Journal of Nuclear Materials 507 (2018) 218e225

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Journal of Nuclear Materials

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

Environmentally benign and novel management route for radioactive

corrosion products by hydroxyapatite
Sajid Iqbal, Muhmood ul Hassan, Ho Jin Ryu, Jong-Il Yun*
Department of Nuclear and Quantum Engineering, KAIST, Daejeon 34141, Republic of Korea

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The direct solidification of the

captured corrosion products by HA
has been investigated.

No organic binders were used for
solidification of M-HA matrix.

The sintered matrix showed good
densification and mechanical
properties.

ASTM PCT test approved the chemi-
cal durability of sintered matrix.

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

Article history: A novel and environmentally benign route for the direct solidification of captured corrosion products (Co,
Received 19 January 2018 Cr, Fe, Ni, Cu, Zn, and Mn) generated from the primary coolant system of nuclear power plants is
Received in revised form introduced in this study. Synthesized calcium hydroxyapatite was used to remove individual and mix-
4 May 2018
tures of corrosion products from aqueous solutions. The results show more than a 95% removal of these
Accepted 6 May 2018
Available online 7 May 2018
corrosion products for both cases. The direct solidification of adsorbed corrosion products was done by
pressure-less conventional sintering. The sintered matrix revealed a good hardness (3.70 ± 0.60 GPa) and
a relative sintered density > 98% after heat treatment at 1150  C. The measured compressive strength
Keywords:
Waste immobilization
(207.3 ± 9.5 MPa) was significantly higher than the established waste immobilization criteria of the US
Nano-ceramic (3.5 MPa) and Russia (4.9 MPa). The corrosion products consolidated matrix had a normalized leaching
Hydroxyapatite rate ranging from 3.4#102 to 3.1#106 g/m2/day. Moreover, no additional chemical treatments, addi-
Radioactive corrosion products tives (gypsum, slaked lime, sodium silicate, etc.), and sophisticated equipment were needed for the
adsorption and solidification process. Therefore, the proposed waste management route has no adverse
effects on the ecosystem and can be highly efficient to immobilize adsorbed waste and to reduce the
secondary waste volume.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Corrosion products, known by Chalk River Unidentified Deposits
(CRUD), such as 58Co, 60Co, 51Cr, 64Cu, 54Mn, and 59Fe are the main
* Corresponding author.
E-mail address: jiyun@kaist.ac.kr (J.-I. Yun).
sources of radiation build-up inside nuclear reactor vessel and pose
serious problems in routine overhaul maintenance work. CRUD are
released into the primary coolant due to the degradation of me-
chanical parts of the primary coolant system in nuclear power
plants. The CRUD are transported to the reactor core and get acti-
vated under the high neutron flux. These are called radioactive
CRUD which consequently increase the radiation level. CRUD can

