3M Advanced Materials Division Influence of Fluoroelastomer Compounding on Rapid Gas ... · 2020....

Influence of Fluoroelastomer Compounding on Rapid Gas Decompression

Energy Polymer Group Technical session, Fall 2019

Karen Hopperstad

3M Advanced Materials Division

2. All Rights Reserved.9 October 2019© 3M

Agenda

• What is Fluoroelastomer (FKM)?

• Major Markets & Industries

• Typical Attributes

• Industry Trends impacting O&G and FKM

• Rapid Gas Decompression (RGD)

• Testing

• Results

• Compound factors impacting results

• 3M Application Engineering

• Acknowledgments


Major FKM and PFE Industries

Military

Medical

Food processing

Transportation Electronics Oil and Gas/Chemical Processing

Miscellaneous

Aerospace

Marine

Heavy duty equipment

Automotive

Rail

Semiconductor processing

Wire and cable

Electronic devices

Fluid transport

Oil and gas production

Hydraulics/Pneumatics

Pollution control

Machinery


Fluoroelastomers (FKM) & Perfluoroelastomers (FFKM/PFE)

Oil Resistance• IRM 903 Oil

NR

SBR

EPDM

VMQ

AEM

CSM

CR

HNBR

NBR

ACM

FVMQ

PFE

FKM

TFE/P

Fluoroelastomer (FKM)• -40 to 225C• 66.5 to 70.1%F• Low Compression set• High Temperature Stability• Fuel, Oil and Chemical resistance

Perfluoroelastomer (FFKM/PFE)• 0 to 316C• 72.5%F• Good Compression set• Highest Temp Stability• Excellent Overall Chemical Resistance


Drilling and production is experiencing harsher environments: 1

• Deeper• Higher pressure• Arctic conditions• Chemical composition leading to changes

in polymer demand

No one polymer answers each issue.

1Drilling and Completion Fluids-Current and Future Challenges and their Impact on Sealing Materials, Harlaw Fluids Ltd May 17, 2019, Berlin

Future concernsAs conditions for oil and gas exploration become more challenging, rapid gas decompression and passing this gateway screening becomes ever more important. Influences on polymer choices include heat and acid resistance as well.


Arctic exploration• Extreme environments in arctic areas present challenging

low temperature needs. • Low Temperature Fluoroelastomer grades are peroxide

cure materials

Deep Water/Ultra Deep Water1

• Deep water expansion creates challenging demands in High Pressure/ High Temperature (HP/HT) needs

• Remote locations of deep water exploration and spars create extensive pipeline needs for transport of oil and gas

Conditions with Challenges

1 Deepwater Gulf of Mexico, December 31, 2014, OCS Report BOEM 2016-057


As conditions evolve, changes in fluids are needed to meet these conditions.• Extreme temperature gradients• High pressure needs

Environmental regulations play a role in changing fluid demands• Lower environmental impact fluids• Discharge restrictions

1 Drilling and Completion Fluids-Current and Future Challenges and their Impact on Sealing Materials, Harlaw Fluids Ltd May 17, 2019, Berlin

Fluid Changes 1


Many industries currently using FKM are shifting towards peroxide cure materials.

• Transition to peroxide cure polymers removes any bisphenol regulatory concerns

• As regulations evolve, polymer curative needs may change

FKM Cure System : Bisphenol vs Peroxide

Benefits of Peroxide Cure Systems:

• Steam/Water resistance• Low Temperature needs• Fluid changes• Environmental affairs


RGD testing : According to ISO 23936-2 (Norsok M710 Rev 3)

Testing done by Element Materials Technology Hitchin Limited, UK

• Test temperature : 100+ 2°C

• Test pressure : 150 +10/-5 bar

• Test medium : 10 mol % CO2 / balance CH4• Test specimen : 312 size O-rings (CSD 5.33 mm)

• Replicates: 4 O-rings tested

• Cycles: 8

• Cycle 1 soak time: 68 hours minimum

• Cycles 2-8 soak time: 6 hours minimum

• Dwell time between cycles: 60 +10/-0 minutes

• Decompression rate: 20+2 bar/minute

Element Report # C4742-1 Rev A

Example of a test jig


Sample preparation can influence testing• O-rings that have been prepared with

extruded pre-forms have performed better than die cut pre-form compression molded O-rings during in house testing

Fixture type can affect the outcome1

• An ISO fixture compared to a Free Flow fixture.

Compound Development• Baseline compounds with one primary

variable for differentiation were used. Optimizing formulations can improve results.

