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Accepted Manuscript

Environmentally benign and novel management route for radioactive corrosion


products by hydroxyapatite

Sajid Iqbal, Muhmood ul Hassan, Ho Jin Ryu, Jong-Il Yun

PII: S0022-3115(18)30076-X
DOI: 10.1016/j.jnucmat.2018.05.016
Reference: NUMA 50945

To appear in: Journal of Nuclear Materials

Received Date: 19 January 2018


Revised Date: 4 May 2018
Accepted Date: 6 May 2018

Please cite this article as: S. Iqbal, M. ul Hassan, H.J. Ryu, J.-I. Yun, Environmentally benign and novel
management route for radioactive corrosion products by hydroxyapatite, Journal of Nuclear Materials
(2018), doi: 10.1016/j.jnucmat.2018.05.016.

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ACCEPTED MANUSCRIPT

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1 Environmentally benign and novel management route for radioactive corrosion products
2 by hydroxyapatite
3
4 Sajid Iqbal, Muhmood ul Hassan, Ho Jin Ryu and Jong-Il Yun*
5

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6 Department of Nuclear and Quantum Engineering, KAIST, Daejeon 34141, Republic of Korea.
*
7 E-mail: jiyun@kaist.ac.kr, Fax: +82-42-350-3810

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10 Keywords: Waste Immobilization, Nano-Ceramic, Hydroxyapatite, Radioactive Corrosion
11 Products

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13 Abstract
14 A novel and environmentally benign route for the direct solidification of captured corrosion
15 products (Co, Cr, Fe, Ni, Cu, Zn, and Mn) generated from the primary coolant system of nuclear
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16 power plants is introduced in this study. Synthesized calcium hydroxyapatite was used to remove
17 individual and mixtures of corrosion products from aqueous solutions. The results show more
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18 than a 95 % removal of these corrosion products for both cases. The direct solidification of
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19 adsorbed corrosion products was done by pressure-less conventional sintering. The sintered
20 matrix revealed a good hardness (3.70 ± 0.60 GPa) and a relative sintered density > 98% after
21 heat treatment at 1150 oC. The measured compressive strength (207.3 ± 9.5 MPa) was
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22 significantly higher than the established waste immobilization criteria of the US (3.5 MPa) and
23 Russia (4.9 MPa). The corrosion products consolidated matrix had a normalized leaching rate
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24 ranging from 3.4⨯10-2 to 5.3⨯10-6 g/m2/day. Moreover, no additional chemical treatments,


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25 additives (gypsum, slaked lime, sodium silicate, etc.), and sophisticated equipment were needed
26 for the adsorption and solidification process. Therefore, the proposed waste management route
27 has no adverse effects on the ecosystem and can be highly efficient to immobilize adsorbed
28 waste and to reduce the secondary waste volume.

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31 1. Introduction
32 Corrosion products, known by Chalk River Unidentified Deposits (CRUD), such as 58Co, 60
Co,
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33 Cr, 64Cu, 54Mn, and 59Fe are the main sources of radiation build-up inside nuclear reactor vessel
34 and pose serious problems in routine overhaul maintenance work. CRUD are released into the
35 primary coolant due to the degradation of mechanical parts of the primary coolant system in

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36 nuclear power plants. The CRUD are transported to the reactor core and get activated under the
37 high neutron flux. These are called radioactive CRUD which consequently increase the radiation

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38 level. CRUD can deposit on the surface of fuel rods and cause a reduction in the thermal
39 conductivity. In certain cases, they may also damage the fuel rods due to stress corrosion

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40 cracking phenomena [1–3]. Therefore, it is necessary to use efficient adsorbents to maintain the
41 coolant chemistry and to remove any metal ions that form due to the corrosion of structural

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42 materials of the nuclear power plant. AN
43 Many natural wastes, organic matter, and synthesized adsorbents have been successfully used to
44 capture cobalt/CRUD from contaminated water [4–8]. For example, Granados et al. reported on
45 the adsorption behavior of cobalt as a function of pH, contact time and initial metal ion
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46 concentrations for Fe-Mn oxide synthetic material [9]. Oliva et al. used commercial apatite to
47 remove trace levels of Cd, Cu, Ni, Co and Hg, which are hard to remove by calcite or other
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48 organic adsorbents [8]. Yuonjin et al. used ammonium molybdophosphate–polyacrylonitrile to


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49 remove Co, Sr and Cs which come from radioactive laundry waste water [10]. However, the
50 solidification of Co/CRUD captured adsorbents (secondary waste produced) was not addressed
51 in the aforementioned studies.
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52 Radioactive waste management procedures can be simplified and more cost-effective if the
53 material being used as an adsorbent also acts as a matrix for the consolidation of captured
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54 nuclear waste. In addition, a significant reduction of secondary waste could be achieved with an
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55 adsorbent that can capture metal ions from waste and simultaneously solidify them thus
56 eliminating the need for additional chemical treatments (addition of binders, excessive acid/base
57 treatments or conditioning), loading to other matrices like Portland cement, glass or unsaturated
58 polyesters.

