Trends and Innovation in SealingMaterials

Media Day 2015, Ernst Osen

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Materials for Global Requirements

New fluids demand materials with improved compatibility

� Global trend towards low viscous oils due to fuel economy

� Next oil generation with aggressive additive packages

� Focus on oils with fuel admixtures and degradation products

Legal and environmental requirements

� Global survey of different regulations:� EU Legislation (e.g.REACh)� TSCA� GADSL� …

� Substitution of critical substances

Technological trends on high performance parts

� CO2-reduction requires low friction materials

� Low wear materials for long time durability

� Broader temperature range of use

� Function integration and metal replacement (2K molding)

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Material innovation derived by market trends

Growing oil & gas segment

Technologies to reduce energy consumption

Alternative energies

Medical technology

Cost reduction

• Reduced friction

• Resistance against alternative fuels and lubricants

• Extended service life

• New, clean materials

• Low cost materials

• Integrated functions

• Intelligent materials

• Processability

Environment and legislation

Ageing society

Energy

Sustainability

Soc

ial a

nd te

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logi

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Core competenciesMaterials

Staff employed in Europe Employees

Mixing facilities 240

thereof Weinheim 170

Material development 75

thereof Weinheim 23

Production of elastomer compounds

In Europe 15,000 t pa

Several billion seals produced per annum

Production in Weinheim 8,500 t pa

Supply from compounders 3,500 t pa

Polymers used:NR, SBR, NBR, CR, ECO, HNBR, ACM, AEM, EPDM, FKM and FFKM

Not just standard rubbers but many specialty rubbers as well!

Number of specific compounds 1,810

Number of raw materials/components 1,000

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NBRVery good low temperature flexibility

Good oil resistance up to120 °C

EPDM

For water, steam, acid and bases up to 180 °C

HNBRSimilar to NBR, but better heat

resistance up to 150 °CBetter rigidity

FKM

Good chemical and thermal resistance up to 220 °C

FFKM

Very good chemical and thermal resistance up to 260 °C

VMQ

Very good temperature resistance up to 230 °C; good chemical resistance

up to 200°C

CR, NR etc.

For specific applications, e.g. boots

ACM, AEMGood heat resistance

Excellent oil resistance

The important role of the sealing material

Exceptions: FFKM, FKM, FVMQ (VMQ)These materials can in general be used in polar as well as in unpolar media.

Media resistance of elastomers

not suitable suitable

non polar rubber

NRIRSBRBR

EPMEPDMIIRCIIR

polar rubber

NBRXNBRCR

AU, EUACM/ AEMEVACO/ ECOHNBR

Mineral oilshydrocarbons(Benzine, aromates)

non polar mediumWater / steamAlkohol/ glycole(brake fluid)Acids/ basesEster/ ketone

polar mediumMedium to be sealed

Material

Syntheticlubricants

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Temperature range of elastomersLimits for low and high temperature applications

The operation temperature of a seal is limited by the base polymer. In special cases the temperature ranges can be extended by compound composition.

Extended low temperature

Extended high temperature

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Sealing materials for low temperature applications

O-Rings e.g.70 NBR 888, Tg (DSC) = -55 �

70 EPDM 281, Tg (DSC) = -52 �70 EPDM 291, Tg (DSC) = -51 �

Elastomeric form partse.g. 72 FKM 215824, Tg (DSC) = -29 �

70 NBR 285974, Tg (DSC) = -29 �Bellowse.g. 50 CR 879, Tg (DSC) = -40 �

Diaphragmse.g.60 FKM 285896, Tg (DSC) = -43 �58 PVMQ 534, Tg (DSC) = -117�

Simmerring®e.g. 70 FKM 260737, Tg (DSC) = -30 �

Attention: For the intended use not only the low temperature flexibility is relevant, but also the media resistance and other product specific properties need to be followed.

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New fluids demand materials with improved compatibilityInfluence of new lubricant generations in the case of Simmerrings

Before change the fluid a compatibility test with the elastomer is required!

� higher wear � accelerated ageing� higher shrinkage

� Absence of lubrication� Insufficient netting of the

surface

� higher temperature on the sealing lip� accelerated chemical and physical

interactions

Occurrence of

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High performance materials for Process Technology

Elastomer materials used for food and beverage applications need to fulfill

�Temperature resistance for sterilisation�CIP-/SIP medium and chemical resistance�Hygienic design�Certification and approvals according Food and Drinking water regulations of

various countries

Examples of market specific materials:�Fluoroprene® XP 41 and 43�White EPDM 253815 and white Simriz® 506�Hygienic Usit®

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Innovative material development

►Development of new innovative material concepts for specific customer solutions

►Advanced development of new materials for highest functional requirements

� temperature from –70°C up to +300°C

� aggressive lubricants and media (bio diesel, oil additive, coolant, ...)

