Silicone Rubbers - Properties and Applications - Hans Mueller

SILICONE RUBBER PROPERTIES AND APPLICATIONS
Johann Mller, Wacker Chemie AG, January 2011
CREATING TOMORROW'S SOLUTIONS
AGENDA Raw materials for silicone rubber Production of silicone rubber Liquid and solid silicone rubber processing crosslinking Properties of silicone rubber
Silicone rubber in comparison to other elastomers
Silicone Rubber Properties and Applications Johann Mller, Wacker- Chemie AG, January 2011
NATURAL RAW MATERIALS: SALT AND SAND Salt:
Natural NaCl production of chlorine via chloro-alkalielectrolysis

Sand: Quartz is mainly Silicondioxide SiO2; production of silicon via reduction process
RAW SILICON
Does not occur as pure element in nature Has to be gained from quartz (SiO2) in an highly energy consuming process Silicone of high purity (>99%) is needed
SiO2 + C Si + CO2
CHLORINE
Does not occur as pure element in nature Has to be gained from salt (NaCl) in a highly energy consuming process (electricity) Corrosive gas
2 NaCl + 2 H2O 2 NaOH + H2 + Cl2
CHLORINE, SILICONE AND ORGANICS: SILANES Reaction of organic chlorides with silicone metal in the MllerRochow-Process
SiCl4 MeSiCl3 Cl2
Si
Cu-cat.
Me2SiCl2 Me3SiCl
Methanol
MeCl
- H2O
Me4Si
+ HCl
DISTILLATION OF SILANES
yield approx. 98%
Me2SiCl2
in >99,9% purity
MAIN COMPONENT 1: POLYMERS
Silicon-Oxygen-Polymer: Polysiloxane (Q)

Me Me2SiCl2 Me Si Cl Me Cl H2O - HCl HO Me Si Me OH Me - H2O Me Me Si Me Me Me3SiCl HO - HCl Si Me
instead of Me (Methyl) also Ph (Phenyl) or Vi (Vinyl)
Si O
Me
Si O Me
CHEMICAL STRUCTURE OF POLYMER CHAIN
Si O Si O Si O
MQ (Methylpolysiloxane) side groups = Methyl

VMQ (Methyl-vinyl-polysiloxane) side groups = Methyl or Vinyl PVMQ (Methyl-phenyl-vinyl-polysiloxane) side groups = Methyl or Vinyl or Phenyl FVMQ (Fluorosilicone) side groups = Methyl or Vinyl or fluorinated organic groups
Si O Si O Si O
Si O Si O Si O
Si O Si O Si O
MAIN COMPONENT 2: SILICA skeleton based on oxygen and silicon, similar to quartz two main production processes:
precipitated silica
water
SiCl4
fumed silica (HDK)
thermolysis
FUMED SILICA: HOCHDISPERSE KIESELSURE (HDK)
SiCl4 + 2 H2 + O2 SiO2 + 4 HCl
burner
SiCl4 + 2 H2 + O2
SiO2 SiO2SiO2 SiO2SiO 2
protoSiO2primary molecules particles particles
aggregates
agglomerates
MIXING OF SILICONE RUBBER
Base Polymer
Active Filler (HDK)

Kneader
Custom Compound (Roll Mill)
Crosslinking System
Additives
PRODUCTION SCHEME
Si-Wafer
quartz sand
silicon
Silicon Silanes Siloxanes
fumed silica
HDK
oils
silicon polymers crosslinker
additives
silicone rubber
AGENDA
Raw materials for silicone rubber Production of silicone rubber
Liquid and solid silicone rubber processing crosslinking Properties of silicone rubber
CLASSIFICATION OF SILICONE RUBBER BY CURING TEMPERATURE AND VISCOSITY

silicon rubber
high temperature curing silicone rubber HTV
room temperature curing RTV
solid silicone rubber HCR
liquid silicone rubber LSR
two component RTV-2
one component RTV-1
peroxide cure
addition cure Pt-catalyzed
condensation cure Sn-catalyzed
condensation cure Sn-catalyzed
LIQUID SILICONE RUBBER: PROCESSING
(1) (2) (3) (4) (5)

