SILANES

John Halsall
Regional Business Segment
Manager
Repair & Grouts

Sydney Opera House

09/03/2011 protected with MASTERSEAL 360 TE 1
 What are Silanes?

• Chemical Compound of Silicone and Hydrogen

• Used as an Adhesion Promoter in
Silane RSi(OR´)3
- Adhesives and sealants
- Coatings
- Fillers and Pigments
• Hydrophobic Treatment for Building / Structure
Protection

09/03/2011 2
 What are Silanes?

• Small Reactive Molecules

• Penetrate Deep Into The Substrate
• Chemically Bond With The Concrete
• Form A Water Vapour Permeable Protective Barrier
Against Harmful Waterborne Substances
Rf
Rf

O O
Si Si Si Silane Molecule
O X
H O
O
O
Si
Si O
Si O
O
Substrate e.g. concrete
09/03/2011 3
 What are Silanes?

• Consider Silanes As Umbrella Protecting The

Substrate

Si

09/03/2011 4
 How Do Silanes Work?

Silanes Make The Surface Of the Substrate Hydrophobic.

They Penetrate Deeply Into Substrate And React With The Surface
Of The Pore System.

Dissolved Chlorides
dissolved
chlorides

capillary pore

silanized
OH-function
capillary pore
alkylsiloxane

water vapor

09/03/2011 5
How Do Silanes Work?

Due To The Protective Function (Umbrella) Silanes Change The

Surface From Hydrophilic To Hydrophobic.

Non Modified Hydrophilic Silane Treated Hydrophobic

Mineral Substrate Causes Porous Mineral Substrate.
Capillary Suction No Ingress Of Water

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 Water Absorption On Structural Concrete

4
Water Absorption [%]

3
Masterseal 360/
Protectosil CIT
2 untreated

0
0 1 2 3 4 5 6 7
Immersion [days]

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Masterseal 360 TE (Protectosil BHN)

• Field Study – Zeebrugge Harbour Wall 1993 -

2005

09/03/2011 8
 Silanes Vs Siloxanes

Silanes are small molecules and Penetrate Deeply into the Substrate and
chemically react with the pore surface (3-10mm deep). This chemical
reaction and deep penetration give a life > 10 years
Silane RSi(OR´)3

Siloxanes are big molecules which form a film within the outer pores
system that creates a water barrier on any mineral building material with
pores (Bricks, roof tiles, concrete). This material is eventually washed out
of the pores and thus has a life of around 5 years..

Siloxane
RO Si O Si O Si O Si OR
OR OR OR OR

09/03/2011 9
 Silanes Vs Siloxanes

Silane Treated Siloxane Treated

Surface modification
can cause less adhesion
of a succeeding coating
No change in surface appearance
No significant penetration
Penetration of the silane
of a siloxane resin based
into dense concrete
water repellent

HIGH PENETRATION DEPTH = LONG SERVICE LIFE

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Silane Protection of Buildings / Structures

• Clear Liquids (Cream)

• Low Viscosity (10 times less than water)
• Simply Applied
• Highly Water Vapour Permeable
• No Change Of Surface Appearance

‘MASTERSEAL 360TE’
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 Advantages of Silanes

They can avoid damage caused by

- Chloride induced corrosion of reinforcement
- Carbonation induced corrosion
- Freezing / thawing
- Acid Rain
- Alkali silica reaction
(Na,K)-Si-OH gel reacts with Ca → solidification → water absorbtion and
swelling

- Sulfate Attack
- Reduce Efforvescence
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 References

• Storebaelt Bridge
• Sydney Opera House
• Zeebrugge Harbour

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 Summary - Silanes

• Very effective for reduction of water absorption

• Excellent penetration depth
• Completely water vapour permeable
• Long-term stability over decades, proved in various field
studies
• Does not change surface and thus will accept
subsequent coatings
• Coated surfaces have a longer service life
• Repels various dissolved pollutants
• Easy spray application
• Available in various forms (is available in liquid, gel and
water dispersed forms
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 Silane Based Corrosion Protection

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 TYPES OF CORROSION PROTECTION

• Mechanical Methods
– Coating Of The Steel Reinforcement (Emaco Nanocrete AP)
– Coating Of Concrete Surface (Masterseal Acylics)
– Non Corrodeable Reinforcement (SS, Carbon , Fibreglass)
• Electrochemical Methods
– Chloride Ion Extraction
– Galvanic Cathodic Protection (
– Impressed Current Cathodic Protection
• Chemical Methods
– CORROSION INHIBITORS (PROTECTOSIL CIT)

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 What Is Protectosil® Cit ?

