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Volume 7, June 2012

03| 2012

Silicone elastomers

Winning against functional competition

The success story of silicones

O. Franssen, H. Bayerl* In the global elastomers market, silicone elastomers continue to be a niche with approximately 1.5 % of the global demand in rubber. However silicones grow faster than many industries and economies. Due to megatrends including aging population, for healthcare applications, environmental awareness in automotive and energy or consumer perception and legislation for example in consumer good applications. While silicones have an almost universal set of physical properties for rubber applications, based on material cost considerations they are often not immediately selected - instead of judging by system costs. Successful silicone elastomer applications can be achieved, when engineers understand the silicone product features and creatively apply their benefits for new applications and designs. This paper will help to position silicone elastomers vs. functionally competing materials including rubber materials like FKM, ACM, EPDM or natural rubber and metal in a spring or thermoplastics and glass in optical applications. Examples show how specific properties of silicone elastomers lead to successful new applications winning against functional competition.

optimum material selection for all individual needs. When many different properties are important at the same time and in the same product, there is a good chance that a silicone elastomer is a suitable choice for the application.

3. Markets for silicone applications

The main market areas for silicone elastomers are: Transportation (automotive, aviation, aerospace, railway, and marine) Energy (high voltage insulation, wire and cable) Consumer goods (E&E, baby care, kitchenware and other) Healthcare. Within those market segments a variety of specialized formulations have been developed which often add value vs. standard elastomers. Examples include: Self-bonding formulations with primerless adhesion to many plastic and metal substrates Self-lubricating LSR which exude a bleeding oil to ease assembly Antimicrobial silicone elastomers for healthcare applications Conductive compounds for energy applications High transparent silicone rubber for optical applications
Fig. 1: Global rubber market 2011
Silicone elastomers 0.3 million t Synthetic rubber 14.4 million t Natural rubber 11.2 million t

1. Overview on elastomers
In comparison to the global rubber market, silicone elastomers continues to play a niche role and represent only approximately 1.5 % of the global elastomers market [1, 2] (g. 1). Due to their -Si-O- backbone, silicones are considered as inorganic elastomers as opposed to all other synthetic elastomers and natural rubber which are based on a C-C- backbone. This difference is root cause reason for the various single advantages and disadvantages of silicone elastomers against their functional competitors (g. 2).

2. Positioning
The ASTM D 2000 was created to make elastomeric materials easier to specify and to standardize for a variety of properties and specifications. Plotting typical performance of standard elastomers in the dened classes on heat-stability and oilresistance, the position of silicones vs. organic elastomers is visualized. The oil-swell test differentiates the elastomers more or less by polarity (and their capability to handle unipolar media such as oils, grease or fuel). The heat-resistant position is often a consequence of double-bonds (to the low end) or strong bonding energies (on the high end) (g. 3). A universal elastomer does not exist. Ideal properties like the dynamic exibility and strength of NR, the barrier properties of BR or FKM, the heat-stability and acid resistance of FKM, the low temperature performance and stable physical properties of silicone (VMQ)

* Oliver Franssen, [email protected], Global Marketing Director Elastomers Transportation Heiko Bayerl, Marketing Manager Elastomers Automotive Europe Momentive Performance Materials GmbH, Leverkusen, Germany Paper, Silicone Elastomers 2012, 27 28 March 2012, Berlin, Germany Smithers Rapra, Shawbury, Shrewsbury, Shropshire, UK

can not be realized in one rubber product. However, certain design changes and optimization on critical properties of an application often open a window for material alternatives. Silicone elastomers are not the

25.9 million t in 2011

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4. Winning against functional competition