pumps color dosage static mixer dosing unit mould
LIQUID SILICONE RUBBER: COMPONENTS Polymer + filler Crosslinker Catalyst Inhibitor A-Component Polymer + filler Pt-catalyst B-Component Polymer + filler Crosslinker
Inhibitor
LIQUID SILICONE RUBBER: KINETICS OF PT-CATALYZED CROSSLINKING REACTION torque 170 C
Pt-catalyzed reaction
Peroxid
time
ELASTOSIL LR: PREPARED FOR VARIOUS APPLICATION AREAS highly transparent electrically conductive heat resistant standard
tear resistant fast curing
non post cure
flame retardant media resistant
self adhesive
self lubricating
LIQUID SILICONE RUBBER: SUMMARY 2 component system: Crosslinking via hydrosilylation of vinyl groups of the VMQ-polymer Curing temperatures above 100 C No vulcanization at 25 C (room temperature - pot life)
Catalyst: platinum compound

Reactants are: VMQ-polymers with terminal vinyl groups (polymer)
VMQ-polymers with at least 3 Si-H-groups (crosslinker)

Pt-catalyst
SOLID SILICONE RUBBER (HCR) DELIVERY FORMS
SOLID SILICONE RUBBER: PROCESSING

Mixing of additives or mixing of 2-K products on the open mill:
Important requirements: Mills have to be cooled (not too cold in order to avoid condensation of H2O on the surface) Pt-catalyzed compounds have to be stored under cooled conditions (< 25 C) Surface of mill has to be polished
Crosslinking is done depending on production process: Extrusion: crosslinking via salt bath, steam, hot air or IRchannel (pressureless) Press vulcanization: crosslinking in presses with heating (under pressure) Injection molding
SOLID SILICONE RUBBER: Pt-CURING GRADES ELASTOSIL R plus Polymer + filler 1K Crosslinker Catalyst Inhibitor ELASTOSIL R plus Polymer + filler 2K Crosslinker Inhibitor
Catalyst - Pt1 respectively Pt2
SOLID SILICONE RUBBER: Pt-CATALYZED GRADES ELASTOSIL R plus Curing catalysed via platinum compounds 2K-grades and 1K-grades Processed at 150-170 C by injection moulding compression molding or extrusion Highest mechanical strength within the silicone elastomer family
SOLID SILICONE RUBBER: PEROXIDE CROSSLINKING

Extrusion:
Cl O Cl C O O O C Cl Cl
crosslinking temperature
> 100 C
Molding:
CH3 CH3 O
C
CH3
165 - 190 C
CH3 CH3 H3C C O O CH3
CH3 O O
CH3 C CH3 CH3
C CH2 CH2 C CH3
170 - 190 C
CH3
CH3
LIQUID SILICONE RUBBER: KINETICS OF PT-CATALYZED CROSSLINKING REACTION torque 170 C
platinum cure
Peroxid
time
SOLID SILICONE RUBBER: KINETICS OF CROSSLINKING torque 170 C
platinum cure
peroxide cure
time
SOLID SILICONE RUBBER: PEROXIDE CURING GRADES ELASTOSIL R Curing through organic radicals by peroxide (E, C1, C6) decomposition Processed at 160-190 C by compression molding or injection moulding or extrusion Very high mechanical strength
POSTCURING OF SILICONE RUBBER ARTICLES

Recommendations for thermal post-treatment of vulcanisates Use of enough fresh air: 120 l per kg and min Duration: 4 hours at 200C (> 4 mm: + 2h/mm) Loose packing of articles Do not mix peroxide and Pt-cured articles Reasons for postcuring:
Minimization of peroxide decomposition products (not in case of Pt-cure)

Decomposition of excess crosslinker components Optimization of physical properties
Minimization of volatiles
SOLID OR LIQUID SILICONE RUBBER? liquid silicone

Advantage: Short cycle time (low viscosity, high vulcanization speed) Fully automized process Molds with up to 128 cavities Possibility of producing articles with complex geometry 2-component-injection molding No reworking (no flash etc.)
solid silicone
Advantage: Better physical properties of products Higher flexibility in processing Molding Extrusion Calendaring Assembly
PEROXIDE OR Pt-CATALYZED CROSSLINKING? Pt-(addition-)cure

