Fluoropolymer for Pumps, Valves

8/17/2019 Fluoropolymer for Pumps, Valves

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1

Arkema’s Fluoropolymers

Confidential Information, October 14, 2015


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CPI

1. Polymer Properties

2. KYNAR Applications for SpecificChemical Service



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1. PolymerProperties



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Polyvinylidene Fluoride

Polyvinyl (difluoride)

PVDF

PVF2 Kynar® PVDF

Arkema uses the trade name Kynar® for its brand of PVDF polymers.

Discussion of Polyvinylidene Fluoride



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What is Kynar ®

PVDF?

Fluorspar Monomer

Polymer


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PVDF Molecule

• The C-F Bond in PVDF is One ofthe Strongest Known

• While the alternating C-H bonds allow for uniqueproperties such as:• Improved processing• Intermolecular strength

• Radiation resistance• Hardness



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KYNAR ® PVDF

Properties

Vinylidene

fluoride(VDF)

F

F

H

HC C

Resistant to UVdegradation

High mechanical strength

High thermal stability Chemically resistant Abrasion resistant

Creep resistant

Low surface energy Semi-crystalline

Easily melt processable Soluble in polar solvents Miscible with other

polymers

KYNAR® polyvinylidenefluoride (PVDF)



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PVDF Among FluoropolymersPVDF Among FluoropolymersPVDF Among FluoropolymersPVDF Among Fluoropolymers

Homopolymers

Polyvinyl Polyvinylidene Polychloro- Polytetrafluoro-

fluoride fluoride trifluoroethylene ethylene

PVF PVDF PCTFE PTFE

Copolymers

Tetrafluoroethylene Tetrafluoroethylene Tetrafluoroethylene Chlorotrifluoroethylene

+ perfluoropropene + perfluoropropylether + ethylene +ethylene

FEP PFA ETFE E-CTFE

C

F F

C

HH

C

F F

C

CClF

C

F F

C

FF

C

F F

C

F FC

C

F F

CF

F F

F

CF F

C

F FC

C

F F

OF

CC

F

F

C

F

F

FFF

C

F F

C

F FC

C

H H

HH

C

F F

C

Cl FC

C

H H

HH

C

F H

C

HH



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Generic Names and FormulasGeneric Names and FormulasGeneric Names and FormulasGeneric Names and Formulas

C C

ClF

F F

Poly(chlorotrifluoroethylene)

(PCTFE)

n

C

H

H

C

H

H

C

F

F

C

F

F

Ethylene tetrafluoroethylene

(ETFE)

n

C

H

H

C

H

H

C

F

F

C

F

Cl

Ethylene chlorotrifluoroethylene

(ECTFE)

n

Fluorinated ethylene-propylene copolymer

(FEP)

C

F

F

C

F

F

C

F

F

C

F

C

F F

F

n


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Generic Names and FormulasGeneric Names and FormulasGeneric Names and FormulasGeneric Names and Formulas

C

H

H

C

F

F

C

F

F

C

F

C

F F

F

Polyvinylidene fluoride-

hexafluoropropylene copolymer

(PVDF/HFP)

n

C C

FH

H F

Poly(vinylidene fluoride)

(PVDF)

n

C C

HH

H F

Polyvinyl Fluoride

(PVF)

n

C C

FF

F F

Poly(tetrafluoroethylene)

(PTFE)

n

C

F

F

C

F

F

C

F

O

C

F

F

C

F

F

CnF2n +1

Perfluoralkoxy copolymer

(PFA)

n

C

F

F

C

F

F

C

F

O

C

F

F

C

F

F

CnF2n +1

Poly (tetrafluoroethylene-

perfluoromethylvinylether)

(MFA)

n

CF3


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Chemical Resistance of FluoropolymersChemical Resistance of FluoropolymersChemical Resistance of FluoropolymersChemical Resistance of Fluoropolymers

SOFTER FluoropolymersSOFTER FluoropolymersSOFTER FluoropolymersSOFTER Fluoropolymers(PTFE, FEP, MFA, PFA)(PTFE, FEP, MFA, PFA)(PTFE, FEP, MFA, PFA)(PTFE, FEP, MFA, PFA)

