kynar
TRANSCRIPT
KYNAR
Chemical resistance tables
BDI MW 005680/01 -hemical resistance tables of Kynar® 2
KYNAR
Chemical resistance tables
Index
Page numbers
1. General Introduction 3
2. Resistance criteria – Standards 4 to 5
3. KYNAR® - General resistance table 6 to 13
4. KYNAR® - Long term ageing and stress resistance behaviour 14 to 17
5. SOLVENTS for KYNAR® PVDF 18
6. Resistance of KYNAR® PVDF to BASES and ALKALIS 19 to 21
7. Resistance of KYNAR® PVDF to CHLORINE 22 to 23
8. Resistance of KYNAR® PVDF to SULFURIC ACID 24 to 25
9. Resistance of KYNAR® PVDF to BROMINE 26 to 27
10. Chemical resistance of KYNAR FLEX® PVDF copolymers 28 to 30
11. Permeability properties of KYNAR® PVDF 31 to 36
12. Comparison of chemical resistance of KYNAR® PVDF with other
thermoplastic materials used in the chemical process industry 3 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 d’Estienne d’Orves - 92705 Colombes (France) Tel. (33) 01 49 00 80 80 - Téléfax (33) 01 49 00 83 96
BDI MW 005680/01 -hemical resistance tables of Kynar® 3
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 150°C:
� 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® is
attacked by :
- amines
- concentrated sulfuric or nitric acid
- alkaline solutions of intermediate
concentration
� KYNAR® swells in certain polar
solvents : - ketones
- esters
� The following solvents dissolve
KYNAR® :
- Dimethyl acetamide (DMA)
- Dimethyl formamide (DMF)
- N-methyl pyrrolidone (NMP)
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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 % and Q ≥ 80 % and
εR2 ≥ 0,9 εS1 and εS2 ≤ 2 εS1
- 2 % ≤ ∆ m ≤ + 10 % and 80 % > Q > 46 % and
εR2 ≥ 0,9 εS1 and εS2 ≤ 2 εS1
or - 2 % ≤ ∆ m ≤ + 10 % and
Q ≥ 80 % and εS1 ≤ εR2 ≤ 0,9 εS1 and
εS2 ≤ 2 εS1
∆ m > 10 % or ∆ m < -2 % Q ≤ 46 % and
εR2 ≥ 0,9 εS1 and εS2 ≤ 2 εS1
or - 2 % ≤ ∆ m ≤ + 10 % and 80 % > Q > 46 % and
εS1 ≤ εR2 ≤ 0,9 εS1 and εS2 ≤ 2 εS1
Q = σS2 / σS1 index 1 = reference sample index 2 = aged sample
∆ m = mean of relative weight change σS = mean value of tensile stress at yield
εs = mean value of elongation at yield εR = 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® 5
2 Resistance criteria - Standards
� Classification based on the factor Q
A simplified approach, which allows chemical compatibility estimations by following the weight
change only, has been established by the German Institut für 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.
