Journal of Membrane Science 409–410 (2012) 242–250

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Journal of Membrane Science

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

Transport and separation of uranium(VI) by a polymer inclusion membrane

based on di-(2-ethylhexyl) phosphoric acid
Alexander M. St John, Robert W. Cattrall, Spas D. Kolev ∗
School of Chemistry, The University of Melbourne, Victoria 3010, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Di-(2-ethylhexyl) phosphoric acid (D2EHPA) is a commonly used extraction reagent for the separation of
Received 6 December 2011 uranium from aqueous solutions. Previous work showed the suitability of a polymer inclusion membrane
Received in revised form 21 March 2012 (PIM) based on D2EHPA and poly(vinyl chloride) (PVC) for the extraction and transport of uranium(VI)
Accepted 23 March 2012
from sulfate solutions. This study details the improvement of the membrane transport by optimising the
Available online 1 April 2012
composition of the source and receiving solutions on one hand and membrane composition with the use
of a plasticizer on the other. Initial fluxes of uranium as high as 3.0 × 10−6 mol m−2 s−1 corresponding
Keywords:
to permeability of 7.2 × 10−6 m s−1 were recorded using a membrane composed of 35% (m/m) D2EHPA,
Polymer inclusion membrane
Di-(2-ethylhexyl) phosphoric acid
10% (m/m) o-nitrophenyloctyl ether and 55% (m/m) PVC from a solution containing 100 mg L−1 U(VI)
(D2EHPA) in 0.1 mol L−1 H2 SO4 into a solution containing 6 mol L−1 H2 SO4 , although transport across a membrane
Uranium containing 45% (m/m) D2EHPA and 55% (m/m) PVC was only slightly slower. The effect of the acid anion
Membrane extraction in the source and receiving solutions on the extraction and back extraction of U(VI) is discussed and the
Membrane transport membranes are tested for durability over repeated cycles of extraction and back-extraction.
Using a 45% (m/m) D2EHPA and 55% (m/m) PVC PIM (m/m), U(VI) is completely separated thermo-
dynamically from a range of common metal cations and successfully separated from Fe(III) kinetically.

© 2012 Elsevier B.V. All rights reserved.

1. Introduction of separation techniques by removing the requirement for a large

The separation of uranium from its ores has been the sub-
ject of a considerable amount of research due to its importance
in the nuclear power industry. Solvent extraction processes for
its purification are mature and efficient [1], but the application
of membrane technology for hydrometallurgical and environmen-
tal separation of uranium has attracted considerable interest for
environmental and economic reasons. Examples of membrane
techniques that have been applied to these areas include bulk liq-
uid membranes, liquid emulsion membranes and supported liquid
membranes (SLM) [2]. Recently, the application of polymer inclu-
sion membrane (PIM) technologies to the separation of uranium
has been studied.
PIMs have shown potential as a safer alternative to traditional
solvent extraction (SX) techniques for the separation of metal ions
[3] and small organic molecules [4]. PIM techniques encapsulate
an extraction reagent (extractant) within a base polymer matrix,
frequently with the addition of plasticizers to lower the diffusive
resistance of the membrane and/or modifiers to improve the sol-
ubility of chemical species of interest within the membrane. It is
hoped that the adoption of PIM techniques may improve the safety
∗ Corresponding author. Tel.: +61 3 8344 7931; fax: +61 3 9347 5180.
E-mail address: s.kolev@unimelb.edu.au (S.D. Kolev).
inventory of flammable, volatile and toxic solvents which are used
as diluents in SX procedures.
Earlier researchers highlighted several potential PIM systems
for the separation of uranium. Bloch et al. [5] and Matsuoka et al.
[6] reported on PIM systems that used tri-n-butyl phosphate (TBP)
as the extractant; however, the practical application of these mem-
branes is limited by the high water solubility of TBP, which leads
to leaching of the extractant from the membrane. Nazarenko and
Lamb [7] showed some extraction of uranium by PIMs based on
crown ethers and Sodaye et al. [8] outlined the analytical applica-
tion of a PIM using di-(2-ethylhexyl) phosphoric acid (D2EHPA) as
the extractant, encapsulated in a cellulose triacetate (CTA) matrix
with liquid scintillation agents and plasticizers, but did not apply
the PIM system to separation processes. More recently, Bayou et al.
[9] demonstrated uranium separation with a PIM based on tri-n-
octylphosphine oxide (TOPO) and CTA, but were unable to show
complete uranium transfer across the membrane. In our previous
paper, we demonstrated preliminary success in completely trans-
porting U(VI) across a PIM composed of 40% (m/m) D2EHPA and
60% (m/m) poly(vinyl chloride) (PVC) [2]. Complete transport was
achieved from a sulfate solution containing 100 mg L−1 U(VI) at
pH 1 to a solution containing 4.0 mol L−1 sulfuric acid. Although in
this initial report we were able to transport U(VI) against its con-
centration gradient, its flux across the membrane was relatively
low.