The decision drivers for new rubber material can be grouped under these headlines: 4.1 Integration of functionality Example: A new part design is based on two-component molding. It saves the manufacturing and assembly of seals or dampening elements as well as assembly mistakes. LSR is available in self-bonding formulations and is compatible in cycle time to molding of many engineering thermoplastics. In many cases LSR can outperform lower cost organic elastomer materials. 4.2 Specication limits Example: Globalization drives part and system specifications to wider application windows. In the transportation sector, functionality has to be maintained at very low and relatively high temperatures (from starting the engine at 40 C to full speed performance on German motorway). Here, the engineers need elastomers which are exible far below freezing point and
Fig. 2: The structure of silicones

have a good heat resistance for under the hood applications, preferably with little change of mechanical properties. Silicone elastomers are the only available products for this range. 4.3 Lower system costs Example: Classical rubber manufacturing is consuming a lot of machine and labor time. The amount of raw material is often much smaller than the costs for conversion, de-ashing, nal inspection plus added cost for scrap (of nal parts plus the cured material of the runner systems). Cycle times in the minute range make investment and payoff of decent automation equipment a nancial challenge. The LSR injection molding process enables fully automated, ash-less, waste-less molding with short cycle times. For those processes, material costs are the biggest share of a part calculation. For high volume part series LSR can often outperform organic elastomers. 4.4 New technologies Example: Lighting is one of the global drivers in innovation. Energy saving, CO2 reduction, and safety accelerate the transformation to LED light. The share of LED in lighting is forecasted to grow from 15 % in 2010 to 45 % in 2015, substituting traditional lighting like the historical Edison lamp [5]. The light power of LEDs is developing rapidly, in combination with emission of strong blue light and increasing temperatures. High transparent silicones combine resistance against high temperatures and against UV light at high optical transparency.

4.5 Feature to benet For a winning development with silicone elastomers, a pure material replacement calculation from an existing drawing/application is often not enough. In LSR, elastomer innovations allow redesigning of parts and systems benetting from values resulting from simple feature differences to individual organic elastomers. Those include: Low viscosity-enables very thin walls and long thin ow paths Low hardness without plasticizers Easy to color, even glass-clear products are available Silicones mechanics are almost linear/similar to a Hooke spring Hydrophobicity Excellent insulation properties. Those features enhance the number of functional competitors (and application potentials) signicantly and silicone elastomers therefore nd usage in: Insulators for high voltage, replacing porcelain Replacements of metal springs Replacements of transparent plastics and glass in optical applications as illustrated in following examples.

R Si - O Si - O Si - R R R
n

R = -CH3 = -CH = CH2 = -Ph = -CH2-CH2-CF3

5. Ultra-transparent LSR vs. glass and plastics

Dispensable, high transparent silicones have replaced engineering thermoplastic resins in packaging of semiconductors in LEDs for some years. Higher temperatures and the hard blue light radiation of the highly efcient new generation LEDs requires UV light resistance and low yellowing for the optical packaging materials. These properties combined with improved crack resistance are provided by silicone-based packaging materials which are basically used in LED packaging nowadays. Innovation in lighting design and the success of highly efcient LEDs are driving the research for new materials which can be processed by injection molding, enabling high complex design at high production vol-

Silicone elastomers: MQ Methyl-silicone VMQ Vinyl-methyl-silicone PVMQ Phenyl-vinyl-methyl-silicone FVMQ Fluoro-vinyl-methyl-silicone

275 250 225 200 175 150 EPDM 125 100 IIR 70 SBR NR not 140 required 120

FFKM FPM FSL VMQ FVMQ = FSE / FQE / FFSL = HCR / HV / HTV = LSR AEM, ACM, HNBR CPE / CSM NBR, ECO CR 100 80 60 40 30 20 10

Temperature / C

Volume swell in IRM 903 oil / %

Fig. 3: Graphical position according to ASTM D 2000

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umes. The new LSR 7000 family from Momentive provides high optical transparency, excellent UV and blue light resistance. The new ultra-transparent LSR is a good candidate to replace transparent plastics like PC and PMMA in lighting applications which require high temperature resistance and exibility in design (g. 5, 6). An obvious next step is to use high transparent LSR for secondary optical lenses which can be directly assembled to the LED (g. 4). The light of a semiconductor is spread in a very simple way by the packaging material, e. g. a globe-top. In order to form and to guide the light, secondary lenses and light guides are needed. So far such optics are mainly made from PC or PMMA. In order to protect these materials against the high temperature of a high power LED, those optical elements can not be assembled directly onto the light source a 1 2 mm gap is necessary to reduce the junction temperature. Resulting reections from plastic to air and from air to plastic reduce the efciency of such optical components. Secondary lenses and light guides made out of high transparent, temperature resistant LSRs can be assembled directly to the LED and higher efciency can be achieved. Additionally, LSR allows a higher freedom of design than PC and PMMA.

