Kynar Kynarflex for Cables IIT

7/25/2019 Kynar Kynarflex for Cables IIT

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Kynar & Kynar Flex for wire & cable applications 1

forfor Wire & Cable applicationsWire & Cable applications


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KYNAR

Semi-crystalline polymer

CF bond is one of thestrongest

Melting point Tm ~ 170C

Outstanding chemical &thermal stability

PVDF homopolymer

[CH2-CF2]n

CC

H H

F F

CC

H H

F F

CC

H H

F F

C C

H H

F F

C

C

H H

F F


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KYNAR processability

Easy processability

Wide processing

window

No need ofHastelloy tools

100

150

200

250

300

350

400

450

PT FE PFA FEP ETFE ECTFE PCTFE PVDF

Temp

/C

melting

decomposition


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KYNAR

General properties of homopolymer :

Flexural modulus = 2000 MPa LOI = 44

When more flexibilityor better LOIis needed,

there is room for KYNAR FLEX !


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KYNAR FLEX

Copolymerization with HFP

Amount and distribution

can be tailored : Homogeneous copolymers Heterogeneous copolymers

Decreased crystallinity : Lower flex modulus Lower melting point

CC

H H

F F

CC

H H

F F

CC

F F

F CF3

C C

H H

F F

C

C

H H

F F

PVDF-HFP copolymers

[CH2-CF2]n [CF(CF3)-CF2)]m


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KYNAR FLEX range

0

200

400

600

800

1000

1200

2500-20 2750-01 or

2950-05

2800-00 2850-00 3120-50

MP

a

020

40

60

80

100

120

140

160

180

(C

)

Modulus

Melting Point


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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 C 159 - 161 165 - 170 130 - 138 140 - 145 155 - 160 132 - 138 165 - 168

Specific gravity ASTM 792 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

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


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KYNAR FLEX Chemical Resistance

A. No changes observed.

B. Some discoloration after 12

weeks at 38C. Little or nochange 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.

Chemical Concentration Temperature Comments

Nitric acid 71% aq 50 C A

Sulfiric acid 96% aq Ambient A,D

Hydrochloric acid 37% aq Ambient A,B

Hydrofluoric acid 49% aq Ambient A

Acetic acid 50% aq Ambient A

Sodium hydroxide 10% aq 90C C

Ammonium hydroxide 30% aq Ambient C

Sodium hydrochloride 5% aq Ambient A

Liquid bromine Ambient A

lodine 10% aq Ambient A

Ethylene glycol 100% aq Ambient A

Distilled water 100% aq Ambient A

Toluene 100% aq 29C C

Methyl-chloroform 100% aq 50C AHeptane 100% aq 90C A

Ethanol 100% aq 21C E

Diethylether 100% aq 0C A

Acetone 10% aq 13C C


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KYNAR Electric Properties

100 Hz 1 kHz 100 kHz 1 MHz 100 Hz 1 kHz 100 kHz 1 MHz700 series 21 11 8 260 2310

Flex 2850 21 10.5 6.5 380 2340

Superflex 2500 12 10.1 7.7 533 955

Kynargrade

Dielectric strength

kV/mm

(ASTM D149)

Dielectric constant

(ASTM D150)

Dissipation factor

(x 10-4

, ASTM D150)


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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


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


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KYNAR Piezo: Cristalline transitions

melt

solution

From

melt

Epitaxialcrystalgrow

th

highP-quenchto6000bar

Fromc

yclohe

xanonesolution

Drawing at low Temp

ultradrawing at high T (> 130C)

annealing at very high P

(> 5000 bar)

poling at very high E

polingathighEAnn

ealin

g

ath

ighT

Fromsolution

DMF,DMA,DMSO

Fromsolution:cyclohexanone,

DMF

poli

ngat

very

highE

anne

alingatv

eryhigh

P

drawi

ng

High T (> 150C)

High P

Annealing at high T


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KYNAR Piezo: Processing

Poled

Step 1 2 3

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 drawingat 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 inthe 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: - It is a continuous process. High field corona poling in the region of Alpha Betatransformation during the mechanical drawing.


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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:


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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 betransmitted).

