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Article

A Bilayered Structure Comprising of Functionalized Carbon

Nanotubes for Desalination by Membrane Distillation
Madhuleena Bhadra, Sagar Roy, and Somenath Mitra
ACS Appl. Mater. Interfaces, Just Accepted Manuscript DOI: 10.1021/acsami.6b05644 Publication Date (Web): 07 Jul 2016
Downloaded from http://pubs.acs.org on July 13, 2016

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A bilayer membrane structure containing functionalized carbon nanotubes of different polarity for enhanced
desalination performance in membrane distillation.
316x271mm (96 x 96 DPI)

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A Bilayered Structure Comprising of Functionalized Carbon

Nanotubes for Desalination by Membrane Distillation
Madhuleena Bhadra, Sagar Roy, Somenath Mitra*
Department of Chemistry and Environmental Science, New Jersey Institute of
Technology, Newark, NJ 07102, USA
* Corresponding author. E-mail: mitra@njit.edu Tel.: 001 (973) 5965611

ABSTRACT
The development of a novel carbon nanotube (CNTs) immobilized membrane
comprising of a double layered structure is presented for water desalination by membrane
distillation. The bilayer structure comprises of CNTs functionalized with a hydrophobic
octadecyl amine group on the feed side, and carboxylated CNTs on the permeate side.
The latter is more hydrophilic. The hydrophobic CNTs provide higher water vapor
permeation while the hydrophilic CNTs facilitated the condensation of the water vapor.
Together these led to superior performance, and flux in a direct contact membrane
distillation mode was found to be as high as 121 kg/m2h at 80oC. The bilayer membrane
represented an enhancement of 70% over the unmodified membrane, and 37% over a
membrane which had a monolayer structure where only the feed side was CNT modified.

Keywords: Functionalized CNTs, Water vapor flux, PTFE, DCMD, Mass transfer

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INTRODUCTION
Membrane distillation (MD) has received widespread attention due to the
escalating demands for desalination as a means to generate freshwater1-3. It is an efcient
membrane process where the theoretical salt rejection reaches 100% and it can also be
carried out using low-grade heat sources, solar and geothermal energy4-9. MD is
thermally driven where water vapor is permeated through a porous hydrophobic
membrane that does not allow salt water to pass through and various MD modes where
the permeate collection is done by water, gas or vacuum have been explored.
Various hydrophobic membrane materials such as polytetrauoroethylene,
polypropylene, and polyvinylidene difluoride have been used as MD membranes, and
surface modification via coating, grafting, and blending with macromolecules have been
reported 10-21. For example, the surface of polyethersulfone membranes have been
modified via silanol chemistry and several commercial polyethylene membranes have
been thermally altered to enhance MD performance19-20. Processing conditions and
additives have been altered to enhance membrane performance with the aim of
maximizing flux while minimizing conductive heat loss22. Incorporation of
nanomaterials with various functionalities can be used to modify overall membrane
characteristics for flux enhancement23-30.
Membranes based on carbon nanotubes (CNTs) have significantly advanced the
desalination field by enhancing ux and lowering biofouling potential. CNTs have high
surface area, thermal stability, hydrophobicity, fast adsorption-desorption properties,
and offer the ease of chemical modification 31-35. They have been effective in the
fabrication of membranes for reverse osmosis36-38, ultrafiltration39-41 and nanofiltration31,

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42-44

. We have reported that the physico-chemical interaction between the solutes and the

membrane can be dramatically altered by immobilizing CNTs on a membrane surface.