https://doi.org/10.1016/j.jnucmat.2018.05.016
0022-3115/© 2018 Elsevier B.V. All rights reserved.
 S. Iqbal et al. / Journal of Nuclear Materials 507 (2018) 218e225
deposit on the surface of fuel rods and cause a reduction in the
thermal conductivity. In certain cases, they may also damage the
fuel rods due to stress corrosion cracking phenomena [1e3].
Therefore, it is necessary to use efficient adsorbents to maintain the
coolant chemistry and to remove any metal ions that form due to
the corrosion of structural materials of the nuclear power plant.
Many natural wastes, organic matter, and synthesized adsor-
bents have been successfully used to capture cobalt/CRUD from
contaminated water [4e8]. For example, Granados et al. reported
on the adsorption behavior of cobalt as a function of pH, contact
time and initial metal ion concentrations for Fe-Mn oxide synthetic
material [9]. Oliva et al. used commercial apatite to remove trace
levels of Cd, Cu, Ni, Co and Hg, which are hard to remove by calcite
or other organic adsorbents [8]. Yuonjin et al. used ammonium
molybdophosphateepolyacrylonitrile to remove Co, Sr and Cs
which come from radioactive laundry waste water [10]. However,
the solidification of Co/CRUD captured adsorbents (secondary
waste produced) was not addressed in the aforementioned studies.
Radioactive waste management procedures can be simplified
and more cost-effective if the material being used as an adsorbent
also acts as a matrix for the consolidation of captured nuclear
waste. In addition, a significant reduction of secondary waste could
be achieved with an adsorbent that can capture metal ions from
waste and simultaneously solidify them thus eliminating the need
for additional chemical treatments (addition of binders, excessive
acid/base treatments or conditioning), loading to other matrices
like Portland cement, glass or unsaturated polyesters.
Calcium hydroxyapatite (Ca5(PO4)3OH) is a phosphate-based
hard ceramic belonging to the apatite family and has the general
chemical formula A5(XO4)3Z. The apatite structure has two cationic
positions (A and X) and one anionic position (Z) [11e14]. On ionic
sites, different ions can be accommodated without affecting the
apatite structure due to its ion exchange properties [11]. Calcium
hydroxyapatite (HA) has excellent biocompatibility and is being
widely used as a bio ceramic material for making artificial dental
roots, teeth implants and artificial bones similar to those living
bodies [15e17]. The HA is also abundantly present in nature in the
form of waste bones and phosphate-based minerals. Both natural
and synthetic HA have been extensively investigated for their
adsorption and substitutional properties to remove pollutants and
toxic heavy metals [8,18,19].
In terms of environmental pollution, it is always desirable to use
waste management methods that are the least harmful to the
environment and nature. The use of organics, lime and cementi-
tious binders for the stabilization and solidification of contami-
nants has been considered the best available technology [20]. The
additional binders such as biochar, starch and carbodiimide have
been used during green shaping of ceramic body to make it easier
to obtain a desired density with less defects while pressing. During
sintering at higher temperatures, the pyrolysis of these binders
results in the emission of carbon dioxide or other hydrocarbon
gases [21,22]. Nowadays, geo-polymers, slag, cement kiln and hy-
droxyapatite have also been tested for the consolidation process
[23].
In this study, we applied the synthesized HA to remove single
metal ions and a mixture of CRUD metals from an aqueous system.
This study further investigated the possibility of binder-free
immobilization of a CRUD captured adsorbent in a form of the
highly dense and durable sintered matrix. This technique involves
the adsorption of CRUD onto the surface of ceramic (calcium hy-
droxyapatite) nanoparticles. The adsorbent was separated from
liquid by centrifugation and ultrafiltration. Then the compaction
and consolidation of separated CRUD captured adsorbent was
achieved by using conventional pressure-less sintering method.
219
2. Experimental procedures
2.1. Synthesis of the adsorbent
The wet precipitation method has been used to synthesize
crystalline apatite as described elsewhere [13]. Anionic and cationic
solutions were prepared by dissolving each of the di-ammonium
hydrogen phosphate (NH4)2HPO4 and calcium nitrate Ca(N-
O3)2$4H2O in 200 ml of ultrapure deionized water, respectively. The
Ca/P molar ratio of both the reactants was theoretical set as 1.67.
The anionic solution was dropwise mixed with the cationic solution
at a speed of 0.06 ml/s under continuous stirring at 200 rpm. Dur-
ing mixing, the temperature and the pH of the solution were
continuously monitored and maintained at 30  C and 10.5,
respectively. To maintain the pH of the solution, a concentrated
ammonia solution was used. The aging of white gel type pre-
cipitates that formed during the synthesis was done inside the
parent solution for 3 h. During the first hour, the stirring continued
at 100 rpm and the temperature was maintained at 30  C, whereas
at the end of the first hour, the reaction vessel was removed from
the hot plate and kept without stirring at room temperature for 2 h.
After that the suspension was filtered, thoroughly washed and
dried overnight at a temperature of 100  C in a vacuum oven. The
dried precipitates were ground to fine powder with a mortar and
pestle.
2.2. Adsorption procedures
A detailed adsorption study of HA can be found elsewhere [24].
First, the maximum removal of Co(II) was optimized by varying the
solid to liquid ratio (S: L ratio) from 2 to 5 g/L with 1 mM of Co(II) at
pH 6. The adsorbent-liquid contact time was set as 24 h with con-
stant stirring at 150 rpm at 25  C. More than 90% removal of the
Co(II) was observed for S:L ratio of 4 g/L. By using the optimized S:L
ratio, a single element Co(II) solution and a series of corrosion
products (Co(II), Cr(III), Cu(II), Ni(II), Mn(II), Fe(II) and Zn(II)) were
removed from the contaminated aqueous solution. In the mixture
of corrosion products, the concentration of each metal ion was kept
constant at 1 mM in 100 ml of deionized water. After 24 h, the solid
and liquid phases were separated with a 0.45 mm syringe filter
followed by a 5 min centrifugation at 3200 rpm. The concentration
of the metal ions in the separated dried adsorbent and the super-
natant were measured by ICP-OES. The percentage removal (% R) of
the metal ions was calculated by equation (1),
%R ¼ ðCo  Ce Þ=Co  100 (1)
where Co and Ce are the initial and final metal ion concentrations
(mM), respectively.
2.3. Sintering of pure HA and corrosion product adsorbed HA
After the separation and drying of the adsorbent in a vacuum
oven at 100  C overnight, the powder was shaped into cylindrical
pellets with a stainless steel mold 13 mm in diameter. The pressing
at room temperature was conducted under 100 MPa for 30 s by a
Carver(R) uniaxial press. For each pellet, 1.20 g of pure HA and the
