Journal of Membrane Science 541 (2017) 281–290

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Journal of Membrane Science

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Continuous dip coating of PVDF hollow fiber membranes with PVA for MARK
humidification
⁎
I. Jessweina, T. Hirthb, T. Schiestelc,
a
Institute for Interfacial Engineering and Plasma Technology IGVP, University of Stuttgart, Germany
b
Karlsruhe Institute of Technology KIT, Germany
c
Fraunhofer Institute for Interfacial Engineering and Biotechnology IGB, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Composite hollow fiber membranes for gas-to-gas humidification were fabricated and their performance was
Hollow fiber membrane tested for use in external humidifiers of polymer electrolyte fuel cells (PEMFC). Therefore porous poly(vinyli-
Dip coating dene fluoride) (PVDF) hollow fibers were manufactured by a wet spinning process, coated with thin layers of
Thin film coating polyvinyl alcohols (PVA) via a continuous dip coating and crosslinked by glutaraldehyde. Coating parameters,
Water vapor transport
such as surface tension and viscosity of the coating solution, were correlated with the layer thicknesses of the
Humidification
coatings. Influences of the layer thickness on crosslinking, water vapor transport and thermal stability of the
membranes were studied.
The layer thickness can be adjusted in the range of 0.3–4.29 μm by controlling the coating parameters. It was
found that thicker coatings have a higher water vapor permeability, which may be caused by a lower degree of
crosslinking.
A layer thickness of 1.75 μm was formed when using, for example, a 5 wt% PVA 67000 g/mol aqueous so-
lution. With this composite membrane, a water vapor permeability of 2890 Barrer and a selectivity over nitrogen
of 289 was achieved at 25 °C. The potential of the designed fabrication process was verified by thermal stability
tests, which almost all membranes withstood.

1. Introduction for optimal efficiency. One approach is the integration of an external

Membranes with good water vapor permeability and high selectivity
towards air are of major interest for humidification or dehumidification
applications. Dehydration of gases such as flue gas [1,2], natural gas
[3–5] or compressed air [5] are promising fields of application. Another
area is in heating, ventilation and air conditioning of buildings where,
besides water vapor transport, a heat transfer is often required [6–10].
Those membrane systems are known as enthalpy exchangers or energy
recovery ventilators.
Furthermore, humidification membranes are used in external hu-
midifiers, a component of polymer electrolyte membrane fuel cells
(PEMFC). Especially in the automotive industry, PEMFCs are a pro-
mising technology to replace the still prevailing combustion engines.
For optimum performance of the PEMFC, hydration of its ionomeric
membrane is essential [11]. On the one hand, not fully hydrated
membranes lead to a loss of proton conductivity which reduces the
performance and durability [12,13]. On the other hand, excess water
also leads to a loss of performance as the diffusion of reactant gases is
impeded [13]. Hence, water management within the PEMFC is essential
membrane humidifier within the PEMFC system. Despite other humi-
dification methods, membranes do not need a liquid water column or a
heating device for humidification. These additional components often
lead to an increasing parasitic energy consumption and are impractical
for mobile applications. In an external membrane humidifier the re-
actant gas of the anode is humidified by transferring the humidity and
heat of the exhaust steam from the cathode [14].
Several polymers have been tested as membrane materials with a
view to their water vapor permeability. Metz et al. has reviewed the
water permeability of various polymer materials and compared the
values with their selectivity against nitrogen [15]. In contrast to gas
separation a tradeoff between permeability and selectivity, which is
known as the Robeson upper bound [16], has not been recognized.
Numerous polymers show a high water to nitrogen selectivity, which
can be explained by a higher solubility and diffusivity for water. Hy-
drophilic polymer materials are primarily suggested for use as mem-
brane materials with a high water vapor transport [17]. As the per-
meation of gases or vapors through dense membranes is based on the
solution diffusion model [18], where the flow of the permeate depends

⁎
Corresponding author.

http://dx.doi.org/10.1016/j.memsci.2017.07.010
Received 10 February 2017; Received in revised form 4 July 2017; Accepted 7 July 2017
Available online 08 July 2017
0376-7388/ © 2017 Elsevier B.V. All rights reserved.
I. Jesswein et al. Journal of Membrane Science 541 (2017) 281–290

Nomenclature Vm molar volume of gas at standard temperature and pressure

(22.414 cm3/mol)
A active membrane area (m2) We Weber number
B gas dependent constant (g/kg) x length (m)
Bo Bond number X mass friction (g/g)
c concentration (g/g)
Ca Capillary number Greek letters
d thickness of dry coating layer (μm)
g acceleration of gravity (m/s2) γ surface tension (mN/m)
h thickness of fluid film (μm) δ membrane thickness (μm)
J flux (kg/m2 h) or (m2/m2s) η viscosity (mPa s)
l length of hollow fiber membrane (m) ϑ transformed temperature
L coefficient of proportionality μ chemical potential
m mass (kg) ρ density (cm3/g)
ṁ mass flow (kg/h) χ molar friction (mol/mol)
MW molecular weight (g/mol)
n mole (mol) Subscripts
p pressure (bar)
P permeability (Barrer) C critical point
r radius (m) F fiber (here of hollow fiber membrane)
R gas constant (8.314 J/mol K) M membrane
RH relative humidity (%) P polymer, coating polymer
STP standard conditions for temperature and pressure permeate permeate side
T temperature (°C or K) Sweep sweep gas
v velocity (m/s) tot ambient
V volume (m3) W water vapor
V̇ volume flux (m3/s) WS saturated water vapor

