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Zero-mode TEM parallel-plate resonator for high-


resolution thin film magnetic resonance imaging
Ziheng Zhang, Andrew E. Marble, Rodney P. MacGregor, Jonathan Martin,
Haijiang Wang, and Bruce J. Balcom

Abstract: A parallel-plate radio frequency resonator has been designed for high-resolution thin film magnetic resonance
imaging. The B1 field produced by the resonator was evaluated through experiment and numerical simulation. The resona-
tor, composed of two conductive plates sandwiching the sample, generates a uniform B1 field parallel to the plates. This fea-
ture renders the resonator largely immune to radio frequency screening from conductive layers parallel to the sample. The
resonator is custom fabricated according to the dimensions of the sample, yielding a high filling factor. The radio frequency
probe is shown to facilitate high-sensitivity depth profiling of thin films. Three variations on the basic design are examined.
Since the intention is to employ these resonators for functional studies of membranes, we introduce perforations in the paral-
lel plates to permit mass transfer in and out of the thin films under study. One-dimensional depth profiles of Nafion 117 are
presented with and without the addition of additional plates of conductive material. One-dimensional depth profiles of Na-
fion 1110 and a two-dimensional image of Nafion 117 in an operating fuel cell, which was integrated into the radio fre-
quency circuit, are also illustrated.
Key words: RF coil, parallel plate, zero-mode transverse electric and magnetic (TEM), Nafion, fuel cell.
Résumé : On a développé un résonateur de radiofréquence à plaques parallèles pour l'imagerie de résonance magnétique à
haute résolution de films minces. On a évalué le champ B1 produit par le résonateur par le biais d'une expérience et d'une
simulation numérique. Le résonateur, qui est composé de deux plaques conductrices maintenant l'échantillon en sandwich,
génère un champ B1 uniforme, parallèle aux plaques. Cette caractéristique fait que le résonateur est grandement protégé de
l'effet d'écran de radiofréquence des couches conductrices parallèles à l'échantillon. Le résonateur a été fabriqué sur mesure,
d'après les dimensions de l'échantillon, ce qui lui assure un facteur de remplissage élevé. On a démontré que la sonde de ra-
diofréquence facilite une grande sensibilité dans la détermination du profil en profondeur des films minces. On a examiné
trois variations sur le modèle de base. Puisque l'intention est d'utiliser ces résonateurs pour des études fonctionnelles de
membranes, on a introduit des perforations dans les plaques parallèles afin de permettre des transferts de masse à partir de
et vers les films minces étudiés. On présente les profils de profondeur unidimensionnelle du Nafion 117, avec et sans addi-
tion de plaques additionnelles de matériel conducteur. On illustre aussi les profils de profondeur unidimensionnelle du Na-
fion 1110 et une image bidimensionnelle du Nafion 117 dans une pile à combustible opérationnelle intégrée dans un circuit
de radiofréquence.
Mots‐clés : bobine RF, plaque parallèle, mode électrotransversal (MET) zéro, Nafion, pile à combustible.
[Traduit par la Rédaction]

Introduction lection for this purpose.2,3 However, the sensitivity of the sur-
face coil decreases rapidly with distance.
In high-resolution magnetic resonance imaging (MRI), se- In previous high-resolution imaging of thin films, we posi-
lecting a suitable resonator is of great significance in deter- tioned a surface coil directly below the thin film sample.4
mining the final signal-to-noise ratio (SNR).1 The surface The B1 field is thus perpendicular to the plane of the film.
coil, due to its strong B1 field strength, is often a natural se- However, in many practical thin film devices, for example,

Received 1 November 2010. Accepted 9 January 2011. Published at www.nrcresearchpress.com/cjc on 3 May 2011.
Z. Zhang†, R.P. MacGregor, and B.J. Balcom. MRI Centre, Department of Physics, University of New Brunswick, Fredericton, NB
E3B 5A3, Canada.
A.E. Marble.‡ Department of Electrical Engineering, P.O. Box 4400, University of New Brunswick, Fredericton, NB E3B 5A3, Canada.
J. Martin and H. Wang. Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC V6T 1W5, Canada.
Corresponding author: B.J. Balcom (e-mail: bjb@unb.ca).
This article is part of a Special Issue dedicated to Professor Roderick E. Wasylishen.
†Present address: Department of Diagnostic Radiology, Yale University School of Medicine, P.O. Box 208043, New Haven, CT 06520-
8043, USA.
‡Present address: Department of Systems and Computer Engineering, 1125 Colonel By Drive, Carleton University, Ottawa, ON K1S 5B6,

Canada.