metal adsorbed HA (Co-HA and M-HA) powder was used. The
pressure-less conventional sintering of the as-pressed pellets of
pure HA Co-HA and M-HA was carried out in the box furnace
(Model: S-1700, HANTECH) under an air environment. In the first
step, the pure HA was studied for a range of temperatures (500  C,
800  C, 900  C, 1000  C, 1150  C and 1300  C) for 120 min at a
heating ramp of 4  C/min to optimize the sintering temperature.
After the sintering, the samples were left inside the furnace to cool
220 S. Iqbal et al. / Journal of Nuclear Materials 507 (2018) 218e225
down to room temperature. In the second step, Co-HA and M-HA
were sintered at 500  C and at the optimized sintering temperature
(1150  C). The dimensions of each pellet were measured before and
after the sintering. The percentage volume contraction was calcu-
lated with equation (2):
ðVb  Va Þ
Vc ð%Þ ¼  100
Vb
where Vc (%) is the percentage volume contraction, Vb and Va are
the volumes of the pellet before and after sintering.
All experiments were performed in triplicate to check the
reproducibility of the results.
2.4. Product consistency test (PCT)
The Product Consistency Test (PCT) is a standard test of the
American Society of Testing Materials (ASTM) to check the chemical
stability and structural durability of ceramic waste forms [25e30].
The PCT is performed by immersing the crushed sintered samples
(specific surface area ¼ 0.27 m2/g) into an ASTM-type I water at
90 ± 2  C for 7 days. All the procedures were performed in triplicate
under static condition in an air-sealed stainless steel autoclave.
After 7 days the leachate was analyzed for elemental degradation
and pH change of the waste matrix. The elemental composition of
the waste matrix was measured before the PCT, and the concen-
trations of the relevant constituents were measured in the leachate
after 7 days PCT test with ICP-OES. The normalized leaching rate of
the ith element was calculated by equation (3) as follows:
mi
NLRi ¼
s,t,wi
where NLRi is the normalized leaching rate, mi is the concentration
of component i leached into the water after a reaction time t, S is the
surface area of the crushed powder, and wi is the weight fraction of
an ith component in the solid matrix.
3. Characterization of the sintered matrices
High-resolution X-ray diffraction (XRD) and scanning electron
microscopy (SEM) were used to study the crystal structure, size and
morphology of the grains in the sintered matrix. The XRD patterns
were measured with XRD (SmartLab, RIGAKU) in a scan range of 10
to 90 with a step size of 0.02 at a tube voltage of 45 kV and a
current of 200 mA. The Cu Ka incident radiation source with a
wavelength (l ¼ 1.54056 Å) in the reflection geometry was used.
For the microscopic analysis of the sintered matrix, SEM (Hitachi
S4800) was used. The elemental mapping with the distribution of
different waste constituents was recorded by energy dispersive
spectrometer (EDS) coupled with SEM. The fractured surface
morphology of the sintered samples was observed by mounting the
samples on a cross-section holder. The sputter coating was per-
formed for 15 s with an HPC-1SW osmium coater before micro-
scopic analysis.
The sintered bulk densities were measured with the Archi-
medes' method [31]. The sintered samples were boiled at 100  C in
ultrapure water (MQ) for 30 min to remove the trapped air and to
avoid chances of error. The densities and the relative percentage
densities were calculated by using the following relationships
[31,32]:
rb ¼ MD  rL =ðWs  WSM Þ
%RD ¼ rb =rR  100 (5)
where rb is the bulk density of the sintered sample, and mD, rL, Ws,
and WSM are the dry weight, the density of deionized water, the
saturated weight, and the suspended weight of pellet inside the
deionized water, respectively. %RD is the relative standard density,
(2)
and rR is the measured bulk density of the starting powder which is
2.94 g/cm3. The bulk density of the starting HA powder was
measured with a helium pycnometer. The rb of the CRUD captured
HA was assumed to be equal to the rb of the pure HA because the
mass fraction of adsorbed CRUD is very small in comparison to
mass fraction of pure HA.
The ASTM E384 testing procedure was followed to measure the
hardness values. The Vickers microindentor (Model: 402 MVD,
Wolpert Wilson Instruments) installed with the software Expert
Hardness 2007 V2.0 was used to quantify the micro-hardness of the
sintered pellets under a constant load of 200 gf for a dwell time of
10 s [33]. All of the samples were fine polished by standard SiC
papers with different grits (800e2000) and then by the diamond
suspension paste before the hardness measurements [34]. The in-
dents were made in a line crossing the center of the specimen so
that the near surface effect could be avoided. The indentation was
done at room temperature and a representative hardness value of
10 measurements was taken for each sample.
The compressive strength of the sintered samples was measured
with the universal testing machine (UTS INSTRON 5583, U.S.A) with
a cross-head speed of 0.4 mm/min and a maximum load capacity of
150 kN at room temperature. Three cylindrical specimens with a
length to diameter ratio (L/D) of 1.24 were prepared for each set of
(3) experiments, and the test was carried out according to the ASTM
C39 standard compressive strength test [35].
4. Results and discussions
This study was divided into three main steps: the synthesis of
HA, CRUD adsorption by HA, and consolidation of the as-spent
adsorbent (CRUD captured HA). Detailed adsorption studies on
HA investigating the function of pH and contact time as well as the
effect of the initial metal ion concentrations have already been
done elsewhere [24,36,37]. We investigated the effect of the
adsorbent amount on the maximum removal of a single metal ion
and a mixture of metal ions from aqueous system. The quantitative
measurements of the metal ions were done by inductively coupled
plasma-optical emission spectrometry (ICP-OES). It is clear from
Fig. 2 that the behavior of the cobalt removal is almost linear with
the increasing adsorbent dose up to 4 g/L. This may be due to the
excess surface binding sites available to the metal ions due to in-
crease of adsorbent dose. After 4 g/L, the breakthrough value has
been achieved with an insignificant effect on the removal of metal
ion at S: L ratio of 5 g/L. Then an equimolar (1 mM each) mixture of
corrosion products (Co(II), Cr(III), Cu(II), Fe(II), Mn(II), Ni(II) and
Zn(II)) has been prepared in 100 ml of MQ water and optimum
removal of metal ions (>95%) was obtained by increasing S:L ratio
to 40 g/L. It is clear from Fig. 3 that more than 95% of corrosion
products can be removed from aqueous media by providing 40 g/L
of HA powder at 7 mM of total metal ion concentrations in a
mixture. During the adsorption process a decrease in pH was
observed from 6 to 4.9, which is due to protons coming from two
types of protonated sites at apatite surface (≡POH and ≡CaOHþ 2 ) by
(4)
the exchange of M(II)/M(III) cations as shown in equations (6) and
(7) [38].
 S. Iqbal et al. / Journal of Nuclear Materials 507 (2018) 218e225 221

