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Article

pubs.acs.org/Langmuir

A Biologically Inspired Hydrophobic Membrane for Application in


Pervaporation
Nora Jullok,*,, Rodrigo Martnez, Christine Wouters, Patricia Luis, Mara Teresa Sanz,
and Bart Van der Bruggen

Department of Chemical Engineering, Process Engineering for Sustainable Systems (ProcESS), KU Leuven, W. de Croylaan 46,
B-3001 Heverlee, Belgium

Department of Chemical Engineering, University of Burgos, 09001 Burgos, Spain

School of Bioprocess Engineering, Universiti Malaysia Perlis, Kompleks Pusat Pengajian Jejawi 3, 02600 Arau, Perlis, Malaysia
ABSTRACT: An articial polydimethylsiloxane/polyphenylsulfone (PDMS/PPSU)
membrane, which emulates the hydrophobic behavior of natural membranes, was
synthesized. Hydrophobicity was achieved by coating the membrane surface sublayer
using conventional silicon material, which imitates the character of epicuticular wax (EW)
of Prunus laurocerasus L. leaves. It was then applied as a separation medium in
pervaporation (PV) of diluted mixtures of ethyl acetate and aroma compounds. The
membranes biomimetic characteristics were evaluated using surface morphology analyses,
that is, Fourier transform infrared (FTIR), water contact angle measurements, and SEM
imaging. A comparison of properties of the membranes synthesized in this work against
selected hydrophobic plant leaves indicated a good agreement. PV using these biologically
inspired articial membranes demonstrated preference for the permeation of ethyl acetate.
Besides intrinsic characteristics, it was also observed that the chemical potential is highly
inuential in activating sorption, diusion, and desorption of a specic compound.
cuticle are called epicuticular waxes.3 Jetter et al. further
explained that wax lms from P. laurocerasus consist of a
mixture of alkanes with dierent chain lengths and other
compound classes.4 Typical wax morphologies include thin
lms and three-dimensional structures such as massive crusts,
granules, plates, platelets, laments, rods, and tubules with
hollow center.3 According to several other studies, cuticles
serve as an ecient transport barrier in controlling dehydration
by transpiration, besides managing the plantpathogen
interactions.3,59 Water movement across plant cuticles is
similar to its movement across membranes, which can be
quantied using the rst Ficks Law. Cuticular water
permeability is highly dependent on the cuticular/water
partition coecient, porosity, membrane thickness, tortuosity
factor, self-diusion, and the hindrance factor.10 On the basis of
these ndings, it can be concluded that membranes exhibiting
these curticular properties are extremely useful for industrial
applications, especially for organic traces removal in aqueous
solution through pervaporation. This work aims to transfer
these cuticular wax properties found in plants by introducing
and synthesizing a composite polymer-based membrane.
Polydimethylsiloxane (PDMS) membranes have been frequently used in PV to recover organic solvents from aqueous
mixtures,1113 and also for gas separation.14 As a support
material, a third member of the polysulfone family,
polyphenylsulfone (PPSU), with better properties than

1. INTRODUCTION
Nature has inspired various inventions and technological
solutions to overcome limitations of mankind in life. Various
improved materials, tools, structures, mechanisms, processes,
algorithms, and methods resulted from the understanding of
nature and its phenomena. Flying, for instance, was inspired by
the mechanism used by birds, while divers ns were replicated
from semiaquatic creatures such as seals.1 The word
biomimetics, which rst appeared in Websters dictionary in
1974, is dened as the study of the formation, structure or
function of biologically produced substances and materials (as
enzymes or silk) and biological mechanisms and processes (as
protein synthesis or photosynthesis) especially for the purpose
of synthesizing similar products by articial mechanisms, which
mimic natural ones.2 Biomimetic research resulted in the
understanding of various phenomena such as wettability and
the self-cleaning eect found in natural leaves such as Nelumbo
nucifera gaern (Lotus leaf), Oryza sativa L. (Rice leaf), Colocasia
(Taro leaf), Prunus laurocerasus L. leaves (Cherry laurel), and
Setcreasea purpurea boom (purple setcreasea). Recently, studies
discovered that leaves in general are laminated with organic
lms containing C, H, and O elements. Others believed that the
majority of lower and higher-altitude plants (e.g., owers,
leaves, fruits, stems) consist of a continuous extracellular
membrane known as cuticle, which covers the outer layer of the
epidermal cell.3 In general, cuticles are cutin-based composite
materials with integrated and superimposed lipids known as
waxes. Plant waxes embedded into the cuticle are called
intracuticular waxes, whereas waxes superimposed onto the
2013 American Chemical Society

