Accepted Manuscript

®
Non-invasive macroscopic and molecular quantification of water in Nafion and
SPEEK Proton Exchange Membranes using terahertz spectroscopy

Nirmala Devi, Shaumik Ray, Avanish Shukla, Santoshkumar D. Bhat, Bala Pesala

PII: S0376-7388(19)30804-X
DOI: https://doi.org/10.1016/j.memsci.2019.117183
Article Number: 117183
Reference: MEMSCI 117183

To appear in: Journal of Membrane Science

Received Date: 20 March 2019

Revised Date: 3 June 2019
Accepted Date: 10 June 2019

Please cite this article as: N. Devi, S. Ray, A. Shukla, S.D. Bhat, B. Pesala, Non-invasive macroscopic
®
and molecular quantification of water in Nafion and SPEEK Proton Exchange Membranes
using terahertz spectroscopy, Journal of Membrane Science (2019), doi: https://doi.org/10.1016/
j.memsci.2019.117183.

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1 Non-Invasive Macroscopic and Molecular Quantification of Water in Nafion®

2 and SPEEK Proton Exchange Membranes using Terahertz Spectroscopy
3 Nirmala Devi a,c 1, Shaumik Raya,c, Avanish Shuklab,c, Santoshkumar D Bhatb,c , Bala Pesalaa,c
a
4 CSIR-Central Electronics Engineering Research Institute, CSIR Madras Complex, Chennai, India
b
5 CSIR-Central Electro Chemical Research Institute, CSIR Madras Complex, Chennai, India
c
6 Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India

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7
8 Abstract
9 Hydration of Proton Exchange Membranes (PEM) is vital in PEM fuel cells as it is critical in determining the overall

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10 proton conductivity. Traditional gravimetric analysis to quantify PEM’s hydration is cumbersome, demands contact
11 and importantly cannot differentiate the nature of water - bulk, bound or free water. As terahertz spectroscopy
12 probes bulk and free water relaxations’ contributions, it is an attractive non-invasive technique for studying
13 membrane hydration dynamics - water uptake and retention. Here, THz spectroscopy measurements for hydrated

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14 Nafion® and sulphonated Polyether Ether Ketone (sPEEK) membranes in ambient atmosphere have been carried out
15 for 100 minutes. Variation in THz absorption by the hydrated membranes with time is used for non-invasive
16 estimation of percentage water content demonstrating good agreement with gravimetric measurements. In addition,
17 proportion of bulk, bound and free water with time has been estimated by fitting the complex permittivity using
double Debye model. Results show that % water content in hydrated sPEEK at 0th minute is 2.36 times than

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19 hydrated Nafion due to its higher porosity at 0th minute. Further, sPEEK has better water retention capability,
20 especially higher bound water proportion at longer time intervals (85% more at 100th minute) than Nafion due to the
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21 presence of widely distributed small pores and comparatively stronger hydrogen bonding between the sulphonic acid
22 and water. Thus, THz spectroscopy can be employed as an effective non-invasive tool for macroscopic and
23 molecular quantification of water in hydrated PEMs.
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24 KEYWORDS: Proton Exchange Membranes, Membrane hydration, Terahertz spectroscopy, Hydration dynamics,
25 Water uptake, Water retention

26 1. Introduction
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27 Proton Exchange Membrane Fuel Cells (PEMFC), known for their unique advantages such as rapid startup,
28 compactness, durability, low temperature operation etc., have a wide range of applications such as energy source for
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29 electric vehicles and in the power sector to meet the base load requirements [1,2]. The vital part of PEMFC is a
30 polymer electrolyte membrane which selectively conducts protons from anode to cathode thereby determining the
31 overall fuel cell efficiency. A typical PEM consists of a hydrophobic polymer backbone for mechanical stability and
32 a hydrophilic tail for proton conduction. The proton conduction happens when the hydrophilic groups are
33 sufficiently connected during hydration. In addition, the mechanism of proton conduction depends on the nature of
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34 water present, either bulk or bound water[3,4]. Bulk water molecules exhibit co-operative reorganization of
35 hydrogen bonds and hence can be attributed to the water molecules that are in the center of the pores or which are
36 having least interaction with the polymer backbone. The water molecules that are bound (via hydrogen bond) to or
37 present relatively close to the hydrophilic groups are respectively known as strongly bound and loosely bound water
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38 [5]. Membrane hydration in PEM has been studied extensively over the years based on water sorption measurements
39 [6,7], small angle X-ray scattering spectroscopy [8], Atomic Force Microscopy (AFM) [9], Nuclear Magnetic
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40 Resonance (NMR) spectroscopy [10], dielectric relaxation spectroscopy [5,11], Fourier Transform InfraRed
41 Spectroscopy (FTIR) in the Mid-infrared (MIR) [12,13] frequency range and molecular dynamics simulations
42 [13,14]. The above studies mainly explore the structure of membrane under hydration [6,8], understanding of the
43 water diffusion [7,10], variation of proton conductivity with hydration [9], dielectric response at varying degrees of
44 hydration [5,11], types of water in Nafion [5], interaction of water in the membrane [13,14] and also performance
45 analysis when an existing membrane is modified [12,14]. Typically, most of the existing techniques are either
46 contact based or necessitate detailed sample preparation or require specialized measurement environment, which in
47 turn make them difficult for carrying out water uptake and retention studies as the membranes continuously lose