reciprocally on the membrane thickness, composite membranes are a further verify the practicability of our manufacturing process, compo-
preferred membrane type. To minimize the thickness of the highly se- site membranes were tested in relation to their thermal stability.
lective material, very thin layers are fabricated on porous support
structures.
2. Theoretical background
Min et al. tested the moisture permeation of porous PVDF, PES and
cellulose membranes and porous PVDF obtained the best results [10].
2.1. Water vapor transport
Furthermore, Pei et al. fabricated PVDF membranes with different
porosity for dehumidification of humid streams [4]. They demonstrated
The transport of gases or vapors through a dense polymeric mem-
that PVDF membranes with the highest porosity showed best water
brane is described by the solution-diffusion model. Here, permeate
vapor transport. PVDF as a hydrophobic material on the permeate side
molecules absorb into the membrane material and diffuse through it
can also show beneficial effects due to better moisture desorption and
until they desorb on the permeate side. The permeability of a gas
reduced concentration polarization [6].
through a polymeric material is described as the product of its solubility
Polyvinyl alcohol (PVA) is widely used in various fields of mem-
and diffusivity, whereas the separation of molecules occurs in con-
brane applications because of its hydrophilicity, good film-forming
sequence of different solubility and diffusivity properties.
ability and good mechanical and thermal properties [19]. PVA mem-
The driving force for the diffusion of a material through a mem-
branes are already used in industry in pervaporation applications such
brane can be summarized as the gradient of its chemical potential and
as dehydration of organic liquids [20] and thus are also very suitable
the flux can be expressed as:
for vapor permeation including humidification applications. Vapor
permeation was already tested by coating PVA blended with lithium dμW
chloride on polyethersulfone (PES) flat sheet membranes [21]. Pan JW = −LW
dx (1)
et al. prepared skin layers of PVA and PVA blends on polysulfone
hollow fibers for dehumidification of propylene gas [22]. Also PVDF where Ji is the flux and Li is a proportionality coefficient (the coefficient
hollow fiber membranes were prepared with a skin layer of PVA for has a negative prefix, as the diffusion is down the gradient). Assuming
liquid to gas humidification of air [8]. an ideal gas behavior and a concentration gradient as driving force, the
The scope of this work is to investigate the potential of PVDF-PVA flux can be converted to:
composite hollow fiber membranes for gas-to-gas humidification in
P
PEMFC, produced with a manufacturing process which could be made JW = ⎡ W ⎤ ∆pM
up as a continuous production line. Hollow fiber membranes were ⎣ ⎥
⎢ δM ⎦ (2)
produced in a small production-scale unit and the coating was fabri-
where PW is the intrinsic permeability, δM (cm) is the thickness of the
cated by a continuous dip coating process followed by a crosslinking
membrane and ΔpM (bar) the pressure difference. The term [PW/ δM]
procedure. Influencing parameters on the dip coating process were
represents the water vapor permeance of a membrane, as it is calculated
observed and correlations to the resulting layer thicknesses were in-
by dividing the flux through the pressure difference at the membrane.
vestigated. Water vapor transport of the membranes were measured
As the permeability of a material is often unknown or not yet
and correlated with the film thickness and crosslinking degree due to
evaluated, several other calculations are used to estimate the water
the production process. PVA material properties were systematically
vapor flux JW. Water flux for water vapor transport through a mem-
varied and their influence on water vapor transfer was studied. To
brane can be described as molar, volumetric or mass related water flux.

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2.2. Mass related water vapor flux 2.4. Film deposition by means of dip coating on fibers

Knowing the water vapor pressure in the permeate, the mixing ratio When an object is drawn out of a liquid bath a liquid film can be
X which represents the mass of water vapor in relation to the mass of deposited on its surface. This method is used especially for coating very
dry gas can be calculated: thin layers on non-planar substrates [24,25]. Compared to other pro-
cesses, like sputtering or chemical vapor deposition, dip coating is a
BpW
X= very simple method where less equipment is needed [25,26].
(ptot − pW ) (3) The fundamental theories for liquid film formation on fibers by
means of dip coating were established by Landau and Levich [27] and
where pW is the vapor pressure of water, ptot the total ambient pressure
enhanced by Derjaguin [28].
and B a gas dependent constant, which is defined as:
When a fiber is drawn out of a pure liquid bath a meniscus is
MW (water ) formed. Because of viscous forces and inertia effects fluid entrainment
B= 1000 occurs on the fiber, whereby gravity and surface forces counteract. For
MW (sweepgas ) (4)
small fibers and moderate coating velocities gravimetric and inertial
with MW as the molecular weight of water and the sweep gas, for ni- forces can be neglected [29,30]. So the formation of a liquid film can be
trogen as sweep gas B = 643.09 g/kg. With the water flow rate ṁ W , the described as a balance between viscous forces and surface tension. With
mass related water vapor flux can then be obtained: the dimensionless capillary number the ratio of these forces are de-
scribed as follows:
̇
ṁ W = ρsweep Vsweep X (5) ηv
Ca =
γ (10)
ṁ ̇
ρsweep Vsweep X kg
Jw = W = ⎡ m2s ⎤ where η is the viscosity of the coating fluid, γ the surface tension and v
AM AM ⎣ ⎦ (6)
the velocity with which the substrate is taken out of the bath [31].
̇
where ρsweep is the density of the sweep gas, Vsweep the volume flow rate With these assumptions the LLD law for the liquid film thickness h
of the sweep gas and AM the active membrane area. was derived as:
h = 1, 34r Ca2/3 (11)
2.3. Volumetric water vapor flux where r is the radius of the fiber [29].
As already mentioned, this law is only valid when gravity and in-
The volumetric water vapor flux is used for the calculation of the ertial forces can be neglected. To ignore gravity the dimensionless Bond
permeance (often in GPU) or the intrinsic permeability (often in number has to be far smaller than unity. The Bond number describes the
Barrer). balance between gravity and capillary forces:
Assuming an ideal gas behavior on the permeate outlet, the water
vapor flux can be calculated through the ideal gas law using the partial ρgr 2
Bo =
pressure of water on the permeate side pW, Permeate: γ (12)