•Tend to resist stressTend to resist stressTend to resist stressTend to resist stresscrackingcrackingcrackingcracking

•Virtually insolubleVirtually insolubleVirtually insolubleVirtually insoluble

•Higher permeationHigher permeationHigher permeationHigher permeation rateraterateratefor small nonfor small nonfor small nonfor small non----polarpolarpolarpolarmolecules (Clmolecules (Clmolecules (Clmolecules (Cl2222, Br, Br, Br, Br2222, etc.), etc.), etc.), etc.)

HARDER FluoropolymersHARDER FluoropolymersHARDER FluoropolymersHARDER Fluoropolymers(ECTFE, ETFE, PVDF hp & cp)(ECTFE, ETFE, PVDF hp & cp)(ECTFE, ETFE, PVDF hp & cp)(ECTFE, ETFE, PVDF hp & cp)

•Some substances canSome substances canSome substances canSome substances cancausecausecausecause stress crackingstress crackingstress crackingstress cracking,,,,especially at higherespecially at higherespecially at higherespecially at highertemperaturestemperaturestemperaturestemperatures

•Typically more resistantTypically more resistantTypically more resistantTypically more resistantto permeation, particularlyto permeation, particularlyto permeation, particularlyto permeation, particularlywith temperatureswith temperatureswith temperatureswith temperatures< 275< 275< 275< 275°F (135F (135F (135F (135°C)C)C)C)

•Some chemicalsSome chemicalsSome chemicalsSome chemicals cancancancandissolvedissolvedissolvedissolve thesethesethesethesefluoropolymersfluoropolymersfluoropolymersfluoropolymers



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Discussion of Molecular

Bonds

C-F bond is very strong and almost totally resistantto chemical attack.

C-H bond is moderately strong and can beattacked by bases and strong oxidizers.

F-F bond is not very strong and favors lubricity over

bonding strength. H-F bond is a strong intermolecular force that adds

to strength and abrasion resistance.

It can be said that Kynar® PVDF and Kynar Flex®

PVDF approach the chemical and thermalresistance of PTFE and PFA, but has improvedstrength over Polyethylene and Polypropylene dueto the H-F interactive bonds in the polymer matrix.



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Polymer Performance Relationships

* Excellent Balance of Properties BetweenPolyethylene (PE) and

Polytetrafluoroethylene (PTFE)

Chemical Inertness & Temperature Rating

Melt Processability

PE PVDF PTFE



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KYNAR®®®® PVDF

HomopolymerResin Melt Point (°C) Flexural Modulus

(PSI)Viscosity (KP)

400 Series

Kynar 450 160 200,000 28-34Kynar 460 160 200,000 23-29

700 Series

Kynar 710 168 280,000 5-8

Kynar 720 168 280,000 7-12

Kynar 740* 168 280,000 15-22

Kynar 760 168 280,000 23-30

Kynar 370* 168 330,000 12-17

1000 Series

Kynar 1000 HD 169 280,000 15-19

Kynar 6000 HD 169 280,000 9-14

Kynar 9000 HD 169 280,000 6-9

IntroductionIntroductionIntroductionIntroduction

*Kynar 740 also offered as red or black. Kynar 740-02 offered with a flame and smoke package.

*Kynar 370 is carbon filled for shrinkage and stiffness.



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KYNAR FLEX®®®®PVDF

Resin Melt Point (°C) Flexural Modulus(PSI)

Viscosity (KP)

2000 Series

Kynar Flex 2500* 115-125 25-45,000 8-15

Kynar Flex 2750* 135 50-60,000 20-25

Kynar Flex 2800* 143 90-120,000 21-27

Kynar Flex 2850* 158 160-180,000 21-27

3000 Series

Kynar Flex 3120* 163 90-120,000 20-26

*Offered in various viscosities and/or with a flame and smoke package.

*Kynar Flex 2850 offered also as standard black or as RC10098 conductive grade.

