the results of that discovery. It revolutionized
the plastics industry and led to vigorous applications
not otherwise possible.”[2]
Figure 1.2 Photograph of two pages from the research
notebook of Dr. Roy Plunkett recording the discovery of
polytetrafluoroethylene on April 6, 1938. (Courtesy DuPont.)
Fundamentals
18

1.2 What are Fluoropolymers? and side chains, or chlorine invoke a variety of polymer
properties which will be dealt with later in this book.
Traditionally, a fluoropolymer or fluoroplastic is de- There is a second class of fluoropolymers called
fined as a polymer consisting of carbon (C) and fluo- “partially fluorinated” in contrast to “perfluorinated
rine (F). Sometimes these are referred to as polymers.” These molecules include hydrogen (H) in
perfluoropolymers to distinguish them from partially addition to fluorine and carbon. Examples include
fluorinated polymers, fluoroelastomers and other poly- polyvinylfluoride, polyvinylidenefluoride, and ethyl-
mers that contain fluorine in their chemical structure. ene tetrafluoroethylene copolymer.
For example fluorosilicone and fluoroacrylate poly-
mers are not referred to as fluoropolymers. An ex- H H H H
ample of a linear fluoropolymer is tetrafluoroethylene
polymer (PTFE): C C C C
Polyvinyl fluoride
H F H F
F F F F
C C C C
H F H F
F F F F
C C C C Polyvinylidenefluoride
A simplistic analogy would be to the chemical
composition of polyethylene [(-CH2-CH2-)n] where all H F H F
the hydrogen atoms have been replaced by fluorine
atoms. Of course, in practice PTFE and polyethylene F F H H F F
are prepared in totally different ways. There are
branched fluoropolymers such as fluorinated ethyl- C C C C C C
ene propylene polymer (FEP):
F F H H F F
Ethylene Tetrafluoroethylene Copolymer
F F F F F F
Partially fluorinated fluoropolymers are signifi-
C C C C C C
cantly different from the perfluoropolymers with re-
F F F F F spect to properties and processing characteristics. For
F C F example, perfluoropolymers are more thermally stable
F but physically less hard than partially fluorinated poly-
mers. The former has much higher “hardness” than
Oxygen (O) and chlorine (Cl) are present in the the latter. Applications for both classes of polymers
chemical structure of some commercial are discussed later in this book and in Vol. 2.
fluoropolymers. Examples include perfluoroalkoxy
and polychlorotrifluoroethylene:
1.3 Fundamental Properties of
F F F F F F Fluoropolymers
C C C C C C
Perfluoroalkoxy The basic properties of fluoropolymers arise from
F F F O F F the atomic structure of fluorine and carbon and their
Rf covalent bonding in specific chemical structures.
These properties are weakened as the chemical struc-
F F F F ture becomes less “perfluorinated,” as in poly-
vinylidene fluoride. Because PTFE has a linear
C C C C
Polychlorotrifluoroethylene structure, it is a good subject for discussion of ex-
F Cl F Cl treme properties. The backbone is formed of carbon-
carbon bonds and carbon-fluorine bonds. Both are
Rf is usually a perfluorinated group consisting of extremely strong bonds (C-C = 607 kJ/mole and C-F
carbon and fluorine. Introduction of nonlinearity, oxygen = 552 kJ/mole.)[4][5] The basic properties of PTFE

