Journal of Colloid And Interface Science

Utilization of modified polymeric composite supported crown ether for selective sorption
and separation of various Beta emitting radionuclides in simulated waste
--Manuscript Draft--

Manuscript Number:

Article Type: Full length article

Section/Category: B. Surfactants and Soft Matter

Keywords: Amidoxime; chemical modification; hydroxylamine hydrochloride; oxime group;

polyacrylonitrile; Sorption

Corresponding Author: Mahmoud Goneam

Egyptian Atomic Energy Authority
Cairo- Egypt, EGYPT

First Author: Mahmoud Goneam, Lecyure

Order of Authors: Mahmoud Goneam, Lecyure

Emad H. Borai, Professor

Sahar Eldessouky, Professor

Abstract: Theoretically crown ethers are expected to contribute the formation of a host-guest
composition with a polymer backbone and improve its disadvantages. Based on this
hypothesis, functionalized polymer/crown ether composite is synthesized. The
preparation of modified multi-functional polymeric composite was carried out by mini
emulsion γ –irradiation of Poly Sodium styrene sulphonate (Acrylonitrile-Di amino
benzo 18-crown-6) PSS(AN-DAB18C6) within the presence of N, N'-
methylenediacrylamide (DAM) as a crosslinker and sodium styrene sulphonate as a-
surfactant and high share ultrasonic. Synthesis, structure mechanism, and
characteristic sorption properties were discussed. The main role of the prepared
adsorbent is to modify of both inert crown ether based and shared monomer to more
reactive forms. The influences of synthesis conditions particularly filler concentration
and radiation dose were examined. The chemical modification reaction was carried out
using hydroxylamine hydrochloride to get the amidoxime function group(AO) within the
modification of the acrylonitrile (AN) system. The sorption of Gd3+,Y3+, La3+, and
Sr2+ ions in aqueous solution on PSS(AN-DAB18C6) and PSS(AO-DAB18C6)
composite sorbents were investigated by batch method. Characterization of the
composites by SEM. FTIR and DLS confirmed that, the modified polymeric composite
exhibit good transformation. The results showed higher selectivity of PSS(AO-
DAB18C6) composite towards Y3+ and La3+ ions more than that of Sr2+ and Gd3+
ions. The experimental data fitted well to pseudo-second-order, elovich kinetic
modeling, and also fitted well to the Langmuir isotherms.

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1: Cover Letter

Dear Dr M. Malmsten

I wish to resubmit a new manuscript entitled “Utilization of modified polymeric

composite supported crown ether for selective sorption and separation of
various Beta emitting radionuclides in simulated waste". for Journal of Colloid

and Interface Science .

We confirm that this work is original and has not been published elsewhere nor
is it currently under consideration for publication elsewhere. Also, it has been
approved by all co-authors.

I hope it will be in acceptable form. Your comments are highly

appreciated. Thanks in advance for considering my request.

