platzhalter titelbild superabsorbent polymers (sap) as water-blocking components in cables martin...
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Platzhalter Titelbild
Superabsorbent Polymers (SAP) as Water-Blocking Components in Cables
Martin Tennie ([email protected])ICC Meeting November 2012St.Petersburg, Florida, USA
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Modern Superabsorbents
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Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Modern Superabsorbents
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SAP is a crosslinked and partely neutralized (mostely with Sodium) poly-Acrylic-Acid forming a 3-dimensional network
COO Na
COO Na
COOH
COOH
COO Na
COO Na
COOH
COO Na
COO Na
COOH COO Na
COO NaCOO Na
COO Na
Na OOCHOOC
Na OOC
Na OOC
HOOC
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Polymerisation
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Radical Chain Polymerisation
I-CH2-CH-CH2-CH-COOH
COOH
I-CH2-CH-COOH
I + CH2=CH-COOH
I-CH2-CH-COOH + CH2=CH-COOH
I : Radicalic Starter
I-CH2-CH-CH2-CH-COOH
COOH
+ CH2=CH-COOH I-CH2-CH-CH2-CH-CH2-CH
COOH COOH COOH
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Crosslinking
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Time
Temp.
Time
Temp.
Time
Temp.
I-CH2-CH-CH2-CH-CH2-CH
COOH
COOH
COOH
- II
I
I
Short chains„Extractables“
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Polymerdesign and Properties
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Absorption/Retention: Funktion of cross-linking
Retention /Absorption
Degree of crosslinking(crosslinker/ monomer ratio)
High retention capacity
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Polymerdesign and Properties
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Elasic Modulus: Funktion of cross-linking
Gel Strength /Absorptionunder load
Degree of crosslinkingSoft swollen gelEasily deformed
High gel strength SAPNot easily deformed
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Polymerdesign and Properties
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Absorption speed: Function of elasticity (cross-linking) and particle size
Small particle large outer surface
Large particle small surface area
Relaxing force vs swelling forceSwelling Force
Relaxing Force
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Hydrolysis Stability
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Turning from a particle of hydrogel into a viscous liquid
Energy/Water Energy/Water
Breaking the x-linking Breaking the chains
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Product Properties
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Absorption Speed
Absorption/RetentionHydrolysis Stability
“Gelstrength”Elastic Modulus
Water Conductivity “Permeability”
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Core Property - Permeability
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Permeability means water transport through a mass of swollen SAP
High permeability Low Permeability
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Influencing the Permeability
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Particle shape
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Influencing the Permeability
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Extractables:
Short to mid chain length and not incorporated to the network and water soluble.
Acting as thickener and increase the viscosity of water.
Darcy´s Law:
LP
dtdv AD
= Pressure difference driving the permeation
D = Specific permeability of sample
APL
= Cross-sectional area of sample
= Length of sample
= Viscosity of fluid
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Tested SAP Materials
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Sample Code
1 2 3 4 5 6
Morphology Bead Bead Bead Crystal Crystal Crystal
Absorption in DI Water [g/g]
460 440 380 260 200 210
Absorption Speed [mm after 1 min.]
> 16 > 16 16 12 3 7
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation at 80 °C
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Degradation of hydrogel made with DI-water(x-axis not linear)
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation at 80 °C
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Degradation of hydrogel made with Synthetic Sea Water (DIN 50900)(x-axis not linear)
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation at 80 °C
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Degradation of hydrogel made with hard tap-water (Grade4) (x-axis not linear)
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation
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What the numbers mean in reality – A non stable product
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation
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What the numbers mean in reality – A non stable product
3 weeks later
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation
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What the numbers mean in reality– A non stable product
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation
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What the numbers mean in reality – A stable product
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation
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What the numbers mean in reality – A stable product
3 weeks later
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Gel Degradation
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What the numbers mean in reality– A stable product
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Rheological Properties
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0
2
4
6
8
10
12
#1 #2 #3 #4 #5 #6
Sample
Vis
cosi
ty/G
elst
ren
gth
[[l
og
Pa]
Quarter Saturated
Half Saturated
Full Saturated
Correlation E-modulus and degree of saturation (DI-water)
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Rheological Properties
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0
1
2
3
4
5
6
7
#1 #2 #3 #4 #5 #6
Sample
Gel
stre
ng
th [
Pa]
Gelstrength of 100% saturated (DI-water) SAP
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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Shematic and real set-up of test equipment
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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Picture of a treated capillary.