7 14 28 56 112 365 73010
100
Days
Q -
val
ue
+
0
-
0
500
1000
1500
2000
2500
0 5 10 15 20 25
change of weight (%)
E m
odul
us (
MP
a)
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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 saturated � Hydrobromic acid 50% � Hydrochloric acid concentr. /35% � Hydrochloric acid gas � Cyanic acid 100% � Hydrofluoric acid 40% � Hydrofluoric acid 70% � Hydrofluoric acid 100% � Nitric acid 30% � Nitric acid 65% � Perchloric acid 70% � Phosphoric acid 85% � Phosphoric acid 98% � Sulfuric acid 50% � Sulfuric acid 80% � Sulfuric acid 93% � Sulfuric acid 98% � Hydrogen sulfide � Chlorsulfonic acid 98% � Fluorosulfonic acid 97% � Fluorosilicic acid � Mixtures of Mineral Acids Conc. 25°C 50° 75° 100° 125° 150°
� Sulfuric / nitric (1 / 1) 40% � Nitric / Hydrochloric (1 / 3) 100% � Phosphochromic :
- phosphoric 80%
- Chromium trioxide 5%
- Sulfuric 3%
� Sulfochromic : - Sulfuric 15%, Water 35%
- Chromium trioxide 50%
� Anhydrides and chlorides
of Mineral Acids Conc. 25° 50° 75° 100° 125° 150°
� Chromic anhydride saturated � Chromic anhydride 60% � Phosphore trichloride 100% � Phosphor pentachloride 100% ✕ � Phosphoroxy trichloride 100% � Thionyl chloride 100% � Sulfuric anhydride 100% � Sulfuryl chloride 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 gas � Ammonia solution 30% � Potassium hydroxide 50% � Sodium hydroxide 45% � Sodium hydroxide 60% � Mineral salts Conc. 25° 50° 75° 100° 125° 150°
� All types of neutral or
acidic mineral salts in
solution up to saturation
� Titanium tetrachloride 100% � Boron trifluoride 100% � Elements Conc. 25° 50° 75° 100° 125° 150°
� Bromine dry � Bromine humid � Chlorine dry -no UV � Chlorine Humid
no UV
� Chlorine with UV ✕ � Fluorine � Hydrogen � Iodine � Mercury � Oxygen � Ozone gas (2%) � Ozone solution � Sulfur
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3 - KYNAR® - General chemical resistance table
� Organic acids Conc. 25° 50° 75° 100° 125° 150°
� Acetic acid 100% � Acetic acid 50% � Acrylic acid � Benzene sulfonic acid concentr. � Benzoic acid satur. � Chloro-acetic acid 75% � Chloro-acetic acid 100% � Citric acid 50% � Formic acid 98% � Gallic acid satur. � Glycolloic acid satur. � Lactic acid (2-hydroxy-
propanoic)
50%
� Lauric acid (dodecanoic) 100% � Linoleic acid (9,12-
octadecadieneoic)
100%
� Maleic acid satur. � Malic acid satur. � Methane sulfonic acid 50% � Oleic ac. (9-octadecenoic ) 100% � Oxalic acid satur. � Palmitic acid 100% � Phtalic acid satur. � Picric acid (2,4,6 trinitro-
phenol)
10%
� Salicylic acid 50% � Stearic acid satur. � Tartric acid satur. � Trichloro-acetic acid 50% � Trichloro-acetic acid 100% � Anhydrides and chlorides
of Organic acids Conc. 25° 50° 75° 100° 125° 150°
� Acetic anh. 100% � Acetic acid chloride 100% � Chloro-acetic acid chloride 100% � Benzoyl chloride 100% � Trichloro-acetic acid
chloride
100%
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3 - KYNAR® - General chemical resistance table
� Alcohols, Glycols, Phenols Conc. 25° 50° 75° 100° 125° 150°
� Pentanol (amyl alc.) 100% � Benzyl alc. 100% � n-Butyl alc. 100% � sec. Butyl alc. 100% � tert. Butyl alc. 100% � Butyl phenol (1-butyl-2-