Can. J. Chem. 89: 745 –753 (2011) doi:10.1139/V11-018 Published by NRC Research Press
746 Can. J. Chem. Vol. 89, 2011

fuel cells and batteries, the thin layer of interest is sand- extended recovery time preceding each k = 0 RF pulse to
wiched between conductive electrodes. In these cases the ra- permit full recovery of longitudinal magnetization, Mz, and
dio frequency (RF) excitation of a surface coil will be are thus immune to T1-contrast.14–16
shielded from the thin film. Moving to lower RF will in- The application of MRI methods to study water content
crease the skin depth and potentially permit better excitation, and water transport in Nafion proton electrolyte membrane
but this is not an appealing strategy. A better choice, which fuel cells was pioneered by Tsushima17,18 and Wasy-
we explore in this paper, is to introduce a B1 field oriented lishen.19,20 This new parallel-plate resonator aims to improve
parallel to the plane of the thin film while still orthogonal to the limited MRI sensitivity of conventional RF probes that
B0. A surface coil is clearly not appropriate for this applica- hinders sensitivity and limits resolution. To demonstrate its
tion, while the use of a standard volume coil will incur a sub- capabilities, an image was acquired of water in the membrane
stantial filling factor penalty. layer of an operating fuel cell. The fuel cell design requires
Parallel-plate resonators have been employed in many sci- that the layer be sandwiched between conductive plates dur-
entific areas,5,6 but their use is relatively new for thin film ing operation. The new resonator design, combined with the
MRI. Zhang et al. have employed a type of parallel-plate res- DHK SE SPI method, allows high-resolution (less than
onator to study liquid crystal properties in both bulk and con- 10 µm) 1D images with SNR > 40 to be acquired in 90 s.
strained thin film capillaries7 and have undertaken chemical Information about the structure and function of an operating
shift resolved velocity mapping in microfluidic systems.8 A fuel cell may be inferred from such high-quality results.
similar RF coil has been developed for MRI histology by The current paper is intended as background justification
Meadowcroft et al.9 The Meadowcroft design was not in- and explanation of the RF probe employed in our recent
tended to be part of a functioning electrochemical device MRI study of an operational fuel cell.21
and does not permit mass transport through the resonator
plates, contrary to the current design.
For thin film MRI, in this study we present a zero-mode Theory
transverse electric and magnetic (TEM)10 parallel-plate reso- RF circuit with an integrated parallel-plate transmission
nator, which uses two parallel conductive plates to sandwich line
the sample. This approach avoids the RF shielding problem, A schematic diagram of the parallel-plate resonator is pre-
as the plates are in the same orientation as the conductors in sented in Fig. 1. The parallel plates sandwich the thin film
the sample, and the resultant B1 field is parallel to the plane sample and are bolted together as illustrated. The B1 field
of the membrane being imaged. A homogeneous current dis- from a plate curls around the flowing current. Therefore, the
tribution on the plates will lead to a homogeneous B1 field fields from both plates add along x in the gap between them
distribution. In addition, such a resonator will structurally and cancel outside. If the thin film sample is layered with
confine the sample and maintain its geometrical shape with conductive material, the cross section seen by B1 is small
controlled pressure if the sample is morphologically sensitive and there is therefore minimal interference from the conduc-
to its environment. The parallel-plate resonator features high tor.
sensitivity, because the excitation volume will structurally The parallel plates chiefly represent a distributed induc-
match the sample size, yielding a high filling factor. tance, but there will be a substantial capacitive component
We compare the experimental B1 field distribution with the for closely spaced plates. The inductance is tuned to reso-
results of numerical simulations for different plate assem- nance with a fixed capacitor, Cm, and a standard matching
blies. We also present the results of high-resolution depth circuit, as shown in the figure.
imaging of Nafion 117 membranes with graphite plates of
different thicknesses inserted inside the parallel-plate resona-
tor. Testing with graphite plates adjacent to the resonator is Numerical simulation
critical in regards to use of the parallel-plate resonator for A design with perforated plates, allowing mass transport
studies of electrochemical cells, for example a fuel cell. The through the resonator to the sample, was required. Changes
graphite plates provide mechanical support and an electrical in the field due to the plate geometry were first studied
connection to the remainder of the electrochemical cell. through simulation. The longest dimension of the resonator
As the resonator is immediately adjacent to the sample, it was ∼9 cm and as a result only the TEM00 mode will be ex-
will distort the B0 field and introduce artifacts into a cited at the 100 MHz operating frequency. This mode will
frequency-encoded image if the plate material’s magnetic have the same field pattern as for a static current flowing in
susceptibility differs substantially from that of the sample. the plates, allowing static methods to be used in modeling
Pure phase-encoding methods were implemented in all meas- the probe.
urements because they are free from distortions due to B0 in- The current distribution in the plates was simulated by
homogeneity, susceptibility variations, and chemical shift.11,12 modeling each plate as a grid of vanishingly small, equal re-
Two-dimensional centric-scan SPRITE imaging was em- sistors. Assuming the current enters the plate at a single point
ployed to visualize the B1 field distribution generated by the and leaves it at a second point, the current distribution in the
parallel-plate resonator. Double half k-space (DHK) spin resistor grid is obtained by numerically solving Kirchoff's
echo (SE) single point imaging (SPI)4,13 was employed to ac- voltage and current laws. The corresponding magnetic field
quire high-resolution water content profiles of Nafion sam- was calculated from the current distribution using the Biot–
ples. Both techniques are centric-scan MRI methods, with an Savart law.

