Journal of Membrane Science 394395 (2012) 8997

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Maximal pore size in UF membranes

Elizabeth Arkhangelsky a , Aviv Duek a , Vitaly Gitis a,b,
a
b

Unit of Environmental Engineering, Ben-Gurion University of the Negev, PO Box 653, Beer-Sheva 84105, Israel
vant Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098XH Amsterdam, The Netherlands

a r t i c l e

i n f o

Article history:
Received 19 September 2011
Received in revised form
20 December 2011
Accepted 21 December 2011
Available online 30 December 2011
Keywords:
Porous materials
Monodispersed nanoparticles
Aquasols
Molecular separation
Pathogens

a b s t r a c t
The ultraltration membrane rejection capability is most often characterized by molecular weight cutoff (MWCO). The value is found by rejection of organic solutes and the evaluation of particle retention
requires a conversion of either MWCO to pore size or particle diameter to molecular weight. The conversion affects the accuracy of reported values and results in a gap between reported and measured
retentions.
We suggest a novel, simple and effective pore size test based on synthesis and membrane transfer of
rigid nanoparticles. Gold and silver 350 nm monodispersions had delivered a comprehensive pore size
distribution including d100 , a pore diameter for which a membrane has a 100% retention capability. The
maximal pore size in UF membrane structure can hardly be detected with other methods although it is
much needed for precise separation analysis.
The d100 values in tested UF membranes vary between 40 nm and 50 nm depending on the membrane
material. The polymer membranes are more exible than the ceramics and their d100 is usually much
higher than MWCO. The d100 increases with high transmembrane pressure or after oxidative chemical
cleaning. For some membranes the d100 values can be correlated with d90 but not with d50 .
2011 Elsevier B.V. All rights reserved.

1. Introduction
The ultraltration (UF) membranes currently become the leading separation method in various elds including biotechnology
[1,2], medicine [3], chemical industry [4] and water treatment [5].
The key feature of UF membranes is the ability to control the permeate quality by effective retention of different species in the feed.
The control is achieved by a careful selection of membrane characteristics such as the material and the pore size. The separation,
in general, can be built on preferential adsorption or electrostatic
attraction but the need to maintain a good ux makes the pore size
exclusion the most important mechanism. The principle is simple
the solutes smaller than the pore size are passing through the pore
while the solutes bigger than the pore size are rejected. A wise UF
membrane separation requires the knowledge of the exact pore
size.
Unexpectedly and rather surprisingly the membrane pore diameter can hardly be determined directly. The actual skin layer
of the asymmetric membranes is covered inside the polymer
matrix and therefore is not observable by microscopic methods.
Water permeability tests connect the ux with the mean pore

Corresponding author at: Unit of Environmental Engineering, Ben-Gurion University of the Negev, PO Box 653, Beer-Sheva 84105, Israel. Tel.: +972 86479031.
E-mail address: gitis@bgu.ac.il (V. Gitis).
0376-7388/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.12.031

diameter d50 [6] only. Other methods, such as the gas ow bubble
point [7] and mercury porosimetry [8], require very high pressure
for small pores, such that the measurement itself destroys the pore
structure [9]. Alternatively, permporometry is based on gas condensation inside the pores and suffers from low accuracy due to
vapor pressure differences on both sizes of the membrane [10].
Poor reproducibility of the results along with difculty of use and
absence of a commercially available apparatus had been named
as major drawbacks of liquidliquid porosimetry [1114]. Diffusional limitations and additional resistance of support layer limit
implementation of recently developed binary gas diffusion [15].
Unisize of gold nanoparticles has limited their implementation in
pore size distribution measurements [16,17]. The current state-ofthe-art method is based on penetration of homogeneous solutes
such as polyethylene glycols (PEGs) [18] or dextrans [19,20] of different molecular weights. The method assumes that solutes can
be rejected by the membrane pore but not adsorbed to the membrane surface, and the solutes with higher MW will be removed
better. We have recently shown that both assumptions are problematic [21,22] and the inherent exibility of the organic solutes
is confusing. A penetration of molecules 300 times larger than the
pore size was recently reported [23]. The PEG/dextran solutes are
therefore applicable for a limited range of pore sizes up to molecular weight cut-off (MWCO) that displays 90% retention capability
of organic molecule. A weak link between MWCO and actual pore
diameter results in inaccurate prediction of particle retention [21]

