The World-Records of Silicones Innovations powered by a ...

The World-Records of SiliconesInnovations powered by a unique elastomer

Copyright © 2018 Momentive Performance Materials Inc. All rights reserved.

Dr. Markus Putzer, Oliver Franssen (speaker)

International Silicone Conference, April 10-11, 2018

The Structure of Silicone Elastomers

2 Copyright © 2018 Momentive Performance Materials Inc. All rights reserved.

Silicone crosslinker

-Si-O- building blocks:

Silicone polymer

Filler treatment

Other additives

Reinforcing filler

In May of 1940, GE research

chemist Eugene G. Rochow’s

monumental discovery of the

direct reaction process began the

journey of scientific innovation

that has led to the application of

silicones in thousands of products

that touch almost every aspect of

daily life.

Eugene Rochow‘s discovery

How It All Started

Ref.: http://www.businesswire.com/news/home/20150512005230/en/Momentive-Celebrates-75-Years-Invention#.VhJqTOztlBc


Müller-Rochow Synthesis And Polymerization


+

From sand and coal …

Si + CH3Cl (CH3)nSiCl4-n

Cu

(Metallic Silicon) (Methyl Chloride) (Methyl Chlorosilanes)

Typical Elastomer Ingredients


z

Polysiloxanes

z

R = -CH3, MQ

-CH=CH2, VMQ

-CH2-CH2-CF3, FMQ

- , PMQ

• Mechanical properties

• Media resistance

• Low temp. properties

Fumed Silica Filler SiO2

Si

O

• Composition

• Surface area

• Structure

• Surface treatment

• Reinforcement

• Hardness

• Tear Resistance

• Optical properties

Crosslinker

• Addition Cure

• UV Cure

• 1K-Addition Cure

• Peroxide Cure

• Curing temperature

• Curing speed

• Mechanical properties

e.g. Hardness

Additive Package

• Adhesion promoters• Metal oxides, salts,

Carbon black• Phenyl silicone oils• Colorants

• Adhesion to substrates• Heat resistance

• Tribology • Colour

Industry Leadership through 70 Years of Silicone Innovation

Innovations & Market “Firsts”

First “direct process”

for making

methylchlorosilanes

1940s

First silane coupling

agents for fiberglass

and composites

1950s

First non-

hydrolyzable silicone

surfactant for

polyurethane foams

1962

First construction

sealant that hardens

at room

temperature

1964

First man walks on

moon in silicone

boot soles enabled

by GE Silicones

1969

First true structural

silicone glazing for

architectural

applications

1974

First commercialized

silicone for 2-in-1

shampoo and

conditioner

1986

First silicone

polyethers

introduced for textile

treatment, laundry

softeners and

personal care

1996

First successful one-

part addition cure

technology for

adhesives and

pharmaceutical

tubing

2001

First introduction of

NXT* sulfur silane for

next generation

automobile tires

2004

First use of Silwet*

hydrolytically stable

super-spreader

silicones for in-can

pesticides

2008

75 Years of Silicone Innovation

*NXT and Silwet are trademarks of Momentive Performance Materials Inc.

1943

Peroxide vulcanization of

silicone rubber

1979

Liquid silicone rubber

175-years of vulcanization (with sulfur invented by Goodyear)


Total view / template

New Axis – Let’s Look At Silicones Differently


Highest purity

Baby pacifier

-2 cm

Highest permeability

Contact lenses

0 cm

Highest

transparency

Diving goggle

2 cm

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest viscosity

Designer part

“Ursula”

0.7 m

Best hydrophobicity

Kitchenware

1 m

Lowest compression set

Connector seals

2 m

Best weather resistance

Insulators / HVI / Solar /

Street lighting

20 m

Highest heat

application

Heat shield

40 km

Lowest temperature

flexibility

Moon boot

384*103 km

Longest distance

travelled

Mars

228*106 km

Inert inorganic polymer:

UV – no absorption

O3 – no reaction

• Clean, formulated without plasticizer, tasteless

and odorless

• No reaction

• No additives/stabilizers needed

Regulatory compliance for food, water and medical applications

is possible, e.g. USP Class VI, FDA 21 CFR 177.2600, BfR XV.


