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
Modern Superabsorbents
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 2
Modern Superabsorbents
SAP is a crosslinked and partely neutralized (mostely with Sodium) poly-Acrylic-Acid
forming a 3-dimensional network
Na OOC
HOOC
COO Na
Na OOC
Na OOC
COO Na
COO Na
COO Na
COOH
COOH
COOH
COO Na
COO Na
HOOC
COO Na
COO Na
COOH
COO Na
COO Na
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 3
Polymerisation
Radical Chain Polymerisation
I

+ CH2=CH-COOH

I-CH2-CH-COOH + CH2=CH-COOH
I-CH2-CH-COOH

I-CH2-CH-CH2-CH-COOH
COOH

I-CH2-CH-CH2-CH-COOH + CH2=CH-COOH
COOH

I-CH2-CH-CH2-CH-CH2-CH
COOH COOH COOH
I : Radicalic Starter
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 4
Crosslinking
Temp.
Time
Temp.
Time
Temp.
Time
COOH
COOH
I
I
I-CH2-CH-CH2-CH-CH2-CH- I
I
COOH
Short chains
„Extractables“
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 5
Polymerdesign and Properties
Absorption/Retention: Funktion of cross-linking
High retention capacity
Retention /
Absorption
Degree of crosslinking
(crosslinker/ monomer ratio)
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 6
Polymerdesign and Properties
Elasic Modulus: Funktion of cross-linking
Gel Strength /
Absorption
under load
Soft swollen gel
Easily deformed
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
High gel strength SAP
Not easily deformed
Degree of crosslinking
Seite | 7
Polymerdesign and Properties
Absorption speed: Function of elasticity (cross-linking) and particle size
Small particle large outer surface
Large particle small surface area
Swelling Force
Relaxing force vs swelling force
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Relaxing Force
Seite | 8
Hydrolysis Stability
Turning from a particle of hydrogel into a viscous liquid
Energy/Water
Breaking the x-linking
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Energy/Water
Breaking the chains
Seite | 9
Product Properties
Absorption Speed
Hydrolysis
Stability
Water Conductivity
“Permeability”
Absorption/Retention
“Gelstrength”
Elastic Modulus
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 10
Core Property - Permeability
Permeability means water transport through a mass of swollen SAP
High permeability
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Low Permeability
Seite | 11
Influencing the Permeability
Particle shape
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 12
Influencing the Permeability
Extractables:
Short to mid chain length and not incorporated to the network
and water soluble.
Acting as thickener and increase the viscosity of water.
dv  D  AP
 L
dt
Darcy´s Law:
 = Specific permeability of sample
A = Cross-sectional area of sample
P = Pressure difference driving the permeation
L = Length of sample
 = Viscosity of fluid
D
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 13
Tested SAP Materials
Sample
Code
Morphology
Absorption
in DI Water
[g/g]
Absorption
Speed
[mm after 1
min.]
1
2
3
4
5
6
Bead
Bead
Bead
Crystal
Crystal
Crystal
460
440
380
260
200
210
> 16
> 16
16
12
3
7
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 14
Gel Degradation at 80 °C
Degradation of hydrogel made with DI-water
(x-axis not linear)
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 15
Gel Degradation at 80 °C
Degradation of hydrogel made with Synthetic Sea Water (DIN 50900)
(x-axis not linear)
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 16
Gel Degradation at 80 °C
Degradation of hydrogel made with hard tap-water (Grade4)
(x-axis not linear)
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 17
Gel Degradation
What the numbers mean in reality – A non stable product
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 18
Gel Degradation
What the numbers mean in reality – A non stable product
3 weeks later
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 19
Gel Degradation
What the numbers mean in reality– A non stable product
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 20
Gel Degradation
What the numbers mean in reality – A stable product
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 21
Gel Degradation
What the numbers mean in reality – A stable product