0376-7388/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2012.03.061
 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250
This study is aimed at improving the flux across the PIM by
optimising the variables associated with the transport process,
including the composition of the membrane and the solution con-
ditions. Sulfuric acid solutions were primarily used as they are of
most interest for Australian uranium processing, however the effect
of using solutions of other strong mineral acids (i.e. HNO3 and HCl)
have also been investigated. In addition, the efficacy of the PIM sys-
tem for separating U(VI) from other cations of interest has also been
investigated.
2. Experimental
2.1. Reagents
Di-(2-ethylhexyl) phosphoric acid (97%, Aldrich, USA) and high
molecular weight poly(vinyl chloride) (Fluka) and tetrahydro-
furan (THF) (HPLC grade, Scharlau) were all used as received.
Uranyl acetate dihydrate (AR, Univar Australia) was standardised
against a 1000 mg L−1 NIST-traceable atomic absorption spectrom-
etry standard (Accutrace, USA). Arsenazo III (99.9%) was supplied
by Fluka. Dioctylphthalate (99%), o-nitrophenyloctyl ether (99%),
dioctylsebacate (97%), and tris-(2-ethylhexyl) phosphate (97%)
were supplied by Sigma-Aldrich, Australia. Concentrated sulfuric,
nitric and hydrochloric acids were supplied by Scharlau Chemie
while NaOH, ZnCl2 , CuCl2 ·2H2 O, MgCl2 ·6H2 O, Al(NO3 )3 ·9H2 O,
FeCl3 ·6H2 O, and MnSO4 ·H2 O were purchased from Unilab.
Deionised water (18.2 M cm, Millipore, France) was used in the
preparation of all solutions. All other reagents were of analytical
grade unless otherwise indicated.
2.2. Membrane preparation
Membranes were prepared in general accordance with the
methods described previously [2,10]. In order to prepare a batch of
membranes, 5 g of membrane components (total mass of polymer,
extractant and plasticizer, if used) in appropriate proportions were
dissolved in 50 mL THF. The components were dissolved whilst stir-
ring using a magnetic stirrer and the casting solution was dispensed
by autopipette into a glass ring (internal diameter 76 mm) sitting on
a glass plate. The amount of casting solution dispensed depended on
the required thickness of the membrane; an aliquot of 4 mL yielded
a membrane of total mass of 400 mg with an approximate thickness
of 50 ␮m, whilst an 8 mL aliquot produced a membrane with double
this mass and thickness. The casting solution was covered by a filter
paper and watchglass and the solvent allowed to slowly evaporate
over 48 h. The membrane was then peeled from the glass plate and
visually examined for any defects.
For use in all experiments, circular segments of diameter 4.5 cm
were cut from the centre of the membrane using a steel punch, as
PIMs have been shown previously to have a more uniform thickness
close to the centre of the membrane compared to the edges [11].
The mass of each segment was approximately one-quarter of the
total membrane mass.
2.3. Membrane transport experiments
The general procedure used for membrane transport experi-
ments was as follows: a membrane segment (mass 0.100 ± 0.005 g,
diameter 45.0 mm, thickness approximately 50 ␮m) was used
to separate the source and receiving phases in a conventional
two-sided membrane transport cell. The membrane segment was
sandwiched between two Teflon flanges, leaving a circular area
of diameter 35.0 mm which was completely exposed to the solu-
tion on each side of the membrane. The Teflon flanges were
attached to water-jacketed glass extraction cells of the general
243
design described earlier [11], with ports for stirring glands and sam-
pling. The volume of solution in each cell compartment was 100 mL.
The solution in each cell was stirred by a glass impeller, driven by
overhead stirring glands attached to a VelpScientifica B5-type over-
head stirrer at 1350 rpm. The stirring speed was monitored using
a laser tachometer (Digitech QM1448, Jaycar, Australia) and the
temperature of the transport cells was maintained at 25.0 ± 0.5 ◦ C
by recirculating water from a water bath equipped with a ther-
moregulator (Ratek TH5, Australia). 1 mL samples of the source and
receiving solutions were taken at regular time intervals and ana-
lysed for uranium. The solution removed for sampling was replaced
with the appropriate initial solution for each phase. All transport
experiments were conducted in duplicate.
2.4. Uranium analysis
For routine transport experiments where U(VI) was the only
analyte of interest, its concentration in each sample was deter-
mined by visible spectrophotometry using Arsenazo III as the
chromophore. For samples with relatively low acidity, 1 mL of sam-
ple was mixed with 9 mL of 0.036% (m/v) Arsenazo III in deionised
water. For samples with acidity greater than 1.0 mol L−1 , 1 mL of
sample was mixed with 9 mL of a solution containing 0.036% (m/v)
Arsenazo III and 1.5 moles of NaOH for each mole of H2 SO4 . This
increased the pH in the final solution to approximately 1.9 (the pKa
of the bisulfate ion), which is close to the ideal pH (ca. pH 2) for
the determination of U(VI) using Arsenazo III [12]. The absorbance
at 665 nm was measured using a Libra S12 UV–visible spectropho-
tometer (Biochrom, UK) and the concentration was determined by
the calibration curve method.
2.5. Optimisation of the acidity in the receiving phase
Membrane transport experiments were carried out with 4.0,
6.0 and 8.0 mol L−1 H2 SO4 in the receiving phase; 100 mg L−1 U(VI)
and 0.10 mol L−1 H2 SO4 in the source phase and membranes con-
taining 40% D2EHPA/60% PVC. The concentrations of all membrane
components quoted in the remaining of this paper are in mass per-
centage (m/m). The transient concentration of U(VI) in the source
and receiving phases was monitored and plotted against time.
2.6. Optimisation of the composition of the membrane
In an earlier work [2], the membrane composition used for
extraction only was 40% D2EHPA/60% PVC. To determine if a more
suitable composition for transport purposes could be used, the
composition was varied and the resulting initial flux of U(VI) trans-
ported across the membrane was used to evaluate the effectiveness
of each PIM composition.
2.6.1. Optimisation of the amount of extractant in the membrane
Preliminary transport experiments were conducted using PIM
segments containing 40% D2EHPA/60% PVC, 50% D2EHPA/50% PVC
and 60% D2EHPA/40% PVC which were contacted with a source
phase containing 100 mg L−1 U(VI) and 0.1 mol L−1 H2 SO4 and a
receiving phase containing 4.0 mol L−1 H2 SO4 . As the 50% and 60%
D2EHPA membranes appeared too unstable for routine use, later
