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T E C H N I C A L W H I T E P A P E R

Introduction to Fluoropolymers

Introduction
Fluorine is one of the most reactive elements in nature and is even more reactive than
its halogen relatives such as chlorine, bromine and iodine (these are all Group 17
elements or, if you prefer the older notation, Group VII). This high, and sometimes
explosive, reactivity delayed research on the material for a long time because scientists
simply couldnt find any material to contain elemental fluorine, not to mention that it was
difficult doing research under those conditions. Two of the first researchers of fluorine
chemistry were Ruff and Bretschnieder of Germany in the 1930s, first synthesizing the
gas tetrafluoroethylene. This was considered to be a topic of purely academic concern
and few people paid much attention to their work. It was also in Germany that the first of
the fluoropolymers was created and the IG Farben conglomerate patented PCTFE in
1934.

Despite this, it was the discovery of PTFE that accelerated the development of the
fluoropolymers. As mentioned in a previous newsletter (Focus on: PEEK), the
discovery of PTFE was purely accidental. In 1938, Roy Plunkett and his team at DuPont
were working on the chemistry of tetrafluoroethylene and noticed that a full cylinder of
the gas appeared to have nothing in it when the valve was opened. Intrigued by the
missing tetrafluoroethylene, they cut the cylinder open and a white residue
(Polytetrafluoroethylene) was found on the inside of the cylinder. PTFE was born!

PTFE may have remained a laboratory curiosity except for the onset of World War II.
Fluorine chemistry in all its forms suddenly became a vital topic of research across the
world in the race to build the first atomic bomb. Concentration of the fissile component
(Uranium-235) from natural uranium required the preparation of uranium hexafluoride
gas what had once been of simple academic interest suddenly had the attention of the
world and almost unlimited finance and personnel.

The polymer chemists were a little faster in attempting to develop useful polymers from
the basic structure, and Carothers carried out some of the first work in the development
of nylon in the 1930s. This basic research continued, and in the 1970s, Rose and his
team at ICI began constructing polymers almost from the first reported principles. Their
work was based on previously successful materials such as the polysulfones, and one of
their first products was the aromatic polyether ketone family.

The result was that a small amount of white residue in a gas cylinder suddenly found
itself the center of considerable scientific attention as researchers attempted to find out


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more about this new material. For a new and accidental material, PTFE had remarkable
properties. It was resistant to almost every known chemical, had excellent heat and
electrical resistance properties, an extremely low coefficient of friction, and a surface
energy so low that it was almost impossible to get anything to stick to it. A fortuitous set
of circumstances for the birth of the fluoropolymer family.


Developing the fluoropolymer family
The high thermal stability of the fluorine-carbon bond and excellent chemical resistance
of the fluoropolymers means that the PTFE and PCTFE polymers have unique
properties. Polymer technologists have continued to develop the fluoropolymer family to
improve melt processability, reduce cost and improve other properties. Technology may
have a history but polymer technologists have no past - they have to constantly invent
new things to improve and modify.

Today the fluoropolymer family consists of a range of homopolymers and copolymers to
meet the demands of the industry.


The fluoropolymer family


Homopolymers and copolymers Whats the difference?
Homopolymers consist of a single monomer (A) that is repeatedly joined together to form
the long chain of the polymer molecule:

A A A A A A A A


Copolymers consist of two different monomers (A and B) that are alternated when joined
together to form the long chain of the polymer molecule:


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A B A B A B A B


Graft copolymers are copolymers with a branched structure in the long chain of the
polymer molecule:

A A
B
A A A
B
A A
B
A


Terpolymers consist of three different monomers (A, B and C) that are alternated when
joined together to form the long chain of the polymer molecule:

C A B C A B A B



Fluoropolymer classification
The fluoropolymers can all be classified as semi-crystalline high performance
thermoplastics. This means that they have a random molecular orientation when in the
molten phase but have densely packed crystallites in the solid phase. The degree of
crystallization varies within the fluoropolymer family but all semi-crystalline plastics have
some general common properties.

The high performance semi-crystalline thermoplastics tend to have the following
properties (in comparison to amorphous plastics):
Higher specific gravity
Higher tensile strength and tensile modulus
Lower ductility
Tend to be translucent or opaque rather than transparent
Higher fatigue resistance
More difficult to bond using adhesives and solvents

These plastics also tend to have the following properties (in comparison to other
plastics):
Outstanding temperature resistance
Outstanding electrical properties
Outstanding chemical resistance
Lower coefficient of friction
Better toughness
Types of fluoropolymers the homopolymers
PTFE Polytetrafluoroethylene


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PTFE is one of the few fully fluorinated polymers and is made by polymerizing TFE. The
repeat unit of PTFE is shown below:

Tetrafluoroethylene
Polymerization
=
C
F
F
C
F
F
C
F
F
C
F
F
n
PTFE
=
C
F
F
C
F
F
+


PTFE was the first fluoropolymer to be manufactured and used by both Germany and
the U.S. during World War II. PTFE was used extensively in the Manhattan Project to
handle corrosive compounds such as uranium hexafluoride. Due to its full fluorination, it
still has some of the best properties of the family today. The major disadvantage with
PTFE is the very high melt viscosity that makes processing difficult by the normal
methods of extrusion and injection molding. Processing technologies have more
similarity to those of powder metallurgy than those of traditional plastics processing. This
led to a search for melt-processable fluoropolymers and the development of other
members of the family.

