Tecnoflon FKM and FFKM portfolio: an overview on · PDF fileTecnoflon FKM and FFKM portfolio:...

Tecnoflon FKM and FFKM Tecnoflon FKM and FFKM portfolio: an overview on portfolio: an overview on

standard grades standard grades andand specialtiesspecialties

R. Villa

Utrecht, 12-02-2009

IntroductionIntroduction

SOLVAY SOLEXIS © 2009, SOLVAY S.A.

History of FKM-FFKM

1892: Development of fluroalkanes (Swarts reaction)

1955: Elastomeric copolymer VDF-CTFE (M.W. Kellogg Co.-US Army)

1956: Copolymer VDF-HFP (Dupont) → improved heat stability

1960: Terpolymer VDF-HFP-TFE (Dupont) → better chemical resistance

1960s: Perfluoroelastomers - copolymers TFE/PMVE (Dupont)

1960s: Copolymers TFE-P (Dupont, Asahi Glass)

1960: Copo and terpolymers using 1HPFP instead of HFP (Montecatini-Edison SpA)

1970: Bisphenol curing chemistry (Dupont and 3M)

1970s: Terpolymers VDF/TFE/PMVE improved low T performance

Late 1970s: Peroxide curing chemistry – Br as CSM (Dupont) – I as CSM (Daikin)

Solvay Solexis: FKM and FFKM portfolio


Presentation overview

1. Introduction – Fluoroelastomers key benefits

2. Fluoroelastomers classification/performances

3. Tecnoflon® grades portfolio: fluoroelastomers

4. Perfluoroelastomers classification/performances

5. Tecnoflon® PFR grades portfolio: perfluoroelastomers

Solvay Solexis tradename forFluoroelastomers (FKM) and perfluoroelastomers (FFKM)

Tecnoflon®


Fluorine plus

Typical properties of fluoroelastomers are:

• Excellent chemicalchemical resistanceresistance• Excellent thermalthermal resistanceresistance• Very low permeabilitypermeability• Very good weatherweather, , OO22 and Oand O33 resistanceresistance ++ FluorineFluorine


Fluorine plus

50

100

150

200

250

300

350

020406080100120140160180

Swelling in IRM 903 oil (%)

Hea

tRes

ista

nce

(°C

)

��

��

��

EAACM

CSM

CR NBR

ECO

FVMQ

FKM

FFKM

ASTM D2000/SAE J200 Spec. SystemASTM D2000/SAE J200 Spec. System

FKM and FFKMare at the top of

the range!


Fluoroelastomers applications

• Automotive industry• Aerospace industry• Chemical & Processing industry• Oil field / Mining• Semicon industry


Fluoroelastomers classification

� FKMs are classified according to monomer composition and ratio � FKMs are manufactured by polymerization polymerization of a limited number of monomers:

� Vinylidene Fluoride (VF2) CH2=CF2

� Hexafluoropropylene (HFP) CF2=CF-CF3

� Tetrafluoroethylene (TFE) CF2=CF2

� Perfluoroalkylvinylether (PAVE) CF2=CF-OCF3 (main monomer MVE when Rf = CF3)

� Ethylene (E) CH2=CH2

� Propylene (P) CH2=CH-CH3

� FKMs can be further differentiated by curing chemistry

Two main cure systems:

� Bisphenol

� Peroxide


Chemical composition

Fluoroelastomers (FKM) are classified according to monomer composition (ASTM D1418):

Perfluoroelastomers (FFKM) are usually TFE / PAVE (MVE) copolymers

Type 1� VF2, HFP (Bisphenol)� Example: Tecnoflon® FOR 80HS

Type 2� VF2, HFP, TFE (Bisphenol or Peroxide)

» Example: Tecnoflon® FOR 4391 (Bisphenol)» Example: Tecnoflon® P 959 (Peroxide)

Type 3� VF2, TFE, PMVE (Bisphenol or Peroxide)

» Example: Tecnoflon® PL 855 (Peroxide)Type 4

� TFE, P, VF2 (Bisphenol)Type 5

� TFE, HFP, VF2, E, PMVE (Peroxide)» Example: Tecnoflon® BR 9151 (Peroxide)


��

�� !

"#��

CF3

CF3

O-( PR4)+( PR4)

+ -O

C=OO=C

C

O

N-CH2-CH=CH2CH2=CH-CH2-N

CH2-CH=CH2

NC=OO=C

C

O

N-CH2-CH=CH2CH2=CH-CH2-N

CH2-CH=CH2

N$#��


��

��

��

%��&��%��&��

!""