59 Calcium hydroxyapatite (Ca5(PO4)3OH) is a phosphate-based hard ceramic belonging to the


60 apatite family and has the general chemical formula A5(XO4)3Z. The apatite structure has two

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61 cationic positions (A and X) and one anionic position (Z) [11–14]. On ionic sites, different ions
62 can be accommodated without affecting the apatite structure due to its ion exchange properties
63 [11]. Calcium hydroxyapatite (HA) has excellent biocompatibility and is being widely used as a
64 bio ceramic material for making artificial dental roots, teeth implants and artificial bones similar
65 to those living bodies [15–17]. The HA is also abundantly present in nature in the form of waste

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66 bones and phosphate-based minerals. Both natural and synthetic HA have been extensively
67 investigated for their adsorption and substitutional properties to remove pollutants and toxic

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68 heavy metals [8,18,19].
69 In terms of environmental pollution, it is always desirable to use waste management methods

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70 that are the least harmful to the environment and nature. The use of organics, lime and
71 cementitious binders for the stabilization and solidification of contaminants has been considered

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72 the best available technology [20]. The additional binders such as biochar, starch and
73 carbodiimide have been used during green shaping of ceramic body to make it easier to obtain a
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74 desired density with less defects while pressing. During sintering at higher temperatures, the
75 pyrolysis of these binders results in the emission of carbon dioxide or other hydrocarbon gases
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76 [21,22]. Nowadays, geo-polymers, slag, cement kiln and hydroxyapatite have also been tested
77 for the consolidation process [23].
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78 In this study, we applied the synthesized HA to remove single metal ions and a mixture of
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79 CRUD metals from an aqueous system. This study further investigated the possibility of binder-
80 free immobilization of a CRUD captured adsorbent in a form of the highly dense and durable
81 sintered matrix. This technique involves the adsorption of CRUD onto the surface of ceramic
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82 (calcium hydroxyapatite) nanoparticles. The adsorbent was separated from liquid by


83 centrifugation and ultrafiltration. Then the compaction and consolidation of separated CRUD
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84 captured adsorbent was achieved by using conventional pressure-less sintering method.


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85 2. Experimental Procedures
86 2.1 Synthesis of the adsorbent

87 The wet precipitation method has been used to synthesize crystalline apatite as described
88 elsewhere [13]. Anionic and cationic solutions were prepared by dissolving each of the di-
89 ammonium hydrogen phosphate (NH4)2HPO4 and calcium nitrate Ca(NO3)2·4H2O in 200 ml of

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90 ultrapure deionized water, respectively. The Ca/P molar ratio of both the reactants was
91 theoretical set as 1.67. The anionic solution was dropwise mixed with the cationic solution at a
92 speed of 0.06 ml/sec under continuous stirring at 200 rpm. During mixing, the temperature and
93 the pH of the solution were continuously monitored and maintained at 30 °C and 10.5,
94 respectively. To maintain the pH of the solution, a concentrated ammonia solution was used. The

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95 aging of white gel type precipitates that formed during the synthesis was done inside the parent
96 solution for 3 hrs. During the first hour, the stirring continued at 100 rpm and the temperature

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97 was maintained at 30 °C, whereas at the end of the first hour, the reaction vessel was removed
98 from the hot plate and kept without stirring at room temperature for 2 hrs. After that the

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99 suspension was filtered, thoroughly washed and dried overnight at a temperature of 100 oC in a
100 vacuum oven. The dried precipitates were ground to fine powder with a mortar and pestle.

101 2.2 Adsorption Procedures


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102 A detailed adsorption study of HA can be found elsewhere [24]. First, the maximum removal of
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103 Co(II) was optimized by varying the solid to liquid ratio (S: L ratio) from 2 to 5 g/L with 1 mM
104 of Co(II) at pH 6. The adsorbent-liquid contact time was set as 24 hrs with constant stirring at
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105 150 rpm at 25 oC. More than 90% removal of the Co(II) was observed for S:L ratio of 4 g/L. By
106 using the optimized S:L ratio, a single element Co(II) solution and a series of corrosion products
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107 (Co(II), Cr(III), Cu(II), Ni(II), Mn(II), Fe(II) and Zn(II)) were removed from the contaminated
108 aqueous solution. In the mixture of corrosion products, the concentration of each metal ion was
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109 kept constant at 1 mM in 100 ml of deionized water. After 24 hrs, the solid and liquid phases
110 were separated with a 0.45 µm syringe filter followed by a 5 min centrifugation at 3200 rpm. The
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111 concentration of the metal ions in the separated dried adsorbent and the supernatant were
112 measured by ICP-OES. The percentage removal (% R) of the metal ions was calculated by
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113 equation (1),

114 %R = (Co − Ce ) / Co ×100 (1)

115 , where, Co and Ce are the initial and final metal ion concentrations (mM), respectively.