IntroductionIntroductionIntroductionIntroduction



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Special Properties of Kynar®®®® and Kynar

Flex®®®®

Resistant to most chemicals and solvents

Low permeability to most gases and liquids

High thermal stability

Mechanical strength at elevated temperature

Cold weather impact strength (specific to KynarFlex®)

High purity,High abrasion resistance Readily processible, formable, and weldable

Resistant to sunlight degradation

Resistant to nuclear radiation Resistant to fungus

Low flame and smoke characteristics



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Chemical Resistance of Polymers

Stress Cracking – where the polymer is embrittled bybeing in contact with the chemical (Polymers don’t rustlike metals, but they can be eaten away by chemicals thatattack their backbone).

Swelling – where the polymer absorbs enough of thechemical that it changes the dimensions of the componentin such a way that it no longer performs its intended use.

Permeation – where the chemical passes through thepolymer to either the atmosphere or to the substrate thatthe polymer is protecting.

Dissolving – where the chemical plasticates the polymer

leaving it as a soft residue independent of its originalshape.

Thermal - where the material cannot handle thetemperature conditions and distorts.

Chemical failure can be broken down into at least 5 categories



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Chemical Resistance of Polymers

Concentration of chemical(s). Is it 100%, 10% or

trace


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Special Properties of PVDF & PVDF Copolymers(Kynar® & Kynar Flex® PVDF)

PVDF is the strongest Fluoropolymer up to 140C.

PVDF has excellent permeation resistance to non polarchemicals such as bromine, chlorine, benzene &

aliphatic hydrocarbons PVDF and some PVDF Copolymers have abrasion

resistance equivalent to Nylon and UHMWPE

PVDF has very good resistance to high levels of gammaradiation as is found in nuclear plants

PVDF meets nearly every flame and smoke testdesigned to measure plastic performance in fire

situations PVDF resins are available that readily bond to metal and

less expensive polymers in composite structures



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Other Important Features of KYNAR ® PVDF

Gas permeation can be more than 100 times lower

than other fluoropolymers (as reported by Intel)

Use temperature continuous at 140°C (many

installations)

Short use temperature to 150°C (case history

examples)

Steamable (repeated steam cycles no effect)

Hardest and most abrasion resistant high purity

polymer

Passed many flame and smoke tests including

Factory Mutual 4910 and ASTM E84



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Listings & Approvals for “Natural” KYNARListings & Approvals for “Natural” KYNARListings & Approvals for “Natural” KYNARListings & Approvals for “Natural” KYNAR®®®® ResinsResinsResinsResins

FDA 177.2510 or 177.2600FDA 177.2510 or 177.2600FDA 177.2510 or 177.2600FDA 177.2510 or 177.2600 3A sanitary standards for multiple3A sanitary standards for multiple3A sanitary standards for multiple3A sanitary standards for multiple----use plasticsuse plasticsuse plasticsuse plastics

materials used as product contact surfaces for dairymaterials used as product contact surfaces for dairymaterials used as product contact surfaces for dairymaterials used as product contact surfaces for dairyequipmentequipmentequipmentequipment

USDA (meat and poultry foods)USDA (meat and poultry foods)USDA (meat and poultry foods)USDA (meat and poultry foods)

United States Pharmacopea (USP) Classification VIUnited States Pharmacopea (USP) Classification VIUnited States Pharmacopea (USP) Classification VIUnited States Pharmacopea (USP) Classification VI

NSF 61 (potable water)NSF 61 (potable water)NSF 61 (potable water)NSF 61 (potable water) NSF 51 (food contact)NSF 51 (food contact)NSF 51 (food contact)NSF 51 (food contact)

Various military specs for physical properties,Various military specs for physical properties,Various military specs for physical properties,Various military specs for physical properties,

weathering and fungus resistanceweathering and fungus resistanceweathering and fungus resistanceweathering and fungus resistance Various flame and smoke tests for cable, piping,Various flame and smoke tests for cable, piping,Various flame and smoke tests for cable, piping,Various flame and smoke tests for cable, piping,

flexible conduit and all encompassing material listingsflexible conduit and all encompassing material listingsflexible conduit and all encompassing material listingsflexible conduit and all encompassing material listings



