3M™ Dyneon™

PTFE Fine Powder

Processing of Dyneon PTFE

Fine Powder
Contents

1 Introduction 4 4 Fundamentals of PTFE Fine Powder Processing 11

1.1 About the Company 4 4.1 Packaging and Storage 11

1.2 About our Flouoropolymer Product Family 4 4.2 Preparation of the Extrusion Mixture  11

2 Physical Fundamentals of 4.3 Powder Screening 11

PTFE Fine Powder Processing 6
4.4 Mixing with Lubricants 12
2.1 Production of 3M™ Dyneon™ PTFE Fine Powder 6
4.5 Pigmentation 13
2.2 Phenomenology of Paste Extrusion 6
4.6 Maturing of the Extrusion Mix 13
2.2.1 Morphology of the Fine Powder 6
4.7 Preform Compression 13
2.2.2 Paste Mixing 6
4.8 Extrusion 13
2.2.3 Preform Fabrication 6
5 Fabrication of Films, Tapes and Sealing Cords 14
2.2.4 Paste Extrusion in Funnel-Flow Design 7
5.1 Profile Extrusion 14
2.3 Morphological Changes during Paste Extrusion 7
5.2 Calendering 15
2.3.1 Morphology of the Paste Extrudate 7
5.3 Film and Sheet Drying 15
2.3.2 Crack-up of the Secondary Particles 8
5.4 Film Stretching 16
2.3.3 Reversible Deformation of the Primary Particles 8
5.5 Fabrication of Unstretched and Stretched Sealing Cords 16
3 Properties and Handling of
Dyneon PTFE Fine Powder 9 6 Fabrication of Tubing and Hoses 17

3.1 Reduction Ratio 9 6.1 Lubricants for Hose Extrusion 17

3.2 Extrusion Pressure  10 6.2 Tube Extrusion 17

3.3 Particle Size and Particle Size Distribution 10 6.3 Drying and Sintering of Tubes 18

3.4 Specific Weight 10 6.4 Tube Testing 19

3.5 Density 10 6.5 Typical Applications of PTFE Tubes 19

2
7 Fabrication of Thick-Walled Pipes 20

7.1 Specimen Preparation and Lubricant 20

7.2 Carbon Black Pigmentation and Antistatic Treatment 20

7.3 Liner Extrusion 20

7.4 Drying and Sintering of the Liner 21

7.5 Typical PTFE Liner Applications 21

8 Fabrication of Cable Insulations 22

8.1 Preparation of the Extrusions Mix 22

8.2 Cable Extruder 23

8.3 Cable Extrusion 23

8.4 Drying and Sintering of Cables 23

9 3M™ Dyneon™ PTFE Fine Powder Compounds 24

9.1 Property Modification by Means of Fillers 24

9.2 Manufacturing Methods of PTFE Fine Powder Compounds 24

9.3 Typical Applications of PTFE Compounds 24

10 Special Applications 25

11 Trouble Shooting Guide 25

12 Compliance and Safety 27

3
1 Introduction

This brochure provides information on how to process

3M™ Dyneon™ PTFE Fine Powder for the manufacture of a va-
riety of products, such as wire and cable insulation, tubes,
pipes, tapes and sealing cords.

1.1 About the Company

Dyneon is one of the world’s leading fluoropolymer suppliers with de-
cades of experience in developing applications. The company develops
userfocused application possibilities for the entire Dyneon product
range in its own technical service laboratories and research facilities
in Europe, USA and Asia.

1.2 About our Fluoropolymer Product Family

Dyneon offers a broad product family of high-performance plastics that
is divided into three product groups:

Fluoroelastomers
Fluoropolymers Fluorothermoplastics

PTFE

Figure 1.1: Division of different fluoropolymers

Fluoroelastomers are cross-linkable, amorphous copolymers with a

molecular weight of 5 x 103 - 5 x 104 kg/kmol. They are extruded at
temperatures of <150 °C and then cross-linked in a heated mould. The
resulting vulcanisates lose their formability and weldability.

Fluorothermoplastics are partially crystalline copolymers with a molec-

ular weight of 5 x 104 - 8 x 105 kg/kmol. Due to a modification of their
copolymer composition, they feature a broad melting-point range of
100 - 320 °C. Fluorothermoplastics can be processed at temperatures
of up to 400 °C with conventional thermoplastic technologies.

4
PTFE is a partially crystalline homopolymer with an exceptionally high
molecular weight of 107 - 108 kg/kmol. This high molecular weight makes
melt-processing of PTFE impossible. The product leaves the polymeriza-
tion process in a highly crystalline form with a crystallization degree of
> 90% providing it with a melting point of 340 - 345 °C. After the first
melt, the crystallization degree decreases to approx. 60% and the melting
point to 327 °C.
The proven properties of PTFE are:
excellent all-round chemical resistance
widest service temperature range of -200 °C to +260 °C
superior dielectric properties
no embrittlement or ageing
very good non-stick properties
dimensional stability and stress cracking resistance.
The PTFE group is subdivided into suspension polymers and emulsion
polymers (Figure 1.2). Three further product groups evolve from the latter:
micro-powders, dispersions and fine powders. Suspension polymers are
divided into pre-sintered ram extrusion powders as well as non-free-flow-
ing and free-flowing powder grades. PTFE compounds, i.e. blends of PTFE
and fillers, are mostly made of suspension polymers. In addition, Dyneon
has a number of fine powder compounds available.
Suspension polymers leave the polymerization process in the form of
up to 2000 μm polymer particles with irregular shapes, so-called reactor
beads. These are then milled until they are just 10 μm fine and, if neces-
sary, agglomerated in an additional process step, where the fineness can
be adjusted to particle sizes in the range of 100 - 600 μm.
Agglomerated products are free-flowing. Milled products are non-free-
flowing and are also used for the manufacture of PTFE compounds. PTFE
powders are processed by specially developed technologies, such as
pressing and sintering as well as ram extrusion. The products that are
particularly well suited for the ram extrusion process are those that are
non-milled, yet pre-sintered, whose dosing and free-flowing properties
are achieved by screening the rough and fine parts. Suspension polymers
are mainly used for the production of semi-finished products which are
then drilled, turned, planed or milled into a variety of finished articles.
Suspension polymers
PTFE
Emulsion polymers
Fig. 1.2: Various product groups within the PTFE family
Emulsion polymers are converted into water-dispersed latex particles
during polymerization. These so-called primary particles are of spherical
shape with a diameter of 180 - 250 nm. The primary particles are coagu-
lated into so-called secondary particles with a diameter of approx. 400 -
600 μm and agglomerated into a free-flowing fine powder.
Emulsion polymers are divided into three groups according to their in-
tended use: fine powders, micro-powders and dispersions.
Fine powders cannot be processed from the melt due to their high mo-
lecular weight in the 107 - 108 kg/kmol range. A special technology, known
as paste extrusion, has therefore been developed to produce high-quality
finished articles, such as tubes, wire and cable insulations, and liners.
Specific fine powder types have been developed for the various fields of
application, described in the “3M™ Dyneon™ Polytetrafluoroethylene Prod-
uct Comparison Guide” brochure.
PTFE dispersions with a solid content of up to 65% are used for impreg-
nation and coating of metal surfaces and fibreglass.
Micropowders are used as additives for a variety of applications to im-
prove slip and non-stick characteristics. Their molecular weight, similar
to that of fluorothermoplastics, is in the range 5 x 104 - 106 kg/kmol. In
contrast to fine powders or suspension polymers, micro-powders cannot
be used for the production of semi-finished products, as a result of their
low molecular weight.
The next chapter describes the theoretical and physical background of
the materials, which helps to explain the careful steps that must be taken
during the paste extrusion process.
Ram extrusion powders
Free-flowing powders
Non-free-flowing powders
Fine powders
Dispersions
Micropowders
5
2 Physical Fundamentals
of PTFE Fine Powder Processing

2.1 Production of
3M™ Dyneon™ PTFE Fine Powders
2.2.2 Paste Mixing
PTFE production starts with the synthesis of the non-natural monomer By adding lubricants, the pore space of the secondary particle is filled.
(tetrafluoroethylene, TFE) and leads through emulsion polymerization of Organic PTFE-wetting fluids are used as lubricants, mostly higher boiling
the monomer in water to the final polymer. The watery emulsions con- point hydrocarbons (benzenes). In practical use, 20 weight parts of ben-
sist of approx. 180 - 250 nm sized particles that agglomerate during the zene are mixed with 100 weight parts of PTFE. The air in the interior of
precipitation process, leading to the formation of secondary particles of the secondary particle is displaced by adding lubricants. The potato-like
approx. 400 - 600 μm in size. Then the water is decanted and the still wet shape of the secondary particle is not modified by this. The paste with the
fine powder is dried. The fine powder is highly shear-sensitive because the additive still retains its free-flow ability, while the specific weight increases
agglomerated particle has a very low mechanical stress resistance. The to about 700 g/l. The air-filled pore space between the secondary particles
following pages describe the processes that occur during paste extrusion is in the range of 500 ml/l.
with the aim of pointing out those that are rheologically1 relevant in order
to get a better understanding of their impact on the final properties of the 2.2.3 Preform Fabrication
paste extrudates. The air between the secondary par-
ticles is removed by compressing
2.2 Phenomenology of Paste Extrusion them in a cylinder with a pressure of
approx. 30 to 50 bar, which increases
2.2.1 Morphology of the Fine Powder the density of the lubricant-containing
As illustrated in Figure 2.1, the fine powder consists of “potato-like” sec- material to 1650 g/l. The shape of the
ondary particles with a diameter of approx. 500 μm and a specific weight secondary particle and the primary
of 500 g/l. The space filling degree is 25 vol %, i.e. 1 l of fine powder has particles is thereby preserved (Fig.
an air-filled pore space of 750 ml. 2.2). The cylindrical rod resulting from
this is called the preform or billet. From 200 μm
The secondary particle consists of some 10 primary particles that are
10
the measured density, a filling degree Fig. 2.2: Morphology of the fracture
statistically packed in a spherical agglomeration. The packing density is of approx 63 vol %. From the rheolog- surface of the compressed billet

