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Materials Chemistry
Cite this: J. Mater. Chem., 2011, 21, 7507
www.rsc.org/materials HIGHLIGHT
Ultra-fine cellulose nanofibers: new nano-scale
materials for water purification
Hongyang Ma, Christian Burger, Benjamin S. Hsiao* and Benjamin Chu*
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DOI: 10.1039/c0jm04308g

The major challenges in membrane technology for water filtration are the development of
new materials (e.g. high durability, low cost and low environmental concerns) and new
structures (e.g. directed water channels) that can produce high permeation flux (thus low
energy input) while maintaining a high selectivity or rejection rate. This highlight discusses the
utilization of ultra-fine cellulose nanofibers (UCN, diameter 5--10 nm), made by TEMPO/NaBr/
NaClO oxidation of natural cellulose (e.g. wood pulp), in different nanofibrous composite
formats that can meet this challenge for microfiltration (MF) and ultrafiltration (UF)
applications. The unique features of ultra-fine cellulose nanofibers include small diameter, high
surface-to-volume ratio, easy surface functionality, good mechanical properties and good
chemical resistance. The electrospun nanofibrous scaffolds with fine pore size defined by the
fiber diameter could be used to remove waterborne bacteria at two to three times higher flux
when compared to that of commercial MF membranes (e.g., Millipore GS9035). When UCN
were used as a functionalized adsorbent infused in the asymmetric two-layered non-woven
fibrous format, the membranes exhibited a high ability to remove bacteria (by size exclusion)
and viruses (by adsorption) simultaneously. When UCN were used as the barrier layer in an
asymmetric three-layered non-woven fibrous format containing fibers of different diameters
(from 5 nm to 20 mm), the membranes exhibited a two- to ten-fold increase in permeation flux
over commercial membranes for ultrafiltration of oil and water emulsions (e.g., for purification
of bilge water in ships or industrially produced water).

1. Introduction
Due to the rapid population growth,
mounting energy concerns and increasing
environmental crisis, the development of
new and more energy efficient membranes
for water purification is becoming an
important task for the materials commu-
nity.1--3 The essential characteristics of
next generation membranes should be
high efficiency, high durability, low
operating pressure (low energy), low cost,
and the ability to fabricate using envi-
ronmentally friendly processes.4--6
In the current technology, the use of thin-
film composite (TFC) membranes has been
proven as a robust and efficient way to
Department of Chemistry, Stony Brook
University, Stony BrookNY, 11794-3400, USA.
E-mail: bhsiao@notes.cc.sunysb.edu; bchu@
notes.cc.sunysb.edu; Fax: +1 (631) 632-6518;
Tel: +1 (631) 632-7793; +1 (631) 632-7928
purify water.7,8 TFC membranes typically
consist of two or three layers, where the
bottom layer is a tough, non-woven fibrous
material (e.g., non-woven mat of poly-
ethylene terephthalate, PET) providing
mechanical strength to support upper layer
(s) with desired barrier or selective proper-
ties. Strategies for increasing the filtration
efficiency are commonly associated with
improvements in the top barrier layer or/
and the mid-layer support. For example,
conventional barrier layers produced by
phase inversion methods in ultrafiltration
(UF) membranes have a lower porosity
(approximately 50% bulk porosity and
20% surface porosity for the barrier).9,10
The cavities in such barriers are asymmetric
and disconnected, thereby increasing the
resistance to water permeation as well as
increasing the fouling of feeding
substances. The filtration efficiency (i.e.,
permeation flux) of TFC membranes can
be improved by adopting a different struc-
ture, consisting of asymmetric layers of
non-woven fibers with different diameters,
which is the purpose as demonstrated in
this highlight. In this structure, the top
barrier layer as well as the mid-layer
support can have high porosity and inter-
connected pores, leading to high perme-
ation flux for both microfiltration (MF)
and UF applications.10--15
For the top barrier layer in TFC
membranes, the choice of polymer mate-
rials has thus far been limited to poly-
acrylonitrile (PAN), polysulfone (PSU),
polyethersulfone (PES), polyvinylidene
fluoride (PVDF), cellulose acetate (CA),
and cross-linked polyamide (PA, prepared
by interfacial polymerization (IP)).3--5,7 All
the aforementioned materials have their
advantages as well as limitations with re-
gards to applications for water filtration.
