m

Product Information
Bulletin 97-01

Rev. 08/2008

Nafion
perfluorinated membranes

General Information on Nafion Membrane for Electrolysis

Introduction
Nafion membranes are made from ion exchange
polymers. The perfluorinated polymer provides
chemical and thermal stability similar to that of Teflon
fluoropolymer resin. Attached to the polymer chains
are perfluorinated cation exchange sites. The polymer
is therefore permeable to many cations and polar
compounds - their size and electrical properties
determine their mobility through the polymer - and can
almost completely reject anions and nonpolar species.

Membranes are thin polymer films that are usually

reinforced with a fabric made of Teflon. They are
useful as separators in a wide range of applications.
In a typical membrane process, a fluid containing
one or more components is in contact with one side
of the membrane. The membrane is normally more
permeable to one component than the others. The
preferred component is transferred through the
membrane under the influence of a driving force,
such as a concentration difference, electric potential
or hydro-static pressure.

___________

Nafion is a DuPont registered trademark for its perfluorinated ion

exchange membranes. Only DuPont makes Nafion .

Teflon is a DuPont registered trademark for its fluoropolymer resins.

Only DuPont makes Teflon .

Figure 1: Nafion Membrane in Chloralkali Electrolysis

1/ Cl
2 2

NaCl + H2O

+ 1 /2H2 + NaOH

1/ Cl
2 2

1/ H
2 2

H2O
Depleted
Brine

Brine

+
A
N
O
D
E

e-

ClNa+ Cl-

M
E
M
B
R
A
N
E

Rectifier

OHH+ OH-

Na+ OH-

C
A
T
H
O
D
E

e-

Caustic

Water

Nafion Membrane for Production of Chlorine and

Caustic
The primary application for Nafion membrane is
production of chlorine and caustic by electrolysis, as
illustrated in Figure 1. This technology is
environmentally sound and has become the preferred
method for chlorine and caustic production, having
significant operating cost advantages over the older
mercury and diaphragm technologies.
DuPont introduced the worlds first commercial
perfluorinated ion exchange membrane in 1969,
capping a 10-year research and development effort.
Nafion membranes were first used in a commercial
chloralkali plant in 1975.
DuPonts manufacturing facility, at Fayetteville, North
Carolina, began production in 1980, and has the
capability to meet the worlds membrane
requirements through the twenty-first century.
Nafion 900 and 2000 series membranes are
designed to give optimum performance in the
production of chlorine and caustic soda. They are
reinforced composite membranes, having sulfonate
and carboxylate polymer layers, as shown in
Figure 2. They also have surface modifications
to enhance gas release from the membrane.

Figure 2: Structure of Nafion

Polymer Structure
-(CF 2 -CF 2 ) n -CF-CF 2 |
O

Nafion 300, 400 and 500 series membranes are

reinforced, all sulfonate polymer, membranes
designed for dilute caustic and caustic potash
production. Nafion 500 series membranes have
surface modification on one or both sides, for
enhanced gas release.
Other Applications for Nafion Membrane
Other applications for Nafion membrane include
electrochemical syntheses, spent acid regeneration,
metal ion recovery, and fuel cells. The product line is
highly diversified, with Nafion membranes designed
for these different applications.

Nafion 100 series membranes are sulfonate

films that are typically used for H2O and HCl
electrolysis and fuel cells.

Nafion 300 series membranes are reinforced

composites of two sulfonate films that differ in
equivalent weight. These membranes are used
for producing 12-20% NaOH and for
electrochemical syntheses.

Nafion 400 series membranes are reinforced

sulfonate films that are frequently applied to
spent acid regeneration, metal ion recovery,
production of 8-10% NaOH, as well as the
production of 30-32% KOH.

M em brane Structure (Cross Section)

Perfluorinated Ionomers
(Chem ical Stability)

Sulfonate
(Low Resistance)

Surface
M odification
(Cl2 Gas Release)

Carboxylate
(High Ion Transport
Selectivity)
Surface
M odification
(H 2 Gas Release)

R
R = SO 3 - Na +
or
COO - Na +

Fabric
(Tear Resistance)

Anode Side

Cathode Side

Caustic Soda Production

The family of Nafion 90209 was introduced in

1982 and is still used throughout industry today.

Nafion 966 was developed in 1991 for

electrolyzers that require very high physical
strength.

Nafion 2020 was introduced in 2002 with the

same strength as 966, lower voltage, and is
becoming the industry standard when very high
physical strength required.

