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KYNAR

Chemical resistance tables

KYNAR
Chemical resistance tables
Index
Page numbers

1. General Introduction 2. Resistance criteria Standards 3. KYNAR - General resistance table 4. KYNAR - Long term ageing and stress resistance behaviour 5. SOLVENTS for KYNAR PVDF 6. Resistance of KYNAR PVDF to BASES and ALKALIS 7. Resistance of KYNAR PVDF to CHLORINE 8. Resistance of KYNAR PVDF to SULFURIC ACID 9. Resistance of KYNAR PVDF to BROMINE 10. Chemical resistance of KYNAR FLEX PVDF copolymers 11. Permeability properties of KYNAR PVDF 12. Comparison of chemical resistance of KYNAR PVDF with other
thermoplastic materials used in the chemical process industry

3 4 to 5 6 to 13 14 to 17 18 19 to 21 22 to 23 24 to 25 26 to 27 28 to 30 31 to 36

The information contained in this document is based on trials carried out by our Research Centres and data selected from the literature, but shall in no event be held to constitute or imply any warranty, undertaking, express or implied commitment from our part. Our formal specifications define the limit of our commitment. No liability whatsoever can be accepted by ARKEMA with regard to the handling, processing or use of the product or products concerned which must in all cases be employed in accordance with all relevant laws and/or regulations in force in the country or countries concerned.

Technical Polymers Division


420, rue dEstienne dOrves - 92705 Colombes (France) Tel. (33) 01 49 00 80 80 - Tlfax (33) 01 49 00 83 96 BDI MW 005680/01 -hemical resistance tables of Kynar

1.

Introduction

KYNAR polyvinylidene fluoride (PVDF), the homopolymer of 1,1-difluoroethylene, is a tough engineering thermoplastic. The unique structure of alternating methylene and difluoromethylene units along the chain creates a polymer material having high crystallinity combined with a high polarity resulting in sharp melting point. Thus KYNAR PVDF has the characteristic stability of fluoropolymers when exposed to harsh thermal, chemical and ultraviolet environments while retaining the properties of a conventional thermoplastic material. KYNAR PVDF can readily be processed by all known extrusion and molding processes.
Important properties of KYNAR

PVDF :

Mechanical strength and toughness High abrasion resistance High thermal stability Very low creep High dielectric strength High purity Readily melt processable Exceptional outdoor weather resistance due to its total inertness to UV radiation Resistance to nuclear radiation Resistance to fungi Very smooth surfaces can be obtained Low permeability to most gases and liquids Low flame and smoke characteristics Rigid and FLEX ible versions available

KYNAR , Polyvinylidene difluoride, offers very good chemical resistance in the presence of a wide variety of different chemicals up to high temperatures of approximately 150C:

KYNAR resists well : - to acids - to salt solutions - to oxydants - to halogens - to alcohols - to chlorinated solvents - to aliphatic hydrocarbons - to petrol
At higher temperatures KYNAR attacked by :

KYNAR swells in certain polar


solvents :

- ketones - esters

The

following

solvents

dissolve

is

KYNAR : - Dimethyl acetamide (DMA) - Dimethyl formamide (DMF) - N-methyl pyrrolidone (NMP)

- amines - concentrated sulfuric or nitric acid - alkaline solutions of intermediate concentration 3

BDI MW 005680/01 -hemical resistance tables of Kynar

2 Resistance criteria - Standards


The following tables show results based on short time scale trials. These laboratory tests allow to screen a great number of chemicals of which sensitive chemicals have been further investigated. The tests have been undertaken as follows: - Tensile specimens according to the standard ASTM 3222-73 and injected sheets are immersed into the indicated chemical. - After 7 days of immersion the samples are tensile tested according to the standard ASTM D 638 and the obtained values compared to the values of non exposed samples. - Swelling measurements are performed on the injected sheets according to the standard ASTM D 543.67.

The judgement on chemical resistance is based on the standard ISO 4433.

It is based on: - variation of weight - surface aspect - coloration - mechanical properties (stress at yield , elongation at break)

+ resistant or satisfactory , if

0 partial or limited resistance , if

- not resistant or not satisfactory resistance , if

- 2 % m + 10 % Q 80 % and R2 0,9 S1 and S2 2 S1

and

- 2 % m + 10 % and 80 % > Q > 46 % and R2 0,9 S1 and S2 2 S1 or - 2 % m + 10 % and Q 80 % and S1 R2 0,9 S1 and S2 2 S1

m > 10 % or m < -2 % Q 46 % and R2 0,9 S1 and S2 2 S1 or - 2 % m + 10 % and 80 % > Q > 46 % and S1 R2 0,9 S1 and S2 2 S1

Q = S2 / S1 index 1 = reference sample index 2 = aged sample m = mean of relative weight change S = mean value of tensile stress at yield s = mean value of elongation at yield R = mean value of elongation at break

It should be noted that this classification does not yet take into account the resistance under mechanical load, such as the pressure bearing of a pipe. For this type of resistance additional tests have to be done. In this brochure the long term ageing tests done with applied stress give information on this subject.