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Zhang et al. 747

Fig. 1. (a) Schematic of a zero-mode parallel-plate resonator. The Results and discussion
sample membrane was sandwiched between the plates. (b) Simpli-
fied diagram of the parallel-plate resonator for numerical simulation. Numerical simulation with experimental examination in
(c) Three different designs for the top plate of the resonator, which three cases
were separately employed for numerical simulation and experimental Three cases, illustrated in Figs. 2–4, were investigated
visualization of the B1 field distribution. The bottom plate of the re- through simulations and imaging experiments. The figures
sonator was solid in all three cases. show current and magnetic field distributions and imaging re-
sults for the cases of a solid top plate, a top plate with several
large longitudinal slits, and a top plate with a large number
of smaller slits cut to permit mass transport. The plate geom-
etry for the three cases is illustrated in Fig. 1c. The bottom
plate was solid in each case. Plot (a) of each figure shows
the simulated current distribution in the top plate. Plot (b) is
a 2D magnetic resonance image of a silicone rubber film
sample acquired with the chosen parallel-plate resonator. The
local image intensity reflects the B1 field strength, which is
expected to be proportional to the local current intensity in
the plates. Plot (c) is the simulated magnetic field in a cut-
plane, as illustrated in Fig. 1b, along x through the center of
the resonator. The position of the plates is indicated by the
horizontal lines. Plot (d) is a 1D MRI profile from a 2D im-
age along x of the rubber phantom, arbitrarily selected from
plot (b) around the middle region of the parallel-plate resona-
tor. The length scale of the simulations is arbitrary but has
been selected to show the features of the field–current distri-
bution.
Figure 2a illustrates that for the solid plate, there is a small
region close to the current feed point where the current is not
uniform. The current quickly becomes uniform in the central
region of the plate. This is reflected experimentally in Fig. 2b.
The image acquisition parameters are such that the signal in-
tensity is proportional to the magnetic field B1. With the ex-
ception of the feed points, which have a higher current
density, the signal intensity is uniform throughout the image.
The uniformity of the field between the plates is clear from
Fig. 2c and is confirmed by the uniform profile in Fig. 2d.
Figure 3a depicts the current distribution for a plate with
several large slits. The current in each remaining “rung” is
equal and reasonably uniform. The current distribution away
from the slits is not substantially changed from that of the
solid plate. In Fig. 3b, gaps in the signal appear in the posi-
tion of the slots and the signal over the rungs is higher than
that over the surrounding plate, owing to the higher current
density. In Fig. 3c, the effect of the slits in the top plate is
pronounced: the field between the plates varies by ∼50%, de-
pending on the position. The variation decreases closer to the
bottom plate. This manifests as a series of peaks and troughs
in the profile (Fig. 3d).
The results for the case of many smaller slits, Fig. 4, are
comparable to those in Fig. 3. However, the effect of the
smaller slits is less pronounced than for the previous case.
This is expected, as it is well known that the extent of a dis-
turbance in a magnetic field will occur on the length scale of
the feature creating the perturbation.22 Thus, many smaller
slits is a better choice.

