understanding the mechanism of improved scratch and ... the mechanism of improved scratch and...
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Understanding the Mechanism of Improved Scratch and
Abrasion Resistance in Automotive Coatings using Surface-
Treated Nanoparticles
European Coatings Conference “Automotive Coatings”, Berlin, November 24th 2011, Dr. Michael Berkei
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
NANOBYK Additives
Nanotechnology basics
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Decreasing electronegativity / Increasing Basicity
Decreasing number
of valent electrons
Size depending
properties
Decreasing electronegativity / Increasing Basicity
Decreasing number
of valent electrons
Size depending
properties
Nanotechnology enables us to obtain more functionalities from chemical elements
Crystal Size [nm]
3 5 10 15 20 30 >100
Gold
Crystal Size [nm]
3 5 10 15 20 30 >100
Gold
Benefits of nanotechnology
Particle size depending change
in colour
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Definition of nanotechnology
En
erg
ie
• Change in properties due to a change in size (below 100 nm)
• Conductivity of metals 2 nm
• Fluorescence of Q-dots 10 nm
• Transparency of ceramics 20 nm
• Colour of metals 50 nm
• Stiffness of metals 250 nm
• Ductility of ceramics 500 nm
0%
20%
40%
60%
80%
100%
0 1 2 3 4 5 6 7 8 9 10
Diameter [nm]
Su
rface A
tom
s [
%]
• Increase in specific surface area
• Reactivity
• Surface energy
• Shape
• Anisotropy of properties
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Potential Applications
• Improvement in scratch and wear resistance
• Permanent UV protection
• Enhanced anti-microbial activity
• Self-cleaning surfaces
• Conductivity
• Fade-resistant dyes
Nano-Advantage
• Small functional particles
• Maintain transparency
• Low Additive concentration needed
Nanotechnology in Coatings and Plastics
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Volume fragment with 1000 µm3 and 2 % particles
particle diameter particle quantity interparticle distance
1 µm 40 2300 nm
20 nm 5,000,000 45 nm
Nanotechnology makes it possible to use
more particles per unit area and to
minimize the particle-particle separation
10 µm
10 µm
10 µm
Advantages of nanoparticles versus microparticles Better distribution at the same concentration level
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
NANOBYK
Increased coating elasticity
by incorporation of nanoparticles
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
How nano-based additives improve scratch resistance
SiO2
Curing process
Impact of nanoparticles on elasticity
Polarity differences between nanoparticle and resin
• These differences cause a gradient in crosslinking density
• Around the particle the crosslinking density is lowered
The coating acts like foam and bounces back after exposure
Oligomeric resin
Resin matrix
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
How nano-based additives improve scratch resistance
Curing process SiO2
R R R
| | |
---Si-O-Si-O-Si---
| | |
R R R
R R
R
| | |
---Si-O-Si-O
-Si---
| | |
R R
R
R R R
| | |
---Si-O-Si-O-Si---
| | |
R R R
R R
R
| | |
---S
i-O
-Si-
O-S
i---
| | |
R R
R
R
R
R
|
|
|
---S
i-O
-Si-O
-Si---
|
|
|
R
R
R
R R R
| | |
---Si-O-Si-O-Si---
| | |
R R R
R R
R
| | |
---S
i-O
-Si-
O-S
i---
| | |
R R
RR
R
R
|
|
|
---S
i-O
-Si-O
-Si---
|
|
|
R
R
R
SiO2
R R R
| | |
---Si-O-Si-O-Si---
| | |
R R R
R R
R
| | |
---Si-O-Si-O
-Si---
| | |
R R
R
R R R
| | |
---Si-O-Si-O-Si---
| | |
R R R
R R
R
| | |
---S
i-O
-Si-
O-S
i---
| | |
R R
R
R
R
R
|
|
|
---S
i-O
-Si-O
-Si---
|
|
|
R
R
R
R R R
| | |
---Si-O-Si-O-Si---
| | |
R R R
R R
R
| | |
---S
i-O
-Si-
O-S
i---
| | |
R R
RR
R
R
|
|
|
---S
i-O
-Si-O
-Si---
|
|
|
R
R
R
SiO2
Curing process
R R R
| | |
---Si-O-Si-O-Si---
| | |
R R R
Additional Polysiloxane
Impact of nanoparticles on elasticity
Silicone treatment enhances the polarity differences between nanoparticle and resin
Resin matrix
Resin matrix
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
How nano-based additives improve scratch resistance
Source: Lee et al., Macromolecules 2007, 40, 7755-7757
Surface-treated nanoparticles can create „free
volume“ inside a polymeric film resulting in
increased elasticity
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Force
Impact of nanoparticles on elasticity
Force
How nano-based additives improve scratch resistance
Force
Enhanced elasticity
Resin matrix Resin matrix Resin matrix