BDI MW 005680/01 -hemical resistance tables of Kynar

2 Resistance criteria - Standards


Classification based on the factor Q
100 +

0 Q - value

10
7 14 28 56 112 365 730

Days

A simplified approach, which allows chemical compatibility estimations by following the weight change only, has been established by the German Institut fr Bautechnik (Institute for construction and building). There it was found that it exists a straightforward relation between weight change and modulus evolution during immersion testing.
2500

2000

E modulus (MPa)

1500

1000

500

0 0 5 10 15 20 25 change of weight (%)

BDI MW 005680/01 -hemical resistance tables of Kynar

Chapter 3

KYNAR

General chemical resistance table

This table designed to serve as a general guide to the chemical compatibility performance of KYNAR PVDF has been based mainly on laboratory experiments, in particular immersion tests with at least 30 days observation time. The performance criteria have been described in chapter 2. Many important chemicals have been tested for considerable longer time scales. These results are described in chapter 4. In separate chapters 5, 6, 7, 8 and 9 particular chemicals are reviewed in detail and their chemical action leading to compatibility limits described. Whenever possible, field trials and observations are included. The results in the General chemical resistance table refer to the chemical compatibility of KYNAR PVDF itself. The performance of equipment where KYNAR PVDF is used for corrosion protection depends on the entire design. For instance, permeation of chemical species can reduce the temperature rating of the equipment design to a lower value than that for KYNAR PVDF.
Use of the table :

A drawn arrow signifies the classification + . A dotted arrow signifies the classification 0 . The sign ! signifies the classification - .

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3 - KYNAR - General chemical resistance table


Mineral Acids Conc. 25 50 75 100 125 150

Boric acid Hydrobromic acid Hydrochloric acid Hydrochloric acid Cyanic acid Hydrofluoric acid Hydrofluoric acid Hydrofluoric acid Nitric acid Nitric acid Perchloric acid Phosphoric acid Phosphoric acid Sulfuric acid Sulfuric acid Sulfuric acid Sulfuric acid Hydrogen sulfide Chlorsulfonic acid Fluorosulfonic acid Fluorosilicic acid

saturated 50%
concentr. /35%

gas 100% 40% 70% 100% 30% 65% 70% 85% 98% 50% 80% 93% 98% 98% 97%

Mixtures of Mineral Acids

Conc.

25C

50

75

100

125

150

Sulfuric / nitric (1 / 1) Nitric / Hydrochloric (1 / 3) Phosphochromic :


- phosphoric 80% - Chromium trioxide 5% - Sulfuric 3%

40% 100%

Sulfochromic :
- Sulfuric 15%, Water 35% - Chromium trioxide 50% Anhydrides and chlorides of Mineral Acids Conc. 25 50 75 100 125 150

Chromic anhydride Chromic anhydride Phosphore trichloride Phosphor pentachloride Phosphoroxy trichloride Thionyl chloride Sulfuric anhydride Sulfuryl chloride

saturated 60% 100% 100% ! 100% 100% 100% 100%

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3 - KYNAR - General chemical resistance table


Mineral Bases *please refer also to chapter 6 Conc. 25 50 75 100 125 150

Ammonia Ammonia solution Potassium hydroxide Sodium hydroxide Sodium hydroxide


Mineral salts

gas 30% 50% 45% 60%


Conc. 25 50 75 100 125 150

All types of neutral or acidic mineral salts in solution up to saturation Titanium tetrachloride Boron trifluoride
Elements

100% 100%
Conc. 25 50 75 100 125 150

Bromine Bromine Chlorine Chlorine Chlorine Fluorine Hydrogen Iodine Mercury Oxygen Ozone Ozone Sulfur

dry humid dry -no UV Humid no UV with UV !

gas (2%) solution

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3 - KYNAR - General chemical resistance table


Organic acids Conc. 25 50 75 100 125 150

Acetic acid Acetic acid Acrylic acid Benzene sulfonic acid Benzoic acid Chloro-acetic acid Chloro-acetic acid Citric acid Formic acid Gallic acid Glycolloic acid Lactic acid (2-hydroxypropanoic) Lauric acid (dodecanoic) Linoleic acid (9,12octadecadieneoic) Maleic acid Malic acid Methane sulfonic acid Oleic ac. (9-octadecenoic ) Oxalic acid Palmitic acid Phtalic acid Picric acid (2,4,6 trinitrophenol) Salicylic acid Stearic acid Tartric acid Trichloro-acetic acid Trichloro-acetic acid
Anhydrides and chlorides of Organic acids

100% 50% concentr. satur. 75% 100% 50% 98% satur. satur. 50% 100% 100% satur. satur. 50% 100% satur. 100% satur. 10% 50% satur. satur. 50% 100%
Conc. 25 50 75 100 125 150

Acetic anh. Acetic acid chloride Chloro-acetic acid chloride Benzoyl chloride Trichloro-acetic acid chloride

100% 100% 100% 100% 100%

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3 - KYNAR - General chemical resistance table


Alcohols, Glycols, Phenols Conc. 25 50 75 100 125 150

Pentanol (amyl alc.) Benzyl alc. n-Butyl alc. sec. Butyl alc. tert. Butyl alc. Butyl phenol (1-butyl-2hydroxy benzene) Cresole Cyclohexanol
4-Hydroxy-4-methyl-2pentanone

100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 10% 100% 100%

Ethanol Ethylene glycol Glucose Glycerol Methanol Phenol Phenol Propanol Pyrogallol (1,2,3-trihydroxy benzene)
Aldehydes, Ketones

Conc.

25

50

75

100

125

150

Acetone Acetone Acetone Acetone Acetophenone Acetyl-acetone Acroleine Benzaldehyde Butanone Chloral Crotonaldehyde Cyclohexanone Diisobutylketone Formaldehyde Furfural Methyl-isobutylketone Salicylic aldehyde

100% 50% 10% 5% 100% 100% 100% 100% 100% 100% 100% 100% 100% 30% 100% 100% 100%

! ! ! ! !

