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Materials of Construction for Use in

Contact with Chlorine

GEST 79/82

8th Edition

June 2004


This document can be obtained from:

EURO CHLOR - Avenue E. Van Nieuwenhuyse 4, Box 2 - B-1160 BRUSSELS
Telephone: 32-(0)2-676 72 65 - Telefax : 32-(0)2-676 72 41
GEST 79/82
8th Edition

Euro Chlor

Euro Chlor is the European federation which represents the producers of chlorine and its primary

Euro Chlor is working to:

improve awareness and understanding of the contribution that chlorine chemistry has
made to the thousands of products, which have improved our health, nutrition, standard
of living and quality of life;
maintain open and timely dialogue with regulators, politicians, scientists, the media
and other interested stakeholders in the debate on chlorine;
ensure our industry contributes actively to any public, regulatory or scientific debate
and provides balanced and objective science-based information to help answer
questions about chlorine and its derivatives;
promote the best safety, health and environmental practices in the manufacture,
handling and use of chlor-alkali products in order to assist our members in achieving
continuous improvements (Responsible Care).


This document has been produced by the members of Euro Chlor and should not be reproduced in
whole or in part without the authorisation of Euro Chlor.

Euro Chlor and its members make no guarantee and assume no liability whatsoever for the use or
the interpretation of any of the information in this document.

Prior to 1990, Euro Chlors technical activities took place under the name BITC (Bureau
International Technique du Chlore). References to BITC documents may be assumed to be to
Euro Chlor documents.

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Chlorine is essential in the chemical industry and consequently there is a need for chlorine to be
produced, stored, transported and used. The chlorine industry has co-operated over many years
to ensure that its activities cause the minimum harm to the well-being of its employees, local
communities and the wider environment. This document is one in a series which the European
producers, acting through Euro Chlor, have drawn up to promote continuous improvement in the
general standards of health, safety and the environment associated with chlorine manufacture in
the spirit of Responsible Care.

The recommendations, techniques and standards presented in these documents are based on the
experiences and best practices adopted by member companies of Euro Chlor at their date of issue.
They should be taken into account in the operation of existing processes and in the design of new
installations. They are in no way intended as a substitute for the relevant national or international
regulations which should be fully complied with.

It has been assumed in the preparation of these publications that the users will ensure that the
contents are relevant to the application selected and are correctly applied by appropriately
qualified and experienced people for whose guidance they have been prepared. The contents are
based on the most authoritative information available at the time of writing and on good
engineering, medical or technical practice but it is essential to take account of appropriate
subsequent developments or legislation. As a result, the text may be modified in the future to
incorporate evolution of these and other factors.

This edition of the document has been drawn up by the Equipment Working Group to whom all
suggestions concerning possible revision should be addressed through the offices of Euro Chlor.

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Summary of the Main Modifications in this version

Section Nature
3.1.1 The words degreased hydrocarbon were added at the end of the fourth
3.1.1 Hydrocarbon based oils replaces oilsin the paragraph below the bullets
3.1.4 In the second paragraph, bursting disc was added
3.1.6 A more detail information is given: used in thin wall applications e.g. bursting
3.2.2 At the end of this section, the following sentence was added: PVC and PVC/GRP
must not be used with liquid chlorine
3.2.5 It has been added that PTFE is not completely impervious to gaseous chlorine at
elevated temperatures
3.3.2 The exception of using graphite for pump bearing was deleted
7 In the second paragraph, water was added (reactive to chlorine)

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3.1. Metallic Materials 7
3.1.1. Carbon Steel 7
3.1.2. Cast Iron 8
3.1.3. Ductile Iron 8
3.1.4. Stainless Steels 8
3.1.5. Alloyed Steels 8
3.1.6. High Nickel Alloys 8
3.1.7. Hastelloy C 9
3.1.8. Titanium 9
3.1.9. Tantalum 10
3.1.10. Copper 10
3.1.11. Silver, Gold 10
3.1.12. Lead 10
3.1.13. Zinc, Tin, Aluminium 10
3.2. Plastics 10
3.2.1. (GRP) Glass Fibre Reinforced Polyester 11
3.2.2. (PVC) Polyvinyl Chloride 11
3.2.3. C-PVC - Chlorinated PVC 11
3.2.4. PVDF (Poly Vinylidene Difluoride), PVDF/GRP 11
3.2.5. PTFE - PolyTetraFluoroEthylene 11
3.2.6. FEP, PFA, TFE/HFP-copolymer, Perfluoro-alkoxypolymer 12
3.2.7. Polypropylene, Polyethylene 12
3.2.8. Other Plastics 12
3.3. Other Materials 12
3.3.1. Rubber or Ebonite 12
3.3.2. Graphite 12
3.3.3. Stoneware, Glass, Enamel 12
3.3.4. Brickwork 13