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116
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117 Fig. 1: Flow diagram showing the synthesis of the adsorbent, and then the adsorption and
118 consolidation of the captured corrosion products by hydroxyapatite
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119 2.3 Sintering of pure HA and corrosion product adsorbed HA

120 After the separation and drying of the adsorbent in a vacuum oven at 100 oC overnight, the
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121 powder was shaped into cylindrical pellets with a stainless steel mold 13 mm in diameter. The
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122 pressing at room temperature was conducted under 100 MPa for 30 sec. by a Carver(R) uniaxial
123 press. For each pellet, 1.20 g of pure HA and the metal adsorbed HA (Co-HA and M-HA)
124 powder was used. The pressure-less conventional sintering of the as-pressed pellets of pure HA
125 Co-HA and M-HA was carried out in the box furnace (Model: S-1700, HANTECH) under an air
126 environment. In the first step, the pure HA was studied for a range of temperatures (500 oC, 800
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127 C, 900 oC, 1000 oC, 1150 oC and 1300 oC) for 120 min at a heating ramp of 4 oC/min to optimize

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128 the sintering temperature. After the sintering, the samples were left inside the furnace to cool
129 down to room temperature. In the second step, Co-HA and M-HA were sintered at 500 oC and at
130 the optimized sintering temperature (1150 oC). The dimensions of each pellet were measured
131 before and after the sintering. The percentage volume contraction was calculated with the
132 equation (2):

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133 Vc(%) = ×100 (2)
Vb

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134 , where Vc (%) is the percentage volume contraction, Vb and Va are the volumes of the pellet

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135 before and after sintering.
136 All experiments were performed in triplicate to check the reproducibility of the results.

137 2.4 Product Consistency Test (PCT)


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138 The Product Consistency Test (PCT) is a standard test of the American Society of Testing
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139 Materials (ASTM) to check the chemical stability and structural durability of ceramic waste
140 forms [25–30]. The PCT is performed by immersing the crushed sintered samples (specific
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141 surface area = 0.27 m2/g) into an ASTM-type I water at 90 ± 2 oC for 7 days. All the procedures
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142 were performed in triplicate under static condition in an air-sealed stainless steel autoclave. After
143 7 days the leachate was analyzed for elemental degradation and pH change of the waste matrix.
144 The elemental composition of the waste matrix was measured before the PCT, and the
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145 concentrations of the relevant constituents were measured in the leachate after 7 days PCT test
146 with ICP-OES. The normalized leaching rate of the ith element was calculated by the equation (3)
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147 as follows:
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mi
148 NLRi = (3)
S ⋅ t ⋅ wi

149 , where NLRi is the normalized leaching rate, mi is the concentration of component i leached into
150 the water after a reaction time t, S is the surface area of the crushed powder, and wi is the weight
151 fraction of an ith component in the solid matrix.

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152 3 Characterization of the sintered matrices

153 High-resolution X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to
154 study the crystal structure, size and morphology of the grains in the sintered matrix. The XRD
155 patterns were measured with XRD (SmartLab, RIGAKU) in a scan range of 10 to 90o with a step

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156 size of 0.02o at a tube voltage of 45 kV and a current of 200 mA. The Cu Kα incident radiation
157 source with a wavelength (λ = 1.54056 Å) in the reflection geometry was used.

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158 For the microscopic analysis of the sintered matrix, SEM (Hitachi S4800) was used. The
159 elemental mapping with the distribution of different waste constituents was recorded by energy

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160 dispersive spectrometer (EDS) coupled with SEM. The fractured surface morphology of the
161 sintered samples was observed by mounting the samples on a cross-section holder. The sputter

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162 coating was performed for 15 sec with an HPC-1SW osmium coater before microscopic analysis.
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163 The sintered bulk densities were measured with the Archimedes’ method [31]. The sintered
164 samples were boiled at 100 oC in ultrapure water (MQ) for 30 min to remove the trapped air and
165 to avoid chances of error. The densities and the relative percentage densities were calculated by
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166 using the following relationships [31,32]:


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167 ρ b = mD × ρ L / (Ws − WSM ) (4)


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168 %RD = ρb / ρ R ×100 (5)


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169 , where ρb is the bulk density of the sintered sample, and mD, ρL, Ws, and WSM are the dry weight,
170 the density of deionized water, the saturated weight, and the suspended weight of pellet inside
171 the deionized water, respectively. %RD is the relative standard density, and ρR is the measured
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172 bulk density of the starting powder which is 2.94 g/cm3. The bulk density of the starting HA
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173 powder was measured with a helium pycnometer. The ρb of the CRUD captured HA was
174 assumed to be equal to the ρb of the pure HA because the mass fraction of adsorbed CRUD is
175 very small in comparison to mass fraction of pure HA.

176 The ASTM E384 testing procedure was followed to measure the hardness values. The Vickers
177 microindentor (Model: 402MVD, Wolpert Wilson Instruments) installed with the software
178 Expert Hardness 2007 V2.0 was used to quantify the micro-hardness of the sintered pellets under

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179 a constant load of 200 gf for a dwell time of 10 sec [33]. All of the samples were fine polished by
180 standard SiC papers with different grits (800-2000) and then by the diamond suspension paste
181 before the hardness measurements [34]. The indents were made in a line crossing the center of
182 the specimen so that the near surface effect could be avoided. The indentation was done at room
183 temperature and a representative hardness value of 10 measurements was taken for each sample.

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184 The compressive strength of the sintered samples was measured with the universal testing

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185 machine (UTS INSTRON 5583, U.S.A) with a cross-head speed of 0.4 mm/min and a maximum
186 load capacity of 150 kN at room temperature. Three cylindrical specimens with a length to

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187 diameter ratio (L/D) of 1.24 were prepared for each set of experiments, and the test was carried
188 out according to the ASTM C39 standard compressive strength test [35].