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3 - KYNAR - General chemical resistance table


Amines *please refer also to chapter 6 Conc. 25 50 75 100 125 150

Aniline n-Butyl amine sec. Butyl amine tert. Butyl amine Diethyl amine Diethylene triamine Dimethyl amine Dimethyl aniline Ethylene diamine Mono ethanol amine Morpholine Phenyl hydrazine Piperazine Pyridine Triethyl amine
Nitriles, Nitro or sulfur products

100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100%
Conc.

! ! ! !

25

50

75

100

125

150

Acetonitrile Acrylonitrile Carbon disulfide Nitro-benzene Nitro-methane


Esters

100% 100% 100% 100% 100% Conc. 100% 100% 100% 100% 100% 100% 100% 100% Conc. 100% 100% 100% 100% 100% 100% 100% 25 50 75 100 125 150

Butyl acetate Butyl acrylate Cyclohexyl acetate Dimethyl phtalate Ethyl acetate Ethyl acrylate Pentyl acetate Tributyl phosphate
Ether oxydes

25 ! ! !

50

75

100

125

150

Chloromethyl methylether Dioxane Diethyl ether Furane Ethylene oxyde Propylene oxyde Tetrahydrofurane (THF)

3 - KYNAR - General chemical resistance table


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Chlorinated hydrocarbons

Conc.

25

50

75

100

125

150

Allyl chloride Benzyl chloride 1-Chloro-pentane Chloro-benzene Chloroforme CFC 113 * CFC 114 * CFC 11 * CFC 12 * Dichloro-benzene Dichloro ethane Epichlorhydrine Ethyl chloride HCFC 22 HFC 134 a HFC 407 c HFC 410 a Lauryl chloride Methyl chloride Methylene chloride Tetra-chloro ethylene Trichloro-benzene 1,1,1-trichloro ethane Trichloro ethylene

100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100%

Other halogenated hydrocarbons

Conc.

25

50

75

100

125

150

1-Bromo-butane 1,2-Dibromo ethane Iodoforme Methyl bromide

100% 100% 100% 100%

The compounds marked by an asterix (*) are chloro-fluoro-carbons, which have been banned because of their atmospheric ozone depletion effect. The information here is given only for general purposes.

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3 - KYNAR - General chemical resistance table


Hydrocarbons

Benzene Butadiene Butene Cyclohexane Dekaline Heptane Hexane Kerosene Methane Naphta Naphthalene Octane Octene Propane Styrene Terpentine Toluene Xylene

Conc. 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100% 100%

25

50

75

100

125

150

Miscellaneous

Conc.

25

50

75

100

125

150

Crude Oil Hydrogen peroxide Kerosene Light Fuel Milk Mineral oil Oil Gilotherme Oil Voltalef 1 Oil Voltalef 3 Petrol E Potable water Pyralene oil Seawater Silicon oil S 510 Toluene diisocyanate (TDI) Urea

30%

50%

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Chapter 4

KYNAR

Long term ageing and stress resistance behaviour

The trials for long term chemical resistance are inspired by the standard ISO 4433 and has been adapted in the following way: Test specimen according to the standard ASTM D 1708 were cut out of an extruded band of 0,7 mm thickness. These specimen were then placed into a recipient in full immersion of the chemical either without tension or in a folded manner according to the description of the standard ASTM D 1693. The evolution of the weight and the tensile properties were then noted and a classification was noted according to the principle of the standard ISO 4433 for test specimen without tension and for the folded ones under tension.
3 categories are thus established:

+ 0 -

non-limited use
(small variations of weight and tensile properties)

limited use
(use only in absence of pressure or stress)

do not use

In case the specimen without tension leads to a positive result and the specimen under tension obtains a negative result, the overall usability must be interpreted such that KYNAR does not sustain strong stress nor tension under the conditions of the chemical exposed.

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4 - KYNAR - Long term ageing and stress resistance behavior

Reactant

Temp. ( C)

Exposure time

under tension

no tension

Acids

Acetic acid 50 % Acetic anhydride conc. Eau rgale HCl 35 % /HNO3 65% 2 / 1 Etching solution H3PO4 (85 %) 85 %, CH3CO2H 5 %, HNO3 (64 %) 5 %, H2O 5 % Hydrobromic acid 66 % (conc.) Hydrochloric acid 35 % (conc.) Hydrochloric acid + dichloroethane (10 %) Hydrochloric acid + dichloroethane (10 %) Hydrochloric acid + methanol (10 %) Hydrochloric acid + methanol + chloroforme Nitric acid 32% Nitric acid 32 % Nitric acid 52 % Nitric acid 65 Nitric acid 98 % (conc) Nitric acid 98 % Oxalic acid 250 gl-1 Phosphoric acid 85 % (conc.) Sulfuric acid 50 % * Sulfuric acid 80 % * Sulfuric acid 80 % * Sulfuric acid 96 % * Sulfuric acid 96 % * Sulfuric acid 99,2 % * Sulfuric acid 99,2 % * Sulfuric acid saturated with chloride 65 - 98 % Sulfuric acid 98 % + chloroforme (10 %) Sulfuric acid 98 % + diethylether (10 %) Sulfochromic acid CrO3 50 %, H2SO4 15 % Trichloroacetic acid 50 % * please also refer to chapter 9

130 23 90 90 90 130 90 130 50 50 90 130 130 90 50 90 75 130 130 130 90 50 75 50 23 23 50 50 90 75

