Nanotechnology in paint applications by Mme. Lefevre, Cori

1. Your Partner in Coatings, Science & Technology
16/01/2015
Overview of nanotechnology in
paints applications

2. 216/01/2015
Avenue Pierre Holoffe, 21
1342 Limelette
BELGIUM
Tel. +32(0)2.653.09.86
E-mail: cori@cori-coatings.be
Website: www.cori-coatings.be
Who we are…
Research
(Contractual &
Collective)
Testing
&
Analysis
Technical
Assistance
&
Appraisal
Training
&
Congress

3. 316/01/2015
Who we are…
Our Mission:
provide assistance, support & services
by offering:
ad hoc
analysisproblem-solving
contract
research
technical
assistance
training
to paint manufacturers, raw materials
suppliers, professional applicators and
industrial users

4. 416/01/2015
Our Customers & members: an entire value chain
Who we are…
Raw materials
suppliers
Paint
Manufacturers
Industrial
“end users”
Equipment
suppliers
Architects
Universities
Other Industries…

5. 516/01/2015
 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

6. 616/01/2015
 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

7. 716/01/2015
nanocomposite coating can be obtained by
 incorporation preformed nanoparticles
 in-situ formation of nanoparticles or nanophase
 nano-structuring  nanostructured coating
nano technology

8. 816/01/2015
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)

9. 916/01/2015
 dispersion of nanoparticles vital for properties
 interaction of nanoparticles with matrix
 surface functionality of particles
 intrinsic nature of particles
addition of preformed
nanoparticles
Zn
O
Al2O3
DMA
analysis

10. 1016/01/2015
 Metal alkoxides
 silanes,
 titanates,
 zirconates
 …
 formation of nanocontent by hydrolysis & condensation
in-situ formation nano
-particles or -phase
GELATION
Ti
OH
Ti
TiTiTi
O O O
O O
OOO
TiTiTi
OOO
OROHOR
O O O
TiOTiOTi
O Ti O O
O
O O O
OR OR
O O
6
Ti
OR
OR
ORRO + H2O
1
Ti OR
OH
OR
RO
2
HYDROLYSIS
+
Ti OH
OR
OR
HO
3
nROH
3 + 3
H2O-
Ti O
OR
OR
HO Ti
OR
OH
OR
1 + 3
- ROH
Ti O
OR
OR
RO Ti
OR
OH
OR

11. 1116/01/2015
 nanoparticles ↔ nanophase depends on
 pH
 catalysts
 ageing of mixture
 …
in-situ formation nano
-particles or -phase

12. 1216/01/2015
PROPRIETES MECANIQUES ET
PROTECTRICES – époxy aqueux 2K
Persoz Hardness
REF P1 P2 P3 P4 P5
0
100
200
300
400
REF
P1
P2
P3
P4
P5
Hardness(s)
Flexibility (conical mandrel)
REF P1 P2 P3 P4 P5
0
10
20
30
40
REF
P1
P2
P3
P4
P5
deformation(%)
Impact Test
REF P2 P3 P4 P1 P5
0
50
100
REF
P2
P3
P4
P1
P5
Fallingheight(cm)
PRECURSORS
Metal alkoxides
REFERENCE
HYBRIDE – P3
Salt spray
450h

13. 1316/01/2015
 interaction of nanophase with matrix important
 Mechanical properties at T > Tg
in-situ formation nano
-particles or -phase
Inorganic network enhanced solvent
resistance

14. 1416/01/2015
 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

15. 1516/01/2015
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
OC
Si TiCa
WOOD PENETRATION
0
1
2
3
4
5
6
0 0.1 0.23
Acetoneresistance
Jatoba
Afzélia
chêne
mélèze
CHEMICAL RESISTANCE
3.3% nanoTiO20% nanoSiO2/TiO2
AGEING

16. 1616/01/2015
INORGANIC STRUCTURE
SILANE
3%NANO-TiO2
SILANE
Colloidal dispersions
Metal oxydes

17. 1716/01/2015
INTERACTIONS
FTIR - DMA
F4
ref
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28Absorbance
16001800
Wavenumbers (cm-1)
1,E-01
1,E+00
1,E+01
1,E+02
1,E+03
1,E+04
0 50 100 150 200
StoragemodulusE'(MPa)
Temperature (°C)
ref
2%
2%C
Coat
Colloidal dispersions
Metal oxydes

18. 1816/01/2015
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

19. 1916/01/2015
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

20. 2016/01/2015
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

21. Your Partner in Coatings, Science & Technology
16/01/2015
THANK YOU FOR YOUR ATTENTION