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Mechanism of scratch resistance - nanoindentation
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Mechanisms of improved scratch resistance NANOBYK-3652 – 20nm surface treated SiO2
0 % 0.75 % 1.75 % 3 %
Scratch Profiles at 49 mN Test system: Solvent based 2K-PU Coating
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Nanoadditives for solvent-born clear coatings
II III
Without nano With 2% SiO2
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
NANOBYK-3610 and NANOBYK-3650 family Lower E-modulus measured by nanoindentation Test system: Solvent based 2K-PU Coating
0
0,5
1
1,5
2
2,5
3
3,5
4
E-M
od
ulu
s [
GP
a]
0 2 4 6 8
% Additive as supplied on total weight formulation
NANOBYK-3651
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
NANOBYK-3650, NANOBYK-3651 and NANOBYK-3652: High level of pendulum hardness (König, DIN ISO 1522)
Test system: 2K-PU Clear Coat
80
Dosage:
NANOBYK-3650: 4%
NANOBYK-3651: 5%
NANOBYK-3652: 4%
as supplied on total formulation
90
100
110
120
130
140
Tim
e [s] Control
NANOBYK-3650
NANOBYK-3651
NANOBYK-3652
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results: Comparison of different surface treated silica nanoparticles in a solvent based 2K-PU clear coat (OEM)
0
10
20
30
40
50
60
70
80
90
100
Con
trol 0
%0,
2%0,
4%0,
6%0,
8%1,
0%1,
2%1,
4%1,
6%1,
8%2,
0%2,
2%2,
4%2,
6%2,
8%3,
0%3,
2%3,
4%3,
6%3,
8%4,
0%
Particle loading [%]
Glo
ss
re
ten
tio
n [
%]
NANOBYK-3650 NANOBYK-3651 NANOBYK-3652
Unpolar surface modification
Medium polar surface modification
Polar surface modification
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results Solvent-borne 1K TSA clear coat (OEM)
Scratch Resistance of 1K TSA Clear- 140°C/30 min
tested by 9 micron paper on Dry Abrasion Tester (ASTM-D2486)
30
45
60
75
90
105
0 5 10 20 30 40 50 60 70 80 90 100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500
Number of Scratch Cycles (double)
Glo
ss (
20°)
1K-Control
NB3652
NB3652+BYK331
NB3652+BYK300
Nanobyk 3652 dosage: 2% as supplied on total formulation
w eight
Gloss (20°)
substrate: BYKO chart 2833, 100 micron WFT by w ire-w ound bar applicator
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results Solvent-borne pigmented coatings – 2K systems
Black Silver White
Macrynal SM 510N 60% 30 30 21,7
CAB 551-0.2 (20%ig in Butylactat) 15 15 10,9
Ceratix 8461 (4,7%) 18,2 18,2 13,2
Special Black 4 Paste (25%) 6
Aluminium Slurry Metallux 2152 (50%) 6
Tronox CR-826 Paste (63%) 31,8
BYK 320 0,2 0,2 0,2
BYK 358 0,5 0,5 0,4
Butylacetate 15 15 10,9
Methoxypropylacetate 2,5 2,5 1,8
Shellsol A 2,5 2,5 1,8
n-Butanol 2 2 1,5
Xylene 8 8 5,8
BYK 410 0,1 0,1 0,1
Polyol : Desmodur N75 BA = 5:1
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application Results 2K-Coating Metallic
17%
77%
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
Glo
ss R
ete
nti
on
[%
] Control
1% Nanobyk 3650
2% Nanobyk 3650
5% Nanobyk 3650
1% Nanobyk 3651
2% Nanobyk 3651
5% Nanobyk 3651
1% Nanobyk 3652
2% Nanobyk 3652
5% Nanobyk 3652
Dosage level of additives: As supplied on TFW (total formulation weight)
10 Cycles Crockmeter Test 9 MIC polishing paper
NANOBYK
3650 NANOBYK
3651 NANOBYK
3652
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Scratch resistance improvement 2K- Coating Metallic
Control with NANOBYK-3652
10 Cycles
Crockmeter Test
9 MIC polishing
paper
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results 2K- Coating Black
27%
80%
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
Glo
ss R
ete
nti
on
[%
]
Control
1% Nanobyk 3650
2% Nanobyk 3650
5% Nanobyk 3650
1% Nanobyk 3651
2% Nanobyk 3651
5% Nanobyk 3651
1% Nanobyk 3652
2% Nanobyk 3652
5% Nanobyk 3652
Dosage level of additives: As supplied on TFW (total formulation weight)
10 Cycles Crockmeter Test 9 MIC polishing paper
NANOBYK
3650 NANOBYK
3651 NANOBYK
3652
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results 2K- Coating White
25%
85%
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
Glo
ss R
ete
nti
on
[%
]
Control
1% Nanobyk 3650
2% Nanobyk 3650
5% Nanobyk 3650
1% Nanobyk 3651
2% Nanobyk 3651
5% Nanobyk 3651
1% Nanobyk 3652
2% Nanobyk 3652
5% Nanobyk 3652
Crockmeter
Dosage level of additives: As supplied on TFW (total formulation weight)
NANOBYK
3650 NANOBYK
3651 NANOBYK
3652
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
NANOBYK-3610 and NANOBYK-3650 family Hardness combined with elasticity
1) Coatings with these additives show lower E-Modulus but hardness