Fig. 1. Flow diagram showing the synthesis of the adsorbent, and then the adsorption and consolidation of the captured corrosion products by hydroxyapatite.

Fig. 2. Effect of the solid to liquid ratio on the removal of Co(II) by hydroxyapatite Fig. 3. Effect of the S: L ratio on the removal of CRUD mixture by hydroxyapatite (Co of
(Co ¼ 1 mM, pH ¼ 6, contact time ¼ 24 h, ionic strength ¼ 0.1 M NaCl, shaking each metal ion ¼ 1 mM, pH ¼ 6, contact time ¼ 24 h, shaking speed ¼ 150 rpm at RT).
speed ¼ 150 rpm at RT).

≡POH þ M 2þ ⇔ ≡POM þ þ Hþ
≡CaOH2þ þ M 2þ ⇔ ≡CaOHM2þ þ Hþ
The main focus of this study was to reduce the secondary waste
volume and to provide a facile route for waste management by
direct consolidation of an as-spent adsorbent after separation and
drying of the adsorbent. Therefore, pure HA, cobalt adsorbed HA
(Co-HA) and corrosion product adsorbed HA (M-HA) powders dried
in a vacuum oven at 100  C for 12 h were shaped into cylindrical
pellets with a stainless steel mold, as shown in Fig. 1. The pellets
were sintered at 500, 800, 900, 1000, 1150 and 1300  C in a box
furnace in an air environment, as already discussed in Section 2.3.
(6) The pellets were crushed into powder and the XRD analysis was
carried out to investigate the effect of sintering temperatures on the
crystallinity and decomposition of the HA and M-HA. The phases
(7) were identified with the standard JCPDS card No. 00-064-0738
available in the system software [39,40]. No peak shifting phe-
nomenon was observed in all samples except the appearance of b-
TCP-Ca3(PO4)2 on XRD patterns for HA-1150  C or M-HA-1150  C as
shown in Fig. 4 which corresponds to the decomposition of HPO2 4
group present in a wet precipitated HA at this processing temper-
ature [11,13].
There is an insignificant increase in crystallinity of samples heat
222 S. Iqbal et al. / Journal of Nuclear Materials 507 (2018) 218e225