55 vol %. A statistical spherical packing of spheres with identical size can,
regardless of the sphere diameter, achieve a maximum filling degree of
62 vol %. The spherical primary particles have an extremely tight particle
size distribution. The PTFE they contain is in a highly crystalline form.
The potato-like form of the secondary particles ensures the free-flow abili-
ty (Fig. 2.1 left). The grainy, island-like structure of the secondary particle,
which can be easily seen, illustrates the statistically packed spherical ag-
glomeration (Fig. 2.1 centre). The particles are “grape-like agglomerates”
of 1010 primary particles that can only be seen at higher magnifications
(Fig 2.1 right).
ical point of view, the fine powder has
a paste-like state in the billet.
Rheologically, the paste can be defined as a heterogeneous 2-part system
consisting of an immobilized fluid and a plastically deformable solid. This
system flows when forces exceeding a certain minimum force are applied,
and it is irreversibly deformed. The immobilized fluid thereby becomes a
lubricant (matrix) and the deformed primary particles are a filling sub-
stance (islands).

200 μm 100 μm 1 μm
Fig. 2.1: Morphology of the fine powder; left: optical-microscope image of a secondary particle; centre and right:
SEM micrograph of the surface of the secondary particle shown in different magnification
1
Rheology, the science of flowing materials and deformation. It was established because the linear elasticity theory with Hook’s law and hydrodynamics with Newton’s law of
friction were not sufficient to describe the deformation behaviour of certain substances.

6
2.2.4 Paste Extrusion
in Funnel-Flow Design
The irreversible deformation during extrusion is
illustrated in Fig 2.3. The billet is transferred to
a cylindrical metallic hopper and then pressed
through a funnel, also made of metal, at a
certain pressure, the so-called paste extrusion
pressure. The narrowing of the cross-section
in the funnel is characterized by the reduction
ratio (RR), which is the ratio of the areas of the
funnel inlet and the funnel outlet. Attached to
the funnel outlet is a very short piece of pipe,
the so-called guide in which the “flowing paste
is calmed”.
In the hopper, the billet material shows plug flow
behaviour, as it does not stick to the metallic
wall. A real flow process, from the rheological
point of view, only starts at the funnel inlet,
shown as flow threads in Fig. 2.3. The flow
velocity increases in direct proportion to the
narrowing of the RR cross-section.
RV=1
RV=2
RV=4
RV=40
RV=400
Fig. 2.3: The irreversible plastic deformation of the paste
during extrusion
The crowding of the flow threads generates a
shear gradient in the direction of the flow. This
forces the paste material into an irreversible,
plastic deformation. The extruded material
gains mechanical stability from the deformation,
the so-called “green stability”, both in its lubri-
cant-containing, wet state and in the dry state.
The wet extruded material has a density of
approx. 1.8 g/cm3, while the dried extrudate 100 μm
has a density of 1.6 g/cm3 and a space filling Fig. 2.4: The fibrous structure of the extruded material.
degree of 70 vol %. This means that the the- SEM micrograph of a split extrudate. The primary particles
in the fibrils are arranged in the direction of flow like beads
oretical maximum packing density for spheres on a string
of identical size has nearly been reached. The
next section provides a phenomenological ex-
planation of the processes that are necessary
to achieve a high filling degree.
1 μm
Fig. 2.5: Scanning electron-microscope image of a split
extrudate
2.3 Morphological Changes during Paste Extrusion
2.3.1 Morphology of the Paste Extrudate
Fig. 2.4 shows the fibrous structure of an externally smooth paste extrudate that has been split in
the direction of flow. The secondary particles, still intact in the billet (Fig. 2.3), have been irreversibly
deformed into fibrils. The fibrils consist of a “pearlstring-like” alignment of primary particles in the
direction of flow.
The electron-microscope image in Fig. 2.5 of the split extruded material shows that individual primary
particles (200 nm) have been preserved. They are clearly recognizable and survived the high shear
gradient that is necessary for extrusion. The preservation of these primary particles is ensured by
the lubricant.
Two processes during extrusion can be clearly distinguished:
irreversible deformation, so-called crack-up, of the potato-like secondary particle in bead-string-like
fibrils,
the kneading of the primary particles as a reversible deformation.
The specific energy necessary for the two forced processes in relation to the volume corresponds to
the extrusion pressure. The two processes are explained in detail in the following section.
7
2.3.2 Crack-up of the Secondary Particles
The crack-up of the secondary particle, also called paste fibrillation, is illustrated in Fig. 2.3. It shows
the longitudinal section of the funnel cone. The fine powder is mixed with lubricant containing dyed
secondary particles before paste preparation. The dye used is benzene insoluble. It is thus possible to
see how the deformation of the dyed secondary particles into “longitudinal cylinders” increases with
increasing reduction ratio RR.

Deformation is an adaptation to the flow threads (see Fig. 2.3). The crosssection of the cylinder
becomes smaller the higher the reduction ratio (RR) gets. The decrease of the cross-section is
inversely proportional to the RR. It is the result of packet-like regrouping of large primary particle
clusters that are transported in the flow direction to the head of the fibrillating secondary particle. The
transportation of the cluster is inevitably coupled with primary particles changing place. This induces
the pearl-stringlike alignment of the primary particles. The secondary particle is cracked up.

The pearl-string-like alignment of the primary particles should ideally be homogeneous up to ranges
of <10 μm, i.e. larger unaligned “grape-like” clusters should be avoided. Such clusters lead to irreg-
ular, unsmooth surfaces of the sintered finished product (orange peel).

2.3.3 Reversible Deformation of Primary Particles

Paste extrusion is accompanied by an enlargement of the extrudate, i.e. the extrudate has a larger
diameter than the guide. This can be proof that an elastic deformation of the primary particles has
taken place, as they are the only ones able to store elastic energy. The shear gradient in the flow
direction deforms the spherical primary particles into ellipsoids. The primary particles are kneaded.
After leaving the guide, the elastic tensions relax and the primary particle returns to its original Fig. 2.6: Reversible deformation of the primary particles.
spherical shape, as shown in Fig. 2.6. This means that the deformation is reversible. All that remains Above: before the area reduction in the extruder. Centre:
maximum deformation at the tip of the extrusion die.
is a more compact structure.
Below: relaxation after leaving the extrusion die.

The changed melting behaviour of the paste material after kneading is another major proof that a
reversible deformation has taken place, as illustrated in Fig. 2.7. The DSC diagram shows a uniform
melting peak for the original and a “bimodal” melting peak for the extruded paste material. The
crystalline structure has obviously been changed through the kneading. The original orderly alignment
has been partly destroyed.

Perkin-Elmer Thermal Analysis

Peak = 345 °C Peak = 347 °C
Onset = 340 °C

Onset = 338 °C Peak = 338 °C

Onset = 335 °C
Area = 714 mJ
Delta H = 66 J/g

Area = 8.6 mJ Area = 662 mJ

Delta H = 0.8 J/g Delta H = 64 J/g

290 300 310 320 330 340 350 360 300 310 320 330 340 350 360
Temperature (°C) Temperature (°C)

Fig. 2.7: DSC diagram: on the left, unkneaded (original from the drum) and on the right kneaded (extruded) PTFE paste; both samples are unsintered