Advantage: Fast crosslinking
peroxide cure
Advantage: Not sensible towards catalyst poisons Unlimited storage time for compounds
No by-products from crosslinker (BfR, FDA, KTW, medical)

High transparency Dry surface Better physical properties (tear resistance, elasticity, etc.)
AGENDA
PROPERTIES OF SILICONE RUBBER
PROPERTIES OF SILICONE RUBBER DERIVATION FROM STRUCTURE OF POLYMER

Inorganic, fully saturated backbone High bonding energy: Si-O 451 kJ/mol (for comparison C-C 352 kJ/mol) Low surface energy, organic side groups shield backbone High flexibility of chains
Excellent high temperature resistance and low temperature flexibility High resistance towards chemicals and environmental influences
Water and dirt repellant surface

Silicone Rubber A Properties General Introduction and Applications Johann Dr. Jrgen Mller, Ismeier, WackerWacker Chemie Chemie AG, AG, January Wacker Academy 2011 29.11.2010, Slide 49
PROPERTIES OF SILICONE RUBBER DERIVATION FROM STRUCTURE OF POLYMER AND FILLER

High similarity of structure of polymer and filler Polymer and filler contain only Si, O, C and H
High transparency
Good mechanics due to effective polymer-filler-interaction

Good flame retardant properties, in case of combustion only non-toxic combustion products
TYPICAL MECHANICAL PROPERTIES OF SILICONE RUBBER Specific gravity Hardness Tensile strength at break Elongation at break Tear resistance (ASTM D 624) Compression set (175C, 22 h) 1.05-1.35 g/cm 3-90 Shore A 5-11 N/mm 100-900 % 5-50 N/mm 10-25 %
Rebound resilience
20-70 %
PROPERTIES OF SILICONE RUBBER

Broad range of usage temperature from -50 C up to +250 C (special grades -110 C up to +300 C) Almost no change of properties between 0 C and 150 C Electrically isolating to semi-conductive Resistant to radiation, ageing and weathering Transparent, easily pigmentable Excellent compression set
Neutral taste and smell (a lot of grades comply with regulations of BfR and FDA)
Easy processing
AGENDA
SILICON RUBBER IN THE WORLD OF ELASTOMERS
RUBBER CLASSIFICATION
price
1 % vol. 10 % turnov. Speciality Elastomers: CR, NBR, EP(D)M, (X)IIR 17 % volume 30 % turnover General Purpose Elastomers: NR, BR, SBR 82 % volume 60 % turnover
High Performance Elastomers FKM HNBR MVQ, PMVQ, FMVQ (E)CO EVM, AEM, ACM CSM
volume
HEAT- AND OIL-RESISTANCE (ACCORDING TO ASTM-D 2000/SAE J 200)

250
FPM FKM
200 heat resistance* (C)

80% VA
FVMQ HT-ACM
MVQ VMQ
150
44% ACN HNBR 34% ACN HNBR 48% ACN
ACM ACM
AEM
EVM
40% VA
EPDM EPDM
NBR NBR
CO/ECO
18% ACN
CM/CSM
IIR
100
CR
SBR SBR BR BR NR NR
50 10 20 30
* temperature at which after 1000 hours, 50 % of initial elongation at break are retained
40 80 100 120 140 60 maximum swelling in oil IRM 903 (%)
no requirements
LOW TEMPERATURE FLEXIBILITY AND HEAT RESISTANCE

0 low temperature flexibility TR (C) according to DIN 53520
ACM ACM EVM CM/CSM HNBR HNBR AEM NBR ECO CO/ECO
IIR
EPDM FVMQ
FKM
-20
CR CR
-40
NR
SBR SBR
-60
BR BR VMQ
-80 60
80
100
120
140
160
180
200
220
240
260
* temperature at which after 1000 hours, 50 % of initial elongation at break are retained
heat resistance* (C)
SUMMARY OF PHYSICAL PROPERTIES