Best regards.
Sincerely yours
Dr. Mahmoud G. M. Hamed
Hot Laboratories Center
Egyption Atomic Energy Authority.
Cairo - Egypt
E-mail: [email protected]
3: Graphical Abstract
4b: Manuscript Click here to access/download;4b: Manuscript;Ultilization of
modified 2 12 2021.doc
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Utilization of modified polymeric composite supported crown ether for selective sorption
and separation of various Beta emitting radionuclides in simulated waste
Mahmoud G. Hamed a*, Sahar.I.El-Dessoukya and Emad H. Boraia
a
Hot Laboratories Center, Egyptian Atomic Energy Authority, 13759
Abstract
Theoretically crown ethers are expected to contribute the formation of a host-guest
composition with a polymer backbone and improve its disadvantages. Based on this hypothesis,
functionalized polymer/crown ether composite is synthesized. The preparation of modified multi-
functional polymeric composite was carried out by mini emulsion γ –irradiation of Poly Sodium
styrene sulphonate (Acrylonitrile-Di amino benzo 18-crown-6) PSS(AN-DAB18C6) within the
presence of N, N'-methylenediacrylamide (DAM) as a crosslinker and sodium styrene sulphonate
as a-surfactant and high share ultrasonic. Synthesis, structure mechanism, and characteristic
sorption properties were discussed. The main role of the prepared adsorbent is to modify of both
inert crown ether based and shared monomer to more reactive forms. The influences of synthesis
conditions particularly filler concentration and radiation dose were examined. The chemical
modification reaction was carried out using hydroxylamine hydrochloride to get the amidoxime
function group(AO) within the modification of the acrylonitrile (AN) system. The sorption of
Gd3+,Y3+, La3+, and Sr2+ ions in aqueous solution on PSS(AN-DAB18C6) and PSS(AO-
DAB18C6) composite sorbents were investigated by batch method. Characterization of the
composites by SEM. FTIR and DLS confirmed that, the modified polymeric composite exhibit
good transformation. The results showed higher selectivity of PSS(AO-DAB18C6) composite
towards Y3+ and La3+ ions more than that of Sr2+ and Gd3+ ions. The experimental data fitted well
to pseudo-second-order, elovich kinetic modeling, and also fitted well to the Langmuir isotherms.
Keywords: Amidoxime; chemical modification; hydroxylamine hydrochloride; oxime group;
polyacrylonitrile; Sorption.
1. Introduction
Yttrium-90 (Y-90) is a radioisotope that has strong emitting beta energy at 2.28 MeV and a
half-life of 64 hours, which is suitable for several applications serve the environment. Generation
of Y-90 is done in a permanent decay from the radioactive strontium-90 (Sr-90). It is one of the
fission products of uranium fuel in nuclear reactors. Y-90 must be high purity and free of Sr-90
and other metal ions to obtain high purity effect uses, although 90Y exists in equilibrium with
its parent isotope Sr-90[1]. Sr-90 is also a β− decay radioisotope and is classified as high-level
waste, which has beta energy at 0.546 MeV and a half-life of 28.79 years[2]. Furthermore,
radioactive Lanthanum-138 (138La) has a half-life of 1.02×1011 years and Gadolinium-158(158Gd),
are also, beta decay, and the primary decay products lighter isotopes are isotopes of terbium[3].
Most probably, Beta emitting radionuclides were measured by a liquid scintillation analyzer,
which measures the total beta count. In this respect, individual beta isotopes measurement is
considered as one of the most important analytical challenge problems. Therefore, selective
polymeric composite is highly requested for individual separation of beta-emitting isotopes [5].
The use of radiation-induced modified polymeric composite has the advantages of simplicity, low
cost, and adjustment of the materials composition[6]. In addition, this method ensures the grafting
of monomers that are difficult to polymerize with traditional methods. Conversion of inert
monomers to an active and selective form containing modified crown ethers (CEs) could be
controlled [7]. Crown ethers (CEs) are series of a macrocyclic compounds containing an ethylene
oxide (CH2CH2O)n ring and have exhibited excellent ability for selectively binding metal ions [8].
Crown ethers have been created in a variety of forms, but they tend to be limited to
macrocyclic molecules with oxygen (O) as a donor atom. Dibenzo 18-crown-6 (DB18C6) is one
of the aromatic crown ethers however, discrete crown ethers suffer from some serious limitations,
1
including expensive and toxicity, which restricts them from being widely used[9–11]. In recent
years, more attention has been focused on the exploration of supramolecular interactions between
polymeric crown ethers and organic compounds[12]. Numerous polymeric systems incorporating
crown ethers have been reported as Crown ether polymers offer various benefits that are lacking in
isolated crown ethers and expressed in crown ether resins: they are recyclable due to their
insolubility in water and most organic phases, and they can be marketed due to their cheap cost
and toxicity[13]. Nowadays Crown ether resins have been used in the extraction and separation of
metal ions up to this moment. DB18C6 is a well-known host molecule, and functionalized
DAB18C6 has attracted a lot of interest may be attributed to its ability to form stable complexes
with various metal ions owing to its relevant high capacity[14-[15]]. In this research (DAB18C6)
was grafted onto PSS and Acrylonitrile, and the resulting polymer was then modified into
a functionalized and porous matrix. The functionalization of DB18C6 from inert crown ether to
active form by in situ surface grafting by nucleophilic substitution between amino groups on
DAB18C6 and free radical on the polymer matrix is a critical factor and essential step in the
produced composite[16]. The in situ surface grafting conditions were adjusted. The sorption
capacity and efficiency of the synthesized polymeric composite supported crown ether were
examined in aqueous solution for Y3+, Gd3+, La3+, and Sr2+ metal ions
2. Experimental.
2.1. Chemicals and Reagents.
All chemicals and reagents were of analar quality and were utilized without being further
filtration, Poly(4-styrenesulfonic acid) sodium salt PSS(C8H7NaO3S)n, was supplied from Aldrich.
Dibenzo 18crown 6 ether, C20H24O6, was supplied from Merck. Acrylonitrile C3H3N, produced by
pubchem chemical laboratory. NH4OH acquired from Fluka, was used to adjust the pH of the
solutions. For all experiments bi-distilled water was used for solvation, preparation, dilution, and
analytical purposes. De-oxygenated water was prepared by boiling bi-distilled water for about 15
minutes followed by cooling under a stream of pure dry nitrogen gas at room temperature[17].

2.2. Synthesis, Characterization, and Instruments.

A SHI-MADZA AA-6880 atomic absorption spectrophotometer was used to determine the
metal ion concentrations (AAS). At the Cyclotron Project in Inshas, Egypt, an irradiation source
for polymerization process using a cobalt-60 gamma cell of type MC-20 (Russia). It includes two
5-liter chambers for irradiating samples. In a glass bottles, the samples were irradiated at room
temperature in the presence of an air compressor.
A computerized Fourier transform infrared spectra (FTIR), Bomem, Hartmann & Braun,
Michelson, MB-Series 157(Canada), was used to perform samples in the range of 4000-400 cm-1.
Scanning electron microscopy (SEM, JEOL-JSM 6510 LA (Japan)) was used to examine the
morphologies at a accelerating voltage of 15 kV[18].
2.2.1. Synthesis of Diamino benzo-18-crown-6 (DAB18C6)
Di(amino benzo)-18-crown-6 (DAB18C6) was prepared via an oxidation reaction of DAB18C6
followed by a reduction reaction[19] as shown in scheme 1. DB18C6 (1 g), acetic acid (10 mL),
and chloroform (25 mL) were stirred in a 250 mL round-bottom flask. The nitric acid (1 mL) and
acetic acid (4 mL) mixture was added dropwise and the reaction continued stirring for 5 hours at
60 °C, to obtain yellow powder Di nitrobenzo-18-crown-6 expressed as (DNB18C6)[15].
The reduction method was used to synthesize DAB18C6 by using hydrazine hydrate in the
presence of Pd/C as the catalyst. DNB18C6 (0.8 g), deionized water (15 mL), and 0.05 g (pd/C)
catalyst was stirred in a 250 ml in round-bottom flask during the reduction

2
process, according to standard procedure, and heated to 80°C[20]. The hydrazine hydrate (20 mL)
was added slowly into the flask in 30 min. The reduction reaction was carried out at 120°C with
stirring for 1 hour under reflux. By filtration at 120°C, the Pd/C catalyst was removed, and the
filtrate was cooled for crystallization. Yellow crystals of DAB18C6 were formed, which were
filtrated, washed with ethanol, and dried at 80°C overnight as illustrated in Scheme 1

