박사 학위논문

Ph. D. Dissertation

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방사성 요오드 기체의 흡착

Adsorption of Gaseous Radioactive Iodine Using

Bismuth-Incorporated Mesoporous Silica

양 재 환(楊 載 煥 Yang, Jae Hwan)

원자력 및 양자공학과
Department of Nuclear and Quantum Engineering

KAIST

2016
비스무스를 담지한 메조기공 실리카를 이용한

방사성 요오드 기체의 흡착

Adsorption of Gaseous Radioactive Iodine Using

Bismuth-Incorporated Mesoporous Silica
 Adsorption of Gaseous Radioactive Iodine Using
Bismuth-Incorporated Mesoporous Silica

Advisor: Professor Yim, Man-Sung

by

Yang, Jae Hwan

Department of Nuclear and Quantum Engineering
KAIST

A thesis submitted to the faculty of KAIST in partial fulfillment of the re-

quirements for the degree of Doctor of Philosophy in the Department of Nucle-
ar and Quantum Engineering. The study was conducted in accordance with
Code of Research Ethics1

2015. 11. 17
Approved by
Professor Yim, Man-Sung

1
Declaration of Ethical Conduct in Research: I, as a graduate student of KAIST, hereby declare that I have not
committed any acts that may damage the credibility of my research. These include, but are not limited to: falsi-
fication, thesis written by someone else, distortion of research findings or plagiarism. I affirm that my thesis
contains honest conclusions based on my own careful research under the guidance of my thesis advisor.
비스무스를 담지한 메조기공 실리카를 이용한

방사성 요오드 기체의 흡착

Thesis(Dissertation) Title
양 재 환

위 논문은 한국과학기술원 박사학위논문으로

학위논문심사위원회에서 심사 통과하였음.

2015 년 11 월 17 일

심사위원장 임 만 성 (인)
심사위원 이 건 재 (인)
심사위원 조 성 오 (인)
심사위원 윤 종 일 (인)
심사위원 유 룡 (인)
DNQE 양 재 환. Yang, Jae Hwan. Adsorption of Gaseous Radioactive Iodine Using Bismuth-
Incorporated Mesoporous Silica. 비스무스를 담지한 메조기공 실리카를 이용한
20135173
방사성 요오드 기체의 흡착. Department of Nuclear and Quantum Engineering. 2016.
124p. Advisor Prof. Yim, Man-Sung. Text in English

ABSTRACT

Radioiodine (129I) generated by nuclear fission reaction is volatilized as gaseous forms when
spent nuclear fuel is reprocessed. The very long half-life (1.57 × 107 y) and high environmental mobility
129
have made the management of I a challenging issue. Currently, silver-exchanged zeolites (AgX or
129
AgZ) are widely used to capture I2(g). However, iodine physisorption within zeolite poses a serious
129
problem related to long-term disposal of I. Furthermore, silver-based sorbents cannot be the ultimate
solution given that high price and toxicity of silver.
In chapter 3, new adsorbents based on bismuth were investigated for the capture of 129I in off-gas
produced from spent fuel reprocessing. Porous bulky materials were synthesized with polyvinyl alcohol
(PVA) as a sacrificial template. Major findings showed that the iodine trapping capacity of as-
synthesized samples could reach 1.9-fold that of commercial silver-exchanged zeolite (AgX). The ther-
modynamic stability of the reaction products explains the high removal efficiency of iodine. It was also
found that the pore volume of each sample was closely related to the ratio of the reaction products.
In chapter 4, bismuth-embedded SBA-15 mesoporous silica was firstly applied for iodine cap-
ture and storage. SBA-15 was functionalized with thiol (-SH) groups, followed by bismuth adsorption
with Bi-S bonding, which was thermally treated to form Bi 2S3 within SBA-15. The bismuth-embedded
SBA-15s demonstrated high iodine loading capacities (up to 540 mg-I/g-sorbent), which benefitted from
high surface area and porosity of SBA-15 as well as the formation of thermodynamically stable BiI3
compound. Iodine physisorption was effectively suppressed due to the large pores present in SBA-15,
resulting in chemisorption as a main mechanism for iodine confinement. Furthermore, a chemically du-
rable iodine-bearing material was made with a facile post-sorption process, during which the iodine-
incorporated phase was changed from BiI3 to chemically durable Bi5O7I. Thus, the results showed that
both efficient capture and stabilization of 129I would be possible with the bismuth-embedded SBA-15, in
contrast to other sorbents mainly focused on iodine capture.
In chapter 5, stabilization of bismuth-embedded SBA-15 that captured iodine gas was studied by
fabrication of monolithic waste forms. The iodine containing waste was mixed with Bi2O3 (a stabilizing
additive), and low-temperature sintering glass, followed by pelletizing and sintering process to produce
glass composite materials. Iodine volatility during sintering process was significantly affected by the ra-

i
tio of Bi2O3 and the glass composition. It was confirmed that BiI3, the main iodine phase within bis-
muth-embedded SBA-15, was effectively transformed to the mixed phases of Bi5O7I and BiOI. The ini-
tial leaching rates of iodine from the glass composite waste forms ranged 10-3-10-2 g/m2∙day, showing
stability of the iodine phases encapsulated by glassy networks. It was also observed that common
groundwater anions (e.g., chloride, carbonate, sulfite, and fluoride) elevate iodine leaching rate by anion
exchange reactions. The results of this dissertation suggest that glass composite waste form of bismuth-
embedded SBA-15 could be a candidate material for stable storage of 129I.