1
Corresponding Author.
Email address : nirmala123.ece@gmail.com
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1 water in an ambient environment. Compared to these techniques, Terahertz (THz) spectroscopy is a rapid, non-
2 invasive technique, requiring no sample preparation and do not mandate sample proximity.
3 Although extensive PEM studies have been carried out in the MIR region, only a few have reported the far-infrared
4 (FIR)/THz studies of PEM [15–17]. THz spectroscopy can be used to probe the low frequency crystalline modes and
5 intermolecular vibrations including hydrogen bond vibrations [18] . Importantly, this frequency region has
6 contribution from the bulk water relaxation peak at around 20 GHz in addition to free/fast water relaxation peak,
7 thus making THz waves extremely sensitive to water [19]. Consequently, water kinetics in a wide range of water

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8 interacting systems such as proteins [20], lipid membranes [21,22] and water solutions [23,24] have been studied
9 using THz spectroscopy. The hydration dynamics, i.e. water uptake and water retention, as well as the nature of
10 water in hydrated membrane depends on the membrane microstructure and the strength of hydrogen bonding
11 between hydrophilic groups and water molecules. Hence, its comparative understanding across various membranes

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12 will eventually lead to engineering of novel, composite and cost-effective membranes. Recently, preliminary studies
13 to understand the hydration dynamics in Nafion for a shorter time duration have been reported by the authors [25].
14 However, a detailed time dependent study for macroscopic and molecular quantification of water in hydrated Nafion
15 and comparison with other fuel cell membranes is yet to be done. Of the several types of PEMs available, the widely

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16 used Nafion® and sPEEK membranes are investigated in the current study. Although, the membranes being studied
17 have different base properties, their comparative understanding will potentially aid in engineering novel membranes.
18 To the best of our knowledge, non-invasive water uptake and retention quantification and understanding the time
19 dependent change in the nature of water viz. bulk, bound, free water in the hydrated sPEEK and Nafion membranes
20 using THz spectroscopy hasn’t been explored.

21 2. Sample preparation and experimental procedure

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22 2.1. Chemicals and materials
23 Granules of sulfonated PolyEther Ether Ketone (sPEEK) polymer (fumion® E-600, IEC ~ 1.65 meq g-1, Mw = 50,000
24 g mol-1, Mn = 14,000) are purchased from Fumatech BWT GmbH, Germany. Commercial Nafion® 117 membrane is
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25 purchased from DuPont Inc. USA. N, N-Dimethyl Acetamide (DMAc) is purchased from Sisco Research
26 Laboratories Pvt. Ltd. India. Sulfuric acid (H2SO4) is from Thermo Fisher Scientific India Pvt. Ltd. India. Deionized
27 water (DI, MQ Res: 18.2 MΩcm) from Milli-Q is used for membrane preparation.
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28 2.2. Polymer membrane preparation

29 SPEEK membrane is prepared using solution casting technique. 1 gm of sPEEK granules are dissolved in 20 ml of
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30 N, N-Dimethyl Acetamide (DMAc) to get 5% wt. sPEEK solution. The homogeneous sPEEK solution is obtained
31 after stirring for 12 h. Further, the solution is poured on a flat glass plate of diameter 10 cm and is allowed to dry at
32 80 oC for 18 h in vacuum oven. The sPEEK membrane is further treated with 0.5M H2SO4 solution for 4 h to
33 activate the ion conducting channels. The membrane is washed thoroughly using DI water to remove the residual
acid on the surface of membrane [26]. The thickness of the Nafion and sPEEK membrane is approximately 160 µm
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35 and 180 µm respectively.
36 2.3. THz–TDS experimental setup
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37 The Nafion and sPEEK membranes are soaked in DI water obtained from Direct-Q (Res: ~11.5 MΩcm) for 24
38 hours. The membranes after being soaked are taken from the water bath and the surface water is removed by gently
39 pat drying the membrane using lint free cotton wipes. This is to ensure that only the water that is being held within
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40 the polymer framework is probed in the measurements. The membranes are henceforth referred to as hydrated
41 membranes. THz Time Domain Spectroscopy system (THz-TDS) also known as THz pulsed system, (TERA K15
42 manufactured by Menlo Systems GmbH) is used for the measurements. The schematic of the setup is given in Fig.
43 1a. Here, a femtosecond laser excites the InGaAs semiconductor in emitter photoconductive antenna (PCA) thus
44 generating a picosecond pulse whose bandwidth spans a frequency range of 0.1 THz - 2.5 THz. A TPX™
45 (polymethylpentene) lens is used to obtain a collimated beam. This is to ensure that the plane wave approximation
46 employed for extracting the material parameters holds good in the measurements. The collimated beam passes
47 through the dry/hydrated membrane and is subsequently focused onto a THz receiver using another TPX lens. A
48 portion of the femtosecond pulse excites the receiver PCA and measures the THz electric field at the instance of
49 sampling. An Optical Delay Unit (ODU) is employed which time shifts the femtosecond laser for sampling the
50 successive time instances of the THz pulse thereby reconstructing the entire THz pulse waveform. The figure also
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1 shows reference THz picosecond pulse (Fig. 1b) i.e. without sample and the corresponding magnitude of its Fourier
2 transform (Fig. 1c).

Optical a
Delay
unit
Femtosecond
Laser

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Membrane –
Hydrated / Dry

Tx Rx

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Fig. 1. a) Schematic of the THz pulsed system employed in this study. ‘Tx’ denotes the THz transmitter/emitter PCA and ‘Rx’ denotes the THz
receiver PCA. b) THz picosecond reference pulse through the ambient atmosphere and its c) Respective magnitude of the Fourier transform.