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E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

Table 1
Synthesis parameters, size and zeta potential of AG gold nanoparticle samples.
Sample

Sodium citrate
(mM/mM of HAuCl4 )

mM of Tannic
acid/mM of HAuCl4

Potassium carbonate
(mM/mM of HAuCl4(aq) )

Size (nm)

A
B
C
D
E
F
G

1.3
1.3
1.3
0.7
0.3
0.3
0.2

0.256
0.031
0.002

3.15
0.31
0.06

3.1
4.8
9.2
18.3
27.5
37.4
45.0

0.5
0.5
0.8
0.9
2.0
1.8
2.2

Zeta potentiala (mV)

52.0
61.0
53.0
47.0
37.0
36.3
41.8

1.9
2.5
0.0
0.3
0.2
0.3
2.4

a
The higher negativity of the smaller nanoparticles is due to addition of citric acid that has higher concentration at the outer core of the particles. The adsorption increases
the negative charge and stability of the aquasols.

and increases a need for pilot UF studies [24]. Higher than predicted penetration is often reported and the gap is explained by
the presence of abnormal pores [25,26].
Here we show that UF membranes are having maximal pores
that can be detected and not just estimated. With a help of a
new tool, monodispersions of gold and silver nanoparticles, we
were able to provide a pore size distribution including the maximal d100 pore size detected by absolute 100% retention of test
solutes. The d100 for tested polymer and ceramic UF membranes
lies between 40 nm and 50 nm, and that value becomes larger if the
membranes are operated at high transmembrane pressure (TMP)
or after oxidative chemical cleaning. For some membranes the d100
can be correlated with d90 but not with d50 .

2. Materials and methods

2.1. Preparation and characterization of the nanoparticles
Seven samples of monodispersed gold aquasols AG were prepared by reduction of hydrogen tetrachloroaurate with sodium
citrate and tannic acid [27,28]. For instance, 4.0 ml of a 1% solution of trisodium citrate and 5.0 ml of tannic acid were added to
40.0 ml of a 0.01% (w/v) solution of HAuCl4 . All chemicals were
purchased from SigmaAldrich. The mixture was stirred for 5 min
under gentle boiling, cooled to room temperature, and stored at
4 C. The six remaining suspensions (BG) were similarly prepared,
using the reagent concentrations listed in Table 1. The initial gold
concentration was 52 mg/L.
The 10 and 20 nm monodispersions of silver nanoparticles were
prepared by reduction of silver nitrate with sodium citrate and tannic acid [28]. For instance, 4.0 ml of 1% trisodium citrate, 5.0 ml of
tannic acid and 5 ml of 25 mM K2 CO3 in 6 ml of DIW were heated
up to 60 C and added to a preheated solution of 1.0 ml of a 1%
AgNO3 solution (v/w). The total mixture volume was completed to
100 ml with deionized water (DIW) and the mixture was boiled for
7 min under gentle stirring. The formation of silver nanoparticles
was controlled by a gradual appearance of yellow-brown color. The
suspension was cooled to room temperature and centrifuged for
30 min at 10,000 rpm. The centrifugation resulted in a separation
of 10 nm particles to supernatant and 20 nm to the sediment. The
30.7 3.1, 40.1 3.9, and 64.7 4.1 nm cubic silver nanoparticles
were purchased from NRF [29].
The AuNP and AgNP suspensions were characterized by transmission electron microscopy (TEM) using a JEM-1230 instrument
(JEOL) at 120 kV. The microscope was equipped with a TemCamF214 (TVIPS) camera. Size distribution and zeta potential were
measured with a ZetaPlus (Brookhaven Instruments) zeta potential and particle size analyzer. The measurements were performed
at a pH of 6, and at a ex angle of 90 . Each measurement was a
composite of 10 runs of 10 s each.