hydroxy benzene)
100%
� Cresole 100% � Cyclohexanol 100% � 4-Hydroxy-4-methyl-2-
pentanone 100%
� Ethanol 100% � Ethylene glycol 100% � Glucose 100% � Glycerol 100% � Methanol 100% � Phenol 100% � Phenol 10% � Propanol 100% � Pyrogallol (1,2,3-trihydroxy
benzene)
100%
� Aldehydes, Ketones Conc. 25° 50° 75° 100° 125° 150°
� Acetone 100% ✕ � Acetone 50% � Acetone 10% � Acetone 5% � Acetophenone 100% ✕ � Acetyl-acetone 100% ✕ � Acroleine 100% ✕ � Benzaldehyde 100% ✕ � Butanone 100% ✕ � Chloral 100% � Crotonaldehyde 100% � Cyclohexanone 100% ✕ � Diisobutylketone 100% � Formaldehyde 30% � Furfural 100% � Methyl-isobutylketone 100% ✕ � Salicylic aldehyde 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 100% � n-Butyl amine 100% ✕ � sec. Butyl amine 100% � tert. Butyl amine 100% � Diethyl amine 100% � Diethylene triamine 100% � Dimethyl amine 100% ✕ � Dimethyl aniline 100% � Ethylene diamine 100% ✕ � Mono ethanol amine 100% ✕ � Morpholine 100% ✕ � Phenyl hydrazine 100% � Piperazine 100% � Pyridine 100% ✕ � Triethyl amine 100% � Nitriles, Nitro or sulfur
products Conc. 25° 50° 75° 100° 125° 150°
� Acetonitrile 100% � Acrylonitrile 100% � Carbon disulfide 100% � Nitro-benzene 100% � Nitro-methane 100% � Esters Conc. 25° 50° 75° 100° 125° 150° � Butyl acetate 100% � Butyl acrylate 100% � Cyclohexyl acetate 100% � Dimethyl phtalate 100% � Ethyl acetate 100% � Ethyl acrylate 100% � Pentyl acetate 100% � Tributyl phosphate 100% � Ether oxydes Conc. 25° 50° 75° 100° 125° 150° � Chloromethyl methylether 100% � Dioxane 100% ✕ � Diethyl ether 100% � Furane 100% ✕ � Ethylene oxyde 100% � Propylene oxyde 100% ✕ � Tetrahydrofurane (THF) 100%
3 - KYNAR® - General chemical resistance table
BDI MW 005680/01 -hemical resistance tables of Kynar® 12
� Chlorinated
hydrocarbons Conc. 25° 50° 75° 100° 125° 150°
� Allyl chloride 100% � Benzyl chloride 100% � 1-Chloro-pentane 100% � Chloro-benzene 100% � Chloroforme 100% � CFC 113 * 100% � CFC 114 * 100% � CFC 11 * 100% � CFC 12 * 100% � Dichloro-benzene 100% � Dichloro ethane 100% � Epichlorhydrine 100% ✕ � Ethyl chloride 100% � HCFC 22 100% � HFC 134 a 100% � HFC 407 c 100% � HFC 410 a 100% � Lauryl chloride 100% � Methyl chloride 100% � Methylene chloride 100% � Tetra-chloro ethylene 100% � Trichloro-benzene 100% � 1,1,1-trichloro ethane 100% � Trichloro ethylene 100%
� Other halogenated
hydrocarbons Conc. 25° 50° 75° 100° 125° 150°
� 1-Bromo-butane 100% � 1,2-Dibromo ethane 100% � Iodoforme 100% � Methyl bromide 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 Conc. 25° 50° 75° 100° 125° 150° � Benzene 100% � Butadiene 100% � Butene 100% � Cyclohexane 100% � Dekaline 100% � Heptane 100% � Hexane 100% � Kerosene 100% � Methane 100% � Naphta 100% � Naphthalene 100% � Octane 100% � Octene 100% � Propane 100% � Styrene 100% � Terpentine 100% � Toluene 100% � Xylene 100% � Miscellaneous Conc. 25° 50° 75° 100° 125° 150°
� Crude Oil � Hydrogen peroxide 30% � 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 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:
+ non-limited use (small variations of weight and tensile properties)