High-resolution depth imaging with and without


integrated graphite plates
A primary goal of the parallel-plate resonator design was
robust behavior in the presence of conductive layers adjacent
to the sample. With this in mind, depth profiles through thin

Published by NRC Research Press


748 Can. J. Chem. Vol. 89, 2011

Fig. 2. (a) Calculated current distribution in a parallel-plate resona- Fig. 3. (a) Current distribution for a plate with several large slits. (b)
tor with a solid top plate. (b) 2D lateral image of a rubber sheet The corresponding 2D image of the rubber phantom. The dashed
phantom, to illustrate the B1 field distribution. The sensitivity of the line illustrates the slice position of figure (d). (c) The calculated
probe at the current input was pronounced. The dashed line illus- magnetic field. The grayscale levels in (a), (b), and (c) for current,
trates the slice position of figure (d). (c) B1 field distribution in the magnetic resonance image intensity, and B1 field strength are all
cross section. The position of the conductive plates is indicated by plotted in arbitrary units, with white corresponding to the highest
the white horizontal lines. The grayscale levels in (a), (b), and (c) relative intensity. (d) The profile across the short axis of image (b),
for current, magnetic resonance image intensity, and B1 field by averaging the profiles located in the area where slots exist. Be-
strength are all plotted in arbitrary units, with white corresponding cause of the finite image resolution, the peaks on the profile are not
to the highest relative intensity. (d) A profile across the short axis of of the same intensity.
the 2D image. The image intensity between the plates is homogeneous.

Published by NRC Research Press


Zhang et al. 749

Fig. 4. (a) Current distribution for a plate with many small slits. (b)
Corresponding magnetic resonance image. The dashed line illus-
trates the slice position of figure (d). The resolution of (b) in direc-
tion x was doubled, compared with Fig. 3b. (c) The B1 magnetic
field distribution between the electrodes (figure from Zhang et al.,21
reproduced with permission of Journal of Magnetic Resonance, ©
2008 Elsevier). The grayscale levels in (a), (b), and (c) for current,
magnetic resonance image intensity, and B1 field strength are all
plotted in arbitrary units, with white corresponding to the highest
relative intensity. (d) The averaged profile across the short axis of
image (b), processed in the same way as in Fig. 3d.

films were obtained with and without the presence of con-


ductive graphite plates.

High-resolution 1D depth profile of Nafion 117


A high-resolution depth profile of a fully hydrated Nafion
117 film, approximately 200 µm thick, was obtained with the
parallel-plate resonator. The DHK SE SPI technique devel-
oped by Ouriadov et al.4 was employed, with the result
shown in Fig. 5a. The image was acquired in ∼90 s with an
SNR better than 40. The blurred edges of the profile indicate
a degradation of the true image resolution compared with the
nominal resolution, 4.5 µm. This occurs because of a mis-
match between the encoding gradient direction and the axis
normal to the sample plane.4

Depth profiles of Nafion 117 with graphite plates inserted


In a functional fuel cell, a thin membrane is sandwiched
between conductive electrodes. Imaging water in this layer in
situ requires the ability to tolerate the presence of conductive
plates on either side of the membrane.
The previous depth-imaging experiments were repeated
with a graphite plate inserted on either side of the sample to
explore the effect of the conductive materials on the probe
system. Two pieces of 0.254 cm thick graphite sheet were
used to sandwich the Nafion 117 layer, and the resultant 1D
depth profile is shown in Fig. 5b. Thicker (0.635 cm) graph-
ite plates were then inserted, yielding the resulting profile
shown in Fig. 5c. The nominal spatial resolution of both pro-
files, with the graphite plates, was approximately 5.5 µm.
The graphite plates degrade the performance of the parallel-
plate resonator, as indicated by the decreased SNR and the
increased blurring observed. Decreased SNR is due to higher
resistive losses as the B1 field induces currents in the conduc-
tive graphite. In addition, the distance between the plates is
increased substantially in the presence of the graphite, which
decreases the filling factor.23,24 The additional graphite plates
will increase the probe resistance without substantially chang-
ing its inductance, therefore decreasing the quality (Q) factor,
according to Q ¼ u0 L=R. If there is electrical contact between
the probe plates and the conductive insert, some current will
flow through the graphite and may contribute to the probe changes minimally, indicating that the B1 strength is little af-
sensitivity. However, because the conductivity of graphite is fected by the presence of the conductors.
approximately 100 times less than that of copper, according
to Ohm's law, the amount of the current in the graphite plates 1D depth imaging and 2D lateral imaging of Nafion in an
will be quite small. operating fuel cell
The corresponding Q value, SNR, and 90° pulse length of This parallel-plate resonator concept was developed specif-
these three cases (no graphite, thin graphite layer, and thick ically for the study of operating proton electrolyte membrane
graphite layer) are reported in Table 1. Notice that while the (PEM) fuel cells.21 The water distribution within the PEM is
Q and SNR decrease as graphite is added, the pulse width a critical parameter in fuel cell operation, and an ongoing