Received: October 24, 2012


Published: January 16, 2013
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Table 1. Physicochemical Properties of the Seven Selected Aroma Compoundsa


properties

formula
functional group
MW, g/mol
SG @ 25 C
boiling point, C
Psat (26 C), Pa
solubility in water @ 20 C, g/L

CH3CO2C2H5
ROCOR
88.1
0.901
77.1
13 045
80

C5H10O
RHCO
86.1
0.803
92.5
7035
15

C5H8O2
ROCCOR
100.1
0.957
108
2918
60

C6H12O
RHCO
100.2
0.814
128.3
1540
IS

C5H10O
ROH
86.1
0.839
114.4
1348
IS

C8H16O
ROH
128.2
0.83
8485
65
IS

C6H5CHO
RHCO
106.1
1.046
179
181
0.3

1 = ethyl acetate, 2 = 3-methylbutyraldehyde, 3 = 2,3-pentanedione, 4 = hexanal, 5 = 1-penten-3-ol, 6 = 1-octen-3-ol, 7 = benzaldehyde, IS =


insoluble, SG = specic gravity.

W (%) = solute 100%


Wsolution

polysulfone (PSf) and polyethersulfone (PES) in terms of


chemicals and temperature resistance was utilized.15 PPSU is
considerably a new membrane material, which potentially
serves as an alternative for other commercially available PV
membranes. Others have studied PPSU as a support to
polymeric liquids in the recovery of aromatic compounds from
wastewater,16 PPSU/PBNPI blend membranes for hydrogen
separation,17 and as a proton-conducting fuel cell membrane.18
Because PPSU has been proven to be very robust,18 this study
explores the use of such material in combination with PDMS.
This investigation also analyzes the eect of operating
conditions by means of solutes concentration and feed
temperature on the permeating components. Structure and
morphologies of the fabricated membranes are analyzed using
contact angle measurements, FTIR, and SEM imaging. Finally,
these synthesized biomimetic membranes are applied in the
pervaporation (PV) process for permeation of hydrophobic
compounds (ethyl acetate, 3-methylbutyraldehyde, 2,3-pentanedione, hexanal, 1-penten-3-ol, 1-octen-3-ol, benzaldehyde).

(1)