Nafion 982 was introduced in 1998 and has

become the industry standard, widely used in
most electrolyzers providing high performance
and high physical strength.

Nafion 2010 introduced in 1998 is similar to

N982 with lower voltage. DuPont achieved this
improved performance through advanced
polymer technology.

Nafion N2030 was introduced in 2004 using the

same proven polymers as N982 and voltage
lower than N2010. This newest product shows
DuPonts leadership and commitment to the
Chloralkali industry.

New Nafion membranes are under development

and trial. Consult your representative for Nafion
membrane for information on new products for
your plant.

Descriptions and laboratory cell performance of the

membranes are shown in Table 1 and Table 2.

Caustic Potash Production

Recommendations for KOH operation are different
than for NaOH. Refer to Technical Bulletin 94-03,
Nafion Perfluorinated Membranes for KOH
Production.

Available Forms of Nafion

Membranes
Nafion perfluorinated membranes are produced
either in the H+ or the Na+ form, depending on the
intended use. For example, N117, used in fuel cells
and sealing applications, is sold in the H+ form.

Table 1
Membrane Description
Membrane
Type
N90209

Surface
Modification
None

Cell Gap
Type
Finite

N966

Anode side and

Cathode side
Anode side and
Cathode side
Anode side and
Cathode side

Finite and
Narrow
Finite and
Narrow
Finite and
Narrow

N2010

Anode side and

Cathode side

N2030

Anode side and

Cathode side

N2020
N982

Features
Introduced in 1982, still widely used worldwide in
many types of cells.
Very high strength provides easier handling, and
more resistance to operational physical upsets.
Same strength as N966 with lower voltage.

Tensile Strength
kg/cm
5.6
7.5
7.5

Same performance as N981 with a stronger fabric.

4.0

Finite and
Narrow

Same strength as N982 with lower voltage through

advanced polymer technology.

4.0

Finite and
Narrow

Same strength and proven polymers as N982 with

lower voltage than N2010

4.0

Table 2

Commercial Performance
Membrane
Type

Finite Gap Cell1

Current
Cell Voltage, V
Efficiency, %

Narrow Gap Cell2

Current
Cell Voltage, V
Efficiency, %

3.43
>95
N90209
3.30
>95
3.05
>96
N966
2.98
>96
N2020
2.95
>96
N982
2.90
>96
N2010
2.87
>96
N2030
o
1
Conditions: 3 mm gap, D.S. Anode, Bare Nickel cathode, 32% NaOH, 200 gpl anolyte, 90 C.
o
2
Conditions: 0 mm gap, D.S. Anode, Activated Nickel cathode, 32% NaOH, 200 gpl anolyte, 90 C.

Nafion 900 and 2000 series membranes are sold in Na+

Form. The membranes used for KOH production are also
+
produced in the Na form, to facilitate a greater degree of
expansion at installation.
Nafion membranes are supplied in one or more of these
states: dry, wet (WX and PW), and dry expanded (TX).
Contact your representative for Nafion for information on the
form available for your application.
+
DRY H Form

k-factor
mV/kA/m2
220
190
165
140
120
110

The WX and PW products have the same physical properties

as the wet, expanded form of DRY Nafion membrane with the

same code number (e. g., N982 and N982WX have the same
physical properties, and perform the same during electrolyzer
operation).
In WX form, the membrane is expanded in hot water. The PW
form is expanded at room temperature.
There are two special considerations for the pre-expanded,
wet form membranes:

DRY H+ form is the state for Nafion 100, 300, and some 400
series membranes. Depending on the application, they
require treatment prior to installation in a cell. Refer to
Technical Bulletin 93-01, Nafion Hydrogen-Form Membrane
Expansion for detailed information.

The pH of the WX membrane packing solution is

approximately 10 and the pH for the PW solution is
neutral. Depending on the requirement for your
electrolyzer, the pH of the membrane may need to be
adjusted.

+
DRY Na Form

Both the WX and PW products are shipped in wet, fully

expanded form, and sealed in polyethylene packaging, to
avoid loss of water. The package contains only a small
amount of excess water. During assembly, dry out can
occur, which must be avoided to prevent slight shrinkage
of the membrane.

DRY Na+ form Nafion membranes require pretreatment in

alkaline water before installation in an electrolyzer, in order to
wet out and expand the membrane. Refer to Technical
Bulletin 91-03, Sodium Form Membrane Expansion in
Alkaline Water, for more information.
If additional expansion is recommended for your electrolyzer,
see Technical Bulletin 92-01, Membrane
Expansion in Alkaline Hot Water.