O O
O O HAC O O
+ HNO3 NO2 NO2
O O CHCl3 O O
O O

DB18C6 O DNB18C6
O O

2
HN NH2 NH2OH.HCl
O O
O
NaOH+ catalyst
DAB18C6
Sch. 1. Synthesis routes of DAB18C6
2.2.2. Synthesis of Poly Sodium styrene sulphonate (Acrylonitrile – Di Amino Benzo 18
Crown-6) PSS(AN-DAB18C6) composite.
Poly sodium styrene sulphonate (Acrylonitrile – Di amino benzo 18 crown-6 ) PSS(AN-
DAB18C6) composite was prepared by grafting polymerization technique of acrylonitrile (AN)
monomers, Diamino benzo 18 crown-6 (DAB18C6) filler, and poly sodium styrene sulphonate
polymer in de-oxygenated and de-ionized water. About 1.5wt% of AN monomer was added to the
reaction medium followed by 0.3 wt% of DAB18C6, then added to 0.5 wt% of PSS and N, N
methylene bisacrylamide as crosslinker at 100 ml de-ionized water and purging of nitrogen at 10
minutes to remove air from the solutions[21]. The mixture was then ultra-sonicated for 15 minutes
at a controlled temperature of approximately 5°C, exposed to gamma radiation and then, washed
successively with acetone multiple times with de-ionized water, then dried until a constant weight
was achieved.
2.2.3. Synthesis of modified Poly Sodium styrene sulphonate (Amidoxime – Di Amino Benzo
18 Crown-6) PSS(AO-DAB18C6) composite.
Several experiments were investigated to prove the reproducibility of the polymerization
process and the product's characteristics. A magnetic stirrer and a reflux condenser equipments
were used to convert AN monomer by adding 2 g of PSS(AN-DAB18C6) composite to a mixture
of 25 ml of methanol and 3 g of hydroxylamine hydrochloride after neutralization by NaOH
solution[22]. The mixture was stirred at ambient temperature for 2 hours before adding 6 mL of
sodium hydroxide (NaOH) solution to neutralize the HCl and maintaining a pH of 8. The reaction
was carried out at 70°C for 6 hours with continuous stirring[23]. PSS(AO-DAB18C6) was filtered
and washed with de-ionized water prior to getting vacuum dried at 70°C. Scheme 2 illustrated the
conversion of acrylonitrile monomer to the amidoxime form.
NH2OH.HCl
NaOH
N
Acrylonitrile Ho-----N
NH2
Scheme (2):- Transformation of acrylonitrile to amidoxime form.
2.3. Batch adsorption Studies.
At room temperature (25 ± 1°C), batch adsorption studies were carried out in aqueous
solution, in which (50 mg) of the composite sample were combined with (10 mL) of metal ions
3
with different initial concentrations ranged from 50 to 200 mg/L. In these experiments, samples
were stirred with metal ion solutions under the experimental conditions described previously. The
concentrations of remaining metal ions were measured at regular times. All studies evaluating the
influence of shaking period, pH values, and initial metal ion concentration were performed, and
the % uptake and resin capacity (q) were calculated as follows: -
  V
q(mg / g )  C i C e ………… (1)
m
(Ci  Ce)
% uptake  100 ………… (2)
Ci
Where (qe) is the amount of metal retained on the composite (mg/gm), Ci and Ce are the
initial and equilibrium concentrations (mg/L) of metal ions respectively. V is the volume of
solution in liter and, m is the weight of the resin in gm.
2.4. Kinetic Studies.
Kinetic studies were performed at pH = 4, metal ion concentration 100 mg/l and at various
shaking times ranged from 5min to 24 hrs. Adsorption isotherms were determined by keeping the
dosage of composite constant (50 mg) with 10 mL of aqueous solution containing different initial
concentrations of studied metal ions (ranging from 50 to 200 mg/L) [24,25].
2.5. Selectivity
The selectivity of the modified crown ether composite for metal ions Y3+ and La3+ was
compared to Gd3+, and Sr2+. The synthesized composite was conducted in 10 mL aqueous solution
containing Y3+, Sr2+, and Gd3+, La3+ separately. The residual concentrations after removing the
synthesized composite were used to calculate the adsorption capabilities of the composite for these
metal ions[16].
2.6. Distribution coefficient and separation factor
For a binary mixture of components, the average separation factor, can be used to predict
whether the adsorbent has a selective tendency for one specific for two components. The
separation efficiency parameter, in terms of Kd, is used to evaluate the separation factor, which is
based on the initial concentrations of the ions in the dilute solution and the concentration of the
ion in the dilute solution after a fixed period of duration and computed as:
q /X
SF  i i  qei / Cei ……...……… (3)
q /X qej / Cej
j j
q Co  Ce V
Kd ( L / g )  e   ………… (4)
C Ce m
e
where the mole fractions of the respective components are xi and xj, qi, and qj, adsorbed
amounts of specific metal ions. The initial and residual metal concentrations in the aqueous
solution are Co and Ce respectively. V The volume of the solution is measured in liter, while M is
the weight of the adsorbing materials and measured in gram.
3. Results and discussion
3.1. Optimization for grafting polymerization of PSS(AO-DAB18C6) composite
To optimize the grafting polymerization of PSS(AN-DAB18C6) composite, various
parameters were investigated, including the effects of radiation dose, and crown ether dosage for
the grafting efficiency[26].
3.1.1. Influence of crown ether dosage on the polymerization process.
4
 At a 20.0 k Gy irradiation dose, 0.5 Wt percent P(SSS), 0.2 Wt percent DAM as a
crosslinker, 0.1 Wt percent ammonium ferrous sulphate, and 1.3 Wt percent acrylonitrile
concentration, the effect of crown ether dosage on the sorption capacity of the produced sorbent
towards Cu2+ ion was investigated. The results are shown in Figure 1. (a and b). At crown ether
concentration of 0.3 Wt%, the greatest Cu2+ capacity was obtained, i.e. at maximum conversion
percent. The coordination between Cu2+metal ions and (–NH2, OH, and COOH) groups in the
sorbent structure, are principally responsible due to the particular binding of metal ions with the
amide, hydroxyl, and sulphonic groups of P(SSS), amidoxime, and DAB18C6. The capacity
increases with increasing of DAB18C6 concentration to 3.0 Wt% and then decrease[27]. With the
increase of filler concentration, the probability of association between the filler and the added
reactants increases which, increases the degree of cross-linking between the polymer chains of the
sorbent, otherwise percent conversion increases. With the overdosage of filler concentration more
than 0.3 wt%, the sorbent becomes blocked, and the capacity decreases[13].
95 86
b
a 84
90
82