8
3 Properties and Handling
of 3M™ Dyneon™ PTFE Fine Powders
PTFE fine powder has a very high specific sur-
face with a porous, spongelike structure that is
characterized by a very high absorption capaci-
ty for liquid hydrocarbons (lubricants).
The emulsion polymer powders are also often
referred to as powder paste. This is because
they undergo a processing step where the ma-
terial has a paste-like feel. Its extremely high
molecular weight, however, results in such a
high melting viscosity that processing requires
a special technology, the socalled paste extru-
sion. The first process step, therefore, is to add
a lubricant to enable processing of the powder
paste. The powder paste with lubricant added is
still powdery with good free-flowing properties.
With special paste extruders (ram extruders),
a variety of profiles, tubes, sealing cords, wire
insulation and even large pipe liners can be
fabricated at slightly elevated temperatures.
The extruded profiles can then be calendered
into tapes and films for use as thread sealing
tapes and electrical insulation films for cables.
If porous structures are required, a subsequent
stretching process can be used. After the dry-
ing process in which the lubricant is removed,
a final sintering process with temperatures of
360 - 380 °C gives the products their high me-
chanical stability and transparency.
The special processing technologies required
for paste extrusion place very high demands on
the raw material. Contaminants such as dust,
lint from garments, or hair would decompose
at the high sintering temperatures, resulting in
discoloration and deterioration of the material’s
properties. The powder paste is soft, deforma-
ble and shear-sensitive. Ensuring proper pack-
aging, storage and transportation conditions
is therefore of the utmost importance. The
free-flowability of 3M Dyneon PTFE fine powder
depends on the temperature and humidity.
Tip:
To avoid contamination of the fine powder when opening the drums,
we recommend that the lid and drum be thoroughly cleaned beforehand
(e.g. wiped with a moist cloth and dried).
Temperature
The higher the temperature, the worse the Peak = 19 °C
free-flow ability of the powder becomes. Good
free-flow behaviour is a prerequisite for homo-
geneous absorption and distribution of the lu- Onset = 11 °C Peak = 29 °C
bricant. The two crystal modification phases at
19 °C and 29 °C (Fig. 3.1) are specific to PTFE. Onset = 24°C
They are coupled with a significant deterioration
of the PTFE powder’s free-flow ability. PTFE is
Area = 3.3 mJ
prone to clumping. Above 30 °C, it is virtually Delta H = 0.3 J/g
impossible to achieve good quality paste pro- Area = 66 mJ
cessing. Delta H = 6.2 J/g
In storage, maximum temperature limits must
therefore be absolutely observed in order to
ensure optimum free-flow ability. Temperatures
-10 0 10 20 30 40
below 19 °C (e.g. 15 °C) have proven to be very
Temperature (°C)
effective.
Fig. 3.1: Determination of PTFE phase transformation with the
help of DSC
Humidity
To prevent flaws in the finished product, the
residual humidity of the fine powders must be 3.1 Reduction Ratio
very low (max. 0.04%). This is taken into ac-
count both during the manufacturing process The reduction ratio (RR) is a unit-less number
and in the selection of packaging and storage. calculated from the ratio of the cross-sec-
The converter of the raw materials has to keep tional area of the extrusion cylinder minus the
these requirements in mind, too. For example, cross-section area of the mandrel rod and the
where the air humidity is very high, cooled crosssection of the extrusion die minus the
drums should only be opened in a cooled sample cross-section of the mandrel tip. When extrud-
preparation room to prevent condensation of the ing full profiles, the crosssections of mandrel
humidity from contaminating the raw material. rod and mandrel tip are not taken into account.
Reduction ratio = EC - M
ED - MT
EC: cross-section of the extrusion cylinder
M: cross-section of the mandrel rod
ED: cross-section of the extrusion die
MT: cross-section of the mandrel tip
Examples of different reduction ratios (RR):
Thick-walled liners: RR = 10 to 50
Thin-walled liners: RR = 50 to 500
Micro-tubes: RR = 500 to 2000
Cable insulations: RR = 300 to 3000
9
 3.2 Extrusion Pressure
As per ISO 12086, 3M™ Dyneon™ PTFE Fine
Powder types are evaluated according to their
extrusion pressure with a reduction ratio of RR =
400 or RR = 1600, which allows a statement
as to their processability with a specific RR.
Extrusion pressure is defined as the pressure
in bar or MPa under standardized conditions
(RR = 400 or 1600) that builds up in the paste
extruder when extruding a mixture of PTFE fine
powder and lubricant, and which is exerted on
the material.
The extrusion pressure is dependent on the
extrusion conditions, e.g. type of fine powder,
lubricant, extrusion velocity, RR, die geometry
(die angle and land length) and temperature.
The extrusion pressure increases with increas-
ing reduction ratio, as illustrated in Fig. 3.2.
140
Material for low RR, e.g. liners
120 Material for medium RR, e.g. large tubes
Material for high RR, e.g. small tubes
100
Extrusion Pressure in MPa
80
60
40
20
0
0 200 400 600 800
Reduction Ratio (RR)
Fig. 3.2: Dependency of extrusion pressure on reduction ratio (RR) for different types of fine powder
3.3 Particle Size and
Particle Size Distribution
The free-flow ability and thus the processability
of the dry powder are determined by the surface
structure of the agglomerate particle and the
particle size distribution. The average particle
size ranges from 500 - 600 μm. The particle
size distribution is determined by means of
fractional screening. When pigments are added
to powder paste that is too coarsegrained, inho-
mogeneous colour distribution can result.
1000 1200 1400 1600 1800
3.4 Specific Weight
The specific weight of PTFE powder is ex-
pressed as kg/m3 (mass per volume). Directly
related to this are mass and volume of the pre-
form (also commonly called billet; see Section
4.7 Compression of the Preform).
The specific weight is thus a value to be taken
into account when dimensioning the preform
press. Fine powders tend to compact during
transportation and storage. This tendency is
even greater when the transition point at 19 °C
has been exceeded, so the powder must be
loosened before processing by means of cooling
and screening.
Due to this tendency to clump, even under light
pressure, a special preparation of the specimen
is necessary in order to measure the specific
weight. It should be determined in accord-
ance with ISO 12086 and should be approx.
500 kg/m3.
3.5 Density
The density of the finished parts made from sin-
tered paste PTFE is, according to product type
and processing parameters, between 2.14 and
2.17 g/cm3 and enables evaluation and quality
control of the finished product. Low molecular
weight or slow cooling results in products with
high crystallinity and thus a density that is too
high. High molecular weight or too rapid cooling
results in products with low crystallinity and
thus a density that is too low.
The density of the crystalline portion is higher
(2.288 g/cm3 ) than the density of the amor-
phous portion (1.966 g/cm3 ).
The mechanical properties of the PTFE are es-
sentially determined by the amorphous portion
of the product and to a lesser extent by the
crystalline portion. For the reasons given above,
a precise interpretation of the density is only
possible if specimen preparation and process-
ing parameters are precisely defined.
The fabrication of plates, the sintering condi-
tions and density measurement (Standard Spe-
cific Gravity, SSG) are described in ISO 12086.
10
4 Fundamentals of
PTFE Fine Powder Processing
4.1 Packaging and Storage 4.2 Preparation of the Extrusion Mixture
3M™ Dyneon™ PTFE Fine Powders are produced in electronically-con- In order to avoid flaws in the finished product, care must be taken during
trolled processes (process control system) and filled under clean-room processing of the fine powder to avoid all excess mechanical stress of the
conditions (clean room class 100). They are packed in tightly-closable powder, as it is highly shear- sensitive. It is recommended to shake the
plastic drums with a filling quantity of 25 kg. powder carefully or scoop it out in order to avoid crushing the particles.

The PTFE production facility, as well as the quality of the drum container
with lid and seal, eliminates the need for dry bags, which also avoids pos-
sible contamination due to damage to the dry bag. The material is filled and
stored at temperatures below 19 °C. In the hotter months of the year, the
product is usually shipped in refrigerated trucks in order to avoid clumping
due to transportation and/or heat and to maintain the good free-flowability
of the fine powder.
In order to preserve these powder properties, it is recommended that
customers store the products in refrigerated rooms; where possible at
temperatures below 19 °C, the point at which crystallite is transformed.
A room temperature of 15 °C is recommended. Should the fine powder be
found to be clumpy or contain agglomerates, despite these precautionary
measures, then the latter can be sieved out (caution: do not apply pressure
to the particles, do not contaminate the powder). The separated agglom-
erates should be refrigerated for 2 to 3 days at a temperature of between
5 and 10 °C, and then shaken in order to break apart the agglomerates.
They should then be screened at temperatures below 19 °C by which the
agglomerates should fall apart into free-flowing powder.
4.3 Powder Screening
Before pouring it into the mixing container, the fine powder should be
screened in order to break apart any agglomerates and to loosen it. The
mesh size of the screen should be 3 to 4 mm. The use of riddle sifters
is also possible, which allows harder agglomerates to be broken apart.
Larger clumps that do not fall apart should be removed from the screen
and collected in a separate container. The separated agglomerate parti-
cles can be reprocessed through cooling and renewed screening (also see
Section 4.1). Utmost cleanliness is important during the open screening
process. Moisture absorption due to air condensation must be avoided by
maintaining the drum at ambient temperature and reclosing it immediately
after powder removal. PTFE is a good electrical insulator, so when dosing
PTFE it is necessary to avoid high pouring speeds, as the material could
otherwise become charged with static electricity and then explode in com-
bination with the lubricant.

Fig. 4.1 shows the cooling curve (determined by experiment) of a fine pow-
der drum with 25 kg content with a temperature of 30 °C. The ambient
temperature is 5 °C; the temperature sensor is in the middle of the powder
in the fine powder drum. It takes more than 24 hours until the fine powder
material is ready for further processing and approx. 3 days to cool the
material down to 5 °C (also see Section 4.3). A more practical solution
would be a cold room temperature of 15 °C where the cooling of the PTFE
down to 15 °C extends over several days.