Keywords: Radioiodine (129I), bismuth, bismuth-embedded SBA-15, chemisorption, stabilization, glass

composite waste form

Table of Contents

ii
 Table of Contents

Abstract ······························································································ i

Table of Contents ··················································································· iii

List of Tables ························································································ vi

List of Figures ······················································································ vii

Chapter 1. Introduction ············································································ 1

Chapter 2. Literature Review ····································································· 9

2.1 Iodine Capture Technology ·································································· 9

2.1.1 Wet scrubbing method ···································································· 9

2.1.2 Solid sorbents methods ·································································· 10

2.1.3 State of the art ············································································ 16

2.1.3.1 Chalcogenide-based aerogels (Chalcogels) ······································· 16

2.1.3.2 Silver-functionalized silica aerogels ··············································· 18

2.1.3.3 Metal-organic frameworks (MOF) ················································· 19

2.2 Bismuth-Iodine-Oxides for Iodine Waste Phases ······································· 19

2.2.1 Redox reactions ·········································································· 20

2.2.2 Anion displacement reactions ·························································· 23

2.2.3 Complexation reactions ································································· 24

2.2.4 Thermal stability ········································································· 27

Chapter 3. Novel Synthesis of Bismuth-Based Adsorbents for the Removal of 129I in Off-

Gas············································································································· 29

3.1 Introduction ·················································································· 29

3.2 Experimental ················································································· 31

3.2.1 Synthesis of porous sorbents ··························································· 31

3.2.2 Iodine trapping test ······································································ 31

3.2.3 Characterization ·········································································· 32

3.3 Results and Discussion······································································ 23

3.3.1 Characterization of the as-synthesized adsorbents··································· 32

3.3.2 Characterization of the reaction products ············································· 38

3.3.3 Mechanism of the iodine trapping reaction ··········································· 45

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 3.3.4 Iodine trapping capacity of the as-synthesized samples ···························· 47

Chapter 4. Bismuth-Embedded SBA-15 Mesoporous Silica for Radioactive Iodine Capture

and Stable Storage················································································· 51

4.1 Introduction ·················································································· 51

4.2 Experimental ················································································· 52

4.2.1 Synthesis of bismuth-embedded SBA-15 ············································· 52

4.2.2 Iodine adsorption experiments ························································· 55

4.2.3 Chemical durability test ································································· 57

4.2.4 Characterization ·········································································· 57

4.3 Results and Discussion······································································ 58

4.3.1 Sample characterization ································································· 58

4.3.2 Iodine adsorption experiments ························································· 72

4.3.3 Adsorption mechanism ·································································· 76

4.3.4 Chemical durability analysis ··························································· 79

4.4 Implications for Waste Management ······················································ 84

Chapter 5. Glass Composite Waste Forms for Iodine Confined in Bismuth-Embedded

SBA-15 ····························································································· 86

5.1 Introduction ·················································································· 86

5.2 Experimental ················································································· 88

5.2.1 Preparation of Bi-embedded SBA-15 ················································· 88

5.2.2 Iodine capturing experiments··························································· 88

5.2.3 Waste form fabrication ·································································· 89

5.2.4 Elemental leaching test ·································································· 92

5.2.5 Characterization ·········································································· 92

5.3 Results and Discussion······································································ 93

5.3.1 Characterization of samples ···························································· 93

5.3.2 Chemical durability studies ···························································· 104

5.3.3 Implications of this study ······························································ 109

Chapter 6. Conclusions of This Dissertation ················································ 111

References ·························································································· 113

Summary (in Korean) ··········································································· 123

iv
Acknowledgement ················································································ 125

Curriculum Vitae ················································································· 127

v
 List of Tables

Table 2-1. Data for the Gibbs free energy of formation (∆Gf°) at 298 K among the many metal

oxides and corresponding iodides ································································· 13

Table 2-2. Solubility of various iodides in water [66] ········································· 14

Table 3-1. Data for Gibbs free energy of formation (∆G f°) at 298 K related to formation of vari-

ous iodine compounds ·············································································· 30

Table 3-2. Textural properties of the as-synthesize samples ·································· 37

Table 3-3. Adsorbed mass resulting from the iodine trapping reaction and pure iodine mass cal-

culated from the relative ratio of iodine or oxygen in the adsorbed mass in different samples 49

Table 4-1. Sample names at different synthesis stages and MPTMS molar ratios ········· 54

Table 4-2. Comparisons of the calculated and measured mass ratios of sulfur in several samples

to estimate the MPTMS utilization for thiol-functionalization ································ 62

Table 4-3. Structural parameters for various samples revealed by N2 adsorption and desorption

isotherms ····························································································· 67

Table 4-4. Mass ratios of sulfur, bismuth, and iodine, and iodine capturing capacities in iodine-

bearing samples ····················································································· 74

Table 4-5. Chemical reactions related to iodine adsorption with Bi2S3 in static air, as well as

Gibbs free energy of formation (ΔGf°) at 473 K ················································ 77

Table 4-6. Fractional iodine loss at different samples calculated from iodine concentrations in

leachates obtained by ICP-AES ··································································· 81

Table 5-1. Sample compositions prior to heat-treatment ······································ 90

Table 5-2. Comparison of the calculated and measured mass ratios for Bi and I by using BiI3

standard sample ···················································································· 102

Table 5-3. Comparison of iodine mass ratio in each sample before and after sintering, as well as

retention ratio of iodine obtained by considering iodine volatilization during heat-treatment 103

vi
 List of Figures

Fig. 1-1. Typical composition of spent nuclear fuel [1] ·········································· 2

Fig. 1-2. A schematic of the head-end process of typical spent nuclear fuel reprocessing where

fission products are released as off-gas [7] ························································ 3

Fig. 1-3. Dose contributions from volatile radionuclides without control to the MEI from a re-

processing facility with a plant size of 1000 t/y and 30 GWd/tIHM PWR UOX fuel [6] ··· 4

Fig. 1-4. Pourbaix diagram for iodine in water at 25 °C [48] ··································· 7

Fig. 2-1. Various activities being performed by the Off-Gas Sigma Team [80] ············ 17

Fig. 2-2. Iodine release behavior in AgI and a mixture of Bi2O3 and Bi5O7I calculated at pH =

9, as a function of p(H2). Stability limits of water and the magnetite and hematite redox buffer

are represented with dashed lines and dotted lines, respectively [44] ························ 22

Fig. 2-3. Equilibrium iodine concentration of AgI and (AgI + AgCl), as a function of the chlo-

ride concentration, calculated using the Gibbs free energy data in Wagman et al.’s document.

