Post on 01-Sep-2018
“Sílica pirogênica hidrofóbicaAEROSIL® e silano organofuncional Dynasylan® como aditivos de alta performance em adesivos para aplicação em compósitos”
Thalita BacciSão Paulo, 9 de Novembro de 2016
1. Company profile
2. Evonik’s Fumed Silica Technologies
3. Fumed Silica in Adhesives and Sealants
4. Evonik’s Organofunctional SilaneTechnologies
5. Silane Monomers vs. Silane Oligomers
6. VPS 7163New adhesion promoter for critical metals and plastics
7. Benefits at a Glance
Page | 2
Public |
Evonik – a modern structure
Page 3
Evonik
Segments
Specialty Chemicals Segments/GmbH
Nutrition & Care
Resource Efficiency
Performance Materials Services
Corporate /Other
� AdministrativeServices
� Technology & Infrastructure
� Corporate Center
� Strategic R&D
Business Lines:
� Personal Care
� Household Care
� Comfort & Insulation
� Interface & Performance
� Baby Care
� Health Care
� Animal Nutrition
Business Lines:
� Active Oxygens
� Catalysts
� Coating & Additives
� Coating & Adhesive Resins
� Crosslinkers
� High Performance Polymers
� Oil Additives
� Silanes
� Silica
Business Lines:
� Performance Intermediates
� Agrochemicals & Polymer Additives
� Functional Solutions
� Acrylic Monomers
� Acrylic Polymers
� CyPlus Technologies
Public |
Silanes
Se
gm
en
t
Catalysts
Bu
sin
es
sL
ine
s
Silanes, a strong pillar within Resource Efficiency
Silica
Active Oxygens
Coating & Adhesive Resins
Oil Additives
High Performance Polymers
Crosslinkers
Coating Additives
Page 4
Resource EfficiencyResource Efficiency GmbH
1. Company profile
2. Evonik’s Fumed Silica Technologies
3. Fumed Silica in Adhesives and Sealants
4. Evonik’s Organofunctional SilaneTechnologies
5. Silane Monomers vs. Silane Oligomers
6. VPS 7163New adhesion promoter for critical metals and plastics
7. Benefits at a Glance
Page | 5
e.g. W 7520 N, W 7330 N
AEROSIL® 90 AEROSIL® 380,
AEROSIL® OX50, AEROSIL® TT 600
e.g. AEROSIL® MOX 80, COK 84,AEROXIDE® TiO2 P 25, Alu C,
AEROPERL® 300/30
e.g. R 7200, R 8200, R 9200
e.g. R 202, R 805, R 812 S,
R 972, R 104
Product portfolio in different dispersion media
Water, ethylene glycol, organic solvents
HydrophilicAEROSIL®
Hydrophobic AEROSIL®
Mixed Oxides,Metal OxidesGranulates
Structure modifiedAEROSIL® grades
AERODISP®
Fumed Silica
AEROSIL®: Most Versatile Product Portfolio for Adhesives & Sealants
e.g. R 711, VP R 511, VP R 604
Functionalizationof AEROSIL® grades
Page | 6
Main Effects of Fumed SilicaWithin the Adhesives & Sealants Industry
• Viscosity Control
• Thixotropy
• Yield Point
• Anti - Sag
• Anti – Settling
• Sprayability
• Reininforcement
• Bonding Strength
• Storage Stability
• Transparency
Page | 7
Surface Modification of Fumed Silica
Si-O
CH3
CH3
AEROSIL® R 974
AEROSIL® R 972
-O
Si8C H17
AEROSIL® R 805
-O
-O
-O
Si
CH 3
CH 3
CH 3
AEROSIL® R 812
-O
Si16C H33
AEROSIL® R 816
-O
-O
-O
Si
AEROSIL® R 711
-O
-O
-O
(CH2)3-O-C(O)-C(CH3)=CH2
-O ( Si- -)n
CH3
CH3
AEROSIL® R 202AEROSIL® R 208
O
Dimethyldichlorsilane Hexamethyldisilazane Methacryloxypropyltrimethoxysilane
Octyltrimethoxysilane Polysiloxane Hexadecyltrimethoxysilane
Page | 8
1. Company profile
2. Evonik’s Fumed Silica Technologies
3. Fumed Silica in Adhesives and Sealants
4. Evonik’s Organofunctional SilaneTechnologies
5. Silane Monomers vs. Silane Oligomers
6. VPS 7163New adhesion promoter for critical metals and plastics
7. Benefits at a Glance
Page | 9
Rheological Measurements
Rotational and dynamic
measurements:
• Flow and viscosity curves
• Thixotropic behaviour
• Yield point
• Viscous behaviour
• Elastic behaviour
Rheometer „Anton Paar, Physica MCR 301“
Page | 10
AEROSIL® Fumed Silica in EP Systems, Viscosity Curve and Anti-sag
10
100
1.000
10.000
100.000
Pa·s
η
0,01 0,1 1 10 1001/s
Scherrate γ.
