SILICONE SURFACE IMPREGNATION & COATING · SILICONE SURFACE IMPREGNATION & COATING Textiles airbags, sportswear, lingerie… but also: tires, ships, corks, etc. Bond Bond energy Si

Paperlabel-release, bakery paper…

Building Materialsstones, concrete, wood…

SILICONE SURFACE IMPREGNATION & COATING

Textilesairbags, sportswear, lingerie…

but also:tires, ships, corks, etc.

Bond Bond energy

Si – OC – C

106 kcal/mol85 kcal/mol

Chain Valence angle

Si-O-SiO-Si-OC-C-C

130-140°110-115°110°

Si

O

Si

O

Si

CH3 CH3 CH3 CH3 CH3 CH3

GENERAL PROPERTIES

hydrophobic methyl groups

C-C-C 110°

Chain flexibility – Lubrication, hydrophicity, relea se propertieslow Tg (-123°C)low surface energy (~20 mN/m)

Thermal stability, weathering resistanceDurability well above organic polymers

npolar flexible siloxane backbone

Environmental Profile

SiO2 (sand)Elemental

Silicon

Chlorosilanes

Manufacturing

Degradation

Manufacturing

Use UseSilicones

WATER REPELLENTS

Risks- Degradation (frost , moss, mold...)

- Appearance (efflorescence, spotting..)- Economic (insulaton loss…)Exposure

- Infiltration,- Raising Damp,- Condensation

Moisture in Buildings

Substrates- Roofing (Tiles…)

- Facades (Stones, Bricks,Concrete, Mortar, Stucco)

- Walls (Plaster…)- Wood

Solutions- Surface treatment

- Injection

Silicones Advantages

� Hydrophobia

� Low surface tension -> spreadability

� UV Resistance -> durability

� Water vapor permeability

Silicones Properties

wall

Liquid water

Water vapourexchange

θ

exchange

Beading effect

Molecular treatment (inside of the capillaries)

• water proof (liquid water)• water vapour permeability (open pores)• No surface modification

deep penetration = durable treatment

Con

tact

ang

le (°)

silicone resins on glass

60

90

120

Building protection Basic principles

Prince’s Palace (Monaco) Arc de Triomf (Barcelona) Basilique de Fourvières (L yon) Colonne di San Lorenzo (Milan)

thickness (Å)

Con

tact

ang

le (

0

30

0 100 200 300

resin 1resin 2resin 3

Few molecular layers are sufficient to provide optimum water-repellency

Factors affecting penetration

Building protection with emulsions

2

3

4

dept

h (m

m)

200

250

300

350

mass deposited (g/m

²)

Need a compromise (too reactive if too concentrated)

0

1

2

0 10 20 30 40 50 60 70 80 90 100

% octyl silane in white spirit

dept

h (m

m)

0

50

100

150

mass deposited (g/m

²)

penetration depth (mm)

hydrophobized depth (mm)

mass deposited (g/m²)

250

300

350

volu

me

cum

ulé

en

mm

^3/g Tuffeau

Saint Vaast

Mortier

Typical EmulsionGranulometry

Molecular &Micellar Range

Substrate pore size vs. emulsion droplet sizeM

ercu

ry P

oros

imet

ry

Cum

ulat

ed v

olum

e (m

m3 /

g) Tuffeau St VaastMortar


0

50

100

150

200

1.00E-03 1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02

diamètres des pores en µm

volu

me

cum

ulé

en

mm

^3/g

Mer

cury

Por

osim

etry

Cum

ulat

ed v

olum

e (m

m

Pore diameter (µm)

solvent-based and water-based will penetrate differently


Should we adapt droplet size to pore size?

Rdroplet < Rpore

=> penetration?

Rdroplet > Rpore

=> no penetration?

… not only a matter of relative size!


When pores are too small:

Favorable for capillarity


Rdroplet > Rpore

=> no penetration?