1y 1y 1y 4m 1 year 1y 6m 6m 6m 6m 1y 6 months 2m 6m 2m 2m 2m 1y 1y 6m 1y 6m 3m 6m 6m 8m 6m 6m 1y 4m

+ 0 + + + + + 0 + + + + 0 + + + + + + 0 0 + + + + +

+ 0 + + + + + + + + + + 0 + + + + + + + + + + + + + + +

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4 - KYNAR - Long term ageing and stress resistance behavior


Reactant Temp. ( C) *please refer also to chapter 6 Exposure time under tension no tension

Bases

Ammonium hydroxide solution 20 % Ammonium hydroxide solution 20 % Ammonium hydroxide solution 20 % Ammonium hydroxide solution 29 % Ammonium hydroxide solution 29 % Ammonium hydroxide solution 29 % Sodium hydroxide 10 % Sodium hydroxide 10 % Sodium hydroxide 10 % Sodium hydroxide 45 % Sodium hydroxide 45 % Sodium hydroxide 10 % +1,7% Triton X100 Sodium hydroxide 10 % +20% methanol Sodium carbonate solution 40 % Tetramethyl ammonium hydroxide (TMAH) Tetramethyl ammonium hydroxide
Halogens and inorganic halogenated derivatives

23 50 90 23 50 75 23 50 90 90 130 23 50 90 23 50

6m 3m 1m 9m 9m 2m 2 months 2m 2m 1 year 3m 1m 1m 6m 4m 2m

+ + + + + -

+ + + + + + + + + + + + + +

Bromine Chlorine gaseous without light Chlorine gaseous with UV light exposure Hypochlorite solution 48 javeline Hypochlorite solution 48 javeline Hypochlorite solution 100 javeline Phosphoroxy trichloride (POCl3) Phosphor trichloride (PCl3) 98 % Sodium chlorite (NaOCl) 845 gl-1 Sodium chlorate (NaClO4) 500 gl-1 Sulfuryl chloride (SO2Cl2) Thionyl chloride (SOCl2)
Surfactants

60 100 30 90 130 90 50 50 60 90 23 50

1y 11 d 11 d 3 months 3m 15 days 4m 1y 6m 1 year 4m 4m

+ + 0 + + + +

+ + + + 0 + 0 + + + + +

anionic surfactants anionic surfactants non-ionic surfactants dish washing detergent

90 130 90 90

2 months 2m 2m 6 weeks

+ + + +

+ 0 + +

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4 - KYNAR - Long term ageing and stress resistance behavior


Reactant Temp. ( C) Exposure time under tension no tension

Hydrocarbon solvents

Crude oil Crude oil Crude oil Cyclohexane Decaline Tetraline Toluene Xylene
Halogenated solvents

90 130 150 90 90 90 90 90

2 years 2y 2y 4m 4m 4m 9 months 2y

+ + + + + + + +

+ + + + + + + +

Benzene / chlorobenzene (1 / 1) Chloro-acetyl chloride Chlorobenzene Chloroforme Chloroforme 1,2-Dichloroethane Dichloromethane Dichloromethane Perchloroethylene Tetrachlorocarbon Trichloroethylene 1,1,1-Trichloroethane
Oxygenated solvents

130 90 23 50 90 50 90 90 90 90 90

6 months 4m 4m 4m 1y 4m 4m 9m 6m 1 year 4m

0 0 + + + + + + 0 + +

0 0 + + + + + + 0 + +

t-Butyl methyl ether Cyclohexanone Cyclohexanone Dibutyl phthalate Ethyl acetate Ethyl 2-ethoxy-acetate Ethylene glycol Glycerol Isopropanol Isopropanol 60 % +H3PO4 23 %+P2O5 17 % Methanol Phenol 10 % Ultra pure water (resistance 18 MO)

50 23 50 90 50 50 130 130 130 130 90 90 150

4m 4m 2 weeks 4m 6m 4m 1 year 1y 4 months 4m 4m 1y 1y

+ 0 + + + + + + + + +

+ 0 + + + + + + + + +

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5 - Solvents for KYNAR PVDF


Active solvents

(Dissolve at least 5 - 10 % KYNAR resin at room temperature.) Boiling point (C) 56 65 80 153 166 177 189 195 202 Flash point (C) - 18 -17 -6 67 70 75 35 95

Acetone Tetrahydrofuran (THF) Methyl ethyl ketone (Butanone) Dimethyl formamide (DMF) Dimethyl acetamide (DMA) Tetramethyl urea Dimethyl sulfoxide (DMSO) Trimethyl phosphate N-methyl-2-pyrrolidone (NMP)

Intermediate solvents

(Do not swell or dissolve KYNAR resin at room temperature, but at elevated temperature and keep the resin in solution when cooled to ambient temperature.) Boiling point (C) 204 215 217 Flash point (C) 98 96 110

Butyrolactone Isophorone Carbitol acetate

Latent solvents

(Do not dissolve or substantially swell KYNAR resin at room temperature, but at elevated temperature. When cooled to room temperature the resin crystallizes / precipitates from the solution.) Boiling point (C) 118 135 157 167 169 180 215 242 280 118 120 Flash point (C) 23 24 54 61 49 84 116 132 149 40 30

Methyl isobutyl ketone N-butyl acetate Cyclohexanone Diacetone alcohol Diisobutyl ketone Ethyl acetoacetate Triethyl phosphate Propylene carbonate Dimethyl phthalate Glycol ethers Glycol ether esters

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6 - Resistance of KYNAR PVDF to BASES and ALKALIS


KYNAR PVDF resists well to a large variety of different chemicals. However, it has been well established that bases and alkalis can chemically attack PVDF resins leading to chemical embrittlement (for a litterature review please refer to the end of this chapter). The extent of the chemical attack of PVDF by different bases is greatly governed by temperature, concentration and, in particuliar, by the type of base.