experiments used amounts of D2EHPA less than 50%.
In these experiments, segments of 40% D2EHPA/60% PVC and
45% D2EHPA/55% PVC were contacted with a source phase contain-
ing 100 mg L−1 U(VI) and 0.1 mol L−1 H2 SO4 and a receiving phase
containing 6.0 mol L−1 H2 SO4 .
2.6.2. Effects of different plasticizers
Transport experiments were carried out using membranes
containing different plasticizers, with a source phase containing
244 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250
100 mg L−1 U(VI) and 0.1 mol L−1 H2 SO4 and a receiving phase
containing 6.0 mol L−1 H2 SO4 . The membranes were composed
of 35% D2EHPA, 10% plasticizer and 55% PVC. The plasticiz-
ers tested were dioctylphthalate (DOP), dioctylsebacate (DOS),
tris(2-ethylhexyl) phosphate (TEHP), and o-nitrophenyloctyl ether
(NPOE). The results were compared against PIMs containing 45%
D2EHPA/55% PVC which can be viewed as a 35% D2EHPA membrane
containing another 10% D2EHPA as plasticizer.
2.6.3. Optimisation of the concentration of plasticizer
The most suitable plasticizer was found to be NPOE and trans-
port experiments were carried out to determine the optimal
concentration of NPOE in the membrane. The membrane com-
positions studied were 35% D2EHPA/10% NPOE/55% PVC, 40%
D2EHPA/5% NPOE/55% PVC and 45% D2EHPA/55% PVC. The source
phase contained 100 mg L−1 U(VI) and 0.1 mol L−1 H2 SO4 and the
receiving phase contained 6.0 mol L−1 H2 SO4 .
2.7. Transport behaviour at different concentrations of U(VI)
Transport experiments were conducted using membranes com-
posed of 45% D2EHPA/55% PVC with source phases containing 30,
100 and 300 mg L−1 U(VI) in 0.1 mol L−1 H2 SO4 . The receiving phase
in each case was 6.0 mol L−1 H2 SO4 .
2.8. Investigation of the effect of the acid anion in the source and
receiving phases
2.8.1. Extraction tests
The effect of the acid anion in the source phase was studied
using membrane segments of 45% D2EHPA/55% PVC and mass
0.200 ± 0.005 g which were placed in covered jars containing
100 mL of 70 mg L−1 U(VI) in 1.000 ± 0.005 mol L−1 of HNO3 , HCl
or H2 SO4 . The concentration of acid was standardised by titration
against 1.0 mol L−1 NaOH which had been standardised directly
against potassium hydrogen phthalate. The concentration of U(VI)
was chosen to give a mole ratio of D2EHPA to U(VI) of approx-
imately 10:1. The jars containing the solution and the PIM were
shaken at 125 rpm on an orbital mixer (Ratek OM5, Australia) and
1 mL samples were taken at regular time intervals over 24 h. The
concentration of U(VI) in solution was determined using visible
spectrophotometry with Arsenazo III as the chromophore and the
standards used to construct the calibration curve were carefully
matrix-matched to each solution. The experiments were conducted
in duplicate.
2.8.2. Back-extraction tests
The effect of each one of the acids investigated (i.e. H2 SO4 , HCl,
HNO3 ) on back extraction was studied using membrane segments
of composition 45% D2EHPA/55% PVC and mass 0.200 ± 0.005 g
which were pre-loaded with uranium (UO2 2+ ) by placing them in
covered jars with 100 mL of solution containing 70 mg L−1 U(VI)
and 0.1 mol L−1 H2 SO4 and shaking for 24 h using an orbital mixer
at 125 rpm. The membrane segments were then blotted dry and
placed in covered jars containing 100 mL of 6.00 ± 0.05 mol L−1 of
HNO3 , HCl or H2 SO4 . The jars were shaken at 125 rpm on an orbital
mixer and 1 mL samples were taken at regular time intervals over
24 h. The experiments were conducted in duplicate.
2.9. Membrane durability tests
Membrane segments of 45% D2EHPA/55% PVC were subjected
to repeated extraction and back-extraction cycles. The PIM seg-
ments of mass 0.200 ± 0.005 g were loaded with U(VI) by placing
them in covered jars with 75 mL of solution containing 90 mg L−1
U(VI) and 0.1 mol L−1 H2 SO4 . The jars containing the solution and
PIMs were shaken at 125 rpm on an orbital mixer and 1 mL sam-
ples were taken at regular time intervals over 24 h. The segments
were removed from solution, blotted dry and carefully weighed.
The segments were then placed in covered jars containing 75 mL of
6.0 mol L−1 H2 SO4 . The jars containing the solution and PIMs were
shaken at 125 rpm on an orbital mixer and 1 mL samples were taken
at regular time intervals over 24 h. The segments were removed
from solution, blotted dry and carefully weighed. The process was
repeated and continued over five extraction and back-extraction
cycles. The concentration of U(VI) in the solutions was analysed by
visible spectrophotometry using Arsenazo III as the chromophore.
2.10. Batch selective extraction studies
Membrane segments of composition 45% D2EHPA/55% PVC and
mass 0.200 ± 0.01 g were placed in covered jars and immersed in
50 mL of solutions containing 0.1 mol L−1 H2 SO4 and 100 mg L−1 of
the cation of interest. The cations used were Fe(III), Al(III), Cu(II),
Mn(II), Mg(II), and Zn(II) and were tested individually. The jars were
shaken on an orbital mixer at 125 rpm and solution samples were
taken after 24 and 48 h. The concentration of the cations in the
solution samples were measured by inductively coupled plasma
optical emission spectrometry (ICP-OES) using a Varian 720-ES
instrument. The extraction of each cation was tested in duplicate.
2.11. Fe(III) pH isotherm
Fe(III) is a major interferent in the extraction of U(VI) by
D2EHPA. Therefore, the extraction of Fe(III) at different acidities
was tested by immersing membrane segments of composition 45%
D2EHPA/55% PVC and an average mass 0.229 ± 0.003 g in 25 mL of
solutions containing 6 mg L−1 Fe(III) (as Fe2 (SO4 )3 ) in various con-
centrations of H2 SO4 . The concentration of Fe(III) was chosen to
provide a mole ratio of D2EHPA:Fe(III) in excess of 100:1. Two sam-
ples were used for each acid concentration. The membrane and
solution were allowed to come to equilibrium over 5 days and
the concentration of Fe(III) in each solution was measured using
ICP-OES.
2.12. Competitive membrane transport experiments
The relative rate and extent of transport of Fe(III) compared
to U(VI) was studied using a membrane of composition 45%
D2EHPA/55% PVC with a mass and thickness of 0.100 ± 0.005 g and
50 ± 10 ␮m, respectively. The source phase contained 100 mL of
100 mg L−1 Fe(III) and 100 mg L−1 U(VI) in different concentrations
of H2 SO4 (0.1, 0.5 and 1.0 mol L−1 ) and the receiving phase con-
tained 100 mL of 6 mol L−1 H2 SO4 . The concentration of U(VI) and
Fe(III) in the samples was measured using ICP-OES.
3. Results and discussion
The rate and selectivity of a PIM-based separation is determined
mainly by the membrane composition and thickness and the com-