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This recommendation is written to provide general advice on the suitability of various

materials for industrial application with chlorine. It does not attempt to define the
various corrosion processes but indicates the conditions under which certain materials
can be used or should be avoided. Care must, however, be taken to consider the
possibility of the presence of other constituents in either the chlorine or the materials of
construction, as the presence of certain trace components can considerably influence the
corrosion behaviour. Practical testing under service conditions is therefore the best
guide to the suitability of any particular material. Temperature and velocity may modify
corrosion resistance.
Mechanical properties are dealt with in more detail in specific engineering
recommendations such as those issued by Euro Chlor. These recommendations, in any
case of uncertainty, should not be taken as a firm guide but reference should be made to
a chlorine producer to confirm the suitability of any material for a given duty.


Materials of construction must be chosen to suit the conditions under which chlorine is
being handled
* Wet or dry
* Gaseous or liquid chlorine
* Temperature
* Pressure
For dry chlorine gas, i.e. containing less than 20 mg H2O/kg chlorine, steel is the usual
material. For liquid chlorine and cold dry chlorine gas, fine grain carbon steel should be
used, taking into account the possibility of depressurizing the system.
For wet chlorine gas, the usual materials are titanium , rubber lined steel, Glass
Reinforced Polyester Resins (GRP), PTFE lined steel, PVC externally reinforced with
Plastic materials must also be chosen taking account of their resistance to ageing and the
possibility of damage caused by external factors. A basic principle in chlorine safety is
to learn from previous experience. Caution is therefore necessary before any new
material is introduced and extensive testing may be required before any equipment is

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3.1. Metallic Materials

3.1.1. Carbon Steel

Liquid chlorine and cold chlorine gas

Carbon steel is the most commonly used material for handling liquid chlorine or dry gas.

A grade of steel must be chosen to suit the temperatures which can arise in each case.
For liquid chlorine and cold dry chlorine gas, fine grain steel should be used, taking
into account the possibility of depressurizing the system (vaporisation of residual
liquid chlorine at minus 34C at atmospheric pressure or lower if pressure can go

All steel components must be thoroughly degreased, cleaned and dried to remove
surplus oxide, oil, hydrocarbons, moisture, etc, before coming into contact with
chlorine, see GEST 80/84 - Code of Good Practice for the Commissioning of
Installations for Dry Chlorine Gas and Liquid.
In contact with dry chlorine, carbon steels become covered by a layer of ferric
chloride. It is this layer that protects the underlaying carbon steel from further
attack1.. The iron chloride layer can be destroyed by:
High velocity (erosion)l
In order to avoid destruction of the protective layer of ferric chloride due to erosion,
the linear velocity of liquid chlorine at the vessel wall should be limited. The normal
practice for pipework is to limit liquid chlorine velocities to less than 2 m/sec.
Moisture (corrosion)
High temperature. The maximum temperature for carbon steel in presence of
dry chlorine should be below 120C.
In certain circumstances where there is a risk of traces of hydrocarbon based oils,
water or rust being present, reaction with chlorine can increase the temperature
sufficiently to lead to spontaneous ignition of steel.
The use of steel with a high specific surface area, such as steel wool, should be
avoided. When chlorine reacts with iron, the temperature can increase sufficiently to
cause ignition of steel.
Forged or cast steel can be used on condition that the mechanical property of the
fabricated components have been studied for the range of temperatures and stress
which might be encountered.