189 4 Results and discussions


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190 This study was divided into three main steps: the synthesis of HA, CRUD adsorption by HA, and
191 consolidation of the as-spent adsorbent (CRUD captured HA). Detailed adsorption studies on
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192 HA investigating the function of pH and contact time as well as the effect of the initial metal ion
193 concentrations have already been done elsewhere [24,36,37]. We investigated the effect of the
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194 adsorbent amount on the maximum removal of a single metal ion and a mixture of metal ions
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195 from aqueous system. The quantitative measurements of the metal ions were done by inductively
196 coupled plasma-optical emission spectrometry (ICP-OES). It is clear from Fig. 2 that the
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197 behavior of the cobalt removal is almost linear with the increasing adsorbent dose up to 4 g/L.
198 This may be due to the excess surface binding sites available to the metal ions due to increase of
199 adsorbent dose. After 4 g/L, the breakthrough value has been achieved with an insignificant
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200 effect on the removal of metal ion at S: L ratio of 5g/L. Then an equimolar (1 mM each) mixture
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201 of corrosion products (Co(II), Cr(III), Cu(II), Fe(II), Mn(II), Ni(II) and Zn(II)) has been prepared
202 in 100 ml of MQ water and optimum removal of metal ions (> 95%) was obtained by increasing
203 S:L ratio to 40 g/L. It is clear from Fig. 3 that more than 95 % of corrosion products can be
204 removed from aqueous media by providing 40 g/L of HA powder at 7 mM of total metal ion
205 concentrations in a mixture. During the adsorption process a decrease in pH was observed from 6

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206 to 4.9, which is due to protons coming from two types of protonated sites at apatite surface
207 (≡POH and ≡CaOH2+) by the exchange of M(II)/M(III) cations as shown in equations 6 & 7 [38 ].

208 ≡ POH + M 2+ ⇔ ≡ POM + + H + (6)

209 ≡ CaOH 2+ + M 2+ ⇔ ≡ CaOHM 2 + + H + (7)

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Removal (%)

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210
S:L Ratio (g/L)
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211 Fig. 2: Effect of the solid to liquid ratio on the removal of Co(II) by hydroxyapatite (Co = 1mM,
212 pH = 6, contact time = 24 hrs, ionic strength = 0.1 M NaCl, shaking speed = 150 rpm at RT).
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100

80

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60
R (%)

Co(II)
Cr(III)

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40 Cu(II)
Fe(II)
Mn(II)

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20 Ni(II)
Zn(II)
0

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20 30 40

S:L Ratio (g/L)


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214 Fig. 3: Effect of the S: L ratio on the removal of CRUD mixture by hydroxyapatite (Co of each
215 metal ion = 1mM, pH = 6, contact time = 24 hrs, shaking speed = 150 rpm at RT).
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216 The main focus of this study was to reduce the secondary waste volume and to provide a facile
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217 route for waste management by direct consolidation of an as-spent adsorbent after separation and
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218 drying of the adsorbent. Therefore, pure HA, cobalt adsorbed HA (Co-HA) and corrosion
219 product adsorbed HA (M-HA) powders dried in a vacuum oven at 100 ˚C for 12 hrs were shaped
220 into cylindrical pellets with a stainless steel mold, as shown in Fig. 1. The pellets were sintered at
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221 500, 800, 900, 1000, 1150 and 1300 ˚C in a box furnace in an air environment, as already
222 discussed in Section 2.3.
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223 The pellets were crushed into powder and the XRD analysis was carried out to investigate the
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224 effect of sintering temperatures on the crystallinity and decomposition of the HA and M-HA.
225 The phases were identified with the standard JCPDS card No. 00-064-0738 available in the
226 system software. [39,40] No peak shifting phenomenon was observed in all samples except the
227 appearance of β-TCP-Ca3(PO4)2 on XRD patterns for HA-1150 °C or M-HA-1150 °C as shown
228 in Fig. 4 which corresponds to the decomposition of HPO42- group present in a wet precipitated
229 HA at this processing temperature [11,13].

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HA-1300oC

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M-HA-1150oC

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HA-1150oC

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Intensity (a.u)

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HA-500oC
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M-HA-As adsorbed
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20 30 40 50 60
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230 2θ (degree)
231 Fig. 4: High-resolution XRD patterns showing the increasing crystallinity of the sintered
232 samples as the temperature was increased (♦ shows the most intense peak of β-TCP-Ca3(PO4)2)
233

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234 There is an insignificant increase in crystallinity of samples heat treated at 500 ˚C (HA and M-
235 HA) compared with the non-heat treated CRUD adsorbed HA (M-HA-As adsorbed) while the
236 samples sintered at 1150 ˚C showed the highest crystallinity which is evident from the sharpness
237 of XRD peaks (Fig 4). The sample sintered at 1300 ˚C also showed good stability and only the
238 formation of small fraction of β-TCP-Ca3(PO4)2 can be seen in the XRD patterns (Fig. 4).

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239 Generally, 1200 -1450 ˚C is the temperature range reported for the decomposition of HA
240 depending on the characteristics of the HA [41].