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3 The measurement time window is about 34 ps and lock-in amplifier integration time constant is set as 30 ms. This
4 will ensure that each scan completes in one minute. The terahertz pulse through the hydrated membrane is recorded
5 for every minute up to 100 minutes. Following that, the membrane is dried in oven for 24 hours at 80 °C to remove
6 the water. Then, the THz pulse through the dry membrane is measured for quantifying water content in hydrated

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7 membranes. The material parameters are extracted through material parameter optimization algorithm described in
8 Appendix B and is used for further analysis. Material parameters in the frequency range of 0.1 - 1.6 THz are
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9 considered for all the analyses to ensure a minimum SNR of 24 dB for both dry and hydrated membranes’
10 measurement. All the measurements were carried out at room temperature (~ 20 °C) and relative humidity of ~45%
11 is maintained throughout the measurements. Thus, the measurements probe the natural water desorption of the
12 hydrated membrane while it is placed in the ambient atmosphere. As the measurements are highly dependent on the
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13 ambient relative humidity, all the measurements are repeated multiple (3-4) times and the corresponding error bar is
14 provided in the results as shaded region in the plots.

15 3. Results and discussions

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16 3.1. Terahertz measurements of the hydrated Nafion and sPEEK membranes

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17 THz picosecond pulse through the hydrated membrane is recorded every minute and is shown in Fig. 2a and b for
18 Nafion and sPEEK membranes respectively. Due to the absence of water, the dry membranes are expected to show
19 less absorption and thus the transmitted THz pulse amplitude through the dry membranes are higher than the
20 respective hydrated membranes. The figure clearly shows the overall expected trend that THz pulse amplitude
21 through the hydrated membrane is lower during the initial measurements where water content is high and the
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22 amplitude is seen to gradually increase as time progresses due to decrease in water content. Interestingly, the rate of
23 drying in the Nafion and sPEEK membranes is distinctly different.
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Fig. 2. THz–TDS measurements of the dry (magenta) and hydrated (colored) a) Nafion and b) sPEEK up to 100 minutes in the ambient
atmosphere showing a distinct difference in the rate of water retention c) THz pulse amplitude of the hydrated Nafion (blue) and sPEEK (red)
membrane at varying time intervals normalised to its respective dry membrane. The error bar for multiple measurements is shown (as shade of
respective line color) around the mean data (shown as line). The initial rate of desorption is shown as dotted line and is less for sPEEK
demonstrating better water retention in sPEEK

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1 Fig. 2c shows the measured THz pulse amplitude of the hydrated membrane normalised to respective dry
2 membrane’s THz amplitude which shows that Nafion and sPEEK membranes exhibit different rates of water
3 retention. Although the curves for Nafion and sPEEK appear similar, quantifying the initial slope shows distinct
4 difference in the rate of water desorption. The initial slope has been calculated by linear fitting the data points

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5 corresponding to initial 20 minutes. This can be attributed to the more tightly bound water molecules present within
6 the ionic channels of the sPEEK membranes than the Nafion membranes as the size of the pores in hydrated sPEEK
7 is significantly smaller than the pores in hydrated Nafion [8]. Thus, the time-domain THz spectroscopy results
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8 clearly confirm the expected trend.
9 3.2. Estimation of water content from THz measurements
10 To estimate the water content in the hydrated membrane, an equivalent model is considered as depicted in Fig. 3a.
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11 Here, the hydrated membrane with embedded water is modelled as a combination of dry membrane and an effective
12 layer of water. The Fast Fourier Transform (FFT) of the THz time-domain pulse has been calculated (E(ω)) and is
13 squared to obtain the frequency dependent intensity (I(ω)). From Beer-Lambert’s equation, the intensity of THz
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14 radiation transmitted through the hydrated membrane (Ihyd) is given by

( ) _ ( )
15 ( )= ( ) ( )
(1)
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16 is sample absorption coefficient in cm-1, is the thickness of the dry membrane, is the absorption coefficient
17 of water (Appendix D) and _ is equivalent thickness of water present in the hydrated membrane. Since the
18 absorption coefficient in the Beer-Lambert’s law is a frequency dependent quantity, _ is calculated as a function
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19 of frequency and is averaged for the final estimate. The material parameter extraction procedure and the
20 characterization of the dry membranes are given in Appendix B and Appendix C respectively. From the equation
21 above, _ can be calculated from below equation.

# ( )
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22 _ ( ) = ( )
ln "# $ ' − ( ) ) (2)
%& ( )
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+$ ( )
23 _ ( )= 2 ln " ' − ( ) ) (3)
( ) +%& ( )

24 The thickness of the effective water layer is calculated at each frequency and is averaged over frequencies from 0.2-
25 1.4 THz to obtain a good estimate. Once _ of water in the hydrated membrane is known, the volume of the
26 water in the irradiated area of the THz beam can be calculated. As the THz beam spot size is the same for dry and
27 hydrated membrane, the water content (WC) can be calculated from
_ ×0
28 % WC = × 100 (4)
×01

29 4 and 45 are the density of water and dry membrane respectively. The density of dry membranes has been obtained
30 by measuring the weight of a known volume of the membrane. The density of Nafion and sPEEK has been
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1 calculated as 1.94 g/cm3 and 1.23 g/cm3 respectively. The calculated _ for Nafion and sPEEK membranes and
2 the corresponding water content estimated using THz measurements is given in Fig. 3b-d respectively.