similar to controls
NANOBYK-3610 and NANOBYK-3650 family of products provide higher coating elasticity without affecting hardness
2) They improve scratch resistance by immediate reflow without creating brittleness or downgrading other coating properties
The coating remains almost unharmed
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
NANOBYK‘s
Increased coating hardness
by incorporation of nanoparticles
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
SiO2
Acrylic functionality
Oligomeric resin
Oligomeric resin
How nano-based additives improve scratch resistance
Impact of nanoparticles on crosslinking density
Curing process
Curing process
Regular crosslinking density
Increased crosslinking density
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results – scratch resistance (15µm polishing paper Crockmeter test)
0
10
20
30
40
50
60
70
80
90
100
Glo
ss
re
ten
tio
n [
%]
Control 1% NB-3605 2% NB-3605 3% NB-3605 5% NB-3605
Gloss retention [%]
Test procedure: Applied force: 9N; polishing paper 15µm; 10 double roubs
Dosage level of additives: As supplied on TFW (total formulation weight)
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results – abrasion resistance (Taber test)
0
2
4
6
8
10
12
NANOBYK-3605
Control 2% NANOBYK-3605 10% NANOBYK-3605 20% NANOBYK-3605
Loss of weight in mg
System: Urethane acrylate (100%) Test procedure: Applied load: 500 g per wheel; 1000 revolutions; CS 10 wheels
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results – abrasion resistance (Scotch BriteTM test)
D % haze (difference between scratched and non-scratched sample)
System: Polyester Acrylate (100%)
0
10
20
30
40
50
NANOBYK-3605
Control 2% NANOBYK-3605 10% NANOBYK-3605 20% NANOBYK-3605
Test procedure: Hammer with Scotch-BriteTM pad; applied load: 1,1 kg; 10 cycles
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results – abrasion resistance (Scotch BriteTM test)
20% NANOBYK-3605 Control
After Scotch BriteTM test (5x magnification)
Test procedure: Hammer with Scotch-BriteTM pad; applied load: 1,1 kg; 10 cycles
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Application results – stain resistance
Control 20 % NANOBYK-3605
Stamping
ink
Mustard
Test results (according to DIN 68861)
Control 20% NANOBYK-
3605
Vinegar 1 0
Mustard 2 1
Ketchup 0 0
Coffee 1 0
Stamping
ink 4 2
0 = no residues, 5 = strong residues
System: Urethane Acrylate, solvent-borne
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
NANOBYK-3605
Benefits
• Reactive diluents are used to adjust the viscosity and reactivity of UV-curable systems.
• It is possible to formulate 100% UV- curable systems.
• Additional acrylic surface modification enables an increased crosslink density in the radical polymerization process with the unsaturated acrylic resin.
• Increase of coatings hardness depending on silica concentration.
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Life cycle analysis of nano-coatings VdL (German Paint Association)
What happens to nanoparticle containing
coatings, once they become damaged?
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
In 2007 the VdL (German Paint Association) started a three-fold study on the life cycle of nanoparticle containing coatings.
This study was supported by BYK, Bayer, BASF, PPG, Akzo Nobel, Wacker, and many more companies.
The question was:
What happens to nanoparticle containing coatings, once they become damaged?
The study is divided into three parts:
1) Abrasion
2) Scratching
3) UV-weathering
Life cycle analysis of nano-coatings VdL (German Paint Association)
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Life cycle analysis of nano-coatings VdL (German Paint Association)
First results are already published and were presented to the German government
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Life cycle analysis of nano-coatings VdL (German Paint Association)
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Conclusion
• Surface treated nanoparticles can increase the elasticity of coatings
• Surface treated nanoparticles can crosslink into a polymeric matrix
AND
• The incorporation of nanoparticles into coatings does not increase the number of airborne particles when the coating is abraded.
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
Thank you very much for your kind attention
European Coatings Conference “Automotive Coatings”, Berlin November 24th 2011, Dr. Michael Berkei
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