0 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 % 130 1 y + +
� Acetic anhydride conc. 23 1 y 0 0
� “Eau régale” HCl 35 % /HNO3 65% 2 / 1 90 1 y + +
� Etching solution H3PO4 (85 %) 85 %,
CH3CO2H 5 %, HNO3 (64 %) 5 %, H2O 5 %
90 4 m + +
� Hydrobromic acid 66 % (conc.) 90 1 year + +
� Hydrochloric acid 35 % (conc.) 130 1 y + +
� Hydrochloric acid + dichloroethane (10 %) 90 6 m + +
� Hydrochloric acid + dichloroethane (10 %) 130 6 m 0 +
� Hydrochloric acid + methanol (10 %) 50 6 m + +
� Hydrochloric acid + methanol + chloroforme 50 6 m + +
� Nitric acid 32% 90 1 y + +
� Nitric acid 32 % 130 6 months + +
� Nitric acid 52 % 130 2 m 0 0
� Nitric acid 65 90 6 m + +
� Nitric acid 98 % (conc) 50 2 m + +
� Nitric acid 98 % 90 2 m - -
� Oxalic acid 250 gl-1 75 2 m + +
� Phosphoric acid 85 % (conc.) 130 1 y + +
� Sulfuric acid 50 % * 130 1 y + +
� Sulfuric acid 80 % * 130 6 m - -
� Sulfuric acid 80 % * 90 1 y + +
� Sulfuric acid 96 % * 50 6 m 0 +
� Sulfuric acid 96 % * 75 3 m - +
� Sulfuric acid 99,2 % * 50 6 m - +
� Sulfuric acid 99,2 % * 23 6 m 0 +
� Sulfuric acid saturated with chloride 65 - 98 % 23 8 m + +
� Sulfuric acid 98 % + chloroforme (10 %) 50 6 m + +
� Sulfuric acid 98 % + diethylether (10 %) 50 6 m + +
� Sulfochromic acid CrO3 50 %, H2SO4 15 % 90 1 y + +
� Trichloroacetic acid 50 % 75 4 m + +
* please also refer to chapter 9
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4 - KYNAR® - Long term ageing and stress resistance behavior
Reactant Temp.
(°C) Exposure
time under
tension no
tension
� Bases *please refer also to chapter 6 � Ammonium hydroxide solution 20 % 23 6 m + +
� Ammonium hydroxide solution 20 % 50 3 m + +
� Ammonium hydroxide solution 20 % 90 1 m - +
� Ammonium hydroxide solution 29 % 23 9 m + +
� Ammonium hydroxide solution 29 % 50 9 m - +
� Ammonium hydroxide solution 29 % 75 2 m - -
� Sodium hydroxide 10 % 23 2 months - +
� Sodium hydroxide 10 % 50 2 m - +
� Sodium hydroxide 10 % 90 2 m - +
� Sodium hydroxide 45 % 90 1 year - +
� Sodium hydroxide 45 % 130 3 m - -
� Sodium hydroxide 10 % +1,7% Triton X100 23 1 m - +
� Sodium hydroxide 10 % +20% methanol 50 1 m - +
� Sodium carbonate solution 40 % 90 6 m + +
� Tetramethyl ammonium hydroxide (TMAH) 23 4 m + +
� Tetramethyl ammonium hydroxide 50 2 m - +
� Halogens and inorganic halogenated
derivatives
� Bromine 60 1 y + +
� Chlorine gaseous without light 100 11 d + +
� Chlorine gaseous with UV light exposure 30 11 d - +
� Hypochlorite solution 48° « javeline » 90 3 months - +
� Hypochlorite solution 48° « javeline » 130 3 m - 0
� Hypochlorite solution 100° « javeline » 90 15 days - +
� Phosphoroxy trichloride (POCl3) 50 4 m 0 0
� Phosphor trichloride (PCl3) 98 % 50 1 y + +
� Sodium chlorite (NaOCl) 845 gl-1 60 6 m - +
� Sodium chlorate (NaClO4) 500 gl-1 90 1 year + +
� Sulfuryl chloride (SO2Cl2) 23 4 m + +
� Thionyl chloride (SOCl2) 50 4 m + +
� Surfactants � anionic surfactants 90 2 months + +
� anionic surfactants 130 2 m + 0
� non-ionic surfactants 90 2 m + +
� dish washing detergent 90 6 weeks + +
BDI MW 005680/01 -hemical resistance tables of Kynar® 17