̇
VSweep pW , Permeate Vm m³(STP ) with ρ the liquid density, g the gravity acceleration. For small fiber
VẆ
Jw = = ⎡ m2s ⎤ diameters the Bond number appears to fulfill the condition Bo < 1 [29].
AM RT AM ⎣ ⎦ (7)
Inertial forces become effective when the Weber number reaches
where Vm is the molar volume, T the temperature and R the ideal gas unity. Then the influence of inertial effects are stronger than capillary
constant. Sometimes the activity φ is added to the ideal gas law, but as forces. The Weber number is defined as [29]:
ideal gas behavior is assumed it is set to unity. ρv 2r
Furthermore, the permeance and permeability can be calculated We =
γ (13)
with:
Permeance (1 bar = 75.01 cmHg): In the case of coating with complex liquids, such as polymer or
surfactants solutions, a thickening effect is described in the literature
Jw 3
⎡∙10−6 cm2 (STP ) = GPU⎤ [32–34]. This so-called Marangoni effect and normal stress effect are
Δp ⎣ m s cmHg (8)
⎦ assumed to cause thickening or swelling of the liquid film. In such cases
a thickening factor has to be evaluated empirically and is added to the
Permeability:
LLD law. For coating solutions containing surfactants the thickening
Jw δm 3 factor can reach values of up to 2.5 [32]. For polymer solutions (e.g.
⎡7, 501∙10−9 cm 2(STP ) cm = barrer⎤
Δp ⎣ m s cmHg ⎦ (9) polyethylene glycol) values between 2 and 8 were determined [34].
Estimating the solid film thickness d is done in correlation with the
Here the pressure difference of the permeate and feed bulk phase is liquid film thickness and the polymer concentration cP [35]:
used, so it has to be considered that the permeance and permeability do
d ~cP h (14)
not exclude the impact of the module geometry or boundary layers,
which can have a significant effect due to process conditions and con-
centration polarization effects. Thus such values are often called ap- 3. Experimental
parent or observed permeability. To estimate the performance of the
membrane, the real driving force at the surface of the membrane must 3.1. Materials
be taken for calculations. The resistance coefficients of the boundary
layers and supporting layers therefore have to be assessed and their For membrane fabrication poly(vinylidene fluoride) (PVDF) KF
influence on the permeance is deducted from the apparent value. This Polymer 1550 was kindly provided from Kureha (Japan). N-ethyl-2-
method requires some more extensive modeling of the process [23]. In pyrrolidone (NEP) was obtained from Carl Roth (Germany) with a
this study only the apparent permeance and permeability is calculated, purity of ≥ 98%. As an additive polyvinylpyrrolidone (PVP) Luvitec
as the focus is set on analyzing the material properties at constant K17 was kindly provided by BASF (Germany).
process conditions. Polyvinyl alcohols (PVAs) of different molecular weights and