The red lines indicates the measured penetration distance.
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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Time Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6Minutes
5 1 1 4 1 1 210 2 2 4 1 1 220 2 2 4 1 1 260 2 2 4 2 2 2
120 2 3 4 2 2 2480 3 3 4 3 3 2
Days 1 6 9 6 4 5 52 8 14 8 6 8 73 10 18 11 8 10 84 12 20 12 9 11 85 15 23 13 10 12 106 18 24 14 12 14 117 30 36 16 13 15 11
Density [g/g]
365 375 385 380 360 385
DI Water at 20 °C
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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DI-Water at 60 °C
Time Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6Minutes
5 0 0 0 0 1 110 0 0 1 1 1 220 0 1 2 1 2 260 1 1 2 1 2 2
120 1 1 4 2 2 3480 2 1 6 3 4 3
Days 1 4 3 8 7 7 52 18 20 14 9 9 83 20 26 18 12 12 104 28 33 21 15 14 125 34 48 23 17 16 146 45 54 25 19 18 157 55 60 26 20 20 15
Density [g/g]
375 385 380 390 380 375
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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Tap Water (Hardness 4) at 20 °C
Time Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6Minutes
5 1 1 2 2 0 310 1 1 3 2 1 420 1 2 4 3 1 460 2 2 4 3 2 4
120 2 2 5 3 2 4480 2 3 5 5 4 4
Days 1 5 7 9 10 8 62 12 13 10 12 12 73 15 16 12 15 15 84 20 23 13 18 17 105 22 25 15 20 20 136 24 28 18 22 22 147 28 31 20 24 24 14
Density [g/g]
365 370 385 390 385 375
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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Tap Water (Hardness 4) at 60 °C
Time Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6Minutes
5 0 0 1 1 1 210 1 1 2 1 1 220 1 1 2 2 1 360 1 1 3 2 1 3
120 2 2 4 3 2 4480 2 3 4 3 2 5
Days 1 7 10 10 12 10 92 15 18 14 14 13 113 18 24 16 17 17 134 25 30 18 21 21 155 30 37 22 24 23 166 35 45 27 29 25 177 40 50 30 32 27 17
Density [g/g]
380 395 375 380 390 370
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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Synthetic Seawater (DIN 50900) at 20 °C
Time Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6Minutes
5 2 2 1 3 1 210 3 5 1 3 2 220 3 5 1 3 2 260 3 5 2 4 2 2
120 3 7 2 4 2 3480 3 7 2 4 3 3
Days 1 5 10 8 10 5 72 14 26 12 14 8 93 16 29 14 16 10 104 20 34 16 17 12 125 22 38 17 18 14 146 24 40 19 18 16 157 26 44 20 24 18 15
Density [g/g]
365 370 395 385 370 375
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Permeability Determination
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Synthetic Seawater (DIN 50900) at 60 °C
Time Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6Minutes
5 0 1 0 1 1 210 1 1 0 1 1 220 1 1 1 2 1 260 2 2 1 2 2 3
120 2 2 2 2 3 3480 3 3 2 3 4 3
Days 1 7 9 6 10 6 82 16 18 15 16 10 113 20 25 19 18 12 134 25 31 22 20 15 145 27 36 25 23 18 176 30 42 27 25 19 187 32 48 29 30 21 18
Density [g/g]
395 390 370 375 365 380
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Discussion and Conclusion
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Correlation E-Modulus and Penetrationlength (DI-Water at 20 °C]
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Discussion and Conclusion
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Not the initial swell speed and high absorption capacity guaranted long term sealing.
Important is rheological structure and hydrolysis stability of swollen SAP is key factor.
Testing the parameters hydrolysis-stability and permeability of swollen SAP at higher temperatures show performance differences in short time.
Martin TennieICC Meeting Nov.2012, St. Petersburg, Florida
Expression of Thanks
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Mr. Alton DeatonDr. Jochen Houben
Mr. Bobby MitraDr. Scott Smith
and
all of you for your interest.