Conversion %
85
Capacity(mg/g)

80
78
80
76
75 74
72
70
70
65
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06

DAB18C-6 (g)
DAB18C-6 (g)

Fig. 1:- Influence of DAB18C-6 concentration on (a) capacity and (b) conversion yield of
PSS(AO-DAB18C6) composite.
3.1.2 Influence of irradiation dose on the polymerization of PSS(AO-DAB18C6) composite.
The effect of irradiation dose on the capacity of the composite towards (Cu2+) was studied at
crown ether concentration 0.3 Wt% as a filler, polymer concentration PSS 0.5 Wt%, 0.2 Wt %
DAM, and various irradiation doses ranging from 5.0 to 25.0kGy.
Figure 2 (a and b) illustrates the results, and demonstrated that the capacity increases to 20.0
kGy and decreases frequently as the irradiation dose is increased. At irradiation dose of 20.0 kGy,
the maximum sorption of (Cu2+) ion was achieved. Increases in the degree of crosslinking between
the polymeric chains of the sorbent, which leads to the creation of appropriate binding between the
reactants, can be attributed to the increase in the sorbent's capacity when the irradiation dose is
increased. With further irradiation dose, the decrease in capacity could be attributed to a high
extent of crosslinking, or it could be related to a loss of relevant functional groups[28].
75 100
[A] 98 [b]
70 96
94
65
(capacity ( mg/g)

92
conversion %

60 90
88
55
86
50 84
82
45
80

40 78
0 5 10 15 20 25 30 0 5 10 15 20 25 30
dose K. gray dose K. gray

Figure (2). Irradiation dose's effect on (a) capacity, and (b) conversion yield of PSS(AO-
DAB18C6) composite.
3.2. Characterization of the Prepared Polymeric composite.
3.2.1. FTIR Analysis of PSS(AO-DAB18C6) composite.

5
 The preparation steps including grafting and functionalization were successfully confirmed
by the FT-IR spectra shown in Fig.3 (a, b, c, d, and e) which correspond to Di Benzo18C-6
(DB18C-6), DNB18C-6, DAB18C-6, PSS(AN-DAB18C6), and PSS(AO-DAB18C6) composite
respectively. Figure 3-e showed that different absorption bands that appeared at 3740, 791, and
651 cm-1 are belonged to free amide (N-H) stretching, and hydroxyl (O-H), groups of AO, and
DAB18C-6 respectively, which exist in the other spectrum of each reactant individually [29]. The
broad band at 1738 cm-1 belongs to the stretching band of carboxylic group COOH. The
absorption bands at 2356 cm-1, 1508 cm-1, 1452 cm-1, 1338 cm-1, and 1232 cm-1, belong to CN,
NH bending, CH2 bending, COOH bending, and C-O stretching[14]. The presence of a strong
band at the regions of 1591 due to the stretching vibration of C = O, broad bands at the regions of
∼3830 and ∼791 cm-1, are corresponded to the stretching vibrations of O-H and = N-O,
respectively, from the oxime function group[30]. The presence of these peaks in comparison with
figure 3-d verifies the successful preparation of PSS(AO-DAB18C6) composite and
functionalization of AN to AO function group and impregnating the amide function group into
DB18C-6 skeleton[28].

1.0 E
T%

0.9
0.8
PSSSAOCE
0.7

1.0
D
T%

0.8

0.6
PSSSANCE
0.4
0.96 C
T%

0.80

0.64
DAB18C6
0.48
0.96
B
T%

0.80

0.64
DNB18C6
0.48

0.96
A
T%

0.84
0.72 Crownether
0.60
0 1000 2000 3000 4000
Wave number Cm-1

Figure ( 3 ):- FTIR spectra of the individual reactants and the prepared PSS(AO-DAB18C-
6) composite
3.2.2. Scaning electron microscope.
A scanning electron microscope was used to examine the morphology of the different phases
during the preparation processes, as clarified in figure 3(a,b,c,d,) which corresponds to DNB18C-
6, DAB18C-6, and PSS(AN-DAB18C6), PSS(AO-DAB18C6) composite respectively. It is clear
to see that, figure 3(a and b) shows the modification stages process for the conversion of nitro to
amino groups and reflects the evolution of the change in morphology to a large deeper one which
reflect the success of the conversion process. From figure 4c it is evident that the unmodified
prepared polymer composite PSS(AN-DAB18C6) has a flakes-like structure and shows that there
are limited porous structures on the surface of the composite. Figure 4(d) shows the diameter of
the PSS(AO-DAB18C6) composite is 980 nm, which indicated also by particle size distribution
and composed of orderly equal arranged spherical particles to form homogenous structures as
shown in figure 4d.

6
 (a) (b)

(c) (d)

Fig. (4): The scanning electron micrograph of (a) DNB18C18C-6, (b) DAB18C18C-6,
(c) PSS(AN-DAB18C-6), (d) PSS(AO-DAB18C-6) composite.
3.2.3. Dynamic Light Scattering (DLS)
The dynamic light scattering (DLS) method is introduced with an emphasis on the raw data,
followed by ways to extract quantitative information about size distribution and size of
(a)PSS(AO-DAB18C-6) and (b) PSS(AN-DAB18C-6) composites. Figure 5(a and b) reveals that
PSS(AO-DAB18C-6) composite with polydispersity index (PDI) of 0.69, has a considerable
particle size distribution and an average particle size of 1068 nm as compared with the non
modified composite PSS(AN-DAB18C-6) with an average particle size (1362 nm) and larger
range of particle sizes (PDI of 0.207). The chemical modification of di benzo18C-6 crown ether
may be the responsible for the lower size and size distribution of the prepared modified composite,
which allows smaller droplets to be formed composite as a result of the ultrasonic homogenizer's
action[31].