Anton Paar GmbH
Epoxy resin
� Low viscosities at highshear rates
� Improved workability� Easier transportation
(pumping e.g.)� High viscosities at low shear rates
� High sag resistance� Excellent thickening in
various polymers
Page | 11
Shear rate
6 % AEROSIL® in Epoxy resin
AEROSIL® R 208 –Improved Thickening Efficiency
Page | 12
0 10 20 30 40 50 60 70 80 90 100
0 1000 2000 3000 4000 5000
AEROSIL® R 202
AEROSIL® R 208
Viscosity at 0.1 s-1
Model formulation: 6 % PDMS-treated Fumed Silica in Epoxy Resin Epon 828
+ 43 % + 2 % Viscosity at 100 s-1
AEROSIL® R 208 gives at lower shear rates a significant higher viscosity in Epon 828 than AEROSIL® R 202
8 % Fumed Silicain Polyol-Component for Polyurethanes
012345678910
0
100
200
300
400
500
600
700
800
900
AEROSIL®R 208
CompetitorA
CompetitorB
AEROSIL®R 202
Vis
co
sit
y a
t 1
00
s-1
[P
a s
]
Vis
co
sit
y a
t 0
.1 s
-1 [
Pa
s]
0,1 s-1
100 s-1
AEROSIL® R 208 performs excellent in polyolsPage | 13
Typical Rotor Blade Cross Section
Outer PU Gel Coat
Spar Box
Blade Shell
Balsa/Foam Core
Assembly Bonding Paste*
Laminating resins and gel coats(Epoxy, Vinyl Ester, Polyester Resin)*
AEROSIL® containing Applications / Polymers, such as Epoxies, Polyurethanes and Vinyl Ester / Polyester
Page 14
Bonding Pastes – Explanation and Use
• Large quantities of bonding pastes are used in themanufacture of wind turbine rotor blades. These bonding pastes must have good thixotropic and specific slumpproperties. That is why AEROSIL® fumed silicas are used as essential thixotropes in bonding pastes based on epoxy, polyurethane, vinyl ester and polyester resins.
• More precisely, the hydrophobic fumed silicas AEROSIL® R 202 and AEROSIL® R 208 are the most used high-performance thixotropes of choice in bonding pastes.
• The normal production procedure is to manufacture the upper and the lower shell of the rotor blade shell in separate moulds and glue them together by the bonding pastes.
Page 15
0
50
100
150
200
250
300
350
400
450
500
0 1 2 3 4 5 6 7
time (days)
Vis
cosity a
t 10 s
-1 [
mP
as]
AEROSIL® 200
AEROSIL® R 202
Storage Stability of AEROSIL® in MS-Polymer Formulations
�Hydrophobic AEROSIL®
increases the storage stability of MS-Polymer-products significantly
�Nearly constant viscosity levels are achievable with AEROSIL® R 202 over time.
* Viscosity of MS-Systems after storage at RTPage | 16
Special AEROSIL® fumed silica for transparent SMP-systems
AEROSIL® R 805, AEROSIL® R 812 S and AEROSIL® R 106 are mostly recommended for transparent hybrid products !