4 - KYNAR® - Long term ageing and stress resistance behavior Reactant Temp. (°C) Exposure
time under
tension no
tension � Hydrocarbon solvents � Crude oil 90 2 years + +
� Crude oil 130 2 y + +
� Crude oil 150 2 y + +
� Cyclohexane 90 4 m + +
� Decaline 90 4 m + +
� Tetraline 90 4 m + +
� Toluene 90 9 months + +
� Xylene 90 2 y + +
� Halogenated solvents � Benzene / chlorobenzene (1 / 1) 130 6 months 0 0
� Chloro-acetyl chloride 90 4 m 0 0
� Chlorobenzene
� Chloroforme 23 4 m + +
� Chloroforme 50 4 m + +
� 1,2-Dichloroethane 90 1 y + +
� Dichloromethane 50 4 m + +
� Dichloromethane 90 4 m + +
� Perchloroethylene 90 9 m + +
� Tetrachlorocarbon 90 6 m 0 0
� Trichloroethylene 90 1 year + +
� 1,1,1-Trichloroethane 90 4 m + +
� Oxygenated solvents � t-Butyl methyl ether 50 4 m + +
� Cyclohexanone 23 4 m 0 0
� Cyclohexanone 50 2 weeks - -
� Dibutyl phthalate 90 4 m + +
� Ethyl acetate 50 6 m - -
� Ethyl 2-ethoxy-acetate 50 4 m + +
� Ethylene glycol 130 1 year + +
� Glycerol 130 1 y + +
� Isopropanol 130 4 months + +
� Isopropanol 60 % +H3PO4 23 %+P2O5 17 % 130 4 m + +
� Methanol 90 4 m + +
� Phenol 10 % 90 1 y + +
� Ultra pure water (resistance 18 MO) 150 1 y + +
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5 - Solvents for KYNAR® PVDF
� Active solvents
(Dissolve at least 5 - 10 % KYNAR® resin at room temperature.)
Boiling point (°C) Flash point (°C)
� Acetone 56 - 18
� Tetrahydrofuran (THF) 65 -17
� Methyl ethyl ketone (Butanone) 80 - 6
� Dimethyl formamide (DMF) 153 67
� Dimethyl acetamide (DMA) 166 70
� Tetramethyl urea 177 75
� Dimethyl sulfoxide (DMSO) 189 35
� Trimethyl phosphate 195
� N-methyl-2-pyrrolidone (NMP) 202 95
� 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) Flash point (°C)
� Butyrolactone 204 98
� Isophorone 215 96
� Carbitol acetate 217 110
� 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) Flash point (°C)
� Methyl isobutyl ketone 118 23
� N-butyl acetate 135 24
� Cyclohexanone 157 54
� Diacetone alcohol 167 61
� Diisobutyl ketone 169 49
� Ethyl acetoacetate 180 84
� Triethyl phosphate 215 116
� Propylene carbonate 242 132
� Dimethyl phthalate 280 149
� Glycol ethers ≥ 118 ≥ 40 � Glycol ether esters ≥ 120 ≥ 30
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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:
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 non-
degraded 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
� 4 gl-1 pH = 13 yellow
� 40 gl-1 pH = 14 brownish
� 100 gl-1 10 % X black
� 450 gl-1 45% X black
CCC
CC
C
H H HH H
F F F FF
CCC
CCC
H HH HH H
F F F F F F
B
B+
H F- +
BDI MW 005680/01 -hemical resistance tables of Kynar® 20
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 25° 50° 75° 100° 125° 150°
� Dimethyl amine (CH3)NH ✕ � Ethanol amine HOC2H4NH2 ✕ � Morpholine (OC4H8NH) ✕ � Pyridine (C5H5N) ✕ � n-Butyl amine C4H9NH2 ✕ � Diethyl amine (C2H5)2NH � Dibutyl amine (C4H9)2NH � Tributyl amine (C4H9)3N � Fatty amine C16H33NH2
� 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
The partial blocking of the dehydrofluorination reaction results in significantly improved colour
retention and reduction of material embrittlement.