Importance of water/oil interfacial tension (droplet deformability) and droplet/solid interfacial tension (=> wetting)

Important parameters are:

Rf mean pore size at frontθθθθws water/solid contact angle=> capillary driving force


Impregnation of a porous material with an emulsion:

L

Rd RpRL

Rf

θθθθw/s

θθθθo/s

L droplet “position”RL mean pore size along L=> pressure loss along pore

Rd droplet sizeRp pore sizeθθθθos oil/solid contact angle=> droplet wetting and deformation

modified Washburn’s Law, with:

tAtx .1)( β−=

2

2cos4

f

Lwsw

RK

RA

θγ=

θ


Impregnation of a porous material with an emulsion:

−−=

d

f

p

osf

wsw

oil

R

R

R

R θθγ

γβcos

cos

Allows to describe different penetration regimes (depending on ββββ)

Washburn, Phys Rev. (1921), 17, 273Marmur et al. JCIS (1989), 189, 299

L

Rd RpRL

Rf

θθθθw/s

θθθθo/s

θo/s > 90°

imp

oss

ible

not enoughsurfactantto deform

the droplets

Rel

ativ

e dr

ople

t siz

e (

Rd/R

f)

Regimes of penetration:


1|cos θo/s|

unhindered

0 αααα |cos θo/s|

θo/s < 90°

1

imp

oss

ible

(αααα = γγγγw/o / γγγγw)

no obstacle

Relative pore size ( Rp/Rf)

Rel

ativ

e dr

ople

t siz

e (

30

40

Pen

etra

tion

Dep

th (m

m)

St Vaast SandstoneConcrete

Penetration depth of different silicone formulation s:

Building protectionwith emulsions

0

10

20

in solvent Emulsion NanoEmulsion MicroEmulsion

Pen

etra

tion

Dep

th (m

m)

Importance of droplet size + derformability

(2x1mn impregnation of 10% active material solutions, allowed to dry out for 48h)

Analysis of silicone penetration:

IR (DRIFT)


00.10.20.30.40.50.60.70.80.9

1

0 0.2 0.4 0.6 0.8 1

Emuls. 5%

Emuls. 5% + 1%surf.

depth / total depth

rela

tive

DR

IFT

inte

nsity

Excess surfactant help droplet penetration


When pores are bigger:

Penetration might


Rdroplet < Rpore

=> penetration?

Penetration might still be hindered,

if affinity between surfactant and solid

is too strong

Rétention de XO80 Sur Tuffeau

0,2

0,4

0,6

0,8

1

1,2

Sig

nal / S

ignal (h

=0)

1%

2%

4%

water

silicone resin

Mortar

Anionic

Surfactant localisation

rel.

DR

IFT

inte

nsity

Importance of interactions between surfactant and s ubstrate:


High retention0

0,2

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1

h / h imbibée

Rétention de XO80 Sur Saint Vaast

0

0,2

0,4

0,6

0,8

1

1,2

0 0,2 0,4 0,6 0,8 1

h / h imbibée

Sig

nal / S

ign

al (h

=0)

0,5%

1%

2% water

silicone resin

Mortar

nonionic

Mortar

Surfactant localisation

depth / total depth

depth / total depth

rel.

DR

IFT

inte

nsity

rel.

DR

IFT

inte

nsity

High retention

Low rentention=> deeper treatment

Influence de la concentration en MQTuffeau - 1l / m²

60%

70%

80%

90%

100%

110%

120%

Rep

ris

e e

n ea

u (%

)

2%

4%

2%Water Uptake on TuffeauInfluence de la concentration e n MQ

St Vaas t - 1 l / m²

50%

60%

70%

80%

90%

100%

Rep

ris

e e

n e

au (

%)

2%

4%

6%

8%

10%

2%

Water Uptake on St Vaast

Macroscopic protection : put enough silicone at mac roscopic level

wat

er u

tpak

e (%

)

wat

er u

tpak

e (%

)

increasing [silicone]

increasing [silicone]


need ≥ 4% silicone

0%

10%

20%

30%

40%

50%

60%

0 5 10 15 20 25 30

Nb de jours

Rep

ris

e e

n ea

u (%

)

4%

6%

8%

10%

10%

28 jours

0%

10%

20%

30%

40%

50%

0 5 10 15 20 25 30

Nb de jours

Rep

ris

e e

n e

au (

%)