After thorough mixing, agitation in the solution was lowered to


reduce the amount of air intake. Bubbles present in the PDMS
solution were removed using vacuum deairing, prior to cooling at
room temperature. The synthesized at sheet PPSU was circularly cut
and capped on one side of a cylinder. Next, the PDMS solution was
carefully poured onto the surface of the membrane, while swirling the
capped cylinder for an even coating distribution. Finally, these coated
PDMS/PPSU membranes were ready for use upon oven-curing for 45
min at 105 C, denoted as M1, M2, and M3 for 5, 10, and 15 wt %
PDMS, respectively.
2.3. Membrane Characterization. 2.3.1. Wettability. Contact
angle measurements were conducted using a standard contact angle
apparatus (KRU SS GmbH Germany, model DSA 10-Mk2) to
determine the degree of wettability. The measurement was performed
using a drop-shape analysis software to study the video images of the
pendant drops. A syringe plunger was utilized for drop depositions on
the surface of the membrane under study.
2.3.2. Microscopy Study of Natural and Synthetic Surface. The
surface and cross-sectional area of lotus leaf, lotus ower, taro leaf, and
the PDMS/PPSU membranes were obtained using SEM (Philip XL30
ESEM FEG, The Netherlands). To analyze PDMS/PPSU as a
function of polymer concentration, the membranes were split during
liquid nitrogen immersion to enable accurate cross-section imaging.
Magnications up to 2500 were obtained at 20 kV.
2.3.3. Analysis of Samples. The compositions of aroma compounds
permeating through the membranes were analyzed using head space
gas chromatography (HS-GC). HS-GC consists of a gas chromatography (Perkim Elmer autosystem) and a headspace sampler (Perkim
Elmer HS16). The GC column was a cpSil8CB 50 m 0.32 mm. The
injector and ame ionization detector temperatures were set at 180
and 250 C, respectively. The oven was operated at temperatures
ranging from 40 to 180 C, while helium with purity of 99.99% was
used as carrier gas.
2.4. Application of Nature-Inspired Membrane in Pervaporation. Besides regulating water content in plants, epicuticular wax
serves as the rst and main barrier to the penetration of agriculturally
important chemicals. Similarly, this concept is applied in this work.
The penetration of seven dierent synthetic chemicals with distinct
physicochemical properties through the membrane was studied: ethyl
acetate, 3-methylbutyraldehyde, 2,3-pentanedione, hexanal, 1-penten3-ol, 1-octen-3-ol, and benzaldehyde. Their physicochemical properties
are summarized in Table 1.
For this investigation, three feed concentrations were used: 1, 5, and
10 ppm in water, containing equal amounts of the seven compounds
while varying the feed temperature from 25 to 45 C. To achieve
equilibrium, the tested membrane was mounted onto the membrane
test cell, and feed was circulated overnight. Because of the dense
structure of the membrane surface, the sorption of liquid into the
dense layer to reach equilibrium between membrane and feed mixture
normally takes a long time at ambient conditions. Thus, overnight
immersion may ensure that both membrane and feed solution are in
equilibrium prior to PV experiments. Vacuum was not employed on

2. MATERIALS AND METHODS


2.1. Materials. Polyphenylsulfone (PPSU, Radel R-5000) with an
average molecular weight of 50 000 g mol1 was obtained from Solvay
Advanced Polymer Belgium. Polydimethylsiloxane (PDMS, Sylgard
184), which consists of two-part liquid component kits (part A/part B
to be mixed in 10:1 ratio by weight), was purchased from Dow
Corning Belgium, while N-methyl-pyrrolidone (NMP, 99%), 1-octen3-ol (98%), 3-methylbutyaldehyde (98%), and 2,3-pentenedione
(97%) were purchased from Acros Organics (Geel, Belgium). Hexanal
(98%) and 1-penten-3-ol (99%) were obtained from Sigma Aldrich
Chemie GmbH (Steinhem, Germany). Ethyl acetate (EtOAc) (HLPC
grade, >99%) was purchased from Fischer Scientic (Loughborough,
UK), benzaldehyde (99+%) was from Avocado Research Chemicals
Limited (Lancs, UK), and n-hexane was from Chem-Lab NV
(Zedelgem, Belgium).
For the synthesis of hydrophilic sublayer membrane, a hydrophilic
PPSU sublayer is rst produced prior to the hydrophobic coating. The
preparation of the hydrophilic sublayer was performed by immersion
precipitation. First, the polymer solution was cast on a glass plate and
immersed in a nonsolvent bath for a few minutes. It was then removed
from the water bath and rinsed with demineralized water. Next, the
membrane was immersed in another clean water bath to allow removal
of excess solvents. Details of this synthesis have been described in
previous work,19 where a membrane with 25 wt % PPSU was used as
sublayer. This composition was chosen due to its proven high ux in
PV dehydration of acetic acid and water solution.19
2.2. Preparation of PDMS/PPSU Membrane. The PDMS
coating was prepared using Sylgard 184 silicone elastomer kit, which
consists of two parts: the lot-matched base (A) and the curing agent
(B). Parts A and B are mixed in a ratio of 10 to 1, by weight. Three
dierent wt % PDMS solutions were prepared, 5, 10, and 15 wt %
PDMS in hexane solution, according to eq 1:
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Figure 1. Top layers of synthesized PPSU and PDMS membranes at lower to higher polymer concentration: (a) 25 wt % PPSU, thickness 0.55
m; (b) 27.5 wt % PPSU, thickness 0.25 m; (c) 30 wt % PPSU, thickness = 0.32 m; (d) 5 wt % PDMS, thickness = 1.4 m; (e) 10 wt % PDMS,
thickness = 2.74 m; and (f) 15 wt % PDMS, thickness = 4.37 m. Panels ac were reprinted with permission from ref 19. Copyright 2011 Elsevier.