2.2. Measuring nanoparticle concentration

The concentration of Au3+ was determined after dissolving the
suspension in 7.6 ml of aqua regia (3 M HCl:1 M HNO3 ). The solution was evaporated to exchange the aqua regia with 5 ml of DIW.
Concentrations of gold in the feed and permeate solutions were
established with atomic absorption spectrometer (Perkin Elmer
AAnalyst200) at a wavelength of 242.8 nm with a slit of 2.7/1.35.
The air ow was 12 L/min and acetylene ow was 1.9 L/min. The
concentration of dissolved in aqua regia Ag+ was found with inductively coupled plasma mass spectroscopy (ICP/MS, Perkin Elmer
ILAN6000).
We also developed a faster and cheaper alternative detection
based on uorescence resonance energy transfer (FRET) between
Rhodamine B (RB) dye and AuNPs. The noncovalent self-adsorption
of RB on AuNPs results in uorescence quenching because of the
FRET of RB to AuNPs. No uorescence was observed after 3 days
of dialysis needed to remove extra dye. The addition of thiols and
release of RB due to formation of stronger AuS bonds results in
renewed uorescence proportional to the number of molecules
released from the AuNPs surface. A pictorial scheme of FRET principle is provided on Fig. 1. The released uorescence was measured
at 540/625 nm excitation/emission wavelengths with FS-2 (Scinco)
uorescence spectrometer, and calibrated against known AuNPs
concentrations assuming equal number of dye molecules per Au
particle. The calibration plots of AuNPs for dissolved gold ions Au3+
and for RB uorescence are shown on Fig. 2. Both plots calibrate
absorbance/uorescence and AuNPs concentration linearly with
Pearsons R2 coefcients higher than 0.999.
2.3. Bacteriophages
The MS2 (ATCC 15597-B1), phi X174 (ATCC 13706-B1), T4 (ATCC
11303) and PRD-1 (ATCC BAA-769-B1) bacteriophages and their
Escherichia coli host cells were purchased from Deutsche Sammlung
von Microorganismen und Zellkulturen GmbH (DSMZ, Germany).
The Vaccinia viruses (VV) were received from Department of Virology at Ben Gurion University of the Negev. Table 2 details the main
characteristics of the microorganisms. A fresh stock was prepared
for each experiment. E. coli cells were propagated by inoculation
on LauriaBertani (LB) agar followed by incubation at 37 C for
1618 h. The concentration of E. coli was determined by plating
100 l of culture solution on LB agar and counting colony forming units (cfu) after overnight incubation at 37 C. Phages were
propagated by inoculation of infected E. coli cells into LB medium
followed by 24 h incubation at 37 C. During this time, the cells
were at the exponential growth phase (suspension turbidity from
0.2 to 0.3 OD). The cell lysis was later performed with chloroform. The resulted suspension was centrifuged at 37,000 rpm for
40 min, the pellet was discarded, and the bacteriophage-containing
supernatant was stored at 4 C. Bacteriophage concentration was
determined by a pfu assay using the double-layer overlay method.

E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

91

Fig. 1. A pictorial FRET scheme where the attachment of RB to AuNPs results in uorescence quenching, and only adsorption of l-cysteine release the sleeping RB and renew
the uorescence.

FRET

AA

R = 0,9999

Abs orbance, AU

0,3

Abs
sorbance, AU

16000

0,2

0,1

R2 = 0,9989

12000

8000

4000

0
20

40

60

20

40

60

80

100

Au3+ concentration, ppm

Au concentration, ppm

Fig. 2. AuNPs calibration curves with Atomic absorption (left) and RB uorescence (right).

The initial phage concentration varied between 1.3 107 and

5.0 107 pfu/ml.
2.4. Membranes and ltration
Fresh polyethersulphone PES-10, PES-20 and PES-30, cellulose
acetate CA-20, polyvinylidene uoride PVDF-30, polycarbonate
PC-30 and PC-100, and ceramic C-50 membranes (Sterlitech Corporation) were tested. In PES, CA, PVDF and C membranes, the
numerical digits indicate the MWCO in kDa as provided by the
supplier. In contrast, the numerical digits in the PC membranes
indicate the pores size in nm. Prior to ltration, the membranes
were soaked in NaOH solution (pH 9) and vibrated at 55 C for 2 h.