CC
CCCC
H HH HH H
F F F F F F
CCCCC
C
H H HH H
F F F FF
HF HF
CCCCC
C
H H H H
F FF F
CC
CCCC
H F CH H
F F F FF
FFF
HFHF
CCCCC
C
H F C H H
F F F FF
FF F
CC
CCCC
H H F CH H
F F F F F F
FFF
PVDF
KYNAR FLEX
BDI MW 005680/01 -hemical resistance tables of Kynar® 21
Laboratory test results :
� Sodium Hydroxide (NaOH) 90°C 3 months
KYNAR®
homopolymer 1000 HD and 740
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
pH 13 0/- + + + pH 14 - +/0 +/0 + 10 % - +/0 +/0 + 20 % - 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)
BDI MW 005680/01 -hemical resistance tables of Kynar® 22
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:
+UV
CC
H
F F
H
Cl Cl Cl* Cl*
CC
F F
HCl
CC
F F
HCl CC
F F
Cl Cl
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
BDI MW 005680/01 -hemical resistance tables of Kynar® 23
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 = 170°C Tm = 170°C Tm = 162°C Tm = 158°C
• Tensile properties
new PVDF tube 54 MPa at yield
tube in service 45,7 MPa at yield
• F19 NMR spectroscopy
Definition of a chlorination coefficient: Ka b
a= − ×100
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:
K-values : near the cellule far away from cellule
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 80°C 10 years in service • Melting point
new PVDF external surface inner surface
Tm = 170°C Tm = 164°C Tm = 152°C
• F19 NMR spectroscopy
external surface inner surface
K value 14,0 33,9
� Black pigmented tube - chlorine gas 70°C 7 years in service • Melting point
new PVDF external surface inner surface
Tm = 170°C Tm = 170°C Tm = 170°C
• F19 NMR spectroscopy
external surface inner surface
K value 0 < 1
• Tensile properties
new PVDF tube tube in service
tensile stress at yield (MPa) 54 54
BDI MW 005680/01 -hemical resistance tables of Kynar® 24
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
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 – 120°C 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.
0
20
40
60
80
100
120
140
0 10 20 30 40 50 60 70 80 90 100
Concentration (%)
Tem
pera
ture
(°C
)
98%
does not resist
resists
BDI MW 005680/01 -hemical resistance tables of Kynar® 25
Table of experiments performed : KYNAR® in Sulfuric acid
Conc.
%
Exp. time 23°C wt
nt 50°C wt
nt 75°C wt
nt 90°C wt
nt 130°C wt
nt
50 � 1 y + +
80
� 3 m
� 6m
� 1 y
+
+
+
- +
-
94
� 2 m
� 3 m
� 6 m
+
0
0
+
+
+
-
+
+
+
+
+
96
� 1 w
� 2 m
� 3 m
� 6m
� 1 y
+
+
0
0
+
+
-
+
+
0
+
0
98
� 1 w
� 7w
� 2 m
� 3 m
� 6 m
+
+
0
0
+
+
-
0
0
-
+
-
99,2
� 1 w
� 7w
� 3 m
� 6m
� 1 y
0
-
+
+
-
-
+
+
-
0
-
-
0
_
« wt » : test specimen under tension « nt » : test specimen without tension
BDI MW 005680/01 -hemical resistance tables of Kynar® 26
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
0
5
10
15
20
25
30
35
40
0 10 20 30 40 50 60
Temp (°C)
Per
mea
bilit
y
permeability units: g / (m
2 day) thickness 50 µm
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
• Melting point new PVDF : Tm = 170°C
Tube : Tm = 170°C
• NMR and IR spectroscopy No bromine bound to PVDF
• Tensile properties
new PVDF tube tube in service
tensile stress at yield (MPa) 52 50.8
elongation at break (%) 200 197
BDI MW 005680/01 -hemical resistance tables of Kynar® 27
9 - Resistance of KYNAR® PVDF to BROMINE
Examples of installed pieces in bromine service � Gas tube temperature 70 - 80°C 9 years in service
• Thermal treatment of tube
Loss of 1,5 % weight, essentially bromine.
Restitution of original color
• Melting point
new PVDF tube
Tm = 170°C Tm = 170°C
• NMR and IR spectroscopy
No bromine bound to PVDF
• Tensile properties
new PVDF tube tube in service
tensile stress at yield (MPa) 53 53
elongation at break (%) 100 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.