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I. Jesswein et al.
hydrolysis grades, listed in Table 1, from Fluka/Sigma Aldrich were
used as coating materials. Glutaraldehyde (GA) was purchased from
Merck as a 50% solution in water.
3.2. Fabrication of hollow fiber membranes
Membranes were made via nonsolvent-induced phase separation
(NIPS). The dope solution consisted of 15 wt% PVDF, 15 wt% PVP and
70 wt% NEP as solvent. The solution was prepared by stirring at 80 °C
overnight. For the wet spinning process a spinneret with an outer dia-
meter of 1 mm, an inner diameter of 0.5 mm and an inner diameter of
the bore fluid tubing of 0.3 mm was used. The polymer dope solution
and the bore fluid, a mixture of NEP and water with a volumetric ratio
of 3:1, were loaded in reservoirs. Their flow was initialized by pres-
surizing the reservoirs with nitrogen. Hollow fibers were directly spun
into the coagulation bath which contained deionized water at room
temperature. The spun fibers were drawn through the 6-meter long
coagulation bath and were then coiled up on a wheel. By rolling the
wheel through a water basin the fibers were washed for 24 h.
Afterwards the fibers dried on the wheel overnight at room tempera-
ture. For further continuous dip coating the approximately 100-meter
long hollow fiber was wrapped on a K250 spool.
To evaluate the geometry of the resulting hollow fibers small pieces
were cut out perpendicular to the length of the fiber. These cross sec-
tions were examined with a digital microscope (VHX-Keyence) and
using six different samples the inner and outer diameter and the wall
thickness of the fibers were measured four times respectively.
3.3. Coating solutions
With all PVAs listed in Table 1 aqueous solutions with a con-
centration of 5 wt% were prepared. In addition, for PVA 27000 con-
centrations were varied from 2.5 wt% to 10 wt%. The PVA was dis-
solved in water by treating the mixtures at 90 °C for several hours.
The viscosity of the solutions was measured using the rotational
rheometer Physica MCR301 (Anton Paar, Germany) with a coaxial cy-
linder test system. The viscosity was determined at shear rates between
10 Hz up to 1000 Hz at 25 °C.
The surface tension of the solutions was measured using the bubble
pressure tensiometer BP50 (Krüss Germany) at surface ages from
300 ms to 3000 ms and at 22 °C (room temperature).
3.4. Continuous dip coating of hollow fiber membranes
With a setup as shown schematically in Fig. 1, fibers were con-
tinuously coated on the outer surface from spool to spool. The fibers
were drawn through a coating bath and afterwards passed up a 1.1-
meter long drying chimney, in which four infrared lamps (TQS-in-
frared-batwing radiator, type FS) were integrated. PVDF hollow fiber
membranes were coated with PVA solutions at room temperature. The
drying temperature varied from 55 °C to 70 °C depending on the coating
solution and the resulting liquid film thickness. The drying temperature
was set as low as possible to avoid thermal damage of the fiber but as
high as necessary to obtain a dry coating layer at the end of the drying
line. With this device the coating velocity could be varied between
0.1 m/min and 30 m/min. In this study the coating velocity was kept
constant at 1 m/min.
To evaluate the thickness of the coating layer, one-meter-long
coated hollow fibers were weighed. Then the coating was washed off
the hollow fibers at 90 °C in water for 3 h. After drying the fibers were
weighed again and the difference in weight was determined. Assuming
a homogeneous thickness of the coatings on the membrane surface the
thickness can be calculated from the mass difference (ΔmF) by Eq. (15).
For this, the outer radius rF of the fiber is needed and a PVA density ρP
of 1.2 g/cm³ was used. Results were compared with the LLD law and
SEM images of the coated fibers.
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Journal of Membrane Science 541 (2017) 281–290
∆mF
d = −rF + rF2 +
ρP πl (15)
3.5. Crosslinking of PVA coating layers
Glutaraldehyde (GA) was used as a crosslinking agent for PVA
layers. In this study, several concentrations of GA in the aqueous
crosslinking solution were tested (0.1 vol%, 0.5 vol% and 5 vol%).
Furthermore, each solution contained 0.15 vol% HCl to catalyze the
reaction.
As coated hollow fibers had to be cut into pieces for analysis,
crosslinking could not be executed continuously anymore and a dipping
robot DR-0 (Riegler & Kirstein GmbH, Germany) was used. With this
robot 20 cm long fibers are pinned to a holder and can be moved
horizontally or vertically at defined velocities. The hollow fiber parts
were dipped with 1.2 m/min into a tube with the crosslinking solution,
remained there for 0.5 s and were then drawn out of the solution with
the same velocity. The high velocity and short time of immersion was
chosen in accordance with the conditions of a continuous dip coating
setup. Furthermore, dissolving of the PVA coating in the aqueous
crosslinking solution must be prevented, so high velocities and short
immersion times are needed. Afterwards the fibers dried at room tem-
perature for 24 h.
From each combination of coated and crosslinked hollow fiber three
single fiber modules were fabricated with four thread ends. The effec-
tive membrane length in the module is approx. 7.5 cm.
3.6. Determination of permeances
Pure nitrogen permeance was measured as a mean value for the air
leakage. Therefore an ADM flowmeter (Agilent Technologies) was used
which measures gas flows volumetrically. For these tests, nitrogen was
applied at 0.5 bar, 1 bar, 1.5 bar and 2 bar at the hollow fiber inside
and the gas flow on the outside was measured using the flowmeter. By
dividing the resulting nitrogen flow through the membrane surface area
and the applied pressure values for the permeance in L/(m2 h bar) were
obtained. Mean values for each module were established from the re-
sults at each pressure and the average from three modules was calcu-
lated.
Water vapor flux was determined with a setup schematically shown
in Fig. 2. Two nitrogen flows are passed in counter-flow over the
membrane. While the nitrogen flow through the hollow fiber inside is
dry, the flow on the outside of the membrane previously passes through
a washing flask with water to humidify the gas. Two sensors measure
temperature and relative humidity, one for the humid nitrogen influent
flow, later referred to as “wet in”. The other sensor measures the outlet
flow of the dry side, so-called “dry out”. The whole setup is built into a
cabinet, so the measurement can be undertaken at different tempera-
tures. In this work measurements were taken at 80 °C in accordance
with the conditions of a humidifier of PEMFCs. To calculate the se-
lectivity over nitrogen some membranes were also tested at 25 °C. The
flow rates of nitrogen were set to 200 ml/min on both sides of the
membrane using mass flow controllers (Bronkhorst, Germany).
Water vapor flux is then calculated through the relative humidity of
Table 1
Molecular weight and hydrolysis grades of used PVAs.
Molecular weight (g/mol) Hydrolysis grade (mol%)
15,000 89
27,000 98
31,000 88
47,000 98
61,000 98
67,000 88
I. Jesswein et al. Journal of Membrane Science 541 (2017) 281–290

3.7. Test procedure

All samples passed the following test sequence to check the stability
of the composite membranes.