Total iodine concentration including AgI(aq) is represented by the dashed line [43, 90] · 25

Fig. 2-4. Stability diagram of Bi5O7I, represented with the equilibrium iodide concentration as

a function of pH and chloride (a) or carbonate (b) concentration [41] ······················· 26

Fig. 2-5. Iodine partial pressures of AgI and Bi5O7I as a function of temperature [41] ···· 28

Fig. 3-1. Optical images of BP3-O (a) and BP3 (b) ············································ 34

Fig. 3-2. XRD patterns of BP3-O (a) and BP3 (b)·············································· 35

Fig. 3-3. SEM images of BP0 (a), BP1 (b), BP2 (c), and BP3 (d) ···························· 36

Fig. 3-4. Optical images of BP0 (a), BP1 (b), BP2 (c), and BP3 (d) after reacting with iodine

crystals at 200 °C for 24 h ········································································· 41

Fig. 3-5. XRD patterns of samples after reacting with iodine ································· 42

Fig. 3-6. TGA-DSC profiles of iodine-reacted BP0 (a), BP1 (b), BP2 (c), and BP3 (d) at a rate

of 10 °C min-1 and N2 flow ········································································ 43

Fig. 3-7. SEM images of BP0 (a), BP1 (b), BP2 (c), and BP3 (d) after reacting with iodine, and

representative EDS spectra of BP0, BP1, BP2, and BP3 (e, f) (Pt signal in EDS spectra origi-

nated from Pt coating of samples) ································································ 44

Fig. 3-8. Schematic diagram representing the main reactions occurring on the outer and inner

surfaces of the samples ············································································· 46

vii
Fig. 3-9. Iodine trapping capacity of each sample compared with that of AgX beads ····· 50

Fig. 4-1. A schematic of the apparatus for iodine capturing experiment in steady air ····· 56

Fig. 4-2. Images of (a) SBA-15-SH1, (b) Bi-SBA-15-SH1, and (c) Bir-SBA-15-SH1 ···· 60

Fig. 4-3. The IR spectra of different samples: (a) SBA-15, (b) SBA-15-SH1, (c) SBA-15-SH2,

(d) SBA-15-SH3, (e) Bi-SBA-15-SH1, (f) Bi-SBA-15-SH2, and (g) Bi-SBA-15-SH3 ··· 61

Fig. 4-4. Small angle X-ray scattering (SAXS) patterns of (a) SBA-15, (b) SBA-15-SH1, (c)

SBA-SH2, and (d) SBA-15-SH3. Inset is a part of the SAXS patterns that are vertically magni-

fied by 12 times ····················································································· 66

Fig. 4-5. N2 adsorption and desorption isotherms and pore size distributions (inset) of SBA-15

(■), SBA-15-SH1 (●), SBA-15-SH2 (▲), SBA-15-SH2A (◆), and SBA-15-SH3 (▼) ····· 68

Fig. 4-6. SEM images of different samples: (a) SBA-15, (b) SBA-15-SH1, (c) SBA-15-SH2,

(d) SBA-15-SH3, (e) Bi-SBA-15-SH2, and (f) Bir-SBA-15-SH2 ···························· 69

Fig. 4-7. TEM images and SAD patterns (insets) for (a) SBA-15, (b) SBA-15-SH1, (c) SBA-

15-SH2, (d) SBA-15-SH3, (e) Bi-SBA-15-SH1, and (f) Bir-SBA-15-SH1 ················· 70

Fig. 4-8. The XRD patterns for different samples: (a) Bi-SBA-15-SH1, Bir-SBA-15-SH1, and

Bir-SBA-15-SH1-I, (b) Bi-SBA-15-SH2, Bir-SBA-15-SH2, and Bir-SBA-15-SH2-I, (c) Bi-

SBA-15-SH3, Bir-SBA-15-SH3, and Bir-SBA-15-SH3-I, (d) Bi-SBA-15-SH2A, Bir-SBA-15-

SH2A, and Bir-SBA-15-SH2A-I ·································································· 71

Fig. 4-9. Iodine capturing capacities in static air for (a) SBA-15, (b) Bi-SBA-15-SH1, (c) Bi-

SBA-15-SH2, (d) Bi-SBA-15-SH3, (e) Bir-SBA-15-SH1, (f) Bir-SBA-15-SH2, (g) Bir-SBA-

15-SH3, (h) Bir-SBA-15-SH2A, and (i) AgX (tested at 150 °C) ····························· 73

Fig. 4-10. Graphs on the relation of mass ratios between (a) sulfur and bismuth and (b) bismuth

and iodine capturing capacity ····································································· 75

Fig. 4-11. TGA data for various samples: curves for the samples prior to iodine capture are

presented with a dashed line. Curves for bismuth-embedded SBA-15 are shown with a solid

line ···································································································· 78

Fig. 4-12. Fractional iodine loss for various samples revealed by the PCT test ············ 80

Fig. 4-13. The XRD patterns for (a) the initial mixture sample composed of BiI3 and Bi2O3, (b)

the heat-treated sample at 250 °C for 3h, (c) the heat-treated sample at 400 °C for 3h, and (d)

the heat-treated sample at 500 °C for 3h ························································· 82

Fig. 4-14. The XRD patterns for (a) Bir-SBA-15-SH2A-I and (b) CD-IP ·················· 83

Fig. 5-1. Images of (a) pelletized samples before sintering (LGC106, LGC113, LGC119,

viii
LGC206, LGC213, and LGC219 from the left) and (b) glass composite samples after sintering

(LGC106, LGC113, LGC119, LGC206, LGC213, and LGC219 from the left) ············ 91

Fig. 5-2. XRD pattern for Bi-embedded SBA-15 after iodine capture, revealing that most io-

dine within Bi-embedded SBA-15 exists as BiI3················································ 96

Fig. 5-3. XRD patterns for the glass-composite waste form samples (after sintering): (a) sam-

ples made with LGC1 binder (LGC1 series), and (b) samples made with LGC2 binder (LGC2

series) ································································································· 97

Fig. 5-4. Microstructural images of LGC1 series provided by SEM: (a) LGC106, (b) LGC113,

(c) LGC119 at low magnification; (d) LGC106, (e) LGC113, (f) LGC119 at high magnification

········································································································· 98

Fig. 5-5. Microstructural images of LGC2 series provided by SEM: (a) LGC206, (b) LGC213,

(c) LGC219 at low magnification; (d) LGC206, (e) LGC213, (f) LGC219 at high magnification

········································································································· 99

Fig. 5-6. TGA for each sample powder mixture (before sintering) during heating at 600 °C for

2 h (heating rate: 10 °C/min) in air ······························································ 100

Fig. 5-7. TG-DSC analysis of Bi2O3 powder from 30 to 1000 °C in air (heating rate:

10 °C/min) ·························································································· 101

Fig. 5-8. Comparison of leaching rates obtained from the results of PCT-A test in different

samples: (a) LGC106 and LGC206; (b) LGC106, LGC113, and LGC119 ················· 107

Fig. 5-9. Iodine leaching rates from LGC106 when deionized water (DIW), 0.005 M solutions

of NaCl, Na2CO3, Na2SO3, and NaF were used as leachant (leaching solution), respectively ·

········································································································ 108

ix
 Chapter 1. Introduction

Nuclear energy is beneficial to the environment in terms of not-producing greenhouse gases

unlike fossil-fuel based energy. However, nuclear energy production is inevitably accompanied by

radioactive waste that must be managed for at least hundreds of thousands of years as a by-product.