E
P
P
= exp x
l
RT
l

the permeate side during this period. A detailed procedure can be


found in our recent investigation.19
The membrane ux (J) was determined experimentally through
gravimetrical weighing of collected PV permeate samples over time.
These sample weights, measured with an accuracy of 104 g, then
enable ux calculation using eq 2:

J=

m
P
= (ioLxiLoPisat
o yio Pi l)
At
l

where P/l is the permeance, (P/l) is the pre-exponential factor of the


permeance, R is the gas constant (J/mol.K), T is the temperature (K),
and Ex is the activation energy (kJ/mol).

3. RESULTS AND DISCUSSION


3.1. Biomimetics of Leaves in the Synthesis of PDMS/
PPSU. Mass transfer during membrane formation occurs
through two mechanisms: delayed demixing and instantaneous
demixing.23 The demixing time delay critically determines the
membrane morphology. Van de Witte et al. have demonstrated
that the nucleation and growth in the polymer poor phase are
responsible for pore generation,22 which allows obtaining a leaflike morphology. In addition, a low polymer concentration
results generally in high membrane porosity, approaching a
porosity that can be found as stomas in the leaf and stem
epidermis areas used for gaseous exchange. In this study, an
instantaneous lm formation was observed once the polymer
solution was brought in contact with the nonsolvent, indicating
a rapid demixing process. Thus, a very thin top layer and
sublayer with large amounts of macrovoids was obtained. This
membrane top layer is expected to contain nodular structures,
and consequently to exhibit some degree of porosity. On the
contrary, increasing the concentration of the polymer solution
results in a decreased membrane porosity, resulting in a denser
and thicker top layer (Figure 1ac) due to interconnectivity of
pores at the inception of demixing.23
Application of a denser membrane with a thicker top layer in
separation typically results in a low membrane permeability.

(2)

where m is the weight of collected permeate (kg), t is the duration of


the experiment (h), A is the eective area of the membrane (0.001963
m2), Lio and xLio are the activity coecient and mole fraction in the feed
liquid, yio is the mole fraction in the permeant vapor, Psat
io is the vapor
pressure of the pure component i, and Pil is the total pressure in the
permeate side. P is the membrane permeability (molm/m2hbar). For
an unknown membrane thickness, l (m), the membrane permeance,
P/l (mol/m2hbar), also known as the component ux normalized
driving force, can be used.
The membrane performance in terms of enrichment factor is
dened as the ratio of concentration in the permeate to the feed:

i =

Wi ,p
Wi ,f

(4)

(3)

where Wi,p and Wi,f are the weight fractions of component i in


permeate and feed, respectively. In the recovery of aroma compounds,
the solvent enrichment factor is close to unity. Therefore, the
enrichment factors of aroma can be assumed to be equal to the
corresponding separation factors, the ratio between permeability or
permeance of components i and j.19 The membrane ux and
permeance were given in molar terms to allow direct result
comparison between PV and the larger body of gas permeation.20
The temperature dependence of the permeance was then analyzed
using an Arrhenius equation (eq 4):21
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Table 2. Characterization of Natural Leaves and Articial Membrane Using DSLR and SEMa