For example, PAN, PSU, PES, and PVDF,

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typically used for fabrication of MF and
UF membranes, have good chemical
resistance, good mechanical properties and
are cost-efficient. However, their hydro-
phobic nature can dramatically decrease
the water permeability during filtration of
wastewater due to the tendency of oil,
particle or biomacromolecule fouling.10,15
Cellulose acetate is pH sensitive and can
only be used within a narrow pH range,
while cross-linked PA has a low tolerance
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for chlorine.16,17 Often, volatile and toxic
solvents have to be used for the utilization
of these materials for membrane fabrica-
tion, causing environmental concerns.
While some new materials exhibiting
excellent properties for water filtration
have been developed,18--22 their complex
preparation process, high cost, and envi-
ronmental concerns make them difficult to
implement on an industrial scale.
All the problems mentioned above
should be carefully addressed for the
development of next generation
membranes with high-flux, high retention,
energy-saving, and durability.23,24 In this
highlight, we demonstrate that the use of
ultra-fine cellulose nanofibers allowed us
to reach this goal, where the different
membrane formats have exhibited very
high-flux MF and UF performance.25--27
2. Correlations between
membrane pore size and fiber
diameter in a non-woven
structure
The new nanofibrous membranes with high
filtration efficiency were designed based on
the principle that the pore size distribution
of a non-woven layer structure is correlated
with the fiber diameter and the bulk
porosity (i.e., the volume fraction of the
void phase). For example, in electrospun
nanofibrous scaffolds, the mean fiber
diameter typically ranges from 50 nm to
over 1 mm. The bulk porosity of electrospun
scaffolds is typically around 75--85%,
which can be compacted further by calen-
daring or pressing for practical filtration
use, thus lowering the porosity to around
65%. In this porosity range
(i.e., 65%--85%), electrospun PAN and PES
non-woven nanofibrous scaffolds (with
layer thicknesses between 10 and 100 mm)
can be used as models to correlate the
membrane pore size and fiber diameter. It
was discovered that, when the scaffold
7508 | J. Mater. Chem., 2011, 21, 7507--7510
layer thickness was above a certain
threshold value (of about 50 mm), both
mean and maximum pore sizes (determined
by capillary flow porometry) reached
a plateau. Fig. 1 illustrates the correlations
between the maximum pore size, mean pore
size (also determined by SEM image anal-
ysis of some previously published data28--31)
and fiber diameter in a non-woven layer of
sufficient thickness. It was found that the
mean and maximum pore size can be scaled
linearly with the fiber diameter, indepen-
dent of the polymer material. The mean
pore size was found to be about 3
1 times
the mean fiber diameter, and the maximum
pore size was about 10
2 times the mean
fiber diameter.
To guide our understanding of the
membrane properties in a non-woven struc-
ture, 3D simulated non-woven web models,
having different fiber diameters, were created
to illustrate the relationship between the fiber
diameter and the pore size. Fig. 2 shows
three non-woven models at a constant
porosity (i.e., 80%) in a fixed volume with
a relative fiber diameter ratio of 1 : 3 : 10,
generated using a random arrangement of
cylinders which were fused together and
visualized using the cylinder blob model
(POV-Ray ray-tracing software32).
Assuming a monodisperse fiber diam-
eter, a random placement of fiber
segments in the reference volume, and the
absence of felting (i.e., 3D entanglement,
which is a valid assumption for electro-
spun fibers and a good approximation for
collapsed fiber suspensions), as well as
neglecting details on how fiber segments
touching each other are fused together, the
3D non-woven structure can be fully
Fig. 1 Correlations between maximum pore
size, mean pore size and mean fiber diameter in
nanofibrous scaffolds, fabricated by means of
electrospinning technology and using different
polymeric materials. Data points were ob-
tained from capillary flow porometry and SEM
of PAN and PES scaffolds electrospun for this
study, as well as image analysis of previously
published SEM images.25,28--31
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defined by only two parameters, the fiber
diameter and the bulk porosity, and has
no other adjustable parameters. The exact
definition of a ‘‘pore size’’ is non-trivial for
the type of scaffold sketched in Fig. 2, but
these figures provide some intuitive insight
into the nature of the pores and their sizes,
which is consistent with our experimental
results in Fig. 1. Thus, the pore sizes can be
adjusted by controlling the fiber diameter
of the electrospun membrane, allowing
them to satisfy the requirements for
various MF and UF applications.
3. High-flux nanofibrous MF
membranes
One of the most important applications of
this type of membrane is to eliminate
bacteria and viruses from contaminated
drinking water. As shown in Fig. 3, elec-
trospun nanofibrous PAN scaffolds (B),
deposited onto PET non-woven
substrates (C), have been fabricated and
used as a base scaffold for such an MF
filter. The fiber diameter of the electro-
spun nanofibers (in the range of 100 nm) is
about two orders of magnitude finer than
that of the PET non-woven substrate
(in the range of 20 mm).