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241 Relative sintered density and the micro-hardness are the key parameters to confirm the sintering
242 phenomena [42]. Fig. 5 (a & b) shows the effect of the sintering temperature on the relative

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243 sintered density and the micro-hardness, respectively. It is worth noting that the relative sintered
244 density (Fig. 5(a)) increased from 60 % to 99.8 % with the increase of sintering temperature from

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245 500 to 1300 oC. The maximum hardness of 4.17 ± 0.27 GPa was measured for the sintered pure
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246 HA sample at 1300 oC. Based on the densification and the volume contraction results, the
247 optimized sintering temperature has been taken as 1150 oC. The micro-hardness values for pure
248 HA, Co-HA and M-HA at the optimized sintering temperature (1150 oC) were 3.70 ± 0.69, 3.63
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249 ± 0.61 and 3.41 ± 0.46 GPa, respectively. The volumetric contraction of pure HA sintered in the
250 temperature range starting from 500 to 1300 oC was also measured. About 60 % of volume was
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251 decreased at 1150 oC, as compared to 4 to 5 % at 500 oC. The full densification at 1150 oC is due
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252 to the removal of the porosity and the grain boundary diffusion to form larger grains which is the
253 temperature-driven phenomenon. The high temperature offers sufficient energy for the thermal
254 activation of the grain boundary migration and diffusion [43]. It can be seen from Fig. 5 (a & b)
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255 that the adsorbed metal ions did not play a significant role in lowering the sintering temperature
256 of the immobilized matrix.
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257

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258 Fig. 5: Effect of the sintering temperature on (a) the relative sintered density and (b) the micro-
259 hardness of the pure HA

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261 The compressive strength is an important physical parameter that ensures the integrity of the
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262 waste form during its interim storage, transportation and final disposal under a geological
263 repository environment. The waste form should have an acceptable value for the compressive
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264 strength which ensures its stable performance during storage and transportation. Fig. 6 shows the
265 behavior of the compressive strength as the strain was increased. It is clear from Fig. 6 that the
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266 samples sintered at 500 oC do not bear a significant load and have a very low compressive
strength. On the other hand, the samples sintered at 1150 oC showed an excellent compressive
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267
268 strength for the pure HA as well as the Co-HA and M-HA. The high compressive strength was
269 achieved because of the high densification and low porosity of the adsorbent. The compressive
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270 strength of 207.3 ± 9.5 MPa achieved in this study is several times higher than the compressive
271 strength of the Portland cement (2.9 to 9.8 MPa) and other consolidation matrices being used for
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272 the immobilization of radioactive waste, as reported in Table 1. The reported compressive
273 strength for HA is considerably higher than the US established regulatory requirements for
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274 Portland cement (3.45 MPa) [44].

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250 HA-500
Compressive Strength (MPa)
Co-HA-500
225
HA-1150
200 Co-HA-1150
175 M-HA-1150

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Strain (mm/mm)
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276 Fig. 6: Compressive strength of the pure HA, Co-HA and M-HA: M is a mixture of corrosion
277 products containing Co(II), Cu(II), Ni(II), Fe(II), Zn(II), Mn(II), and Cr(III)
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278 Table 1: Comparison of our data with standard compressive strength data [44,45]
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Solidified matrix Minimum Requirement (MPa)


Portland Cement U.S standard 3.45 MPa
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Portland Cement Russian standard 4.93 MPa


Unsaturated Polyester 5.17 MPa
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Polyethylene 6.89 MPa


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Vitrified Glass 34.50 MPa


Calcium Hydroxyapatite (this study) 207.34 ± 9.46 MPa
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280 SEM images in Fig. 7 show the effect of the sintering temperature on the grain size of the pure
281 HA, Co-HA, and M-HA at 500 oC and 1150 oC. It is obvious from the SEM images that the
282 particles are loosely packed and less diffused in both the HA and Co-HA at 500 oC. On the other

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283 hand, more compact and densely packed structures can be seen in the images for the HA, Co-HA,
284 and M-HA at 1150 oC which show a significant grain growth and enlarged particle size. The
285 increase in micro-hardness (Fig. 5(b)) and compressive strength (Fig. 6) are in agreement with
286 studies by Muralitharan et al. and Karimzadeh et al. [34,46]. They investigated the effect of
287 sintering temperature on the strength of HA and showed that the micro-hardness and

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288 compressive strength increases with increase in temperature unless dehydroxylation starts and
289 HA structure collapses. Different microstructures in the sintered matrix can be obtained at a

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290 given temperature depending on the characteristics of the starting powder which lead to the
291 different mechanical properties. However, the microstructure obtained in our study had shown no

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292 adverse effects on mechanical properties of the sintered matrix. The presence of cobalt/CRUD in
293 the sintered matrices was observed from the EDS and in the area mapping results of the sintered

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294 samples. The EDS results showed the homogenized distribution of the CRUD elements in the
295 sintered matrix.
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296

297 Fig. 7: SEM micrographs of the fractured surfaces of the pure HA, the enlarged view in the inset
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298 of each at top left corner, the mapping and distribution of metal ions in the sintered pellets with
299 different colored dots were observed by EDS analysis.
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300 PCT was performed as described in Section 2.4 to check the chemical stability of the
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301 consolidated matrix and the leaching rate of the immobilized corrosion products. The calculated
302 NLRi values for each metal are listed in Table 2. It is obvious from Table 2 that the NLRi values
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303 for all the metals are in the range of 3.1⨯10-6 to 4.4⨯10-6 g/m2/day except for Cr (3.4⨯10-2
304 g/m2/day). Usually, the NLRi values in the range of 10-4 to 10-6 g/m2/day, calculated based on
305 PCT, are considered to be reasonable for nuclear waste management [47,48]. In the case of Cr,
306 the significantly higher NLRi value might be due to the lower Cr(III)-HA complex stability at a
307 higher temperature [49]. Overall, the good mechanical properties and chemical durability make
308 the sintered matrix a suitable candidate for nuclear waste immobilization.