Relative sintered density and the micro-hardness are the key

parameters to confirm the sintering phenomena [42]. Fig. 5 (a & b)
shows the effect of the sintering temperature on the relative sin-
tered density and the micro-hardness, respectively. It is worth
noting that the relative sintered density (Fig. 5(a)) increased from
60% to 99.8% with the increase of sintering temperature from 500 to
1300  C. The maximum hardness of 4.17 ± 0.27 GPa was measured
for the sintered pure HA sample at 1300  C. Based on the densifi-
cation and the volume contraction results, the optimized sintering
temperature has been taken as 1150  C. The micro-hardness values
for pure HA, Co-HA and M-HA at the optimized sintering temper-
ature (1150  C) were 3.70 ± 0.69, 3.63 ± 0.61 and 3.41 ± 0.46 GPa,
respectively. The volumetric contraction of pure HA sintered in the
temperature range starting from 500 to 1300  C was also measured.
About 60% of volume was decreased at 1150  C, as compared to
4e5% at 500  C. The full densification at 1150  C is due to the
removal of the porosity and the grain boundary diffusion to form
larger grains which is the temperature-driven phenomenon. The
high temperature offers sufficient energy for the thermal activation
of the grain boundary migration and diffusion [43]. It can be seen
from Fig. 5 (a & b) that the adsorbed metal ions did not play a

Fig. 4. High-resolution XRD patterns showing the increasing crystallinity of the sin-
tered samples as the temperature was increased (A shows the most intense peak of b-
TCP-Ca3(PO4)2).

treated at 500  C (HA and M-HA) compared with the non-heat

treated CRUD adsorbed HA (M-HA-As adsorbed) while the sam-
ples sintered at 1150  C showed the highest crystallinity which is
evident from the sharpness of XRD peaks (Fig. 4). The sample sin-
tered at 1300  C also showed good stability and only the formation
of small fraction of b-TCP-Ca3(PO4)2 can be seen in the XRD patterns
(Fig. 4). Generally, 1200e1450  C is the temperature range reported
for the decomposition of HA depending on the characteristics of the
HA [41]. Fig. 6. Compressive strength of the pure HA, Co-HA and M-HA: M is a mixture of
corrosion products containing Co(II), Cu(II), Ni(II), Fe(II), Zn(II), Mn(II), and Cr(III).

Fig. 5. Effect of the sintering temperature on (a) the relative sintered density and (b) the micro-hardness of the pure HA.
 S. Iqbal et al. / Journal of Nuclear Materials 507 (2018) 218e225 223

significant role in lowering the sintering temperature of the compressive strength for the pure HA as well as the Co-HA and M-
immobilized matrix. HA. The high compressive strength was achieved because of the
The compressive strength is an important physical parameter high densification and low porosity of the adsorbent. The
that ensures the integrity of the waste form during its interim compressive strength of 207.3 ± 9.5 MPa achieved in this study is
storage, transportation and final disposal under a geological re- several times higher than the compressive strength of the Portland
pository environment. The waste form should have an acceptable cement (2.9e9.8 MPa) and other consolidation matrices being used
value for the compressive strength which ensures its stable per- for the immobilization of radioactive waste, as reported in Table 1.
formance during storage and transportation. Fig. 6 shows the The reported compressive strength for HA is considerably higher
behavior of the compressive strength as the strain was increased. It than the US established regulatory requirements for Portland
is clear from Fig. 6 that the samples sintered at 500  C do not bear a cement (3.45 MPa) [44].
significant load and have a very low compressive strength. On the SEM images in Fig. 7 show the effect of the sintering tempera-
other hand, the samples sintered at 1150  C showed an excellent ture on the grain size of the pure HA, Co-HA, and M-HA at 500  C
and 1150  C. It is obvious from the SEM images that the particles are
loosely packed and less diffused in both the HA and Co-HA at
Table 1 500  C. On the other hand, more compact and densely packed
Comparison of our data with standard compressive strength data [44,45]. structures can be seen in the images for the HA, Co-HA, and M-HA
Solidified matrix Minimum Requirement (MPa)
at 1150  C which show a significant grain growth and enlarged
particle size. The increase in micro-hardness (Fig. 5(b)) and
Portland Cement U.S standard 3.45 MPa
compressive strength (Fig. 6) are in agreement with studies by
Portland Cement Russian standard 4.93 MPa
Unsaturated Polyester 5.17 MPa Muralitharan et al. and Karimzadeh et al. [34,46]. They investigated
Polyethylene 6.89 MPa the effect of sintering temperature on the strength of HA and
Vitrified Glass 34.50 MPa showed that the micro-hardness and compressive strength in-
Calcium Hydroxyapatite (this study) 207.34 ± 9.46 MPa creases with increase in temperature unless dehydroxylation starts