3 weeks later
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 22
Gel Degradation
What the numbers mean in reality– A stable product
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 23
Rheological Properties
Correlation E-modulus and degree of saturation (DI-water)
12
Viscosity/Gelstrength [[logPa]
10
8
Quarter Saturated
6
Half Saturated
Full Saturated
4
2
0
#1
#2
#3
#4
#5
#6
Sample
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 24
Rheological Properties
Gelstrength of 100% saturated (DI-water) SAP
7
6
Gelstrength [Pa]
5
4
3
2
1
0
#1
#2
#3
#4
#5
#6
Sample
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 25
Permeability Determination
Shematic and real set-up of test equipment
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 26
Permeability Determination
Picture of a treated capillary.
The red lines indicates the measured penetration distance.
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 27
Permeability Determination
DI Water at 20 °C
Time
Minutes
5
10
20
60
120
480
Days
1
2
3
4
5
6
7
Density
[g/g]
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Sample 6
1
2
2
2
2
3
1
2
2
2
3
3
4
4
4
4
4
4
1
1
1
2
2
3
1
1
1
2
2
3
2
2
2
2
2
2
6
8
10
12
15
18
30
365
9
14
18
20
23
24
36
375
6
8
11
12
13
14
16
385
4
6
8
9
10
12
13
380
5
8
10
11
12
14
15
360
5
7
8
8
10
11
11
385
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 28
Permeability Determination
DI-Water at 60 °C
Time
Minutes
5
10
20
60
120
480
Days
1
2
3
4
5
6
7
Density
[g/g]
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Sample 6
0
0
0
1
1
2
0
0
1
1
1
1
0
1
2
2
4
6
0
1
1
1
2
3
1
1
2
2
2
4
1
2
2
2
3
3
4
18
20
28
34
45
55
375
3
20
26
33
48
54
60
385
8
14
18
21
23
25
26
380
7
9
12
15
17
19
20
390
7
9
12
14
16
18
20
380
5
8
10
12
14
15
15
375
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 29
Permeability Determination
Tap Water (Hardness 4) at 20 °C
Time
Minutes
5
10
20
60
120
480
Days
1
2
3
4
5
6
7
Density
[g/g]
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Sample 6
1
1
1
2
2
2
1
1
2
2
2
3
2
3
4
4
5
5
2
2
3
3
3
5
0
1
1
2
2
4
3
4
4
4
4
4
5
12
15
20
22
24
28
365
7
13
16
23
25
28
31
370
9
10
12
13
15
18
20
385
10
12
15
18
20
22
24
390
8
12
15
17
20
22
24
385
6
7
8
10
13
14
14
375
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 30
Permeability Determination
Tap Water (Hardness 4) at 60 °C
Time
Minutes
5
10
20
60
120
480
Days
1
2
3
4
5
6
7
Density
[g/g]
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Sample 6
0
1
1
1
2
2
0
1
1
1
2
3
1
2
2
3
4
4
1
1
2
2
3
3
1
1
1
1
2
2
2
2
3
3
4
5
7
15
18
25
30
35
40
380
10
18
24
30
37
45
50
395
10
14
16
18
22
27
30
375
12
14
17
21
24
29
32
380
10
13
17
21
23
25
27
390
9
11
13
15
16
17
17
370
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 31
Permeability Determination
Synthetic Seawater (DIN 50900) at 20 °C
Time
Minutes
5
10
20
60
120
480
Days
1
2
3
4
5
6
7
Density
[g/g]
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Sample 6
2
3
3
3
3
3
2
5
5
5
7
7
1
1
1
2
2
2
3
3
3
4
4
4
1
2
2
2
2
3
2
2
2
2
3
3
5
14
16
20
22
24
26
365
10
26
29
34
38
40
44
370
8
12
14
16
17
19
20
395
10
14
16
17
18
18
24
385
5
8
10
12
14
16
18
370
7
9
10
12
14
15
15
375
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 32
Permeability Determination
Synthetic Seawater (DIN 50900) at 60 °C
Time
Minutes
5
10
20
60
120
480
Days
1
2
3
4
5
6
7
Density
[g/g]
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Sample 6
0
1
1
2
2
3
1
1
1
2
2
3
0
0
1
1
2
2
1
1
2
2
2
3
1
1
1
2
3
4
2
2
2
3
3
3
7
16
20
25
27
30
32
395
9
18
25
31
36
42
48
390
6
15
19
22
25
27
29
370
10
16
18
20
23
25
30
375
6
10
12
15
18
19
21
365
8
11
13
14
17
18
18
380
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 33
Discussion and Conclusion
Correlation E-Modulus and Penetrationlength (DI-Water at 20 °C]
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 34
Discussion and Conclusion
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 Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 35
Expression of Thanks
Mr. Alton Deaton
Dr. Jochen Houben
Mr. Bobby Mitra
Dr. Scott Smith
and
all of you for your interest.
Martin Tennie
ICC Meeting Nov.2012, St. Petersburg, Florida
Seite | 36