ldry a
leff_w
Dry membrane
Hydrated

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+
membrane
Effective water layer

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Fig. 3. a) Schematic of the model used to estimate the water content in the hydrated membranes b) The variation of effective length of water in
hydrated Nafion (blue) and sPEEK (red) membranes. The initial slope of desorption is shown as a dotted line and is less for sPEEK showing
better water retention in sPEEK. Comparison of the water content in c) Nafion and d) sPEEK membranes estimated using THz measurements
with that of gravimetric measurements.
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3 Fig. 3b shows that in the 0th minute, the sPEEK membrane with a thickness of around 180 µm has an effective water
4 length of 74.9 ± 1.2 µm whereas the Nafion membrane with a thickness of around 160 µm has 48.6 ± 1.4 µm. This
5 indicates better water absorption/uptake property of sPEEK membranes. At the end of 100 minutes, the effective
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6 lengths of water in hydrated sPEEK and Nafion membranes are 41.7 ± 1.2 µm and 18.3 ± 0.87 µm respectively
7 indicating better water retention property of sPEEK membranes. The initial slope has been calculated (using the
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8 method mentioned in section 3.1) to quantify the change in the effective thickness of water with time and is about
9 0.8 µm/min and 1.2 µm/min for sPEEK and Nafion respectively. This shows the better water retention capacity of
10 sPEEK membrane. Fig. 3c and d compares the % water content as estimated from THz measurements with the
11 corresponding gravimetric studies (Appendix A details the gravimetric studies) showing good match between the
12 non-invasive THz studies and traditional contact based gravimetric technique. It is observed that at 0th minute water
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13 uptake of hydrated sPEEK membrane is 2.36 times that of hydrated Nafion. The slight difference in water content
14 calculated using THz and gravimetric measurements at longer time intervals (after 40 min) could possibly be due to
15 ignoring multiple reflections while calculating the effective layer thickness and certain minor variations in the
16 ambient conditions. Also, the absorption for the bulk water has been considered for the calculation of effective water
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17 length for all time intervals. However, the bulk and bound water exhibit different absorption which will have a
18 certain effect on the water content estimation especially at longer time intervals. In addition, certain difference is
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19 observed between the THz and gravimetric measurements at the initial time interval especially at 0th minute. This
20 percentage incongruity is about 8.5% and 9.8% for sPEEK and Nafion respectively. As expected, since constant
21 thickness is assumed in calculations and also the swelling is more in Nafion compared to sPEEK, Nafion shows
22 higher percentage inconsistency than sPEEK. In addition, the manual removal of the surface water from the soaked
23 membranes could possibly introduce certain errors, especially at the initial stages of the measurements. Further,
24 equation 1 indirectly assumes the membrane thickness is constant. However, this may introduce an error of < 5 %
25 (on average over the entire measurement duration) as the polymer membrane, especially Nafion swells more than
26 sPEEK when hydrated. However, it is to be noted that, the overall trend shows good reliability of the THz
27 measurements and its agreement with the traditional gravimetric techniques.
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1 3.3. Molecular quantification of water in hydrated membranes

2 Although the water content estimation is a macroscopic quantification of the hydrated membranes, the proton
3 conduction mechanism also strongly depends on the nature of the water present. For example, the fastest Grötthuss
4 mechanism predominantly occurs in bulk-like water and contributes to maximum proton conductivity at higher
5 hydration levels and the surface/bound water diffusion is the slowest which is dominant at lower hydrations [3].
6 Typically, three types of water: bulk, free (also known as fast water) and bound water (also known as
7 slow/irrotational water) are studied in water interacting model systems [21]. In PEMs, the irrotational water can be
8 attributed to the water molecules with slower relaxation dynamics such as strongly bound and loosely bound water.

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9 The bulk water molecules can be attributed to the water molecules that are in the center of the pores or which are
10 having least interaction with the polymer backbone. The free water molecules are the ones which have few or no
11 hydrogen bonds [19]. Thus, it is highly desirable to understand the nature of water present in the hydrated
12 membranes at different time intervals which will help in better understanding of the proton conduction mechanisms

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13 under different hydration levels. To clearly delineate the proportion of bulk, free and bound water during the water
14 retention studies, the complex permittivity is extracted from the time domain THz pulse for all the time intervals for
15 hydrated Nafion and sPEEK membranes using the procedure mentioned in Appendix B. In each set of

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16 measurements, a reference THz pulse i.e without the sample is measured before and after the measurement. Ideally,
17 both the references should be same. However, in some cases, a small time shift is observed between the references.
18 This could be due to slight changes in the ambient conditions. Hence, for such cases, a linear time shift is assumed
19 and the intermediate references are obtained by interpolating the measured reference THz pulses (before and after
20 the measurement duration) for calculating the material parameters of the hydrated membranes.
21 3.3.1. Calculation of double Debye parameters