Figure (5): Particle size distribution of (a) PSS(AO-DAB18C-6) and (b) PSS(AN-DAB18C-6)
composite.
Based on the previous findings, the proposed reaction mechanism for the synthesis of the
PSS(AN-DAB18C6) composite is shown in Sch. (3).
7
 * n*
O
O O
N HN NH2
2
O O
O S O + +
O

ONa Acrylonitrile DAB18C6

Poly sodium styrene sulfonate

NH2OH.HCl
O O S OO S O O S O
O O
ONa
NaOH
NH O ONa
2
HN
O O
O

n N OH
H2N

O O S OO S O O S O
O O
O ONa ONa
2
HN NH
O O
O

Sch. (3): Synthesis of PSS(AO-DAB18C6) composite.

3.3 Adsorption ability of La3+ ,Y3+ , Gd3+ and Sr2+ metal ions from aqueous solution.
3.3.1. Effect of Contact Time.
Batch experiments were carried out to test the adsorption ability for both PSS(AN-
DAB18C6), and PSS(AO-DAB18C6) composite toward Sr(II), Y(III), La(III), and Gd(III) at
different times. As shown in Fig. 6(a, b), the uptake % of the prepared PSS(AN-DAB18C6), and
PSS(AO-DAB18C6) composites increased with the increase of contact time until equilibrium was
reached. The uptake% for PSS(AO-DAB18C6) composite is more kinetically effective than
PSS(AN-DAB18C6) composite for all the investigated metal ions. The maximum uptake % was
reached at 3 hours for studied metal ions. The maximum uptake % of PSS(AN-DAB18C6)
composite obey the order La3+ > Y3+ > Gd3+ > Sr2+ ions (37, 28.7, 26.3 and 22), respectively. The
maximum uptake % of PSS(AO-DAB18C6) composites follows the order La3+ > Y3+ > Sr2+ >
Gd3+ ions (75, 60.3, 26 and 21), respectively. These higher adsorption could be owing to the
existence of several functional groups as a result of the acrylonitrile function group being
converted to amidoxime, in addition to the active sites on the adsorbent surface[32].
40 80
La La
Y3
a 70 Y3
b
35
Gd Sr
30 Sr 60 Gd
Uptake %

Uptake %

25 50

20 40

15 30

10 20

5 10

0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time (Sec) Time (Sec)

Fig.(6): Effect of contact time on the amount sorbed of Y3+ ,Gd3+, La3+, and Sr2+ ions from
aqueous solutions onto (a) PSS(AN-DAB18C6) and (b) PSS(AO-DAB18C6) composite.
3.3.2. Sorption kinetic modeling
Several kinetic models were tested to predict variations in the sorption process of the
investigated ions with time progressed. Using Lagergren pseudo-first-order, pseudo-second-order

8
rate models, Elovich, and intraparticle diffusion kinetic models, the rate constants of each metal
ion removal from the solution using PSS(AN-DAB18C6) and PSS(AO-DAB18C6) composite
were calculated.
3.3.2.1. Pseudo-first-order model
The Lagergren pseudo first-order expression is written as[33].
K1
log(qe  qt )= log qe 
t (5)
2.303
where k1 is the pseudo first order rate constant (min−1) and qe and qt (mg/g) at equilibrium
and at time t, is the amount of metal ion sorbed onto the composite
Figure(7) illustrates the plots of log(qe − qt) versus t. and the slopes and intercepts were
implemented to locate the theoretical equilibrium sorption capacities (qe) and the first order rate
constant (k1). The applicability of the pseudo-first-order kinetic model to fit the experimental data
over the initial sorption process required that the experimental and calculated theoretical
equilibrium sorption capacity, qe, should be in accordance with others. As seen in tables 1 and 2,
the metal ion sorption onto prepared composites isn't first-order reaction, due to the qe (calculated)
values are not in agreement with qe (experimental) values, although the linear correlation
coefficients of the plots are relatively high value (>0.78).
0.9

a Y
La
1.2
b Y
La
Sr
Sr
1.0 Gd
Gd
0.6
log(qe-qt)

0.8
log(qe-qt)

0.6
0.3
0.4

0.2
0.0

0.0

-0.3 -0.2

0 20 40 60 80 100 0 25 50 75 100
Time( min) Time( min)

Figure (7): Plots of Pseudo-first-order kinetic models of (a) PSS(AN-DAB18C6) and (b)
PSS(AO-DAB18C6) composite For sorption of Y3+ ,Gd3+, La3+, and Sr2+ ions.
3.3.2.2. pseudo-second-order model
The pseudo-second-order rate model is expressed as[34]:
t 1 1
= 2
 t (6)
qt K 2 qe qe
where k2 is the rate constant of the pseudo-second-order equation (g/mg min). The product k2qe2 is
the initial sorption rate represented as h = k2qe2.
Figure(8) shows the kinetic plots of t/qt versus t for Y3+, Gd3+, La3+, and Sr2+ metal ions.
As given in tables 1 and 2, for PSS(AN-DAB18C6) and (b) PSS(AO-DAB18C6) composite the
calculated equilibrium sorption capacity (qe) is consistent with the experimental data, and its
correlation coefficient R2 has an extremely high value (>0.99), As shown in a result, the pseudo-
second-order sorption mechanism predominate the data, and the chemical sorption process has
seemed to dictate the overall rate constant of each sorption process[25].

9
 20
32
a Y
La
18 Y
La
b
28 Sr
Sr 16 Gd
Gd

-1
t/qt (min g mg )

t/qt min g mg
24 14

-1
20 12

16 10

12 8

6
8

4
4
2
0

0 50 100 0 20 40 60 80 100
Time (min) Time( min)

Figure (8): Plots of Pseudo-second-order kinetic plots for the sorption of La3+, Y3+ ,Gd3+
and Sr2+ ions onto (a) PSS(AN-DAB18C6) and (b) PSS(AO-DAB18C6) composite.

Table (1): Kinetic parameters of pseudo-first-order and pseudo-second-order kinetic

models for sorption of La3+, Y3+ ,Gd3+ and Sr2+ions onto PSS(AN-DAB18C6) composite.