28 joursdays days

wat

er u

tpak

e (%

)

wat

er u

tpak

e (%

)need > 10% silicone

[silicone] [silicone]

Solution Impregnation

Porous Substrate:• Specific Surface, S• Specific Porous Volume, Vp

Mean Thickness, h

CVp

h .=

Macroscopic protection : put enough silicone at mac roscopic level

Solution concentration, C


CS

h .=

Examples : S Vp h C

St Vaast Stone 2 m²/g 0,25 cm3/g 50Å 4%

Tuffeau Stone 15 m²/g 0,31 cm3/g 50Å 24%

knowing basic substrate characteristics can help provide a suitable treatment

Treating porous materials with emulsions can be tri cky,but formulations can be optimized:

Importance of surfactant type and proportion

Concluding remarks

Importance of droplet size but also deformability (play on interfacial tension to allow large droplets to enter smaller pores)

Importance of surfactant interaction with solid (avoid chromatographic retention of surfactants on solids)

WATER REPELLENT(different forms)

� Creams and pastes :are designed more particularly to ensure better penetration of the silanes in concrete. Two problems inherent to this type of formula are identified: form of application in thick coats, which seems restrictive, and the risk of losing active material through volatilisation.

� Microemulsionable concentrates : appear to be fairly economical � Microemulsionable concentrates : appear to be fairly economical solutions (100% active, hydrodispersible but without the need for any excess agitation). Main disadvantage is their very low stability after dilution

SILOXANES VERSUS SILANES

SILANES � small molecules penetrate deeper and more easily� very high reactive site � not necessarily require a perfectly dry surface for application;…but also numerous downsides:� volatility� toxicity (often irritants)� need for humidity and a catalyst to react� low beading effect� risk of leaching where insufficient cross linking.� risk of leaching where insufficient cross linking.� So as to attenuate these disadvantages, possible to use oligomerised or

“advanced” silanes.(= siloxane oligomers )have the following advantages :� less volatile� less toxic� less alcohol salted out;� …but:� the silane’s functionalities are less well distributed throughout the network;� less penetration in non-porous materials.

SILOXANES VERSUS SILANES

SILOXANES� non volatile� very low toxicity� good beading effect as of the first hours� no risk of leaching

…with the following downsides:� high viscosity: sometimes have to be diluted in solvents;� require very dry surface for application;� require very dry surface for application;� molecular weight of several thousand g/mol => poor penetration

That means silane content must be modulated according type of surface/ application conditions. For example a low-porosity surface such as fresh concrete is very reactive, requiring the high penetration of silanes, . On the other hand, a much lower level of silane content is recommended for treating neutral and porous materials

WATER REPELLENT DILUTION (solvent based products)

� Generally: aliphatic (white spirit ,isoparaffin) and aromatic hydrocarbons. Some products( with high silane content )can also be diluted in anhydride alcohols, typically ethanol or 2-propanol (anhydride aspect is essential because of the cross linking before it is applied). These alcohols are suitable for formulations, better compatibility with materials which are sensitive to aromatic solvents potentially exposed during application (tar seals, or polystyrene for example).The type of solvent used will affect the product’s penetration � The type of solvent used will affect the product’s penetration capacity: low-polarity solvents tend to be considered more effective . Their low superficial tension makes them easier to spread on a varied range of surfaces, and their relatively low density is a benefit in the case of treatments by capillarity.

WATER REPELLENT DILUTION (water based product)

� Recommending demineralised water gets round local water hardness variations (content of calcium and magnesium ions). the presence of electrolytes modifies interactions between water and surfactants, and can lead to the and surfactants, and can lead to the destabilisation of droplets and therefore the destruction of the emulsion.

� This risk is in fact fairly limited since most water repellent emulsions tested tend to be non-ionic surfactant based.

Rhodorsil BP 9400 is versatile: it can be used on many porous substrates and is particularly recommended for thetreatement of stone, brick, and « old » concrete (carbonated).

