40 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
AGENDA
processing
crosslinking

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
Si
Cl2
Cu-cat.
Me2SiCl2
Me3SiCl
Methanol
+ HCl
MeCl
Me4Si
- H2O

DISTILLATION OF SILANES
yield approx. 98%
Me2SiCl2
in >99,9% purity

AGENDA
processing
crosslinking

MAIN COMPONENT 1: POLYMERS

Silicon-Oxygen-Polymer: Polysiloxane (Q)
Me
Me2SiCl2
Me
Cl
Si
Cl
Me
Si
H2O
OH
Me
Si
- HCl
HO
Me
- H2O
Me
Si
O
Me
Me
Si
Me
Me3SiCl HO
Si
Me
Me
Me
- HCl
Me
instead of Me (Methyl)
also Ph (Phenyl)
or Vi (Vinyl)

CHEMICAL STRUCTURE OF POLYMER CHAIN
Si O Si O Si O
MQ (Methylpolysiloxane)
side groups = Methyl
Si O Si O Si O
VMQ (Methyl-vinyl-polysiloxane)
side groups = Methyl or Vinyl
Si O Si O Si O
PVMQ (Methyl-phenyl-vinyl-polysiloxane)
side groups = Methyl or Vinyl or Phenyl
Si O Si O Si O
FVMQ (Fluorosilicone)
side groups = Methyl or Vinyl or
fluorinated organic groups
MAIN COMPONENT 2: SILICA

skeleton based on oxygen and
silicon, similar to quartz
two main production processes:
water
precipitated
silica
SiCl4
thermolysis
fumed silica
(HDK)

FUMED SILICA:
HOCHDISPERSE KIESELSURE (HDK)
SiCl4 + 2 H2 + O2 SiO2 + 4 HCl
burner
SiCl4 +
2 H2 + O 2
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
processing
crosslinking

CLASSIFICATION OF SILICONE RUBBER

BY CURING TEMPERATURE AND VISCOSITY
silicon
rubber
high
temperature
curing silicone
rubber HTV
solid
solidsilicone
silicone
rubber
rubber
HCR
HCR
peroxide
peroxidecure
cure
liquid silicone
rubber
LSR
addition
additioncure
cure
Pt-catalyzed
Pt-catalyzed
addition cure
Pt-catalyzed
room
temperature
curing RTV
two component
RTV-2
addition cure
Pt-catalyzed
condensation
cure
Sn-catalyzed
one
component
RTV-1
condensation
cure
Sn-catalyzed

LIQUID SILICONE RUBBER:

PROCESSING
(1)
(2)
(3)
(4)
(5)
pumps
color dosage
static mixer
dosing unit
mould


COMPONENTS
Polymer + filler
Crosslinker
Catalyst
Inhibitor
A-Component
B-Component
Polymer + filler
Polymer + filler
Pt-catalyst
Crosslinker
Inhibitor

KINETICS OF PT-CATALYZED CROSSLINKING REACTION
torque
170 C
Pt-catalyzed reaction
Peroxid
time
ELASTOSIL LR:
PREPARED FOR VARIOUS APPLICATION AREAS
highly
transparent
tear resistant
electrically
conductive
fast curing
standard
heat resistant
non post cure
self adhesive
flame retardant
media resistant
self lubricating


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

Pt-CURING GRADES ELASTOSIL R plus
Polymer + filler
Crosslinker
1K
Catalyst
Inhibitor
2K
ELASTOSIL R plus
Catalyst
Polymer + filler
- Pt1 respectively Pt2
Crosslinker
Inhibitor

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


PEROXIDE CROSSLINKING
Extrusion:
crosslinking temperature
Cl
Cl
Cl
> 100 C
Cl
Molding:
CH3
C
CH3
O
CH3
CH3
H3C
CH3
CH3
CH3
165 - 190 C
CH3
C CH2 CH2 C
CH3
CH3
CH3
O
CH3
170 - 190 C
CH3


KINETICS OF PT-CATALYZED CROSSLINKING REACTION
torque
170 C
platinum cure
Peroxid
time

KINETICS OF CROSSLINKING
torque
170 C
platinum cure
peroxide cure
time

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
solid silicone
Advantage:
Advantage:
Short cycle time (low viscosity, high

vulcanization speed)
Better physical properties of

products
Fully automized process
Higher flexibility in processing

Molding
Extrusion
Calendaring
Assembly
Molds with up to 128 cavities

Possibility of producing articles with
complex geometry
2-component-injection molding
No reworking (no flash etc.)

PEROXIDE OR Pt-CATALYZED CROSSLINKING?

Pt-(addition-)cure
peroxide cure
Advantage:
Advantage:
Fast crosslinking
Not sensible towards catalyst

poisons
No by-products from crosslinker

(BfR, FDA, KTW, medical)
High transparency
Unlimited storage time for

compounds
Dry surface
Better physical properties (tear
resistance, elasticity, etc.)