PCTFE Polychlorotrifluoroethylene
PCTFE is a partially fluorinated polymer and is made by polymerizing CTFE monomer in
a very similar manner to that for PTFE. The repeat unit is shown below:

C
F
F
C
Cl
F
n
PCTFE

The introduction of the Cl atom distorts the symmetry of the crystal packing and leads to
a lower softening point and reduced electrical and chemical resistance properties. It also
results in a harder polymer with higher tensile strength. PCTFE is melt-processable but it
is still difficult to process because of the high melt viscosity (brand names are Kel-F

and
Neoflon

).

PVDF Polyvinylidene fluoride
PVDF is a partially fluorinated homopolymer and is made by polymerizing vinylidene
monomer. The repeat unit is shown below:



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PVDF
C
F
F
C
H
H
n

PVDF is a high molecular weight fluoropolymer that has better mechanical properties
and wear and creep resistance than the majority of the family. It is melt-processable and
is somewhat less expensive than many other fluoropolymers. The first use of PVDF was
in architectural coatings applications (Pennsalt discovered it in 1960 but sold the rights
to the company that is now Arkema, brand name Kynar

), and the excellent weather

resistance properties resulted in many applications in cars and electrical products in
exposed situations.


The copolymers
FEP Fluorinated ethylene propylene
FEP is a fully fluorinated copolymer made by polymerizing TFE and hexafluoropropylene.
The repeat unit of FEP is shown below:

Tetrafluoroethylene FEP Hexafluoropropylene
+
C
CF
3
F
C
F
F
C
F
F
C
F
F
C
F
F
n
=
C
F
F
C
F
F
Polymerization
C
F
F
C
CF3
F
=

FEP was first produced by DuPont in 1956 (Teflon

FEP) and was the first commercially

produced material to attempt to combine the unique mechanical and chemical properties
of PTFE with the melt-processability of more conventional polymers. FEP has very
similar mechanical and chemical properties to PTFE but better impact strength.
Compared to PTFE, FEP has a maximum service temperature thats approximately
100
o
F lower and a slightly higher coefficient of friction.

ETFE Ethylene tetrafluoroethylene
ETFE is a partially fluorinated copolymer made by polymerizing TFE and ethylene, and
the repeat unit of ETFE is shown below:

C
F
F
C
F
F
C
H
H
C
H
H
n
ETFE



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ETFE was first produced by DuPont in 1970 (Tefzel

) and is another melt-processable

fluoropolymer. ETFE has mechanical properties that approach those of the fully
fluorinated polymers but has a lower maximum service temperature. Despite this, ETFE
excels in specific applications because of greatly increased cut through and abrasion
resistance and impact strength.

ECTFE Ethylene chlorotrifluoroethylene
ECTFE is a partially fluorinated copolymer made by polymerizing chlorotrifluoroethylene
and ethylene, and the repeat unit of ECTFE is shown below:


C
F
Cl
C
F
F
C
H
H
C
H
H
n
ECTFE


ECTFE was first produced by Allied Chemicals (Halar

) at the same time as ETFE and

the mechanical properties are very similar to those of ETFE. ECTFE also has
mechanical properties approaching those of fully fluorinated polymers, with a lower
maximum service temperature and the lowest density. As with ETFE, ECTFE has
excellent cut through and abrasion resistance and impact strength.

PFA Perfluoroalkoxy
PFA is a partially fluorinated copolymer made by polymerizing TFE and Perfluoroalkoxy.
The repeat unit of PFA is shown below:

C
F
F
C
F
F
n
C
F
F
C
OC
3
F
7
F
0.01n
PFA

PFA was first produced by DuPont in 1972 (Teflon

PFA) and is also melt-processable.

In many ways PFA is similar to FEP but generally has better mechanical properties at
higher temperatures and a maximum service temperature very similar to that of PTFE. It
is considered by some to be the best melt-processable fluoropolymer alternative to
PTFE.


General properties
The fluoropolymers have unique properties but the large range of materials within the
family can make it difficult to choose between the various materials. Future Whitepapers


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will focus on individual material properties in detail but it is useful to present some simple
results for a few critical materials properties at this stage. The results are indicative only
and are not definitive. The graphs are designed more to show the relative strengths and
weaknesses of individual materials.

Tensile strength:

Tensile Modulus:









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Maximum Service Temperature:


While it is often easy to see that a specific application requires the special properties of
the fluoropolymers, it is often less easy to determine which of the materials is best for
the application. Potential users should contact experienced processors, such as Zeus,
for detailed guidance on specific applications.


Summary
Fluoropolymers are a group of plastics that are still being explored and developed by the
polymer industry for growing market applications. Their unique set of properties makes
them natural candidates for very demanding applications, but engineers and buyers
should use the skills of the production and development specialists to select the best
material for their application. For more information on fluoropolymers, see Zeus
previous Whitepapers at http://www.zeusinc.com/whitepapers.asp


How Zeus Can Help
With a technical inside and outside sales force backed up with engineering and polymer
experts, Zeus is prepared to assist in material selection and can provide product
samples for evaluation. A dedicated R&D department staffed with PHD Polymer
chemists and backed with the support of a world-class analytical lab allows Zeus an
unparalleled position in polymer development and customization.

Since 1966 Zeus has been built upon the core technology of precision extrusion of high
temperature plastics. Today, with a broad portfolio of engineered resins and secondary


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operations, Zeus can provide turnkey solutions for development and high-volume supply
requirements.



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