•• Rhodorsil H224 (69% AM) & Rhodorsil BP 9400 (100% AM)Rhodorsil H224 (69% AM) & Rhodorsil BP 9400 (100% AM)

Building Protection : Solvant based products

40

60

80

100Mortier

BriqueGrès Rouffach

hydrofuge standard RHODORSIL BP 9400

Rhodorsil BP 9400 has been certified by CSTC : HD-340/133-150

Generally these products are applied diluted down to 6 -8 % into solvent

020

40

Massangis

St vaast

Tuffeau

Euville

SavonnièreH

••RHODORSIL BP 9710 (44% AM)RHODORSIL BP 9710 (44% AM)

40

60

80

100Mortier

BriqueGrès Rouffach

RHODORSILBP 9710 HYDROFUGE STANDARD"BP 9710 is an emulsion of an alkylpolysiloxane oligomer designed to protect buildings againts moisture.

BP 9710 is versatile : it can be used on many porous substrates , particularly on

Building Protection : Water based product

0

20

40

Massangis

St vaast

Tuffeau

Euville

Savonnière

many porous substrates , particularly on lime stones, sand stones, mortars , renderings or bricks.

Rhodorsil BP 9710 has been certified by CSTC : HD-340/133-151

Generaly, RHODORSIL BP 9710 is diluted between 4% and 8% of active material in water.

RHODORSIL BP 97XX Range

� Rhodorsil BP 9710 : Ready to use water based water repellent : � versatile (performances on many different porous substrates )� good storage stability ( 12 months concentrated / 12 months diluted)� controlled reactivity

� Rhodorsil BP 9705 : Ready to use water based water repellent :� Rhodorsil BP 9705 : Ready to use water based water repellent :� low reactivity � Designed as an additive for various formulations� Stability 12 month

BP9710

PRODUCTS POSITIONNING

• Technology

4

6

8

10Reactivity

Beading effectdurability

Solvant based

Water based

Fluorinated

Waxes

0

2

penetration depth

water repellency

oil repellency

BS1

Diapositive 31

BS1 Sandrine Millot; 28/09/2010

• BP9710 - 4% on wall

Building Protection : Water based products

• BP9710 - 4% in mortar

• BP9710 - 4% on ciment

BP water repellents after 3 years outdoor exposure

Product X BP9400 untreated BP9710

TUFFEAU : lime stone

north exposure

Product X BP9400 untreated BP9710

SAVONNIERE : lime stone

south exposure

All products have been diluted down to 8% in the appropriate solvent

Damp-proof course system

The aim is to make the capillary network of the material water-repellent to avoid water working its way upwards.

•When the degree of humidity is very high, solvent based Rhodorsil H 224 makes it solvent based Rhodorsil H 224 makes it possible to quickly achieve the required results.

•Standard dilution: 1 part of H 224 for 10 parts white spirit

� BP 9600 : for lime paints

Surface treatment to protect lime paints against water damages (stains ….)

Building Protection : Solvent based products

Building Protection – stone consolidation

Inorganic material loses its binder and cohesion under the action of water and harmful elements, mainly acid, which penetrate it, causing reactions.

RHODORSIL RC are designed to treat materials which show signs of damage show signs of damage � Formation of a new binder to recover the mechanical properties of the substrate.� Reduction of the water absorption (RC 80)

• The Rhodorsil RC70-80-90 Range:

� RHODORSIL RC 70 : based on ethyl silicate

� RHODORSIL RC 80 : based on ethyl silicate + polysiloxane resin

= Consolidation + water repellent action

� RHODORSIL RC 90 : based on ethyl silicate + methylphenylpolysiloxane resin


� RHODORSIL RC 90 : based on ethyl silicate + methylphenylpolysiloxane resin

= Consolidation : more flexibility and binding effect

Under the action of the residual water in the pores and a catalyst , it is transformed into silicic acid gel.

Si (OC2H5)4 + 4 H2O Si (OH)4 + 4 C2H5OH

200

300

400

Porosity %

24

26

28

30

32

stone untreated

•• The Rhodorsil RC70The Rhodorsil RC70--8080--90 Range90 Range


Flexural strengthNewtons

Untrea

tedRC 70

RC 80

RC 90

0

100

200

St VAAST

TUFFEAU

SAVONNIERE

size of sample (cm)

0 1 2 3 4 5 6 7 816

18

20

22

décayed strcturehealthy stone

Treated with RC 70

direction of the alteration

After consolidation, the porosity of initial stone is recovered (filling of holes and grain joints).