Hammink, M.W.J. and Westen, P.C. - Modern Chlor-Alkali Technology [3] 71-81

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Moist Chlorine or Hot Dry Chlorine Gas

Not acceptable

3.1.2. Cast Iron

In the past cast iron was frequently used for dry chlorine, its use on pressurised
chlorine duties should be abandoned for safety reasons.
The corrosion behaviour in the presence of chlorine is similar to that of normal steels.
Its use in chlorine, however, is not advisable except under specific well defined
circumstances for the manufacture of components where there will be no problem due
to mechanical shock or tensile forces. With cast iron components, the material needs
to be checked for absence of defects which could cause porosity to chlorine under

3.1.3. Ductile Iron

The corrosion behaviour in the presence of chlorine is similar to that of carbon steels.
Its use in chlorine however, is not advisable except under specifically well-defined
circumstances for the manufacture of components where there will be no problem due
to mechanical shock or tensile forces e.g.PTFE-lined valves for wet chlorine.

3.1.4. Stainless Steels

Stainless steels are suitable for use with dry chlorine. In general however, they should
not be used if there is the likelihood of contamination with water. Chlorine
contaminated with moisture causes pitting corrosion. Almost all chlorine equipment
is periodically cleaned and pressure tested with water, which causes the risk of
For the reasons stated above, stainless steels are not recommended for thin section
applications e.g. bellows and bursting disc.
They are sometimes used in preference to normal steel :
. for components where improved qualities are required at low temperature
. with dry chlorine gas because of their improved resistance at higher temperatures.
This resistance to chlorine at higher temperature increases with the nickel content.
For stainless steels containing less than 10% nickel the upper temperature limit is
150C. Steels with more than 10% nickel, however, can be used on certain duties
with chlorine gas up to a maximum of 250C.

3.1.5. Alloyed Steels

The presence of small quantities of metals, such as titanium, in an alloy is normally
acceptable. However, due to the variety of high alloyed steels available, it is
impossible to give detailed information in this document. In such cases, it is therefore
recommended to consult a specialist.

3.1.6. High Nickel Alloys

- For dry chlorine gas: Monel is suitable up to 350C.

Nickel and Inconel up to 400-500C.
Nickel is used in thin wall applications e.g. bursting disks, and as a lining material
because of its poor mechanical properties.

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3.1.7. Hastelloy C
Hastelloy C-4 and Hastelloy C-276 are often used for components for dry
chlorine and chlorine with traces of moisture. The low temperature mechanical
properties are excellent.
They can be used up to 400C-500C.

3.1.8. Titanium

Titanium metal (or titanium stabilised with palladium or nickel/molybdenum to avoid

crevice corrosion) is frequently used in pipework, fans, valves and heat exchangers to
handle wet chlorine gas or water solutions containing chlorine but there are
precautions which have to be observed carefully.
With dry chlorine gas, titanium reacts spontaneously to form titanium tetrachloride; it
is an exothermic reaction producing a huge amount of reaction heat.
Ti(s) + 2Cl2 (g) TiCl4 (l) _G = -726,8 kJ/mol
TiCl4 is a liquid at room temperature (Tm = -22C) and evaporates easily
(Tb = 135C); so it cannot give any protection to the metal below. On the contrary, the
reaction heat will increase the temperature, increasing the evaporation and eventually
ignite a titanium chlorine fire.
TiCl4 itself is not stable in contact with water vapour. It reacts very fast to titanium
TiCl4 + 2H2O TiO2 (s) + 4 HCl (g) _G = -54,1 kJ/mol
From the above it follows that the reaction of titanium is controlled by the
"competition" between the forming rates of a protective TiO2 layer and an evaporation
TiCl4 liquid.
Its consequences is that the water concentration (partial water pressure) of the
chlorine and the mass transfer of the water to the titanium surface determine the
forming of a passive TiO2 layer or the ignition of a titanium chlorine fire.
On Appendix 1(graph) there are three areas:
Safe stable conditions, no fire
Danger ignition and fire
Unstable flow dependant zone
As can be seen:
- The water content in the gaseous phase has to be at least equal to the water partial
pressure at 13C.
- Below about 13C (atmospheric pressure) the water vapour pressure becomes too
low to be safe. Under conditions of chlorine-hydrate formation ignition is still
- Up to about 70C the minimum water content to prevent a fire is flowrate
dependant and not so much temperature dependant. Keeping the water partial
pressure above 15 mbar (about 0,4 w-% H2O at atmospheric pressure) means safe

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- At higher temperatures (75C and up) exponentially more water is needed for safe
conditions (not flow rate dependant).
- The unstable transition area between safe and unsafe conditions is dependent on
mass transfer of water to the metal surface and should be avoided.
Care shall be taken of local situations e.g. depressurisation after a valve, erosion of
the titanium dioxide layer. ....