30
Tip:
Cooling cure at 15 °C ambient temperature
It is recommended that you earth all
Cooling cure at 5 °C ambient temperature
25 containers coming in contact with
PTFE and PTFE lubricants and use
20 metallic containers.

15
Powder temperature in °C

10

0
0 10 20 30 40 50 60 70 80 90
Cooling time in hours

Fig. 4.1: Cooling time of a 25 kg powder drum at an ambient temperature of 5 °C and of 15 °C, curves determined by experiment

11
 4.4 Mixing with Lubricants
Aliphatic hydrocarbons with different boiling ranges have proven useful as lubricants for paste extru-
sion. The choice of the lubricant is dependent on the type of extrusion material.

Warning!
Lubricant mixing may cause the formation of ignitable lubricant air mixes in the range of 0.8 vol %
to 6.5 vol % lubricant (also see the material safety data sheet of the respective lubricant as well
as safety regulations concerning the handling of flammable solvents or vapours).

Lubricants with a higher boiling range are usually used for thin-wall applications requiring a calender-
ing process, such as films. Lubricants with a lower boiling range are used for thick-walled extrusion
materials such as liners. Tip:
The selected lubricant should be well absorbed by the fine powder and equally well removed after the Ignitable lubricant/air mixes can be avoided
extrusion. It should also not cause discolorations during sintering. Depending on the application and by using a good suction ventilation system
the lubricant type, the lubricant content amounts to 17 to 25 parts by weight related to 100 parts by with a high air-flow rate. The lower explo-
weight of 3M™ Dyneon™ PTFE Fine Powder. The quantity of the lubricant is stated in parts by weight sion limit is not attained.
for simplicity’s sake. However, it would be more correct to say that the optimum volume of lubricant
is added to the PTFE fine powder, as the void volumes between the primary particles that has to be
filled. Here, the density of the lubricant, that may vary by around 10 - 15 %, plays a role.

The lubricant is added to the powder in the centre of the mixing container, not at its edge. Table 4.1
shows a selection of usable lubricants. The mixing procedure should be carried out at a temperature
below 19 °C as the fine powder has a better free-flow behaviour at these temperatures. Depending
on the type of mixer (dolly or tumbling mixer), the mixing time is between 20 and 30 minutes with a
speed set at 20 to 30 revolutions per minute. The powder mix should flow and not splash in the mixing
container. The lubricant is absorbed uniformly by the powder. The mixing containers must be tightly
sealed in order to avoid evaporation losses. The mixing container should be filled to a maximum of
2/3 of its volume in order to attain a good mix.

Earthing is important when mixing the fine powder with the flammable lubricant due to the ignition
risk of the lubricant vapours, e.g. ignition caused by electrostatic charge (also see Section 4.3). The
benzene concentration in the working rooms must be monitored with the help of suitable room air
monitoring devices. Good ventilation should also be provided.

Lubricant Manufacturer Boiling range Density Applications

of the lubricant
Shell Sol 100/140 Shell 105 - 137 °C 0.730 g/cm3 Pipes, cables, tubes

Isopar E Exxon 118 - 143 °C 0.724 g/cm3

Shell Sol T Shell 187 - 215 °C 0.761 g/cm3 Tapes

Shell Sol D70 Shell 190 - 250 °C 0.798 g/cm3

Isopar K Exxon 181 - 204 °C 0.766 g/cm3

Isopar L Exxon 189 - 210 °C 0.773 g/cm3

Isopar M Exxon 206 - 245 °C 0.790 g/cm3

Table 4.1: Selection of lubricants for use in paste extrusion

12
4.5 Pigmentation
The following procedures are recommended
for pigmenting or colouring the powder paste:
When using liquid colour suspensions, add
these to the lubricant before mixing with the
powder paste. If the pigment is to be mixed with
the powder paste in a dry state (e.g. for anti-
static applications, carbon black dyeing), the
pigment is screened directly onto the powder
and the mix is then homogenized in dry state
through rolling. After that, the lubricant is added
and handled as described in Section 4.4. This
avoids formation of agglomerates to a large
extent. If any agglomerates persist, cooling as
per Section 4.1 or screening as per Section 4.3
should be carried out.
4.6 Maturing of the
Extrusion Mix
A homogeneous distribution of the lubricant in
the PTFE can be obtained by letting the mix “ma-
ture”. This ripening process should take over-
night or at best over 24 hours in tightly sealed
containers. Longer times are not necessary.
Tip:
Higher temperatures (e.g. 30 °C) during
the maturing process ensure improved
distribution of the lubricant and provide
more homogeneous extrusion quality.
4.7 Preform Compression 4.8 Extrusion
In this processing step, the mix of 3M Dyneon
™ ™
Because of the different handling procedures,
PTFE Fine Powder and lubricant is fed into a the topic of “extrusion” is dealt with in specific
preform press where it is compacted into a cy- sections titled “Fabrication of Films and Tapes”,
lindrical preform. “Fabrication of Tubes”, “Fabrication of Thick-
Walled Pipes (Liners)” and “Fabrication of Ca-
The aim of the compression is to eliminate the ble and Wire Insulations”. For paste extrusion,
air contained in the mix of powder paste and ram extruders with a relatively simple design
lubricant and to bring the mix into a form that are used where the preform is extruded through
can be fed into the extrusion cylinder without the die of a ram extruder.
any problems. The cylinder of the preform press
should be three times the length of the preform,
as the powder is compressed to 1/3 of its vol-
ume. The mix of powder and lubricant should be
compacted slowly so as to allow the air to com-
pletely escape from the mix in the preform cyl-
inder. This process can be supported by a vacu-
um placed at the ventilation bores. Pre-pressing
takes several minutes at a pressure of approx.
30 - 50 bar. The quality of the finished products
is, among other things, dependent on a preform
without cracks. The compression pressure is
therefore only slowly decreased and care must
be taken when removing the preform from the
preform cylinder. The compacted part must
then be immediately processed to reduce evap-
oration of the lubricant from the surfaces to a
minimum.
Inhomogeneous distribution of the lubricant
results in quality and dimensional variations of
the finished product. The preform is fed into the
paste extruder – the cylinder of which should
have a diameter that is 1 mm larger than the
outer diameter of the preform.
Tip:
Preforms containing lubricant can be stored
in air-tight, sealed containers. In order to
ensure a uniform lubricant atmosphere in
the storage drum, a cloth impregnated with
lubricant is enclosed in the container. This
prevents the surface of the preform from
drying out. In doing so, the precautionary
measures stated in Section 4.3 must be
observed.
13
5 Fabrication of Films,
Tapes and Sealing Cords
Films, tapes and sealing cords can be fabricat- The key processing steps for the fabrication of The content of lubricant is 21 - 25 parts by
ed from 3M™ Dyneon™ PTFE extrusion paste in films and tapes are shown in Fig. 5.1: weight related to 100 parts by weight of PTFE.
stretched, unstretched, sintered or unsintered Preparation of the extrusion mix In contrast to tube extrusion, higherboiling lu-
forms. The following applications are known: (Section 4.2 - 4.6) bricants (boiling range of 180 - 250 °C, also
Thread sealing tapes Preform compression (Section 4.7) see Tab. 4.1) are used in order to avoid lubricant
Flat or plate seals Profile extrusion loss during calendering. This also has a favour-
Electrical insulation tapes for wound Film calendering able impact on the calendering behaviour (even
insulations Film drying edges, splice tendency).
Tape cable Mono- or biaxial film stretching
Varns Film sintering, cutting and packaging,
if required

a b c d e f
Fig. 5.1: Diagram of a tape facility: a extrusion, b calendering, c drying, d stretching, e cutting and f wind-up

5.1 Profile Extrusion

Extruders for profile fabrication can be of relatively simple design. A cylinder
with a nozzle or a ram with a mechanical or hydraulic drive that runs pres-
sureindependently at a constant velocity are basically all that is needed.
The latter is necessary as the pressure can change during extrusion. A
small-dimensioned extruder is normally enough to attain the reduction ratio
of 100:1 that is required for profile extrusion.
It is possible to set preform on preform, in order to minimize loss of mate-
rial that stays in the cone of the extruder due to the design. The touching
surfaces of the two preforms can be roughened with a fork or similar device
in order to improve the mixing of the two materials and thus avoid a prede-
termined breaking point in the profile. The forming tool consists of a conical
reducer and a die with parallel guide.
The enclosed angle of the cone is between 20° and 40° (also refer to
Section 6.2, Fig. 6.2, but without mandrel rod). In practical use, the round
extrudate has proven to be a useful solution for extrusion profiles.
For broader tapes, a rectangular or “dog-bone” profile is preferable. Fig.
5.2 shows possible extrusion profiles. The tools or areas coming into con-
tact with the preform should be smoothly polished and made of stainless
steel. Steps or edges at the transition from cylinder to cone should also
be avoided. Profiles of the highest quality are attained when the extrusion
cylinder and die have a temperature of approx. 30 to 40 °C. After extrusion,
the extrudate is wound up and calendered. If the extrudate is to be stored,
it should be placed in a tightly sealed container to avoid lubricant escape.