Highest Purity / Intrinsic Chemical Stability

-2 cm

Highest purity

Baby pacifier

Pictures: Momentive Performance Materials

• Open space in network /

compressibility

• High freedom of polymer chain

motion

• High solubility of penetrant

• High diffusivity of penetrant

=> High gas permeability

9

1) https://imageserv5.team-logic.com/mediaLibrary/99/D116_20Haibing_20Zhang_20et_20al.pdf; Haibing Zhang, Ph.D., Andy Cloud (2006)

2) http://www.cchem.berkeley.edu/dtlgrp/papers/DL1.pdf; Rutherford et al. (2007); Polymer 48 (2007) 6719-6727

Picture: Momentive Performance Materials


Highest Permeability – Barrier Properties

Highest purity

Baby pacifier

-2 cm 0 cm


Contact lenses

Material O2 Permeability

[Barrer]3

IIR (Butyl-rubber)1) 1.4

EPDM2) 8.8

NR1) 24

Nitrile-rubber1) 85

FVMQ1) 110

VMQ1) 6003) Barrer = 10-10 cm3*cm/(s*cm2*cm Hg) at 30 °C

https://imageserv5.team-logic.com/mediaLibrary/99/D116_20Haibing_20Zhang_20et_20al.pdf

http://www.cchem.berkeley.edu/dtlgrp/papers/DL1.pdf


Highest Permeability – Application: Contact Lenses

0

50

100

150

200

250

300

350

20 30 40 50 60 70 80 90

Pe

rme

ab

ility

Dk

% Siloxane

O2 Permeability vs Siloxane Content

Ref.: http://www.optometry.co.uk/uploads/articles/CET%20290110%202%20POINT.pdf

Gas permeable contact lenses

frequently contain silicone to impart

superior oxygen permeability.

• PDMS polymers are highly

transparent to visible light

• Pyrogenic silica with different RI

scatters light

• Other fillers found with same RI

Ultraclear elastomers possible

New application areas in

consumer goods and LED


Highest Transparency

Highest purity

Baby pacifier

-2 cm 0 cm


Contact lenses

Highest

transparency

Diving goggle

2 cm

Pictures: Cressi Sub, Momentive Performance Materials

Test data. Actual results may vary

Innovative lighting applications

need cutting edge materials.

• High Transparency over a wide range of wavelengths

• Isotropic optical properties, no birefringence

• Low chromatic aberration

• Low thermo-optical coefficient

• High resistance to micro-cracking

• Temperature resistance from -40 °C up to > 150 °C

• High resistance against rapid climatic changes

• High resistance against ozone and strong UV-light

• Freedom of design

• High-precision molding of microstructured surfaces

• Highly efficient and automated injection molding process

Objectives

12* Silopren is a trademark of Momentive Performance Materials Inc. and/or its affiliates.


Ultra Clear Silopren* Silicone Elastomers

Typical properties are average data and are not to be used as or to develop specifications.

• Very low intermolecular forces

• High flexibility of chains

• Selective linking of endgroups possible

• Chain extension option

Range of LSR Hardness: 5-90 Shore

Application example: coupling pad of

automotive driver assistance camera


Lowest Hardness Without Plasticizer

Highest purity

Baby pacifier

-2 cm 0 cm


Contact lenses

Highest

Transparency

Diving goggle

2 cm

Picture: Kostal

Softest elastomer

Transparent sensor

coupling pad

0.5 m

Rubber Hardness

NR 30-95

BR 45-80

SBR 30-95

HNBR 30-95

EP/EPDM 30-90

FKM 50-95

ACM 40-90Test data. Actual results may vary

• Very low viscosity with limited

temperature dependency

• Excellent pumpability of LSR

(optimized filler coating)

• Shear thinning, easier material flow

under stress

• Enables very long flow length and/or

thin wall thickness without scorch

• Application Example: Bottlenet “Ursula”


Lowest Viscosity

Highest purity

Baby pacifier

-2 cm 0 cm


Contact lenses

Highest

Transparency

Diving goggle

2 cm

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest viscosity

Designer part

“Ursula”

0.7 m

Pictures: CVA Silicone, Sigma Engineering, Momentive Performance Materials

15

Material Selection with Sigmasoft† Virtual Molding

Part fills completelyPart only fills to approx. 90%

Material 2: Silopren* LSR 2670Material 1: LSR 70 Shore A

† Sigmasoft is a trademark of MAGMA Gießereitechnologie GmbH.

Simulation data in cooperation with Sigma Engineering, CVA Silicone, Momentive Performance Materials

*Silopren is a trademark of Momentive Performance Materials Inc.