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750 Can. J. Chem. Vol. 89, 2011

Fig. 5. (a) Depth profile of a static, fully hydrated Nafion 117 film. Table 1. Quality (Q) factor, signal-to-noise ratio (SNR), and 90°
The image was derived from the first echo. (b and c) Similar depth pulse length for a Nafion 117 sample in the parallel-plate resonator.
profiles of water content across Nafion 117 film, with 2.54 mm and
90° pulse
6.35 mm graphite plates sandwiching the membrane, respectively.
SNR Q factor length (µs)
The SNR and the resolution were degraded compared with (a).
No graphite 41 115 10.5
Thin graphite (2.54 mm thick) 26 70 12.5
Thick graphite (6.35 mm thick) 15 52 13.5

Nafion 1110) sandwiched between two conductive gas diffu-


sion electrodes, which represent the catalyst-sprayed gas dif-
fusion layers. The MEA is held by two conductive plates,
perforated to allow the ingress of water, hydrogen, and oxy-
gen.25,26 The presence of the metal electrodes has previously
hindered attempts to image operating fuel cells using MRI.27
A homemade operating fuel cell was designed following
the schematic shown in Fig. 6a. The electrodes of the home-
made fuel cell were made of gold-plated printed circuit (PC)
boards, with slots cut in the surface to allow gas flow. The
Nafion layer, sandwiched by two catalyst-sprayed gas diffu-
sion layers, is held between the electrodes. This assembly
was tightened by brass bolts to a desired pressure and sealed
with homemade Teflon O-rings. As shown in Fig. 6a, this
assembly was then connected with capacitors to complete
the RF circuit and achieve probe tuning and matching. The
capacitors block DC currents and thus do not affect the oper-
ation of the fuel cell. A 3 U carbon resistor was directly con-
nected with the electrodes of the cell as the electrical load of
the fuel cell. This resistor was located inside the magnet bore
to reduce the external RF noise introduced to the experiment.
In this design, the parallel plates of the RF resonator also
function as electrodes of the fuel cell. The cell operated for
7 h, at which point several 1D depth profiles of the water
content in Nafion during quasi-steady-state operation and a
2D lateral image of water in Nafion were acquired.
Four 1D 128-pixel profiles are illustrated in Fig. 6b, with
the anode on the left side of the profiles and the cathode on
the right side. During operation, the chemical reaction at the
cathode generates water as a byproduct. Condensed water ad-
jacent to the Nafion layer in the flow channels could intro-
duce undesired signal into the water content profiles.28
However, as illustrated in Fig. 4c, with small slots applied as
flow channels, the B1 field beside the slots is approximately
10 times less than that beside the intact plate. In addition, the
B1 fields inside the gas channels are very small and will not
efficiently excite the water or vapor in the channels.21 As a
result, water content serves as a marker for chemical activity
in the cell. We estimate the edges of the Nafion layer to be at
230 µm and 520 µm. The poor edge definition is due to sam-
ple misalignment with the imaging axis and potentially due
to nonlinearity of the Nafion surface. An apparent peak is ob-
served close to the cathode side, as predicted. The signal then
decreases and levels out near the center of the profile. Near
the anode, the signal intensity decreases once again. Less
water is anticipated near the anode. All the above observa-
tions agree with our common understanding of an operational
fuel cell.25,26 MRI results of this type, however, offer the
challenge is to obtain quantitative water maps within an oper- prospect of quantifiable studies.
ating cell. At the heart of a typical fuel cell is the membrane In the 2D image shown in Fig. 6c, a generally uniform water
electrode assembly (MEA), which is a PEM (in this case, signal intensity was observed. The slightly higher signal inten-