Spent nuclear fuel is the most dangerous waste due to its high level of radioactivity and heat at-

tributed to fission products. As shown in Fig. 1-1, spent nuclear fuel is mostly composed of urani-

um, and transuranic elements and fission products occupy minor portions [1]. Among the many fis-

sion products produced by nuclear fission reactions, iodine isotopes (e.g., 127I, 129I, 131I, 133I, and 135I)

constitute less than 0.1 % by mass of the spent nuclear fuels. Of these, beta-emitting 129I with a half-

life of 1.57 × 107 y is the most problematic radioisotope when considering the dramatically long

half-life and negative health effects. Accumulating in the thyroid with a biological half-life of 80

days in adults, 129I could cause diseases such as thyroid nodules or cancer [2]. Volatile fission prod-

ucts are removed during spent nuclear fuel reprocessing – or pyroprocessing – which includes sev-

eral sub-processes such as shearing, voloxidation, and fuel dissolution (Fig. 1-2). In spent nuclear

fuel, most iodine molecules are known to be present as CsI, with a small portion of I2, due to the

high thermodynamic stability of CsI [3,4]. However, CsI dissociates to Cs+ and I- in hot nitric acid

used for fuel dissolution, and the chemical form of volatilized iodine becomes I2(g). Therefore,
129
I2(g) is dispersed into the air when off-gas evolved from spent nuclear fuel is discharged from the

reprocessing facilities.

According to the current regulations on radiation, they specify that the annual dose equiva-

lent cannot be higher than 25 millirems to the whole body for the general public [5]. The dose

amount for a maximally exposed individual (MEI) is shown in Fig. 1-3 when volatile radionuclides

such as 3H, 14C, 85Kr, and 129

I are emitted into the air without any control. As shown in the graph,

the total whole body dose from uncontrolled radionuclides is much higher than the allowable dose

limit. Thus, the emission of radionuclides must be reduced with proper controls to satisfy the crite-

rion. The amount of volatile radionuclides generated from spent nuclear fuel depends on a few pa-

rameters: plant size, fuel type, cooling period, and burn-up [6]. If we fix these parameters, the remo-

1
Fig. 1-1. Typical compositions of spent nuclear fuel [1].

2
Fig. 1-2. A schematic of the head-end process of typical spent nuclear fuel reprocessing

where fission products are released as off-gas [7].

3
 Fig. 1-3. Dose contributions from volatile radionuclides without control to the MEI from a

reprocessing facility with a plant size of 1000 t/y and 30 GWd/tIHM PWR UOX fuel [6].

4
val efficiency for each radionuclide required to meet the dose limit is determined by code calcula-
129
tions. In the case of I, the removal efficiency must be at least 99.4% when we assume that the

condition of the spent nuclear fuel is LWR uranium oxide fuel with a burn-up of 30 GWd/tIHM

processed in a 1000 t/y facility [6]. Conservatively, this number would be higher given that other

sources additionally contribute to the total dose.

Many studies on iodine capture have been done to satisfy environmental regulations. Iodine

sequestration is usually done with caustic or alkaline scrubbing solutions (e.g., NaOH, HNO3, and

Hg(NO3)2) by passing iodine-containing off-gas through the solutions [8]. Various solid sorbents

have also been developed to capture I2(g): activated charcoal [9], macroreticular resin [10], silver-

exchanged zeolites – or mordenites – (AgX [11,12] or AgZ [13,14]), silver-functionalized silica

aerogels [15,16], metal-organic frameworks (MOFs) [17,18], and chalcogen-based aerogels

(chalcogels) [19–21]. Among them, silver-exchanged mordenite (AgZ) is commonly used for iodine

capture in the USA and considered as a benchmark sorbent [14].

Safe disposal, which is long-term isolation of 129I-loaded wastes from humans, is another big
129
issue when considering the very long half-life of I. Several schemes have been suggested for the
129
long-term disposal of I. Ocean disposal is one of them [22]. It is based on the principle that the
129
concentration of I is diluted to the background level by the vast amount of stable isotope (127I)
129
present in the ocean. It is reported that the annual production of I by nuclear energy generation

and the amount of 127I in the oceans are on the order of 1010 and 1017 grams, respectively [23]. Alt-

hough this method has been done to dispose of iodine waste, gaining the public acceptance of ocean

dumping is difficult due to the changed perception on nuclear waste especially after the Fukushima

Daiichi nuclear accident. Disposal in space with artificial satellites has also been suggested [24]: If
129
the I waste orbited around the earth or solar system permanently, the waste could be perfectly

isolated from humans. However, technology for this strategy is yet to be developed, and extremely
129
high costs are expected for extraterrestrial disposal. Another method is to transmute I into stable

elements such as 130Xe by neutron irradiation [25]. Unfortunately, the feasibility of transmutation is
129
very low within the current technology. Thus, a viable scheme for I disposal is to bury the waste

deep in the ground. Currently, high-level radioactive waste is destined to be buried in mined reposi-

tory systems within a depth of 500 m [26].

