for Wire & Cable applications

Kynar & Kynar Flex for wire & cable applications

KYNAR
PVDF homopolymer
[CH2-CF2]n
H H
H H
C
H H
C
C
H H
C
C
H H
F F
C C
F F
C C
F
F
C
F F
F F

Kynar & Kynar Flex for wire & cable applications

Semi-crystalline polymer

CF bond is one of the

strongest

Melting point Tm ~ 170C

Outstanding chemical &

thermal stability

KYNAR processability

melting
decomposition

450
400

Easy processability

Wide processing
window

No need of
Hastelloy tools

Tem p / C

350
300
250
200
150
100

PTFE

PFA

FEP

ETFE

Kynar & Kynar Flex for wire & cable applications

ECTFE

PCTFE

PVDF

KYNAR

General properties of homopolymer :



Flexural modulus = 2000 MPa

LOI = 44

When more flexibility or better LOI is needed,

there is room for KYNAR FLEX !

Kynar & Kynar Flex for wire & cable applications

KYNAR FLEX
PVDF-HFP copolymers
[CH2-CF2]n [CF(CF3)-CF2)]m
H H
H H
C
F F
C C
H H
C
C
H H
F F
C C
F F
C C
F
CF
C
3
F F
F F

Copolymerization with HFP

Amount and distribution

can be tailored :



Decreased crystallinity :



Kynar & Kynar Flex for wire & cable applications

Homogeneous copolymers
Heterogeneous copolymers
Lower flex modulus
Lower melting point

KYNAR FLEX range

Modulus

180

Melting Point

160

1000

140

MPa

800

120
100

600

80

400

60
40

200

20

0
2500-20 2750-01 or 2800-00
2950-05

Kynar & Kynar Flex for wire & cable applications

2850-00

3120-50

(C)

1200

KYNAR range general properties

Physical properties

Method

Units

460

700 series

Flex 2750

Flex 2800

Flex 2850

Flex 2950

Flex 3120

Melting point range

ASTM D3418

159 - 161

165 - 170

130 - 138

140 - 145

155 - 160

132 - 138

165 - 168

Specific gravity

ASTM 792

Refractive Index

ASTM D542

O23D

1.420

1.420

1.410

1.410

1.420

1.407

1.405

Water Absorption

ASTM D570

0.03

0.01 - 0.03

0.03

0.03

0.03

0.03

0.03

Tensile Strength at Yield

ASTM D638

MPa

35 - 46

41 - 55

20

26

35

20

28

Tensile Strength at Break

ASTM D638

MPa

35 - 48

35 - 45

23 - 26

24 - 41

28 - 41

23 - 25

48

Elongation at Yield

ASTM D638

8 - 15

7 - 13

n. a.

12

10

16

12

Elongation at Break

ASTM D638

50 - 250

50 - 250

250 - 500

200 - 450

200 - 300

n. a.

200-300

Tensile Modulus

ASTM D648

MPa

1000 - 1600 1700 - 2400 280 - 400

550 - 900

750 - 1000

n. a.

n. a.

Flexural Modulus

ASTM D790

MPa

1100 - 1800 1400 - 2200

480

650

1000

480

690

Unnotched Impact Strength

ASTM D256

kJ/m

0.8 - 2.1

1 - 4.3

Non break

Non break

Non break

Non break

Non break

Notched Impact Strength

ASTM D256

kJ/m

0.1 - 0.2

0.1 - 0.2

Non break

Non break

0.2 - 0.5

Non break

Non break

Hardness

ASTM D2246

Shore D

76 - 80

76 - 80

n. a.

65 - 70

70

n. a.

68

Limited Oxygen Index

ASTM D2863

43

43

43

43

43

> 80

43

Vertical Burn

UL94

V-0

V-0

n. a.