Thermal Insulation with Silicone Paints and Water Repellents

IntroductionIntroduction

� In France, Building contributes to 43% of the total consumed energy

� Thermal regulations in Europe , (2000,2005,…) comes into a range in France :• 2012 => new building energy consumption = 50kw/m2/year.• 2012 => new building energy consumption = 50kw/m2/year.• 2020 => Buildings with positive energy

� HQE (france) & BREEAM (UK) should be joined in 2012

Studied systems :

Breeze blocks + cement render Breeze blocks + cement render + water repellent + water repellent

� Cement render : • 400 kg of cement / m3 dry sand ,• 400 kg of cement / m3 dry sand ,• water/cement = 0.5.

� Application of 2 coats of render : • 1st coat thickness : 13mm - Drying : 7 days at 23°C and 60% RH • 2nd coat thickness : 7 mm - Drying : 7 days at 23°C and 60% RH

APPLICATIONS

For water repellents : � Application with a brush until substrate

saturation.� Drying 7 days at 23°C 60% RH

systems are then :� Coated with wax � dried at 45°C during 48h,� weighted,� And placed onto the rain apparatus

Rain test :

• water is pulverized with the help of compressed air • 2 blocks can be tested • 2 blocks can be tested at the same time • good repeatability of the results (% water uptake +/- 0.2%)

Results of rain test for water repellents

Breeze block + cement

2,5

3

3,5

4

4,5

wat

er u

ptak

e (%

)

Blank

0

0,5

1

1,5

2

2,5

0 5 10 15 20 25Time (hours)

wat

er u

ptak

e (%

)

BP 9400 8% (SB)

BP 9710 8% (WB)

BP9600 8% (WB)

BP 9500 8% (SB)

Comparison rain test / capillarity test

Water repellentsWater repellents

2

2,5

3

3,5

Wat

er u

ptak

e (%

) BP9400 (8%-WS) rain test

BP9400 (8%-WS) capillarity test

0

0,5

1

1,5

0 5 10 15 20 25

Time (hours)

Wat

er u

ptak

e (%

)

BP9710 (8% water) rain test

BP9710 (8%-water) capillarity

BP9600 (8%-water) rain test

BP9600 (8%-Water) capillarity test

Note :

capillarity test = immersion of the treated face into 3 mm of water

THERMAL LOSS CALCULATION

� Q = U x S x deltaT x h= coeff thermal transmission x Surface x Delta T°C x time (h)

With U = 1 / termal resistance = λ/e = termal conductivity / thicknessAnd λ= λ0 e 0.08 * %humidity

And λ0 = termal conductivity of dry material

Postulates (individual house)� Total surface = 80 m2 of façade, exposed surface= 40 m2.� Chosen place= Nan Yueh in China (1874mm rain/ year)� Number of days with maximal humidity for our system = 50 days for Nan

Yueh � Internal comfort temperature : 19°C. � External temperature when heating (October – April) is 6°C in Nan Yueh.� Price: 1kW.h chinois= 0.0479 euros� λ 0= 1

THERMAL LOSS COST / IMPACT OF SILICON

With water repellent BP9400Breeze block

aloneBreeze blockwith cement render

Saving for one year( / breeze block without cement

render )reference 4.3%

� CalculationQ TOT = Q exposed wet wall + Q exposed wall during drying + Q dry exposed wall + Q non exposed

wall

render )

Breeze block + cement render untreated

Breeze block + cement render

Treated with BP9400

Saving for one year ( / breeze block with cement

render without treatment) reference 13.3%

Photos hydrofugation

terra bricks hydrofugation

photos hydrofugation consolidationhydrofugation hydrofugation consolidation

Documents

SILICONE SURFACE IMPREGNATION & COATING · SILICONE SURFACE IMPREGNATION & COATING Textiles airbags, sportswear, lingerie… but also: tires, ships, corks, etc. Bond Bond energy Si