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ChemicalChemicalChemicalChemicalResistanceResistanceResistanceResistance

1 KYNAR ® polyvinylidene

fluoride – Type I

2 Polypropylene

3 Polyvinylidene chloride

4 Polyvinyl chloride* --

Type I

5 Polyester

(glass fiber reinforced)* Above recommended operating temperature of plastic

Chemical Resistance Pictograph:

200°F


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Widest Processing WindowWidest Processing WindowWidest Processing WindowWidest Processing Window

0

50

100

150

200

250

300

350

400

450

PTFE PFA FEP ETFE ECTFE PCTFE PVDF PVF

Fusion

Decomposition

Widest processing window among fluoropolymers 180Widest processing window among fluoropolymers 180Widest processing window among fluoropolymers 180Widest processing window among fluoropolymers 180 ---- 290290290290 ° C (360C (360C (360C (360 – 550550550550 °F)F)F)F)

T e m p

e r a t u r e

T e m p

e r a t u r e

T e m p

e r a t u r e

T e m p

e r a t u r e ° C CC C

Actual melting point will vary depending on Kynar grade 120Actual melting point will vary depending on Kynar grade 120Actual melting point will vary depending on Kynar grade 120Actual melting point will vary depending on Kynar grade 120----170170170170 °CCCC (248(248(248(248----340340340340 °F)F)F)F)



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1995

1981

Taiyo Steel, Funabashi, Japan

Kynar500 ®

Polyester Kynar500 ®

SiliconePolyester

Acrylic

Kynar®®®®Weathering – 14 Years



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Protection of Solar Panels Using Kynar®Film Due to excellent UV stability, Kynar® based films are a leading material

used to protect solar panels in the growing Solar energy market.

Solar “farms” Solar roofing for houses

Solar roofing forcommercial buildings

Foldable battery charger

for military applications



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Plastic Pipes vs. Metal pipes: Coefficient of Friction

Material Static CoefficientFriction

(ASTM1894, 73ºF, vs.Steel)

Steel (clean dry) 0.7 – 0.8

Nylon 0.15 – 0.25

Kynar 0.15 – 0.30

HDPE 0.20 – 0.30

PTFE 0.04 – 0.06

Plastic materials: lower coefficient of friction than metals



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2. Applications for Specific Chemical

Servicea) Bromine

b) Chlorine

c) Metal Preparation

d) Pharmaceutical and Biotech

e) Nuclearf) Fuel Handling

g) Water Treatmenth) General Chemical Handling

i) High Purity Applications

Flam R tardant R uir m nt


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Kynar® PVDF is easily manufactured intoChemical handling components by:

Extrusion (pipes, tubing, monofilament, sheet, rod/bar)

Injection Molding (pumps, nozzles, valves, tower packing

fittings, baskets, flow meters)

Compression Molding (block/slab, thick parts)

Rotomolding (tanks, tubs)

Powder Coating (tanks, containers, valves, pipes)

Solution Casting (membranes)

Welding & Thermoforming (tanks, filters)


Reasons that Kynar® is used in Bromine


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Reasons that Kynar® is used in BromineApplications

Bromine is very corrosive to even some of the most high performingmetals

Kynar® & Kynar Flex are not swelled or appreciably attacked bybromine at room temperature.

Chemical resistance to bromine and chlorine which are often foundtogether.

The unique high polarity of Kynar® resins repel the non-polar Br2structure and the not so polar HBr acid.

Kynar® polymer is strong enough to be used as a cost effectiveunsupported piping system unlike other fluoropolymers.

Kynar® is easily welded and fabricated for special structures.

Long term case histories of success are readily available from happychemical companies that are willing to share their stories ofproblems solved by using Kynar® PVDF

Kynar has food listings and pharmaceutical industry listings forspecial formulations of bromine compounds used in food and drugapplications



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Materials in Contact with Bromine Common Metals and Stainless steel are rusted

quickly by bromine.

Nickel and other high priced metals perform inbromine, but at a high cost and a limited life.

