Surface Morphology of Nafion 117 Membrane

by Tapping Mode Atomic Force Microscope

A. LEHMANI, S. DURAND-VIDAL, P. TURQ

Laboratoire d’Electrochimie URA CNRS 430, Université Pierre et Marie Curie, 8 rue Cuvier,
75252 Paris Cedex 05, France

Received 7 July 1997; accepted 2 November 1997

ABSTRACT: Surface morphology of Nafion 117 membrane was studied by tapping mode
atomic force microscopy. Three different samples were analyzed and correspond respec-
tively to dry membrane and wet membrane equilibrated either with water or with
tributylphosphate. These studies show the supermolecular structure of the membrane,
which is made of nodules or spherical grains of a mean diameter of 11 nm, and are
surrounded by interstitial regions of a mean thickness of 50 Å. Roughness analysis of
the samples shows the influence of the swelling properties of the membrane on its
surface morphology. q 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 503–508, 1998

Key words: membrane; atomic force microscopy; swelling

INTRODUCTION molecular level structure of Nafion focuses on the

cluster network model proposed by Gierke, 22 who
Ion exchange membranes play a vital role in nu- described the membrane as a series of clusters or
merous areas of life sciences and technological en- inverted micelles, interconnected by narrow pores.
gineering, 1 including batteries, 2,3 fuel cells, 4 elec- In order to model their ionic diffusional results,
trochemical sensors and electrochemical reac- Yeager and Steck 23 proposed to describe the
tors.5 – 8 The perfluorinated sulphonic acid cation Nafion structure as three regions, as shown in
exchange Nafiont membrane, manufactured by Figure 1. Region A consists of fluorocarbon back-
E.I. du Pont de Nemours and Co. in 1972, shows bone material, some of which is in a microcrytal-
unusual and very interesting properties that justify line form.24 The interfacial region B is seen as a
the great deal of research still performed on such large fractional void volume, which contains side-
a polymeric film. Nafion membrane shows a good chain material, a small amount of water, and
chemical stability when it is immersed in the re- some free sulfonate exchange sites. Region C con-
quired electrolyte solution 9,10 and it has a remark- tains ion clusters, in which exist the sulfonate
able mechanical strength, a good thermal stabil- exchange sites, counterions, and sorbed water.
ity, 11,12 and a high electrical conductivity.13–16 More- In this article, the perfluorosulphonated iono-
over, this membrane shows a high selectivity to the mer (PFSI) membrane studied was Nafion 117,
desired ionic species, 17–20 even in a high-salt concen- with the following chemical formula:
tration environment. Various studies were per-
formed to devise sophisticated models linking mac-
©(CF¤CF¤)n©CFO(CF¤©CFO)mCF¤CF¤SO2‹ H1
roscopic transport rates to the molecular level struc-
ture of the solute, solvent, and membrane.21 The CF¤ CF‹

Correspondence to: S. Durand–Vidal.

Journal of Applied Polymer Science, Vol. 68, 503 – 508 ( 1998 )
where n Å 6.5 and m Å 1, with an equivalent
q 1998 John Wiley & Sons, Inc. CCC 0021-8995/98 / 030503-06 weight of 1100 g meq 01 .
503

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504 LEHMANI, DURAND-VIDAL, AND TURQ

Figure 1 Three regions structural model for Nafion.23

We focused on the structural properties of this under vacuum at 807C. The sample M2 was first
membrane because of its good physical and chemi- dried, and, before the AFM measurement, a drop
cal properties and for its wide industrial applica- of deionized water was put on the membrane. The
tions.1 We have investigated the structural analy- AFM apparatus was kept under a box in Plexi-
sis of the membrane surface by using atomic force glass and several petri dishes filled with water
microscopy (AFM). This high-resolution tech- were placed around the AFM apparatus in order
nique is newly developed to study the morphology to have a constant rate of humidity. Nothing was
of the surface of thin films. In the study of mem- changed during the measurement. The sample
branes, it has been especially used for the study M3 was first dried, and, before the measurement,
of the morphology of biological membranes.25 – 30 a drop of TBP (Prolabo) was put on the mem-
However, few articles have appeared in the litera- brane, and the same precautions were observed.
ture for the study of the structural properties of Small squares of an approximately 1-cm2 area
synthetic membranes by AFM.31 – 33 In the present were cut from each prepared membrane and
article, we report the surface morphology of stuck with reversible Scotch tape on metal
Nafion 117 membrane by tapping mode atomic disks. The images of the surfaces were obtained
force microscope (TM AFM). Three samples have using TM AFM on a Nanoscope III from Digital
been analyzed when the membrane was dry and Instruments.34 We used a Si – n tip whose curva-
equilibrated either with water or tributylphos- ture radius is in the range of 5 – 10 nm. The
phate (TBP) in order to determine the influence spring constant of the tip is in the range of 30 –
of the swelling properties of the membrane on the 92 N m01 , and the resonance frequency range
structural investigation. is 305 – 440 kHz.
The tapping mode is a new technique developed
by Digital Instruments for operating the AFM.
EXPERIMENTAL The lateral resolution is quite comparable for the
contact and noncontact AFM. Moreover, the pres-
Before any measurement, a pretreatment of the sure force applied to the sample in TM AFM is
membrane was carried out in order to expel impu- much lower than in the contact AFM. The applied
rities. The membranes samples were immersed pressure is lower by a factor of ten; therefore, the
successively in aqueous hydrochloric acid, (Pro- sample is less perturbated by the tip.
labo, 35%) 1 mol dm03 for 24 h, and washed in The membrane surfaces were compared by
deionized water for 24 h. This cycle was repeated means of roughness parameters, such as the mean
one more time before boiling the samples for 1 h roughness Ra , the root mean square (rms) of the
in deionized water. Z data Rq , the maximum height Rmax , and the
Three samples of the Nafion membrane have surface area difference SAD. The mean roughness
been studied. The sample denoted M1 was dried is the mean value relative to the center plane,