dominated by paciers and bottle nipples made from natural rubber latices. Studies show that LSRs not only fulll necessary food compliancy, their allergene potential is far less than the natural rubber product. LSR is UV resistant and will survive cooking water without signicant change of appearance or physical properties. The decision to choose LSR in baby care at the end was a decision from many mothers and even more babies, which preferred the silicone elastomer vs. natural rubber. The baby care market today is amongst the biggest LSR application volumes globally. Also, in this mature segment the elastomer innovation continues to fulll expectations for the next generation of products e. g. with higher tear resistance. A new development is for example Momentives LSR 2645 with improved hot tear resistance according to EN 1400-2 (g. 7).

7. Silicone vs. porcelain in high voltage applications

Silicone elastomers in high voltage applications came up in the late 1960s when experts tried to nd a lighter and maintenance-free solution to replace glass and porcelain in composite insulators like hollow cores (g. 9).
Fig. 4: Multifunctional lens based on LSR 7070 [4]

PMMA

PMMI Typ 1

PC

COP

LSR 7060

LSR 7070

LSR 7080

Fig. 5: Plastics and LSR 7000 after heat aging 6480 h 150 C [6]

PMMI Typ 1

PMMI Typ 2 LSR 7005 WRL 4984

6. LSR vs. NR in baby care

When LSR was brought to the market some 30 years ago, baby bottle nipples were the rst application, the industry immediately started to work on. LSR brought a transparent appearance, was easy to injection mold at high yield and neutral in odor and taste. At the time the market was
Fig. 7:
140 120 Performance / % 100 80 60 40 20 0 LSR 2640 LSR 2645 Competitor Cooked in water Aged hot air 70 C Tear resistance

Fig. 6: Transparency over wavelength of LSR 7070 [7]

100 90 80 70 60 50 40 30 20 10 0 200

LSR 7070 (thickness 1.97 mm)

LSR7070 transmission at 6 incidence angle LSR7070 reflection at 6 incidence angle

LSR 7070, 655 nm: 2,8 dB/m 30 cm: 82 % transparency 100 cm: 53 % transparency

300

400

500 600 700 Wavelength / nm

800

900

1,000

LSR 2645 in comparison [6]

Fig. 8:
250 200 USA/ year 150 100 50 0

Life cycle cost for insulators [3]

Silicone composite Coated ceramic disc Ceramic disc with washing

132 kV

275 kV

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Key expectations for this application are: Low weight high mechanical strength Easy handling Pollution performance low maintenance costs Flexibility/explosion safety (seismic behavior). A functional elastomer competitor to silicones is EPDM with as good weatherability and insulation properties. Silicone insulators benet from standard silicone features, the most important are: Flexibility Low density Hydrophobicity Low viscosity.
Silicone hollow core insulator

Hydrophobicity (which prevents contaminations and ashovers on the insulator surface) and low viscosity (enables casting of big shapes) are key properties differentiating silicones vs. EPDM. Silicone also has the ability to transfer its water repellent properties into contamination layers that might be built up in heavily polluted environments. A good example here is Momentives Silopren Electro 242-0, that additionally features excellent tracking and erosion resistance (1A 4.5 kV according to IEC 60587). Looking at manufacturing costs, silicone leads to the most expensive part. However, in system costs which include assembly, longterm maintenance and disassembly, silicone insulators are the most cost efcient solution [3] (g. 8). One of the main reasons is the need for regular cleaning of conventional insulators including those made with EPDM which is unnecessary with the hydrophobic silicones.