Fig. 7. SEM micrographs of the fractured surfaces of the pure HA, the enlarged view in the inset of each at top left corner, the mapping and distribution of metal ions in the sintered
pellets with different colored dots were observed by EDS analysis.
224 S. Iqbal et al. / Journal of Nuclear Materials 507 (2018) 218e225
Table 2
The normalized leaching rate (NLRi) of each element from the HA matrix.
Metal Co(II) Cr(III) Cu(II)
NLRi (g/m2/day) 4.4  106 3.4  102 3.1  106
and HA structure collapses. Different microstructures in the sin-
tered matrix can be obtained at a given temperature depending on
the characteristics of the starting powder which lead to the
different mechanical properties. However, the microstructure ob-
tained in our study had shown no adverse effects on mechanical
properties of the sintered matrix. The presence of cobalt/CRUD in
the sintered matrices was observed from the EDS and in the area
mapping results of the sintered samples. The EDS results showed
the homogenized distribution of the CRUD elements in the sintered
matrix.
PCT was performed as described in Section 2.4 to check the
chemical stability of the consolidated matrix and the leaching rate
of the immobilized corrosion products. The calculated NLRi values
for each metal are listed in Table 2. It is obvious from Table 2 that
the NLRi values for all the metals are in the range of 3.1#106 to
5.3#106 g/m2/day except for Cr(III) (3.4  102 g/m2/day). Usually,
the NLRi values in the range of 104 to 106 g/m2/day, calculated
based on PCT, are considered to be reasonable for nuclear waste
management [47,48]. In the case of Cr(III), the significantly higher
NLRi value might be due to the lower Cr(III)-HA complex stability at
a higher temperature [49]. Overall, the good mechanical properties
and chemical durability make the sintered matrix a suitable
candidate for nuclear waste immobilization.
5. Conclusions
In this study, a simplified route to capture and directly solidify
CRUD radionuclides was introduced. We found that the direct so-
lidification of CRUD captured hydroxyapatite is possible without
compromising the micro-hardness, compressive strength and
chemical stability. The captured CRUD remained stable in the sin-
tered matrices at high temperatures (1150  C). It was observed that
the waste volume was reduced up to 60% during the sintering
process achieving the relative sintered density of 99.8 ± 0.8%. The
solidified matrix provides an excellent compressive strength
(207.3 ± 9.5 MPa) which fulfills the criteria for the waste confine-
ment in a solid body. Because no additional chemical treatments,
additives and sophisticated equipment involved during this
consolidation process, this adsorption and solidification process is
simple and highly efficient to immobilize the primary waste as well
as to reduce secondary waste.
Acknowledgement
This work was supported by the Nuclear Safety Research Pro-
gram through the Korea Foundation of Nuclear Safety (KOFONS)
with the granted financial resource from the Nuclear Safety and
Security Commission (No. 1305032) and by the Basic Science
Research Program through the National Research Foundation of
Korea (NRF) funded by the Ministry of Science and ICT ((No. NRF-
2015R1A5A1037627) and (No. NRF-2016R1A5A1013919)), Republic
of Korea.
References
[1] J.W. Yeon, Y. Jung, S.I. Pyun, Deposition behaviour of corrosion products on the
Zircaloy heat transfer surface, J. Nucl. Mater. 354 (2006) 163e170.
[2] G. Hirschberg, P. Baradlai, K. Varga, G. Myburg, J. Schunk, P. Tilky, P. Stoddart,
Accumulation of radioactive corrosion products on steel surfaces of VVER type
Fe(II) Mn(II) Ni(II) Zn(II)
5.3  106 3.8  106 4.4  106 3.3  106
nuclear reactors. I. 110mAg, J. Nucl. Mater. 265 (1999) 273e284.
[3] C.C. Lin, A review of corrosion product transport and radiation field buildup in
boiling water reactors, Prog. Nucl. Energy 51 (2009) 207e224.
[4] A. Bhatnagar, A.K. Minocha, M. Sillanpa €a
€, Adsorptive removal of cobalt from
aqueous solution by utilizing lemon peel as biosorbent, Biochem. Eng. J. 48
(2010) 181e186.
[5] P.A. Nishad, A. Bhaskarapillai, S. Velmurugan, S.V. Narasimhan, Cobalt (II)