position of the source and receiving solutions.
In the present work, the thickness of the PIMs has been
reduced to approximately 50 ␮m from 67 ␮m reported earlier [2].
D2EHPA/PVC PIMs which are made much thinner than 50 ␮m can
be difficult to produce reproducibly and handle and are often poorly
self-supporting. Therefore, in this study, we report on the optimi-
sation of the compositions of the membrane on one hand and the
source and receiving solutions on the other.
The membrane extraction of uranium by D2EHPA proceeds
according to Eq. (1) [2],
UO2 2+ (s) + 2(HA)2(m)  UO2 (AHA)2(m) + 2H+ (s) (1)
 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250
where HA and A− represent D2EHPA and its conjugate base, and
subscripts m and s refer to the membrane and solution phase,
respectively.
The reaction proceeds in the forward direction at the inter-
face between the PIM and the source phase (extraction) and in the
reverse direction at the interface between the PIM and the receiv-
ing phase (back-extraction). Back-extraction is therefore favoured
by a higher concentration of acid in the aqueous phase.
Eq. (2) has been frequently used for the description of membrane
transport [3].
C A
ln =− Pt
C0 V
where C0 and C are the initial and transient concentrations of the
transported species in the source phase in (mol m−3 ); t is time in
s; A is the membrane surface area in (m2 ), V is the source phase
volume in (m3 ); P (= JC) is the permeability; and J is the flux.
P of the PIMs studied can be determined by fitting the solu-
tion of Eq. (2) (i.e. Eq. (3)) to the corresponding transient U(VI)
concentration curve (C) for the source phase.
C = C0 e(−A/V )Pt
The initial flux (J0 ) can be calculated by dividing P by C0 . The ini-
tial flux can be used for comparing the transport properties of
membranes studied under the same experimental conditions and
therefore has been used in the current PIM optimisation studies.
However, for comparing membranes studied under different exper-
imental conditions (e.g. different C0 , A and V) it is more appropriate
to use P.
The mass transfer resistance of PIMs may be viewed as being
comprised of contributions from diffusion through the stagnant
layers on either side of the membrane and through the membrane
itself, as given in Eq. (4):
Rtotal = Ra,s + Rm + Ra,r
where R is the uranium(VI) mass transfer resistance through the
membrane (m) and the stagnant diffusion layers in the aqueous
source (a,s) and receiving (a,r) phases. The mass transfer resistance
in each layer is given by Eq. (5):
xi
Ri =
Di
where Ri is the mass transfer resistance of layer i, Di is the ura-
nium(VI) diffusion coefficient in that layer and xi is the layer
thickness [13].
In our previous study, we demonstrated that the thickness
of the stagnant layer in this PIM system was 30 ␮m [2]; the
combination of the layers on either side of the membrane rep-
resents a total stagnant layer thickness of approximately 60 ␮m.
This thickness is comparable to the thickness of the membrane
used in these transport experiments (ca. 50 ␮m), however the
diffusion coefficient of the uranyl cation in aqueous solutions
(6.6 × 10−10 m2 s−1 , [14]) is several orders of magnitude higher than
the generally determined range of diffusion coefficients for PVC-
based PIMs (10−12 –10−13 m2 s−1 , [15,16]). This suggests that the
greatest contribution to the overall mass transfer resistance comes
from diffusion through the PIM; therefore the optimisation of the
transport of uranium(VI) through PIMs relies heavily on the optimi-
sation of the composition of the membrane to minimise diffusive
resistance.
3.1. Optimisation of the acidity in the receiving phase
The transport of U(VI) from the source to receiving phase is
counter-coupled to the transport of H+ in the opposite direction;
245
100
90
Concentration of U(VI) (mg L-1)
80
70
60
50
40
(2) 30
20
10
0
0 10 20 30 40 50
Time (h)
Fig. 1. Transport of U(VI) across a 40% D2EHPA/60% PVC PIM with different H2 SO4
concentrations in the receiving phase. (Source phase: 100 mg L−1 U(VI) in 0.1 mol L−1
(3) H2 SO4 ; receiving phase: 4.0 (䊉), 6.0 (×) and 8.0 () mol L−1 H2 SO4 ).
therefore increasing the H+ concentration gradient across the mem-
brane increases the driving force of the transport process. Since
previous experiments have shown that lowering the acidity in the
source phase leads to increased leaching of D2EHPA from the mem-
brane [2], the acidity in the source phase should not be lower
than 0.1 mol L−1 H2 SO4 . Therefore, the concentration gradient of
H+ across the membrane can only be increased by increasing the
concentration of sulfuric acid in the receiving phase.
In Fig. 1, transient U(VI) concentrations in the source and
receiving phases at different concentrations of sulfuric acid in the
(4) receiving phase are shown. Concentrations of H2 SO4 in the receiv-
ing phase higher than 4 mol L−1 were used as lower concentrations
lead to incomplete back-extraction [2]. The figure indicates that
the optimum acid concentration for back-extraction under trans-
port conditions is 6.0 mol L−1 . Although back-extraction is largely
complete with a concentration of acid of 4.0 mol L−1 , the flux is sub-
stantially improved by using a higher concentration. No discernible
(5)
benefit is observed by increasing the concentration of acid higher
than 6 mol L−1 and it is desirable that acid concentrations should
be as low as possible for reasons of cost and safety.
3.2. Optimisation of the concentration of extractant
Another important system parameter affecting the membrane
transport process is the concentration of extractant in the mem-
brane. A higher initial concentration of extractant leads to a
higher initial concentration of the extracted complex at the mem-
brane/source phase interface, thus enabling more uranyl ions to be
transported across the membrane. Although it remains unclear as
to whether the extracted U(VI) is passed along a chain of immo-
bile extractant molecules (as in the fixed site model [17]) or the
extracted complex diffuses freely through the membrane (as in
the mobile carrier model), an increase in the amount of extrac-
tant should improve the flux of U(VI) across the membrane in both
cases.
Preliminary experiments showed a large improvement in the
membrane flux as the concentration of D2EHPA in the PIM was
raised from 40% to 60%. However, the 50% and 60% D2EHPA PIMs
were mechanically unstable and difficult to handle for routine
usage. This showed that although concentrations of D2EHPA in
the PIM higher than 50% lead to faster transport, membranes can
246 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250