1 The Bleeding Edge of RGD, Alpine Polytech, Buc Slay, June 2017, AMI Oil and Gas Polymer Engineering

ISO Fixture Free Flow Fixture

Parameters Effecting RGD Results


Polymers used in Formulations

• No metal oxides required for cure providing

improved acid resistance

• Improved processing compared to current 3M PO

Cure FKM products

• High fluorine grades offer excellent resistance

against chemicals and fluids

• Good physical properties right out of the press

• Blendable to achieve desired properties

FPO 3820FPO 3850 (E-22028)

FPO 3620FPO 3650 (E-22396)

Flu

ori

ne

Co

nte

nt

Mooney Viscosity

The new 3M™ Dyneon™ Peroxide Cure (PO) Fluoroelastomers are terpolymers of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene plus cure site monomer.


Element Report # C4742-1 Rev A

Table 1.1: RGD Testing Results

Compound Element Identification Number Edn.3 NORSOK rating Overall NORSOK Pass/Fail

Sample 1 M23409 0000,3210,3000, 0000 Pass

Sample 2 M232416 1000,1000,2100,3000 Pass

Sample 3 M23410 0000,0000,2000,0000 Pass

Sample 4 M23411 1100,0000,1000,0000 Pass

Sample 5 M23412 5300,3200,2000,0000 Fail

Sample 6 M23413 1000,0000,0000,2000 Pass

Sample 7 M23414 4300,4410,4000,2000 Fail

Sample 8 M23415 3200,3300,2200,2000 Pass

Results


The results showed variation across Mooney Viscosity levels indicating that Mooney may not be a primary indicator of performance in RGD.

The Mooney selected for applications may be influenced more by processing parameters and compound design.

Mooney Viscosity ImpactTable 1.1: RGD Testing Results

Compound Element Identification Number Edn.3 NORSOK rating Overall NORSOK Pass/Fail Polymer Recipe Mooney

Sample 1 M23409 0000,3210,3000, 0000 Pass FPO 3620 1 20

Sample 2 M232416 1000,1000,2100,3000 Pass FPO 3620 2 20

Sample 3 M23410 0000,0000,2000,0000 Pass FPO 3650 1 50

Sample 4 M23411 1100,0000,1000,0000 Pass FPO 3650 2 50

Sample 5 M23412 5300,3200,2000,0000 Fail FPO 3820 1 20

Sample 6 M23413 1000,0000,0000,2000 Pass FPO 3820 2 20

Sample 7 M23414 4300,4410,4000,2000 Fail FPO 3850 1 50

Sample 8 M23415 3200,3300,2200,2000 Pass FPO 3850 2 50


As an overall observation, High fluorine FKM material is less likely to pass without true compounding optimization.

Percent Fluorine has an impact on chemical resistance.

Note: FFKM, 72% F, can pass with skilled compounding and testing knowledge. PFE 40Z, PFE60Z and PFE90Z are currently in use in proprietary formulas.

% Fluorine ImpactTable 1.1: RGD Testing Results

Compound Element Identification Number Edn.3 NORSOK rating Overall NORSOK Pass/Fail Polymer %F

Sample 1 M23409 0000,3210,3000, 0000 Pass FPO 3620 67

Sample 2 M232416 1000,1000,2100,3000 Pass FPO 3620 67

Sample 3 M23410 0000,0000,2000,0000 Pass FPO 3650 67

Sample 4 M23411 1100,0000,1000,0000 Pass FPO 3650 67

Sample 5 M23412 5300,3200,2000,0000 Fail FPO 3820 70

Sample 6 M23413 1000,0000,0000,2000 Pass FPO 3820 70

Sample 7 M23414 4300,4410,4000,2000 Fail FPO 3850 70

Sample 8 M23415 3200,3300,2200,2000 Pass FPO 3850 70


24 hour Methanol swell


% Fluorine impact on swell

89% 28% 0.3%

65.9%F 67.3%F 70.1%F

24 hour immersion in Methanol


Conductive carbon black increased the likelihood of passing as well as improving ratings with all other inputs the same.

In house testing has also showed that combining large and small particle size carbon black (N990, N115 or N110) didn’t improve our results as clearly as combining N990 with a conductive black.

Table 1.1: RGD Testing Results

Compound Element Identification Number Edn.3 NORSOK rating Overall NORSOK Pass/Fail Polymer %F Recipe Mooney Carbon Black

Sample 5 M23412 5300,3200,2000,0000 Fail FPO 3820 70.1 1 20Non-

conductive

Sample 6 M23413 1000,0000,0000,2000 Pass FPO 3820 70.1 2 20 Conductive

Sample 7 M23414 4300,4410,4000,2000 Fail FPO 3850 70.1 1 50Non-

conductive

Sample 8 M23415 3200,3300,2200,2000 Pass FPO 3850 70.1 2 50 Conductive

Carbon Black Impact


Process Aids: Used in small amounts, usually around 1phr, exhibit little impact on testing. They have more of an impact on processing.

Glass Bubbles: Limited testing, can influence processing and hardness.