3.1.9. Tantalum

Tantalum is the only metal that can be used without restriction on wet and dry
chlorine. Because of its high price, however, it is used only for special equipment
parts such as transmitter membranes and bursting disks.

3.1.10. Copper
Copper is resistant to dry chlorine gas or liquid. The use of copper is restricted to
flexible connections for drums and cylinders filling, but it becomes embrittled by
frequent stressing and requires regularly stress relieving by moderate heat treatment.
Certain alloys of copper (such as brass or bronze), used in components that have been
proved by long service experience, are accepted for the manufacture of certain
cylinder valves because of the regular checks carried out on such equipment and their
frequent replacement.

3.1.11. Silver, Gold

These metals are resistant to dry chlorine but they have poor mechanical properties.
They are sometimes used for protective membranes and bursting disks.

3.1.12. Lead
Lead is resistant to dry chlorine and the rate of attack upon lead by moist chlorine is
Lead can be used as a trapped gasket in some circumstances, but otherwise its use
with chlorine is not recommended on safety reasons because of its poor mechanical
Lead-antimony alloys are sometimes used for protective membranes, because they are
resistant in the presence of moisture.

3.1.13. Zinc, Tin, Aluminium

None of the above metals should be used for chlorine, nor should alloys based on
these materials. They are not resistent to chlorine.

3.2. Plastics

The following comments deal only with the use of the materials on construction duties
or as a lining. Their behaviour when used on specialised duties is dealt with in sections 5
and 6. Most of these plastics are slowly attacked by chlorine and require a schedule of
inspection and replacement before they become defective. Many of them are liable to
stress corrosion cracking and the fabrication of components or systems from plastics
should avoid regions of high stress during manufacture or service.

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3.2.1. (GRP) Glass Fibre Reinforced Polyester

Certain polyester resins form a protective chlorinated layer resistant to wet or dry
chlorine gas at temperatures up to 80C. There are a number of commercially available
materials that have been confirmed as suitable for use on chlorine. Advice on this type
of resin and its method of fabrication and use should be checked with an experienced
chlorine manufacturer before installation.
GRP must not be used where liquid chlorine can be present.

3.2.2. (PVC) Polyvinyl Chloride

PVC is satisfactory with gaseous chlorine, either wet or dry. After prolonged use the
wall thickness will reduce due to surface chlorination (it has to be checked). The
material may become brittle and therefore can be susceptible to failure due to impact.
PVC is subject to stress corrosion and it is recommended that the material should be
stress-relieved before use. Operating pressures must be limited and support must be
provided., PVC externally reinforced with GRP should be used to improve the
mechanical strength,. especially when temperature exceeds 40C
. Because the thermal expansion of PVC is different from that of GRP the reinforcement
is often done so that there is an adhesive strength between the PVC/GRP. This is
achieved by using a priming coat in the PVC/GRP interface so that PVC and GRP are
chemically bond to each other. This procedure unfortunately gives a brittle behaviour in
the PVC which can be dangerous2. The use of PVC/GRP with no adhesion between the
PVC and the GRP should be considered for pipes.
PVC and PVC/GRP must not be used where liquid chlorine can be present.

3.2.3. C-PVC - Chlorinated PVC

Chlorinated PVC has similar uses and limitations to PVC but is more difficult to weld.
It can have a slight advantage if one is looking for greater mechanical strength at
slightly higher temperatures.