!!#

!#"

!$#

'&&��(��)

�%��

��*� � ��&��

)��

��&'(��)�&#"%��

�#"

�*"

�+"

�!"

�&"

"

��*�� +�)��",-. ./ -

∆∆ ∆∆)��

�,�

-��

. ��

��

&��*� �&��*� ��


• A full range of products for all kinds of items and processing technologies (compression, injection, transfer, extrusion)

• Tailor made materials for special requirements• New copolymers with improved performances (HS gradesHS grades

manufactured in US plant)

Tecnoflon® Bisphenol Curable

For bisphenol curable FKM, Solvay Solexis supplies:For bisphenol curable FKM, Solvay Solexis supplies:

• Raw gum• Cure incorporated materials (rubber + bisphenol +

accelerator + possibly processing aids)• Cure incorporated materials for rubber-metal bonding


Tecnoflon® Bisphenol Curable

Portfolio

�&��0�� 11/01/20�/'"230��

/�4"23

�5601�56�("230�

�56�#"&230�

�56�'"0��

�56�#+&!0��&$

)�&��0�� 12 3,�01�/�#"�0��

#+(0��4+(

�5601�56��0�

�56�#+(&

�56�$+("0��

�56�4+(#��&+�7��$

��'+'0��'+'78�56��'+'0��

�56�#+'&�&4

8�'+'0�8�'+'8 �!&

��4�

��

&��

)�",��5�

/�6�) 1-#- 11

�� 6�.�� #7�


• A full range of products both for compression and injection moulding (high – low Mooney viscosity)

• Very fast curing rate•• Excellent mechanical propertiesExcellent mechanical properties•• Very low compression setVery low compression set•• Very low postVery low post--curing timescuring times (1 – 2 h)• Excellent processabilityprocessability

Tecnoflon® Peroxide Curable

For Peroxide curable FKM, Solvay Solexis supplies:For Peroxide curable FKM, Solvay Solexis supplies:

• Raw gum


Tecnoflon® Peroxide Curable

Portfolio

�� 7� 78 ��6�.�� )�",�5�

13 "93 -�*#$0�-�$#$ �&#

3, "9$ -�*#40�-�4#4 �$

1: "92 -8�*##0�-8�(## �+"

11 "91 -8�##$ �!4

11 "9$ -8�*#(0�-��4#( �!*

1192 "9,- 9-8�(#$+":�9-8�*#$+" �+"

1-9" "9;- 9-8�*##+# �+#

1-9" "9"1 9-8�(##*"0�9-8�###*" �*"

��

��3" ,9$- -�6�4& �4

<�0�/�6�)

/�6�)

8��

��

)�&��0��


Main features / Applications:

• Good processability

• Excellent mechanical properties

• Permeation reduction: automotive industry (low

emissions)

• Friction reduction: automotive industry (shaft

seals, valve stem seals)

• Good chemical resistance: oil industry

• High purity: semicon / food industry

Tecnoflon® PTFE nanocomposites FKMs

NFT 7030

P757/30M

P959/30M


Solexis FFKMs: Tecnoflon® PFR


FFKM: Chemical structure

nF

- C -

F

O

C -

F

CF3

F

- C -

F

F

C -

F

- -

mF

- C -

F

X

C -

F

- -

z

TFE MVE

Cure sitemonomer

Perfluoroelastomers (FFKM) are basicallyTFE / MVE (PAVE) copolymers + CSM


FFKM: Thermal resistance

FFKM 320 FFKM 320 °°C C

Their thermalresistance

is the highest oneamong rubbers !


FFKM: Chemical resistance

Fluid type Typical example FFKMa FKMb Fluorine Content 72.5% 66% Aliphatic hydrocarbon Propane Excellent Excellent Aromatic hydrocarbons Benzene Excellent Excellent Organic acids Acetic acid Excellent Fair-good Inorganic acids Sulfuric acid Excellent Excellent Alcohols Methanol Excellent Fair-excellent Inorganic base Sodium hydroxide Excellent Poor-fair Organic base Aniline Excellent Fair Ethers MTBE Excellent Fair-poor Ketones Acetone Excellent Poor Nitrous oxidizers Ammonium nitrate Excellent Good Halogen oxidizers Chlorine Excellent Excellent Heat transfer fluids Ethylene glycol Excellent Excellent Oils & greases Mineral oil Excellent Excellent Halogenated refrigerants HFC-134a Fair-good Poor-fair Polar solvents Water Excellent Excellent

Chemical resistanceis by far improved

with respect to FKM !