The general mechanism of base attack on PVDF relies on the dehydroflourination reaction which is initiated by absorbed base molecules. The resultant double bonds formed by the elimination of HF from the polymer backbone give rise to coloration. In case the dehydrofluorination reaction is very pronounced the material becomes brittle.
Molecular mechanism of the base attack:

B H C F HH C C F F HH C C F F H C F H H F
-

+ +

H C C F C

HH C F C

H C F

F F

Since the absorption of a base is the prerequisite for the chemical attack, the solubility of the base in PVDF becomes a most dominant factor. The other important factor is the reactivity of the base. For a given base these factors depend on temperature and concentration. The solubility of sodium hydroxide in PVDF is very low. At higher temperatures this leads to a distinct surface degradation with the formation of a black brittle degraded skin with underlying nondegraded PVDF which is impermeable and protects underlying material as long as it is undamaged. Under stress the cracks formed in the brittle skin can propagate into the bulk material leading to failure. For most applications in the chemical process industry we recommend to follow the indications given in the table for KYNAR homopolymer:
Sodium hydroxide aqueous solution

25

50

75

100

125

Comments yellow brownish black black

4 gl-1 pH = 13 40 gl-1 pH = 14 100 gl-1 10 % 450 gl-1 45%

X X

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The importance of the solubility in PVDF and the reactivity of the base in the chemical degradation of PVDF are illustrated in the following table comparing the chemical compatibility of different amines in a series of increasing molecular size :
Amines Formula
(CH3)NH HOC2H4NH2 (OC4H8NH) (C5H5N) C4H9NH2 (C2H5)2NH (C4H9)2NH (C4H9)3N C16H33NH2

25

50

75

100

125

150

Dimethyl amine Ethanol amine Morpholine Pyridine n-Butyl amine Diethyl amine Dibutyl amine Tributyl amine Fatty amine

! ! ! ! !

KYNAR FLEX PVDF copolymers offer improved base resistance

KYNAR FLEX , PVDF copolymers, offer a significantly improved chemical resistance due to two effects. - The higher flexibility reduces stress cracking significantly. - The perfluorinated comonomer disrupts the dehydrofluorination process suppressing the embrittlement.
Dehydrofluorination and the blocking of its progress in KYNAR FLEX PVDF copolymers
PVDF H C F HH C C F F HH C C F F H C F HF H C H C F C F HH C C F F H C F HF H C H C F C H C F C F H C F

KYNAR FLEX F C F F F F CH C C F F HF F H C C F F C F C F FF CH C C F F H C F HF H C F C F C F F F F CH C C F F H C F

H C

HF C F

The partial blocking of the dehydrofluorination reaction results in significantly improved colour retention and reduction of material embrittlement.

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Laboratory test results :


Sodium Hydroxide (NaOH)

90C KYNAR FLEX


3120-50

3 months KYNAR FLEX


2850

KYNAR

KYNAR FLEX
2800

homopolymer 1000 HD and 740

pH pH 10 20

13 14 % %

0/-

+ +/0 +/0 0/-

+ +/0 +/0 0

+ + + +

Based on our laboratory tests and experience in applications using KYNAR FLEX grade 2850 we recommend the following temperature concentration limits for practical use in chemical process units :
Sodium hydroxide aqueous solution

20

40

60

90

125

Comments

4 gl-1 pH = 13 40 gl-1 pH = 14 100 gl-1 10 % 200 gl-1 45%

Litterature on PVDF resistance to bases : Cracking of Poly(Vinylidene Fluoride) linings in chemical tankers P.ACID Lepoutre, C.D. Sterling, V.S.M. Van Tilburg, Corrosion Australia 15(6), 9 (1991) Stress corrosion cracking of Poly(Vinylidene Fluoride) in sodium hydroxide S.V. Hoa, P. Oulette, Pol. Eng. And Sci. 23(4) , 202 (1983) Cracking of Poly(Vinylidene Fluoride) due to chemical attack , C.D. Sterling, V.S.M. Van Tilburg, N.ACID Miller, Polymers + Polymer Composites, 1(3), 167 (1993) Phase transfer catalysis in Dehydrofluorination of Poly(Vinylidene Fluoride) by aqueous sodium hydroxide solutions H. Kise, H. Ogata, J. Pol. Sci. 21, 3443 (1983) Verhalten von Polyvinylidenfluorid (PVDF) gegen Natronlauge E. Barth, Kunststoffe 72, 5 (1982) The stability of fluorine-containing polymers to amines M.I. Bro J. Appl. Pol. Sci. 1(3), 310 (1959)

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7 - Resistance of KYNAR PVDF to CHLORINE

KYNAR PVDF resists well to molecular chlorine. However, chlorine radicals, which are formed under UV-radiation, higher temperatures or other radical sources, attack PVDF. Thus, to effectively protect the installation for use in chlorine service an appropriate UV-shielding must be provided by either pigmentation of the resin or an UV-filter varnish on the outside.