Fundamentals © Plastics Design Library


stem from these two very strong chemical bonds. The
PTFE molecule resembles a carbon rod completely
blanketed with a sheath of fluorine atoms.[6]
The size of the fluorine atom allows the forma-
tion of a uniform and continuous sheath around the
carbon-carbon bonds and protects them from attack,
thus imparting chemical resistance and stability to the
molecule. The fluorine sheath is also responsible for
the low surface energy (18 dynes/cm)[7] and low co-
efficient of friction (0.05-0.8, static)[6] of PTFE. An-
other attribute of the uniform fluorine sheath is the
electrical inertness (or non-polarity) of the PTFE
molecule. Electrical fields impart only slight polar-
ization in this molecule, so volume and surface resis-
tivity are high. Table 1.1 summarizes the fundamen-
tal properties of PTFE.
The basic properties of PTFE provide beneficial
attributes with high commercial value (Table 1.2).
Table 1.1. Fundamental Properties of PTFE
• High melting point, 342°C (648°F)
• High thermal stability
• Useful mechanical properties at extremely
low and high temperatures
• Insolubility
• Chemical inertness
• Low coefficient of friction
• Low dielectric constant/dissipation factor
• Low water ab/adsorptivity
• Excellent weatherability
• Flame resistance
• Purity
Table 1.2. Useful Attributes of PTFE
• Stability
– high continuous use temperature
– excellent weatherability
– excellent chemical resistance
– excellent fire properties
• Low Surface Energy
– good release properties
– biological inertness
– low friction
• Cryogenic Properties
– retains flexibility
• Electrical Properties
– low dielectric constant
– low dissipation factor
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19
1.4 Developmental History of
Fluoropolymers
The development of fluoropolymers began with
the invention of PTFE in 1938 and continued to 1992
when a soluble perfluoropolymer (Teflon® AF) was
introduced. Table 1.3 summarizes the timeline for
the development of fluoropolymers that have brought
about major changes in properties and/or fabrication
processes.
The discovery of PTFE was a major leap forward
in material science. Yet, the new polymer could not
be fabricated by melt-processing. The next two forms
of PTFE, fine powder and dispersion, were also not
melt-processible. The pursuit of a more easily
processible polymer led to FEP, which could be melted
in an extruder. Compared with PTFE the major dis-
advantage of FEP is its reduced thermal stability and
lower maximum continuous use temperature (200°C)
(Table 1.3). PFA, which was introduced in 1973, of-
fers both melt-processing and the same upper con-
tinuous use temperature as PTFE (260°C).
ETFE addresses the need for a mechanically
stronger polymer, albeit at a loss of fluoropolymer
properties because of the presence of hydrogen in its
molecule:
F F H H F F
C C C C C C
F F H H F F
Compared to PTFE, ETFE has a lower continuous use
temperature (150°C) less chemical resistance, and a
higher coefficient of friction. Mechanical properties,
including tensile strength, elongation at break, and ten-
sile modulus is increased, leading to cut-through re-
sistance in wire insulation.
Teflon® AF is an amorphous polymer which is
soluble in certain halogenated solvents. It can be ap-
plied as a solution, followed by the removal of the sol-
vent. The remaining coating will be as resistant to
almost as many chemicals as PTFE. The thickness of
the coating can range upward from less than a
micrometer.
There are a number of other polymers in this fam-
ily including polychlorotrifluoroethylene (PCTFE),
polyvinylfluoride (PVF), polyvinylidenefluoride, ethyl-
ene chlorotrifluoroethylene (ECTFE), tetrafluoro-
ethylene/hexafluoropropylene/vinylidene fluoride co-
polymers, perfluoroacrylates, fluorinated polyurethanes,
and chlorotrifluoroethylene/vinylether copolymers.
Fundamentals
20

Table 1.3. Commercialization Timeline of Major Fluoropolymers vs Key Processing/Application Trade-Offs

Year Trade-off Trade-off

Fluoropolymer Monomers
Commercialized + -
Continuous Use
PTFE 1947 TFE Non-melt Processible
Temperature 260°C
Maximum Continuous
Melt Processible/
PCTFE 1953 CTFE Use Temperature
Non-Melt Processible
180°C
Maximum Continuous
FEP 1960 TFE,HFP3 Melt-Processible Use Temperature
200°C
Maximum Continuous
PVF 1961 VF1 Thin film/Weatherable Use Temperature
107°C
Maximum Continuous
PVDF 1961 VDF2 Melt Processible Use Temperature
150°C
Maximum Continuous
ECTFE 1970 CTFE, E4 Hardness/Toughness Use Temperature
150°C
Melt Processible.
TFE, Low Molecular
PFA 1972 Continuous Use
PAVE5 Weight
Temperature 260°C
Maximum Continuous
ETFE 1973 TFE, E Hardness/Toughness Use Temperature
150°C
Soluble in Special
TeflonAF 1985 TFE, PDD 6 High Cost
Halogenated Solvents
1 6
Vinyl fluoride (CH2=CHF) 2,2-Bistrifluoromethyl-4,5difluoro-1,3-dioxole: FC CF
2
Vinylidene fluoride (CH2=CF2) O O
3
Hexafluoropropylene (CF2=CF-CF3) C
4 F3 CF 3
Ethylene (CH2= CH2)
5
Perfluoroalkylvinylether (CF2=CF-O-Rf)

1.5 Examples of Uses of flame resistance. Applications for fluoropolymers al-

Fluoropolymers ways exploit one or more of the properties (Table 1.4)
that set them apart from other materials, particularly
other plastics.
The consumption of PTFE has increased over the
In the chemical process industry, for example,
years as technological advancement has required the
fluoropolymers are selected for their unmatched re-
properties of fluoropolymers. The applications of
sistance to chemical attack. They serve as linings for
PTFE, and fluoropolymers in general, span all facets
carbon steel vessels, and for piping and other fluid
of human life, from household uses to the aerospace
handling components. They provide durable, low
and electronic industries. Basic properties (Table 1.1)
maintenance and economical alternatives to exotic
of PTFE lead directly to its applications: chemical re-
metal alloys. In these applications, fluoropolymers
sistance, thermal stability, cryogenic properties, low
also offer thermal stability for use at high tempera-
coefficient of friction, low surface energy, low dielec-
tures. And because they do not react with process
tric constant, high volume and surface resistivity, and
streams, they help prevent contamination of products.