SEM gure of cherry laurel was adapted from the work of Koch and Ensikat.3

reported that the three hydrophobicities of the Homo sapiens


(human skin) with contact angles of 100 18 (underarm skin
washed with water), 76 20 (underarm skin washed with
soap), and 104 16 (underarm skin washed with ethanol) are
potentially comparable to this synthesized membrane.
3.2.2. FTIR Studies: Natural Leaves versus Articial
Membrane. Measured FTIR spectra for the cherry laurel,
lotus leaf, taro leaf, and the M1 membrane are shown in Figure
3, indicating spectrum similarities across all natural leaves. On
the contrary, their natural surfaces micro- and nanostructures
are observed to be dissimilar when compared in Table 2. Guo
and Liu27 obtained similar ndings when evaluating these leaves
using X-ray photoelectron spectroscopy (XPS) against FTIR
measurements.
It can be seen from Figure 2 that all ngerprints of leaves and
membranes are nearly identical. The broad band ranging from

Although the variation of the demixing rate for dierent


polymer concentrations cannot be accurately determined,
observations of SEM images have proven that an increased
polymer content increases the thickness of the dense top layer
(Figure 1df). This then decreases the porosity of the
membrane and the interconnectivity of the pores.19 For
biological epicuticular wax, the construction of various crystals
geometry in shape (i.e., massive crusts, granules, plates,
platelets, laments, rods, and tubules with hollow center) is
strongly dependent on the crystal habits.3 Recrystallization of
isolated wax from organic solutions shows that the wax
morphologies originate from a self-assembly process. It is a
general process of structuring in biological system, in which
atoms, molecules, particles, or other building units interact and
self-organize to form well-dened structure.24 Although only
several plants are sampled and studied in this investigation, the
vastly available literature on biomimetics enables our results to
be easily compared to other plant samples.
3.2. Characterization. 3.2.1. Wettability: From Natural
Models to Synthetic Membranes. Images of the three natural
models (i.e., Lotus, Taro, and Cherry laurel leaf) and a
synthetic membrane (M1) taken at macro to micro scales are
shown in Table 2. The replication of the hydrophobic
characteristic similar to those of a natural plant leaf was
performed using a combination of coating and curing
procedures. Results show that PDMS facilitates replication of
complex topographic patterns, besides exhibiting a at-surface
water contact angle of 115 2. This signies nearly 50
increment in comparison to the reference PPSU membranes
contact angle, which was also observed by Tserapi et al. and
Cortese et al.25,26 The higher 161 and 159 2 water contact
angles for lotus and taro leaf, respectively, are mainly
contributed by the existence of the combined micro- and
nanostructure at their surfaces (Table 2), as was also observed
by related researchers.2,2730 This then minimizes the total
surface contact area for other materials as well.27 However,
these properties are not found in cherry laurel and the synthetic
PDMS/PPSU membrane, as can be deduced from the SEM
images in Table 2. This is in agreement with the ndings by
Wosten et al.31 They discovered that the contact angle of cherry
laurel is between 65 and 81, which is lower as compared to
the synthetic PDMS/PPSU membrane. They have also

Figure 2. The surface functional group analysis of the hydrophobic


wax-like materials by means of using FTIR.

3200 to 3600 cm1 is attributed to OH groups aected by


hydrogen bonding. The strong peak at 1653 cm1 is due to
CO stretching from the carboxylate group, while bands 2852
and 2922 are assigned to CH stretching vibration of CH,
CH2, and CH3 groups. Comparison between the leaves and
membranes indicates the absence of three signicant peaks in
the synthetic membranes spectra: 1653, 2852, and 2922 cm1.
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However, the relation between surface functional groups and


hydrophobicity in this study is yet to be fully comprehended.
This is because in Figure 2, the leaf of cherry laurel indicates a
trend similar to that of the other two superhydrophobic leaves.
Nevertheless, the contact angle analysis indicates that the
hydrophobicity of cherry laurel is much less than that of the
PDMS/PPSU membrane. Thus, it is concluded that the FTIR
analysis may enable the study of supercial functionality but is
unable to distinguish up to the level of molecular speciation.
3.3. PV Using Biologically Inspired Membrane.
3.3.1. Permeation of Aroma Compounds. It was found that
among the seven volatile compounds, only ethyl acetate
permeated signicantly. While other compounds were still
detected on the permeate side, quantitative analyses using HSGC indicated that their permeation was either signicantly
lower or did not take place at all, as can be seen from Table 3.