Do not unseal the package until ready to transfer to the water

bath. Also, keep any unused membranes in the original
container, packed as received, or store them wet in water.

WX and PW Form

Prior to the installation of the membrane, the membrane

should be removed from the package and put in a water bath
at the required pH. During installation, keep the membranes
wet by spraying with water every few minutes.

WX and PW products of Nafion membrane are supplied in

pre-expanded, wet form. They provide an easy to use
membrane, while offering improved resistance to membrane
damage from handling. Refer to Technical Bulletin 93-03,
Nafion Membrane WX Products, for more information.

TX FORM

TX products of Nafion membrane are pre-expanded,

dry, and ready to install directly into chloralkali
electrolyzers without any pretreatment. They are easy
to handle and offer improved resistance to damage from
handling.

The agent used to convert Nafion membrane to the TX

form is diethylene glycol (DEG). The DEG must be
removed before electrolyzer startup to prevent foaming
and product contamination. The removal is done by
filling and draining the electrolyzer twice with water or
dilute caustic and brine. DEG, in water solution, can be
biodegraded before disposal. Please refer to Technical
Bulletin 93-02, Nafion Membrane TX Products, for
detailed information.
After being installed and rinsed to remove the DEG, TX
products have the same physical properties as the wet,
expanded form of DRY Nafion membranes with the
same code number (e.g., N966 and N966TX have the
same physical properties and perform alike during
electrolyzer operation).
When TX form membranes are being installed, the
electrodes, and other cell components that the
membrane may contact, must be clean and dry. Any
residual water may cause partial removal of DEG, which
results in uneven expansion of the membrane. This will
cause installation difficulties, and may result in wrinkle
formation in the membrane during operation.

Size and Packaging

Nafion membranes are available in custom sizes with
widths up to 1.5 meters and lengths up to 4 meters.
Dry sheets are rolled on fiberboard tubes, wrapped with
a polyethylene sheet, and shipped in a plastic tube.
WX membranes are shipped wet, in pH 10 solution. PW
membranes are shipped wet in a pH neutral solution.
Small sheets are sealed in polyethylene pouches, and
shipped flat, in wooden containers. Large sheets are
rolled on plastic tubes, wrapped with a polyethylene
sheet, and shipped in a watertight plastic container.

TX membranes are shipped dry and are rolled on a

polyethylene covered fiberboard tube, wrapped with a
polyethylene sheet, and shipped in a plastic container.

Chloralkali Operation Using Nafion

Membranes

Refer to the Nafion Users Guide for detailed

information regarding the use of Nafion membranes for
chloralkali production. Also refer to Table 3 and Table 4
for general operating conditions recommendations. For
operation at higher current density (above 4 kA/sq.m.),
some specifications differ. Consult your representative
for Nafion membrane.

Table 3
Recommended Operating Conditions and
Monitoring Frequency For Nafion Membrane
Parameter

Operating Conditions

Monitoring
Frequency

As required to control current density

1.5-6.0 kA/sq.m.
< 4.0 Volts
Determined by membrane condition

Continuous
Continuous
Continuous1
As required

>210 gpl NaCl4

As required to control anolyte strength
As required to control anolyte acidity
200 30 gpl NaCl
>2 pH
<20 gpl NaClO3
80-90C

Continuous5
Continuous1
Continuous1
Continuous1
Continuous1
Once/day
Continuous1

Electrolyzer
Current
Current density 7
Voltage
Current efficiency
Anolyte Compartment (Brine Side)
Brine feed concentration2,3
Brine feed flow
Acid addition rate6
Anolyte strength2,3
Anolyte acidity3,6
Sodium chlorate in anolyte3
Anolyte temperature
Feed brine impurities:
Calcium/magnesium
Strontium
Sodium sulfate
Iodine
Barium
Aluminum
Silica
Iron

Continuous1,5
Once/week
Once/day
Once/week
Once/week
Once/week
Once/week
Once/week

See Table 4
for
Brine Impurity
Specifications

Catholyte Compartment (Caustic Side)

Water addition rate
As required to control caustic strength
Water resistance
>200,000 ohm-cm
Caustic strength7,8
32.5 2.5 wt % NaOH
Chloride in caustic
Results from operating conditions
Temperature
80-95C
1
2
3
4
5
6
7
8

Continuous
Continuous
Continuous1
Once/week
Continuous1

Alarm recommended.
Correct density for temperature and sulfate and chlorate.
Measured at 23C.
>210 gpl NaCl for systems using a circulation brine loop; >270 gpl NaCl for once-through brine systems.
If continuous is not possible, measure at least once per 8 hours.
When controlling anolyte pH by HCl acid addition.
For higher Current Density, consult your representative for Nafion membrane.
Not to exceed 32.0 % for the first 48 hours after initial start-up.