Typically, the diameter of most water-
borne bacteria is larger than 0.2 mm. To
test the bacterial retention capability of
nanofibrous MF membranes, two
common water-borne bacteria, E. coli and
B. diminuta, having dimensions of 0.5 
2.0 mm and 0.3  0.9 mm, respectively,
were used. According to Fig. 1, to design
a non-woven scaffold with a mean pore
size of 0.3 mm, the mean fiber diameter
should be around 100 nm. This was
accomplished by electrospinning a PAN
or polyvinyl alcohol (PVA) nanofibrous
layer (thickness of 45
5 mm, fiber
diameter of 110
30 nm) onto the PET
non-woven substrate.26 In these
membranes, the log reduction value
(LRV) against E. coli was found to be
higher than 6.0 (the original concentration
of E. coli was 107 plaque forming units per
millilitre (pfu mL1) in phosphate buffer
solution, PBS, pH ¼ 7.2. The LRV against
B. diminuta (107 pfu mL-1) was over 4.0.
To evaluate the high-flux nature of these
membranes (e.g. PAN electrospun
membranes in Fig. 3(G)), the water
permeability and pressure drop were
investigated. When the water flow rate was
kept constant at 192 L m2 h1, the pressure
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adsorption. The adsorption capacity would

depend on the total surface area of cellulose
nanofibers and the charge density on the
surface. Ultra-fine cellulose nanofibers have
a very high surface-to-volume ratio of
600 m2 g1 and a relatively high surface
charge density of 1.0 mmol g1 cellulose.
To design a high-flux MF membrane with
simultaneous bacteria and virus retention
capability, an infusion method was used to
Fig. 2 Illustration of the correlations between pore size and fiber diameter at a constant porosity of
80% in a fixed volume.
load ultra-fine cellulose nanofibers (diame-
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ters  5 nm, lengths  200 nm) into the

connected cavities of an electrospun PAN
scaffold. It was found that by limiting the
loading amount of UCN to 10 mg cm3, the
pressure drop could be maintained at 0.4 psi
and the water/aqueous solution flux could
be maintained at 192 L m2 h1. Naturally,
the mean pore sizes of such a membrane
became smaller after the modification.
Upon infusion with 10 mg cm3 UCN, the
mean pore size of the electrospun PAN top-
layer decreased from 0.38 to 0.22 mm, and
the rejection ratio of 0.20 mm nanoparticles
(in 100 ppm) increased significantly from
13.8% to 97.7%. Most importantly, the log
reduction value (LRV) of this membrane
against the virus MS2 at pH 7 increased
from 0 to 2.0, which was higher than that of
the negatively charged commercial GS9035
microfilter (Millipore, 1.0 LRV under the
same conditions). Further modification of
Fig. 3 (A) TEM image of ultra-fine cellulose nanofibers with 5 nm fiber diameter. (B) and (C) are this membrane involving the coating of
SEM images of PAN electrospun nanofibers (100 nm fiber diameter) and PET non-woven mi- positively charged polymers, such as poly-
crofibers (20 mm fiber diameter), respectively. (D) A depiction of a two-layered fibrous structure ethylenimine (PEI), could increase the LRV
for microfiltration of bacteria ((B) + (C)). (E) A depiction of a two-layered fibrous structure infused to 4.0 against MS2, while only slightly
with ultra-fine cellulose nanofibers for microfiltration of both bacteria and viruses ((A) in (B) + (C)). increasing the pressure drop to 0.7 psi.