Molecular mechanism of the chlorine attack:

Cl Cl

UV

Cl* + Cl*

F C H C H F C Cl C H

F Cl* Cl F Cl*

F C C H F C C Cl Cl

The chlorination can be analyzed by the following methods:

increase in weight measurement of the melting point: chlorination results in a drop in melting point NMR spectroscopy: i.e. by NMR of the F19 isotope it is possible to establish the degree of chlorination mechanical measurements, i.e. tensile testing, chlorination results in a drop in mechanical strength melt viscosity

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7 - Resistance of KYNAR PVDF to CHLORINE


The following examples give an idea of the scope of the analysis methods cited and of the performances of PVDF :
Tube at the exit of a chlorine electrolysis cellule 7 years in service Melting point new PVDF exterior of tube inside of tube particularly degraded part inside Tm = 170C Tm = 170C Tm = 162C Tm = 158C Tensile properties new PVDF tube tube in service F19 NMR spectroscopy Definition of a chlorination coefficient: K =

54 MPa at yield 45,7 MPa at yield

a b 100 a

where: a = integration of all fluorine signals, b = all fluorine signals due to VF2 The measurement was done at 2 sites of the tube - near the cellule and further away: near the cellule far away from cellule K-values : inner surface of tube 17,0 12,8 middle of tube wall 1,2 1,0 outer surface of tube 0 0 Chlorine collector - humid chlorine gas 80C Melting point new PVDF external surface Tm = 170C Tm = 164C F19 NMR spectroscopy K value external surface 14,0 inner surface 33,9 7 years in service inner surface Tm = 170C 10 years in service inner surface Tm = 152C

Black pigmented tube - chlorine gas 70C Melting point new PVDF external surface Tm = 170C Tm = 170C F19 NMR spectroscopy K value Tensile properties tensile stress at yield (MPa) external surface 0

inner surface <1

new PVDF tube 54

tube in service 54

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8 - Resistance of KYNAR PVDF to SULFURIC ACID


KYNAR PVDF resists well to diluted sulfuric acid up to concentrated sulfur. However, KYNAR PVDF can be attacked when the concentration of the sulfuric acid passes from concentrated to fuming sulfuric acid (96 to 98%). The reason for this behaviour is that sulfur trioxide (creating the fumes) can by absorbed by PVDF. This compound can react with PVDF leading to dehydrofluorination similar to bases. Therefore coloration occurs and when the degradation is advanced a black brittle surface layer forms. Therefore the chemical resistance of KYNAR PVDF follows a clear concentration/temperature pattern which is clearly related to the appearance of sulfur trioxide.

Chemical resistance of KYNAR PVDF as a function of temperature and concentration

140 98% 120 100 Temperature ( C) 80 60 40 20 0 0 10 20 30 40 50 60 70 80 90 100 Concentration (%) does not resist

resists

Example of an application :
Pipe at the exit of an acid distillation tower 10 years in service

Characteristics : pipe made by thermoforming and welding of sheet with 15 mm thickness Operation conditions 110 120C at vacuum of 70 mbar vapours of aqueous sulfuric and nitric acids

Yearly inspections have never revealed any problem, nor was there any maintenance operation necessary.

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Table of experiments performed : KYNAR in Sulfuric acid


Conc. % Exp. time

23C
wt nt

50C
wt nt

75C
wt nt

90C
wt nt

130C
wt + + nt

50 80 94 96

98

99,2

wt

1y 3m 6m 1y 2m 3m 6m 1w + + 2m 3m 6m 1y 1w 7w + + 2m 3m 6m 1w 7w 3m 0 + 6m + 1y : test specimen under tension

+ + -

+ 0 0

+ + +

+ + + + + 0

+ + + + 0

0 0

+ +

+ 0 + -

0 0

+ + 0 _ 0

+ + nt

: test specimen without tension

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9 - Resistance of KYNAR PVDF to BROMINE


KYNAR PVDF resists very well to bromine - even at higher temperatures. During the service time bromine diffuses into the PVDF layer, an effect which is readily visible by eye due to the red-orange coloring of the PVDF. However, this effect is perfectly reversible. After desorption of the bromine KYNAR PVDF regains its original color.

Permeability of bromine in KYNAR PVDF as a function of temperature 40 35 Permeability 30 25 20 15 10 5 0 0 10 20 30 Temp (C)


permeability units: g / (m2 day) thickness 50 m

40

50

60

Examples of installed pieces in bromine service


DN 40 tube ambient temperature 8 years in service

Thermal treatment of tube

Loss of 1,4 % weight, essentially bromine. Restitution of original color


new PVDF : Tube : Tm = 170C Tm = 170C

Melting point

NMR and IR spectroscopy


Tensile properties

No bromine bound to PVDF

tensile stress at yield (MPa) elongation at break (%)

new PVDF tube 52 200

tube in service 50.8 197

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9 - Resistance of KYNAR PVDF to BROMINE

Examples of installed pieces in bromine service

Gas tube

temperature 70 - 80C

9 years in service

Thermal treatment of tube Loss of 1,5 % weight, essentially bromine. Restitution of original color Melting point new PVDF Tm = 170C

tube Tm = 170C

NMR and IR spectroscopy No bromine bound to PVDF Tensile properties

tensile stress at yield (MPa) elongation at break (%)

new PVDF tube 53 100

tube in service 53 96

Isocontainer for bromine transport by rail

Ambient temperature, welded KYNAR sheets glued into steel container, service since 9 years No problem detected since beginning of service.

