1. Platzhalter Titelbild Superabsorbent Polymers (SAP) as Water-Blocking Components in Cables Martin Tennie (martin.tennie@evonik.com) ICC Meeting November 2012 St.Petersburg, Florida, USA

2. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Modern Superabsorbents Seite | 2

3. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Modern Superabsorbents Seite | 3 SAP is a crosslinked and partely neutralized (mostely with Sodium) poly-Acrylic-Acid forming a 3-dimensional network COO Na COOH COO Na COOH COO Na COOH COO Na Na OOC HOOC Na OOC HOOC

4. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Polymerisation Seite | 4 Radical Chain Polymerisation I-CH 2 -CH-CH 2 -CH-COOH COOH  I-CH 2 -CH-COOH  I  + CH 2 =CH-COOH I-CH 2 -CH-COOH  + CH 2 =CH-COOH I  : Radicalic Starter I-CH 2 -CH-CH 2 -CH-COOH COOH  + CH 2 =CH-COOH I-CH 2 -CH-CH 2 -CH-CH 2 -CH COOH 

5. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Crosslinking Seite | 5 Time Temp. Time Temp. Time Temp. I-CH 2 -CH-CH 2 -CH-CH 2 -CH COOH -I I I I Short chains „Extractables“

6. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Polymerdesign and Properties Seite | 6 Absorption/Retention: Funktion of cross-linking Retention / Absorption Degree of crosslinking (crosslinker/ monomer ratio) High retention capacity

7. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Polymerdesign and Properties Seite | 7 Elasic Modulus: Funktion of cross-linking Gel Strength / Absorption under load Degree of crosslinking Soft swollen gel Easily deformed High gel strength SAP Not easily deformed

8. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Polymerdesign and Properties Seite | 8 Absorption speed: Function of elasticity (cross-linking) and particle size Small particle large outer surface Large particle small surface area Relaxing force vs swelling force Swelling Force Relaxing Force

9. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Hydrolysis Stability Seite | 9 Turning from a particle of hydrogel into a viscous liquid Energy/Water Breaking the x-linkingBreaking the chains

10. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Product Properties Seite | 10 Absorption Speed Absorption/Retention Hydrolysis Stability “Gelstrength” Elastic Modulus Water Conductivity “Permeability”

11. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Core Property - Permeability Seite | 11 Permeability means water transport through a mass of swollen SAP High permeability Low Permeability

12. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Influencing the Permeability Seite | 12 Particle shape

13. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Influencing the Permeability Seite | 13 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: = Pressure difference driving the permeation = Specific permeability of sample = Cross-sectional area of sample = Length of sample = Viscosity of fluid

14. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Tested SAP Materials Seite | 14 Sample Code 123456 MorphologyBead Crystal Absorption in DI Water [g/g] 460440380260200210 Absorption Speed [mm after 1 min.] > 16 161237

15. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation at 80 °C Seite | 15 Degradation of hydrogel made with DI-water (x-axis not linear)

16. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation at 80 °C Seite | 16 Degradation of hydrogel made with Synthetic Sea Water (DIN 50900) (x-axis not linear)

17. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation at 80 °C Seite | 17 Degradation of hydrogel made with hard tap-water (Grade4) (x-axis not linear)

18. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation Seite | 18 What the numbers mean in reality – A non stable product

19. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation Seite | 19 What the numbers mean in reality – A non stable product 3 weeks later

20. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation Seite | 20 What the numbers mean in reality– A non stable product

21. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation Seite | 21 What the numbers mean in reality – A stable product

22. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation Seite | 22 What the numbers mean in reality – A stable product 3 weeks later

23. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Gel Degradation Seite | 23 What the numbers mean in reality– A stable product

24. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Rheological Properties Seite | 24 Correlation E-modulus and degree of saturation (DI-water)

25. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Rheological Properties Seite | 25 Gelstrength of 100% saturated (DI-water) SAP

26. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 26 Shematic and real set-up of test equipment

27. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 27 Picture of a treated capillary. The red lines indicates the measured penetration distance.

28. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 28 TimeSample 1Sample 2Sample 3Sample 4Sample 5Sample 6 Minutes 5114112 10224112 20224112 60224222 120234222 480334332 Days 1696455 28148687 31018118108 41220129118 5152313101210 6182414121411 7303616131511 Density [g/g] 365375385380360385 DI Water at 20 °C

29. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 29 DI-Water at 60 °C TimeSample 1Sample 2Sample 3Sample 4Sample 5Sample 6 Minutes 5000011 10001112 20012122 60112122 120114223 480216343 Days 1438775 2182014998 320261812 10 4283321151412 5344823171614 6455425191815 755602620 15 Density [g/g] 375385380390380375

30. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 30 Tap Water (Hardness 4) at 20 °C TimeSample 1Sample 2Sample 3Sample 4Sample 5Sample 6 Minutes 5112203 10113214 20124314 60224324 120225324 480235544 Days 15791086 212131012 7 315161215 8 4202313181710 522251520 13 624281822 14 728312024 14 Density [g/g] 365370385390385375

31. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 31 Tap Water (Hardness 4) at 60 °C TimeSample 1Sample 2Sample 3Sample 4Sample 5Sample 6 Minutes 5001112 10112112 20112213 60113213 120224324 480234325 Days 1710 12109 2151814 1311 318241617 13 425301821 15 5303722242316 6354527292517 7405030322717 Density [g/g] 380395375380390370

32. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 32 Synthetic Seawater (DIN 50900) at 20 °C TimeSample 1Sample 2Sample 3Sample 4Sample 5Sample 6 Minutes 5221312 10351322 20351322 60352422 120372423 480372433 Days 15108 57 21426121489 31629141610 42034161712 52238171814 6244019181615 7264420241815 Density [g/g] 365370395385370375

33. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Permeability Determination Seite | 33 Synthetic Seawater (DIN 50900) at 60 °C TimeSample 1Sample 2Sample 3Sample 4Sample 5Sample 6 Minutes 5010112 10110112 20111212 60221223 120222233 480332343 Days 17961068 2161815161011 3202519181213 4253122201514 5273625231817 6304227251918 7324829302118 Density [g/g] 395390370375365380

34. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Discussion and Conclusion Seite | 34 Correlation E-Modulus and Penetrationlength (DI-Water at 20 °C]

35. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Discussion and Conclusion Seite | 35 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.

36. Martin Tennie ICC Meeting Nov.2012, St. Petersburg, Florida Expression of Thanks Seite | 36 Mr. Alton Deaton Dr. Jochen Houben Mr. Bobby Mitra Dr. Scott Smith and all of you for your interest.