1. Nitrogen permeance (NP 1)

2. Water vapor transport (WVT 1)
3. Nitrogen permeance (NP 2)
4. Coating stability test: treating modules for 3 h at 90 °C in water
5. Nitrogen permeance (NP 3)
6. Water vapor transport (WVT 2)
7. Nitrogen permeance (NP 4)

After determining the nitrogen permeance and the water vapor flux
of a system a second nitrogen permeance test follows. The stability of
the coating is therefore observed, as damage or loss of the coating layer
would be visible with a significant increase of the nitrogen permeance.
In point 4. a stability test is performed under extreme conditions.
Modules are stored at 90 °C in hot water for 3 h, which correlates with
the solution conditions of PVA when not crosslinked. Afterwards the
permeance tests of nitrogen and water vapor are repeated and com-
pared with the previous results.
Fig. 1. Schematic diagram of the continuous dip-coating device; 1 – hollow fiber spool, 2
– thread tension regulation, 3 – drying chimney.
4. Results and discussion

4.1. Coating solutions and resulting coating thickness

The viscosity and surface tension of the coating solutions were

measured, as these two parameters have a major influence on film
deposition by dip coating. In our experiments the coating thickness was
evaluated through the weight of coating material on the fiber, as ex-
plained in Section 3.4. Data points for the LLD thickness were calcu-
lated with the LLD law (see Section 2.2) using the radius of the PVDF
hollow fiber, a velocity of 1 m/min and the surface tension and visc-
osity of the respective coating solution.
The viscosity and surface tension of different PVA 27000 solutions
are shown in Fig. 3. Here an increasing viscosity can be observed with
increasing concentration whereas the surface tension stays constant at a
value of 66 mN/m. The resulting coating thicknesses of these solutions
are shown in Fig. 4. As expected, the thickness of the layers increases
with the PVA concentration due to the increasing viscosity of the so-
Fig. 2. Schematic diagram of the water vapor flux measuring system.
lutions.
Fig. 5 shows the viscosity and surface tension of 5 wt% PVA solu-
tions. The viscosity of the solutions increases with the molecular weight
the dry out stream. Relative humidity RH% is defined as the quotient of
of PVA. Comparing the solutions with PVA 27000 and 31000 as well as
vapor pressure pW and saturation vapor pressure pWS:
PVA 61000 and 67000, it can be seen that a higher hyd. degree leads to
pW
RH % =
pWS (16)

With the actual temperature (here 80 °C), the saturated vapor

pressure can be calculated [36]:

p T
ln ⎛⎜ WS ⎞⎟ = C (C1 ϑ + C2 ϑ1,5 + C3 ϑ3 + C4 ϑ3,5 + C5 ϑ 4 + C6 ϑ7,5)
⎝ pC ⎠ T (17)

with
T
ϑ = 1−
TC (18)

Knowing the saturated vapor pressure and the relative humidity, the
vapor pressure in the permeate stream can be determined by trans-
forming Eq. (16):
pW = RH pWS (19)

With this value, the water vapor flux can be determined using the Fig. 3. Viscosity and surface tension of PVA 27000 solutions with different concentra-
equations in Section 2.1. tions.

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I. Jesswein et al. Journal of Membrane Science 541 (2017) 281–290

using the viscosity and surface tension and the experimental thickness
is plotted against the LLD thickness (Fig. 7). With a correlation coeffi-
cient of 0.97, a good linear correlation between the equation of the LLD
law in Fig. 7 and the experimental thicknesses is found. The introduc-
tion of a thickening factor, as mentioned earlier in Section 2.2, is not
necessary. Some values are even slightly below the prediction from the
LLD law, predominantly for PVA coatings with a hyd. degree of 98 mol
%.
It can be concluded that the LLD law can be used for predicting the
coating thickness of our PVDF fibers with PVA accurately.
In addition, most of the coated fibers were analyzed by SEM. An
example of a coated and an uncoated hollow fiber can be found in
Fig. 8. The thicknesses measured through the change of weight were
confirmed by these investigations. Also, an adequate binding between
the hollow fiber substrate and the coating layer was observed in the
images.
Fig. 4. Resulting coating thickness from PVA 27000 solutions of different concentrations.