Tip:
Place a lint-free cloth impregnated with lubricant
into the container to ensure a uniform lubricant at-
mosphere and to prevent the extrudate surface from
a b c
drying out. In doing so, the precautionary measures
described in Section 4.3 must be observed. Fig. 5.2: Extrusion profiles for tape fabrication: a dog-bone, b rectangular and c round profile

14
 Extrudate
Fishtail profile

Fig. 5.3: Feeding of the extrudate through the fishtail profile of a two-roll calender

5.2 Calendering 5.3 Film and Sheet Drying

Two-roll calenders equipped with an appropriate feeding system are used
to calender profiles. The shape of the feeding system is similar to a fishtail
or coat hanger profile, as shown in Fig. 5.3.
The calender rolls usually have a diameter of 300 to 400mm and widths of
approx. 400 mm.
A temperature of around 40 °C is recommended for the tool surface and
a roll speed of approx. 30 revolutions per minute (depending on the roll
diameter). The adjustment of the sheet thickness requires a highly precise
fine adjustment of the roll gap across the width of the film.
Calendering from profile to sheet is usually done in one step. For thick-
walled profiles, this process can be performed in several steps until the
required width and thickness are obtained. The calendered width of the
sheets is dependent on both the PTFE type and the following parameters:
shape of the profile
t ype and shape of the fishtail guide and its distance to the roll gap
The film or sheeting is dried at a temperature of 160 to 200 °C. The line
speed or the length of the oven must be selected so as to enable complete
removal of the lubricant. Calendering and drying should be performed
independently of each other as both steps achieve their optimal results at
different speeds.
Warning!
The drying process of the sheet may cause the formation of ignitable
lubricant air mixes in the range of 0.8 vol % to 6.5 vol % lubricant (also
see the material safety data sheet of the respective lubricant as well
as safety regulations concerning the handling of flammable solvents or
vapours).

s heet thickness

lubricant content
Tip:
roll surface
Ignitable lubricant/air mixes can be avoided by ensuring a high air
In general, sheet widths of 240 to 270 mm at a tape thickness of 100 μm throughput in the drying oven. The lower explosion limit is not attained.
can be achieved by using a dog-bone profile and a calender of the type
described above.

Tip:
The surface of the roll should not have a high-gloss polish but have
a slight coarseness or a coarse polish of the crosssection in order
to ensure enhanced creep of the sheet. This can be achieved by
treating the surface with abrasive with a grit of 200, for example.

15
5.4 Film Stretching
The dried films or tapes are stretched for cer- 2.0
tain applications. In practical use, stretching of
the free-running PTFE sheets at temperatures
of between 280 °C and 300 °C has proven 1.5

Tape thickness in g/cm3

effective (used for thread sealing tapes). The
sheet is stretched with two different roll sys-
1.0
tems that are running at different speeds in the
running direction. The sheet is clamped with roll
systems that can be made of steel or combina-
0.5
tions of steel and rubber rolls.

The film or sheet can be stretched up to a ratio

0
of between 1:10 and 1:15 without formation of 0 10 20 30 40 50 60 70 80 90
irregularities, with minimal reduction of thick- Stretch ratio 1 : x
ness and width. The material becomes highly
porous and stretching results in a substantial Fig. 5.4: Dependence of film density to the stretching ratio at a stretching temperature of 300 °C and a stretching speed
reduction of the specific weight of the sheet/ of 1.7 m/min
film. Fig. 5.4 shows the development of the film
or sheet’s density in relation to the stretch ratio.

The films and sheets are distinguished as ei- 5.5 Fabrication of Unstretched and Stretched Sealing Cords
ther monoaxially and biaxially stretched. Fig.
Sealing cords generally refer to round or rectangular extrudates that can be used in stretched or
5.5 shows SEM micrograms of monoaxially
unstretched form, depending on their application. The technology used for fabricating sealing cords
stretched (left) and biaxially stretched (right)
is very similar to that used for tape fabrication. As with tape production, the profiles are fabricated by
PTFE. The fibres between the PTFE particles can
means of extrusion with appropriate dies being used to correspond to the profile dimension. The ex-
be seen. Monoaxially stretched PTFE is used for
trudate is subsequently dried. For stretched sealing cords, the extrudates are stretched using similar
thread sealing tape. The magnified image part
equipment and conditions as for sheet stretching. The final product should generally have a density of
in Fig. 5.6 shows the transition from an island to
approx. 0.65 g/cm3, which corresponds to a stretch ratio of around 1:3 to 1:4.
a fibre. Biaxially stretched PTFE is widely used
for breathable, impermeable membranes in the
Uniform cord dimensions can be achieved by feeding the extrudates through special calibrating rolls.
clothing industry. The space between fibres is
During the same process step, adhesive tape can be applied to provide the sealing cords with a
large enough to let water vapour pass through
fixation aid for installation.
the membrane (breathable), yet small enough
to keep water drops out (impermeable). Films,
sheets or tapes can also be sintered and then
stretched after the sintering process in order
to produce high tensile-strength films, sheets,
tapes or yarns.

Fig. 5.5: SEM micrographs of monoaxially and biaxially stretched PTFE sheeting Fig. 5.6: SEM micrographs of monoaxially stretched PTFE sheeting.
The image shows the transition from an island to a fibre

16
6 Fabrication of
Tubing and Hoses
Tip:
Paste extrusion is used to fabricate extremely thin-walled micro- and spaghetti hoses as well as
thin-walled industrial tubes from 3M™ Dyneon™ PTFE Fine Powder. Dimensions range from approx. To keep investment costs and the number of ex-
0.1 mm to approx. 25 mm interior diameter with wall thicknesses of around 0.1 to 2 mm. truders low, it has proven useful to apply different
The extruded tubes can be further processed to fabricate: sleeves and rams, thus making it possible to
shrink tubes achieve the optimum reduction ratio of a material.
corrugated tubes and
braided tubes

6.1 Lubricants for Hose Extrusion

The lubricants used for hose extrusion have a lower boiling range (100 to 150 °C) than those used for
tape fabrication to enable easier evaporation of the lubricant during the short time spent in the drying
oven. The following lubricants listed in Table 6.1 can be used:
Suction
Cross-bar
Boiling range
Lubricant Manufacturer Specific gravity Application Ram
of the lubricant
Hydraulic cylinder
Shell Sol 100/140 Shell 105 - 137 °C 0.730 g/cm3 Pipes,
Extrusion cylinder
cables,
Isopar E Exxon 118 - 143 °C 0.724 g/cm3 hoses

PTFE filling
Table 6.1: Lubricants suitable for use in tube extrusion
Mandrel rod with
mandrel tip
Extrusion die

6.2 Tube Extrusion

Tubes made from paste are fabricated using special ram extruders (paste extruder) with an inner
mandrel that determines the interior diameter of the tube, and the extruders can be set up either
horizontally or vertically. The extrudates are then dried and sintered. Specimen preparation and fab- Oven Suction
rication of the preforms is described in Sections 4.2 to 4.7.
Chain mechanism

The extrusion process is discontinuous. Extrusion is stopped after each extruded preform to return
the ram and insert a new preform. Large paste extruders are able to process several preforms with a
total weight of up to 100 kg in one step. Arbitrary enlargement of the preform’s diameter is not possi-
ble as this might lead to excess reduction ratios and high local shear resulting in flaws of the extrusion Drying zone (2-3 m)
materials. Limits are imposed by the material here, as high reduction ratios result in high extrusion
pressures. This means that you must have a cylinder with suitable diameter depending on the tube
dimension. Cylinder diameter can vary in a range of 25 mm to 250 mm as the various tube types have
different maximum reduction ratios. The extruder drive has to ensure that the set extrusion speed Sintering zone (2-3 m)
stays constant regardless of the changing extrusion pressure. This is necessary to achieve constant
drying and sintering conditions in the downstream drying oven – a precondition for consistent tube
dimensions and quality. The extruder can have either a hydraulic or mechanical drive. Experience has
shown that extruders with hydraulic drives now provide precise extrusion conditions and can be more
Cooling zone
easily produced. Fig. 6.1 shows the set-up of an extruder used for processing 3M Dyneon PTFE.