The cleaning resulted in similar feed and permeate total organic

carbon (TOC) levels in ltration of deionized water DIW (RO quality). Filtration was performed in a 150 ml autoclaved stirred cell
(magnetic stirring, 400 rpm) equipped with a back-pressure TMP
controller [30]. The pore size was measured in ambient conditions,
at a pH of 6 and 2 bars N2 TMP (99.99% purity), after 30 min compaction with DIW. The oxidative chemical cleaning of CA-20 was
performed in closed Petri dishes with a fresh 0.15 g/l free NaOCl
solution (Unilever) prepared daily. The cleaning time period varied
between 1 min and 240 h, and after that the cleaned membrane
was washed with DIW. The cleaning intensity was displayed as
a Ct, a product of concentration of cleaning agent C and cleaning
time t.

Table 2
Main virus characteristics.
Virus

Family/group

Morphology

Nucleic acida

Size (nm)

Isoelectric point, pH

MS2
Phi X174
T4
PRD1
VV

Leviviridae
Microviridae
Myoviridae
Tectiviridae
Poxviridae

Symmetry icosahedral
Icosahedral
Tailed phage
Symmetry icosahedral
Icosahedral

Linear ss RNA
Circular ss DNA
Linear ds DNA
Linear ds DNA
Linear ds DNA

2627
3132
65 80, tail 120 20
65
360 250

3.9
6.6
3.2
4.2
4.8

ss, single-strained; ds, double-strained.

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E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

2.5. Pore size tests

The water permeability test determines the mean pore diameter
d50 (nm) in symmetric membranes with Hagen-Poiseuille equation
[6]

d50 = 2

8xM
Ak

(1)

where  is the water viscosity (kg/m s1 ), x is the membrane

thickness (100 50 nm), Ak is the membrane porosity determined
by weighing the dry and wet samples, and M is the membrane
permeability (L/m2 h1 bar1 ) calculated gravimetrically as:
M=

m
St P

(2)

where m is the permeate weight difference (kg) measured with

Kern PLS 2100-2 (Germany), t is the frequency interval (h), P
is the transmembrane pressure (TMP, bars), S is the active membrane surface area (0.0025 m2 ), and  is the permeate density
(1000 kg/m3 ).
The nanoparticle test determines the pore size with AG gold
or with 10, 20, 30, 40 and 65 nm silver suspensions. The tests
were performed with constant 5.6 1010 particles/ml concentration achieved by diluting more concentrated suspensions of small
nanoparticles. The tests were performed in a sequence of 15 min
ltration of DIW, 5 min ltration of nanoparticle suspension, and
additional 20 min of DIW ltration. Only 25 ml permeate were collected, to minimize a bias due to concentration polarization. The
tests were performed with fresh suspensions to minimize possibilities for shape change and aggregation [31,32]. Retention was
calculated with a ratio of total mass of nanoparticles in permeate
and feed.
The microorganism tests were used to detect the d100 only. The
absolute 3.7 LRV and higher retentions were calculated from an
average virus concentration of 3.1 107 pfu diluted in 150 ml ltration cell and the minimum countable 30 pfu/ml. Here LRV is a
log removal value, a logarithm to base 10 of the ratio of microorganism concentrations in the feed to those in permeate. The pore
diameter for the retentions lower than 3.7 logs was recalculated
back from Ferry formulae [33]
2

R = 1 2(1 size ) + (1 size )

R = 1 for

size > 1

for

size 1

(3)

Cp
Cf

100 %

(5)

where Cp and Cf are the solute concentrations (g/L) in the permeate

and in the feed respectively. For PEG, PEO and dextran, the conversion of MW into nm was performed with the correction formulae
[34],
d50 = 0.11(MW50 )0.46