FFKM: Classification

Differences in perfluoroelastomer performance are due to the different “weak points” nature (i.e. curing chemistry)

F

F

F3C-C-CF3

o

o

Curing point: Phenoxy groups

X-linking agent: Bisphenol AF




NN

N

X-CH2CH-CH

2 -X

-CH 2CH-CH 2

-

X-C

H2 C

H-C

H2 -

00

0

Curing point: Halogen atoms (Br/I)

X-linking agent: TAIC




N

N

N

CN

R4Sn

Curing point: Nitrile –CN groups

X-linking reaction: Triazine formation

Curing catalyst: R4Sn, etc.


Performances comparison

� 8��

� )��=��! ;"1�5�

� ��&��! $2,�5

� ��*� �! $;,�5�

� )0&��&��3,��>�$,,�5�

� ��*� �! "-�7 ��

� )��=��! ;-�7 �

� ��&��! -,�7

� ��

� ��*� �! ��%��6��?��

%��

� )��=��! &��6��?�� %��

Tecnoflon® PFR grades are peroxide curable


Performances comparison

Chemical resistance

�� *� � ��&�� )��=��

+�� ;�� <�� -��

+�� ;�� <�� -��

8��6��@�� ;�� <�� -��

�� ;�� ;�� ;��

��(�� ;�� ;�� ;��

��@�� ;�� ;�� ;��

+�� <�� -�� ;��


Grade Cross-linker Feature Max T (°C)

PFR 91 TAIC Not a true FFKM - Chemical Resistance 230PFR 94 TAIC Chemical Resistance 230

PFR 06HC TAIC Very high chemical resistance (strong amines) 230

PFR 95HT Incorporated Very high thermal resistance 320

PFR 5910M Incorporated High purity - low hardness 320PFR 5920M Incorporated High purity - medium hardness 320

Tecnoflon® PFR grades portfolio

All are peroxide curable !

All are peroxide curable !

Next Generation of Low Next Generation of Low Temperature Temperature

FluoroelastomersFluoroelastomers


Overview

� History of Low Temperature Fluoroelastomers

� MOVE - new Low Temperature Monomer Technology

� Tecnoflon® VPL - a New Series of Low Temperature

Grades

� Testing Data on VPL versus standard LT FKM

� Applications Examples


The Fluoroelastomer Challenge

Chemical resistance

TR10

Per

form

ance

Target

High F wt%

Low F wt%

Current grades

� Could we have good low temperature properties and high chemical resistance as well?


The Fluoroelastomer Challenge

IncreaseIncreaseTFE

CF2=CF2

Slightly DecreaseDecreasePMVE

CF2=CF-O-CF3

IncreaseIncreaseHFP

CF2=CF-CF3

DecreaseDecreaseVDF

CH2=CF2

Fluid Resistance EffectTR10 EffectMonomer

� Low temperature performance and chemical resistance are dependent upon polymer composition

The only way to improve low temperature performance is to design a new monomer.


MOVE Monomer Solution

Tg = -39°CTg = -8°CTg = 160°C

MOVEPMVEHFP

CF2=CF

CF3

O

CF2=CF

CF3

CF2

O

O

CF2=CF

CF3

Fully Fluorinated Fully Fluorinated MonomerMonomer

No weak point !No weak point !


Unique Properties of MOVE monomer

-60

-55

-50

-45

-40

-35

-30

0 20 40 60 80 100

MOVE3 (mol%)

Tg (°

C)

Johnston eq.

PMOVEPVDF

MOVE (mol%)

2. Tg of copolymer lower than two homopolymers

1/Tg = wAPAA/TgA + wBPBB/TgB + (wAPAB + wBPBA)/TgAB

TgAB= -55 °C


Market NeedsAutomotiveAutomotive

• Lower Sealing Temperature (cold environments)

• High pressure generates Tg shift �� GDI engines require FKM with lower Tg compared to standard solutions

• Increased chemical resistance (biofuels) maintaining Low T performance

AerospaceAerospace• Low T Service combined

with high thermal resistance

• Low T combined with Fuels and HTS oils compatibility

Oil & GasOil & Gas• Drilling in cold

environments

• ED Resistance

• Chemical Resistance

FKM for low FKM for low

TemperatureTemperature

SealingSealing

...with good process...with good process--ability as well!ability as well!