• Only low polarity side-groups (CH3) on

the surface

• Easy rearrangement of surface groups

after wetting

• Hydrophobicity transfer and recovery

• Typical contact angle of

silicone elastomers: >100 °


Best Hydrophobicity

Highest purity

Baby pacifier

-2 cm 0 cm


Contact lenses

Highest

Transparency

Diving goggle

2 cm

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest Viscosity

Designer part

“Ursula”

0.7 m

Best hydrophobicity

Kitchenware

1 m

Pictures: Momentive Performance Materials

Contact angle

Adhesiveness

Wettability

Solid surface free energy

θ θ

high

poor

poor

low

low

good

good

high

high

poor

poor

low

Hydrophobic Hydrophilic



Lowest Compression Set

Highest purity

Baby pacifier

-2 cm 0 cm


Contact lenses

Highest

Transparency

Diving goggle

2 cm

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest Viscosity

Designer part

“Ursula”

0.7 m

Best hydrophobicity

Kitchenware

1 m


Connector seals

2 m

Compression set scheme: http://korzet.info/2017/Compression-Set.html

Picture: Momentive Performance Materials

CS(%) = (H0 − H2)/(H0 −H1) × 100 %

0

20

40

60

80

100

0 500 1000

CS in

%

hours at 175 °C exposure

Compression set

Low CS LSR

Improved CS LSR

Ultra low CS LSRRubber at the free state Rubber compressed by 25% Resuming position of the elastomer

to the free state

http://korzet.info/2017/Compression-Set.html


Best Weather Resistance

Highest purity

Baby pacifier

-2 cm


Contact lenses

0 cm

Highest

Transparency

Diving goggle

2 cm

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest Viscosity

Designer part

“Ursula”

0.7 m

Best hydrophobicity

Kitchenware

1 m


Connector seals

2 m 20 m

Test site: Atlas Materials Testing Technology LLC

• Avg. high temp.: 34°C (summer), 26°C (winter)

Avg. low temp.: 23°C (summer), 13°C (winter)

• Avg. rel. humidity: 78 %

• Total UV (295–385 nm): 280 MJ/m2



Street lighting

Overall durability ratings after 22 years of real Florida exposure1:

1) Errol D. Bull and Gary M. Lucas; Journal of ASTM International, Vol. 6, No. 4 Paper ID JAI101946, available online at www.astm.org

Ratings:

3 = Excellent

2 = Good

1 = Poor


Best Weather Resistance

Test Conditions:

Xenon-arc weatherometer (XAW) with 0.55 W/m² at 340 nm (Volkswagen PV3930, 45,000 hrs corresponds to

approx. 28 year real Florida outdoor weathering). Measurement of Yellowing Index according to ASTM E313.

0

0,5

1

1,5

2

2,5

3

0 5000 10000 15000 20000 25000 30000 35000 40000 45000 50000 [h] at exposure

sample 1 Silicone

sample 2 Silicone

sample 1 EVA

sample 2 EVA

YI standardized laminate material between optiwhite glass after storage at Florida

conditions (thickness of material about 0,15 mm)

X (Delamination)

Test samples under accelerated weathering conditions:


• Heat shield sleeves for the two nozzles of the Ariane 5

boosters

• Gasket production using LSR injection molding

• External diameter of 1.75 meters / weight of almost 60 kg

• Has withstood temperatures of up to 3000 ºC for a period

of two minutes.


Highest Heat Application

Highest purity

Baby pacifier

-2 cm 0 cm


Contact lenses

Highest

Transparency

Diving goggle

2 cm

Pictures: Momentive Performance Materials, Arianespace

Ref: press release Momentive Leverkusen Oct 2007

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest Viscosity

Designer part

“Ursula”

0.7 m

Best hydrophobicity

Kitchenware

1 m


Connector seals

2 m



Street lighting

20 m

Highest heat

application

Heat shield

40 km

• Low rotational barrier of chains

• Remains elastic where organic

rubbers turn brittle

• Little change of physical properties

at low temperature

• Some grades perform below -100 °C

• NMR studies at -196 °C (liquid N2)

show clearly significant freedom of

rotation and vibration

Application example: moon boot

21

Lowest Temperature Flexibility

Highest purity

Baby pacifier

-2 cm


Contact lenses

0 cm

Highest

Transparency

Diving goggle

2 cm

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest Viscosity

Designer part

“Ursula”

