05 overview of nanotechnology in paints applications-lefevre-cori
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Your Partner in Coatings, Science & Technology
16/01/2015
Overview of nanotechnology in paints applications
2 16/01/2015
Avenue Pierre Holoffe, 21 1342 Limelette BELGIUM Tel. +32(0)2.653.09.86 E-mail: [email protected] Website: www.cori-coatings.be
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4 16/01/2015
Our Customers & members: an entire value chain
Who we are…
Raw materials suppliers
Paint Manufacturers
Industrial “end users”
Equipment suppliers Architects
Universities
Other Industries…
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coatings industry: history of working with nano content
fumed silica ( Aerosil®, …)
carbon black
FexOY in varnishes
abrasion of coatings containing nanoparticles* :
once embedded in coating no longer released as nano-content
nature of nanoparticles themselves
nano-content in coatings a health hazard ?
* Vorbau M. et al., European Coatings Journal (2011) 2:29
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Optical transparency particles < wavelength light in visible range
hardly any light scattering
clearcoat with enhanced properties
surface/volume ratio ↑↑ interface particles-resin ↑
properties interface ≠ those of both bulk materials interfacial effects become relevant at macroscopic scale
high surface area relevant for surface active compounds
interest of adding nano-content to coatings
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nanocomposite coating can be obtained by
incorporation preformed nanoparticles
in-situ formation of nanoparticles or nanophase
nano-structuring nanostructured coating
nano technology
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addition of preformed nanoparticles
http:/nanograde.ch
~ unlimited range of compositions SiO2, TiO2, Al2O3, ZnO, CeO2, …
clay platelets carbon nanotubes
powder / dispersion (aqueous, solvent based)
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dispersion of nanoparticles vital for properties interaction of nanoparticles with matrix surface functionality of particles
intrinsic nature of particles
addition of preformed nanoparticles
ZnO
Al2O3
DMA analysis
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Metal alkoxides silanes, titanates, zirconates …
formation of nanocontent by hydrolysis & condensation
in-situ formation nano -particles or -phase
GELATION
TiOH
Ti
TiTiTiO O O
O OOOOTiTiTiOOO
OROHOR
O O OTiOTiOTi
O Ti O OO
O O O
OR OR
O O
6
TiOR
ORORRO + H2O
1
Ti OROH
ORRO
2
HYDROLYSIS
+
Ti OHOR
ORHO
3
nROH
3 + 3
H2O-
Ti OOR
ORHO Ti
OROH
OR
1 + 3
- ROH
Ti OOR
ORRO Ti
OROH
OR
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nanoparticles ↔ nanophase depends on pH catalysts ageing of mixture …
in-situ formation nano -particles or -phase
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PROPRIETES MECANIQUES ET PROTECTRICES – époxy aqueux 2K
Persoz Hardness
REF P1 P2 P3 P4 P50
100
200
300
400
REFP1P2P3P4P5
Har
dnes
s (s
)
Flexibility (conical mandrel)
REF P1 P2 P3 P4 P50
10
20
30
40
REFP1P2P3P4P5de
form
atio
n (%
)
Impact Test
REF P2 P3 P4 P1 P50
50
100
REFP2P3P4P1P5Fa
lling
hei
ght (
cm)
PRECURSORS Metal alkoxides
REFERENCE
HYBRIDE – P3
Salt spray 450h
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interaction of nanophase with matrix important Mechanical properties at T > Tg
in-situ formation nano -particles or -phase
Inorganic network enhanced solvent resistance
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in-situ formed inorganic IPN + nanoparticles
pre-formed nanoparticles + in-situ formed nanophase
reference
+ 5wt% SiO2
nanoparticles attach on IPN
Clemen Scratch resistance 2300 g 2600 g
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Wood paints– Water based acrylic Mechanical and protective properties
Coatings
Falling height (cm)
Jatoba Afzelia Chêne Larch
Reference F2 F3 F7 F8 F9 F11 F12 F16
25 50 15
100 75
100 10
100 -
10 20 50 25 20 25 10 20 25
10 25 25 20 20 20 20 15 20
15 10 10 10 10 20 10 20 15
IMPACT
FLEXIBILITY
Colloidal dispersions Metal oxydes
O C
Si Ti Ca
WOOD PENETRATION
0
1
2
3
4
5
6
0 0.1 0.23
Acet
one
resi
stan
ce
JatobaAfzéliachênemélèze
CHEMICAL RESISTANCE
3.3% nanoTiO2 0% nanoSiO2/TiO2
AGEING
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INORGANIC STRUCTURE
SILA
NE
3% N
ANO
-TiO
2 SI
LAN
E
Colloidal dispersions Metal oxydes
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INTERACTIONS FTIR - DMA
F4ref
0.04 0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26 0.28
Abso
rban
ce
1600 1800 Wavenumbers (cm-1)
1,E-01
1,E+00
1,E+01
1,E+02
1,E+03
1,E+04
0 50 100 150 200St
orag
e m
odul
us E
' (M
Pa)
Temperature (°C)
ref
2%
2%C
Coat
Colloidal dispersions Metal oxydes
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Colloidal silica – Paint formulation Surface modified colloidal silica Bindzil CC301 Typical properties SiO2: 30 % by weight pH: 5-9 Density: 1.2 g/cm³ at 20 °C Viscosity: 5 cPs at 20 °C Average particle size: 7 nm Appearance: Transparent liquid, no smell
Paints Note
REF Reference = Alkyd paint without Co salt
REF + H2O Reference + water
REF + Co/Zr Reference + Co/Zr salts
REF + Zr Reference + Zr salt
REF + CC301 Reference + 15 w% colloidal silica CC301
REF + CC301/Zr Reference + 15 w% colloidal silica CC301/Zr salt
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Colloidal silica (CC301) is a valid alternative to surface siccative agents such as Co salts in alkyd based paints.
Properties such as drying time, open time, hardness, blocking and dirt pick-up resistance are preserved in presence of colloidal silica (CC301) and in some cases even improved.
These results have to be attributed to a thin layer of silica covering the paint surface. The inorganic layer originates from migration and accumulation of the silica nanoparticles (CC301) during the film formation.
Colloidal silica – Paint formulation
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Being green in paint composition
POPCORN (2013- 2015: CIRMAP, CoRI)
Development of new anticorrosive paints (aqueous) with modified clays Replacement of anti-corrosion pigments by non toxic ingredient Oxygen barrier Less dependency on the nature of metal substrate and the corrosive environment
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16/01/2015
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