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22 Most of the water-based model systems follow double Debye model in the THz frequency range which provides
23 information on the bulk and free water [17,21–23]. Here, the bound water contributions are not included because the
24 respective relaxations occur at low frequencies (in MHz frequency range) which is outside the measurement range
25 of THz instruments. However, assuming that the system has only bulk, bound and free water and by quantifying the
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26 bulk and the free water, the bound water proportion can be obtained [21]. In addition, the bulk water relaxation peak
27 is around 20 GHz [5,21] which is outside the measurement window but still, a significant contribution is observed in
28 the THz range and hence included in the Debye model. Further, the free water relaxations completely prevail in the
29 measurement window. The following double Debye equation is used to quantify the relative contributions of bulk
and free water from the extracted complex permittivity6̂( ).
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30
∆; < ∆;B
31 6̂( ) = 68 + = + (5)
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>(? @< )A = >(? @B )A

32 where 68 - dielectric constant at the high-frequency limit, τ - relaxation time for the cooperative reorganization of
33 hydrogen bonds in bulk-like water, τD - relaxation time for rotational or translational motions of free water
34 molecules and ∆6 and ∆6D quantify the dielectric strength which are proportional to the population of water
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35 molecules exhibiting respective relaxations. The dielectric strengths can in turn be used to obtain the respective
36 water fractions in the hydrated membranes. The fraction of bound water can be obtained by subtracting the
37 contributions from bulk and free water. In addition, as the bulk water relaxation time (τ ) doesn’t change
38 significantly with varying hydration levels [5], it is assumed constant (τ = 8 ps), and the other four parameters
(68 , ∆6 , ∆6D , FD ) are fitted to the double Debye model for each time interval and the same is shown in Fig. 4a-d.
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Fig. 4. Variation of double Debye model parameters - a) 68-High frequency limit of dielectric constant b) ∆6 - dielectric strength of the bulk
water relaxation which is proportional to the population of water molecules exhibiting the relaxation c) ∆6D - dielectric strength of the free

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water relaxation which is proportional to the population of water molecules exhibiting this relaxation d) τD - relaxation time of free water
present in the hydrated membrane.
1 Fig. 4a shows a steady decrease of 68 of sPEEK and Nafion membranes until 40 minutes due to the continuous loss
2 of water from the membrane. The rate of decrease is seen to reduce after 40 min. At the 100th minute, 68 reaches

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3 the values of 3.8 ± 0.12 and 2.35 ± 0.15 respectively, thus tending to reach 68 of the respective dry membranes (~
4 3.5 for sPEEK and ~ 2.3 for Nafion – Appendix C). Since the measurements are carried out approximately at 45%
5 RH, there is still a certain amount of water left in the membrane even at 100th minute (Fig. 3c-d) and hence the
6 corresponding 68 is greater than 68 of the respective dry membranes. Fig. 4b shows that the dielectric strength of the

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7 bulk relaxation is greater in sPEEK membranes and decreases for both the membranes with time indicating the loss
8 of bulk water. However, even at the 100th minute, the values are not approaching zero showing the presence of bulk
9 water in the membranes. Fig. 4c shows that the free water dielectric strength is more for sPEEK than Nafion and
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10 decreases with time for both the membranes. This could possibly be due to the presence of comparatively smaller
11 and discontinuous channels in sPEEK membranes [8] (the pore size is in the order of 1-2 nm in sPEEK and 5-6 nm
12 in Nafion). Fig. 4d shows that the free water relaxation time varies minimally over the entire measurement duration.
13 Interestingly, the free water relaxation time in Nafion membrane is slightly greater than that of the sPEEK
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14 membrane. This could possibly be due to the confinement of the water in comparatively larger pores in Nafion
15 making more hydrogen bonds on average in free water. This results in free water molecules with relatively more
16 hydrogen bonds and hence longer relaxation time compared to the free water molecules with less or no hydrogen
17 bonds [27].
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18 3.3.2. Estimation of bulk, bound and free water

To obtain the relative water fractions at time t from the calculated dielectric strength of bulk and free water (∆6 (G)
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20 and ∆6D(G)) in hydrated membranes, the overall water content (% HI(G)), density of the respective membranes,
21 dielectric strength of bulk and free water for pure water have been used (detailed in Appendix E) [27]. Also, by
22 assuming that the system has only bulk, bound and free water and by quantifying the fraction of bulk and the free
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23 water, the bound water proportion is obtained (Equation E.5 in Appendix E). The obtained water fractions for
24 Nafion and sPEEK membranes is summarized in Fig. 5 which shows the variation of the relative fraction of bulk,
25 bound and free water in the hydrated membranes with time. The 0th and 100th minute bulk, bound and free water
26 proportions for hydrated Nafion and sPEEK membranes are given in the table 1. Error bar for the bound water
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27 proportion is not provided since it is calculated indirectly from the THz measurements and not directly. Thus, its
28 error bar will be in the order of the error bar of bulk or free water.
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29 Table 1. Percentage of bulk, bound and free water proportions in hydrated Nafion and sPEEK membranes at 0th and 100th minutes.