Page | 17
Tensile Strength of Transparent MS-Sealant With AEROSIL® Fumed Silica
0
50
100
150
200
250
300
350
1
Te
ns
ile S
tre
ng
th [
Ind
ex
= 1
00
] MS-Sealant without AEROSIL
10% AEROSIL® R 805 in MS-Sealant
10% AEROSIL® R 974 in MS-Sealant
10% AEROSIL® R 812 S in MS-Sealant
10% AEROSIL® R 202 in MS-Sealant
10% AEROSIL® R 106 in MS-Sealant
* Performance of formulation w/o AEROSIL® = Index 100
AEROSIL® improves the tensile strength of MS-Sealant significantly !
Page | 18
1. Company profile
2. Evonik’s Fumed Silica Technologies
3. Fumed Silica in Adhesives and Sealants
4. Evonik’s Organofunctional SilaneTechnologies
5. Silane Monomers vs. Silane Oligomers
6. VPS 7163New adhesion promoter for critical metals and plastics
7. Benefits at a Glance
Page | 19
What are Organofunctional Silanes? Bifunctional Molecules!
Y (CH2)nSi (OR)3
n = 0, 3
R = CH3, C2H5, (CH2)2OCH3
Y = Organofunctional group
Y (CH2)n
Si OR
OR
ORhydrolyzablenon hydrolyzable
Organofunctional group can
react with polymers, resins…
Silicon functional group
can react with inorganic
fillers, metals, glass…
Silanes combine „the organic and inorganic world“ for adhesives, sealants and silicones !
Page | 20
Mode of action of organofunctional silanes
1. Stepwise
hydrolysis Si(OR)3Y
Catalyst H+(*)
+ 3 H2O/- 3 ROHSi(OH)3
Silanetriol
3. Filmforming and interaction
with polymer matrix via Y
Polymer Matrix
2. Bonding by
condensation
Substrate
Si(OH)3 + HOY SiOY
O- x H2O
Y
SiOY
O
Silanes are used as: Primer 0.05 – 5 % in water or alcohol/water (pH = 3 - 5)
Additive 0.05 – 2 % without solvent
(*)exception: aminosilanes
Page | 21
Example for Efficient Adhesion Promotion
Lap shear of 1 comp. PU-sealants on aluminum and glass,with and without Dynasylan® Silanes
0
1
2
3
lap
sh
ea
r [N
/mm
²]
no silane Dynasylan®
GLYMO
Glass Aluminum
adhesion failure cohesion failure
PU-sealant with Dynasylan® GLYMO
PU-sealant without silane
Page 22
1. Company profile
2. Evonik’s Fumed Silica Technologies
3. Fumed Silica in Adhesives and Sealants
4. Evonik’s Organofunctional SilaneTechnologies
5. Silane Monomers vs. Silane Oligomers
6. VPS 7163New adhesion promoter for critical metals and plastics
7. Benefits at a Glance
Page | 23
Five Generations of Functional Silane Adhesion Promoters Developed by Evonik
Time
TraditionalAdhesionPromoters
Dynasylan®
AMMODAMO-T
Sophistication
1970 2014-2016
Dynasylan®
HYDROSIL‘s
OligomericAdhesionPromoters
Dynasylan®
1146
SpecialAdhesionPromoters
Dynasylan®
11891124
VPS SIVO 260VPS SIVO 280
New MultifunctionalAdhesion Promoters
AdvancedAdhesionPromoters
SIVO 202SIVO 203
Page | 24
Key Benefits
• Chemical multifunctionality within one product
• Storage stable, low viscous liquid, easy dosing
• Reduced VOC
• High flash point, no evaporation(enhanced product processability and safety)
• Better compatibility to polymers/resins
• One diffusion rate and one reactivity
• Improved film forming properties on fillers
• Excellent reactivity and surface modification
• Polymer by OECD definition
1. Better performance & low VOC content
2. Multifunctionality („two in one“!)
3. Safer handling & less environmental impact
4. Low water uptake during storage
A, B = organofunctional groupsOR = methoxy or ethoxy
Two functions = One product
A B+
R O Si
A
OR´
O Si O R´
B
OR´a b
Page | 25
Dynasylan® 1146 is a Multifunctional Silane SystemTM
Dynasylan® 1146 influence on adhesion performance? Good !