4.2. Nitrogen permeance

Nitrogen permeance was measured to determine if the membrane

surface was completely covered with a dense layer of PVA. Uncoated
PVDF hollow fiber membranes have a nitrogen permeance of about
100 m3/m2 h bar. By coating the membranes with different PVA 27000
solutions, nitrogen permeance was reduced to over 96% (Fig. 9). With a
higher concentration of the coating solution the layer thickness in-
creases and the expected trend of a decreasing nitrogen permeance
could be observed with increasing layer thickness.
Also, coatings with PVA of different molecular weight reduce the
nitrogen permeance, as shown in Fig. 10. Here a reduction of per-
meance of over 98% can be seen.
With our continuous dip coating and crosslinking process, dense
layers of PVA could be fabricated on PVDF hollow fiber membranes.
The nitrogen permeance was significantly reduced by over 96%. At
25 °C membranes coated with PVA 47000 and crosslinked with 0.1 vol
% GA or 0.5 vol% GA achieved a nitrogen permeance of approx.
Fig. 5. Viscosity and surface tension of 5 wt% PVA solutions of different molecular 0.06 m3/m2 h bar. PVA 67000 coatings crosslinked with 0.1 vol% GA
weights. even had a nitrogen permeance of 0.01 m3/m2 h bar.

a slightly higher viscosity of the aqueous solution. This may be an effect 4.3. Water vapor transport
of increased interactions caused by the amount of hydroxyl groups
within the polymer. The surface tension of solutions with a hyd. degree For all modules the water vapor flux was investigated at 80 °C, as
of 98 mol% is independent of the molecular weight at approx. 66 mN/ the operating conditions of external humidifiers of PEMFCs range from
m, while PVA solutions with a hyd. degree of ca. 88 mol% show lower 65 °C to 80 °C [37]. To compare the different membrane coatings, the
values, increasing from 45 mN/m to 53 mN/m with molecular weight. apparent intrinsic permeability was calculated in accordance with Eqs.
With a lower degree of hydrolysis, PVA seems to have a more amphi- (7) and (9) in Section 2.1, using the coating layer thickness as mem-
philic character, which leads to a larger reduction of the surface ten- brane thickness.
sion.
In Fig. 6 the coating thicknesses of 5 wt% PVA solutions are shown.
The layer thickness increases with the molecular weight of PVA. This
effect may be traced back to the increase of the viscosity, shown in
Fig. 5. PVA 27000 and 31000 as well as PVA 61000 and 67000 have
similar molecular weights, but different degrees of hydrolysis. Fig. 6
shows, that in both cases the PVAs with a hyd. degree of 88 mol% form
thicker coating layers. PVA solutions with a hyd. degree of 88 mol%
have significantly lower surface tensions, which implies the formation
of thicker coating layers compared to solutions of 98 mol% hydrolyzed
PVA.
For all coating solutions the dimensionless Capillary number, the
Bond number and the Weber number were calculated, using the mean
fiber radius of 0.99 mm and a coating velocity of 1 m/min. Capillary
numbers are in a range of 0.001 – 0.007. The Bond numbers appear to
range from 0.18 to 0.21 so gravity effects can be neglected. Similarly,
inertia effects can be ignored as the values for the Weber numbers are
between 0.004 and 0.006. The measured coating thicknesses can
therefore be compared to predictions from the LLD law. The theoretical Fig. 6. Resulting coating thickness from 5 wt% PVA coating solutions of different mole-
LLD thickness is calculated for all coating solutions (Eqs. (11) and (14)) cular weight.

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I. Jesswein et al. Journal of Membrane Science 541 (2017) 281–290

Fig. 7. Correlation of experimental coating layer thicknesses with the LLD law. Fig. 9. Nitrogen permeance of PVDF hollow fiber membranes coated with PVA 27000
solutions with different concentrations, crosslinked with different GA solutions (* per-
meance below measurement range).
In Fig. 11 the water vapor permeability of PVA 27000 layers is
presented as a function of the layer thicknesses. It can be seen that the
permeability increases with the thickness of the coating layers. As by
definition the permeability of a given membrane is independent of the
membrane thickness, differences according the material properties of
the layers have to exist. We suggest that this phenomenon can be ex-
plained by the crosslinking process. As the procedure is the same for all
coatings, equal amounts of crosslinking solution are deposited on each
membrane. Due to a thicker coating layer the degree of crosslinking
may differ, as the ratio of GA to PVA decreases with increasing PVA
layer thickness. Therefore, it can be assumed that the thicker the
coating layer the lower the degree of crosslinking is. Hence, the free
volume of the polymeric film increases and the diffusion of molecules
through the polymer is facilitated. Also, it is quite likely that the degree
of crosslinking may not be homogeneous over the thickness of the layer,
so nearer the outer surface the degree of crosslinking may be higher
than towards the supporting structure.
Up to a layer thickness of 1.8 μm no significant differences can be Fig. 10. Nitrogen permeance of PVDF hollow fiber membranes coated with 5 wt% PVA
recognized among the concentration of GA in the crosslinking solution. solutions of different molecular weights, crosslinked with different GA solutions (* per-
meance below measurement range).
With a coating thickness of 4.3 μm there is a distinct correlation with
the GA concentration.
The water vapor permeability of PVA coatings with different mo- crosslinking of the PVA coating. The differences with 0.1 vol% and
lecular weights are shown in Fig. 12 for PVAs with a hyd. degree of ca. 0.5 vol% GA solutions are much smaller.
88 mol% and in Fig. 13 for a hyd. degree of 98 mol%. The water vapor permeability of the PVA coatings with a hyd. de-
In Fig. 12, analogous to the results presented in Fig. 11, the per- gree of 98 mol% in Fig. 13 also increases with the coating layer
meability of the membranes increases with the thickness of the coating thickness, but no significant graduation according to the concentration
layers according to the process-related effect, that the ratio of cross- of the crosslinking solutions occurs.
linker towards PVA decreases with the layer thickness of PVA on the When comparing Fig. 11 with Fig. 12 the influence of the hyd. de-
hollow fiber membrane. Furthermore, the values are clearly graduated gree of the PVAs can be examined. For lower crosslinking concentra-
according to the concentration of GA in the crosslinking solutions. For tions (0.1 vol% and 0.5 vol% GA) the water vapor permeability of PVA
all systems the coatings crosslinked with 5 vol% GA solutions have the layers with a lower degree of hydrolysis show higher permeability va-
smallest water vapor permeability, which is due to the higher degree of lues than 98 mol% hydrolyzed PVAs. A PVA layer with a hyd. degree of