Radioactive contaminants stored in subterranean regions could leach into the surface soil

5
due to the existence of lateral and longitudinal movement of groundwater [27]. Thus, the mobility of
129
I along by groundwater transport is a serious concern. Iodine has various oxidation states includ-

ing -1, 0, +1, +3, +5, and +7. When dissolved in water, iodine mostly exists as I-, HOI, I2, and IO3-

in normal environmental conditions (Fig. 1-4). Among them, I- is the prevalent species under reduc-

ing conditions which is common in deep groundwater [28]. This anion is not readily adsorbed in

silicate-based soils [29] and becomes highly mobile along groundwater flow paths. Thus, the chem-

ical durability of iodine-incorporated materials must be improved to guarantee the safe disposal of
129
I for extensive periods of time.

Several technologies have been studied to synthesize stable iodine-bearing materials. Low-

temperature sintering glass was used to fabricate waste forms with AgZ [30] or MOFs [17]. A spe-

cial type of glass (AgI-Ag2O-P2O5) was also studied to incorporate silver iodide (AgI) into the glass

structure [31]. Iodine-bearing phases such as apatite [32] and sodalite [33–36] were synthesized to

determine stable iodine phases. However, the feasibility of these technologies is questionable due to

the lack of sufficient data. AgI, which is made when iodine is chemically adsorbed in silver-

exchanged zeolites or silver-functionalized silica aerogels, is a chemically durable phase with the

least solubility [37]. However, it has been reported that a significant portion of iodine in silver-

exchanged zeolite is bound as I2 instead of AgI [38], making the silver-exchanged zeolites a less

attractive option for long-term storage of iodine. Additionally, the high price and toxicity of silver

are other problems as well [39].

Some researchers studied the applicability of bismuth for iodine waste forms [40–47]. Tay-

lor et al. studied the hydrolytic stability of various bismuth iodine compounds, suggesting a bismuth

oxyiodide system for the final iodine waste phase [40,41,43–45]. Recent studies have shown that the

iodine present in aqueous solutions could be separated with a simple precipitation method through

in-situ crystallization of layered bismuth oxide compounds [46,47]. A study on the chemical stabil-

ity of these compounds under possible repository conditions showed that bismuth-iodine-oxides

have low solubility in solutions with some common ground water anions (Cl-, HCO3-, SO42-), which

suggests the potential of bismuth-iodine-oxides as candidate phases for long-term disposal.

6
Fig. 1-4. Pourbaix diagram for iodine in water at 25 °C [48].

7
 Although many studies have been performed for sequestration and stabilization of 129I, stud-

ies are still needed to develop a whole technology that includes both the efficient capture of 129I2(g)

and the stabilization of the iodine-captured sorbent for long-term disposal. In this regard, the aim of

this dissertation is to propose novel sorbents for iodine capture and stabilization. For this purpose,

bismuth was first used for I2(g) capture instead of silver which has been traditionally used. SBA-15

mesoporous silica was used as a supporting matrix to incorporate bismuth in place of commonly

used zeolites. Iodine capture and stabilization were investigated using this sorbent. This Ph. D. dis-

sertation is composed of (1) a literature review on iodine capture technologies including state-of-

the-art technology, and an assessment of bismuth oxyiodide phases for final iodine disposal, (2) ex-

perimental work on iodine capture with porous bismuth granules, (3) experimental work on iodine

capture with bismuth-embedded SBA-15, and (4) experimental works on iodine stabilization with

bismuth-embedded SBA-15 after iodine capture.

8
 Chapter 2. Literature Review

2.1 Iodine Capture Technology

Due to the long-term hazards of 129I to humans, release of 129I in off-gas into the air from nu-
129
clear fuel reprocessing facilities is strictly regulated. Thus, sequestration of I in off-gas prior to

discharge into the air is necessary to satisfy regulations. Many studies have investigated how to ef-
129 129
fectively trap I. Capture technologies for I have been developed following two different ap-

proaches: the wet scrubbing method and adsorption by solid sorbents. Some methods have been

adopted by actual reprocessing facilities, and others are not used any more. The following sections

review the representative methods for iodine capture.

2.1.1 Wet scrubbing method

129
In the wet scrubbing process, off-gas containing I passes an alkaline or acidic scrubbing
129
solution; I is trapped in the scrubbing solution through a chemical reaction. The representative

processes are the alkaline scrub, Iodox and Mercurex processes [8–10]. The alkaline scrub uses a 1-

2 M NaOH solution to capture iodine. The Iodox process removes iodine by using a 20-23 M HNO3

solution. The Mercurex process uses a mixture of 0.4-14 M Hg(NO3)2 and HNO3 as a scrubbing so-

lution. The chemical reactions involved to trap iodine are as follows [8,10,49]:

- Alkaline scrub: 3I2 + 6OH- ↔ 5I- + IO3- + 3H2O (2-1)

- Iodox process: 2CH3I + 4H(NO3) ↔ 2CH3NO3 + I2 + N2O4 + 2H2O (2-2)

I2 + 4HNO3 ↔ 2I+ + 2NO3- + N2O4 + 2H2O (2-3)

I+ + 3HNO3 + NO3- ↔ IO3- + H+ + 2N2O4 + H2O (2-4)

- Mercurex process: 6I2 + 6Hg(NO3)2 + 6H2O ↔ 5HgI2 + Hg(IO3)2 + 12HNO3 (2-5)

2CH3I + Hg(NO3)2 ↔ HgI2 + 2CH3NO3 (2-6)

2CH3I + Hg(NO3)2 + 2H2O ↔ HgI2 + 2CH3NO3 + 2HNO3 (2-7)

As can be seen in the above equations, both methyl iodide and elemental iodine can be re-

9
moved by wet scrubbing methods. After trapped into scrubbing solutions, iodine exists in the solu-

ble iodide (I-)/iodate (IO3-) or insoluble HgI2/Hg(IO3)2 forms. It has been reported that elemental

iodine (I2) as well as methyl iodide (CH3I) is effectively removed by wet scrubbing (DF: 102-104),

although the removal efficiency for CH3I with an alkaline scrub is significantly low (DF: ~1)

[9,25,50–52]. Among the several processes discussed above, the alkaline scrub was scaled up to an

engineering scale for use at an actual facility [10]. Although iodine is effectively trapped with wet

scrubbing, an additional process is inevitably necessary to separate the iodine from the scrubbing
129
solution and convert it into stable iodine phases for the safe disposal of I. Formation of Ba(IO3)2

or HI3O8 has been suggested because these are sparingly soluble. Finally, these are immobilized

with cement or other binding materials [10,53]. The wet scrubbing process cannot be used if other

iodine phases are required for the final waste form [10]. In addition, the maintenance cost of the wet

scrubbing process is relatively high due to the use of highly corrosive scrubbing solutions [10].