Ions Qe, exp. First-order Second-order

(mg/g) Kinetic equation Kinetic equation
q1(mg/g) K1(min-1) R2 Q2(mg/g) K2(mg/g min) R2
Y3+ 5.9 1.80 -0.0018 0.783 7.0 0.0048 0.997
La3+ 7.6 2.10 -0.0016 0.988 7.4 0.0089 0.991
Sr2+ 4.6 1.46 -0.0013 0.991 4.2 0.0234 0.992
Gd3+ 5.6 1.68 0.0011 0.963 4.8 0.0157 0.995

Table 2: Kinetic parameters of the pseudo-first and second-order kinetic models for La3+,
Y3+, Gd3+ and Sr2+ ions sorbed onto (a) PSS(AO-DAB18C6) composite.

Ions Qe, exp. First-order Second-order

(mg/g) Kinetic equation Kinetic equation
q1 K1 R2 Q2(mg/g) K2 R2
(mg/g) (min ) -1 (g/mg/min)
Y3+ 12.4 2.82 -0.009 0.71 11.49 0.0019 0.999
La 16.2 3.07 -0.013 0.78 15.62 0.0019 0.992
Sr2+ 5.8 1.82 -0.032 0.84 5.74 0.0123 0.999
Gd 5.6 1.71 -0.032 0.88 5.49 0.0135 0.996

3.3.2.3. Elovich model

The Elovich or Roginsky–Zeldovich equation has been used to describe adsorption
mechanisms that agree with the type of chemical reactions that occur with heterogeneous
adsorbing surfaces[36] and is frequently represented as follows[35].
dqt
  . exp( qt ) ………………………(7)
dt
1 1
qt  ln(  )  ln t ………………………(8)
 
where qt is the number of metal ions sorbed on the polymer at a time t, α is the initial metal
ions sorption rate (mg.g-1min-1) and β is the desorption constant (g/mg). The Elovich equation,
which supports chemisorptions reaction in (Fig. 9), shows a linear relationship between metal ions
sorbed, qt, and ln t well over a whole sorption period, with high correlation coefficients (> 0.99)
for most lines, as shown in the regression results for the adsorption of La3+, Y3+, Gd3+ and Sr2+
metal ions on PSS(AO-DAB18C6) composite by (Table 3).
10
Table (3) Kinetic parameters of Elovich model for the sorption La3+, Y3+, Gd3+ and Sr2+
metal ions.

PSS(AN-DAB18C6) composite PSS(AO-DAB18C6) composite

β (g /mg) α (mg.g- β (g/ mg) α (mg.g-1min-
1min-1) R2 1) R2
La3+ 1.12 0.70 0.997 0.314 1.176 0.986
Y3+ 0.64 0.64 0.996 0.450 0.734 0.996
Sr2+ 2.99 1.63 0.990 0.842 0.937 0.999
Gd3+ 1.19 1.16 0.994 0.913 1.008 0.999
12 y
la
sr
10 gd

8
qt (mg/L)

1.5 2.0 2.5 3.0 3.5 4.0 4.5

Ln t
Fig. 9. Elovich regression analysis of the adsorption of La3+, Y3+, Gd3+ and Sr2+ ions on
PSS(AO-DAB18C6) composite.
3.3.2.4. Intraparticle diffusion model
The intra-particle diffusion models are used to represent the process of species moving from
the bulk of a solution to the solid phase. In many sorption conditions, Weber-Morris reported that
solute uptake changes approximately proportionately with t1/2 rather than that of the contact time t
[25]. The rate constant (slope of the plot) is calculated by plotting the quantity of sorbate
adsorbed, qt (mgg-1), against the square root of the time, and is expressed in equation (9):
qt = Kadt1/2+C …………………(9)
where kad is the intraparticle transport rate constant (mgg-1min-1(1/2)). C intraparticle diffusion
constant (intercept of the line) (mgg-1).
The values of Kad were estimated from the slope of the linear plots obtained and reported in
Table 4. As seen in Fig. 10, the straight line does not pass through the origin when plotting qt
versus t1/2 according to this model, indicating that intra-particle diffusion is not the only rate-
limiting factor for the sorption process, and that other kinetic models may also influence the rate
of adsorption.

11
 14 y
la
12 sr
gd

10

q t (mg/L)
8

0
2 4 6 8 10 12
T1/2 , hr
Fig. 10. Morris–Weber kinetic graphs of Y3+, Gd3+, La3+, and Sr2+ ions sorption on the
PSS(AO-DAB18C6) composite.
Table 4: Intraparticle diffusion rate constant for the sorption of Y3+ ,Gd3+, La3+, and Sr2+
ions PSS(AO-DAB18C6) composite.
PSS(AN-DAB18C6) composite PSS(AO-DAB18C6) composite
Temprature Kad(mg/gh1/2) R2 Kad(mg/gh1/2) R2
(K) 298 313 333 298 313 333 298 313 333 298 313 333
Y3+ 0.6 0.67 0.69 0.998 0.997 0.995 1.1 1.13 1.16 0.93 0.96 0.94
Gd3+ 0.3 0.36 0.40 0.996 0.987 0.991 0.3 0.35 0.38 0.93 0.94 0.95
La3+ 0.5 0.53 0.58 0.996 0.998 0.997 1.0 1.06 1.10 0.95 0.94 0.96
Sr2+ 0.2 0.23 0.28 0.997 0.999 0.998 0.4 0.49 0.55 0.94 0.95 0.96