Fig. 8. Cross section of the hollow fiber membranes

at the outer surface, uncoated PVDF hollow fiber
(left side) and with PVA 47000 coating (right side).

287
I. Jesswein et al.
Fig. 11. Water vapor permeability of PVDF hollow fiber membranes coated with PVA
27000 solutions with different concentrations, crosslinked with different GA solutions.
Fig. 12. Water vapor permeability of PVDF hollow fiber membranes coated with 5 wt%
PVA solutions of different molecular weights and a hyd. degree of ca. 88 mol%, cross-
linked with different GA solutions.
Fig. 13. Water vapor permeability of PVDF hollow fiber membranes coated with 5 wt%
PVA solutions of different molecular weights and a hyd. degree of 98 mol%, crosslinked
with different GA solutions.
98 mol% and a thickness of ca. 1.5 μm, crosslinked with 0.1 vol% or
0.5 vol% GA, reaches a water vapor permeability of ca. 2500 Barrer. An
equal system with a hyd. degree of ca. 88 mol% achieves values of
3000–3500 Barrer, according to the linear regression in Fig. 12. As
mentioned earlier the permeability of a material is defined as the pro-
duct of the solubility and the diffusivity by the solution-diffusion
model. When using very low concentrated crosslinking solutions with
both hyd. degrees a great amount of hydroxyl groups remain after the
crosslinking reaction and a good solubility of water vapor is given in
288
Journal of Membrane Science 541 (2017) 281–290
both cases. Hence, the observed effect can be traced back to the free
volume within the PVA layers which influences the diffusivity of water
vapor through the coating layer. PVA with a hyd. degree of 88 mol%
may have a larger free volume according to a higher amount of acetate
groups in the polymer chain.
When crosslinking with 5 vol% GA the PVA layers with 98 mol%
degree of hydrolysis succeed over those with 88 mol% hyd. degree.
With such a high concentration of crosslinking agent the amount of
residual hydroxyl groups may significantly be higher in PVAs with a
higher degree of hydrolysis, which leads to a better solubility involving
a better permeance of water vapor through the membrane.
To investigate if a correlation of water vapor permeability and
molecular weight of the PVA layer exists, the results of the PVAs with a
hyd. degree of 98 mol% (Fig. 13) were compared with those of the PVA
27000 (hyd. degree of 98 mol%) coatings in Fig. 11 for comparable
layer thicknesses. As the permeability values of PVA 47000 and PVA
61000 coatings fit well into the linear regression of the PVA 27000
coatings, the molecular weight of the PVA has no major impact on the
water vapor permeability.
All measurements were carried out at 80 °C. To calculate the se-
lectivity towards nitrogen, water vapor flux tests at 25 °C were carried
out with some systems. Afterwards the apparent water vapor perme-
ability was calculated without considering boundary layers. Also the
permeability towards nitrogen was calculated to determine the se-
lectivity. The results in Table 2 show that there are distinct differences
in permeability and selectivity depending on the coating and cross-
linking solution used. Systems with a very thin PVA skin layer, for
example when coated with 2.5 wt% PVA 27000, have quite poor se-
lectivity due to comparably high nitrogen permeability. Coatings with
PVA 15000 in Table 2 show that higher crosslinking of the coating layer
both reduces the permeability of water vapor and nitrogen. But using
PVA of higher molecular weight, which also results in thicker layers as
the coating velocity stays constant, the water vapor permeability in-
creased while the permeability of nitrogen is reduced. Accordingly, the
selectivity significantly increases.
Values for water vapor transport depend on the process conditions,
i.e. flow condition in the module and relative humidity of the feed.
Comparing the values measured at 25 °C in Table 2 with the collected
data of Metz et al. [15], much higher water vapor permeability values
were reached. It should be borne in mind that our values are not ex-
trapolated to a water vapor activity of 0, which can reduce the per-
meability to a significant extent. On the other hand, the calculated
selectivity towards nitrogen tends to be lower than shown by Metz.
4.4. Stability of composite membranes
To check the crosslinking of the PVA layers and the stability of the
coatings on the PVDF hollow fiber membrane modules underwent a
special treatment. They were stored in hot water at 90 °C for 3 h, which
represents the solvation conditions of non-crosslinked PVA. Nitrogen
permeance was used as a reference test, as damage to the coated layer
would result in a significant increase of permeance.
The results of the stability tests are summarized in Table 3. The
nitrogen permeance of most membranes, 20 out of 27, had completely
constant values through the stability tests. Only seven membrane sys-
tems showed striking changes. In Fig. 14 the nitrogen permeance of
PVDF hollow fibers coated with 10 wt% PVA 27000 solution and
crosslinked with 0.1 vol% GA and 5 vol% GA are shown. Coatings with
this PVA solution resulted in the thickest coating layer with approx.
4.29 μm. Permeance tests showed that crosslinking with only 0.1 vol%
GA is not sufficient for a stable PVA layer as the nitrogen permeance
constantly increases with the treatments. Crosslinking the coating layer
with 5 vol% GA results in a sufficiently crosslinked PVA layer which has
a stable nitrogen permeance through the test procedure, like most of the
composite systems.
Also the coatings of 2.5 wt% PVA 27000 showed some unstable
I. Jesswein et al. Journal of Membrane Science 541 (2017) 281–290