100
100

Concentration of U(VI) (mg L-1)

90
Concentration of U(VI) (mg L-1)

80 80
70

60 60

50
40
40

30
20
20

10
0
0 0 5 10 15 20 25 30
0 10 20 30 40 50
Time (h)
Time (h)
Fig. 3. Transport of U(VI) across D2EHPA/PVC PIMs with different plasticizers in
Fig. 2. Transport of U(VI) across D2EHPA/PVC PIMs with different D2EHPA concen- the membrane. (Source phase: 100 mg L−1 U(VI) in 0.1 mol L−1 H2 SO4 ; Receiving
trations. (Source phase: 100 mg L−1 U(VI) in 0.1 mol L−1 H2 SO4 ; Receiving phase: phase: 6.0 mol L−1 H2 SO4 ; Membranes: 45% D2EHPA/55% PVC (䊉), 35% D2EHPA/55%
6.0 mol L−1 H2 SO4 ; Membranes: 45% D2EHPA/55% PVC (䊉) and 40% D2EHPA/60% PVC/10% TEHP (), 35% D2EHPA/55% PVC/10% DOP (), 35% D2EHPA/55% PVC/10%
PVC ()). DOS (×), and 35% D2EHPA/55% PVC/10% NPOE ()).

be manufactured and handled more reproducibly when they con-
tained less than 50% D2EHPA.
Fig. 2 illustrates the significant improvement in the transport
rate for a 45% D2EHPA membrane compared to a 40% D2EHPA
membrane, due to the increase in the number of available extrac-
tant molecules (or carriers). As D2EHPA also has a plasticizing effect
on the membrane, increasing its concentration lowers the diffusive
resistance of the PIM, thus further improving the flux. As reported
earlier [2], PIMs containing less than 40% D2EHPA exhibit vastly
poorer extraction characteristics as the anti-plasticizing threshold
is crossed. Therefore PIMs containing less than 40% D2EHPA were
not studied.
3.3. Plasticizer studies
It was hoped that the addition of a plasticizer to the membrane
would lead to a further improvement in the transport rate since the
common plasticizers used in PIMs generally have a lower viscosity
than D2EHPA and might be expected to increase the diffusivity of
species through the membrane [3].
Fig. 3 shows the effect of different plasticizers in the membrane
composition. In these experiments, each membrane had the same
concentration of D2EHPA (i.e. 35%) and the same concentration of
plasticizer (10%). The membrane containing 45% D2EHPA can be
viewed as containing 35% of extractant (D2EHPA) and 10% of plas-
ticizer. It can be seen that the initial flux increases in the order
TEHP < DOP < DOS < D2EHPA < NPOE (Table 1).
It is interesting to note that all of the plasticizers tested except
for NPOE slow the transport process when compared to a 45%
D2EHPA/55% PVC PIM. This would suggest that the viscosity of the
Table 1
Initial uranium flux values (J0 ) with their standard deviations (SD) for PIMs of differ-
ent composition, which were tested under the same conditions. In each composition,
the balance of mass is PVC.
Composition 106 × J0 (mol m−2 s−1 )
40% D2EHPA 1.85
45% D2EHPA 2.92
35% D2EHPA/10% NPOE 3.04
40% D2EHPA/5% NPOE 3.03
35% D2EHPA/10% DOP 2.08
35% D2EHPA/10% DOS 2.50
35% D2EHPA/10% TEHP 1.20
plasticizer is relatively unimportant in improving the flux through
the membrane; the viscosities of NPOE, TEHP, and DOS (11, 13 and
18 cP) [18] are substantially lower than that of D2EHPA (35 cP)
[19]. Similarly, changes in dielectric constant cannot fully explain
the observed trends. Although NPOE has a high dielectric constant
(24), the variance in transport performance between the other plas-
ticizers is not explained by their dielectric constants, which lie in a
narrow range between 4 and 5 [18].
The particularly poor performance of TEHP as a plasticizer is
noteworthy. The related compound tri-n-butyl phosphate is com-
monly used in solvent extraction synergistically with D2EHPA [20]
and both TEHP and TBP plasticize PVC very well, although in our
previous work we were not able to use TBP to successfully extract
U(VI) into a PVC membrane [2]. It is likely that there is some chem-
ical interaction between U(VI) and the TEHP; alkyl phosphates
complex readily with the uranyl cation and it may be possible
that a large uranyl-TEHP complex at the source phase/membrane
interface interferes with the extraction of U(VI) by D2EHPA.
Given that NPOE was observed to be the best plasticizer for the
transport of the uranyl-D2EHPA complex across the D2EHPA/PVC
PIM, the amount of plasticizer in the membrane was optimised. The
most compatible and stable membranes were found to be those
containing 35% D2EHPA/10% NPOE and 40% D2EHPA/5% NPOE.
Membranes with other compositions were found to be too fragile
or had oily surfaces.
The results in Table 1 show that the addition of NPOE into
the membrane only slightly improves the membrane performance
compared to the corresponding 45% D2HEPA membrane. Although
the membranes plasticised by NPOE appear to transport ura-
nium(VI) slightly faster than those composed of 45% D2EHPA and
55% PVC, the uncertainty in the initial flux values represented by
their standard deviations suggests that those differences are not
significant. This result does not justify the use of this expensive
plasticizer. Therefore, 45% D2EHPA/55% PVC PIMs were used for all
further experiments. Using a PIM that contains only extractant and
polymer also has the advantage of being simpler to fabricate and
easier to characterise using relatively simple instrumental methods
± 0.06 [10].
± 0.05
± 0.02
± 0.23 3.4. Transport behaviour at different concentrations of U(VI)
± 0.04
± 0.17 As shown in Fig. 4, the transport of U(VI) across a 45%
± 0.15
D2EHPA/55% PVC PIM varies greatly with the initial concentration
 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250 247

1
70

Concentration of U(VI) (mg L-1)

0.8 60

50
0.6
40
C/C0

0.4 30

20
0.2
10

0 0
0 5 10 15 20 25
Time (h)
Fig. 4. Transport of U(VI) across 45% D2EHPA/55% PVC PIMs with different initial
concentrations of U(VI) in the source phase. C/C0 represents the concentration of
uranium(VI) in the source and receiving phases as a fraction of the initial con-
centration of uranium(VI) in the source phase. (Source phase: 30 mg L−1 U(VI) in
0.1 mol L−1 H2 SO4 (䊉), 100 mg L−1 U(VI) in 0.1 mol L−1 H2 SO4 () and 300 mg L−1
U(VI) in 0.1 mol L−1 H2 SO4 (); Receiving phase: 6.0 mol L−1 H2 SO4 ).
of uranium(VI). Taking into account that the stoichiometric ratio
of U(VI) to D2EHPA is 1:4 (Eq. (1)), the most profound difference
is between the transport of uranium from a solution containing a
stoichiometric excess of U(VI) (300 mg L−1 corresponds to U(VI):
D2EHPA mole ratio of approximately 1:1.1) on one hand, and the
transport from solutions where D2EHPA is in excess (100 and
30 mg L−1 correspond to U(VI): D2EHPA mole ratios of approxi-
mately 1:3.3 and 1:11, respectively) on the other.
The extraction stoichiometry is an important consideration
where U(VI) is extracted by D2EHPA. Although Fickian diffusion
predicts that the flux across the membrane will increase in direct
proportion to the concentration of U(VI) in the source phase, the
actual average flux after 3 h followed the predicted behaviour only
for the 30 and 100 mg L−1 cases where D2EHPA was in excess
(J = 0.36 and 1.2 ␮mol m−2 s−1 respectively), whereas in the case of
excess U(VI) (300 mg L−1 ), the flux was much lower than expected
(J = 1.1 ␮mol m−2 s−1 ).
The capacity of D2EHPA to form oligomeric complexes with
the uranyl cation as the ratio of D2EHPA to U(VI) decreases is
well known [21]. It is likely that as the concentration of U(VI) is
increased in the source phase beyond the ideal stoichiometric ratio
(4 D2EHPA: 1 U(VI)), the formation of larger complexes, which
will be more bulky to transport through the constricted membrane
environment, is favoured. This explains the lower than expected
flux values in the case of excess of U(VI) (300 mg L−1 ). Previous
0 5 10 15 20 25
Time (h)
Fig. 5. Extraction of U(VI) by a 45% D2EHPA/55% PVC PIM from source phases
containing 70 mg L−1 U(VI) and 1.0 mol L−1 HNO3 (䊉), 1.0 mol L−1 HCl () and
1.0 mol L−1 H2 SO4 ().
sulfuric acid in the source phase dramatically slows the extraction
of U(VI) by D2EHPA.
The particular effect of the sulfate anion on the extraction of
U(VI) may be explained by the complexation of the uranyl cation
by the acid anions, in accordance with the corresponding complex
formation constants. While chloride and nitrate complex the uranyl
cation to a small degree, (log K1 = 0.22 and 0.34, respectively [22])
the complexation of U(VI) by sulfate is much more pronounced
(log K1 = 1.70, log K2 = 2.45 and log K3 = 3.30 [22]). It is likely that
complexation (and extraction) of the uranyl cation by D2EHPA is in
competition with its complexation by sulfate, which slows down
the membrane extraction and transport.
Although the complexation of U(VI) by sulfate is a hindrance
during extraction, Fig. 6 shows that sulfuric acid solutions provide
the fastest back-extraction. It is likely that the complexation of the
uranyl cation by sulfate assists in stripping U(VI) from the PIM.
Although there is a difference in the capacities of hydrochloric acid
and sulfuric acid as stripping agents, the very poor back-extraction
performance of nitric acid cannot be explained by the complexa-
tion constants. Nitric acid has been demonstrated to be an efficient
stripping agent in solvent extraction studies of the uranium(VI)-
D2EHPA system [23], so the reasons why HNO3 is not an effective
stripping agent in the PIM analogue remain unclear.
70
Concentration of U(VI) (mg L-1)

work showed that the extraction behaviour of D2EHPA/PVC PIMs

60
becomes less predictable as the concentration of U(VI) is increased
beyond its stoichiometric ratio with D2EHPA [2]; therefore it is 50
essential to properly control the amount of U(VI) in contact with
the membrane so as to not over-saturate the available D2EHPA at 40
the source/membrane interface.
30