)��A <�/!

��/�=�3�� 8�=��<��

--3030--4040TR10 (TR10 (°°C)C)

VPL 85730 (45 MU)VPL 85730 (45 MU)VPL 45730 (25 MU)VPL 45730 (25 MU)

VPL 85540 (45 MU)VPL 85540 (45 MU)VPL 55540 (25 MU)VPL 55540 (25 MU)

TecnoflonTecnoflon®®

Beside the 2 main family of -40°C and -30°C, the new MOVE monomer technology allows us to improve other FKMs in term of

low T behaviour and chemical resistance.

MOVE Monomer Technology


Volume Swell in M15 168h @ 23 °C

0

10

20

30

40

50

-45 -40 -35 -30 -25 -20 -15 -10 -5 0Tr10 (°C)

�V

(%

)

MOVE Monomer Technology

PL -30

PL -24

66%F

68.5%F

70%FVPL VPL --3030

VPL VPL --4040


Rheological Properties

100Polymer VPL

5phrZnO

30phrMT N990

4

2phrLuperox 101XL 45

phrDrimix TAIC 75

Compound recipeCompound recipe

454554MUPolymer Viscosity ML (1+10) @ 121°C

3.74.33.6minT90

1.92.11.8minT50

0.90.90.9minTs2

26,228,127,5lb*inMH

1,11,21,7lb*inMLMDR

6 minutes@

160160°°CC

474658MUCompound Viscosity ML (1+10) @ 121°C

VPL 85540

VPL 85730

TecnoflonPL -30

Product Name

Excellent cure profile due to SolvayExcellent cure profile due to Solvay’’ss

Branching & Pseudo Living Polymerization TechnologyBranching & Pseudo Living Polymerization Technology

Small difference Small difference between Polymer between Polymer and Compound and Compound

viscosity: excellent viscosity: excellent processprocess--abilityability


Physical Properties

186177248%Elongation @ Break

C-Set 70h @ 200 °CO-Rings #214, 25% def.

Modulus @ 100%

Tensile Strength

Hardness Shore A

Product Name

%

MPa

MPa

pts

212223

6.27.54.8

15.015.820.8

677169

VPL 85540

VPL 85730

L.T. -30°C

Sealing behavior has not been Sealing behavior has not been affected by the new monomer !!affected by the new monomer !!


0

10

20

30

40

50

60

70

80

-45 -40 -35 -30 -25 -20 -15

Temperature (°C)

Ret

entio

n (%

)

VPL 85540 VPL 85730 PL -30°C PL -24°C

Temperature of Retraction

Due to correct monomer sequences in the polymer Due to correct monomer sequences in the polymer chain, TR10 and TR70 values are very close chain, TR10 and TR70 values are very close

Example of bad low T

Example of bad low T

relaxation behavior

relaxation behavior


0

5

10

15

20

25

30

35

40

45

VPL 85540 VPL 85730 PL -30°C FKM 70% F (TR10 = -7°C)

Vol

ume

Sw

ell (

%)

Fuel C: 70h @ 60°CCE10: 70h @ 60°CCE22: 70h @ 60°CCE85: 70h @ 60°CEthanol: 70h @ 60°C

Fluid Testing in Ethanol Blends

Comparable fluid Comparable fluid resistance as 70% resistance as 70% fluorine terpolymerfluorine terpolymerSuperior fluid Superior fluid

resistanceresistance


Fluid Testing in Methanol Blends

0

20

40

60

80

100

120

VPL 85540 VPL 85730 PL -30°C PL -24°C FKM 70% F (TR10 = -7°C)

Vol

ume

Sw

ell (

%)

M15: 168h @ 23°CM85: 168h @ 40°C

Methanol: 168h @ 23°C

Superior fluid Superior fluid resistanceresistance

Comparable fluid Comparable fluid resistance as 70% resistance as 70% fluorine terpolymerfluorine terpolymer


Fluid Testing in Additional Fuels

0

5

10

15

20

25

30

35

40

VPL 85540 VPL 85730 PL -30°C PL -24°C

Vol

ume

Sw

ell (

%)

PN-180: 336h @ 60°CFAM B: 168h @ 60°C

Superior fluid Superior fluid resistanceresistance

FKM 70% F (TR10 = -7°C)


Fluid testing in Biodiesel

No problem No problem also in also in

BiodieselBiodiesel !!