Table 2
Permeability and selectivity of some composite membranes at 25 °C.

Coating system Coating thickness Water vapor flux Water vapor permeability Nitrogen permeability Selectivity
(μm) (kg/m2 h) (Barrer) (Barrer) (H2O/N2)

5 wt% PVA 15000; 0.85 0.11 1406.9 163.4 8.6

0.5 vol% GA
5 wt% PVA 15000; 0.85 0.07 832.6 70.8 11.7
5 vol% GA
2.5 wt% PVA 27000; 0.3 0.12 547.3 254.7 2.2
0.5 vol% GA
5 wt% PVA 27000; 0.52 0.09 724.95 24.4 29.7
0.1 vol% GA
5 wt% PVA 47000; 1.31 0.09 1824.4 31.2 58.5
0.1 vol% GA
5 wt% PVA 67000; 1.75 0.11 2890.1 10 289.0
0.1 vol% GA

Table 3
Stability evaluation of the membrane systems, coating solutions over crosslinking solutions; + stable nitrogen permeance; o slight change in nitrogen permeance; − significant changes in
nitrogen permeance.

5 wt% PVA solutions (g/mol) PVA 27000 solutions (wt%)

15000 27000 31000 47000 61000 67000 2.5 5 7.5 10

0.1 vol% GA o + o + + + – + + –
0.5 vol% GA + + + + + + o + + +
5 vol% GA + + + + + + o + + +

5. Conclusion

Different PVAs were coated and crosslinked on PVDF hollow fiber

Fig. 14. Nitrogen permeance at different states of PVDF membranes coated with a 10 wt
% PVA 27000 solution and crosslinked with 0.1% GA (unstable layer) and 5% GA (stable
layer) (* permeance below measurement range).
behavior in the stability tests. With approx. 0.3 μm, layers from this
coating solutions are the thinnest fabricated in this study. Their un-
stable nitrogen permeance occurred with all crosslinking solutions. For
0.1 vol% GA and 0.5 vol% GA some changes in permeance could be
recognized which may be an indication of gradual coating damage.
With a high crosslinking using 5 vol% GA solution a significant increase
of permeance towards the first measurement occurred.
Comparing the water vapor transfer before and after the stability
test, no changes of the water vapor flux could be recognized. Values for
the water vapor flux of all membranes appeared to be very stable from
WVT 1 to WVT 2.
In summary, most of the membrane systems passed the test proce-
dure with stable nitrogen permeance and water vapor flux. Only the
thinnest and thickest layers showed a significantly increasing nitrogen
permeance, some of which is explained by a degradation of the PVA
coatings.
membranes to fabricate composite membranes for gas-to-gas humidi-
fication. A nearly continuous process was set up for manufacturing the
composite membranes. Several parameters showed influence on the
performance of the composite membranes.
The fabricated layer thickness plays a crucial role in the perfor-
mance of the membrane. The thickness of the layers depends largely on
the surface tension, the viscosity of the coating solution and the coating
velocity. For the system used here, layer thicknesses were in good
agreement with the LLD law. The thickness of the skin layer produced
influenced the degree of crosslinking. With increasing layer thickness
higher water vapor permeability were measured, due to a lower degree
of crosslinking. With our layers the permeance of nitrogen could ef-
fectively be reduced and a selectivity towards water vapor up to 289
was obtained at 25 °C.
In the stability test, damage to the coatings was mainly observed in
membrane systems with the thinnest (0.3 μm) and thickest layers
(4.29 μm). All other systems with skin layers of 0.52–1.8 μm exhibited
stable behavior throughout the tests.
Our nearly continuous manufacturing process turned out to be
suitable for the fabrication of composite membranes for humidification.
Membranes could be fabricated with good water vapor permeability
and selectivity towards nitrogen. The coating and crosslinking method
could be directly coupled with the wet spinning of the hollow fibers
forming a simple and fast continuous production process with the po-
tential for reducing costs.
Acknowledgements
I.J. was supported by a grant of the state of Baden-Württemberg
(Landesgraduiertenförderung). We gratefully thank Maria Fernanda
Ramirez for her help with module fabrication and nitrogen permeance
measurements.

289
I. Jesswein et al.
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