For the adhesion test, it wasapplied, washed, rinsed surfaces and cured for 14 days - ambient conditions.
� Improved adhesion on critical substrates
� Significantly improved wet adhesion
� High performance adhesives & sealants can be formulated for critical substrates
Page | 26
Dynasylan®
DAMO-TDynasylan® 1146
- 40 % !
Dynasylan® 1146 improves hydrophobicity, thus minimizes water uptake !
For this test, the hybrid sealant was stored in H2O at 23ºC
0
0,2
0,4
0,6
0,8
1
1,2
1,4
3 7 14 21 28
Storage in water [days]
Water Uptake [%]
DAMO-T
1146
Page | 27
Dynasylan® 1146 improves water resistance from a finally cured A&S
1. Company profile
2. Evonik’s Fumed Silica Technologies
3. Fumed Silica in Adhesives and Sealants
4. Evonik’s Organofunctional SilaneTechnologies
5. Silane Monomers vs. Silane Oligomers
6. VPS 7163New adhesion promoter for critical metals and plastics
7. Benefits at a Glance
Page | 28
VPS 7163 = N,N,N-Tris (3-trimethoxy-silylpropyl) triisocyanurate
Performance / technical data
• Low volatility
• High thermal stability
• Good adhesion on metal, glass, plastics
• Good crosslinker
• colorless transparent liquid
Applications
• Primer for coatings, adhesives & sealants
• Adhesion promoter for PU & silicones
• Co-adhesion promoter for SMP
• Hotmelt adhesives (e.g. EVA, PA, PU …)
• Adhesion promoter in EP, ….
Page | 29
Improved Adhesion Performance in 2 Component Polyurethane Adhesive
0 20 40 60 80 100 120
Aluminium
Stainless steel
PolystyreneVPS 7163
Dynasylan®
GLYMO
Rel. Lap Shear Performance [%]
Improved adhesion performance of VPS 7163 in Polyurethane’s !
Silane addition:1 %
Page | 30
1. Company profile
2. Evonik’s Fumed Silica Technologies
3. Fumed Silica in Adhesives and Sealants
4. Evonik’s Organofunctional SilaneTechnologies
5. Silane Monomers vs. Silane Oligomers
6. VPS 7163New adhesion promoter for critical metals and plastics
7. Benefits at a Glance
Page | 31
Benefits at a Glance
VPS 7163 act as low volatile and heat resistant adhesion
promoter and crosslinker with excellent adhesion properties
on critical substrates in PU, silicone and other systems
Page | 32
To illustrate Evonik’s efforts for green solutions for
silanes, significant less alcohol will be released upon
moisture by using oligomeric silanes (low VOC)
The high efficient adhesion promoter Dynasylan® 1146
provide additional benefits in labeling, flexibility, joint
curring and imparts excellent water shielding properties
AEROSIL® R 208 showed an outstanding rheology in
epoxy, polyurethane, SMP and other systems
AEROSIL® R 805, AEROSIL® R 812 S, AEROSIL® R 106
can be used in highly transparent adhesive and sealants
Juergen FritzManager AT Adhesives & SealantsResource Efficiency
Evonik GmbH
Untere Kanalstrasse 3
D-79618 Rheinfelden
phone: +49 7623 91-8592
fax: +49 7623 91-8571
juergen.fritz@evonik.com
Thalita BacciEvonik Resource
Efficiency GmbH
EVONIK Contacts for Dynasylan® & AEROSIL® in Adhesives & Sealants
Page | 33
Renato StoicovSales Manager SilanesResource Efficiency
Evonik Degussa Brasil Ltda
Alameda Campinas, 579
8º and.
01404-000 - São Paulo – SP
phone: +55 11 3146 4123
fax: +55 11 3146 4148
renato.stoicov@evonik.com
Thalita BacciSales Manager SilicasResource Efficiency
Evonik Degussa Brasil Ltda
Alameda Campinas, 579
8º and.
01404-000 - São Paulo – SP
phone: +55 11 3146 4128
fax: +55 11 3146 4148
thalita.bacci@evonik.com