3.2.4. PVDF (Poly Vinylidene Difluoride), PVDF/GRP

PVDF has good resistance up to 140C on wet or dry chlorine gas. At higher
temperatures, it stands up better than PVC and polyesters, but is subject to a degree of
chlorination. Like most plastics already listed, the material is liable to stress corrosion
The stress cracking problem for PVDF is caused by atomic chlorine radicals (for
example due to UV light or in certain chemical reaction conditions). PVDF qualities
specified as "Atomic chlorine resistant" should be used on chlorine duties. PVDF can
also be reinforced externally with GRP to give improved mechanical strength for
applications at higher temperatures or pressures.
PVDF and PVDF/GRP must not be used with liquid chlorine.

3.2.5. PTFE - PolyTetraFluoroEthylene

PTFE resists wet, dry and liquid chlorine well. Because of its poor mechanical
properties, PTFE should always have a supporting material. However, it should be noted
that chlorine can diffuse through PTFE, which is not completely impervious
(particularly to liquid chlorine and gas at elevated temperatures). The problem of

Bergman G. and Petersson K. - Brittle Behaviour of PVC-lined FRP structures. Swedish Corrosion
Institute, Project report 66 226:2
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permeability can be reduced by using greater material thicknesses. Where PTFE is used
as a protective layer, the integrity of the supporting material must be regularly inspected.

3.2.6. FEP, PFA, TFE/HFP-copolymer, Perfluoro-alkoxypolymer

Various fluorinated copolymers are also used because of their corrosion resistance to
wet or dry chlorine. They can be more easily fabricated than PTFE with fewer problems
of permeability.

3.2.7. Polypropylene, Polyethylene

These materials have some resistance to wet or dry chlorine gas. However, both
polyethylene and polypropylene are more severely attacked by chlorine above 30C. In
general they are less resistant than PVC. It is recommended that polypropylene be
stress-relieved before use.
They must not be used with liquid chlorine.

3.2.8. Other Plastics

Several other specialised plastics have been developed and tested on chlorine duty (e.g.
Acrylonitrile/butadiene/styrene copolymers). Their use with chlorine gas can only be
recommended where their use has been demonstrated as suitable for a particular duty
(check with experienced chlorine manufacturers).

3.3. Other Materials

3.3.1. Rubber or Ebonite

All forms of synthetic or natural rubber lack mechanical strength and they are attacked
by chlorine. The slow rate of attack on rubber in chlorine gas means that it is frequently
used as a lining material for chlorine duty at up to 85C (depending on the grade of
It must not be used on liquid chlorine duty.

3.3.2. Graphite
In spite of the strong oxidising properties of wet chlorine, impregnated graphite (to
avoid problems with its porosity) can be used with wet chlorine gas at temperatures up
to 80C. However, the impregnating resin (such as PTFE) must be confirmed as chlorine
resistant. It is frequently used on certain wet chlorination systems but above this
temperature of 80C there is a greater rate of oxidation. Corrosion rates are also greater
at pH values higher than 2, i.e. in the presence of hypochloride ions. It may also be used
in dry chlorine where there is a risk of moisture being present.
Graphite must not be used on liquid chlorine.

3.3.3. Stoneware, Glass, Enamel

Ceramics and glass show good resistance to wet as well as to dry chlorine. But their
breaking strength is so low that their use in technical applications has constantly
declined. They are still used today in laboratories and to a small extent for lining steel
vessels, also as enamelled steel containers.
These materials must not be used on liquid chlorine duty since they are very sensitive to
thermal shocks.

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3.3.4. Brickwork
Anti-acid bricks are used for lining of wet chlorine towers. A cement should be chosen
with good chemical resistance to all the chemicals which are present. An impervious
lining should be used between the brickwork and the steel vessel.


The table below gives general information on the corrosion resistance of various
materials for contact with chlorine. Corrosion resistance is not the only factor in
selecting the materials and therefore the table should only be used in conjunction with
the comments which follow in the rest of the note.