Wind-up (optional)

Fig. 6.1: Hydraulic paste extruder for tube fabrication

17
 Fig. 6.2: Extrusion die of a paste extruder for tube a uniform wall thickness of the tube. There have determined by lubricant content, temperature,
fabrication been good results with flexible mandrels made die angle, land length and extrusion speed.
of polyacetale or polyimide. The tool consists of Excess extrusion pressure may not only lead to
Cylinder a conic reducer and a die with parallel guide high extruder stress but also to excess shear
(land length). The land length L is determined in the tube (cracks, deformations, etc.). If the
Mandrel rod
by the die diameter D. For thick-walled and extrusion pressure is too low, the extruded
large-dimensional extrudates, the ratio is material may have irregularities in the form of
surface coarseness. The relation between ex-
L >1 L = land length
D trusion pressure and lubricant content during
D = die diameter
tube extrusion with different reduction ratios
and for thin-walled, small-dimensioned tubes is illustrated in Fig. 6.3. The impacts of the
20°- 40° Closing jaws
the maximum ratio is lubricant quantity on the extrusion pressure,
L =10
i.e. shrinkage of a selected tube dimension, are
D summarized in Table 6.2. The mechanical prop-
erties are not affected by the lubricant quantity.
Mandrel tip, The enclosed angle of the cone is between Fig. 6.4 shows the possibility of variations of the
exchangeable
20° and 40°. The higher the reduction ratio, final tube dimensions in relation to the removal
Die tool, speed of different lubricant contents in parts
exchangeable the smaller this angle must become in order to
Die heating keep the extrusion pressure in limits. Fig. 6.2 by weight (PW). It also provides information on
Land length illustrates the dies of a paste extruder for tube the relationship between the shrinking proper-
fabrication. ties of the tube and the lubricant content. The
extrusion velocity is dependent on the tube di-
In contrast to profile extrusion, tube extrusion To ensure a smooth tube surface, the die is mension or wall thickness and the length of the
requires an additional mandrel in the extruder. heated to a temperature of approx. 50 - 60 °C. drying and sintering oven. It can be in the range
This mandrel is fixed to a cross-bar or a frame The tools or areas coming into contact with the of 1 to 20 m/min.
plate and runs freely without any fixation in the product should be smoothly polished and made
die area. During extrusion the ram presses the of stainless steel. The necessary extrusion
material over the mandrel. Precise centring of pressure is mainly dependent on the reduc-
6.3 Drying and
the mandrel tip in the die is required to achieve tion ratio and the product type. It is also it is Sintering of Tubes
The extruded tube is dried and sintered in a
continuous oven. In the drying zone, the lubri-
Processingparameter Unit cant is evaporated and removed above the boil-
Tool mm 13.3 x 11.4 ing point of the lubricant and below the sintering
temperature of the PTFE (150 to 250 °C).
Reduction ratio 210 : 1
The evaporation speed is dependent on the
Extrusions speed m/min 2.0 oven temperature, the throughput speed, the
Lubricant Boiling range 100 bis 140 °C wall thickness and the tube dimensions. Com-
plete evaporation of the lubricant at high extru-
Lubricant quantity Parts by wgt. 18 19 20 21 22 sion pressures requires higher temperatures or
Wgt. % 15.3 16 16.7 17.4 18
longer ovens. After drying, the tube is sintered
Extrusion pressure bar 205 161 135 101 91 at a temperature of 360 to 380 °C. Sintering
Final tube dimensions conditions are dependent on
tube dimensions,
Outer diameter mm 12.0 11.7 11.6 11.5 11.3
extrusion velocity and
Interior diameter mm 10.2 9.9 9.8 9.7 9.5
temperature and length of the oven.
Shrinkage of outer diameter % 9.8 12.0 12.8 13.5 15.0
The drying and sintering process changes the
Tensile strength, lengswise N/mm2 29 30 31 30 31 dimensions of the tube. Crosswise shrinkage of
Tensile strength, crosswise N/mm2 26 28 26 28 26
0 to 15 % and lengthwise shrinkage of 15 to
25 % are expected. This dimensional change
Elongation at break, lengthwise % 315 280 340 300 365 must be taken into account when selecting the
Elongation at break, crosswise % 625 605 620 615 585 extrusion tool. It is influenced by the lubricant
content, the temperature management and the
Table 6.2: The impact of the lubricant quantity on extrusion pressure, shrinkage and mechanical properties of a selected tube weight drawing on the extrusion die.
tube dimension

18
 6.4 Tube Testing
To monitor tube fabrication it is advisable to carry out regular checks of
the specific gravity and the mechanical properties such as tensile strength
and elongation at break. Tip:
Determination of the specific gravity The converter may fine-tune the
The “buoyancy method” has proven useful to determine the specific gravi- final tube dimensions with removal
ty of the tube specimen. The test method is described in DIN 53479 under speed and lubricant content.
“Method A”.

Determination of Tensile Strength and Elongation at Break

Specimen preparation and test conditions must be precisely defined as
they have an influence on the measurement results. Testing of tensile Warning!
strength and elongation at break is described in ISO 12086.
Formation of explosive mixes of
lubricant and air can be avoided by
6.5 Typical Applications of PTFE Tubes using a proper ventilation system
Chemical industry: for storage of aggressive media, e.g. use in tank vehi- (also see Section 4.3).
cles, sniffer probe lines for operation monitoring, lab devices.
Pharmaceutical and food industries
Biotechnology
E ngineering
Steam lines for laminating and vulcanization presses, extruders, calen-
ders, purification equipment, plastic foaming equipment, spraying and
painting equipment, glue lines for wood processing, hydraulics, air condi-
tioning and cooling equipment
Engine and vehicle construction
E xhaust pipes, fuel lines
Bowden pulleys
Electrical industry and electronics
Insulations for electronic components

120 3.5
Diameter die
100
RV =1900 3.0 Oute
r dia
Extrusion pressure in MPa

met
80 er a
Tube diameter in mm

t 19
2.5 GT Diameter mandrel

60 RV =950
Interio
r diam
2.0 eter a
t 19 G at 22 GT
40 RV =460 T

1.5
20 at 22 GT

0 1.0
17 18 19 20 21 22 23 24 25 26 4 6 8 10 12
Lubricant quantity in parts by weight per 100 weight parts PTFE Removal speed in m/min

Fig. 6.3: Influence of extrusion pressure and lubricant content in tube extrusion at Fig. 6.4: Dependency of the tube diameter on the removal speed and the lubri-
different reduction ratios cant in parts by weight (PG)

19
7 Fabrication of
Thick-Walled Pipes
Liners are thick-walled pipes with wall thick-
nesses of approx. 2 to 15 mm used for corro-
sion-resistant lining of steel pipes in chemical
plants. This brochure is limited to the descrip-
tion of how seamless liner pipes are fabricated
by means of paste extrusion. It does not deal
with alternative linings implemented with 3M™
Dyneon™ PTFE suspension polymers (isostatic
pressing, ram extrusion, peel films).
7.1 Specimen
Preparation and Lubricant
Specimen preparation does not differ from tube
fabrication. The lubricants described in Section
6.1 can also be used for liner fabrication. Liner
extrusion usually has lower reduction ratios in
the range of 20 to 100. They cause low extru-
sion pressure and low green strength of the liner
pipes. The green strength of a liner refers to the
stability of the extruded PTFE tube right after it
leaves the extrusion die. At this point, the PTFE
still contains lubricants and is very sensitive
to mechanical stress. In order to increase the
extrusion pressure and thus the green strength,
3M Dyneon PTFE liner types have a very high
pressure level of their own. In addition, lubricant
quantities of 17 to 20 parts by weight relating to
100 parts of PTFE by weight are used.
Horizontal extruder
Liner
Supported by holed supporting half pipe
Fig. 7.1: Horizontal extrusion of a liner along an inner supporting pipe into a supporting half pipe followed by drying and sintering in the oven
7.2 Carbon Black
Pigmentation and Antistatic
Treatment
The highly conductive, fine carbon black pow-
der must be added in its dry state. The carbon
black is screened onto the PTFE powder. The
mixture is homogenized in mixing vessels with
the help of rolls or tumble mixers. 0.1 to 0.3 %
weight of carbon black have proven efficient for
black coloration, and around 1 to 3 % weight for
antistatic treatment. The lubricant is added af-
terwards. More detailed information is provided
in Chapter 9, PTFE Fine Powder Compounds.
7.3 Liner Extrusion
For liner extrusion the same ram extruders
as described for tube extrusion (see Section
6.2) are used. Due to the heavy weight of the
liner pipes, the extruders are generally set up
horizontally and require substantially larger ex-
trusion cylinders as a result of the large pipe
dimensions. Fig. 7.1 shows how liners are fab-
ricated.
The extruded liner is drawn over an interior
supporting pipe, if required, and put into a sup-
porting half pipe, taking the low green strength
into account. Pipe and half pipe must be cor-
Drying and
sintering oven
Inner
supporting pipe
rosion-resistant in order to avoid liner discolor-
ation. Unlike with tube extrusion, the mandrel
diameter may exceed the size of the mandrel
rod in order to enable the large liner dimension.
The mechanical stress may be very high, which
requires the use of large dimensioned mandrel
rods made of high-strength steel. The marked
areas at the mandrel of the tool in Fig. 7.2 show
the spots exposed to the highest stress.
When fabricating thick-walled liners, the phe-
nomenon of orange peel sometimes occurs.
Due to the low reduction ratios, the shear gra-
dient is sometimes reduced to such an extent
that a sufficiently homogeneous crackup of
the secondary particle is no longer ensured.
This problem is obviously not caused by “over-
shear” as is often assumed, and can therefore
be solved by dramatically increasing the shear
gradient, e.g. through a substantial increase of
the extrusion speed.
Tip:
The inner supporting pipe and the supporting
half pipe have deburred holes to enable easier
lubricant evaporation during drying as well as
reduced drying times. Alloys with high nickel
content or aluminium are considered as dis-
colorationfree materials.
2
1 3
1 Supporting half pipe (stainles steel)
2 Liner
3 Inner supporting pipe (stainles steel)
20
7.4 Drying and Sintering of the Liner
The tube sections of up to 10 m length are both
dried and sintered horizontally in the oven. The
pipes are put in metal supporting half pipes with
the interior supporting pipe so as to avoid defor-
mation of the liner pipes during drying and sin-
tering (Fig. 7.1). The drying conditions must be
adjusted to the dimensions of the semifinished
products and the boiling range of the lubricant.
This is necessary to allow complete removal of
the lubricant thus avoiding the sintering process
being impacted by the lubricant.
Lubricant residues may lead to discoloration,
cracks and bubble formation. The following dry-
ing and sintering times and temperatures are
recommended in accordance with wall-thick-
ness and diameter:
Drying: 2 to 3 hours at 150 to 200 °C
Sintering: 1 to 3 hours at 360 to 380 °C
Cooling can be performed quickly or slowly,
depending on the desired crystallinity level. The
speed when passing through the gelling point
at 310 to 320 °C defines the crystallinity. Fast
cooling reduces the crystallinity and enhances
the flexibility, while slow cooling increases the
crystallinity and the specific gravity while reduc-
ing permeability.