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309 Table 2: The normalized leaching rate (NLRi) of each element from the HA matrix

Metal Co(II) Cr(III) Cu(II) Fe(II) Mn(II) Ni(II) Zn(II)


NLRi
4.4⨯10-6 3.4⨯10-2 3.1⨯10-6 5.3⨯10-6 3.8⨯10-6 4.4⨯10-6 3.3⨯10-6
(g/m2/day)

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311 Conclusions

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312 In this study, a simplified route to capture and directly solidify CRUD radionuclides was

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313 introduced. We found that the direct solidification of CRUD captured hydroxyapatite is possible
314 without compromising the micro-hardness, compressive strength and chemical stability. The
315 captured CRUD remained stable in the sintered matrices at high temperatures (1150 ˚C). It was
316
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observed that the waste volume was reduced up to 60 % during the sintering process achieving
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317 the relative sintered density of 99.8 ± 0.8 %. The solidified matrix provides an excellent
318 compressive strength (207.3 ± 9.5 MPa) which fulfills the criteria for the waste confinement in a
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319 solid body. Because no additional chemical treatments, additives and sophisticated equipment
320 involved during this consolidation process, this adsorption and solidification process is simple
321 and highly efficient to immobilize the primary waste as well as to reduce secondary waste.
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322
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323 Acknowledgement
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324 This work was supported by the Nuclear Safety Research Program through the Korea Foundation
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325 of Nuclear Safety (KOFONS) with the granted financial resource from the Nuclear Safety and

326 Security Commission (NSSC) (No. 1305032) and by the Basic Science Research Program

327 through the National Research Foundation of Korea (NRF) funded by the Ministry of Science

328 and ICT ((No. NRF-2015R1A5A1037627) and (No. NRF-2016R1A5A1013919)), Republic of

329 Korea.

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330 References

331 [1] J.W. Yeon, Y. Jung, S.I. Pyun, Deposition behaviour of corrosion products on the
332 Zircaloy heat transfer surface, J. Nucl. Mater. 354 (2006) 163–170.

333 [2] G. Hirschberg, P. Baradlai, K. Varga, G. Myburg, J. Schunk, P. Tilky, P. Stoddart,

PT
334 Accumulation of radioactive corrosion products on steel surfaces of VVER type nuclear
335 reactors. I. 110mAg, J. Nucl. Mater. 265 (1999) 273–284.

RI
336 [3] C.C. Lin, A review of corrosion product transport and radiation field buildup in boiling
337 water reactors, Prog. Nucl. Energy. 51 (2009) 207–224.

SC
338 [4] A. Bhatnagar, A.K. Minocha, M. Sillanpää, Adsorptive removal of cobalt from aqueous
339 solution by utilizing lemon peel as biosorbent, Biochem. Eng. J. 48 (2010) 181–186.

U
340 [5] P.A. Nishad, A. Bhaskarapillai, S. Velmurugan, S.V. Narasimhan, Cobalt (II) imprinted
AN
341 chitosan for selective removal of cobalt during nuclear reactor decontamination,
342 Carbohydr. Polym. 87 (2012) 2690–2696.
M

343 [6] E. Repoa, T. A. Kurniawana, J. K.Warcholb, M. E.T. Sillanpaa, Removal of Co(II) and
344 Ni(II) ions from contaminatedwater using silica gel functionalized with EDTA and/or
D

345 DTPA as chelating agents, J. Hazard. Mater. 171 (2009) 1071–1080.

346 [7] S. Iqbal, J.-I. Yun, EDTA-functionalized mesoporous silica for the removal of corrosion
TE

347 products: Adsorption studies and performance evaluation under gamma irradiation,
348 Microporous Mesoporous Mater. 248 (2017) 149–157.
EP

349 [8] J. Oliva, J. De Pablo, J.L. Cortina, J. Cama, C. Ayora, Removal of cadmium, copper,
350 nickel, cobalt and mercury from water by Apatite IITM: Column experiments, J. Hazard.
C

351 Mater. 194 (2011) 312–323.


AC

352 [9] F. Granados-Correa, S. Bulbulian, Co(II) adsorption in aqueous media by a synthetic Fe-
353 Mn binary oxide adsorbent, Water. Air. Soil Pollut. 223 (2012) 4089–4100.

354 [10] Y. Park, Y.C. Lee, W.S. Shin, S.J. Choi, Removal of cobalt, strontium and cesium from
355 radioactive laundry wastewater by ammonium molybdophosphate-polyacrylonitrile
356 (AMP-PAN), Chem. Eng. J. 162 (2010) 685–695.