Figure 3. Variation of PV ux for dierent feed concentrations and


feed temperatures for the M1 membrane.

Table 3. Eect of Temperature on Permeating Components


in PV Using MR-1 and 1 ppm HAc in Feed Solutiona
avg sep factor MR-1 in 1 ppm HAc
temp ( C)

25
35
45

4.7
6.1
4.3

0
0
0

0.3
0
1.16

0
0
0

0
0
0

2.13
0
0

0
0
0

1 = ethyl acetate, 2 = 3-methylbutyraldehyde, 3 = 2,3-pentanedione, 4


= hexanal, 5 = 1-penten-3-ol, 6 = 1-octen-3-ol, 7 = benzaldehyde.

Thus, our further discussions will focus on the permeation of


ethyl acetate because hexanal, 1-penten-3-ol, and 1-octen-3-ol
investigated in this work are insoluble. This property may be
advantageous to the permeating components, because a loose
hydrogen bond between solvent and solute facilitates surface
boundary contact between the feed mixture and the membrane.
The hydrophobic surface of the synthesized membrane repels
water molecules, but may be attracted to other organic
materials by chemical interaction at the boundary layer.
Moreover, when the organic compounds are totally insoluble
in water, the likelihood of chemical transport onto the
hydrophobic surface of the membrane is reduced. This
increases the possibility that the water-insoluble aroma
compounds remain on top of the liquid layer in the feed
tank. Another reason that restricts the component permeation
through the membrane is due to the high boiling point of the
solutes. Increasing the feed temperature from 25 to 45 C gives
no signicant eect on the solubility, although, in general, a
better permeation rate is to be expected.
3.3.2. Eect of Operating Conditions on Pervaporation
Performance. Permeation through the synthesized membranes
was then studied using PV, by analyzing the total ux as a
function of feed temperature for dierent feed concentrations,
as presented in Figure 3. No signicant permeation of ethyl
acetate can be observed when using thicker PDMS layers for
M2 and M3. Thus, only the permeation behavior through M1
membrane matrix is discussed here. As can be seen, the total
ux increases with increase of feed temperature and
concentration. For all examined temperatures, the highest
total ux was achieved at 45 C in 10 ppm solution, while the
lowest was obtained at 25 C using 1 ppm feed concentration.
The behavior of the bioinspired synthetic PDMS/PPSU
membranes showed selectivity to only one particular
compound, that is, ethyl acetate. In Figures 4 and 5, the eect

Figure 4. Permeance of ethyl acetate as a function of feed


concentration obtained in PV using M1 for dierent temperatures.

Figure 5. Enrichment factor of ethyl acetate for dierent temperatures


and feed concentrations.

of feed concentration and temperature for the permeance of


ethyl acetate in multicomponent system is presented. From
Figure 4, it is deduced that the permeance of ethyl acetate
decreases with concentration and temperature, and reaches a
constant plateau value when concentrations are higher than 5
ppm. Meanwhile, in Figure 5, it can be seen that the
enrichment factor decreases with an increasing feed concentration. This is contributed by the presence of other organic
compounds, which aects membrane selectivity due to the
interactions between dierent aroma compounds.32 To further
investigate the permeance behavior of the compounds, pure
water and binary mixture containing water and ethyl acetate
were also investigated. The permeation of pure water through
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the PDMS/PPSU membrane was determined using eq 2. For


pure water, x = y = 1, and thus eq 2 reduces to J = P/l Pperm.
Hence, pure water permeances were determined from the slope
of the plot between uxes against reciprocal permeate pressure
(driving force), 2.72 mol m2 h1 bar1. The uxes of water in a
single and binary mixture are illustrated in Figure 6. It is shown

Figure 7. Eect of temperature on ethyl acetate permeance for


dierent feed concentrations.

a decreasing permeability with the increase in temperature.