imprinted chitosan for selective removal of cobalt during nuclear reactor
decontamination, Carbohydr. Polym. 87 (2012) 2690e2696.
[6] E. Repoa, T.A. Kurniawana, J.K. Warcholb, M.E.T. Sillanpaa, Removal of Co(II)
and Ni(II) ions from contaminated water using silica gel functionalized with
EDTA and/or DTPA as chelating agents, J. Hazard Mater. 171 (2009)
1071e1080.
[7] S. Iqbal, J.-I. Yun, EDTA-functionalized mesoporous silica for the removal of
corrosion products: adsorption studies and performance evaluation under
gamma irradiation, Microporous Mesoporous Mater. 248 (2017) 149e157.
[8] J. Oliva, J. De Pablo, J.L. Cortina, J. Cama, C. Ayora, Removal of cadmium, copper,
nickel, cobalt and mercury from water by Apatite II™: column experiments,
J. Hazard Mater. 194 (2011) 312e323.
[9] F. Granados-Correa, S. Bulbulian, Co(II) adsorption in aqueous media by a
synthetic Fe-Mn binary oxide adsorbent, Water Air Soil Pollut. 223 (2012)
4089e4100.
[10] Y. Park, Y.C. Lee, W.S. Shin, S.J. Choi, Removal of cobalt, strontium and cesium
from radioactive laundry wastewater by ammonium molybdophosphate-
polyacrylonitrile (AMP-PAN), Chem. Eng. J. 162 (2010) 685e695.
[11] J.C. Elliott, Structure and chemistry of the apatite and other calcium ortho-
phosphate, in: Stud. Inorg. Chem vol 18, Elsevier B.V, 1994.
[12] J. Wang, Incorporation of iodine into apatite structure: a crystal chemistry
approach using Artificial Neural Network, Front. Earth Sci. 3 (2015) 1e11.
[13] S. Raynaud, E. Champion, Calcium phosphate apatites with variable Ca/P
atomic ratio II. Calcination and sintering, Biomaterials 23 (2002) 1073e1080.
[14] J.T.B. Ratnayake, M. Mucalo, G.J. Dias, Substituted hydroxyapatites for bone
regeneration: a review of current trends, J. Biomed. Mater. Res. B Appl. Bio-
mater. 105 (2017) 1285e1299.
[15] Y. Oshida, E.B. Tuna, O. Akto €ren, K. Gençay, Dental implant systems, Int. J. Mol.
Sci. 11 (2010) 1580e1678.
[16] V.P. Orlovskii, V.S. Komlev, S.M. Barinov, Hydroxyapatite and hydroxyapatite-
based ceramics, Inorg. Mater. (2002) 973e984.
[17] S.J. Kalita, A. Bhardwaj, H.A. Bhatt, Nanocrystalline calcium phosphate ce-
ramics in biomedical engineering, Mater. Sci. Eng. C 27 (2007) 441e449.
[18] A. Dybowska, D.A.C. Manning, M.J. Collins, T. Wess, S. Woodgate, E. Valsami-
Jones, An evaluation of the reactivity of synthetic and natural apatites in the
presence of aqueous metals, Sci. Total Environ. 407 (2009) 2953e2965.
[19] M.D. Williams, B.N. Bjornstad, B.G. Fritz, R.D. Mackley, D.P. Mendoza,
D.R. Newcomer, M.L. Rockhold, J.E. Szecsody, P.D. Thorne, V.R. Vermeul, Y. Xie,
Interim report: 100-NR-2 Apatite treatability Test: low-Concentration Cal-
cium-citrate- Phosphate Solution injection for In situ Strontium-90 Immobi-
lization, 2008. PNNL-17429.
[20] IAEA TECDOC No 1701, The Behaviours of Cementitious Materials in Long
Term Storage and Disposal of Radioactive Waste, 2013.
[21] Z. Laili, M.S. Yasir, M.A. Wahab, Solidification of radioactive waste resins using
cement mixed with organic material, Advancing of Nuclear Science and En-
ergy for National Development, AIP Conf. Proc. 1659 (2015), 050006-1-
050006-6.
[22] K. Sato, Y. Hotta, T. Nagaoka, K. Watari, C. Duran, Novel cermaic forming
methods with are active organic binder, in: Environmental Issues Waste
Manag. Technol. Mater. Nucl. Ind. XII, 2009, pp. 235e242.
[23] W.Y. Xia, Y.S. Feng, F. Jin, L.M. Zhang, Y.J. Du, Stabilization and solidification of
a heavy metal contaminated site soil using a hydroxyapatite based binder,
Construct. Build. Mater. 156 (2017) 199e207.
[24] I. Smiciklas, S. Dimovi c, I. Ple
cas, M. Mitri
c, Removal of Co2þ from aqueous
solutions by hydroxyapatite, Water Res. 40 (2006) 2267e2274.
[25] ASTM C1285-02, Standard test methods for determining chemical durability
of nuclear, hazardous, and mixed waste glasses and multiphase glass Ce-
ramics : the product consistency test ( PCT ) 1, ASTM, Conshohocken, USA 15
(2002) (2002) 1e26.
[26] A. Wagh, Chapter 18 e applications of CBPCs to radioactive and hazardous
waste immobilization, in: Chemical Bonded Phosphate Ceramics, second ed.,
Elsevier, 2016, pp. 283e346, 2016.