3.5. Effect of the U(VI) acid anion 20

Although the extraction and back-extraction reactions (Eq. (1)) 10

do not contain any reference to the acid anion in solution, it should
0
be taken into account that the uranyl cation complexes with many 0 5 10 15 20 25
anionic species, particularly oxygen-containing ligands. It is there-
fore likely that the acid anion is involved in the overall membrane
Time (h)
transport process.
Fig. 6. Back-extraction of U(VI) from a 45% D2EHPA/55% PVC PIM into receiving
Fig. 5 shows the influence of the acid anion on the extraction of phases containing 6.0 mol L−1 HNO3 (䊉), 6.0 mol L−1 HCl () and 6.0 mol L−1 H2 SO4
U(VI) by a 45% D2EHPA/55% PVC PIM. It is clear that the presence of ().
248 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250

Table 2
The 95% confidence intervals of the average initial U(VI) fluxes for the first 3 and 8 h of 5 repeated cycles of extraction and back-extraction (Membrane: 45% D2EHPA/55%
PVC; Source phase: 90 mg L−1 U(VI) in 0.1 mol L−1 H2 SO4 ; Receiving phase: 6 mol L−1 H2 SO4 ).

106 Jav (mol m−2 s−1 ) - extraction 106 Jav (mol m−2 s−1 ) - back-extraction

3h 8h 3h 8h

Cycle 1 0.59 ± 0.14 0.29 ± 0.01 −0.61 ± 0.06 −0.28 ± 0.01

Cycle 2 0.57 ± 0.10 0.29 ± 0.01 −0.58 ± 0.20 −0.27 ± 0.01
Cycle 3 0.56 ± 0.11 0.28 ± 0.01 −0.58 ± 0.13 −0.26 ± 0.02
Cycle 4 0.53 ± 0.11 0.28 ± 0.01 −0.55 ± 0.18 −0.26 ± 0.02
Cycle 5 0.61 ± 0.18 0.29 ± 0.01 −0.56 ± 0.07 −0.27 ± 0.01

Table 3
Comparison of selected membrane systems for uranium extraction and transport.

Membrane system 106 P m s−1 Reported stability

Polymer inclusion membranes

45% D2EHPA/55% PVC (this study) 6.96 >10 days/cycles#
75% TBP/25% PVCa [5] 2.40 1.2 days
62% TBP/38% CTAb [6] 4.76 <1 h
18% TOPO/42% NPOE/40% CTA [9] 2.15 >16 days#

Supported liquid membranes

S: Celgard 2500; L: TOPO in NPOE (450 g L−1 ) [9] 0.38 <8 days
S: PTFE; L: 0.60 mol L−1 PC-88A and 0.15 mol L−1 Cyanex 923 in dodecane [20] 20.6 <10 cycles
S: PTFE; L: 1.5 mol L−1 D2EHPA and 0.20 mol L−1 TOPO in dodecane [21] 6.71 Not reported

S, support; L, liquid phase.

a
Membrane not self-supporting (cast on Kraft paper).
b
Permeability determined graphically.
#
Membranes indicated to be stable beyond the period tested.

3.6. Membrane durability tests
The durability of the membrane over repeated cycles of extrac-
tion and back-extraction over 8 h is demonstrated in Table 2.
As can be seen in Table 2, there is a small variation in perfor-
mance over 5 cycles of extraction and back-extraction; however the
variation in performance is well within the range of the experimen-
tal error corresponding to the 95% confidence interval. Of particular
note is the small variation in the average initial flux over 8 h, which
indicates that the overall performance of the PIMs in extraction
and back-extraction remains very similar over 5 cycles. Although
the last cycle of extraction appears to show a slight increase in
the average initial flux value, this increase is insignificant when
experimental errors are taken into account.
The main reason for the decline in the performance of PIMs over
time is the loss of extractant through leaching into the aqueous
phases in contact with the membranes. Although the PIM-based
extraction technique vastly reduces these losses when compared
to SX and SLM techniques [3], the extractive performance of PIMs
can be sensitive to the loss of small amounts of extractant due
to the very small amount of extractant encapsulated within the
membrane. Where a PIM is constantly exposed to a single solu-
tion, the small amount of extractant leached from the PIM will
rapidly saturate the aqueous phase (due to the low water solubility
of the extractants used) and any further leaching will be signifi-
cantly retarded. In this case, the PIM segment was exposed to fresh
solutions for each extraction and back-extraction experiment,
meaning that no saturation could occur and extractant loss would
be maximised.
The loss of mass (assumed to be loss of extractant) suffered by
the 45% D2EHPA/55% PVC PIMs was relatively small. The average
PIM mass was 94.3 ± 4.7% of its initial mass after 5 extraction-back
extraction cycles, suggesting that the PIMs were relatively durable
and would be expected to have a useful life-span with repeated
use. These results are promising for the commercial application of
the proposed PIM technology as longer lasting PIMs will prove less
costly to use.
3.7. Comparison of membrane systems
Table 3 compares the performance of the proposed 45%
D2EHPA/55% PVC PIM system in terms of transport properties and
stability with other PIM- and SLM-based systems for the transport
of uranium. As mentioned earlier, due to the fact that the membrane
systems listed in Table 3 operated under different experimental
conditions, the permeability, rather than the initial flux, should be
used to compare their transport properties. On the basis of such a
comparison it can be concluded that the PIM developed as part of
this study has superior transport properties except for the Cyanex
923 SLM (Table 3). However, the latter membrane has poorer
stability. This comparison demonstrates the potential of PIMs as
an attractive alternative to SLMs, which have traditionally been

Table 4
Extraction of U(VI) and common base metal cations by a 45% D2EHPA/55% PVC PIM over 24 h and 48 h periods. Source phase: 50 mL 0.1 mol L−1 H2 SO4 and 100 mg L−1 of the
metal cation studied.