3.3.3. Effect of pH.

Based on the prior findings, more work was done to optimize the metal ion sorption process
onto the PSS(AO-DAB18C6) composite. To avoid metal hydrolysis, the sorption behavior of the
studied metal ions on the synthesized PSS(AO-DAB18C6) composite was investigated at various
pH values ranging from 3 to 12 for Sr2+ and 1 to 6 for the other studied metal ions. With an
elevation in pH value of the medium, the amount of La3+ ions adsorbed (qe) increased from 2.0 to
5.0 mg/g, as shown in Fig. 11a [33]. The adsorption capacity of La3+ is higher than that of Y3+ and
Gd3+ metal ions in this pH range. The increased amount of La3+ adsorbed could be attributed to the
protonation of significantly more N-atoms in the constituent polymers, which attracts La3+ ions
electrostatically[23]. The adsorption of Sr2+ increased with pH elevation, as seen in Fig. 11b, with
a plateau adsorption value achieved after pH 6.
14
Y
La a 6
Sr
b
Gd
12

10 5
qe
qe

4
6

3
2

2 3
pH 4 5 2 4 6
pH
8 10 12

Fig. (11): Effect of pH on the sorption of (a)Y3+ ,Gd3+, La3+, and (b) Sr2+ ions onto PSS(AO-
DAB18C6) composite.
Table(5): Effect of pH on the separation factor of Y3+ ,La3+,Sr2+ and Gd3+, ions at different
pH values.

pH Sep(Y3+ /Sr2+) Sep(La3+/ Y3+) Sep(Y3+ / Gd3+) Sep(La3+/ Gd3+)

2 2.90 1.15 4.67 5.39
3 2.68 1.52 3.35 5.12
12
 4 2.48 1.78 2.59 4.64
5 4.34 1.53 4.50 6.88

The influence of different pH values on the separation factor between Y3+, La3+, Sr2+ and
3+
Gd ions was investigated at metal ion concentration 100 mg/L in the range pH of 2 to 5. Based
on the results in Table 5, it could be stated that Sr2+ (parent isotope) could be separated efficiently
from Y3+ (daughter isotope) using the modified polymeric composite supported crown ether. Also
the obtained separation factors of La3+/ Gd3+, Y3+/ Gd3+, and La3+/ Y3+ ions, are high and allowing
a promising separation efficiency the modified polymeric composite supported crown ether for
light REEs from both intermediate and heavy rare REEs at pH 5.0.
3.3.4. Effect of initial metal ion concentration on the adsorption process of PSS(AO-
DAB18C6) composite.
Figure 12 shows the quantity of Y3+, Gd3+, La3+, and Sr2+ ions adsorbed at three different
temperatures and varied initial metal ion concentrations. The results showed that when the initial
sorbate concentration is increased, the sorption of investigated ions increases. This is attributed to
a greater number of metal ions per unit mass of adsorbent being exposed. The metal ion capacity
increased as the temperature increases, demonstrating that the reaction was endothermic[36].
60 70 30
27 27
27
35 a 35 b 35 C
60
50 45 25 45
45
50
40 20

40
qe (mg/g)

qe (mg/g)
qe (mg/g)

30 15
30

20 10
20

10 5
10

0 0 0
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
Cemg / l Cemg / l Cemg / l
30
27
35 d
45

20
qe (mg/g)

10

0
0 50 100 150 200 250 300 350 400 450
Cemg / l

Fig.(12): Effect of initial metal ion concentration on the sorption of (a)Y3+ , (b)La3+,
(c)Sr2+ and (d)Gd3+, ions onto PSS(AO-DAB18C6) composite. (0.05 g composite, 10ml
and time= 3 hr's at 27°C and pH=4).
3.3. Adsorption isotherms
Adsorption isotherms are important in describing the mechanism of adsorbate interaction
with the adsorbent and identifying the adsorbent surface where physicosorption and chemisorption
can occur[37]. There are different commonly mathematical expressions to describe the sorption
equilibria such as Langmuir, and Freundlich, isotherms.

Langmuir adsorption isotherm model is mathematical expressed as flowing:

K L .Ce
qe  Q 0 (10)
1  K L .Ce

13
 Ce 1 C
 0  e0 (11)
qe Q . K L Q
where qe is the saturation capacity of sorbent used (mg/g) and K L is the Langmuir equilibrium
constant or affinity parameter (mg/g). Q0 and KL were deduced from the linear form of the
Langmuir isotherm.
Freundlich adsorption isotherm model[32] which applies to the adsorption process
characterized by heterogeneous surfaces:
1
log qe  log K f  log C e (12)
n
Where Kf is the constant of the relative adsorption capacity (mg/g) and 1/n is the constant
expressed in the sorption intensity.
Figure 13, shows the linearity of the different isotherm types of prepared composite for
sorption of Y3+, La3+, Sr2+ and Gd3+, ions at three different temperatures viz. 27, 35, and 45 °C
with varying initial concentrations of metal ions from 50 to 500 mg/l) have different linearity. The
correlation coefficient (R2), which reaches the value of 0.9 in table 6.0, indicates that the proper
adsorption isotherm model of Y3+, La3+, Sr2+ and Gd3+, ions was determined using PSS(AO-
DAB18C6) composite. From the intercept and slope of the linear plot Ce/qe vs. Ce (regression
coefficient is equal to 0.999) (Fig. 13), the following qe, KL and RL(the dimensionless constant
separation factor or equilibrium parameter), defined by:
1
RL  (13)
1  K L .Co
where Co is the initial metal ion concentration, RL parameter from the mathematical calculations
that, indicates the shape and type of the isotherm to be irreversible (RL=0), favorable (0<RL<1),
linear (RL=1), or unfavorable (RL<1). All of the RL values (Table 3) were found to be less than 1
and greater than 0, showing that the metal ions have favorable sorption isotherms.
2.75
298 298
2.50 a 1.2 333 b 12 313 C
313 333
2.25
10
Ce/qe (g/L)

1.0
Ce/qe (g/L)

Ce/qe (g/L)

2.00

1.75 8
0.8

1.50
298
6
313 0.6
1.25 333

1.00 4
0.4
0.75
25 50 75 100 125 150 2
0 10 20 30 40 50 60 70 80 90
Cemg / l Ce(mg / L) 0 50 100 150 200 250 300
Ce(mg / L)
12
298
313
333
d
11
Ce/qe (g/L)

10

0 50 100 150 200 250 300

Ce(mg / L)