Non-alloyed carbon steel N G to 120C G 3.1.1
Cast iron N G to 120C G XX 3.1.2
Stainless steels N G to 150C G 3.1.4
Nickel N G to 500C G 3.1.6
Inconel N G to 400-500C G 3.1.6
Monel N G to 350C G 3.1.6
Hastelloy C P G to 400-500C G 3.1.7
Aluminium N N N 3.1.13
Copper N G to 150C G 3.1.10
Silver P G to 200C G 3.1.11
Lead A G to 100C A XX 3.1.12
Titanium G N N 3.1.8
Tantalum G G to 150C G 3.1.9
Brickwork G G N 3.3.4
Stoneware and glazed pottery G G G XX 3.3.3
Glass G G G XX 3.3.3
Enamelled Steel G G N 3.3.3
Ebonite G A N 3.3.1
Synthetic rubbers A A N 3.3.1
Silicone rubbers or greases N N N 3.3.1
PVC G to 60C G to 60C N 3.2.2
CPVC G to 80C G to 80C N 3.2.3
Polyethylene A to 30C A to 30C N 3.2.7
Polypropylene A to 30C A to 30C N 3.2.7
PTFE G to 20C G to 20C A 3.2.5
PVDF G to 140C G to 140C N 3.2.4
Corrosion resistant polyester
G to 90C G to 90C N 3.2.1
resins (reinforced)
Graphite A G N 3.3.2

* less than 20 mg H2O/kg chlorine

Key Behaviour: see next page

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Key behaviour
G = Good A = Acceptable
P = Poor N = Must not be used
XX only taking into account corrosion resistance, is not a construction material
Temperatures stated above give an indication of the maximum value, without safety
The above table refers to the non-reinforced plastics without any plasticiser.


For gas containing systems (wet or dry), a certain amount of corrosive attack on rubber
based on a synthetic elastomer is acceptable so long as the jointing system retains the
necessary seal under service conditions. However, for liquid chlorine systems, whatever
the pressure, reactive gasket materials such as rubber must not be used. In these
circumstances, a gasket material specifically proven on chlorine duty. See GEST 94/216
- Experience of Non-Asbestos Gaskets on Liquid and Dry Chlorine Gas Service.


Certain duties such as flexible bellows, bursting discs, etc., demand the use of thin cross
section components. In these circumstances the material must be effectively non-
reactive to chlorine and not rely on a protective ferric chloride surface layer.
The most commonly used materials are :
. for dry chlorine : nickel, tantalum, Monel , Hastelloy C
. for chlorine with traces of moisture : Hastelloy C, tantalum, PTFE
. for wet chlorine : tantalum, PTFE, graphite


The above comments under sections 3.1, 3.2 and 3.3 concern the pure materials, without
plasticisers, fillers, coatings, greases or other potentially reactive ingredients. Therefore
the choice of materials of construction for many systems must be controlled to avoid the
introduction of materials which could react with chlorine.
It is also important when using any component (which is itself made from a satisfactory
material for use with chlorine) to separate chlorine from other fluids, that account is
taken of the potential for leakage occurring between two fluids. This could occur in
components associated with heat transfer or hydraulic systems, where it is important to
make sure that the fluid is not reactive with chlorine and to avoid products such as
water, silicone fluids, hydrocarbon oils, etc. Suitable materials for lubrication or
hydraulic or heat transfer fluids are fully chlorofluorinated fluids which are non-reactive
to chlorine gas or liquid. Perchloroethylene may be used for heat transfer fluid.
All ancillary equipment (instruments, sealing arrangements, etc.) should always be
checked as made from materials which are compatible with chlorine. Materials used for
thermal insulation should also be selected from those, which do not react readily with
chlorine or generate corrosive products under service conditions.
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GEST 80/84 - Code of Good Practice for the Commissioning of Installations for Dry
Chlorine Gas and Liquid
GEST 94/216 - Experience of Non-Asbestos Gaskets on Liquid and Dry Chlorine Gas

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Appendix 1 Page 1 of 1


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Industrial consumers of chlorine, engineering and equipment supply companies worldwide and
chlorine producers outside Europe may establish a permanent relationship with Euro Chlor by
becoming Associate Members or Technical Correspondents.

Details of membership categories and fees are available from:

Euro Chlor
Avenue E Van Nieuwenhuyse 4
Box 2
B-1160 Brussels

Tel: +32 2 676 7211

Fax: +32 2 676 7241

June2004 Page 17 of 17