No cavity effects (stretch the polymer at melt state)

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


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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 PVDF: Piezo Cable


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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


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KYNAR main applications / properties

Kynargrade Application

Melting

point

(C)

Tensile

strength at

yield (MPa)

Elongation

at break (%)

Flexural

modulus

(MPa)

Melt viscosity

@ 100 s-1

(Pa.s)

Limiting

Oxygen Index

(LOI)

Flex 2850-04150C UL rating

low viscosity cable jackets158 35 200-300 1000 800 > 42

Flex 2800-00125C non-FR cable jackets

Tubing for harsh chemical environments142 26 200-300 650 2500 > 42

Flex 2950-05125C copper and optical fiber

plenum cable jackets134 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


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Cladding of Plastic Optical Fibers (POF) :

Key properties :

Lower refraction index than PMMA Very pure thermoplastic

(residuals lower than 200 ppm)

X m

X + 20 m

PMMA

nR = 1.492

Fluorinated polymer cladding

nR ~ 1.40

Incident

light

beams

Kynargrade

Refractive Index

(ASTM D542)

Flex 2850 1.420

Flex 2800 1.410

Flex 2950 1.407

Superflex 2500 1.410

Flex 3120 1.405


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Outer sheathing for automotive cables :

Kynar 3120-50, often crosslinked, recommended for T4-typecable sheathing

Key properties :

Crosslinkable under light e-beam radiation

Good compromise between flexibility and thermalresistance

Excellent extrudability (> 1000 m/min) for thin walls

UL temperature rating : 150C


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Crosslinking KYNAR

By e-beam radiation, PVDF crosslinks rather before theoccurrence of strong degradation

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

Crosslink promoter TAIC or TAC (generally a liquid) 2-6%

Antioxidant for stabilizing crosslink promoter - Irganox 1010 2% incrosslink 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

TAIC Triallyl isocyanate.mht


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Crosslinking efficiency vs. Radiation dose

0

10

20

30

40

50

60

70

80

90

100

0 25 50 75 100 125 150

Radiation dose (kGray)

%gel

Kynar 720

Kynar 740

Kynar 460

Kynar Flex 2850

Kynar Flex 2800

Kynar Flex 3120After dissolution in TEP


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Color vs. Radiation dose

0

1

2

3

4

5

0 25 50 75 100 125 150


Color

Kynar 720

Kynar 740

Kynar 460

Kynar Flex 2850

Kynar Flex 2800

Kynar Flex 3120

Black

Dark Brown

Brown

Tan

Pale Tan


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Tensile stress at yield vs. Radiation dose

0

20

40

60

80

100

0 10 20 30 40 50


Tensilestr

essatyield(MPa)

Kynar 720

Kynar 740

Kynar 460

Kynar Flex 2850Kynar Flex 2800

Kynar Flex 3120

ASTM D638 No yield at 100 Mrad


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Tensile strain at break vs. Radiation dose

0

50

100

150

200

250

300

350

400

0 25 50 75 100 125 150


Tensilestrainatbreak(%)

Kynar 720

Kynar 740

Kynar 460

Kynar Flex 2850Kynar Flex 2800

Kynar Flex 3120

ASTM D638


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Tensile Modulus vs. Radiation dose

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

0 25 50 75 100 125 150


TensileModulus(MPa)

Kynar 740

Kynar 460

Kynar Flex 2850

Kynar Flex 3120

ASTM D638


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300

350

400

450

500

0 25 50 75 100 125 150


Temperatureo

f5%weightloss(underair)

Kynar 720

Kynar 740

Kynar 460

Kynar Flex 2850

Kynar Flex 2800

Kynar Flex 3120

Thermal Stability vs. Radiation dose


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0

20

40

60

80

100

0 25 50 75 100 125 150


HeatDeflectionT

emperature(unde

r1,8MPa)

Kynar 720

Kynar 740

Kynar 460

Kynar Flex 2850

Kynar Flex 2800Kynar Flex 3120ASTM D648

HDT vs. Radiation dose


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DMA on crosslinked Vs. uncrosslinked

Storage modulus

1E+03

1E+04

1E+05

1E+06

1E+07

1E+08

1E+09

1E+10

-60 0 60 120 180 240T (C)

Pa

3120-50 uncrosslinked

3120-50 (10 Mrad)

= +30C

break

break


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KYNAR and KYNAR FLEX resins are among the cheapestfluorinated polymersand 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

Conclusion

www.kynar.com

Kynar Kynarflex for Cables IIT

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