Fig.(13): Linear form of the langmuir isotherm plots for the sorption of (a)Y3+ , (b)La3+,
(c)Sr2+ and (d)Gd3+, ions Sorbed onto (0.05 g PSS(AO-DAB18C6) composite, 10ml and time=
3 hr's at 27°C and pH=4) at different temperatures.
Table(6): Langmuir isotherm for the sorption of (a)Y3+ , (b)La3+, (c)sr2+ and (d)Gd3+, ions at
different temperatures.
Metal Temperature Statistical parameter constants
ions K R2 Qo(mg/g) RL
14
 (l/mg)
298 0.941 62.83 0.199
Y3+ 313 0.943 64.16 0.08
333 0.865 65.72 0.07
298 0.916 75.85 0.13
La3+ 313 0.98 76.92 0.10
333 0.977 77.92 0.09
298 0.983 29.41 0.17
Sr2+ 313 0.988 34.48 0.10
333 0.983 37.03 0.10
298 0.964 26.32 0.65
Gd3+ 313 0.935 27.32 0.58
333 0.988 28.91 0.48

The Freundlich equation is developed To model multilayer sorption and sorption on

heterogeneous surfaces, . Figure 8 shows a visual representation of log qe vs log Ce, illustrating
that sorption of Y3+, La3+, Sr2+, and Gd3+ ions not obeys Freundlich isotherm for sorption
concentration studied. Table 6 also contains the numerical values of the constants 1/n and Kf,
which are derived from the slope and intercepts using a linear least square fitting methodology.
The Freundlich intensity constant (n) is more than unity for the examined ions, as can be observed
from the data. This has physical effects for the qualitative properties of the isotherms as well as
interactions between metal ions species and the composite. In our case, n > 1 for both ion species,
the prepared material shows an increasing tendency for sorption with increasing polymeric
composite concentration. This is due to the fact that when the adsorbent's surface coverage
increases, the attractive forces between metal ion species, such as vander Waals forces, get
stronger than the repulsive forces, and consequently, the metal ions manifest a stronger tendency
to bind to the prepared polymeric composite.
1.8 1.5
298
298
313 a 1.8 333 b 298
C
313
333 313 1.4
333
1.6
1.6 1.3
log qe (mg/g)

logqe (mg/g)
logqe (mg/g)

1.4 1.2
1.4

1.1
1.2
1.2
1.0

1.0 1.0 0.9

0.8
0.8 0.8

0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6
log Ce(mg / L) logCe(mg / L) log Ce(mg / L)

27
1.4 C1 d
B1

1.2
logqe (mg/g)

1.0

0.8

0.6

0.4

1.4 1.6 1.8 2.0 2.2 2.4 2.6

log Ce(mg / L)

Fig.(13): Linear form of the freundlich isotherm plots for the sorption of (a)Y3+ , (b)La3+,
(c)Sr2+ and (d)Gd3+, ions at different temperatures.
Table(7): Freundlich isotherm for the sorption of (a)Y3+ , (b)La3+, (c)Sr2+ and (d)Gd3+, ions
at different temperatures.
Metal Temperature Statistical parameter constants
ions K R2 n (mg/g) Kf (mg/g)
298 0.999 1.41 1.20
Y3+ 313 0.982 2.02 1.86
333 0.983 2.02 1.96
298 0.998 1.27 1.39
La3+ 313 0.997 1.80 1.68
333 0.965 1.91 2.15

15
 298 0.954 1.60 0.92
Sr2+ 313 0.959 1.64 0.98
333 0.958 1.73 1.07
298 0.997 1.22 1.80
Gd3+ 313 0.998 1.11 2.19
333 0.999 1.03 2.53

4. Conclusion
The synthesis of polymeric composite based on functionalized crown ether and
functionalization of the basic polymer using gamma irradiation were carried out in this research.
This new adsorbent was characterized by FTIR and showed spherical structures with suitable
specific areas with an average particle size of 1068 nm. The batch studies showed higher
selectivity towards La3+ and Y3+ more than from Sr2+ and Gd3+respectivly, with an optimal
maximum capacity of 63, 52, 25, and 24 mg/g. Studies of adsorption kinetics indicated that
PSS(AO-DAB18C6) composite exhibited compatibility with second-order and elovich kinetic
models with high adsorption affinity (with b value of 0.024, 0.015, 0.01, and 0.002) for La3+ and
Y3+, Sr2+ and Gd3+respectively. The separation factor for Sr2+ can be separated efficiently from
Y3+ using the modified polymeric composite supported crown ether and also the obtained results
provided a promising efficiency separation factors for La3+/ Gd3+, Y3+/ Gd3+, and La3+/ Y3+ ions at
pH 5.0. Depending on these results, it is possible to suggest a possible application for the selective
removal and treatment of radioactive waste containing La3+ and Y3+ ions.
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Declaration of Interest Statement

Declaration of interest and authorships confirmation

The work described has not been published previously, that it is not under consideration for
publication elsewhere, that its publication is approved by all authors and tacitly or explicitly by the
responsible authorities where the work was carried out, and that, if accepted, it will not be
published elsewhere in the same form, in English or in any other language, including electronically
without the written consent of the copyright-holder.
Yes All authors have participated in (a) conception and design, or analysis and
interpretation of the data; (b) drafting the article or revising it critically for
important intellectual content; and (c) approval of the final version.

Yes The Article I have submitted to the journal for review is original, has been written
by the stated authors and has not been published elsewhere.

Yes The Images that I have submitted to the journal for review are original, was taken
by the stated authors, and has not been published elsewhere.

Yes This manuscript has not been submitted to, nor is under review at, another journal
or other publishing venue.

Yes The authors have no affiliation with any organization with a direct or indirect
financial interest in the subject matter discussed in the manuscript

Yes The below authors have affiliations with organizations with direct or indirect
financial interest in the subject matter discussed in the manuscript:

Dr. Mahmoud G. M. Hamed

Hot Laboratories Center

Egyption Atomic Energy Authority.

Cairo - Egypt

E-mail: [email protected]