Because EP/l has been determined and the enthalpy of
vaporization of ethyl acetate is known, EJ can easily be
calculated: EJ = EP/l +Hv.21 Hence, EJ = 27.13 kJ/mol.
Alternatively, EJ can be evaluated from the plot of ln J versus 1/
T.

Figure 6. Permeation ux of water in binary mixtures waterethyl


acetate at dierent operating conditions.

4. CONCLUSION
A plant cuticle is a membrane that covers primarily aboveground plants such as leaves, owers, stems, and fruits. The
superimposed waxes onto the cuticle are called epicuticular
waxes. This natural membrane is very ecient as a transport
barrier. Thus, a biologically inspired membrane was engineered,
synthesized, and investigated for application in the recovery of
aroma compounds using pervaporation. The synthesized
hydrophobic PDMS/PPSU was characterized and compared
against three selected natural leaves, and it was observed that
the synthesized membrane was comparable to cherry laurel leaf.
Evaluating PDMS-coated PPSU membrane against the uncoated membrane indicated a 50 contact angle improvement,
besides resembling the complex topography patterns of the
biological leaves. As was proven in previous investigations,
surface structure is not an obligatory condition to enable
hydrophobicity. Instead, the wax-like material that covers the
surface has enabled this feature. Among the seven aroma
compounds used, only ethyl acetate is able to permeate through
the synthesized hydrophobic membrane matrix in pervaporation due to its high hydrophobic property. This will then
improve the selective permeation of less hydrophobic
compounds through the interaction with dierent aroma
species, consequently enabling the developed membranes to
be applicable to a wider variety of chemicals.

that when more than one component tries to cross the barrier,
the resistance of penetration increases, resulting in lower
permeation. It is hypothesized that besides permeation of single
component, there exists the possibility of couple molecule
(water and ethyl acetate) permeation, which could be the
reason for delay in penetration through the membrane matrix
as can be seen in Figure 6.
The decrease of water ux in the permeate side of the
membrane when the feed concentration is 1 ppm of ethyl
acetate is expected due to the higher solubility of ethyl acetate
in the solution. The hydrogen bond between both water and
ethyl acetate has made the couple molecule more hydrophilic,
which easily repels by the hydrophobic membrane. As the
concentration of ethyl acetate increases in the feed stream, the
solubility of the solute decreases, resulting in only water
molecule permeating across the barrier.
Considering the importance of feed temperature in PV, its
eect on the biologically inspired membrane was studied.
Burggraaf33 has related both of the activated microscopic
models based on the conguration and surface diusion with
temperature dependence in the classical adsorptiondiusion
model as shown in eq 5:
EJ = Hs + E D + H vap

(5)

where Hvap is the heat of vaporization of the permeant (ethyl


acetate) through the membrane (32.33 kJ/mol). The term
(Hs + ED) is the activation energy of permeance, EP/l (kJ/
mol), and when the permeate pressure is suciently low; thus
eq 5 can be written as follows:
EJ = EP / l + H vap

AUTHOR INFORMATION

Corresponding Author

*E-mail: nora.jullok@cit.kuleuven.be.
Notes

The authors declare no competing nancial interest.

(6)

ACKNOWLEDGMENTS
Financial support from the Malaysian Ministry of Higher
Education (MOHE) is gratefully acknowledged.

The ethyl acetate permeance dependence on temperature is


presented in the logarithmic plot versus the reciprocal
temperature (1/T) shown in Figure 7. The activation energy,
EP/l, for ethyl acetate in this particular application was 5.2 kJ/
mol. Positive activation energy indicates that the permeation
ux increases with temperature increase. On the contrary, the
activation energy obtained in Figure 7 is negative, thus implying

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dx.doi.org/10.1021/la3050253 | Langmuir 2013, 29, 15101516