V-0

V-0

V-0

V-0

Kynar & Kynar Flex for wire & cable applications

1.75 - 1.77 1.77 - 1.79 1.76 - 1.80 1.76 - 1.80 1.76 - 1.80 1.76 - 1.80 1.76 - 1.80

KYNAR FLEX Chemical Resistance

Chemical

Concentration Temperature

Comments

Nitric acid

71% aq

50 C

Sulfiric acid

96% aq

Ambient

A,D

Hydrochloric acid

37% aq

Ambient

A,B

Hydrofluoric acid

49% aq

Ambient

Acetic acid

50% aq

Ambient

Sodium hydroxide

10% aq

90C

Ammonium hydroxide

30% aq

Ambient

Sodium hydrochloride

5% aq

Ambient

Ambient

Liquid bromine
lodine

10% aq

Ambient

Ethylene glycol

100% aq

Ambient

Distilled water

100% aq

Ambient

Toluene

100% aq

29C

Methyl-chloroform

100% aq

50C

Heptane

100% aq

90C

Ethanol

100% aq

21C

Diethylether

100% aq

0C

Acetone

10% aq

13C

Kynar & Kynar Flex for wire & cable applications

A. No changes observed.
B. Some discoloration after 12
weeks at 38C. Little or no
change in physical properties
including elongation, tensiles
strength, and weight gain.
C. Darkened surface at listed
temperature with littles or no
change in physical properties.
D. At 98% concentration and 18C,
some color change after 6 weeks
with littmle or no change in
physical properties.
E. Darkened surfaceafter 12 weeks
with little or no change in
physical properties.

KYNAR Electric Properties

Kynar grade

Dissipation factor
Dielectric constant
Dielectric strength
-4
(ASTM D150)
kV/mm
(x 10 , ASTM D150)
(ASTM D149)
100 Hz 1 kHz 100 kHz 1 MHz 100 Hz 1 kHz 100 kHz 1 MHz

700 series

21

11

260

2310

Flex 2850

21

10.5

6.5

380

2340

Superflex 2500

12

Kynar & Kynar Flex for wire & cable applications

10.1

7.7

533

955

KYNAR Piezo & Pyroelectric Properties



Typical properties of Piezo film: (bi-oriented, poled & non metalized film)

X31 = extrusion direction

X32 = perpendicular to extrusion direction
X33 = thickness

Kynar & Kynar Flex for wire & cable applications

10

KYNAR Piezo: Structure and effects



Crystalline structure influences the properties of PVDF

3 types of crystalline structures:

Alpha Phase:

Most commun phase

Non Polar

Results when polymer is cooled from melt

Beta Phase:

Polar

Results from deformation of alpha or gamma phase crystals (solid or melt state deformation)

Gamma Phase:



Polar
Results from high pressure stress on alpha phase crystals during crystalization.

Beta phase is the only structure which can be used for Piezoelectric.

To obtain long term Piezo & Pyroelectric effects the beta phase must be poled

(durably orientate the dipoles).

The using of the KYNAR Piezo film is limited by the temperature of environment
90C 95C maximum
above start loosing Piezo properties

Kynar & Kynar Flex for wire & cable applications

11

(105C / 1year = lost of half the initial value)

KYNAR Piezo: Cristalline transitions

elt

Drawing at low Temp

ultradrawing at high T (> 130C)
annealing at very high P
(> 5000 bar)
P
poling at very high E
igh
h
ry
ve
t
a
poli
ng a
i ng
l
a
t hig
ne g
hE
an win
dr a

Annealing at high T

Fro
DM m s
F, olut
D M i on
A,
DM
SO

Kynar & Kynar Flex for wire & cable applications

12

solution

From cyclohexanone solution

Annealing
at high T

From solution : cyclohexanone, DMF

om
Fr

melt

Ep
hig itax
h P ial
- q crys
ue tal
nc
h t grow
o 6 th
00
0b
ar

poling at
very high E

High T (> 150C)

High P

KYNAR Piezo: Processing

Step 1

Poled

Typical process is:

1.

Extrude PVDF resin and get a film (this provide Alpha crystalline form).

2.

Stretch the polymer or the film (in order to orientate the polymer chain into Beta crystalline form).

3.

Pole the polymer or the film.

Stretching conditions:

Solid state: (stretch a film)

- Highest content of well oriented Beta crystallite was achieved during drawing
at 87C with a deformation from 300 to 400%. Below70C orientation is too low.
Orientation is driven by T, time and drawing rate. Cool slowly at room temperature.

Liquid state: (stretch a melt)

- The most tricky way to orientate. Critical temperature for transformation is in

the range of 130 140C but depending of DDR (DDR mini is 3).
- We generally recommend to stretch the melt to 1/5 original thickness. Above
140C orientation doesnt occur. Cool fast at room temperature.