Nafion Membranes for Chloralkali

Impurities

Table 4
Brine Specifications and Their Effect on Performance of Nafion Membrane(1)
Typical
Typical Limits
Typical Control
Performance
2
Limits
4-6 kA/m
Physical Effects
Effects
2

<4 kA/m

<30 ppb
Combined
Ca and Mg
See
Calcium

<20 ppb
Combined
Ca and Mg
See
Calcium

Precipitates in
membrane.

May reduce CE
to 80%.

Ion exchange
treatment.

Precipitates in
membrane.

Increases
voltage.

Flocculation and settling in Primary

Brine Treatment, filtration in
Secondary Treatment, and Ion
Exchange Treatment.

Strontium

<500 ppb

<400 ppb

Precipitates in
membrane.

Less severe
than Ca.

<1ppm

<500 ppb

Precipitates in
membrane.

Less severe
than Ca and Sr.

Sodium
Sulfate

<10 gpl as
Na2SO4

4-8 gpl as
Na2SO4

Iodine

<1ppm

<200 ppb

Diffuses through
membrane; some
precipitates in
membrane.
Is oxidized to iodate in
the anolyte, and to
periodate if it enters
the membrane. At
higher concentrations,
sodium paraperiodate
will precipitate
damaging the
membrane.

Concentrations
in excess of 10
gpl can cause
CE decline.
Reduces CE to
80-85%.

Ion exchange treatment (Sr

may break through resin beds
sooner than Ca and Mg).
Settling in Primary Brine
Treatment, and some Ion
Exchange resins will remove
Barium.
Barium or calcium precipitation
or brine purge.

Barium

Calcium

Magnesium

Aluminum/
Silica

Al<100
ppb
SiO2<10
ppm

Al<100 ppb
SiO2<6 ppm

Iron

Fe<1 ppm

Fe<1 ppm

Sodium
Chlorate

<20 gpl

<20 gpl

[1]

At lower
concentrations Iodine
may precipitate with
alkaline earth cations.
Under acidic
conditions aluminum
will dissolve and
combine with silicates
and precipitate in
membrane.
Iron oxide forms in
anolyte, collects on
anode and membrane
surfaces, and can cause
anode side blinding.
Interferes with NaCl
measurement.

Methods for removing iodine

from brine are not
commercially available.
Purging can provide some
reduction.

Less severe CE
reduction.

May reduce CE
to 90-93%.

Careful settling in Primary

Brine Treatment and
subsequent filtration helps
control clays.

May increase
Limit in salt supply; sodium
voltage and
ferrocyanate (YPS) is common
reduce CE below anti-caking agent.
90%.
Increases
chlorates in
caustic.

Purge, or destroy in
recirculation loop.

For special brine conditions outside of these specifications, consult with your Nafion Representative.

For more information about Nafion

or to place an order, contact:

DuPont
Nafion Global Customer Service
22828 NC 87 HWY W.
Fayetteville, NC 28306, U.S.A.
Telephone: (910) 678-1380 or (910) 678-1337
Domestic U.S.A. Only: (800) 436-1336
Fax: (910) 678-1342
____________________________________________________________________________________________

Nafion is a registered trademark for its brand of perfluorinated polymer products, made and sold only by E.I. duPont de Nemours and
Company.
The data listed here fall within the normal range of product properties, but they should not be used to establish specification limits nor used alone
as the basis of design. This information is based on technical data DuPont believes to be reliable. It is intended for use by persons having
technical skill, at their own discretion and risk. This information is given with the understanding that those using it will satisfy themselves that
their particular conditions of use present no health or safety hazards. Because conditions of product use are outside our control, DuPont makes
no warranties, express or implied, and assumes no obligation or liability in connection with any use of this information or for results obtained with
respect to these products. This information is provided gratis, and buyer assumes the sole responsibility for results obtained in reliance thereon.
The disclosure of the information is not a license to operate under or a recommendation to infringe any patent of DuPont or others.
CAUTION: Do not use in medical applications involving permanent implantation in the human body. For other medical applications, see DuPont
Medical Caution Statement, H-50102.

m
Nafion
Only by DuPont