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 SURFACE MORPHOLOGY OF NAFION 117 MEMBRANE 505

The rugosity factor G is related to SAD by the

following relation:

G Å 1 / SAD

RESULTS AND DISCUSSION

Figures 2 and 3 show the representative three-

dimensional images of the M1 sample in the fol-
lowing two different scan sizes: 1 1 1 mm 1 30
nm and 50 1 50 1 3 nm, respectively. The light
areas correspond to the maximal heights in the Z
direction, and the dark areas are related to the
minimal heights. Figure 2 shows supernodular
aggregates, which is characteristic of the super-
molecular structure of ionomeric materials.36 This
Figure 2 Surface plot of the image by TM AFM of the superstructure is constituted of spherical do-
M1 sample. mains having an average diameter of 45 nm. At a
lower scan size (Fig. 3), the structure is conserved
and presents spherical grains with an average di-
which is parallel to the mean plane; the volumes ameter of 11 nm. The section analysis of this mi-
enclosed by the image surface above and below crostructure (Fig. 4) shows that the interstitial
the center plane are equal.35 Ra is defined as regions have a mean thickness of 49 Å, which may
correspond to the pore (or cluster) size in Nafion

* *
Ly Lx
1 membranes.12 However, it could be also assumed
Ra Å Éf ( x, y)É dxdy
Lx Ly 0 0 that the interstitial regions are not free of matter
but rather that they are the region of lower poly-
where f ( x, y) is the surface equation relative to mer density.33 As we can see, between the two
the center plane, and Lx and Ly are the dimensions triangles on Figure 4, there is no hole.
of the sample under study. Rmax is the height dif- Figure 5 shows the three-dimensional image of
ference between the highest and lowest points on the M2 sample in the scan size (1 1 1 mm 1 30
the surface relative to the mean plane. Rq is the nm). It is seen that the supernodular structure is
standard deviation of the Z values within the
given area, and is calculated as

Rq Å S ∑ (Zi 0 Zavg ) 2 /N
i
D 1/2

where Zavg is the average of the Z values, Zi , the

current Z value; and N, the number of points.
The surface area difference SAD, in percentage,
is defined as

SAD Å F Surface area

Projected area
01 G 1 100

where the surface area is the three-dimensional

surface obtained by the sum of the triangles
formed by three adjacent points, and the projected
area is the two-dimensional surface produced by Figure 3 Surface plot of the image by TM AFM of the
projecting the surface onto the threshold plane. M1 sample for a lower scan size.

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506 LEHMANI, DURAND-VIDAL, AND TURQ

Figure 4 Section analysis of the TM AFM image of the M1 sample.

always conserved with larger interstitial regions Figure 6 shows the three-dimensional image of
and a lower roughness (1.7 nm instead of 3.1 nm). the M3 sample in the scan size (1 1 1 mm 1 150
It is known that for the Nafion 117 membrane, nm), when the membrane is equilibrated with
the volume increase with water is about 40%, 37 TBP. A real change of the membrane structure
which may imply a distribution density of the with a nonuniform distribution of the grains and
spherical grains less important than for the M1 wide and deep rifts ( Ra Å 9.9 nm) can be seen.
dry sample. It is known that the volume increase of the

Figure 5 Surface plot of the image by TM AFM of the Figure 6 Surface plot of the image by TM AFM of the
M2 sample. M3 sample.

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 SURFACE MORPHOLOGY OF NAFION 117 MEMBRANE 507

Table I Roughness Parameters for Membrane 3. F. G. Will and H. S. Spacil, J. Power Sources, 5,
Surfaces of the Three Samples 173 (1980).
4. E. Gileadi, S. Srinivasan, F. J. Salzano, C. Braun,
Ra Rmax Rq SAD A. Beaufrere, S. Gottesfeld, L. J. Nuttal, and A. B.
Sample (nm) (nm) (nm) (%) G LaConti, J. Power Sources, 2, 191 (1977).
5. H. L. Yeager, B. Kipling, and R. L. Dotson, J. Elec-
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M2 1.7 18.4 2.2 1.2 1.01 6. R. S. Yeo, J. McBreen, G. Kissel, F. Kulesa, and S.
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portant ( É 360% ) , 37 which can justify such a
(1979).
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The analysis of the roughness parameters of 11. A. Eisenberg and M. King, Polymer Physics, R. S.
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the surface membrane is quite rough, especially 4.
for the M3 sample. We must add that these 12. T. D. Gierke in Proceedings of the Symposium on
roughness parameters depend on the curvature Perfluorocarbon Ion Exchange Membranes, The
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The AFM equipment was purchased on D. Devilliers’s
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