Nafion sPEEK
Nature of Water 0th minute 100th minute 0th minute 100th minute
% proportion % proportion % proportion % proportion
Bulk water 87.8 ± 4.2 74.6 ± 6.2 83.3 ± 9.1 57.6 ± 1.2
Free water 6.0 ± 0.4 7.8 ± 1.4 9.5 ± 0.6 9.8 ± 0.3
Bound water 6.2 17.6 7.2 32.6
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Fig. 5 Relative water fractions for a) Nafion and b) sPEEK membranes showing the relative fraction of bulk, bound and free water in
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hydrated membranes with time when the membrane is placed in ambient atmosphere. Zooming a) and b) showing the relative change in free
water proportion for c) Nafion and d) sPEEK membranes showing the rate of increase in free water proportion is more for Nafion than
sPEEK.
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1 It is observed that in Nafion the decrease in bulk water proportion with time is significantly less compared to sPEEK
2 membrane. Also, at later time intervals, Nafion exhibits more bulk water proportion than sPEEK membranes. To
3 understand this, MIR measurements of the hydrated and dry Nafion and sPEEK membranes have been carried out
4 (detailed in Appendix F). The experimental redshift observed for the –OH bond stretching frequency band in the
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5 hydrated membrane with respect to the respective dry membrane is larger for sPEEK than Nafion. This shows that
6 the water molecules in sPEEK form a stronger hydrogen bond which explains the larger proportion of bound water
7 for sPEEK than Nafion as the time progresses (Fig. 5). Thus, it may be inferred that with time Nafion is losing
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8 bound water also along with the bulk water. In addition, even though the table shows an increase in the percentage
9 of bound water from 6.2% to 17.6%, it is to be noted that these are relative percentages of the total number of water
10 molecules present at that time instant. The presence of higher bulk water proportion in addition to the continuous
11 channels in Nafion could possibly explain the proton conduction through Grötthuss mechanism even at low
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12 hydrations (45 % RH) [3]. Although the overall water content in sPEEK membrane is higher than Nafion, Nafion
13 has highly connected pores which explains the better overall proton conductivity of Nafion compared to sPEEK.
14 Similarly, bound water is becoming more dominant with time in sPEEK which could be due to the presence of a
15 wide distribution of comparatively small pores and the stronger bonding between the water and sulfonic acid in
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16 sPEEK than Nafion. This increased bound water proportion explains the higher water retention observed in hydrated
17 sPEEK membranes (Fig. 3d). Fig. 5c and 5d shows that the free water proportion increases with time for both the
18 membranes. However, this increase is slightly more for Nafion than sPEEK. This could possibly be due to the fact
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19 that at low hydrations, the flexible polymer backbone of Nafion deviates from its reverse micelle structures trapping
20 more water in the hydrophobic regions and thus these water molecules have few or no hydrogen bonds (free water)
21 [28]. Although Nafion shows better proton conduction, sPEEK membranes have better mechanical stability in a fuel
22 cell environment. Thus, in future, engineering of novel membranes with a continuous and connected water channel
23 in sPEEK like structures will be highly desirable for realizing high proton conducting membranes with better
24 mechanical stability.
25 Even though Fig. 5 provides information about the proportion of various types of water present in the hydrated
26 membranes, the accuracy of the results depends on two factors. First, the water proportion depends on the accurate
27 estimation of water content which depends on the absorption spectrum of water. This has majorly bulk water and
28 hence at lower hydration levels where the bound water dominates, this assumption of bulk water absorption will
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1 introduce certain error. However, THz spectroscopy can be used in combination with the MIR spectroscopy to
2 estimate the water fractions more accurately [21]. Secondly, while estimating the density of the hydrated
3 membranes, it is assumed that the volume of the hydrated membrane remains unchanged which may not be true for
4 hydrated Nafion, as it swells by a certain amount. Hence, optical microscopy studies have been carried out to
5 quantify the initial swelling of the hydrated Nafion and is measured to be approximately 10 µm. This swelling
6 resulted in the error of less than 7.7% at 0th minute in the calculation of water fractions which eventually decreases
7 with time as the membrane dries. Even then, the overall trend between the 0th and 100th minute remains same.
8 Nevertheless, from this study, it is clear that THz spectroscopy can be employed as a potential stand-alone non-

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9 invasive technique to understand both the macroscopic and the molecular level dynamics of water in hydrated fuel
10 cell membranes.

11 4. Conclusion

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12 In this paper, a novel method for non-invasive characterization of water dynamics in hydrated Proton Exchange
13 Membranes (PEM) - Nafion® and sPEEK using THz spectroscopy has been demonstrated. Macroscopic
14 quantification i.e water content estimation shows that sPEEK has higher water uptake capability than Nafion.

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15 Molecular quantification through the extraction of frequency dependent complex permittivity and employing double
16 Debye model reveals that sPEEK has more bound water proportion than Nafion especially at longer time intervals
17 due to the presence of widely distributed small pores and stronger hydrogen bonding between the sulphonic acid and
18 water. In future, other models such as Cole-Cole, Cole-Davidson and Havriliak-Negami will be explored.
19 Furthermore, low-frequency (10-100 GHz) dielectric relaxation spectroscopy measurements will be carried out to

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20 complement the THz spectroscopy measurements in order to provide a deeper understanding of the changes in bulk
21 water dynamics during water retention studies as they play a major role in proton conduction.
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22 Appendix A Gravimetric studies on hydrated Nafion and sPEEK membranes
23 Conventionally, gravimetric measurements are used to measure the water content in fuel cell membranes [29].
24 Hence, the gravimetric studies have been carried out for hydrated membranes for comparison and validation of THz
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25 measurements. Gravimetric studies are carried out using the Shimadzu BL2200 H series whose precision is 0.001g.
26 Here, the weight of the hydrated membrane is measured for every minute continuously up to the 100th minute (Wwet)
27 and the dry membrane weight (Wdry) is taken after being dried for 24 hours in oven at 80 °C. The water content
28 (WC) is calculated as per the below equation and is given in Fig. A.1.
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J K JLMN
29 %WC = × 100 (A.1)
JLMN
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30 From the figure, it is seen that the sPEEK membrane shows more absorption as well as retention compared to the
31 Nafion membrane.
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Fig. A.1. Gravimetric studies of the hydrated membranes showing the variation of the water content with time. sPEEK shows higher water
absorption and higher water retention compared to Nafion membrane.