BDI MW 005680/01 -hemical resistance tables of Kynar® 28
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®
homopolymer 1000 HD and 740
KYNAR FLEX®
3120-50 KYNAR FLEX®
2850
KYNAR FLEX®
2800
Melting Temperature (°C) 170 163 - 166 155 - 160 141 - 145 FLEX ural Modulus (MPa) 1800 659 1100 700 Vicat Softening Point (B50) ISO 306 (°C)
140 70 90 70
Heat Deflection Temperature ISO 75 (°C)
118 40 - 50 55 40 - 50
Tensile stress at yield (MPa)
49 - 52 27 - 29 32 - 39 23 - 27
Elongation at yield (%) 10 12 10 - 12 10 - 12 ∆ ∆ ∆ ∆ T (°C) 15 20 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.
BDI MW 005680/01 -hemical resistance tables of Kynar® 29
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 80°C 15 days
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX®
2800
resistance - + + +
� Chlorine gas under UV 80°C 15 days
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
resistance -- 0 0 0
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) 99.2% 50°C 3 months
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
resistance - + + +
� Hydrogen peroxide (H202) 70% 50°C 3 months
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
resistance - 0 +
� Sodium Hydroxide 20 % and Sodium hypochlorite “50°” – active chlorine 15,7% 4 months
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
resistance - + +/0 +
BDI MW 005680/01 -hemical resistance tables of Kynar® 30
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 23°C 4 months
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
resistance 0 + + +
� Sodium Hypochlorite – “56°” or active chlorine 17,8% - pH = 12,5 23°C 6 months
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
resistance +/0 + + +
� Sodium Chlorate (600g/l) 78°C 5 months
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
resistance 0 +/0 +/0 +
� Sodium Hydroxide (NaOH) 90°C 3 months
KYNAR®
homopolymer
KYNAR FLEX®
3120-50
KYNAR FLEX®
2850
KYNAR FLEX ® 2800
pH 13 0/- + + + pH 14 - +/0 +/0 + 10 % - +/0 +/0 + 20 % - 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.
BDI MW 005680/01 -hemical resistance tables of Kynar® 31
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 :
tpA
LmP
⋅∆⋅⋅=
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 :
tA
LmP
⋅⋅=
P : permeation m : amount of permeant L : layer thickness
A : exposed surface for permeation t : time
Permeation through thermoplastics is temperature dependent and can be approximated by an Arrhenius
equation.
( ) ( ) ( )
−⋅−
⋅=01
10 expττ
ττR
EPP A
P(τ0) : permeability at temperature 0 P(τ1) : permeability at temperature 1 EA : activation energy 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.
BDI MW 005680/01 -hemical resistance tables of Kynar® 32
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.
0,01
0,1
1
10
100
1000
0,01 0,1 1 10
Thickness (mm)
Per
mea
bilit
y (g
/(da
y.m
^2)
50°C20°C80°C
BDI MW 005680/01 -hemical resistance tables of Kynar® 33
11 - Permeability properties of KYNAR
® PVDF
Water permeation – different KYNAR® grades and temperature dependence
0,100
1,000
10,000
100,000
1 / temperature (K)
Per
mea
bilit
y (g
.mm
/(da
y.m
^2)
KYNAR 740
KYNAR 720
KYNAR 460
KYNAR FLEX 2850
KYNAR FLEX 2800
Série6
KYNAR 720
KYNAR 740
KYNAR 460
KYNAR FLEX 2850
KYNAR FLEX 2800
100°C 80°C 60°C 40°C 20°C
BDI MW 005680/01 -hemical resistance tables of Kynar® 34
11 - Permeability properties of KYNAR
® PVDF
Permeation data of KYNAR® PVDF homopolymer grades for gases
Measurements according to ASTM D 1434 on extruded films
0,1
1
10
100
1000
10000
0,0024 0,0026 0,0028 0,003 0,0032 0,0034 0,0036
1 / temperature (K)
perm
eabi
lity
(cm
^3.m
m/m
^2.d
ay.b
ar)
O2
N2
He
CO2
Cl2
H2S
SO2
HCl
NH3
NO2
CH4
140°C 120°C 100°C 80°C 60°C 40°C 20°C
BDI MW 005680/01 -hemical resistance tables of Kynar® 35
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
0,01
0,1
1
10
100
Temp (°C)
perm
eabi
lity
(g.
mm
/ m
^2.d
ay)
methanol
toluene
chloroforme
2030405060708090100
ethanol
perchlorethylene
dichloroethane
hexane
BDI MW 005680/01 -hemical resistance tables of Kynar® 36
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.