The resulting membrane referred to as carbon nanotube immobilized membrane (CNIM)
has been shown to enhance pure water permeation in MD 25, 33, 45.
As of now, CNT immobilization has been only on the feed side of the membrane
to facilitate water vapor sorption as well as rapid mass transfer10, 24, 28, 45. It is conceivable
that CNTs can also be immobilized on the permeate side to rapidly condense water
vapors that will lead to higher overall flux22, 46. There have been efforts to increase
turbulence and consequently flux by using spacers on the permeate side, but flux
enhancement by surface modification of the permeate side is yet to be reported47-49.
The objective of this paper is to develop a bilayer structure with different CNTs
on the two sides of the membrane; namely hydrophobic CNTs on the feed side and
hydrophilic CNTs on the permeate side. The hydrophobic CNTs would provide higher
water vapor permeation while the hydrophilic CNTs will provide surface for the
condensation of the water vapor. Together these would lead to superior performance.

EXPERIMENTAL
Materials and methods
The schematic diagram of experimental system is shown in Figure 1. The
membrane module used in the DCMD set up was a flat, disk-shaped module with 4.3 cm
ID and an active contact area of 14.5 cm2. The membrane comprised of a
polytetrafluoroethylene (PTFE) laminate supported on polypropylene fabric (Goretex,
0.45 m pore size, 74% porosity). The salt water feed used in these experiments

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contained 15000-34000 ppm NaCl solutions (Sigma Aldrich). The collecting fluid on the
permeate side was deionized water. Peristaltic pumps (Cole Parmer, model 7518-60)
were used to circulate water through the membrane module. The hot brine was circulated
on one side of the membrane and the cold distilled water was on the other side. The
permeate was collected in a tank while the feed was recycled. The materials of
construction for the tubings and connectors (Cole Parmer) were Viton and PFA. The
concentration of the salt in the feed and the permeate were measured using a Jenway
Electrode Conductivity Meter (Model 4310).
Triplicate MD experiments, each lasting 2 hours were carried out to study the
permeation process. The coefficient of variation of the replicates were found to be less
than 1%. The hydrophobicity of the membrane was studied based on contact angle
measurements. A micro syringe pump (Hamilton 0-100 l) was used to generate 2 l
droplets for contact angle measurement. Five measurements were made and the average
was reported.
Multiwalled carbon nanotubes (CNTs) were purchased from Cheap Tubes, Inc.,
Brattleboro, VT, USA. This was used to synthesize hydrophilic carboxylated (CNTCOOH) as well as hydrophobic octadecylamine functionalized CNTs (CNT-ODA). CNT
carboxylation was followed by amidation with ODA in a Microwave Reactor (CEM
Mars). The procedures have been reported before50-51. The CNT-ODA and CNT-COOH
have different polarity to the point that the former is easily miscible in organic solvents,
does not disperse in water while the latter is water dispersible50-51.
Two types of CNIMs were fabricated. The first contained CNT-ODA on the feed
side and the CNT-COOH on the permeate side (bilayer membrane). The other contained

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CNT-ODA on the feed side and no CNT on the permeate side (monolayer membrane).
Both membranes were prepared on the Goretex PTFE membrane mentioned before.
Membrane preparation was carried out as follows. 10 mg of CNTs were dispersed in a
solution that contained 5 mg of Teflon powder in 10 ml of Fluorinert FC-40 (Sigma
Aldrich). This was sonicated for three hours. The CNT-polymer dispersion was coated on
the original membrane as reported before25, 33, 45. The excess PTFE was removed by
flushing with Fluorinert FC-40.
The CNIMs were studied using a scanning electron microscopy (Model LEO
1530, Carl Zeiss) by coating 0.5 cm long membrane pieces with carbon. Raman spectra
were measured using a Thermo Electron Raman spectrometer, thermal gravitational
analysis (TGA) was performed using a Perkin Elmer Pyris 7 TGA instrument and gas
permeation test was carried out to measure surface porosity over the effective pore length
using a method published before 25, 52.