357 [11] J. C. Elliott, Structure and Chemistry of the Apatite and Other Calcium Orthophosphate,

18
ACCEPTED MANUSCRIPT

358 in: Stud. Inorg. Chem. 18, Elsevier B.V, 1994.

359 [12] J. Wang, Incorporation of iodine into apatite structure: a crystal chemistry approach using
360 Artificial Neural Network, Front. Earth Sci. 3 (2015) 1–11.

361 [13] S. Raynaud, E. Champion, Calcium phosphate apatites with variable Ca / P atomic ratio II .

PT
362 Calcination and sintering, Biomaterials. 23 (2002) 1073–1080.

363 [14] J.T.B. Ratnayake, M. Mucalo, G.J. Dias, Substituted hydroxyapatites for bone

RI
364 regeneration: A review of current trends, J. Biomed. Mater. Res. Part B Appl. Biomater.
365 105 (2017) 1285–1299.

SC
366 [15] Y. Oshida, E.B. Tuna, O. Aktören, K. Gençay, Dental implant systems, Int. J. Mol. Sci. 11
367 (2010) 1580–1678.

U
368 [16] V.P. Orlovskii, V.S. Komlev, S.M. Barinov, Hydroxyapatite and hydroxyapatite-based
AN
369 ceramics, Inorg. Mater. (2002) 973-984.

370 [17] S.J. Kalita, A. Bhardwaj, H.A. Bhatt, Nanocrystalline calcium phosphate ceramics in
M

371 biomedical engineering, Mater. Sci. Eng. C. 27 (2007) 441–449.

372 [18] A. Dybowska, D.A.C. Manning, M.J. Collins, T. Wess, S. Woodgate, E. Valsami-Jones,
D

373 An evaluation of the reactivity of synthetic and natural apatites in the presence of aqueous
374 metals, Sci. Total Environ. 407 (2009) 2953–2965.
TE

375 [19] M.D. Williams, B.N. Bjornstad, B.G. Fritz, R.D. Mackley, D.P. Mendoza, D.R.
376 Newcomer, M.L. Rockhold, J.E. Szecsody, P.D. Thorne, V.R. Vermeul, Y. Xie, Interim
EP

377 Report: 100-NR-2 Apatite Treatability Test: Low-Concentration Calcium-Citrate-


378 Phosphate Solution Injection for In Situ Strontium-90 Immobilization, PNNL-17429
C

379 (2008).
AC

380 [20] IAEA TECDOC No. 1701, The Behaviours of Cementitious Materials in Long Term
381 Storage and Disposal of Radioactive Waste, 2013.

382 [21] Z. Laili, M.S. Yasir, M.A. Wahab, Solidification of radioactive waste resins using cement
383 mixed with organic material, Advancing of Nuclear Science and Energy for National
384 Development, AIP Conf. Proc. 1659 (2015) 050006-1-050006-6.

385 [22] K. Sato, Y. Hotta, T. Nagaoka, K. Watari, C. Duran, Novel cermaic forming merhods with

19
ACCEPTED MANUSCRIPT

386 areactive organic binder, in: Enivironmental Issues Waste Manag. Technol. Mater. Nucl.
387 Ind. XII, (2009) 235–242.

388 [23] W.Y. Xia, Y.S. Feng, F. Jin, L.M. Zhang, Y.J. Du, Stabilization and solidification of a
389 heavy metal contaminated site soil using a hydroxyapatite based binder, Constr. Build.

PT
390 Mater. 156 (2017) 199–207.

391 [24] I. Smičiklas, S. Dimović, I. Plećaš, M. Mitrić, Removal of Co2+ from aqueous solutions

RI
392 by hydroxyapatite, Water Res. 40 (2006) 2267–2274.

393 [25] ASTM C1285-02, Standard Test Methods for Determining Chemical Durability of

SC
394 Nuclear , Hazardous , and Mixed Waste Glasses and Multiphase Glass Ceramics : The
395 Product Consistency Test ( PCT ) 1, ASTM, Conshohocken, USA, 2002. 15 (2002) 1–26.

U
396 [26] Wagh, A. Chapter 18 – Applications of CBPCs to Radioactive and Hazardous Waste
397 Immobilization, in: Chemical bonded phosphate ceramics, 2nd Edition, Elsevier, 2016, pp.
AN
398 283-346. 2016.

399 [27] K. Gray, F. Poc, Project Title : Radionuclide Incorporation and Long Term Performance
M

400 of Apatite Waste Forms 11-3105, U.S. Deptt. Enegy. (2015).

401 [28] S.E. Vinokurov, Y.M. Kulyako, O.M. Slyuntchev, S.I. Rovny, B.F. Myasoedov, Low-
D

402 temperature immobilization of actinides and other components of high-level waste in


TE

403 magnesium potassium phosphate matrices, J. Nucl. Mater. 385 (2009) 189–192.