[27] K. Gray, F. Poc, Project Title: radionuclide Incorporation and Long Term Per-
formance of Apatite Waste Forms 11-3105, U.S. Deptt. Enegy, 2015.
[28] S.E. Vinokurov, Y.M. Kulyako, O.M. Slyuntchev, S.I. Rovny, B.F. Myasoedov,
Low-temperature immobilization of actinides and other components of high-
level waste in magnesium potassium phosphate matrices, J. Nucl. Mater. 385
(2009) 189e192.
[29] G.L. Smith, D.R. Bates, R.W. Goles, L.R. Greenwood, R.C. Lettau, G.F. Piepel,
 S. Iqbal et al. / Journal of Nuclear Materials 507 (2018) 218e225
M.J. Schweiger, H.D. Smith, M.W. Urie, J.J. Wagner, Vitrification and Product
Testing of C-104 and AZ-102 Pretreated Sludge Mixed with Flowsheet
Quantities of Secondary Wastes, Pacific north west national laboratory, 2001.
WTP-RPT-006, Rev.0.
[30] C.M. Jantzen, N.E. Bibler, The product consistency test (PCT): how and why it
was developed, in: Ceram. Trans, John Wiley & Sons, Inc, Hoboken, NJ, USA,
2009, pp. 155e167.
[31] J. Wang, L.L. Shaw, Nanocrystalline hydroxyapatite with simultaneous en-
hancements in hardness and toughness, Biomaterials 30 (2009) 6565e6572.
[32] J. Wang, L.L. Shaw, Morphology-enhanced low-temperature sintering of
nanocrystalline hydroxyapatite, Adv. Mater. 19 (2007) 2364e2369.
[33] ASTM E384, Standard test method for knoop and vickers hardness of mate-
rials, ASTM Standard (2012) 1e43.
[34] G. Muralithran, S. Ramesh, The Effects of sintering temperature on the
properties of hydroxyapatite, Ceram. Int. 26 (2000) 221e230.
[35] ASTM C39, Standard test method for compressive strength of cylindrical
concrete specimens, Am. Soc. Test. Mater (2016) 1e7.
[36] I. Smiciklas, A. Onjia, S. Rai
cevi
c, Ð. Jana
ckovi
c, M. Mitri
c, Factors influencing
the removal of divalent cations by hydroxyapatite, J. Hazard Mater. 152
(2008) 876e884.
[37] N. Gupta, A.K. Kushwaha, M.C. Chattopadhyaya, Adsorptive removal of Pb2þ,
Co2þ and Ni2þ by hydroxyapatite/chitosan composite from aqueous solution,
J. Taiwan Inst. Chem. Eng 43 (2011) 125e131.
[38] L. Wu, W. Forsling, P.W. Schindler, Surface complexation of calcium minerals
in aqueous solution: 1. Surface protonation at fluorapatite-water interfaces,
J. Colloid Interface Sci. 147 (1) (1991) 178e185.
[39] K. To~nsuaadu, K.A. Gross, L. Pluduma, M. Veiderma, A review on the thermal
stability of calcium apatites, in: J. Therm. Anal. Calorim, Springer, Netherlands,
2012, pp. 647e659.
225
[40] P.S. Prevey, X-ray diffraction characterization of crystallinity and phase
composition in plasma-sprayed hydroxyapatite coatings, J. Therm. Spray
Technol. 9 (2000) 369e376.
[41] A.J. Ruys, M. Wei, C.C. Sorrell, M.R. Dickson, A. Brandwood, B.K. Milthorpe,
Sintering effects on the strength of hydroxyapatite, Biomaterials 16 (1995)
409e415.
[42] E. Champion, Sintering of calcium phosphate bioceramics, Acta Biomater. 9
(2013) 5855e5875.
[43] D. Malina, K. Biernat, A. Sobczak-Kupiec, Studies on sintering process of
synthetic hydroxyapatite, Acta Biochim. Pol. 60 (2013) 851e855.
[44] S. Mattigod, J. Westsik, C. Chung, M. Lindberg, K. Parker, Waste Acceptance
Testing of Secondary Waste Forms ;Cast Stone, Ceramicrete and DuraLith, U.S.
Dep. Energy, 2011. PNNL-20632.
[45] Martin Brownstein G.T.S Duratek Kingston, Tennessee, Radioactive Waste
Solidification, 1991.
[46] A. Karimzadeh, M.R. Ayatollahi, A.R. Bushroa, M.K. Herliansyah, Effect of sin-
tering temperature on mechanical and tribological properties of hydroxyap-
atite measured by nanoindentation and nanoscratch experiments, Ceram. Int.
40 (2014) 9159e9164.
[47] S.V. Yudintsev, E.V. Aleksandrova, T.S. Livshits, V.I. Mal’kovskii, Y.V. Bychkova,
B.R. Tagirov, Crystalline matrices for immobilization of actinides: corrosion
resistance in water, in: Dokl. Earth Sci, 2014, pp. 1281e1284.
[48] R.L. Russell, M.J. Schweiger, J.H. Westsik, a B. Gallegos, M.R. Telander, Low
Temperature Waste Immobilization Testing, 2006.
[49] J.V. Flores-Cano, R. Leyva-Ramos, F. Carrasco-Marin, A.A. Pina, J.J. Salazar-
Rabago, S. Leyva-Ramos, Adsorption mechanism of Chromium(III) from water
solution on bone char: effect of operating conditions, Adsorption 22 (2016)
297e308.