32 Appendix B Extraction of material parameters from THz measurements

33 To estimate the water content (WC) of the membrane using THz measurements, the absorption coefficient has to be
34 extracted from the time domain information. As THz-TDS is a coherent technique, the THz pulse can directly
35 provide the complex material parameters of the sample being probed without resorting to Kramer-Kronig relations.
36 For the material parameter extraction, a model which considers the Fabry-Perot reflections has been employed in the
37 present study [30]. Here, a theoretical transfer function is derived considering the Fabry-Perot reflections [30–32].
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a
Distance = x
Medium n0 b
Tx Rx
1
Distance = l 2
Medium n1 . 3
Tx Rx l .
.

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Distance = x-l
Medium n0

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Fig. B.1. a) Model used for extracting material parameters. ‘Tx’ denotes the THz transmitter/emitter PCA and ‘Rx’ denotes the THz receiver PCA.
b) Multiple reflections in the sample due to Fabry-Perot modes.

1 Fig. B.1a and b shows the simplified schematic assumed for deriving the transfer function. The reference electric
2 field (without sample) received by the detector after travelling a distance of ‘O’ from the emitter is given by

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3 P = P? QR (O) (B.1)

4 where Ei is incident electric field and QR (O) is propagation term and is given as
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? ST

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5 QR (O) = VT (B.2)

6 where WX is the complex refractive index of the ambient medium, YX is the velocity of light in the ambient medium
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7 and is the angular frequency of the electromagnetic radiation. Considering multiple reflections as shown in
8 Fig.B.1b, the electric field through the sample of thickness ‘l’ is the summation of the intensities 1, 2, 3 and so on
9 reaching the detector and is given by
a
PZ[5 = P? QR (O − )Q ( )\X \ X ∑bacX^Q D ( )_D X `
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10 (B.3)
DSd Se Sd
11 where \?a = and _?a = denotes the complex transmission and reflection coefficients respectively for the
Sd >Se Sd >Se
12 electromagnetic radiation travelling from medium i to medium j and W? & Wa are complex refractive indices of the
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13 medium i and j respectively. g is the number of Fabry-Perot modes considered in the calculation and is dependent on
14 the measurement time window. This is calculated from the below inequality:
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iT j1kU
15 g< ( − 1) (B.4)
D S<

16 As the above equation does not involve absorption incurred within the medium, g gives the upper limit on the
17 number of modes contained in the measurement window. The theoretical transfer function is given by
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r r a
q? (S< ST ) s ? DS< S< ST D
18 \lj R
on ( ) = +pk1(
= m
)
= VT
tS< ST
B
∑bacX " VT u v ' (B.5)
+$ ( ) (S< >ST ) S< >ST

y
If m wx ( ) is the measured transfer function, functional minimization is carried out to calculate the complex value
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19
20 of ‘n( )’ which makes the difference between the theoretical and the experimental transfer function a minimal
21 value. The equation for the minimization is given by
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22 on ( )s − _ } qm
z{R[ = |_ } qm y o y
wx ( )s| + | ~}• qmn ( )s − ~}• qm wx ( )s| (B.6)

23 Minimization is carried out using an inbuilt function in MATLAB which is based on Nelder-Mead simplex
24 algorithm. The complex frequency dependent refractive index (n(ω)-iκ(ω)) obtained is used to calculate the complex
25 permittivity and absorption coefficient using the standard expression as given below.
D €( )
26 ( )= (B.7)
i

27 6 • ( ) = W( )D − ‚( )D (B.8)
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1 ε•• ( ) = 2W( )‚( ) (B.9)

2 The thickness has been corrected for measurements considering the total variance as explained by Dorney et. al [32].
3 The material parameters have been extracted over the frequency range of 0.1 - 1.6 THz as this range ensures a
4 minimum SNR of 24 dB in all measurements for both dry and hydrated membranes.
5 Appendix C Material parameters for the dry Nafion and sPEEK membranes
6 To understand the water contribution in hydrated membranes, material properties of dry Nafion and sPEEK
7 membranes are calculated as mentioned in Appendix B. The absorption coefficient and refractive index of dry

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8 Nafion and sPEEK membranes are given in Fig. C.1a-b. Average of material parameters obtained using multiple
9 measurements are plotted along with the respective error bars.

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Fig. C.1. a) Frequency dependent absorption coefficient of the dry Nafion and dry sPEEK membrane over the frequency range of 0.1 – 1.6 THz
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b) Refractive index of the dry Nafion and dry sPEEK membrane over the frequency range of 0.1 – 1.6 THz. The error bar for multiple
measurements is shown (as shade of respective line colour) around the mean data (shown as a line).
10 Fig. C.1a shows a steady increase in the absorption coefficient with frequency for both dry Nafion and sPEEK
11 membranes. From Fig. C.1b, it is seen that the refractive index of Nafion and sPEEK in this frequency range are 1.6
12 and 2 respectively. As there is no significant variation of refractive index for both Nafion and sPEEK in this range, it
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13 can be concluded that the dry membranes exhibit only a minimal dispersion over this frequency range. In addition, it
14 is seen that the sPEEK membrane exhibits low absorption in the range below 0.5 THz compared to Nafion whereas
15 for frequency greater than 0.7 THz, sPEEK is showing higher absorption than Nafion. Material properties of the dry
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16 membranes are crucial for understanding the loss and dispersion characteristics of native membranes.
17 Appendix D Absorption coefficient of water
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18 To calculate the % water content of the hydrated membranes, the absorption coefficient of the DI water ( ) is
19 calculated by placing the DI water in the transmission cell of 50 µm thick which has fused silica window. The empty
20 transmission cell is taken as reference. The model for estimating the material parameters is derived for the
21 transmission cell measurements using the similar method as mentioned in Appendix B. The calculated absorption
22 coefficient of water is given in Fig. D.1.
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Fig. D.1. Absorption coefficient of DI water used in experiments.