bine necessary oil resistance with high temperature performance and acceptable static low temperature performance. Most specied materials have been FKM (expensive and problematic in low temperatures) and ACM (better in low temperatures and cheaper, but limited in heat resistance). HCR silicone compounds came up (modied with mineral llers to achieve lower oil swell), but also these compounds had the same potential scorch problems in traditional rubber molding. In the early 2000s, a major OEM qualied LSR 2670 black from Momentive. The LSR features t perfectly to the difcult to manufacture geometry, however LSR has higher swell in oil than any of the mentioned functional competitors. The very low viscosity of the shear-thinning LSR allows fast lling. The inhibition of LSR prevents scorch of the material. The platinum catalyzed addition cure makes full automation affordable. No material losses with an automated waste-less and trim-free molding system. Good high temperature resistance and compression set. LSR 2670 contributed to signicant cost savings in this application and is in successful mass production.

Fig. 9:

Core

8. Heat-resistant LSR against ACM and FKM in charge-aircooler gaskets

The demand for more efcient vehicles continues to drive the share of turbo-charged engines. Since turbochargers are running in a loss-oil lubrication with engine oil, their compressed hot charge air contains oil. The compressed air passes through a cooler to increase the density. The charge-air-coolergasket is normally a big square seal. In manufacturing, the necessary ow length of the thin shape can cause problems in mold and process design with organic elastomers being high in viscosity. Materials have to com-

Silicone housing

Flange/fitting Mechanical strenth: Core: glass fiber enforced tube epoxy or polyester Fittings: aluminum Housing: silicone (RTV, HTV, LSR)

9. LSR against a metal spring Silicone HCR against NR in engine mounts

Movement is creating vibration and noise. Electrical motors as well as combustion engines need to be xed and in the same time decoupled. The ideal material provides constant rebound resilience combined with good mechanical properties along the working temperature range of the application (g 10). Silicone elastomers are relatively constant in modulus and spring properties from very low temperatures 40 C and up to high temperatures above 150 C. Thanks to such outstanding properties, LSR substituted TPE as the decoupling element in the xing device of the electrical cooling van under the hood. A special self-bonding LSR allows two-component injection molding of a thermoplastic xing device with chemically bonded dampening elements made out

DMA 10,000 -71.62 C Storage modulus / MPa 1,000 Crystallization temperature: 72 C Low temperature standard < 80 C Loss modulus / MPa Remarks: According to DBL 5555, issue 06-2004, the low temperature standard is defined by the main maximum of the loss modulus. 0.15 10 100

100

tan

0.10

10

0.05

0.1

1 -100

-50

50 Temperature / C

100

150

0.01 200

Fig. 10: DMA LIM 8040 [6]

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of silicone rubber to keep the device in place to dampen the noise and vibration over a wide range of temperature (g 11). Another example is the substitution of NR by a special, low dampening silicone rubber used in the engine mount of the combustion engine of a power station. NR is destroyed at temperatures above 120 C. High efcient combustion engines have to be encapsulated for noise reduction. As a consequence the temperatures around the engine are increasing and new materials are required to replace NR as dampening material. Engine mounts made out of silicone elastomer work consistently at temperatures of 150 C (g. 12).

tors who can think outside of the box and utilize necessary freedom of design to function.

Fig. 11: Dampening cage for cooling fan motor

11. References
[1] Dr. Stephen Evans, IRSG, Presentation on China Rubber Conference, March 2011 [2] Momentive Market Estimates 2011 [3] EPRI, Transmission Line Reference Book, 115 138 kV Compact Line Design, RP 260, pp: 29. [4] Foto by KIMW Ldenscheid, Germany [5] Philips Global Lighting Market Study [6] Momentive Lab Data [7] Prof. Neyer, Techn. University Dortmund

10. Outlook
The next successful application of silicone replacing a functional competitor requires bright engineers and innovative raw material suppliers teaming up with each other. Unique silicone formulations can add value in use above and beyond just higher processing efciency. More important are creative innova-

Fig. 12: Silicone engine mounts

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