Fig. 3 shows a design for a bubble point test. A 3.0 3.0 cm membrane piece was circle cut out with a sharp metal ring, placed on a
metal-free lter (A-424, Upchurch Scientic) and held by two frits
(A-346, Upchurch Scientic). The frit assembly, held by nuts (A-510,
Upchurch Scientic), was tightly screwed into a PEEK uoropolymer body so that the Teon tube coming out of the N2 cylinder
delivered the gas straight to the membrane surface. The loose end
of the tube was immersed into a 50-ml beaker lled with DIW so
a stream of nitrogen bubbles coming through the membrane could
easily be visualized. The d100 maximal pore size was determined as
[35]
d100 (m) =

41.6
Pb (psi)

(7)

where Pb is a bubble point pressure.

3. Results and discussion
3.1. Detection of d100 with gold and silver nanoparticles

(4)

where R is the retention calculated as a function of

size = dparticle /dpore and dparticle and dpore are the particle and
pore diameters, respectively.
The polymer tests were performed with 0.3 g/L solutions of
PEGs, polyethylene oxides (PEOs) and dextrans (SigmaAldrich).
The 0.6, 3.4, 6.0, 10.0, 20.0, 35.0 kDa PEG; 100, 200, 600 kDa PEO; 6,
40, 70, 100 kDa dextran polymers were used unmodied. The polymer concentration was measured with Apollo 9000 TOC analyzer
(Tekmar Company). The rejection of test solutes was calculated
using the formula:
R=

Fig. 3. Bubble point test setup.

(6)

Here MW50 is the molecular weight of a large organic molecule that

displays 50% rejection capability [21].

The TEM micrographs and size distributions of gold nanoparticles are depicted in Figs. 4 and 5, respectively. The highly stable,
monodispersed, spherical gold nanoparticle suspensions with no
visible aggregation are observable. Zeta potential measurements
at pH of 6 (Table 1) demonstrated decreasing negative values
from 61 mV for 3.1 nm colloids to 33 mV for 45 nm colloids
(suspensions with absolute zeta potential values above 30 mV are
considered stable, [36]). Fig. 6 shows the retention of gold nanoparticles by PVDF-30, C-50, PC-30, and PC-100 membranes. Note that
connecting the tops of the retention bars results in sigmoidal
curves, which are typical of natural processes [37]. Indeed, similar curve forms were reported also with PEG [18]. Conversion of 30
and 50 kDa in PVDF-30 and C-50 membranes to diameters (Eq. (6))
gives roughly 12.6 nm and 16.0 nm, however particles as large as
28 nm easily permeate through PVDF-30. This reects the exibility
of the polyvinyl membrane that allows larger particles to pass. Conversely, the rigid pores of the ceramic membrane indeed retain 90%
of particles of ca. 18 nm and fully retain the 37 and 45 nm particles.
The pore size of PC-100 assumes that all the particles smaller than
100 nm will pass through. However, the average 1015% retention
of particles starting from 18.3 nm was measured. More than 99%
retention of particles bigger than 9.2 nm by PC-30 was observed.

E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

93

Fig. 4. High resolution transmission electron micrographs of the gold nanoparticle suspensions AF.

Fig. 5. Size distribution of gold nanoparticle suspensions determined with dynamic light scattering. The distribution function analysis is displayed as scattered intensity per
particle sizes of 3.1, 4.8, 9.2, 18.3, 27.5 and 45 nm.

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E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

Fig. 6. Percentage of gold nanoparticle rejection by C-50 (grey bars) and PVDF-30 (hatched bars) membranes (left), and by PC-30 (hatched bars) and PC-100 (grey bars)
membranes (right). The tests were performed with constant 5.6 1010 particles/ml concentration. The error bars are the maximum and minimum values obtained during
multiple tests.