Mand-
rel rod
Closing clamps Cylinder Cylinder
152.4
(6“)

60°

70°

Die
30
50

Mandrel

117
127 (5“)

Fig. 7.2: Head of a liner extruder with extrusion tool

7.5 Typical PTFE Liner Applications

PTFE liners are generally used in chemical plant construction and in the pharmaceutical industry for
pipes, columns, compensators and fittings to provide protection against aggressive media.

Warning!
For safety and health reasons it is important to
ensure good suction ventilation of the vapours
generated during drying and sintering (also see
Section 4.3).

21
8 Fabrication of
Cable Insulations

The superior dielectric properties of 3M™ vapour extraction system

Dyneon™ PTFE coupled with high temperature
resistance, all-round chemical resistance and
inflammability under normal conditions (limiting
oxygen index, LOI >95), are the key features drying zone sintering zone
that define 3M Dyneon PTFE as the material of
choice for wire and cable insulations.

Similar to tube extrusion, paste extrusion with electrical

special wire cable extruders has established control cabinet
itself as a suitable processing method. The
individual steps are described in Sections 8.2
to 8.4.

nozzle heating
8.1 Preparation
of the Extrusion Mix
barrel heating

Especially for cable fabrication, a prepared

paste mix already containing lubricant is
screened again into the preform press through wire take-up roll
a sifter of 3 to 5 mm mesh sizes. Cable insu-
lations mostly have a low wall strength, which
means that larger agglomerates in the insula-
tion may not lead to flaws. Care must be taken
that the compacting process in the prepress
is slow so that the air can completely escape
from the lubricant-containing powder paste. In unwind roll dancer roll screw drive wire puller electrical dreakdown test device
addition, the pressure used to compress the
preform should not exceed 30 to 50 bars and Fig. 8.2: PTFE cable extruder consisting of an unwind roll (a1) and dancer roll (a2), extruder (b), a drying- (c) and sinter-
ing oven (d), deflector roll (e), a wire puller (f), electrical breakdown test device (g) and wire take-up roll (h)
should be maintained for approx. 5 minutes.
The quality of the cable insulation is highly de-
pendent on the flawless fabrication of the pre-
form which should therefore be given closest
attention. The preform is then slowly relaxed in order to avoid cracks. It should either be immediately processed
or stored in an airtight container in order to avoid lubricant loss caused by evaporation (also see
Section 5.1). Lubricants with a low boiling range are preferred as the dwell time in the drying oven
is very short due to the high extrusion speed. The lubricant quantity is variable over a wide range in
order to lower the extrusion pressure when reduction ratios are very high. The range for an optimum
lubricant quantity is, however, very small in order to minimize the number of electrical breakdowns
(Fig. 8.1, also see 6.2 and Fig. 6.3).
Number of electrical
breakdowns

Lubricant amount
Fig 8.1: Qualitative representation of the optimal lubri-
cant amount for cable extrusion related to the number of
electrical breakdowns

22
 Warning!
Sufficient ventilation must be ensured
(also see Section 5.3).
8.2 Cable Extruder
Fig. 8.2 provides an overview of a cable insulation facility. The extrusion system consists of a wire
unwind roll (a1), a dancer roll (a2), the extruder (b), a drying- (c) and sintering oven (d), a deflector
roll (e), a wire puller (f), the electrical breakdown test device (g) and the wire take-up roll (h).The
cable extruder can be set up either vertically or horizontally. A wire guiding pipe is used instead of
an extrusion dome in the centre of the extrusion cylinder in order to ensure uniform thickness of the
cable insulation. Due to the high extrusion speed, the production of cable insulations requires long
drying and sintering ovens, which are usually arranged parallel to each other to ensure better space
utilization and also require a deflector roll, as shown in Fig. 8.2. The alignment of drying and sintering
ovens as shown here is a compromise solution as the ovens are in vertical position on top of each
other. For construction reasons it is often necessary to deflect the wire by 180 degrees after leaving
Land length
the drying oven in order to go through the sintering oven afterwards. Alternatively, the wire can also
be deflected several times in the oven in order to increase the dwell time. After leaving the sintering
Distance (a)
route the coated wire passes through a thickness meter and its dielectric strength is tested.

Wire guiding pipe

8.3 Cable Extrusion
Die
The preform with inner bore is inserted into the extrusion cylinder of a paste extruder and then
pressed through a die with the help of a ram. The extruded paste material coats the wire that is
guided through the extruder head at the same time. As the extrusion pressure changes during pro-
cessing, the machine design has to ensure that ram speed and therefore extrusion speed are kept at
a constant level. This is particularly important for high reduction ratios during extrusion (compare Fig.
6.3 of tube fabrication). The diameter of the extrudate after leaving the die is higher than the inner
diameter of the die. This is referred to as the PTFE “swelling rate” explained by the release of the Mandrel rod
elastic deformation energy of the particles.
Wire
It is also advisable to heat both the extrusion cylinder and the extrusion die (40 to 60 °C) in order
to ensure that the surface of the extrudate is as smooth as possible. For thin wires, a dancer device
Fig. 8.3: Extrusion die of the wire cable extruder
is used after unwinding that compensates for pull variations and prevents the wire from breaking.
Apart from the die angle, the die diameter and the land length, extrusion is decisively influenced by
the clearance (“a” in Fig. 8.3) between the upper edge of the wire guide tip and the lower edge of the
cylindrical guiding system (land length).

The clearance “a” is correctly set when the material speeds of the PTFE and the wire are identical
at the exit from the wire guiding pipe. When clearance “a” gets bigger, product quality deteriorates
which is reflected in low insulation strengths. When clearance “a” gets smaller the ring gap immedi-
ately in front of the land length can be narrowed to such an extent that it leads to material over-shear
and increase of the extrusion pressure. The adhesion of PTFE to the wire is equally reduced. In
practical use, the optimum clearance “a” should be determined for each type of material and wire and
for each tool. Depending on the reduction ratio, the optimum die angle is between 20° and 30° (Fig. Tip:
8.3). In addition, all edges coming into contact with the paste material should be rounded. The ex-
trusion speed is determined by the material’s shear sensitivity and the conditions in the downstream It may be advantageous to have a wire speed that
drying and sintering ovens. is slightly above the speed of the extrudate as it
allows better coating of the wire and therefore
better insulation properties.
8.4 Drying and Sintering of Cables
After the extrusion, the insulation must be dried at a temperature of around 150 to 200 °C. Any
remaining lubricant in the extrudate may lead to brownish discolorations, cracks and electrical flaws
during sintering. Sintering takes place at temperatures of above 345 °C, preferably at 360 to 380 °C.
The coated wire must be run at decreasing speed the thicker the insulation material gets. PTFE is a
good thermal insulator and prevents complete drying or sintering of the cable insulation if drying and
sintering times are too short or temperatures are too low.

23
9 3M™ Dyneon™
PTFE Fine Powder Compounds
PTFE offers a variety of excellent properties including: Combinations of these and other suitable fillers make it possible to tailor
b roadest service temperature range of all plastic materials custom compounds for specific applications.
lowest coefficient of friction of all known solids
excellent chemical resistance
non-stick properties 9.2 Manufacturing Methods
superior electrical and dielectric properties
non-flammable under normal conditions
of PTFE Fine Powder Compounds
(limiting oxygen index, LOI >95) There are two different methods for producing Dyneon PTFE Fine Powder
Compounds. In the first, the filler is added to the fine powder in the form
However, PTFE does have some properties that restrict its use in applica- of powder or as a suspension together with the lubricant. This process
tions like seals, self-lubricating bearings, etc: is often called the dry-mix method. In the second, since Dyneon has the
deformation under load (cold flow) ability to produce compounds directly from the dispersion, the filler can be
poor thermal conductivity added to the PTFE dispersion and the powder paste is then mixed together
high thermal expansion coefficient with the filler (wet mix). Which production method is the most appropriate
limited wear resistance is mainly determined by the requirements placed on the compound and the
specific application. Dyneon will be glad to help you find the appropriate
By incorporating selected fillers into the fine powder, these properties can compound for your needs.
be offset. It is therefore possible to create property profiles that are tai-
lored to specific applications.