� service life (life time, wear)

►Raw material and material characterization with modern analysis methods for a detailed quality analysis of our compounds

►Computer Aided Compounding (CAC) to increase the efficiency in material development

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Activities in Material Development

Simulation of the behavior of a rod seal; comparison of two TPU compound with respect of the resetting of the sealing lip

New low temperature-PU results in faster closure time of the sealing lip and therefore more reliability in usage at low temperature

Modeling / Simulation

� Determination of Tg using different test methods and correlation with part testing in order to improve the accuracy of forecast

� Studies on acidic medias (e.g. blow-by) in order to understand the deterioration mechanism and influence of multi-components fluids

� Studies on various fuels and new lubrication oils

� Long-term compression set tests for pipe couplings according to DIN requirements

Lab testing

� Measurement of leakage behavior of seals on test rigs, e.g. low temperature test rig for Simmerrings

� Test rigs for O-Rings at low temperature:o static without side loado static with side loado Short-term dynamic load

(shock)o Permanent dynamic load

(vibration)

Part testing

Reaction time too long: leakage

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Low and high temperature elastomers

NBR for extreme lowtemperature, very lowcrystallisation Temp andgrease resistance

New high temperatureFKM materials for up to280 °C

70 NBR 286210

70 NBR 286211

Mech. propertiesHardness Shore

A72 74

Density g/cm³ 1,21 1,21Modulus 100% N/mm² 4,9 5,3Tensile N/mm² 12,1 12,4Elongation at break

% 250 254

Tear resistance N/mm 12,9 11,3CS 24h/100°C % 26,8 19,0Tg (DSC) °C -72,3 -72,4

75 FKM 177884

75 FKM 177884

After Heat aging280 °CTIME 168 h 336hMech. Prop./ChangeHardness Shore

A75/0 74/-1

Modulus 100% N/mm² 16/6,7 8,1/-38,2

Tensile N/mm² 16/-29,6 14,4/-38,2Elongation at break

% 205/39,5 224/ 52,4

Vol.Change % -1 -1,6CS (ISO 815) % 28 39

Innovative Sealing Solutions | ZF Friedrichshafen AG – Tech-Day | March 2014 | 14

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75 ACM 380 DF:

CS at higher temperatures of HT-ACM: Reset forces remain significantly longer to ensure sealing function.

High-performance material with higher temperature r ange

Higher C-N bonding enthalpy in in combination with a new polymer design yields higher temperature resistance

S-S 268 kJ/molS-C 289 kJ/molC-N 305 kJ/molC-C 331 kJ/mol

Compression set in air at 170 °C

Bonding enthalpie

Innovative Sealing Solutions | ZF Friedrichshafen AG – Tech-Day | March 2014 | 15

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75 ACM 380 DF:

75 ACM 380

70 ACM 121433

0,01 0,1 1 10 100 1000 10000

Time [h]

Cha

nge

in %

0,00

10,00

20,00

30,00

40,00

50,00

60,00

70,00

80,00

90,00

100,00

ACM Standard

ACM HT

175 °CTensile Stress relaxation in Esso Gear Oil MB 317► Material: ACM Standard & ACM HT for Simmerrings► Temperature: 175°C; continuous measurement► Deflexion: 20%

High-performance material with higher temperature r ange

Thermochromic Coating: O-Rings NBR in air

O-Ring coated withThermo- color 1

120°C, 24 h

L*(D65) Light index

O-Ring coated withThermo- color 1

120°C, 6 h / 140°C, 1 h / 120°C, 17 h

30

35

40

45

50

120°C Luft Ring 120/140/120°C Luft

Ring

L*[D65]

L*[D65]

1h at 140 °C

Maximum temperatureson a seal can be identifiedand quantifiedwith an optical device

Further colors and temperature ranges available

Intelligent materials: Electrial conductive Materials

No electrical circuit:Non-conductive rubber

Electrical circuit:Conductive Rubber

Intelligent materials: Dielectrical Materials

Tensile Stress applied to the elastomer sample can be measured on the device.

Idea for the demonstrator : Measurement of the compression of a sealing

Intelligent materials: Dielectrical Materials