Even worse, iodine removal by the Mercurex process is not desirable due to environmental protec-

tion, considering the toxicity of mercuric iodide (HgI2).

2.1.2 Solid sorbents method

Compared with the wet scrubbing method, iodine capture with solid sorbents are favorable

in several aspects: iodine gas is trapped with a relatively simple system and few moving parts;

maintenance costs are decreased due to no use of corrosive media; additional processes are not re-

quired to separate iodine compounds from aqueous media [54].

Many materials have been investigated to capture iodine, and activated charcoal and various

kinds of metal-incorporated zeolites have been most widely studied due to their high porosity [8–

10,53,54]. Activated carbon usually produced by thermal activation at 600-900 °C has a very high

surface area up to 3500 m2/g [55]. It has been extensively used to prevent 131
I from escaping to the

air at nuclear reactors [9,50,53,56]. It can adsorb iodine gas sufficiently well without any modifica-

tion, but it is usually impregnated with KI, I2, or triethylenediamine (TEDA) to induce either chemi-

sorption or isotropic exchange of iodine at less than 120 °C shown in the following reactions

[8,38,53]:

CH3131I + K127I → CH3127I + K131I (2-8)

10
R3N + CH3131I → R3N+CH3131I- (2-9)

There are many control parameters that affect the iodine removal performance: inlet iodine

concentration, amount of moisture, trapping temperature, working time and weathering, radiation,

impregnation, producing condition, particle size, and flow velocity of the sample passing the acti-

vated carbon [38]. Although successfully used in reactor systems, activated carbon suffers from a
129
few severe drawbacks when used for I trapping in reprocessing plants: (1) poor performance at

high temperature and the presence of nitrogen oxides, (2) a relatively low ignition point, which is

serious in the case of the accumulation of decay heat from radioiodine as well as the presence of
129
nitrogen oxides [38]. For these reasons, activated carbon is not appropriate to separate I from off-

gases that evolve at high temperature and normally contain nitrogen oxides.

Macroreticular resin is a material that can selectively trap gases based on their degree of hy-

drophobicity or hydrophilicity [8,50,53]. The Amberlite XAD series is a commercial product made

of macroreticular resin generally consisting of acrylic esters or polystyrene functionalized with

cross-linked di-vinyl benzene [10]. Because it has a strong attraction for uncharged molecules such

as I2 and CH3, its removal efficiency for iodine is reported to be significantly high: maximum DFs at

dry air reaches 104 [8]. In addition, it is highly resistant to acids and radiation, so the efficiency does

not fall in NOx-containing air unlike activated carbon [53]. However, the performance is adversely

affected in a high humidity or high temperature environment [10,53].

Iodine sequestration with activated carbon or macroreticular resin is based on physisorption

that binds iodine molecules by van der Waals interactions. If iodine is chemisorbed, the thermal and

chemical stability of the trapped iodine could be significantly improved through the formation of

stable iodine compounds, which is advantageous for long-term disposal of 129I waste. In this regard,
129
metal-loaded materials have been studied as I scavengers by many researchers. Zeolites have

been used as a matrix for metal incorporation due to the facile metal incorporation by cation ex-

change, as well as its many adsorption sites attributed to the high surface area. Thus, many metal

(e.g., Ag, Cd, Cu, Pb, K, Hg, Zn, Mn, Co, Tl, and Ni)-incorporated zeolites have been investigated

to assess their feasibility as an iodine sorbent [57–64]. Unfortunately, most metals except Ag have

been revealed to be ineffective in adsorbing iodine [8,50,53]. This is attributed to the relatively low

affinity for iodine compared with oxygen. In other words, metals exist as oxides in zeolites after

11
exchange with cations, and these oxides are thermodynamically more stable than the corresponding

metal iodide [57]. The Gibbs free energies of formation (∆Gf°) in metal oxides and corresponding

iodides are listed in Table 2-1. In addition to the high affinity toward iodine, the use of silver is ben-

eficial to the long-term stability of iodine. Silver iodide (AgI) is one of the most insoluble iodine

compounds shown in Table 2-2. Considering radionuclides in wastes are dispersed only by ground-

water intrusion, solubility in water is a decisive factor for long-term stability. Due to these charac-

teristics of silver, various kinds of silver-loaded sorbents have been developed.

Silver exchanged zeolites, produced by exchanging a portion of sodium in the zeolite

(xNa2O∙yAl2O3∙zSiO2) with silver, trap iodine gas and convert it to silver iodide (AgI) through the

following reaction [10]:

Ag2O + I2(g) → 2AgI + 0.5 O2(g) (2-10)

Due to the small zeolite pores with a size of less than 2 nm, zeolites can effectively accommodate

iodine molecules in their pores, which corresponds to physisorption. In other words, physisorption

as well as chemisorption are two mechanisms for iodine capture in silver-exchanged zeolites. Ac-

cording to a study by Thomas et al. [38], the chemisorption limit in silver-exchanged faujasite

(AgX) is 60 wt%. AgX with silver contents of 10-30 wt% can effectively remove iodine at 150 °C

with a DF value of 103-105 [10]. However, its performance deteriorates in the presence of water va-

por and NOx.

12
 Table 2-1. Data for the Gibbs free energy of formation (∆Gf°) at 298 K among the many

metal oxides and corresponding iodides

Oxide ∆Gf° (kJ/mol) Iodide ∆Gf° (kJ/mol)

Ag2O* -11.28 AgI* -66.27

PbO* -187.9 PbI2* -173.6

Cu2O* -147.9 CuI* -69.4

CdO* -228.5 CdI2* -201.3

MnO# -363.0 MnI2# -262.8

PdO# -83.5 PdI2# -90.4

Tl2O* -143.5 TlI* -125.5

HgO* -58.6 HgI2* -102.2

*: referenced from Strachan et al.’s work [15].