Cation Initial conc. (mg L−1 ) Conc. after 24 h (mg L−1 ) %E (24 h) Conc. after 48 h (mg L−1 ) %E (48 h)

U(VI) 100 0.5 100% – –

Al(III) 101 100 1% 101 0%
Cu(II) 109 110 −1% 112 −2%
Fe(III) 106 79 26% 68 35%
Mg(II) 109 109 0% 110 −1%
Mn(II) 109 109 −1% 109 −1%
Zn(II) 105 106 −1% 107 −2%
 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250
100%
80%
% Extraction
60%
40%
20%
0%
-1.0 0.0 1.0 2.0
pH
Fig. 7. pH isotherm of a 45%/55% D2EHPA PIM extracting Fe(III) from sulfate solu-
tions (). The pH isotherm for U(VI) reported previously [2] is also shown (䊉).
considered to provide superior transport properties [3]. In addition,
the D2EHPA/PVC and CTA/TOPO/NPOE PIMs also have demonstra-
bly greater stability than the SLMs listed in Table 3.
3.8. Batch selectivity studies
The usefulness of D2EHPA as an extractant lies in its ability to
separate U(VI) from base metal ions commonly found in environ-
mental and hydrometallurgical applications. The data in Table 4
demonstrate that when using 0.1 mol L−1 H2 SO4 in the source
phase, the only metal ions extracted by the D2EHPA/PVC PIM were
the uranyl and ferric cations. Although this is not an exhaustive
list of all ions which may be encountered, the strong selectivity of
D2EHPA for U(VI) at high acidities has been widely reported [24].
Some cations which are commonly found in uranium ores (such
as Pb2+ and Ca2+ ) have not been tested with this membrane system
due to their poor solubility in sulfate media. These results show that
D2EHPA/PVC PIMs may successfully separate U(VI) from a variety
of other metal cations.
3.9. Fe(III) pH isotherm
Although the results from the batch selectivity tests indicated
that U(VI) can be selectively extracted from 0.1 mol L−1 H2 SO4 in
the presence of other base metal cations, Fe(III) will be co-extracted.
As D2EHPA is an acidic extractant, the selectivity of extraction
can be manipulated by varying solution pH [24]. Fig. 7 compares
the extraction of Fe(III) and U(VI) as a function of solution pH.
Although the extraction of the ferric ion is markedly lower than
that of the uranyl cation at H2 SO4 concentrations greater than
0.1 mol L−1 , there does not appear to be a H2 SO4 concentration
where a substantial amount of U(VI) may be extracted with no
Fe(III) co-extraction. Unfortunately, this indicates that it is not pos-
sible to completely separate U(VI) and Fe(III) thermodynamically.
Although it is possible to eliminate co-extraction of Fe(III) by mask-
ing it with orthophosphate [25] or by reducing it to Fe(II) [20], these
approaches are not applicable to the U(VI) extraction system stud-
ied. High concentrations of sulfate in both the source and receiving
phases make the orthophosphate complexation impractical and
the ferric ion is commonly used in hydrometallurgical processes
to keep uranium in the +6 oxidation state, making reduction of the
ferric ion undesirable.
3.10. Competitive membrane transport experiments
Although thermodynamic separation of U(VI) and Fe(III) is not
possible from sulfuric acid solutions, the rates of extraction of Fe(III)
249
a 100
Concentration of U(VI) (mg L-1)
80
60
40
20
3.0
0
0 10 20 30 40 50
Time (h)
b 100
Concentration of U(VI) (mg L-1)
80
60
40
20
0
0 20 40 60 80
Time (h)
Fig. 8. Separation of U(VI) (䊉,) and Fe(III) (,) by a 45% D2EHPA/55% PVC PIM.
(Source phase: 100 mg L−1 U(VI), 100 mg L−1 Fe(III) in 0.1 mol L−1 (a) or 1.0 mol L−1
(B) H2 SO4 ; Receiving phase: 6 mol L−1 H2 SO4 ; Symbols 䊉 and  refer to the source
phase while symbols  and  refer to the receiving phase.).
and U(VI) are markedly different, as demonstrated in the batch
extraction experiments. This raises the possibility of kinetic separa-
tion of U(VI) from Fe(II). Fig. 8(a) shows the competitive transport of
U(VI) and Fe(III) across the 45% D2EHPA/55% PVC PIM and demon-
strates how U(VI) is almost completely separated from Fe(III) in the
receiving phase; however a small but non-trivial amount of Fe(III)
is still transported across the membrane when the concentration of
H2 SO4 in the source phase is 0.1 mol L−1 . Fig. 8(a) also shows that
U(VI) is clearly extracted by D2EHPA in preference to Fe(III); the
extraction and transport of Fe(III) occurs mostly after the bulk of
U(VI) has been removed from the source phase.
A reasonably simple way to reduce the amount of Fe(III)
transported across the membrane is to slow its extraction rate.
Increasing the acidity in the source phase will slow the extraction
rate of both U(VI) and Fe(III); however as the extraction of Fe(III)
releases three H+ ions into the source phase compared to only two
H+ ions released for each UO2 2+ ion extracted, an increase in acidity
hinders more strongly the extraction of Fe(III) and therefore slows
its rate of extraction to a larger degree.
Fig. 8(b) shows the separation of U(VI) from Fe(III) when the
acidity in the source phase has been increased to 1.0 mol L−1 . In
this case, the rate U(VI) transport across the membrane has been
reduced, however the transport of Fe(III) across the membrane
has been almost completely eliminated. The transport of U(VI) is
250 A.M. St John et al. / Journal of Membrane Science 409–410 (2012) 242–250
essentially complete after 50 h, whilst a negligible amount of Fe(III)
(<1 mg L−1 ) has been transported into the receiving phase. This
clearly demonstrates that U(VI) may be completely separated from
Fe(III) kinetically using a D2EHPA/PVC PIM.
4. Conclusions
Transport of U(VI) from sulfuric acid solutions has been suc-
cessfully demonstrated using PIMs with PVC as the base polymer
and D2EHPA as the extractant; the main system parameters affect-
ing the rate of transport (i.e. composition of the membrane and
the source and receiving solutions) have been investigated and
optimised. The fastest transport was observed when using a PIM
composed of 35% D2EHPA, 10% NPOE and 55% PVC from a receiving
phase containing 0.1 mol L−1 H2 SO4 to a receiving phase contain-
ing 6.0 mol L−1 H2 SO4 , although the transport was only slightly
faster than in the case of a PIM composed of 45% D2EHPA and
55% PVC. This illustrates the possibility of using PIMs contain-
ing only polymer and extractant that will be cheaper to produce
than those containing an expensive plasticizer. Although the role
of the acid anion in the source and receiving solutions is commonly
ignored when using D2EHPA, complexation of U(VI) by sulfate
appeared to substantially slow U(VI) extraction but enhanced its