Property Increased* Reduced* 9.3 Typical Applications

Deformation under load of PTFE Fine Powder Compounds
Wear resistance Bowden pulleys, for example, are applications where low wear and low
Hardness friction are important. Here, it is not only important that the PTFE part has
Thermal expansion coefficient a lower wear but also that the opposing surface is not prematurely worn by
Thermal conductivity the filler. Ideal fillers here would be carbon, graphite or high-performance
polymers, such as PPSO2. Often, increased pressure resistance is required
Electrical conductivity
in addition to chemical and thermal resistance. This is particularly impor-
Tensile strength
tant for seals. Glass would be an ideal filler for such an application. Carbon
Elongation at break black is used for antistatic treatment of liners and tubes. Here you need a
Service temperature range surface resistivity of ≤ 109 Ω.
Chemical resistance
Coefficient of friction
*depending on filler type and quantity

Tab. 9.1: Property changes of fine powders through filler compounds

9.1 Property Modification by Means of Fillers

3M™ Dyneon™ PTFE Compounds are able to broaden the application scope
of PTFE fine powders even further. Fillers make it possible to optimize
properties thus enabling use of PTFE in applications where pressure- and
wear resistance are of utmost importance. The addition of fillers changes
the properties of fine powders, as shown in Table 9.1. The following fillers
are generally used to reduce abrasion and deformation under load or to
increase thermal or electrical conductivity:
Glass Bronze
Carbon High-performance polymers,
Graphite such as PEEK, PPSO2 or PI.
Carbon black

24
10
Special Applications
3M™ Dyneon™ PTFE Fine Powders are also used as anti-drip agents for thermoplastic plastics. In this
special field of use, the fibrillation properties of the PTFE powder paste are used, in order to prevent
melting of the thermoplastics in the case of fire.

11
Trouble Shooting Guide
Production processes do not always run trouble-free. The reasons for this are manifold. This chapter
therefore provides a number of suggestions on how to find possible causes and solutions for such
problems. As causes can be very complex the following table 11.1 does not claim to be exhaustive.

Problem Possible cause Suggested remedy

Contamination of the semi-finished Contaminated lubricant has been added F ilter lubricant
product Change the lubricant batch

During opening of the powder drum B efore opening, remove dirt particles from the outside
of the drum to avoid contamination
Earth the drum to avoid electrostatic charges
Clean the preparation room

Prior extrusion contained fillers Clean extruder

Brown coloration of the semi-finished Lubricant has not been fully removed Increase drying period
product Increase drying temperature
Use lubricant with lower boiling point
Improve suction in the oven
Repeat sintering, brown colour will disappear
in most cases

Extrudate is brittle E xtrusion pressure is too low, green strength is too low Increase reduction ratio
Reduce lubricant quantity
Use material with higher extrusion pressure
Increase extrusion speed

Semi-finished product is torn in extrusion Mechanical damage in green state T reat extrudate more carefully
direction Use lubricant with higher boiling point
Check die for mechanical damage

Sintered semi-finished product has low Sintering of semi-finished product too long or too hot  heck temperature profile of the sintering oven
C
tear resistance but high density and Choose lower sintering temperature (360 to 380 °C)
elongation at break Check for oven malfunctions

Liner is torn lengthwise and crosswise to Inner supporting pipe was too big Use smaller inner supporting pipe
extrusion direction
Irregular cooling after sintering E nsure uniform cold air distribution
Check for malfunctions of oven or cooling unit

Inner tensions or irregular shrinkage because cooling S low down cooling process
was too fast Check for malfunctions of oven or cooling unit

S emi-finished product stuck to contact surface during Check contact surface for roughness or flaws
sintering

Table 11.1: Problems occurring during paste extrusion, their possible causes and remedy suggestions.

25
Table 11.1: Problems occurring during paste extrusion, their possible causes and remedy suggestions (continued).

Problem Possible causes Suggested remedy

Semi-finished product burst open Drying temperature is too high R educe drying temperature to the range between boiling
point of the lubricant and sintering temperature
Check for oven malfunctions

Moisture  ry lubricant
D
Water condensation when opening the powder drum,
bring drum to room temperature

Trapped air during preform fabrication  heck machine parameters (pressure, time, closing
C
speed, etc.)
Drill ventilation bores

Partial tapering of the tube diameter or Too much lubricant Reduce lubricant content
wavy extrudate, “snake-effect”

White dots in the semi-finished product Contamination or PTFE residues from prior extrusions Clean extruder

Squeezed powder paste T reat powder more carefully

Check lubricant level
Screen agglomerates

Partial occurrence of streaks E xcess lubricant Reduce lubricant level

Squeezed powder paste T reat powder more carefully

Screen agglomerates

Irregular lubricant distribution E xtend mixing time

Let lubricant-powder mix rest overnight at 30 °C

Scaly surface of the semi-finished pro- Shearing in extrusion die too low Increase reduction ratio
duct (orange peel) Increase extrusion speed

Rough tool finish P olish

If lateral polish is applied, polish longitudinal

L ack of lubricant Increase lubricant level

Irregular surface L ack of lubricant Increase lubricant level

Irregular lubricant distribution Let lubricant/powder mix rest overnight at 30 °C

Inconsistent drying and sintering conditions Check for oven malfunctions

Filler agglomerates in dry-mixed fine powder compound R educe filler-particle size

Increase dimensions of semi-finished product
Grind, crush or screen filler
Filler or filler additives not temperature-resistant enough

Pressed billet does not fit into extruder T rapped air during preform pressing; preform has Increase compression pressure suddenly to let air
expanded escape

26
12
Compliance and Safety
If you have any questions regarding compliance with national and inter-
national regulations of legislators or associations, please contact Dyneon
GmbH (contacts see last page).
Due to lack of experience, we cannot recommend applications in the
medical field (implants). Applications in this field are therefore the sole
responsibility of the manufacturer.
General recommendations on health and safety in processing, on work
hygiene and on measures to be taken in the event of accident are detailed
in our material safety data sheets.
You will find further notes on the safe handling of fluoropolymers in the
brochure “Guide for the safe handling of Fluoropolymers Resins” by
PlasticsEurope, Box 3, 1160 Brussels, Belgium, Tel. +32 (2) 676 17 32.
27
Technical Information and Test Data Important Notice
Technical information and guidance provided by Dyneon personnel is based All information set forth herein is based on our present state of knowledge and
upon data and testing which is believed to be reliable. Such advice is intended is intended to provide general notes regarding products and their uses. It should
for use by persons with appropriate technical understanding, knowledge and not therefore be construed as a guarantee of specific properties of the products
skills relating to PTFE compounds. No licence under any Dyneon or third party described or their suitability for a particular application. Because conditions of
intellectual rights is granted or implied by virtue of this information. product use are outside Dyneon’s control and vary widely, user must evaluate
and determine whether a Dyneon product will be suitable for user’s intended
General recommendations on health and safety in processing, on work hygiene
application before using it. The quality of our products is warranted under our
and on measures to be taken in the event of accident are detailed in our material
General Terms and Conditions of Sale as now are or hereafter may be in force.
safety data sheets.
You will find further notes on the safe handling of fluoropolymers in the brochure
“Guide for the safe handling of Fluoropolymers Resins” by PlasticsEurope, Box 3,
B-1160 Brussels, Tel. +32 (2) 676 17 32.
The present edition replaces all previous versions. Please make sure and inquire
if in doubt whether you have the latest edition.

Where to go for
more information

Dyneon Customer Service Dyneon GmbH Dyneon B.V. 3M Advanced Materials Division
Europe Carl-Schurz-Str. 1 Tunnelweg 95 6744 33rd Street North
Phone: 00 800 396 366 27 41453 Neuss 6468 EJ Kerkrade Oakdale, MN 55128
Fax: 00 800 396 366 39 Germany The Netherlands USA
Italy Phone: +49 (0) 2131 14 2265 Phone: +31 45 567 9600 Phone: +1 800 810 8499
Phone: 800 791 018 Fax : +49 (0) 2131 14 3857 Fax: +31 45 567 9619 Fax: +1 800 635 8061
Fax: 800 781 019

www.dyneon.eu

Dyneon GmbH
3M Advanced Materials Division
Carl-Schurz-Straße 1
41453 Neuss, Germany Dyneon is a 3M company.
Phone +49 (0) 2131 14 2265 Dyneon is a trademark of 3M.
Fax +49 (0) 2131 14 3857 03/2015 All rights reserved.
www.dyneon.eu © Dyneon 2015 | PTFEFP201503EN