NR BR SBR EPDM IIR CR NBR CSM/CM ACM EVM AEM ECO/CO VMQ HNBR FKM FVMQ
heat resistance low temperature flexibility oil resistance fuel resistance ozone-/weathering resistance mechanical properties (23 C) mechanical properties (100 C) tear resistance abrasion resistance low temperature C.S. (-20 C) high temperature C.S. (120 C) gas impermeability processing prics Rating (all properties except price) excellent fair weak price low medium high
SILICONE RUBBER APPLICATIONS
Sports and Fashion Others
Electrical Energy T&D, Cable
10% 10%
Automotive
20% 20%
Electronics Photonics Solar
Silicone Elastomer 25% 25% Market 2009 1.8 BN EUR*

15% 15%
10% 10%
20% 20%
Household Machinery Sanitary
Medical and Health Care Baby Care
* Source: WACKER estimates

THANK YOU FOR YOUR ATTENTION!

Silicone Rubbers - Properties and Applications - Hans Mueller

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SILICONE RUBBER PROPERTIES AND APPLICATIONS

Johann Mller, Wacker Chemie AG, January 2011

CREATING TOMORROW'S SOLUTIONS

Silicone rubber in comparison to other elastomers

Silicone rubber in comparison to other elastomers

NATURAL RAW MATERIALS: SALT AND SAND Salt:

Natural NaCl production of chlorine via chloro-alkalielectrolysis

2 NaCl + 2 H2O 2 NaOH + H2 + Cl2

yield approx. 98%

Silicone rubber in comparison to other elastomers

MAIN COMPONENT 1: POLYMERS

Silicon-Oxygen-Polymer: Polysiloxane (Q)

CHEMICAL STRUCTURE OF POLYMER CHAIN

MQ (Methylpolysiloxane) side groups = Methyl

FUMED SILICA: HOCHDISPERSE KIESELSURE (HDK)

SiCl4 + 2 H2 + O2 SiO2 + 4 HCl

SiO2 SiO2SiO2 SiO2SiO 2

protoSiO2primary molecules particles particles

MIXING OF SILICONE RUBBER

Active Filler (HDK)

Custom Compound (Roll Mill)

Silicon Silanes Siloxanes

silicon polymers crosslinker

CLASSIFICATION OF SILICONE RUBBER BY CURING TEMPERATURE AND VISCOSITY

high temperature curing silicone rubber HTV

room temperature curing RTV

solid silicone rubber HCR

liquid silicone rubber LSR

two component RTV-2

one component RTV-1

addition cure Pt-catalyzed

addition cure Pt-catalyzed

addition cure Pt-catalyzed

condensation cure Sn-catalyzed

condensation cure Sn-catalyzed

LIQUID SILICONE RUBBER: PROCESSING

(1) (2) (3) (4) (5)

pumps color dosage static mixer dosing unit mould

LIQUID SILICONE RUBBER: KINETICS OF PT-CATALYZED CROSSLINKING REACTION torque 170 C

tear resistant fast curing

non post cure

flame retardant media resistant

Catalyst: platinum compound

VMQ-polymers with at least 3 Si-H-groups (crosslinker)

SOLID SILICONE RUBBER (HCR) DELIVERY FORMS

SOLID SILICONE RUBBER: PROCESSING

Catalyst - Pt1 respectively Pt2

SOLID SILICONE RUBBER: PEROXIDE CROSSLINKING

CH3 CH3 H3C C O O CH3

CH3 C CH3 CH3

C CH2 CH2 C CH3

LIQUID SILICONE RUBBER: KINETICS OF PT-CATALYZED CROSSLINKING REACTION torque 170 C

SOLID SILICONE RUBBER: KINETICS OF CROSSLINKING torque 170 C

POSTCURING OF SILICONE RUBBER ARTICLES

Minimization of peroxide decomposition products (not in case of Pt-cure)

SOLID OR LIQUID SILICONE RUBBER? liquid silicone

PEROXIDE OR Pt-CATALYZED CROSSLINKING? Pt-(addition-)cure

No by-products from crosslinker (BfR, FDA, KTW, medical)

PROPERTIES OF SILICONE RUBBER

PROPERTIES OF SILICONE RUBBER DERIVATION FROM STRUCTURE OF POLYMER

Water and dirt repellant surface

PROPERTIES OF SILICONE RUBBER DERIVATION FROM STRUCTURE OF POLYMER AND FILLER

Good mechanics due to effective polymer-filler-interaction