23°C 75°C 90°C Kynar®
740 Kynar®
Flex 2850 Kynar®
Flex 2800 Kynar® Flex 2850
Kynar® 740
HCl 37% 0 0 0 0,14 H2SO4 96% 0,01 0,02 0,02 0,19 HF 100% 0,3 0,32 0,28 0 Cl2 gas (4 bar) 0,32 water 0,01 0,01 0,01
toluene 0,2 1,8 2,4 4,1 cyclohexane 0 0,03 0,04 0,54 2-butanone 9,2 14 X MTBE 0,65 0,9 6,3 methanol 0,03 0,06 0,08 2,9
X signifies dissolution
BDI MW 005680/01 -hemical resistance tables of Kynar® 37
12 - Comparison of chemical resistance of KYNAR
® PVDF
with others thermoplastic materials used in the chemical process industry
012345
halogenated solvents
esters, ketones
aromatic solvents
aliphatic solvents
weak basesstrong bases
strong acids
halogens
strong oxidants
PVDFPVCHDPEPPPES-GF
5 : excellent resistance 4 : fair resistance 3 : limited resistance 2 : low resistance
1 : no resistance comparison for 90°C
� Comparative pressure resistance based on long term creep (25 years)
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.
0
2
4
6
8
10
12
20 40 60 80 100 120 140
Temperature (°C)
Nom
inal
Pre
ssur
e (b
ar)
PVC-UPPPVDF
BDI MW 005680/01 -hemical resistance tables of Kynar® 38
KYNAR
Chemical resistance tables
� For questions regarding availability and prices please contact :
ARKEMA S.A. Technical Polymers Division
420, rue d’Estienne d’Orves - 92705 Colombes (France) Tel. (33) 01 49 00 80 80 - Téléfax (33) 01 49 00 83 96
� Adresses of regional sales offices:
ARKEMA NORDEN ARKEMA UK Ltd. ARKEMA NORDEN (Danmark) Colthrop Way - Thatcham (Suede)
Herlev Hovegarde 195 Newbury - Berkshire Sveagarten 65 B
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1066 XT Amsterdam Yildiz Cad. Kessaf Sok n° 4
Tel : (20) 614 25 11 Besiktas 80700
Fax : (20) 669 2231 Istanbul Tel : (212) 227 6384 Fax : (212) 227 6386
ARKEMA DEUTSCHLAND GmbH ARKEMA BELGIUM S.A. - N.V. Tersteegenstr. 28, Postfach 300152 Rue de Stalle 63 - Bte 1
40474 Düsseldorf 1180 Bruxelles Tel : (0211) 4552 00 Tel : (2) 370 20 32 Fax : (0211) 4552 112 Fax : (2) 332 12 84
ARKEMA ÖSTERREICH ARKEMA SCHWEIZ AG Handelsges. m. b. H. Luegisland 2/4
Karlsplatz 1 / Steige 1 / Büro n°8 8143 Stallikon
A 1010 Wien Tel : (1) 701 8121
Tel : (1) 503 5055 Fax : (1) 700 3921 Fax : (1) 503 505520
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Degli Artigianelli 10 Rua Artilharia UM 63 Poligon Industrial Pratenc
20159 Milano 4’ Dto Lisboa Calle 100s/n Acesso A
Tel : (02) 668 111 Tel : 113 806 004 08820 - El Prat De Llobregat
Fax : (02) 668 03 607 Fax : 113 862 281 Barcelone Tel : (3) 403 9500 Fax : (3) 337 94307
Technical Polymers Division 420, rue d’Estienne d’Orves - 92705 Colombes (France)
Tel. (33) 01 49 00 80 80 - Téléfax (33) 01 49 00 83 96