404 [29] G.L. Smith, D.R. Bates, R.W. Goles, L.R. Greenwood, R.C. Lettau, G.F. Piepel, M.J.
EP

405 Schweiger, H.D. Smith, M.W. Urie, J.J. Wagner, Vitrification and Product Testing of C-
406 104 and AZ-102 Pretreated Sludge Mixed with Flowsheet Quantities of Secondary Wastes,
C

407 Pacific north west national laboratory, WTP-RPT-006, Rev.0 (2001).


AC

408 [30] C.M. Jantzen, N.E. Bibler, The product consistency test (PCT): How and why it was
409 developed, in: Ceram. Trans., John Wiley & Sons, Inc., Hoboken, NJ, USA, 2009: pp.
410 155–167.

411 [31] J. Wang, L.L. Shaw, Nanocrystalline hydroxyapatite with simultaneous enhancements in
412 hardness and toughness, Biomaterials. 30 (2009) 6565–6572.

413 [32] J. Wang, L.L. Shaw, Morphology-enhanced low-temperature sintering of nanocrystalline

20
ACCEPTED MANUSCRIPT

414 hydroxyapatite, Adv. Mater. 19 (2007) 2364–2369.

415 [33] ASTM E384: Standard Test Method for Knoop and Vickers Hardness of Materials,
416 ASTM Standard, (2012) 1–43.

417 [34] G. Muralithran, S. Ramesh, The Effects of sintering temperature on the properties of

PT
418 hydroxyapatite, Ceram. Int. 26 (2000) 221–230.

419 [35] ASTM C39, Standard Test Method for Compressive Strength of Cylindrical Concrete

RI
420 Specimens, Am. Soc. Test. Mater. (2016) 1–7.

421 [36] I. Smičiklas, A. Onjia, S. Raičević, Đ. Janaćković, M. Mitrić, Factors influencing the

SC
422 removal of divalent cations by hydroxyapatite, J. Hazard. Mater. 152 (2008) 876–884.

423 [37] N. Gupta, A.K. Kushwaha, M.C. Chattopadhyaya, Adsorptive removal of Pb2+, Co2+ and

U
424 Ni2+ by hydroxyapatite/chitosan composite from aqueous solution, J. Taiwan Inst. Chem.
AN
425 Eng. 43 (2011) 125–131.

426 [38] L. Wu, W. Forsling, P.W. Schindler, Surface complexation of calcium minerals in aqueous
M

427 solution: 1. Surface protonation at fluorapatite-water interfaces, J. Colloid and Inter. Sci.,
428 147 (1) (1991) 178-185.
D

429 [39] K. Tõnsuaadu, K.A. Gross, L. Pluduma, M. Veiderma, A review on the thermal stability
430 of calcium apatites, in: J. Therm. Anal. Calorim., Springer Netherlands, 2012: pp. 647–
TE

431 659.

432 [40] P.S. Prevéy, X-Ray Diffraction Characterization of Crystallinity and Phase Composition
EP

433 in Plasma-Sprayed Hydroxyapatite Coatings, J. Therm. Spray Technol. 9 (2000) 369–376.

434 [41] A.J. Ruys, M. Wei, C.C. Sorrell, M.R. Dickson, A. Brandwood, B.K. Milthorpe, Sintering
C

435 effects on the strength of hydroxyapatite, Biomaterials. 16 (1995) 409–415.


AC

436 [42] E. Champion, Sintering of calcium phosphate bioceramics, Acta Biomater. 9 (2013)
437 5855–5875.

438 [43] D. Malina, K. Biernat, A. Sobczak-Kupiec, Studies on sintering process of synthetic


439 hydroxyapatite, Acta Biochim. Pol. 60 (2013) 851–855.

440 [44] S. Mattigod, J. Westsik, C. Chung, M. Lindberg, K. Parker, Waste Acceptance Testing of
441 Secondary Waste Forms : Cast Stone, Ceramicrete and DuraLith, U.S. Dep. Energy,

21
ACCEPTED MANUSCRIPT

442 PNNL-20632, (2011).

443 [45] Martin Brownstein G.T.S Duratek Kingston, Tennessee, Radioactive Waste Solidification,
444 (1991).

445 [46] A. Karimzadeh, M.R. Ayatollahi, A.R. Bushroa, M.K. Herliansyah, Effect of sintering

PT
446 temperature on mechanical and tribological properties of hydroxyapatite measured by
447 nanoindentation and nanoscratch experiments, Ceram. Int. 40 (2014) 9159–9164.

RI
448 [47] S. V. Yudintsev, E. V. Aleksandrova, T.S. Livshits, V.I. Mal’kovskii, Y. V. Bychkova,
449 B.R. Tagirov, Crystalline matrices for immobilization of actinides: Corrosion resistance in

SC
450 water, in: Dokl. Earth Sci., 2014: pp. 1281–1284.

451 [48] R.L. Russell, M.J. Schweiger, J.H. Westsik, a B. Gallegos, M.R. Telander, Low

U
452 Temperature Waste Immobilization Testing, 2006.
AN
453 [49] J.V. Flores-Cano, R. Leyva-Ramos, F. Carrasco-Marin, A. A. Pina, J.J. Salazar-Rabago, S.
454 Leyva-Ramos, Adsorption mechanism of Chromium(III) from water solution on bone char:
455 effect of operating conditions, Adsorption. 22 (2016) 297–308.
M
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Research Highlights

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.

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ASTM PCT test approved the chemical durability of sintered matrix.

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