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Transcript of 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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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)
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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KYNAR applications in W&C
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
Radiation dose (kGray)
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
Radiation dose (kGray)
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
Radiation dose (kGray)
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
Radiation dose (kGray)
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
Radiation dose (kGray)
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
Radiation dose (kGray)
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