Poling conditions:


Static:

- High electrical field

- Electrical polarization by Corona or Plasma poling

Dynamic:

Kynar & Kynar Flex for wire & cable applications

- It is a continuous process. High field corona poling in the region of Alpha Beta
transformation during the mechanical drawing.

13

KYNAR Piezo: Poling



Poling parameters: (for film at solid state).



Easily pole 30m. 50 m is the maximum thickness.

Usual conditions to pole:



80MV/m at 80C during 1h

60MV/m at 100C during 30minutes

30MV/cm at 130C pendant 3-5minutes + cool at 50C.

Remark: When we pole at high temperature the polarization must be made by impulsion (ms) and not continuously. Time of
orientation must be shorter than the relaxation time.

Curves of pyroelectric activity are existing:

Kynar & Kynar Flex for wire & cable applications

14

KYNAR PVDF: Piezo Cable



Possible structure:

PVDF Jacketing: 2 options

Wrap a metallic and poled film around a copper core.



Influence of overlap? Overlap possible but should disturb the electrical response.

Metallization is absolutely necessary because of cavity due to the stretching at solid state.

Make a stretched jacketing by crosshead extrusion around a copper core.



Main difficulty is to stretch the jacket without stretching the cable.

Metallization is not needed because following construction is possible core/jacket/braid (electrical signal can be

transmitted).


No cavity effects (stretch the polymer at melt state)

Can be poled a step after extrusion or during melt stretching.

Kynar & Kynar Flex for wire & cable applications

15

KYNAR PVDF: Piezo Cable



Alternative to bi-orientation: (in order to create Beta phase)



Introduce in PVDF:

 Nucleating agent

Nano Strenght for example.

 Other polymer

PMMA can favorise Beta phase

(60/40% is the optimal ratio. d33 decreases above this ratio).

Use a copolymer:
 VF2 + VF3

- The most explored way. Beta phase by default. d33 = 30pC/N before poling.
- Safety issue.
- Production is strictly confidential (army applications).

 VF2 + HFP

- Is working under specific conditions by Solvant way.

- Has to be explored.

Kynar & Kynar Flex for wire & cable applications

16

KYNAR applications in W&C

Outer sheathing for plenum cables (US market) :



Kynar 2950-05 used for copper & optical fiber,

communication cable jacketing and buffer tubes

Kynar 2850-04 for fire alarm cables insulation & jacketing

Kynar 2900-04 for race ways

Key properties :

Flexibility, abrasion & chemical resistance

UL910 approved (low smoke & flame spread)
LOI > 95

Kynar & Kynar Flex for wire & cable applications

17

KYNAR main applications / properties

Limiting
Melting
Tensile
Flexural Melt viscosity
Elongation
-1
Oxygen Index
point
strength at
modulus
@ 100 s
at break (%)
(LOI)
(C)
yield (MPa)
(MPa)
(Pa.s)

Kynar grade

Application

Flex 2850-04

150C UL rating
low viscosity cable jackets

158

35

200-300

1000

800

> 42

Flex 2800-00

125C non-FR cable jackets

Tubing for harsh chemical environments

142

26

200-300

650

2500

> 42

Flex 2950-05

125C copper and optical fiber

plenum cable jackets

134

20

300-400

480

900

> 95

Superflex 2500-20

90-105C high-flex copper and

optical fiber cable jacket

117

12

> 400

220

1050

> 42

Flex 3120-50

150C UL rating automotive cable

166

28

200-300

690

2350

> 42

Kynar & Kynar Flex for wire & cable applications

18

KYNAR applications in W&C

Cladding of Plastic Optical Fibers (POF) :



Key properties :

Lower refraction index than PMMA

Very pure thermoplastic
(residuals lower than 200 ppm)

Incident
light
beams
X m
X + 20 m

PMMA Fluorinated polymer cladding

nR = 1.492
nR ~ 1.40

Kynar & Kynar Flex for wire & cable applications

19

Kynar grade

Refractive Index
(ASTM D542)

Flex 2850

1.420

Flex 2800

1.410

Flex 2950

1.407

Superflex 2500

1.410

Flex 3120

1.405

KYNAR applications in W&C

Outer sheathing for automotive cables :



Kynar 3120-50, often crosslinked, recommended for T4-type

cable sheathing
Key properties :

Crosslinkable under light e-beam radiation

Good compromise between flexibility and thermal
resistance
Excellent extrudability (> 1000 m/min) for thin walls
UL temperature rating : 150C

Kynar & Kynar Flex for wire & cable applications

20

Crosslinking KYNAR

By e-beam radiation, PVDF crosslinks rather before the

occurrence of strong degradation


Typical dose : 20 to 50 kGrey = 2 to 5 Mrad

Crosslink promoter TAIC or TAC

Antioxidant for stabilizing crosslink promoter - Irganox 1010 2% in

TAIC Triallyl isocyanate.mht

(generally a liquid)

2-6%

crosslink liquid.