#
: calculated using HSC chemistry 6.0 [65].

13
Table 2-2. Solubility of various iodides in water [66]

Iodide Solubility (g/100 mL, 293 K)

AgI 3х10-7

BiI3 7.761х10-4

CuI 4.2х10-3

HgI2 6х10-3

PbI2 7.56х10-2

CdI2 84.7

LiI 167 (at 298 K)

NaI 178.8

BaI2 221

14
 Silver mordenite (AgZ) is different from AgX inasmuch as AgZ uses mordenite

(Na2O∙Al2O3∙10SiO2∙6H2O) as a matrix. Mordenite has a higher Si/Al ratio than that of faujasite

with a much higher chemical stability. Thus, AgZ can be safely used in NOx-containing off-gases

without deterioration. Silver is usually incorporated into mordenite by cation exchange, and chemi-

cal reduction often conducted prior to service has been reported to improve the adsorption perfor-

mance [10]. The typical silver content of AgZ is approximately 15 wt% which is a little smaller than

that of AgX. The lower percentage of Al in AgZ is directly related to determining the ratio of cati-

ons that can be exchanged with silver. Due to the high resistance to NOx which is generally found in
129
the reprocessed off-gases, AgZ is currently considered as a baseline sorbent for I removal in the

U.S. [14]. Several studies have been done on dynamic adsorption with AgZ in various conditions

[67–69]. Nevertheless, AgX and AgZ have a few drawbacks when used as sorbents. First, not all of

the iodine is chemisorbed with significant portions physisorbed in the zeolite pores [38].

Physisorbed iodine is fatal for two reasons: First, the weakly bound iodine could readily be de-

sorbed during heat-treatment which is generally done to produce durable waste forms prior to per-

manent disposal; second, physisorbed iodine is much weaker to groundwater attack than that of

chemisorbed iodine (AgI phase) resulting in the facile dispersion of 129I along groundwater transport

paths. In addition, the high price of silver (643 USD/kg, 2014) makes silver unattractive for use in

iodine adsorption. The requirement for very high temperatures (>1200 °C) for zeolite densification

is another problem with using AgX or AgZ as sorbents [70–73].

Along with zeolites, silica and alumina have also been used as matrices to incorporate silver.

Silver nitrate impregnated substrates can effectively remove either elemental iodine or alkyl iodide

with the following reactions [74]:

(a) For elemental iodine,

AgNO3 + I2 → AgI + INO3 (2-11)

2INO3 + AgNO3 → AgIO3 + 3NO2 + 0.5I2 (2-12)

INO3 ↔ NO2 + 0.5O2 + 0.5I2 (2-13)

(b) For alkyl iodide,

AgNO3 + RI → RNO3 + AgI (2-14)

15
 Silver nitrate impregnated amorphous silicic acid, called AC-6120, is a sorbent that was de-

veloped by German researchers [74–78]. AC-6120 has a surface area of 65-110 m2/g, a pore size of

20-40 nm, a grain size of 1-2 mm, and 8-12 wt% of silver [10]. It was actually used at the WAK

reprocessing plant in Karlsruhe from 1975 to 1992 [9]. Silver nitrate impregnated alumina (AgA)

was developed in Japan [9,79]. It was also used to remove 129I in off-gas streams at the Tokai repro-

cessing plant [10]. Both AC-6120 and AgA have high removal efficiencies for elemental and organ-

ic iodides at elevated temperature (150 °C) and high resistance to NOx [10]. In addition, the price of

silver nitrate impregnated sorbents is known to be 3-10 times cheaper than that of silver zeolites [9].

However, the performance diminishes in the presence of organic contaminants and moisture [10].

2.1.3 State of the art

Although AgZ has been considered as a benchmark sorbent for many decades to separate
129
I(g), efforts to develop advanced materials are on-going. To systematically support the R&D, the

U.S. Department of Energy (DOE) has launched an Off-Gas Sigma Team along with the Fuel Cycle

Research and Development (FCR&D) program in 2009 [80]. Currently, several U.S. national labor-

atories are involved in developing overall process technologies for volatile radionuclides (Fig. 2-1).

2.1.3.1 Chalcogenide-based aerogels (chalcogels)

Chalcogenide means an element that belongs to an oxygen group such as S, Se and Te.

Chalcogels consist of binary nanocrystal systems (e.g., CdS, ZnS, PbS, and CdSe) or a structural

unit made of chalcogenido clusters (e.g., Ge4S104-) and metal ions (e.g., Pt2+) [19]. Due to selective

affinity for specific ionic species, chalcogels can be used to adsorb toxic gases or pollutants within

liquids. In particular, these have an excellent adsorbing capacity for iodine gas. Reportedly, the

maximum iodine loading capacity of chalcogel is 2390 mg of iodine per unit gram of sorbent. Addi-

tionally, chalcogel has a removal efficiency of higher than 99.8% [19,20]. The iodine loading per-

formance of chalcogels is the highest among existing sorbents. This high performance of chalcogel

is generally explained by the HSAB principle [81,82]. According to Pearson’s HSAB principle,

molecules or elements are categorized into Lewis acids or bases based on chemical hardness defined

by the difference in ionization energy and electron affinity.

16
Fig. 2-1. Various activities being performed by the Off-Gas Sigma Team [80].

17
 Because I2(g) is a soft Lewis acid and chacogenides such as Te, S and Se are soft Lewis ba-

ses, iodine molecules are strongly attracted to chalcogels. Various kinds of chalcogels have been

synthesized. However, Se- and Te- based chalcogels are not appropriate for iodine capture due to

the toxicity of Se and the air-sensitivity of Se and Te [19]. Therefore, chalcogels synthesized with S

are only being studied for the adsorption of I2(g). Despite the excellent adsorption capacity,

chalcogels are not proper matrices for iodine with respect to long-term disposal: iodine molecules

bind weakly to chalcogels and do not form stable iodine compounds. Thus, the attached iodine

could readily be dissolved into groundwater as well as easily vaporized by thermal elevation

[19,21,83].