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Zhang et al. 751

Fig. 6. (a) Schematic of a homemade operating fuel cell combined sity to the left and right suggests that water vapor in the hu-
into the RF probe circuit (figure from Zhang et al.,21 reproduced midified reactant gases may have condensed at the flow inlets.
with permission of Journal of Magnetic Resonance, © 2008 Else- The 2D image also confirms the essentially uniform excita-
vier). Outer load (⊗) and tuning capacitors are connected to com- tion of this parallel-plate resonator. No pattern due to the perfo-
plete the DC circuit for fuel cell operation and the high-frequency rated electrodes is observed in the image. The signal in this
AC circuit for RF resonance. The outlets of the reactant gases, H2 case is averaged over the depth of the Nafion. One-dimensional
and air, are marked, while the inlet connections are on the left side depth profiles of course do not reveal information about lat-
but not shown. Grooves, as shown by discrete lines, are machined eral variation in water content.
on two G10 fiberglass substrates, which support the PC boards, to The parallel-plate resonator employed for this experiment
generate paths for gas flow. (b) Four 1D depth profiles of water, ac- used 30 slits, each 0.5 mm wide, to allow gas to flow to the
quired during quasi-steady-state operation of the cell. Each profile is membrane. The size of the slots was empirically determined
from the first echo. Experiments (●), (○), (▼), and (▽) corre- through balancing the B1 uniformity in the lateral plane with
spond to experimental times of 3.4, 3.6, 3.8, and 4.0 h, respectively. the efficiency of feeding the reactant gases. As discussed
(c) Lateral 2D image, acquired with 2D SE SPI, of the operating above, because of the large number of small slits the spatial
fuel cell. The dashed lines indicate the position of the flow inlets/ variation of signal intensity is minimal. In the 1D images,
outlets on the left and right sides of the image. The flow inlets are averaging over the lateral extent of the Nafion yields a
illustrated in (a). smooth image with no manifestation of the slots employed
for mass transport through the plates.

Conclusion
A novel parallel-plate RF resonator was investigated
through experiment and simulation. The RF probe has an in-
herently high filling factor, which permits high-SNR imag-
ing.
The parallel-plate resonator allows high-resolution depth
imaging of thin films and can be employed in a fully func-
tioning fuel cell. The presence of auxiliary conductive mate-
rials does not significantly degrade the performance of the
probe.

Experimental
Design of the parallel-plate resonators and homemade
operating fuel cell
Figure 1a shows the geometry of a typical parallel-plate
resonator. Two pieces of 2.54 cm wide, 7.62 cm long copper
tape were affixed to two pieces of G10 fiberglass substrate,
5.08 cm wide and 7.62 cm long, purchased from McMaster
(Cleveland, Ohio). The phantom employed in the B1 field
visualization measurements, a 381 µm thick silicone rubber
sheet purchased from AAA-ACME (Tempe, Arizona), was
cut to the same size as the copper tape.
The top plates with slots employed in the imaging meas-
urements were made of PC board and were of the same size
as the bottom copper tape. The slots were all cut 2.54 cm
long, with a width of 2.38 mm for the larger ones and
0.79 mm for the smaller ones.
Each plate of the homemade operating fuel cell, 5 cm long
and 4 cm wide, consists of a gold-plated PC board and the
substrate to which it is affixed. Thirty slots, 3 cm long,
0.5 mm wide, and 0.5 mm deep, were cut and homogene-
ously distributed in a 3 cm × 3 cm area on the PC board,
1.59 mm in thickness. The substrate, 9.53 mm thick G10 fi-
berglass, was fabricated following the discrete line shown in
Fig. 6a to construct a path for flow. Each gas-diffusion elec-
trode was cut into a 3.2 cm × 3.2 cm square, and the Nafion
was cut into a 3.5 cm × 3.5 cm square.