Silane Based Corrosion Inhibitor To Reduce Active But Not Yet Visible
Corrosion (Ie Rusting Has Not Yet Resulted In Cracks, Spalling, Rust
Stains Etc)

Protectosil® CIT Consists Of Small, Reactive Molecules, That

Penetrate Deeply Into The Concrete And React With The Concrete
Pore Walls

⇒ Prevents Ingress Of More Water, Chloride Ions And Other

Pollutants

⇒ Can React With The Oxide Layer Of The Rebar

Strengthening Of The Passivation Layer

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 Incipient Anodes (Ring Anode Effect)

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 Corrosion In Reinforced Concrete

e-
cathode

4 Fe 4 Fe2+ + 8 e-
e- anode

4 Fe2+ + O2 + 8OH-
8OH- 4 FeOOH + 2 H2O

cathode
e-
2 O2 + 4 H2O + 8 e-
e- 8 OH-
OH-

09/03/2011 19
 Specimen Set-
Set-up For Laboratory
Testing Of Corrosion
Inhibitors

PONDED SALTWATER

25 mm
HUMIDITY PROBE

25 mm FHWA TEST METHOD

DRAWING NOT TO SCALE

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 Test Set-up

Acrylic glass edging

Filled with
15 % NaCl

Steel rebars

Sensor for
concrete
humidity

Steel
rebars

The idea is to cycle the salt water ponding to drive the salt into the
concrete to initiate corrosion much faster than in real life
09/03/2011 21
 Decrease in Corrosion Current Following
Application Of Protectosil Cit

drying / CIT application

Corrosion current [µA]

800
wetting/drying cycles wetting/drying cycles
700
600
500
untreated
400
300
200
100 After CIT application

Days ponding
Concrete sepcimen according to FHWA (30x30x17,5 cm), 15 % NaCl solution, Total
corrosion current
(macro- + microcell corrosion) measured,

09/03/2011
> 90 % reduction of corrosion current 22
 Performance On Cracked Concrete

Cracks are 0.3 mm wide

and 25 mm deep

Corrosion
products
visible

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 PROTECTOSIL® CIT PREVENTS CORROSION ON
CRACKED CONCRETE
Corrosion current [µA]

600
Untreated
500 Protectosil CIT

400

300

200

100

0
0 1 5 10 15 20 25 30 35 40 45 48

Time - Weeks

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 Protectosil® Cit Reduces
Existing Active Corrosion On
Cracked Concrete

600
Untreated
500
Current, µA

Protectosil
400 CIT

300
Slabs Treated
200 with CIT
100

0
0 1 5 10 15 20 25 30 35 40 45 48
Weeks of Salt Water Exposure

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 Application Of Protectosil® Cit

• Spalled concrete and delaminations are repaired; totally corroded

reinforcement has to be replaced; the surface has to be cleaned from
dust, effluorences and oil

• Protectosil® CIT should be applied to ALL concrete using low-pressure

pumping equipment

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 Field Performance of
Protectosil® CIT
Balconies Near Salt Water
• 20 Year Old Building Located in Florida, USA
• Total Repairs = US $ 1.2 million
• Repairs Made and Protectosil® CIT Applied in 1994

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 Field Performance of
Protectosil® CIT
Balconies Near Salt Water
• Spalls and Delaminations were repaired using standard meth
• Protectosil® CIT was applied to all the exposed concrete
• Corrosion testing was performed annually to verify perform

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 Field Performance of
Protectosil® CIT
Balconies Near Salt Water
/cm2
µA/cm

1.6
Corrosion Rate Before CIT
1.4
urrent, µA

1.2
current,

1.0
0.8 Corrosion Rate After CIT-
CIT- steel
remains in passive condition for
Corrosion c

0.6 at least 8 years

0.4
0.2
0
1994 1994 1995 1996 1997 1998 1999 2000 2001
>1.0 µA /cm2 = < 2yrs to defects
µA/cm
< 0.2 µA /cm2 = passive conditions
µA/cm
09/03/2011 29
 Field Performance of Protectosil® CIT
Bridge Deck Exposed to Deicer Salts

• 1.8 miles long bridge

• 98,000 m2 of concrete deck
• Built in 1970
• Corrosion damage due to
chloride
ingress & transverse
cracking

GeCor 6
Linear
Polarisation
test
apparatus
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 Commodore Barry Bridge - Corrosion Rate
Measurements from 1997 to 2000
/cm2
µA/cm

0.9 Treated
urrent, µA

0.8 Untreated
current,

0.7
0.6
0.5
0.4
Corrosion c

0.3
0.2
0.1
0
B Gantry E Gantr
Gantry F Gantry Actual core
showing
> 0.5 - 1.0 µA = 3- nature of
3-10yrs to deterioration
transverse
< 0.2 µA /cm2 = passive conditions
µA/cm cracks
09/03/2011 31
Protectosil® CIT – Independant testing

J Bennett Associates - USA

‘Protectosil by Degussa Corporation effectively reduced

corrosion of reinforcing steel in ASTM G109JJ.’

Mott MacDonald - UK
‘..an effective alternative to the existing methods of durability
enhancement for reinforced concrete and the avoidance of
secondary effects such as incipient anode behavior.’

SGK - Switzerland
J.‘Protectosil CIT treatment resulted in a clear decrease
in corrosion current, and even repassivation is observed
on the sensors initially showing active corrosion.’
09/03/2011 32
SUMMARY

Protectosil CIT should be considered as an solution in part of A long

term repair package
- Effective preventative measure to prevent incipient anodes
- Excludes of water borne chlorides
- Strengthens the passive layer on the steel surface
- Simply applied
- Cost effective
- Proven track record
- Backed up by independent testing
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 END

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