RESULT AND DISCUSSIONS

SEM of the unmodified PTFE membrane and the bilayer-functionalized membranes
are shown in Figures 2a-d. Figure 2a and b illustrates the top and bottom surfaces of the
unmodified membrane. The change in morphology in Figure 2c and d clearly indicates
the incorporation of the functionalized CNTs of the top and the bottom surfaces. As seen
from Figure 2c and d, the functionalized CNTs were well immobilized in the membrane.
Raman spectra of the unmodified PTFE membrane and bilayer membrane are
shown in Figure 3a and b, respectively. Both spectra showed dominant Raman bands
corresponding to PTFE at 291, 386, 774, 1329, 1362 cm-1 ; these were attributed CF2

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wagging, twisting, symmetric stretch, asymmetric stretch and CF stretching

respectively53. The PTFE-ODA spectra shows peaks at 1586 cm-1 and 2611 cm-1 which
were attributed to the amine group and the secondary amine connected to the
octadecylamine chain of the CNT-ODA respectively54. The Raman bands corresponding
to the polypropylene backing were observed at 2881 and 2951 cm-153. Additional peaks
were observed which confirmed the inclusion of CNT-COOH. The peak at 1581 cm-1 was
attributed to CNT backbone, peak at 1600 cm-1 was due to C=O stretch and peak at 2800
cm-1 could be attributed to OH stretch. The Raman bands at 1350 and 1580 cm1 were
assigned to the D and G-bands of CNTs55. The peak ~2600 cm-1 was from the dispersive
G band for sp2 carbon nanotubes56.
TGA was used to study the thermal stability of bilayer membrane. The membranes
in MD contact high temperature brine solution and their stability is an important
parameter. The initial weight loss in Figure 4 was ascribed to the decomposition of
organic functional groups of CNTs. The weight loss in the range of 250oC to 325oC was
due to the decomposition of support PP layer, and finally at around 470oC, the PTFE
began to decompose. It is evident that the thermal stability of the membrane increased
with CNT incorporation. This is similar to what has been reported previously where the
enhanced stability has been attributed to the adsorption of free radicals generated during
polymer degradation as well as the increase in activation energy in presence of
nanofillers.57
The nominal pore size of the original membrane was found to be 0.03 m,
porosity was 72% and the effective porosity over pore length (/Lp) was found to be
3.09 106. Since the amount of CNTs was so small, these parameters did not alter

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significantly during the bilayer formation.

Membrane hydrophobicity was measured via contact angle measurements using
deionized water. The relative standard deviation of five repeat measurements was less
than 1%. The unmodified membrane in Figure 5a showed a contact angle of 110o,
whereas in the presence of the CNT-ODA showed a contact angle of 125o (Figure 5b),
indicating an increase in hydrophobicity. On the other hand, contact angle measurement
after immobilization with CNT-COOH on the permeate side (Figure 5c) showed a
decrease to 85o from 94oC. This implied that the CNT-COOH had enhanced the
hydrophilicity in the permeate side of the membrane.

DCMD performances:
The water vapor flux, Jw, is measured as:
Jw =

wp
tA

(1)

where, wp is the mass of permeated water in time t through surface area A. Also, Jw can
be denoted as:
J w = k ( Pf Pp )

(2)

where k is the mass transfer coefficient, and Pf and PP are the feed and permeate side
water vapor concentrations and the overall mass transfer coefficient was computed as:

k=

Jw
Pf Pp

(3)

In the DCMD process, the operating temperature is an important parameter

because the vapor pressure gradient increases exponentially with temperature. The effect
of temperature on water vapor flux in the three membranes (at feed flow rate 212 ml min-

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and distillate flow rate of 164 ml min-1) is shown in Figure 6a. In all cases the permeate