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10 - Chemical resistance of KYNAR FLEX PVDF copolymers


Due to the more recent apparition of the KYNAR FLEX PVDF copolymers and their more restricted use in the chemical process industry no extensive testing of chemical compatibility exists. Nevertheless, the available data and a sound reasoning of the influence of the nature of the PVDF copolymers in comparison to the PVDF homopolymers allows to dress general guidelines which will be discussed here. The comonomer used to synthesize the KYNAR FLEX grades is hexafluoro-propene (HFP) which is a completely fluorinated molecule. Thus, the major factor responsible for the outstanding chemical resistance of KYNAR PVDF is not changed by the incorporation of a comonomer. The main change induced by the incorporation of the HFP comonomer is a reduction in cristallinity of the originally highly crystalline PVDF material. The reduced cristallinity directly results in a decrease of the moduli and hence in a reduced mechanical strength at higher temperatures. Also the reduced cristallinity results in an enhancement of permeation rates which in turn leads to a further decrease in mechanical strength at higher temperatures. As a conclusion we can state that the chemical resistance to organic compounds such as hydrocarbons, halogenated organics and oxygenated organic compounds is reduced in its maximum temperature limit in comparison to PVDF homopolymers. We have defined a temperature increment T which should be subtracted from the maximum use temperature given for the PVDF homopolymer.
A comparative overview is given in the table below: Property

KYNAR
170 1800 140 118 49 - 52 10

homopolymer 1000 HD and 740 Melting Temperature (C) FLEX ural Modulus (MPa) Vicat Softening Point (B50) ISO 306 (C) Heat Deflection Temperature ISO 75 (C) Tensile stress at yield (MPa) Elongation at yield (%) C) T (

KYNAR FLEX 3120-50 163 - 166 659 70 40 - 50 27 - 29 12 15

KYNAR FLEX 2850 155 - 160 1100 90 55 32 - 39 10 - 12 20

KYNAR FLEX 2800 141 - 145 700 70 40 - 50 23 - 27 10 - 12 35

There is an important exception to the logic defined above. In the case where the attack of PVDF by the chemical occurs on the surface and/or by stress cracking the resistance of KYNAR FLEX can be considerably higher than the PVDF homopolymer. The main reason for this advantage is the reduced amount of stress build-up due to the lower modulus of the copolymers.

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10 - Chemical resistance of KYNAR FLEX PVDF copolymers


The following list gives an idea of the comparative chemical resistance in conditions where the performance of the PVDF homopolymer is reduced due to stress cracking.
Chlorine gas without UV KYNAR resistance

80C KYNAR FLEX


3120-50

15 days KYNAR FLEX


2850

KYNAR FLEX
2800

homopolymer

under UV KYNAR

+
80C KYNAR FLEX
3120-50

+
15 KYNAR FLEX
2850

+
days KYNAR FLEX 2800

Chlorine gas

homopolymer

resistance

--

With applied stress no material resists, but on unbent samples the following order in resistance has been established:
KYNAR FLEX

2800 = KYNAR FLEX

3120-50 > KYNAR FLEX 2850 >> KYNAR

1000 HD

Sulfuric acid (H2SO4) KYNAR resistance

99.2% KYNAR FLEX


3120-50

50C

3 months

KYNAR FLEX
2850

homopolymer

KYNAR FLEX 2800

+
50C

+
3 months KYNAR FLEX
2850

Hydrogen peroxide (H202) 70% KYNAR resistance

KYNAR FLEX
3120-50

homopolymer

KYNAR FLEX 2800

Sodium Hydroxide 20 % and Sodium hypochlorite 50 active chlorine 15,7% 4 months KYNAR resistance

KYNAR FLEX
3120-50

KYNAR FLEX
2850

homopolymer

KYNAR FLEX 2800

+/0

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10 - Chemical resistance of KYNAR FLEX PVDF copolymers

The following list gives an idea of the comparative chemical resistance in conditions where the performance of the PVDF homopolymer is reduced due to stress cracking.
Sodium Hypochlorite - 107 or active chlorine 33,9% - pH = 13 23C 4 months KYNAR resistance

KYNAR FLEX
3120-50

KYNAR FLEX
2850

KYNAR FLEX
2800

homopolymer

Sodium Hypochlorite 56 or active chlorine 17,8% - pH = 12,5 23C 6 months KYNAR resistance

KYNAR FLEX
3120-50

KYNAR FLEX
2850

KYNAR FLEX
2800

homopolymer

+/0

Sodium Chlorate

(600g/l) KYNAR

78C KYNAR FLEX


3120-50

5 months KYNAR FLEX


2850

homopolymer

KYNAR FLEX 2800

resistance

+/0

+/0

Sodium Hydroxide

(NaOH)

90C KYNAR FLEX


3120-50

3 months KYNAR FLEX


2850

KYNAR pH pH 10 20 13 14 % %

KYNAR FLEX
2800

homopolymer

0/-

+ +/0 +/0 0/-

+ +/0 +/0 0

+ + + +

Comments:
In alkaline solutions the surface will often be colored after a short period of time depending on concentration and temperature. This coloration is due to a limited surface attack. It is less strongly pronounced with the FLEX grades.

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11 - Permeability properties of KYNAR PVDF


The permeability of gases and liquids is an important design factor for thermoplastics in chemical process applications. KYNAR PVDF has outstanding barrier properties to a large variety of chemicals. In the case of permeation of a gas permeability is proportional to the gas pressure and inverse proportional to the polymer layer thickness : Gas permeation :

P=

mL A p t

In the case of liquids no pressure dependence exists, but there might be a dependence of concentration in the case of mixtures or solutions. In many cases the pure liquid permeability gives a good indication. Luid permeation :

P=
P: A:

mL At

permeation m: amount of permeant exposed surface for permeation t: time

L:

layer thickness

Permeation through thermoplastics is temperature dependent and can be approximated by an Arrhenius equation.