Nafion and its preparation


The sample films, Nafion 117, 178 µm thick, and Nafion

Published by NRC Research Press


752 Can. J. Chem. Vol. 89, 2011

1110, 250 µm thick, were purchased from Ion Power (New applied prior to Fourier transform for all the measurements.
Castle, Delaware). The Nafion films were cut to desired sizes The SNR of the two experiments was, respectively, 40 and
(2.03 cm × 6.10 cm for Nafion 117 and 2.54 cm × 2.54 cm 15.
for Nafion 1110) and pretreated by heating in ~3–5 wt %
H2O2 solution at 80 °C for 1 h. The sample was then rinsed Acknowledgements
in deionized water at 80 °C for 1 h and then heated in B.J.B. thanks NSERC of Canada for operating and equip-
0.5 mol/L H2SO4 at 80 °C for 1 h. The sample was finally ment grants. B.J.B. also thanks the Canada Chairs program
cleaned by prolonged heating in deionized water at 80 °C for a Research Chair in MRI of Materials (2002–2016). The
for 1 h to remove any possible chemical residues. The basic MRI Centre was supported through an NSERC Major Re-
procedure was based on the work of Jalani et al.29 and Moore sources Support award. We thank M. Olive and B. Titus for
and Martin.30 fabricating the plates and the frame of the probe.
MRI details References
The 2D DHK SPRITE and DHK SE SPI experiments were
(1) Callaghan, P. T. Principles of Nuclear Magnetic Resonance
implemented on a Nalorac (Martinex, California) 2.4 T
Microscopy; Clarendon Press: Oxford, 1991.
32 cm i.d. horizontal-bore superconducting magnet. A water-
(2) Blumich, B. NMR Imaging of Materials; Clarendon Press:
cooled 7.5 cm i.d. gradient set driven by a Techron (Elkhart, Oxford, 2000.
Indiana) 8710 amplifier, which provided maximum gradients (3) McDonald, P. J. Prog. Nucl. Magn. Reson. Spectrosc. 1997 30
of 100 Gauss/cm, was employed for all experiments. The (1–2), 69. doi:10.1016/S0079-6565(96)01035-7.
imaging console was a Tecmag (Houston, Texas) Apollo in (4) Ouriadov, A. V.; MacGregor, R. P.; Balcom, B. J. J. Magn.
all cases. Reson. 2004 169 (1), 174. doi:10.1016/j.jmr.2004.04.015.
The homemade RF probes, driven by a 2 kW AMT (Brea, (5) Reible, S. A.; Wilker, C. W. IEEE Trans. Magn. 1991 27 (2),
California) 3445 RF amplifier, were respectively custom-built 2813. doi:10.1109/20.133794.
single-channel parallel plate probes and an operating fuel cell (6) Talanov, V. V.; Mercaldo, L. V.; Anlage, S. M.; Claassen, J. H.
style resonator. They were tuned to 100 MHz with three tun- Rev. Sci. Instrum. 2000 71 (5), 2136. doi:10.1063/1.1150596.
ing capacitors, Cf, Cc, and Cb, in a standard series-parallel (7) Zhang, J.; MacGregor, R. P.; Balcom, B. J. Chem. Phys. Lett.
tank circuit. The fixed capacitor, Cm, illustrated in Fig. 1a 2008 461 (1–3), 106. doi:10.1016/j.cplett.2008.06.090.
and Fig. 6a, was 1000 pF. (8) Zhang, J.; Balcom, B. J. Magn. Reson. Imaging 2010 28 (6),
In the 2D DHK SPRITE measurement, the encoding time, 826. doi:10.1016/j.mri.2010.03.033.
tp, was 150 µs. The flip angle was 4.3° with a pulse duration (9) Meadowcroft, M. D.; Zhang, S.; Liu, W.; Park, B. S.; Connor,
of 0.5 µs. The dwell time was 4 µs with a repetition time of J. R.; Collins, C. M.; Smith, M. B.; Yang, Q. X. Magn. Reson.
2 ms. The 90° pulse length was 10.5 µs in all three cases. Med. 2007 57 (5), 835. doi:10.1002/mrm.21213.
(10) Collin, R. E. Field Theory of Guided Waves; IEEE Press: New
Nafion 117, a form of perfluorosulfonic acid, is a hydro-
York, 1991; Chapter 3.
philic ionic polymer with measured 1H relaxation times that (11) Balcom, B. J.; MacGregor, R. P.; Beyea, S. D.; Green, D. P.;
are reasonably long (T1, 100 ms; T2, 13 ms31,32) and ideally Armstrong, R. L.; Bremner, T. W. J. Magn. Reson. 1996 123
suited to these measurements. (1), 131. doi:10.1006/jmra.1996.0225.
In DHK SE SPI and 2D SE SPI measurements, the repeti- (12) Gravina, S.; Cory, D. G. J. Magn. Reson. B. 1994 104 (1), 53.
tion time was maintained at 500 ms, a period approximately doi:10.1006/jmrb.1994.1052.
equal to 5T1. The encoding time, tp, was 2.2 ms and the echo (13) Zhang, Z.; Marble, A. E.; MacMillan, B.; Promislow, K.;
time was 5.5 ms. Dwell times were set to 200 µs to narrow Martin, J.; Wang, H.; Balcom, B. J. J. Magn. Reson. 2008 194
the filter width in all measurements. (2), 245. doi:10.1016/j.jmr.2008.07.011.
In high-resolution depth imaging measurements, the Na- (14) Mastikhin, I. V.; Balcom, B. J.; Prado, P. J.; Kennedy, C. B.
fion film cannot be exactly positioned at the origin of the J. Magn. Reson. 1999 136 (2), 159. doi:10.1006/jmre.1998.
gradient Gy. Experimental profiles therefore wrap around the 1612.
field of view (FOV) and are translated into the center of the (15) Halse, M.; Rioux, J.; Romanzetti, S.; Kaffanke, J.; MacMillan,
FOV for display and subsequent data processing. B.; Mastikhin, I.; Shah, N. J.; Aubanel, E.; Balcom, B. J.
Matrices of 64 points by 64 points were collected for most J. Magn. Reson. 2004 169 (1), 102. doi:10.1016/j.jmr.2004.04.
of the 2D lateral images, with one exception, a 64 by 128 008.
k-space matrix employed in measurement of the B1 distribu- (16) Zhang, Z.; Ouriadov, A. V.; Willson, C.; Balcom, B. J.
J. Magn. Reson. 2005 176 (2), 215. doi:10.1016/j.jmr.2005.06.
tion with the presence of small slits in the top plate. For 1D
009.
depth images, 64 k-space points were collected. In the 2D
(17) Teranishi, K.; Tsushima, S.; Hirai, S. Therm. Sci. Eng. 2002
DHK SPRITE measurements, 4 signal averages were accu-
10, 59.
mulated for each profile, with an acquisition time of 30 min. (18) Shim, J.; Tsushima, S.; Hirai, S. ECS Trans. 2009 25, 523.
In the DHK SE SPI measurements, the acquisition time was doi:10.1149/1.3210602.
90 s with 4 signal averages. Four averages, with a 2 h acquis- (19) Feindel, K. W.; LaRocque, L. P.-A.; Starke, D.; Bergens, S. H.;
ition time, were acquired for 2D SE SPI measurement. Wasylishen, R. E. J. Am. Chem. Soc. 2004 126 (37), 11436.
In the operational fuel cell measurement, the nominal reso- doi:10.1021/ja0461116.
lution for the 1D depth image (Fig. 6b) is approximately (20) Wang, M.; Feindel, K. W.; Bergens, S. H.; Wasylishen, R. E.
6 µm with an 800 µm FOV. The 2D lateral image (Fig. 6c) J. Power Sources 2010 195 (21), 7316. doi:10.1016/j.
had a resolution of approximately 1.2 mm × 1.2 mm, with a jpowsour.2010.05.029.
FOV of 7.5 cm × 7.5 cm. No filtering or zero-filling was (21) Zhang, Z.; Martin, J.; Wu, J.; Wang, H.; Promislow, K.;