flux increased with temperature because it led to a higher vapor pressure gradient. Flux
reached as high as 126 kg/m2h for the bilayer membrane at a temperature of 84oC as
compared to 112 kg/m2h for the monolayer. The bilayer membrane consistently showed
higher flux at all temperatures among all three membranes. At a temperature of 60oC and
feed flow rate of 270 ml min-1, the bilayer membrane showed a flux of 79 kg/m2h. This
was higher than what the unmodified PTFE showed (74 kg/m2h) at 84oC. In both mono
and bilayer membranes, the CNT-ODA on the feed side provided additional pathways for
water permeation whereas the hydrophilic CNT-COOH on the permeate side facilitated
the condensation of permeated water vapor. Together these enhanced overall flux in the
bilayer structure, which is 5-10 times higher than what is reported at the same
temperature range 58-61.
Figure 6b illustrates the performance of the bilayer CNIM as a function of brine
flow rate in the range of 36 to 270 ml min-1 while the permeate side flow rate was
constant at 164 ml min-1. The feed temperature was 80oC. Results indicate that the ux
increased with flow rate and reached 126 kg/m2h at a flow rate of 270 ml min-1. This was
due to the reduction in boundary layer and temperature polarization at higher flow rates.
The effect of salt concentration on flux was investigated at an inlet temperature of
80o C, feed flow rate of 212 ml min-1 and permeate flow rate of 164 ml min-1. This is
shown in Figure 6c. In NaCl concentration range between 5000-34000 ppm, the average
flux declined for the unmodified PTFE. This was attributed to the fact that high salt
concentration led to the development of a more significant boundary layer that impeded
mass transfer. On the other hand, the both monolayer and bilayer membranes showed

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only minimal reduction in flux because the presence of CNTs appeared to prevent
boundary layer expansion even at high salt concentration. This could be attributed to the
nanostructured surface morphology in presence of the CNTs and is in line with
previously published data25-26, 33, 45, 62.
Table 1 shows the mass transfer coefficients at different temperatures. The
coefficients increased with temperature for all three membranes. It is also evident from
the table that the bilayer membrane showed the highest mass transfer coefficients of the
three membranes. Very small amounts of CNTs were used in the bilayer membrane,
which did not offer any additional mass transfer resistance for water vapor permeation.
Additionally, CNTs are known to exhibit rapid sorption/desorption properties for water
vapors which has been demonstrated to increases the overall vapor transport62-63.
Enhancement as high as 61% was observed in case of the bilayer membrane compared to
the original PTFE membrane. The inclusion of the CNT-ODA on the feed side led to
enhanced hydrophobicity and favorable interactions with the water vapor molecules and
CNT-COOH led to faster and efficient removal of vapor on the permeate side. These led
to an overall higher mass transfer coefficient.

Stability and Salt Breakthrough:

Salt breakthrough was not observed in any of the MD experiments. The permeate
from all experiments showed very low conductivity (2.6-3.0 S/cm at 20oC) which was
equivalent to over 99.9% purity. The ability to retain the CNT coating on both surfaces
was tested over long periods of operation. MD was carried out continuously for 120 days
during which the water vapor flux did not decline for monolayer as well as the bilayer

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membranes these are shown in Figure 7. The permeate side water was tested using
ICPMS and it didnt show any presence of CNTs in the permeate side water ensuring the
quality of water.

Proposed Mechanism of water vapor permeation through bilayered membrane:

The proposed mechanism in the bilayer membrane is shown in Figure 8. A
significantly higher flux was observed with the inclusion of CNT-ODA. Octadecylamine
group consists of carbonyl, amine as well as octadecyl group as long chains. The
carbonyl and amine groups initiated polar-polar interactions with the water vapor
molecule thereby enhancing its adsorption. On the other hand, the nonpolar
CH2(CH2)16CH3 group provided some repulsion to the water vapor and led to efficient
desorption. The simultaneous presence of hydrophobic and hydrophilic groups on the
CNTs led to the hopping of water vapor molecules along the CNTs. At the same time the
CNT-ODA was hydrophobic enough to repel liquid water to eliminate salt intrusion35.
The inclusion of hydrophilic CNT-COOH in the bilayer membrane enhanced
hydrophilicity and allowed water vapors to interact with the COOH groups33, 45. It is
conceivable that the CNT-COOH served as sites for vapor-liquid interactions leading to
rapid removal of permeated water. Overall, the simultaneous presence of the top
hydrophobic and the bottom hydrophilic CNTs led to specific interactions with pre and
post permeated water vapor molecules. Additionally, the inclusion of high thermal
conductivity CNTs on the membrane surface reduced temperature polarization on both
sides of the membrane. At the same time since the CNTs did not completely fill the pore
structure, it did not increase overall thermal conductivity to enhance heat loss.