back-extraction from the membrane, compared to hydrochloric
acid.
PIMs composed of 45% D2EHPA and 55% PVC demonstrated their
potential to separate U(VI) completely from 0.1 mol L−1 H2 SO4 solu-
tions containing a variety of common base metal cations, although
some co-extraction of Fe(III) was observed. U(VI) could not be ther-
modynamically separated from the ferric ion through manipulating
pH, but successful kinetic separation was shown when the concen-
tration of H2 SO4 in the source phase was increased to 1.0 mol L−1 .
The proposed PIM was characterised by a small loss of mass and
negligible loss of extractive performance over 5 cycles of extraction
and back-extraction, which showed promise for industrial applica-
tions of this PIM technology. It also compared favourably with other
PIMs and SLMs in terms of transport properties and stability.
Acknowledgements
The authors would like to gratefully acknowledge the staff of the
School of Chemistry Workshops, especially the expert assistance
of Mr Lesley Gamel for the fabrication of the glassware used in
this study and Mr. Richard Mathys and Mr. Marino Artuso for the
fabrication of custom mechanical components.
References
[1] C. Musikas, W. Schulz, J.-O. Liljenzin, Solvent extraction in nuclear science
and technology, in: J. Rydberg, M. Cox, C. Musikas, G. Choppin (Eds.), Solvent
Extraction Principles and Practice, Marcel Dekker, New York, 2004.
[2] A.M. St John, R.W. Cattrall, S.D. Kolev, Extraction of uranium(VI) from sulfate
solutions using a polymer inclusion membrane containing di-(2-ethylhexyl)
phosphoric acid, Journal of Membrane Science 364 (2010) 354–361.
[3] L.D. Nghiem, P. Mornane, I.D. Potter, J.M. Perera, R.W. Cattrall, S.D. Kolev,
Extraction and transport of metal ions and small organic compounds using
polymer inclusion membranes (PIMs), Journal of Membrane Science 281 (2006)
7–41.
[4] M. O’Rourke, R.W. Cattrall, S.D. Kolev, I.D. Potter, The extraction and transport
of organic molecules using polymer inclusion membranes, Solvent Extraction
Research and Developement, Japan 16 (2009) 1–12.
[5] R. Bloch, A. Finkelstein, O. Kedem, D. Vofsi, Metal-ion separation by dialy-
sis through solvent membranes, Industrial & Engineering Chemistry Process
Design and Development 6 (1967) 231–237.
[6] H. Matsuoka, M. Aizawa, S. Suzuki, Uphill transport of uranium across a liquid
membrane, Journal of Membrane Science 7 (1980) 11–19.
[7] A.Y. Nazarenko, J.D. Lamb, Metal Ion Transport through Polymer Inclusion
Membranes with Crown Ether Carriers, in: Polymeric Materials Science and
Engineering, American Chemical Society Proceedings of the American Chemi-
cal Society Division of Polymeric Materials: Science and Engineering, 1997, p.
282.
[8] S. Sodaye, R. Tripathi, A.K. Pandey, A.V.R. Reddy, Scintillating polymer inclusion
membrane for preconcentration and determination of a-emitting actinides,
Analytica Chimica Acta 514 (2004) 159–165.
[9] N. Bayou, O. Arous, M. Amara, H. Kerdjoudj, Elaboration and characterisation
of a plasticized cellulose triacetate membrane containing trioctylphosphine
oxyde (TOPO): application to the transport of uranium and molybdenum ions,
Comptes Rendus Chimie 13 (2010) 1370–1376.
[10] A.M. St John, S.P. Best, Y. Wang, M.J. Tobin, L. Puskar, R. Siegele, R.W. Cattrall,
S.D. Kolev, Micrometer-scale 2D mapping of the composition and homogeneity
of polymer inclusion membranes, Australian Journal of Chemistry 64 (2011)
930–938.
[11] G. Argiropoulos, R.W. Cattrall, I.C. Hamilton, S.D. Kolev, R. Paimin, The study of
a membrane for extracting gold(III) from hydrochloric acid solutions, Journal
of Membrane Science 138 (1998) 279–285.
[12] S.B. Savvin, Analytical use of arsenazo III: determination of thorium, zirconium,
uranium and rare earth elements, Talanta 8 (1961) 673–685.
[13] G. Salazar-Alvarez, A.N. Bautista-Flores, E.R. de San Miguel, M. Muhammed,
J. de Gyves, Transport characterisation of a PIM system used for the extrac-
tion of Pb(II) using d2ehpa as carrier, Journal of Membrane Science 250 (2005)
247–257.
[14] Y. Awakura, K. Sato, H. Majima, S. Hirono, The measurement of the diffusion
coefficient of uranium(VI) in aqueous uranyl sulfate solutions, Metallurgical
Transactions B 18B (1987) 19–23.
[15] L. Wang, R. Paimin, R.W. Cattrall, W. Shen, S.D. Kolev, The extraction of cad-
mium(II) and copper(II) from hydrochloric acid solutions using an Aliquat
336/PVC membrane, Journal of Membrane Science 176 (2000) 105–111.
[16] S.D. Kolev, G. Argiropoulos, R.W. Cattrall, I.C. Hamilton, R. Paimin, Mathematical
modelling of membrane extraction of gold(III) from hydrochloric acid solutions,
Journal of Membrane Science 137 (1997) 261–269.
[17] C. Fontàs, R. Tayeb, M. Dhahbi, E. Gaudichet, F. Thominette, P. Roy, K. Steenkeste,
M.-P. Fontaine-Aupart, S. Tingry, E. Tronel-Peyroz, P. Seta, Polymer inclusion
membranes: the concept of fixed sites membrane revised, Journal of Membrane
Science 290 (2007) 62–72.
[18] Y.M. Scindia, A.K. Pandey, A.V.R. Reddy, Coupled-diffusion transport of Cr(VI)
across anion-exchange membranes prepared by physical and chemical immo-
bilization methods, Journal of Membrane Science 249 (2005) 143–152.
[19] L.R. Koekemoer, M.J.G. Badenhorst, R.C. Everson, Determination of viscosity
and density of di-(2-ethylhexyl) phosphoric acid + aliphatic kerosene, Journal
of Chemical & Engineering Data 50 (2005) 587–590.
[20] C.A. Blake, C.F. Baes, K.B. Brown, Solvent extraction with alkyl phosphoric com-
pounds, Industrial and Engineering Chemistry 50 (1958) 1763–1767.
[21] T. Sato, The extraction of uranium (VI) from sulphuric acid solutions by di-(2-
ethylhexyl)-phosphoric acid, Journal of Inorganic and Nuclear Chemistry 24
(1962) 699–706.
[22] J.A. Dean, Lange’s Handbook of Chemistry, 14th ed., McGraw-Hill, New York,
1992.
[23] D. Koladkar, P. Dhadke, Extraction and separation of Th(IV) and U(VI) from nitric
acid media using PIA-8 and HDEHP, Journal of Radioanalytical and Nuclear
Chemistry 253 (2002) 297–302.
[24] M. Cox, Solvent extraction in hydrometallurgy, in: J. Rydberg, M. Cox, C.
Musikas, R. Choppin Gregory (Eds.), Solvent Extraction Principles and Practice,
Marcel Dekker, New York, USA, 2004.
[25] S.D. Kolev, Y. Baba, R.W. Cattrall, T. Tasaki, N. Pereira, J.M. Perera, G.W. Stevens,
Solid phase extraction of zinc(II) using a PVC-based polymer inclusion mem-
brane with di(2-ethylhexyl)phosphoric acid (D2EHPA) as the carrier, Talanta
78 (2009) 795–799.