EA P( 0 ) = P( 1 ) exp R ( 1 0 )
P(0) : permeability at temperature 0 EA : activation energy P(1) : permeability at temperature 1 R: universal gas constant

Ideally, permeation is inverse proportional to the sheet thickness. In some cases different types of cristallinity or surface quality can change the permeability value to a slight extent. These parameters may depend on the manufacturing of the sheet, pipe or film. Some solvents which have a strong swelling effect will also effect the layer thickness dependence of the permeation.

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11 - Permeability properties of KYNAR PVDF


Water permeation KYNAR 1000HD PVDF homopolymer The symbols correspond to measured points. Thin samples are extruded films. Thicker samples are measured on extruded pipes.
1000

100

Permeability (g/(day.m^2)

10

50 C 20 C 80 C

0,1

0,01 0,01

0,1 Thickness (mm)

10

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11 - Permeability properties of KYNAR PVDF


Water permeation different KYNAR grades and temperature dependence
100,000

10,000

Permeability (g.mm/(day.m^2)

KYNAR 740 KYNAR 720 KYNAR 460 KYNAR FLEX 2850 KYNAR FLEX 2800 1,000 Srie6 KYNAR 720 KYNAR 740 KYNAR 460 KYNAR FLEX 2850 KYNAR FLEX 2800

100 C 0,100

80 C

60 C

40 C

20 C

1 / temperature (K)

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11 - Permeability properties of KYNAR PVDF


Permeation data of KYNAR PVDF homopolymer grades for gases Measurements according to ASTM D 1434 on extruded films

10000

1000

permeability (cm^3.mm/m^2.day.bar)

100 O2 N2 He CO2 Cl2 10 H2S SO2 HCl NH3 NO2 CH4 1

C 140 120 100C C 0,1 0,0024 0,0026

80 C 0,0028

60 C 0,003

40C 0,0032

20 C 0,0034 0,0036

1 / temperature (K)

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11 - Permeability properties of KYNAR PVDF


Permeation data of KYNAR PVDF homopolymer grades for organic solvents Measurements by weight loss method on extruded films of approx 1 mm thickness
100

chloroforme methanol 10 toluene

dichloroethane permeability (g.mm / m^2.day)

perchlorethylene

0,1 hexane

ethanol 0,01 100 90 80 70 60 50 40 30 20 Temp ( C)

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11 - Permeability properties of KYNAR PVDF


Tables with data on swelling and weight gain of KYNAR PVDF homopolymer and KYNAR FLEX copolymer grades Measurements on immersed samples of extruded sheet. Weight gain expressed in percent.

HCl 37% H2SO4 96% HF 100% Cl2 gas (4 bar) water toluene cyclohexane 2-butanone MTBE methanol

Kynar 740 0 0,01 0,3 0,01 0,2 0

23 C Kynar Kynar Flex 2850 Flex 2800 0 0 0,02 0,02 0,32 0,28 0,01 1,8 0,03 9,2 0,65 0,06 0,01 2,4 0,04 14 0,9 0,08

75 C Kynar Flex 2850 0,14 0,19 0 0,32

90 C Kynar 740

4,1 0,54 X 6,3 2,9

0,03

X signifies dissolution

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12 - Comparison of chemical resistance of KYNAR PVDF


with others thermoplastic materials used in the chemical process industry

halogenated solvents 5 4 strong oxidants esters, ketones 3 2 1 halogens aromatic solvents 0

strong acids strong bases

aliphatic solvents weak bases

PVDF PVC HDPE PP PES-GF

5 : excellent resistance 1 : no resistance

4 : fair resistance

3 : limited resistance

2 : low resistance

comparison for 90C

Comparative pressure resistance based on long term creep (25 years)

12 PVC-U PP PVDF

10 Nominal Pressure (bar)

0 20 40 60 80 Temperature ( C) 100 120 140

Wall thicknesses are not the same for a standard 10 bar nominal pressure piping system. As an example for a 63-mm diameter pipe wall thickness would be: PVC-U 3,0 mm PP 5,8 mm PVDF 2,5 mm.

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KYNAR
Chemical resistance tables
For questions regarding availability and prices please contact :

ARKEMA S.A. Technical Polymers Division


420, rue dEstienne dOrves - 92705 Colombes (France) Tel. (33) 01 49 00 80 80 - Tlfax (33) 01 49 00 83 96

Adresses of regional sales offices:


ARKEMA NORDEN ARKEMA UK Ltd. ARKEMA NORDEN

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Tel : 44 503 939 Fax : 44 503 940

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Tel : (01635) 87 0000 Fax : (01635) 86 1212

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Tel : 14014755 Fax : 14019950

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Tel : (20) 614 25 11 Fax : (20) 669 2231

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Tel : (212) 227 6384 Fax : (212) 227 6386

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Tel : (2) 370 20 32 Fax : (2) 332 12 84

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Tel : (1) 701 8121 Fax : (1) 700 3921

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Poligon Industrial Pratenc Calle 100s/n Acesso A 08820 - El Prat De Llobregat Barcelone
Tel : (3) 403 9500 Fax : (3) 337 94307

Technical Polymers Division


420, rue dEstienne dOrves - 92705 Colombes (France)

Tel. (33) 01 49 00 80 80 - Tlfax (33) 01 49 00 83 96


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