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CONCLUSIONS:
CNT-ODA and CNT-COOH dispersions were incorporated on the feed and
permeate sides of a bilayer PTFE membrane to enhance flux in DCMD. The desalination
performance was compared with the original membrane and a monolayer membrane
comprising of CNT-ODA on the feed side. The flux was consistently higher in the bilayer
membrane and reached as high as 126 kg/m2hr. The bilayer membrane showed the
highest mass transfer coefficients of all the membranes studied here. It was also stable
over long periods of operation. It is evident from the results presented here that the
incorporation of two different functionalized CNTs on the two membrane surfaces is
effective in enhancing membrane performance.

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Table 1: Mass transfer coefficient of various membranes as a function of temperatures:

Mass transfer coefficient (kg/m2.sec-1.Pa)
Temperature(oC)
Unmodified Membrane

Monolayer

Bilayer

60

1.01E-06

1.2E-06

1.5E-06

70

1.1E-06

1.3E-06

1.6E-06

80

1.1E-06

1.5E-06

1.8E-06

85

1.2E-06

1.7E-06

1.9E-06

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Figure Captions:
Figure 1. Schematic representation of experimental setup.
Figure 2. Figure 2. Scanning electron micrographs of (a) top surface (feed side), (b)
bottom surface (permeate side) of unmodified membrane, (c) top surface (feed
side), (d) bottom surface (permeate side) of modified PTFE membrane (inset:
CNTs on the support layer).
Figure 3. (a) Raman analysis spectra of the top surface and (b) the bottom surface of
unmodified and bilayer membranes.
Figure 4. TGA curve of Unmodified and Bilayer membrane.
Figure 5. The contact angle and the photograph of the water drop on (a) unmodified
membrane top surface, (b) bilayer membrane top surface, (c) unmodified
membrane bottom surface, and (d) bilayer membrane bottom surface.
Figure 6. Figure 6 (a) Effect of temperature on permeate flux; (b) Effect of flow rate on
permeate flux at 80oC; (c) Effect of feed concentration on permeate flux at
80oC.
Figure 7. Long term stability of the membranes at 70oC feed temperature and 3500 ppm
salt concentration.
Figure 8. Schematic presentation of proposed mechanism.

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Figure1. Schematic representation of experimental setup.

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Figure 2. Scanning electron micrographs of (a) top surface (feed side), (b) bottom surface
(permeate side) of unmodified membrane, (c) top surface (feed side), (d) bottom surface
(permeate side) of modified PTFE membrane (inset: CNTs on the support layer).

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Figure 3: (a) Raman analysis spectra of the top surface and (b) the bottom surface of
unmodified and bilayer membranes.

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Figure 4. TGA curve of Unmodified and Bilayer membrane

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Figure 5. The contact angle and the photograph of the water drop on (a) unmodified
membrane top surface, (b) bilayer membrane top surface, (c) unmodified membrane
bottom surface, and (d) bilayer membrane bottom surface.

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(a)

(b)

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(c)

Figure 6 (a) Effect of temperature on permeate flux; (b) Effect of flow rate on permeate
flux at 80oC; (c) Effect of feed concentration on permeate flux at 80oC.

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Figure 7. Long term stability of the membranes at 70oC feed temperature and 4000 ppm
salt concentration.

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HO

Water vapor
transport
R

Condensation
on
hydrophilic
C
O OH
CNTs

HN O
C
R

HN

Cold
Distillate

Hot
Brine

Membrane
Salt
water

Water
vapor

CNTs

Pure water

Figure 8. Schematic presentation of proposed mechanism

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