(F) A depiction of a three-layered fibrous structure with the barrier layer coated with ultra-fine
cellulose nanofibers for ultrafiltration of oil/water wastewater ((A) + (B) + (C)). (G)--(I) are SEM
images of the cross-sectional view of (D)--(F), with mean pore sizes of 300, 200 and 20 nm, 4. High-flux nanofibrous UF
respectively. membrane
Based on the dimensions and surface prop-
drop was only 0.2 psi; significantly lower cellulose sources (e.g., wood pulps or erties of cellulose nanofibers, another
(by about an order of magnitude) than that cotton pulps) using a TEMPO/NaBr/ important application is their utilization as
of commercial MF membranes. NaClO oxidation process in an aqueous a barrier layer for ultrafiltration.26,27
While the above two-layered non- solution and mild mechanical treat- According to Fig. 1, a non-woven scaffold
woven fibrous membranes are efficient to ment.26,33--35 The high surface-to-volume of UCN with 5 nm diameter would define
remove bacteria by size exclusion, ratio, highly hydrophilic and functional- a mean pore size of 15 nm in the barrier
their pore sizes are too large to retain ized surface, good chemical resistance, layer, which would be suitable for ultrafil-
viruses (e.g., MS2 bacteriophage with high crystallinity, good mechanical tration. A 3-layered asymmetric fibrous
dimensions of 27  32 nm). To maintain properties, and relative microbial inert- membrane (termed thin-film nanofibrous
the high-flux nature (i.e., avoid an ness of ultra-fine cellulose nanofibers have composite (TFNC) membrane), containing
increase in pressure drop), ultra-fine led to many interesting applications.34,35 a UCN barrier layer, an electrospun mid-
cellulose nanofibers (UCN) were infused From the TEMPO/NaBr/NaClO treat- layer support and a bottom non-woven
into the above membrane as adsorbents ment, C6-positioned hydroxyl groups in substrate, has been constructed for this
to remove viruses based on charge inter- cellulose molecules are partially oxidized purpose. Its schematic structure is shown in
actions with the nanofiber surface. The into carboxylate/aldehyde groups, resulting Fig. 3(F) and the SEM cross-sectional view
ultra-fine cellulose nanofibers (diameters in coverage of a negatively charged of the barrier layer is shown in Fig. 3(I). As
 5 nm) can be fabricated from various surface,33 which is suitable for virus the hydroxyl/carboxylate groups in the

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barrier layer are hydrophilic, this TFNC
membrane should also possess an anti-
fouling property against organic molecules
in water (e.g., oil/water wastewater).36
It has been shown that in TFNC
membranes, high porosity in the mid-
layer and directional water channels in the
barrier layer can lead to a higher perme-
ation flux than those of conventional
membranes produced by the phase
inversion method.11--15,25,37,38 In TFNC
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membranes containing a UCN barrier
layer, its permeation flux was found to be
about ten times higher than that of
commercial PAN10 (Sepro) membranes,
while maintaining a similar rejection
ratio, for ultrafiltration of oil/water
emulsions (a model fluid for bilge water).
When compared with other high-flux
commercial UF membranes, such as
PAN400 (Sepro) or M180 (KOCH),
a higher permeation flux (3 times
higher) was still observed after 2 days of
operation at 30 psi. It was noted that the
rejection ratio of these UCN-based
TFNC membranes was above 99.5%,
significantly higher than that of these two
commercial membranes (typically
<98.5%). Moreover, the UCN-based
TFNC membranes exhibited superior
anti-fouling properties when compared to
PAN-based or PES-based UF
membranes, which also contributed to the
prolonged high permeation flux. Finally,
it should be noted that the coating process
to fabricate the UNC barrier layer
involved only an aqueous suspension of
ultra-thin cellulose nanofibers with
minimum environmental concerns. This
implies that a cost-effective industrial-
scale fabrication process of UCN-based
TFNC membranes can be achieved.
5. Outlook
Ultra-fine cellulose nanofibers represent
a new generation of natural nano-scale
materials with excellent properties that
can be very useful for water purification as
demonstrated by high-flux microfiltration
and ultrafiltration. Likewise, other
natural polysaccharides, such as chitin,
fabricated into ultra-fine nanofibers with
high crystallinity and good anti-bacterial
properties at low cost, may also provide
a similar benefit.26,27 However, in spite of
all the aforementioned advantages of
these unique nanofibrous membranes,
there are still challenges, which can hinder
7510 | J. Mater. Chem., 2011, 21, 7507--7510
their applicability. One problem is that the
capacity and the lifetime of the UNC
based MF membranes for virus removal is
limited by the adsorption mechanism.
Heavy loading of ultra-fine cellulose
nanofibers into the cavities of electrospun
scaffolds can lead to an undesired increase
in the pressure drop. Modifying the
surface of cellulose nanofibers to possess
a higher charge density, as well as
increasing the overall surface area-to-
volume ratio via the formation of
a 3-dimensional cross-linked network
structure within the electrospun scaffold
could be the next step to improve the
UCN-based MF membranes. Moreover,
to further expand the family of UCN-
based TFNC membranes for UF appli-
cations, grafting of other hydrophilic/
hydrophobic polymer segments onto the
nanofibrous cellulose surfaces could
further tune the pore sizes and anti-fouling
properties for different applications.
Acknowledgements
Financial support of this work was
provided by the Office of Naval Research
(N000140310932) and the National
Science Foundation (DMR-1019370).
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