0.7 m

Best hydrophobicity

Kitchenware

1 m


Connector seals

2 m



Street lighting

20 m

Highest heat

application

Heat shield

40 km

Lowest temperature

flexibility

Moon boot

384*103 km


Pictures: www.nasa.gov, GE Silicones, now part of Momentive

http://www.nasa.gov/


The Longest Distance Travelled

Highest purity

Baby pacifier

-2 cm


Contact lenses

0 cm

Highest

Transparency

Diving goggle

2 cm

Softest Elastomer

Transparent sensor

coupling pad

0.5 m

Lowest Viscosity

Designer part

“Ursula”

0.7 m

Best hydrophobicity

Kitchenware

1 m


Connector seals

2 m

Best weatherability

Insulators / HVI /

Solar / Street lighting

20 m

Highest heat

application

Heat shield

40 km

Lowest temperature

flexibility

Moon boot

384*103 km

Longest distance

travelled

Mars

228*106 km

Pictures: www.nasa.gov

http://www.nasa.gov/

DISCLAIMER: THE MATERIALS, PRODUCTS AND SERVICES OF MOMENTIVE PERFORMANCE MATERIALS INC. AND ITS SUBSIDIARIES AND AFFILIATES DOING BUSINESS

IN LOCAL JURISDICTIONS (COLLECTIVELY “SUPPLIERS”) ARE SOLD BY THE RESPECTIVE LEGAL ENTITY OF THE SUPPLIER SUBJECT TO SUPPLIERS’ STANDARD CONDITIONS

OF SALE, WHICH ARE INCLUDED IN THE APPLICABLE DISTRIBUTOR OR OTHER SALES AGREEMENT, PRINTED ON THE BACK OF ORDER ACKNOWLEDGMENTS AND

INVOICES, AND AVAILABLE UPON REQUEST. ALTHOUGH ANY INFORMATION, RECOMMENDATIONS, OR ADVICE CONTAINED HEREIN IS GIVEN IN GOOD FAITH,

SUPPLIERS MAKE NO WARRANTY OR GUARANTEE, EXPRESS OR IMPLIED, (I) THAT THE RESULTS DESCRIBED HEREIN WILL BE OBTAINED UNDER END-USE CONDITIONS,

OR (II) AS TO THE EFFECTIVENESS OR SAFETY OF ANY DESIGN INCORPORATING SUPPLIERS’ PRODUCTS, MATERIALS, SERVICES, RECOMMENDATIONS OR ADVICE.

AFOREMENTIONED EXCLUSIONS OR LIMITATION OF LIABILITY ARE NOT APPLICABLE TO THE EXTENT THAT THE END-USE CONDITIONS AND/OR INCORPORATION

CONDITIONS CORRESPOND TO THE RECOMMENDED CONDITIONS OF USE AND/OR OF INCORPORATION AS DESCRIBED BY SUPPLIER IN ITS PRODUCT DATA SHEET

AND/OR PRODUCT SPECIFICATIONS. EXCEPT AS PROVIDED IN SUPPLIERS’ STANDARD CONDITIONS OF SALE, SUPPLIERS AND THEIR REPRESENTATIVES SHALL IN NO

EVENT BE RESPONSIBLE FOR ANY LOSS RESULTING FROM ANY USE OF ITS MATERIALS, PRODUCTS OR SERVICES DESCRIBED HEREIN. Each user bears full responsibility

for making its own determination as to the suitability of Suppliers’ materials, services, recommendations, or advice for its own particular use. Each user must

identify and perform all tests and analyses necessary to assure that its finished parts incorporating Suppliers’ products, materials, or services will be safe and

suitable for use under end-use conditions. Nothing in this or any other document, nor any oral recommendation or advice, shall be deemed to alter, vary,

supersede, or waive any provision of Suppliers’ Standard Conditions of Sale or this Disclaimer, unless any such modification is specifically agreed to in a writing

signed by Suppliers. No statement contained herein concerning a possible or suggested use of any material, product, service or design is intended, or should

be construed, to grant any license under any patent or other intellectual property right of Suppliers or any of its subsidiaries or affiliates covering such use or

design, or as a recommendation for the use of such material, product, service or design in the infringement of any patent or other intellectual property right.

Momentive and the Momentive logo are trademarks of Momentive Performance Materials Inc.

*NXT, Silwet and Silopren are trademarks of Momentive Performance Materials Inc. and/or its affiliates.


Thank You – Time For Questions

Oliver Franssen

Global Marketing Director

Elastomers – Transportation

Momentive Performance Materials GmbH

Building R20

51368 Leverkusen

Germany

T +49 6187 932327

C +49 173 650 2386

F +49 6187 932328

[email protected]

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