The d100 at 27.5 nm reected more on the test sensitivity highlighting the difference between 99.9 and 100% retention. Despite
a relative success with the application is soon become apparent
that gold nanoparticles are having a high afnity towards PES and
CA, and therefore cannot be used for the entire membrane polymer range. The problem was considered related to the membrane
hydrophobicity and therefore inherent.
Fig. 7 depicts the retention of silver nanoparticles by PVDF-30,
PES-30, PC-30 and PC-100 membranes. Here the retention of the
smallest 10 nm nanoparticles is already more than 90% for all of
the membranes excluding the PC-100. No rejection of 10 and 20 nm
particles by PC-100 was obtained. There is no real explanation for
reduced retention of 20 nm except for an insufcient separation
of 10 and 20 nm particles after the synthesis. The procedure however was repeated many times, and always with the same result.
Although the 20 nm were retained less than 10 nm particles, the
retention of 30, 40 and 65 nm particles was close to 100% for all
of the membranes except for PC-100. Even PC-100 showed a signicant retention of 30 and 40 nm that accidently dropped down
to 0% retention of 65 nm particles. Despite the good retention, the

application of silver nanoparticles was less informative, mainly due

to their initial larger size and once again membrane hydrophobicity. Opposite to gold nanoparticle suspensions, here we were able
to obtain a pore size distribution in PES membranes.
Table 3 lists the d100 determined with gold and silver nanoparticle tests. The C-50 membrane has an absolute cut-off value of 37 nm,
while the PVDF-30 membrane gives 100% retention at 45 nm. More
than 99% retention of 18.3 nm gold nanoparticles by PC-30 was
received, however the absolute retention of PC-30 is 27.5 nm for
gold and 51.4 nm for silver. The absolute retention of PC-100 is
above 45 nm. The absolute pore size of tested UF membranes lies
between 40 nm and 50 nm, except for the PES-10 and PES-30, where
the membrane d100 was below the smallest probe diameter.
3.2. Detection of d100 with bacteriophages and with bubble point
tests
Although not many, there are other methods to determine the
absolute pore size. We were able to detect the d100 with viruses
and bubble point tests. For the former, the d100 was set equal to the

Fig. 7. Percentage of silver nanoparticle rejection by PES-30 (grey bars) and PVDF-30 (hatched bars) membranes (left), and by PC-30 (hatched bars) and PC-100 (grey bars)
membranes (right).

E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

95

Table 3
Absolute d100 membrane pore diameter (nm) obtained with gold and silver nanoparticle tests.

AuNPs
AgNPs

PES-10

PES-30

PVDF-30

PC-30

C-50

PC-100

3.1 1.4<
10.0 0.6<

3.1 1.4<
50.4 1.1

47.8 1.7
52.3 1.1

27.5 0.2
51.4 5.1

37.4 1.2
40.4 0.9

>45.0
>65.0

hydrodynamic diameter of virus being rejected by 100%. The 3.7

LRV and higher retention was considered the absolute, and only
E. Coli cells and large VV, T4, and PRD1 viruses were completely
retained. The d100 for both PES-20 and PES-30 were 1000, 250,
80 and 65 nm in tests with E. Coli, VV, T4, and PRD1 respectively.
The obtained value clearly reected on the size of microorganism used in detection (Table 2). Retention of smaller MS2 and
phi X174 bacteriophages was below 3.7 logs barrier. The similar
method was earlier applied by Urase [26], and determined absolute (so called abnormal) pore diameters varied between 23 nm
and 80 nm. Fig. 8 depicts the changes in absolute pore size in PES20 for the experiments performed with 15 bars transmembrane
pressure. The absolute pore diameter was affected by the probe
size and by the applied TMP. In a response to TMP raise from 1
to 5 bars, the d100 values increased from 80 nm to 82 nm and from
65 nm to 68 nm in T4 and PRD1 experiments respectively.
The bubble point test and its derivatives such as diffusive air
ow (DAF) and pressure decay test (PDT) are routinely applied
for detection of membrane integrity [38]. The methods however
are more applicable to assure the membrane impermeability to
oocysts of Cryptosporidium parvum. A 100 bar TMP is needed to
detect the 28 nm pores (Eq. (7)). The recommended TMP for the
majority of UF membranes do not exceed 5 bars. We tried to detect
d100 in all membranes but found the bubble point of PC-100 only.
The 23.3 bars TMP was converted to 123 nm close to the supplier
reported value. The bubble point of other intact membranes was
above 50 bars, the self-limiting TMP value. However the maximal
pore size drops quickly if the membrane is cleaned with an oxidant.
Fig. 9 presents the inuence of oxidative NaOCl cleaning of CA-20
membrane on d100 . Although the virgin membrane pore size was
below 30 nm, already at 20 gh/L the d100 increased to 57 nm. The