23 Appendix E Estimation of water fractions in the hydrated membranes

24 The obtained ∆6 and ∆6D along with the estimated water content is used to calculate the fraction of bulk and free
25 water and in turn the bound water [27] at time t.
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q XX > % „…(j)s
1 4 5 (G) = % †‡(K) <TT
(E.1)
" > '
ˆ ˆ1

% „…(j)
Œ‹
2 Y‰B Š (G) = (E.2)
q XX > % „…(j)s
Œ
0%1 (j)

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…T ∆;< (j)
3 •Ž • (G) =… (E.3)
•B ‘ (j) ∆;<,’“r” >∆;B,’“r”

…T ∆;B (j)
4 (G) = (E.4)
…•B ‘(j) ∆;<,’“r” >∆;B,’“r”

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5 •RŽS (G) = 1 − •Ž • (G)− [Zj (G) (E.5)

4 5 , 4 and 45 are respectively the density of hydrated membrane (at time t), water and dry membrane in g/L. Also,

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6
7 it has been assumed that the density of bulk and bound water are same and hence 4 of 1000 g/L is used for all
8 calculations. The molecular weight of water (• ) is in g/mol. IX is the concentration of water molecules in pure
9 water and is 55 mol/L. I‰B Š (G) is the time dependent concentration of water in the hydrated membranes and is in
mol/L. ∆6 ,•Ž • and ∆6D,•Ž • are the values of the dielectric strength for pure water and has been taken from the

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10
11 reference [27]. The above equations are used at every time instant to calculate the proportion of bulk ( •Ž • ), free
12 ( ) and bound (and loosely bound [5]) ( •RŽS ) water at that time instant. The data is smoothened using robust
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13 locally weighted linear regression method using an inbuilt function in MATLAB for better representation.
14 Appendix F Estimation of the hydrogen bond strength in Nafion and sPEEK membranes
15 Even though Nafion and sPEEK have the same hydrophilic functional group, sulphonic acid (-SO3H), the strength of
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16 the hydrogen bond between the hydroxyl group of the sulphonic acid and the oxygen in the water molecule (O-
17 H….O) may not be same. This is due to the fact that the hydrophilic group is attached to the different type of
18 hydrophobic backbones in both the systems – aliphatic backbone in Nafion and aromatic backbone in sPEEK. The
19 strength of this hydrogen bonding can be quantified by a red shift in the –OH stretching peak with and without the
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20 hydrogen bond i.e. with and without water molecule [33]. The higher the redshift observed, stronger is the hydrogen
21 bond.
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22 FTIR spectroscopy is carried out in the MIR region using Nicolet 6700 FTIR spectrometer from Thermo Fisher
23 Scientific. Attenuated Total Reflectance (ATR) spectroscopy measurements of the dry membranes and the hydrated
24 membranes at 0th minute are carried out. Since the OH stretching vibration is occurring around 3400 cm-1 [13], the
25 measured spectra is normalised around the 3400 cm-1 for better depiction and is shown in fig F.1a and b for Nafion
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26 and sPEEK respectively.

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Fig. F.1. MIR spectra of the dry and hydrated a) Nafion and b) sPEEK membrane normalised to the amplitude of the peak around 3400 cm-1.

27 It is observed from the experiments that the redshift of the -OH bond stretching vibrations in sPEEK is more than
28 Nafion. Hence, it can be inferred that water molecules in sPEEK form a stronger hydrogen bond than in Nafion. In
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1 future, cluster and crystal DFT simulations will be carried out to obtain the precise redshift of the OH stretching
2 frequency.
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Non-Invasive Macroscopic and Molecular Quantification of Water in Nafion®

and SPEEK Proton Exchange Membranes using Terahertz Spectroscopy
Nirmala Devi a,c 1, Shaumik Raya,c, Avanish Shuklab,c, Santoshkumar D Bhatb,c , Bala Pesalaa,c
a
CSIR-Central Electronics Engineering Research Institute, CSIR Madras Complex, Chennai, India
b
CSIR-Central Electro Chemical Research Institute, CSIR Madras Complex, Chennai, India
c
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, India

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Highlights

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• Terahertz spectroscopy of hydrated Nafion and sPEEK fuel cell membranes have been carried out to study
the hydration dynamics
• The macroscopic quantification - water uptake of the hydrated membranes has been estimated

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demonstrating excellent match with gravimetric studies
• The molecular quantification – relative fraction of bulk, bound and free water has been carried out by
fitting the complex permittivity of the hydrated membranes using double Debye model
• SPEEK shows comparatively stronger hydrogen bonding between the sulphonic acid and water hence
higher bound water proportion and better water retention

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1
Corresponding Author.
Email address : nirmala123.ece@gmail.com