Thermal Stability Antimony Oxide or Zinc Oxide

Improved physical properties :



Better resistance to stress-cracking

Better resistance to abrasion

Better service temperature and chemical resistance

Imparts shrink memory property to heat shrinkable tubing

Kynar & Kynar Flex for wire & cable applications

21

Crosslinking efficiency vs. Radiation dose

100
90
80
70

% gel

60
50
40

Kynar 720
Kynar 740
Kynar 460
Kynar Flex 2850
Kynar Flex 2800
Kynar Flex 3120

30
20
10

After dissolution in TEP

0
0

25

50

75

100

Radiation dose (kGray)

Kynar & Kynar Flex for wire & cable applications

22

125

150

Color vs. Radiation dose

5
Black

4
Dark Brown

Color

3
Brown

Kynar 720
Kynar 740
Kynar 460
Kynar Flex 2850
Kynar Flex 2800
Kynar Flex 3120

Tan

Pale Tan

0
0

25

50

75

100

Radiation dose (kGray)

Kynar & Kynar Flex for wire & cable applications

23

125

150

Tensile stress at yield vs. Radiation dose

100

Kynar 720
Kynar 740
Kynar 460
Kynar Flex 2850
Kynar Flex 2800
Kynar Flex 3120

Tensile stress at yield (MPa)

80

60

40

20

ASTM D638

No yield at 100 Mrad

0
0

10

20

30

Radiation dose (kGray)

Kynar & Kynar Flex for wire & cable applications

24

40

50

Tensile strain at break vs. Radiation dose

400

ASTM D638

Kynar 720
Kynar 740
Kynar 460
Kynar Flex 2850
Kynar Flex 2800
Kynar Flex 3120

Tensile strain at break (%)

350
300
250
200
150
100
50
0
0

25

50

75
Radiation dose (kGray)

Kynar & Kynar Flex for wire & cable applications

25

100

125

150

Tensile Modulus vs. Radiation dose

5000

ASTM D638

Kynar 740

4500

Kynar 460

4000
Tensile Modulus (MPa)

Kynar Flex 2850

3500

Kynar Flex 3120

3000
2500
2000
1500
1000
500
0
0

25

50

75

100

Radiation dose (kGray)

Kynar & Kynar Flex for wire & cable applications

26

125

150

Thermal Stability vs. Radiation dose

Temperature of 5% weight loss (under air)

500

Kynar 720
Kynar 740
Kynar 460
Kynar Flex 2850
Kynar Flex 2800

450

Kynar Flex 3120

400

350

300
0

25

50

75
Radiation dose (kGray)

Kynar & Kynar Flex for wire & cable applications

27

100

125

150

HDT vs. Radiation dose

Heat Deflection Temperature (under 1,8 MPa)

100

80

60

40

Kynar 720
Kynar 740
Kynar 460
Kynar Flex 2850
Kynar Flex 2800

20

ASTM D648

Kynar Flex 3120

0
0

25

50

75
Radiation dose (kGray)

Kynar & Kynar Flex for wire & cable applications

28

100

125

150

DMA on crosslinked Vs. uncrosslinked

Storage modulus
1E+10
3120-50 uncrosslinked
1E+09

3120-50 (10 Mrad)

1E+08
1E+07
Pa

break

1E+06
1E+05

break
= +30C

1E+04
1E+03
-60

60

120
T (C)

Kynar & Kynar Flex for wire & cable applications

29

180

240

Conclusion

KYNAR and KYNAR FLEX resins are among the cheapest

fluorinated polymers and offer :

A wide range of melting point and flexural modulus

The possibility to crosslink by e-beam

An excellent chemical resistance

An excellent flame resistance

A very good extrudability

A very pure material

An excellent Weatherability

Agency Listings in place

Slippery and Bendable

A good abrasion resistance

www.kynar.com
Kynar & Kynar Flex for wire & cable applications

30