0,0

5,0

10,0

15,0

Terpolymer 68.5%Bisphenol Curable

(TR10 = -13°C)

FKM 70%F (TR10 = -7°C)

PL -24 PL -30 VPL 85540

Vol

ume

Sw

ell (

%)

RME 336h @ 150 °C


Compression Set Testing for 70 hours

0

5

10

15

20

25

30

VPL 85540 VPL 85730 L.T. -30°C L.T. -24°C

Com

pres

s S

et (%

)200°C150°C23°C

Improved compression set

resistance


Heat Aging

Effect of heat aging @ 200°C

0%

50%

100%

150%

0 100 200 300 400 500 600

time (h)

Ret

aine

d m

echa

nica

l pr

oper

ties

TS M100 EB HDS


Compression Stress Relaxation

CSR via Elastocon at 150°C

70

75

80

85

90

95

100

0 200 400 600 800 1000

Hours

% R

etai

ned

Sea

ling

Forc

e

VPL 85540 VPL 85730 PL -30°C PL -24°C

Very Similar CSR to standard gradesVery Similar CSR to standard grades


VPL Performance in Fuel System Sealing

++Fuel resistance≅≅≅≅≅≅≅≅Compression set≅≅≅≅≅≅≅≅CSR

+≅≅≅≅Low Temperature Performance

VPL 85540VPL 85730Property

VPL -30 & VPL -40 versus standard PL -30°C


Conclusions

� Breakthrough Monomer Technology (MOVE)

� Expanded low temperature performance of Fluoroelastomers � Superior Chemical resistance compared to standard PL -30 °C� Chemical Resistance comparable to 70%F PC� Excellent sealing behavior� Very good process-ability

Base resistant Base resistant technologytechnology


Tecnoflon® BR grades

-(CF2-CF)-(CH2-CF2)-(CF2-CF)-

CF3 CF3

In order to reduce “Schmiegel” Sequences we can introduce Ethylene into VDF based polymers.

-(CF2-CF)-(CH2-CF2)-(CF2-CF)-(CH2- CH2)-

CF3 CF3

Protecting monomer

Standard Technology: “Schmiegel” Sequences:Weak point

BR Technology:


Base resistant materials

FKM Type 5 definition accounts for our BR technology


GoodPoorGoodGoodGoodFuels

PoorPoorGoodGoodGoodLow Temperature

GoodGoodGoodPoorPoorAmines

GoodGoodGoodGoodPoorSteam

GoodGoodGoodPoorPoorHydrogen Sulfide

GoodGoodGoodGoodPoorMethanol

GoodGoodGoodGoodGoodOil

GoodPoorGoodGoodGoodAromatic Hydrocarbons

FFKMFFKMTFE/PTFE/PBR 9151BR 9151FKM TerpoFKM TerpoFKM copoFKM copo

BR 9151: Performance comparison


New BR 9171

BR 9152BR 4152

New !

Chemical resistanceC

old

flexi

bilit

y

BR 9151

BR 9171


BR 9171

• A new grade with by far improved chemical resistance compared toBR 9151 was developed

• Application targets:� Axle seals: Gear oil + 6% Sturaco additive (vs TFE/P)

NEWNEW

��B"3" ��B"-" ��B"-$ )��@� ��&��" ��B: )��

#��C ��D$":�

$"��)�!""�%� , +$ *! *+ #* *( !&

)�",�+�)��";$B� %� B �$ �&* + �$ �! >��&"

./ -�4��17 � "12��>�"-,5

∆ �� 3�� , $7 �*', �+", �!&, �&(, �&",

∆ ;�� ? , ":7 �!', �&$, $, �!, �!,

∆ 2�� 3�� + �! �& �' �+ �!

∆ @�� , &:#, &, &, +, &, ",

./ -�4��17 � ",,,��>�"-,5

∆ �� 3�� , B7 �#&, �#!, A��#",

∆ ;�� ? , 37 �+#, �+#, A��#",

∆ 2�� 3�� ! ! �&

∆ @�� , &:', &:$, &:(,


Thank you!

Tecnoflon FKM and FFKM portfolio: an overview on · PDF fileTecnoflon FKM and FFKM portfolio:...

Documents

Transcript of Tecnoflon FKM and FFKM portfolio: an overview on · PDF fileTecnoflon FKM and FFKM portfolio:...