“sílica pirogênica hidrofóbica aerosil® e silano ... · anton paar gmbh epoxy resin low...

“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

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

Resource EfficiencyResource Efficiency GmbH

1. Company profile







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







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

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.

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 812 S 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







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

1. Company profile







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







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







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

[email protected]

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

[email protected]

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

[email protected]

“sílica pirogênica hidrofóbica aerosil® e silano ... · anton paar gmbh epoxy resin low...

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