Carbon Nano Tubes: Used in combinations with larger size carbon black has not been as effective at obtaining results as conductive carbon black in our internal testing.

Zinc Oxide: Frequently used in peroxide cure recipes, improves heat resistance, impacts steam resistance. Impact on RGD is not clear at this time.

Other compound ingredient impacts


Heat Aging Effects on FPO 3650 formulations at 250⁰CNote 250°C is above recommended continuous use temperature

-10

-5

0

5

10Hardness

Tensile Strength

Modulus

Elongation

Baseline

336 h

554 h

1008 h

-10

-5

0

5

10Hardness

Tensile Strength

Modulus

Elongation

Baseline

336 h

554 h

1008 h

FPO 3650 is 67% fluorine, 50 Mooney viscosity PO Cure FKM50 MV Grade to be commercialized at a later time. Currently experimental product E-22396

With Zinc Oxide Without Zinc Oxide

At 250°C, both compounds see changes across multiple aspects.


Heat Aging Effects on FPO 3820 formulations at 250°CNote 250°C is above recommended continuous use temperature

-10

-5

0

5

10Hardness

Tensile Strength

Modulus

Elongation

FPO 3820 w/ZnO @ 250⁰C

Baseline

336 h

554 h

1008 h

-10

-5

0

5

10Hardness

Tensile Strength

Modulus

Elongation

FPO 3820 w/o ZnO @ 250⁰C

Baseline

336 h

554 h

1008 h

FPO 3820 is 70% fluorine, 20 Mooney viscosity PO Cure FKM

With Zinc Oxide Without Zinc Oxide

At 250°C, both compounds see changes across multiple aspects. The most striking change is in elongation.


Improved Acid Resistance Curing without metal oxides improves FKM resistance to acids.

Before After

Without Zinc Oxide

With Zinc Oxide

3M™ Dyneon™ Peroxide Cure Fluoroelastomer FPO 3850*

3M™ Dyneon™ Peroxide Cure Fluoroelastomer FPO 3520

*50 MV Grades to be commercialized at a later time. Available as experimental product at this time.

19% Volume Swell

59% Volume Swell

Immersion Testing, Acetic Acid (168 h @ 100⁰C), ASTM D471, Tho Nguyen, 3M, 2018


Peroxide Cure FKM polymers have improved steam resistance over bisphenol cure polymers.• FE5840 is bisphenol cure• LTFE 6400 and FPO 3520 are peroxide cure

-15

-10

-5

0

5Change in Hardness

Change in Tensile Strength

Change in Modulus

Change in Ultimate elongation

168 hours in 230°C Steam

FE5840 LTFE6400 FPO3520 No Change

-15

-10

-5

0

5Change in Hardness


Change in Modulus


168hrs in 215C Steam

FE5840 LTFE6400 FPO3520 No Change

Steam Resistance


Water Resistance

-5

-3

-1

1

3

5

Change in Hardness


Change in Modulus


168hr in 302°F water

No Change FPO 3740 FE5642

Peroxide Cure FKM polymers have improved water resistance over bisphenol cure polymers.• FE5642 is bisphenol cure• FPO 3740 are peroxide cure


Application EngineeringThe 3M difference At a time when technical support is becoming tougher to find, 3M is

doubling down on our commitment to your success, with investments

that include:

• Direct access to some of the best and brightest minds in the industry

– experienced application engineers devoted exclusively to

fluoroelastomer application development and troubleshooting.

• State-of-the-art lab facilities inside 3M’s new, 470,000 s.f. Carlton

Science Center. Here we maintain a wide range of testing, formulating

and processing equipment, designed to replicate real-world conditions.

• Advanced analytical services, available through 3M’s corporate

laboratories You get the industry’s most comprehensive and

personalized technical support included with every box of Dyneon

fluoroelastomer.

Resource links are towards the bottom of the page

3M Fluoroelastomers and Application Engineering

https://www.3m.com/3M/en_US/company-us/all-3m-products/~/All-3M-Products/Advanced-Materials/Fluoropolymers/Fluoroelastomers/?N=5002385+8711017+8721867+8733376+8745513+3294857497&rt=r3https://www.3m.com/3M/en_US/company-us/all-3m-products/~/All-3M-Products/Advanced-Materials/Fluoropolymers/Fluoroelastomers/?N=5002385+8711017+8721867+8733376+8745513+3294857497&rt=r3


Recognition

This presentation would not have been possible without help, guidance or conversations with the

following people:

Mandy Hulke, 3M

Jarod Lowry, 3M

Allen Sohlo, 3M

Yan Van Haegenbergh, 3M

Neil Mendes, Alpine Polytech

Thank you

3M Advanced Materials Division Influence of Fluoroelastomer Compounding on Rapid Gas ... · 2020....

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