Published by NRC Research Press


Zhang et al. 753

Balcom, B. J. J. Magn. Reson. 2008 193 (2), 259. doi:10.1016/ Handbook of PEM Fuel Cell Durability; Wong, H., Yuan, Y.,
j.jmr.2008.05.005. and Li, H., Eds.; Taylor and Francis: Oxford, UK, 2011.
(22) Lupu, M.; Briguet, A.; Mispelter, J. NMR Probeheads: For (28) Dunbar, Z. W.; Masel, R. I. J. Power Sources 2008 182 (1), 76.
Biophysical and Biomedical Experiments; Imperial College doi:10.1016/j.jpowsour.2008.03.057.
Press: London, 2006; Chapter 7. (29) Jalani, N. H.; Choi, P.; Datta, R. J. Membr. Sci. 2005 254 (1–
(23) Hoult, D. I.; Richards, R. E. J. Magn. Reson. 1976 24, 71. 2), 31. doi:10.1016/j.memsci.2004.12.020.
(24) Hoult, D. I. Prog. Nucl. Magn. Reson. Spectrosc. 1978 12 (1), (30) Moore, R. B., III; Martin, C. R. Macromolecules 1988 21 (5),
41. doi:10.1016/0079-6565(78)80002-8. 1334. doi:10.1021/ma00183a025.
(25) Wielstich, W.; Gasteiger, H. A.; Lamm, A. Handbook of Fuel (31) MacMillan, B.; Sharp, A. R.; Armstrong, R. L. Polymer
Cells: Fundamentals, Technology and Applications; John (Guildf.) 1999 40 (10), 2481. doi:10.1016/S0032-3861(98)
Wiley & Sons: New York, 2003. 00483-2.
(26) Hoogers, G. Fuel Cell Technology Handbook; CRC Press: (32) MacMillan, B.; Sharp, A. R.; Armstrong, R. L. Polymer
New York, 2000. (Guildf.) 1999 40 (10), 2471. doi:10.1016/S0032-3861(98)
(27) Zhang, Z.; Balcom, B. J. Magnetic Resonance Imaging. In 00484-4.

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