AGENDA
processing
crosslinking

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
CH
Si
CH3
CH2
Si
CH3
CH3
Excellent high temperature resistance and low temperature flexibility

High resistance towards chemicals and environmental influences
Water and dirt repellant surface
Silicone Rubber A General Introduction
Silicone
Rubber
AG,
Properties
Applications
Dr. Jrgen Ismeier,
Wacker Chemie
Wacker Academyand
29.11.2010,
Slide 49

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
CH CH2
SiO2
SiO2
SiO2
Si O
Si O
CH3
CH3
CH3
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
1.05-1.35 g/cm
Hardness
3-90 Shore A
Tensile strength at break
5-11 N/mm
Elongation at break
100-900 %
Tear resistance (ASTM D 624)
5-50 N/mm
Compression set (175C, 22 h)
10-25 %
Rebound resilience
20-70 %

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
processing
crosslinking

SILICON RUBBER IN THE WORLD OF ELASTOMERS

RUBBER CLASSIFICATION
High Performance
price
Elastomers
1 % vol.
10 % turnov.
Speciality Elastomers:
CR, NBR, EP(D)M,
(X)IIR
17 % volume 30 % turnover
FKM
HNBR
MVQ, PMVQ, FMVQ
(E)CO
EVM, AEM, ACM
CSM
General Purpose Elastomers:

NR, BR, SBR
82 % volume 60 % turnover
volume
HEAT- AND OIL-RESISTANCE

(ACCORDING TO ASTM-D 2000/SAE J 200)
250
FPM
FKM
heat resistance* (C)
200
80% VA
150
MVQ
VMQ
FVMQ
HT-ACM
ACM
ACM
44% ACN HNBR

HNBR
48% ACN
34% ACN
CO/ECO
NBR
NBR
AEM
EVM
40% VA
EPDM
EPDM
CM/CSM
IIR
18% ACN
CR
100
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
low temperature flexibility

TR (C) according to DIN 53520
-20
ACM
ACM
EVM
CM/CSM
HNBR
HNBR AEM
NBR
ECO
CO/ECO
CR
CR
IIR
SBR
SBR
-40
FKM
EPDM
FVMQ
NR
-60
BRBR
-80
60
80
VMQ
100
120
* temperature at which after 1000 hours, 50

% of initial elongation at break are retained
140
160
180
200
220
240
heat resistance* (C)

260
SUMMARY OF PHYSICAL PROPERTIES

SILICONE RUBBER APPLICATIONS
Sports and Fashion

Others
10%
10%
Automotive
Electrical Energy
T&D, Cable
20%
20%
Silicone
Elastomer
25%
25%
Market 2009
1.8 BN EUR*
15%
15%
Medical and
Health Care
Baby Care
10%
10%
Electronics
Photonics
Solar
20%
20%
Household
Machinery
Sanitary
* Source: WACKER estimates

THANK YOU
FOR YOUR ATTENTION!


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SILICONE RUBBER

PROPERTIES AND APPLICATIONS

CREATING TOMORROW'S SOLUTIONS

Silicone Rubber Properties and Applications

Silicone Rubber Properties and Applications

NATURAL RAW MATERIALS: SALT AND SAND

Silicone Rubber Properties and Applications

2 NaCl + 2 H2O 2 NaOH + H2 + Cl2

Silicone Rubber Properties and Applications

CHLORINE, SILICONE AND ORGANICS: SILANES

Silicone Rubber Properties and Applications

yield approx. 98%

Silicone Rubber Properties and Applications

Silicone Rubber Properties and Applications

MAIN COMPONENT 1: POLYMERS

Silicone Rubber Properties and Applications

CHEMICAL STRUCTURE OF POLYMER CHAIN

MAIN COMPONENT 2: SILICA

Silicone Rubber Properties and Applications

SiCl4 + 2 H2 + O2 SiO2 + 4 HCl

Silicone Rubber Properties and Applications

MIXING OF SILICONE RUBBER

Silicone Rubber Properties and Applications

Silicone Rubber Properties and Applications

CLASSIFICATION OF SILICONE RUBBER

Silicone Rubber Properties and Applications

LIQUID SILICONE RUBBER:

Silicone Rubber Properties and Applications

LIQUID SILICONE RUBBER:

LIQUID SILICONE RUBBER:

non post cure

Silicone Rubber Properties and Applications

LIQUID SILICONE RUBBER:

SOLID SILICONE RUBBER (HCR)

Silicone Rubber Properties and Applications

SOLID SILICONE RUBBER:

SOLID SILICONE RUBBER:

- Pt1 respectively Pt2

SOLID SILICONE RUBBER:

Silicone Rubber Properties and Applications

SOLID SILICONE RUBBER:

Silicone Rubber Properties and Applications

LIQUID SILICONE RUBBER:

SOLID SILICONE RUBBER:

SOLID SILICONE RUBBER:

Silicone Rubber Properties and Applications

POSTCURING OF SILICONE RUBBER ARTICLES

SOLID OR LIQUID SILICONE RUBBER?

Short cycle time (low viscosity, high

Better physical properties of

Fully automized process

Higher flexibility in processing

Molds with up to 128 cavities

Silicone Rubber Properties and Applications

PEROXIDE OR Pt-CATALYZED CROSSLINKING?

Not sensible towards catalyst

No by-products from crosslinker

Unlimited storage time for

Silicone Rubber Properties and Applications

Silicone Rubber Properties and Applications

PROPERTIES OF SILICONE RUBBER

Silicone Rubber Properties and Applications

PROPERTIES OF SILICONE RUBBER