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Table 1.4. Major Applications and Some Uses of PTFE

INDUSTRY/
KEY PROPERTIES TYPICAL USES
APPLICATION AREA
Chemical Resistance Gaskets, Vessel Liners, Valve and
Chemical Processing Good Mechanical Properties Pipe Liners, Tubing, Coatings
Thermal Stability
Cryogenic Properties
Low Dielectric Constant
Electrical High Volume/Surface Resistivity Wire and Cable Insulation,
& Communications High Dielectric Break-down Voltage Connectors
Flame Resistance, Thermal stability
Automotive & Office Low Coefficient of Friction Seals and Rings in Automotive Power
Equipment Good Mechanical Properties Steering, Transmission, and Air-
Cryogenic Properties, conditioning. Copier Roller and Food
Chemical Resistance Processing Equipment Covering.
Thermal Stability
Houseware Low Surface Energy Cookware Coatings.
Chemical
Low Surface Energy Cardiovascular Grafts, Heart Patches,
Medical Stability Ligament Replacement
Excellent Mechanical Properties
Chemical Resistance
Excellent Weatherability Coated Fiberglass Fabric for Stadiums
Architectural Fabric Flame Resistance and Airport Roofs
Low Surface Energy

Electrical properties of fluoropolymers are highly
valuable in electronic and electrical applications. In
data communications, for example, FEP is used to in-
sulate cables installed in air-handling spaces (plenums)
in office buildings. FEP provides the excellent di-
electric properties these cables require to perform well
at high data transmission rates as well as long-term
stability so performance will not change over the life
of the cabling system. Most importantly, FEP helps
these cables meet strict building code requirements
for low flame spread and low smoke generation.
Fluoropolymers are used to insulate wire for criti-
cal aerospace and industrial applications where chemi-
cal and thermal resistance is essential. They are also
materials of construction for connectors for high-fre-
quency cables and for thermocouple wiring that must
resist high temperatures.
In the automotive, office equipment and other in-
dustries, mechanical properties of fluoropolymers are
beneficial in low-friction bearings and seals that re-
sist attack by hydrocarbons and other fluids. In food
processing, the Food and Drug Administration (FDA)
approved fluoropolymer grades are fabrication mate-
rial for equipment due to their resistance to oil and
cleaning materials, and their anti-stick and low friction
properties.
In houseware, fluoropolymers are applied as non-
stick coatings for cookware and appliance surfaces.
These applications depend on thermal and chemical
resistance as well as anti-stick performance. PTFE
and ETFE are chosen to insulate appliance wiring that
must withstand high temperatures.
Medical articles such as surgical patches and car-
diovascular grafts rely on the long-term stability of
fluoropolymers as well as their low surface energy
and chemical resistance.
For airports, stadiums and other structures, glass
fiber fabric coated with PTFE is fabricated into roof-
ing and enclosures. This architectural fabric is sup-
ported by cables or air pressure to form a range of
innovative structures. PTFE provides excellent resis-
tance to weathering, including exposure to ultraviolet
rays in sunlight, flame resistance for safety, and low
surface energy for soil resistance and easy cleaning.

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References

1. Plunkett, R. J., US Patent 2,230,654, assigned to DuPont Co., Feb. 4, 1941.

2. Plunkett, R. J., “The History of Polytetrafluoroethylene: Discovery and Development,” in High
Performance Polymers: Their Origin and Development, Proceed. Of Symp. On the Hist. Of High
Perf. Polymers at the ACS Meeting in New York, April 1986, (R. B. Seymour and G. S.
Kirshenbaum, eds.), Elsevier, New York, 1987.
3. Gangal, S. V., “Polytetrafluoroethylene, Homopolymers of Tetrafluoroethylene,” in Encyclopedia of
Polymer Science and Engineering, 2nd ed., 16:577–600, John Wiley & Sons, New York, 1989.
4. Cottrell, T. L., The Strength of Chemical Bonds, 2nd ed., Butterworths, Washington, D. C., 1958.
5. Sheppard, W. A., and Sharts, C. M., Organic Fluorine Chemistry, W. A. Benjamin, Inc., New York,
1969.
6. Gangal, S. V., “Polytetrafluoroethylene” in Encyclopedia of Chemical Technology, 4th ed., 11:621–
644, John Wiley & Sons, New York, 1994.
7. Zisman, W. A., “Surface Properties of Plastics,” Record of Chemical Progress, 26:1 1965.

Fundamentals © Plastics Design Library