continuous oxidation increased the value up to 430 nm observed

after 180 gh/L NaOCl cleaning. At that TMP the bubble point test
can be destructive so the real values can be lower. Signicant error
bars at low Ct values are a good evidence of less conclusive results.
Both the trend and the measured values are less surprising as the
cellulose acetate is not a chlorine-resistant polymer [38]. Using
two independent methods we showed that chemical membrane
cleaning and applied TMP can affect maximal pore size in virus
membranes.
3.3. Comparison between d50 , d90 and d100
Measurements of the absolute pore size can accurately predict retention of viruses and small particles [24]. However, our
method will not be implemented immediately and therefore we
searched for correlations between d100 and other membrane pore
sizes detectable by already existing tests. Conventionally the membrane is characterized by d50 and d90 pore values found by
transmembrane water ux and PEG/PEOs and dextrans solute tests
respectively. Table 4 indicates that PEG/PEOs tests predict the d50
value of 28 nm regardless of the MWCO value displayed by the
supplier. The water permeability displayed larger 335 nm d50 values, suggesting a wider pore size distribution that is in closer
agreement with the supplier data. The d90 diameter (Table 5) was
mainly predicted by gold and silver nanoparticles, and only for 2
out of 6 membranes with PEG/PEO tests. The predicted d90 values
in track-etch PC-30 and PC-100 membranes were conrmed by the
supplier data and by microscopic observations [24], and therefore
resulted in greater accuracy. The d90 in PC-30 and C-50 is 27 and
18 nm, signicantly higher than MWCO-based conversion values of
9 and 11 nm, respectively.
Fig. 10 presents the correlations between d50 , d90 and d100 . Insufcient correlation with d50 found by water permeability, PEG/PEO

500

Pore size d100, nm

400

300

200

100

0
20

40

60

80

180

Ct, g-h/L
Fig. 8. The d100 determined with T4 and PRD1 bacteriophages in TMP range of
15 bars. The error bars are the maximum and minimum values obtained during
multiple tests.

Fig. 9. The d100 in PE-20 as a function of NaOCl concentration C and contact time t.
The tests were performed with CA-20 membrane.

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E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

Table 4
Mean d50 membrane pore diameter (nm) obtained with gold and silver nanoparticles, PEG/PEO, dextrans and water permeability tests.
PES-10

PES-30

4.3 0.6
2.1 0.3
6.1 0.6

3.1 0.6
6.0 1.5
8.7 1.5

AuNPs
AgNPs
Water permeability
PEG/PEO
Dextrans

PVDF-30
10.5

2.9
6.9
6.9

0.4
0.4
1.5
1.5

PC-30

C-50

18.1 0.4
6.2 0.2
6.7 0.9

3.1

3.3
6.5
6.5

PC-100
0.2
0.2
1.5
1.5

26.2 0.8
35.1 4.2
7.8 0.7

Table 5
Geometric d90 membrane pore diameter (nm) obtained with gold and silver nanoparticles, PEG/PEO, dextrans and water permeability tests.
PES-10

PES-30

3.1 1.4<
10.0 0.6<

AuNPs
AgNPs
Water permeability
PEG/PEO
Dextrans

3.1 1.4<
24.2 0.8

and dextran tests was related to the complexity of membrane

properties. The membrane cannot be simplied into a sieve, and
therefore an initially low ux through PVDF and C membranes
resulted in absence of signicant correlation. Along with that
the general trend of increased d100 for higher d50 with signicantly different membranes was observed. More reliable prediction
of the maximal pore size can be obtained with d90 measured
with either nanoparticles or PEG/PEO. The former correlation in
a form of d100 = 1.21 d90 with R2 = 0.78 is not surprising, the latter in a form of d100 = 3.15 d90 with R2 = 0.89 is encouraging. The
detection of d90 in many membranes with the PEG/PEO tests is
however, problematic [18], mainly due to pressure-induced linearilization of the molecules in water. At current the correlation is
build on insufcient number of points and further investigation is
needed.