Common plastics and rubbers are cracked fromchemical attack from bromine service over time.

Fully fluorinated polymers such as PTFE, FEP and

PFA are swelled and/or permeated by bromine. FRP generally cannot effectively handle bromine for

continuous service without cracking in service.

Kynar® & Kynar Flex® PVDF resist brominechemicals for long duration and are not readily proneto permeation and swelling in bromine or brominatedsolvents below 60C.



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Test data of Kynar® PVDF in Bromine

Permeation studies at Southwest ResearchInstitute (SWRI) in Texas for thin wall tubingat ambient temperature.

Several fluoropolymers tested and Kynar® andKynar Flex® showed no significant measuredpermeation after 6 weeks of static testing. Other

fluoropolymers and polypropylene showedmeasurable permeation.

Container/Bottle tests conducted toinvestigate swelling.

No measured weight gain observed after 1 weekof storage.



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Testing in Acid Environments

Handles most acids to elevatedtemperature without significant change inphysical properties.

Common acids handled by PVDF inindustrial applications are: Hydrochloric (0-

37%); Nitric Acid (0-71%); Sulfuric (0-97%);Hydrofluoric (0-70%); Acetic (0-50%);Hydrobromic; Phosphoric, Citric, Salicylic,

Methane Sulfonic; Chromic. In extraction testing, exhibits purity to

Semiconductor Grade acids equal to PFA.



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Testing in Water Systems

Handles Steam up to 140 C without loss ofproperties over many cycles.

Commonly used to handle 16-18 megohmdeionized water in Semiconductor andPharmaceutical Facilities since 1982.

Meets ASTM F-1673 chemical testingrequirements for laboratory waste drainagesystems (water combined with acids, bases,hydrocarbons, chlorinated cleaning solutions, &

ketones)



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Chemical Processing Industry

General Chemical

High Purity


G l Ch i l P i


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General Chemical ProcessingPiping System

A complete line ofcomponents is available forall chemical processing

applications:• Welded, flanged and

mechanical systems

• in-line, socket, IR andelectro-fusion joints


General Chemical


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Dual Containment

Pressure Pipe

General ChemicalProcessing Piping System



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Chemical Processing Tank and Pipe Lining

Kynar Flex® LinedVessel (metal or FRP)

Kynar Flex® LinedPipe (metal or FRP)

Chemical Resistance

pH Range of 1 - 13.5



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Calvert City’s High Purity DI Water System for Washing KYNAR



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Kynar® for High Purity Components

Pumps

Filters and Filter Housings

Fittings

Valves

Stock Shapes

Tubing


Waste Water and Water


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Waste Water and Water

Purification Industry Tower Packing Potable Water

Filters


KYNAR H ll Fib M b


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KYNAR Hollow Fiber Membrane



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Tank Linings



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Plastic Lined Steel for Handling Sulfuric Acid


Kynar®®®® PVDF and Kynar Flex®®®® PVDF Flame and Smoke Related


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Kynar®®®® PVDF and Kynar Flex®®®® PVDF Flame and Smoke RelatedApprovals

Unfilled Kynar® resin has a limiting oxygen index(LOI) of 44%.

Special grades of Kynar® resin have an (LOI) ofgreater than 95%.

Kynar ® and Kynar Flex® meet many

Underwriters Laboratories (UL) standards. Kynar® and Kynar Flex ® meet Factory Mutual

FM 4910 criteria.

Kynar® and Kynar Flex® have been tested toBritish Standards.

Over 15 flame and smoke approvals existworldwide.


St i T l


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Steiner Tunnel

Both ASTM E 84 and ULC S 102.2 use theSteiner Tunnel


Chemical Drainage Piping System


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ASTM E-84 Rated for FireSafety

Can be used for almostany chemicalcombination in dilutedwaste streams

Chemical Drainage Piping System


Kynar Flex® PVDF as Wire & Cable Insulation


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Kynar Flex® PVDF as Wire & Cable Insulationand Jacketing Flexible Corrugated Protective Conduits



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Documents

Fluoropolymer for Pumps, Valves