4. Analysis
The pore size is the most important and complex characteristic
of UF membranes. The UF pore size can be measured by many indirect methods of which the microscopy, water ux, and PEG/dextran
passive tests are the most popular. The tests link the pore size
with visible cavities in the membrane upper layer, with water ux
and with retention of linear polymers. Additional complications
50

PVDF-30

PC-30

C-50

PC-100

32.3 1.2
31.8 1.1

26.7 0.8
27.2 2.3

9.3 2.4

18.3 0.9
17.1 0.7

11.4 1.6

>45.0
>65.0

arise from wide diversity in pore sizes in a majority of polymer

membranes. Thus, we need methods that can determine not only
a mean pore size, but the entire pore size distribution. The passive
solute tests [18] are the only method that is able to provide a pore
size distribution based on rejection of test solutes. Two main problems of the linear polymer tests are the partial adsorption to the
membrane surface [22], and TMP-induced stretch causing partial
penetration through virtually any membrane [2,23,39]. Thus, there
is no possibility to determine the absolute retention. In addition, the
membrane pore size is related to MWCO, specied as a molecular
mass of solute for which a membrane has a retention capability of
greater than 90% [40]. Despite a variety of empirical relationships
between the molecular weight and hydrodynamic radius of neutral polymer [34], PEG cannot be equalized to a rigid sphere of any
diameter, since a spatial arrangement of this linear molecule is not
steady under pressure [41].
Application of rigid inert nanoparticles provides the option to
evaluate the size of the biggest pore in membrane matrix. The
evaluation, based on 100% retention of particles of a certain diameter, provides the maximal instead of the abnormal pore size used
before [25,26]. The new denition is way beyond the semantics as
it states that the maximal is a part of normal that regularly exists
in the membrane matrix. Thus a proper pore size characterization
should now include the d100 for a better retention perspective of
any solute having a hydrodynamic diameter. The found d100 values
50 PEG/PEO

PEG/PEO
dextrans

A NP
AuNPs

40

40

AgNP
30

water permeability
20

10

d100, n
nm

d100, n
nm

30

20

10

0
0

10

20

d50, nm

30

40

20

40

60

d90, nm

Fig. 10. Correlation between d50 and d100 (left) and d90 and d100 (right). The plots are based on Tables 35.

E. Arkhangelsky et al. / Journal of Membrane Science 394395 (2012) 8997

differ from one membrane to another, and that is not surprising.

More surprising is that d100 do not depend much on the membrane characteristics provided by the manufacturer. The d100 of
polymer membranes is usually much higher than MWCO while the
d100 of ceramic and polycarbonate membranes is much closer to
the values provided by the manufacturer. Separation by PC and C
membranes can be related to the pore size provided by the supplier,
the extended exibility of polymer membranes force to measure
the d100 value. The provided correlation between d90 and d100
in polymer membranes is weak and can only be used for rough
approximations. Besides, the MWCO test fails to provide the d90
value for many membranes and therefore MWCO-based prediction
possibilities are narrow.
5. Conclusions
Monodispersions of inert nanoparticles can conveniently determine the pore size distribution in a variety of UF membranes.
The monodospersions are easily synthesized, non-pathogenic, and
detectable by simple and rapid methods. The highly concentrated
aquasols are stable for long periods of time.
In addition, the nanoparticles offer a possibility to determine
the absolute membrane pore size. The versatility of the tool will
enhance the accurate determination of the relative and absolute
retention of rigid nanoparticles. In addition to being a valuable
research tool, this method may provide the means to conrm
compliance of membrane systems with the stringent regulatory
requirements of the drinking water industry.
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