2.1.3.2 Silver-functionalized silica aerogels

129
Another kind of aerogel under development for I(g) removal is silica aerogels which in-

corporate silver. In contrast to the case with zeolites, it is impossible to embed silver into aerogel

surfaces by the cation exchange reaction. In this regard, the surfaces of silica aerogels are modified

by thiol-groups. Then, silver ions readily attach to the surfaces of thiol-functionalized silica through

the formation of Ag-S bonds [83]. Then, silver nanoparticles form on the silica surface through

chemical reduction. This process enables silica aerogel to retain silver up to the extent of 30 wt%

[15]. Due to the high content of silver and high surface area of silica aerogel, I2(g) can be success-

fully adsorbed onto silver-functionalized silica aerogels. The maximum iodine adsorption test per-

formed at 150 °C shows that iodine could be trapped up to 476 mg per unit gram of sorbent [15].

Dynamic adsorption tests have been done with simulated off-gas environments to evaluate the fea-

sibility of silver-functionalized silica aerogels [69,80]. However, this sorbent also appears not to

avoid the problem of iodine physisorption due to the existence of micropores within the aerogel.

The amount of chemisorbed iodine was estimated based on the silver content, which sets the chemi-

sorption limit at approximately 350 mg-I2/g-sorbent. Based on the estimation, the ratio of

physisorbed iodine is at least 26%. A preliminary study was also performed to consolidate the io-

dine-bearing silica aerogel [83,84]. In this study, densified materials were fabricated under high

pressure and temperature. Given that physisorbed iodine is present inside the consolidated samples,

more study is needed to improve the durability of the consolidated silica aerogels.

18
 2.1.3.3 Metal-organic frameworks (MOF)

A metal-organic framework (MOF) is a highly porous material synthesized by coordinate

covalent bonding between metal ions and organic ligands [85]. This chelate compound has a high

void fraction in its structure, providing many active sites for the accommodation of gaseous mole-

cules. Due to its very high surface area (<3500 m2/g) and facile functionalization, MOFs are now

being studied for efficient storage of gases such as CO2 and H2 [86]. Reportedly, I2(g) is also effec-

tively captured by MOFs, with an adsorption capacity of approximately 1500 mg_I2/g_MOF. Be-

cause metal ions inside MOFs do not participate in iodine trapping, iodine adsorption by MOF is

inherently physical adsorption. Therefore, weakly bound iodine molecules easily escape from MOFs

by thermal elevation at above 100 °C [18]. Furthermore, MOFs cannot function as a long-term stor-

age matrix for 129I given that iodine molecules bound in MOFs could readily be leached by ground-

water intrusion.

2.2 Bismuth-Iodine-Oxides as an Iodine Waste Phase

Bismuth iodine compounds were extensively studied by P. Taylor et al. to judge their poten-
129
tial as candidate waste forms for I [40–45,87]. The hydrolytic stability of various compounds

composed of bismuth and iodine were investigated in view of the thermodynamics and kinetics.

Considering that groundwater intrusion into waste forms dissolves radiotoxic isotopes, one of the

most important parameters is hydrolytic stability when evaluating the long-term stability of waste

forms. Thus, Taylor el al. investigated the hydrolysis reactions of bismuth iodine compounds, and

tentatively concluded that the mixture of Bi2O3 and Bi5O7I was a promising waste form among oth-

ers, based on a comparison of aqueous equilibria between bismuth systems [41,43]:

Bi5O7I(s) + OH-(aq) ↔ 5/2Bi2O3(s) + I-(aq) + 1/2H2O(l), KI,1 = {I-}/{OH} = 10-3.39±0.20 (2-15)

5/4BiOI(s) + OH-(aq) ↔ 1/4Bi5O7I(s) + I-(aq) + 1/2H2O(l), KI,2 = {I-}/{OH} = 103.49±0.18 (2-16)

1/2BiI3(s) + OH-(aq) ↔ 1/2BiOI(s) + I-(aq) + 1/2H2O(l), KI,3 = {I-}/{OH} = 1010.0±1.0 (2-17)

, where KI,x (x = 1, 2, or 3) is an equilibrium constant estimated at 25 °C in the pH range of 9.5-13

[43]. The significant difference between the values of KI,1 and others suggests that the hydrolytic

stability of Bi5O7I is much higher than those of BiOI or BiI3. More importantly, the equilibrium

19
concentration of iodide can be decreased further by using a mixture of Bi 2O3 and Bi5O7I, which ac-

tivates the reverse reaction in equation (2-15). The iodide activity in a mixture of Bi2O3 and Bi5O7I

is expressed as a function of pH at 25 °C [41]:

log{I-} = pH – 17.4 ± 0.2 (2-18)

Therefore, the equilibrium concentration of iodide at neutral medium (pH = 7) is calculated

as log{I-} = -10.4 ± 0.2. This value is even lower than that of AgI, which is log{I-} = -8.0 ± 0.5 at

25 °C for most ranges of pH [43,88]. However, equation (2-18) is valid only in neutral or slightly

basic solutions due to the rapidly increasing solubility of Bi2O3 in acidic solutions [89].

A profound understanding of the iodine behavior is acquired by considering other factors

that affect chemical equilibrium. P. Taylor et al. examined 4 types of main reactions in AgI and

bismuth oxyiodide to determine the behavior of these compounds in repository environments

[40,41,43].

2.2.1 Redox reactions

Iodine dissolution characteristics in reducing conditions can be obtained from the study of

the Gibbs free energy of formation for various chemical reactions. Fig. 2-2 shows the iodine con-

centrations released from AgI and a mixture of Bi2O3 and Bi5O7I as a function of p(H2) at pH = 9

[44,88]. As the nearly vertical line indicates, iodide solubility in a mixture of Bi2O3 and Bi5O7I is

hardly dependent upon p(H2) until log[p(H2), Pa] reaches -8, suggesting a strong resistance to reduc-

ing conditions. Further reducing conditions lead to the reduction of Bi2O3 to Bi and iodide release

by the reduction of Bi5O7I which proceeds through the following reaction:

Bi5O7I(s) + OH-(aq) + 15/2H2(g) ↔ 5Bi + 8H2O(l) + I-(aq) (2-19)

In this region, iodide release from the bismuth compound becomes extremely dependent on

p(H2) shown by the near-horizontal line in Fig. 2-2. In even further reducing conditions, iodine can-

not be retained by the bismuth system any more.

Resistivity to redox conditions in the case of AgI is relatively weak compared to that of the

20
bismuth system because iodine release is apparently dependent on p(H2) when the log[p(H2), Pa] is

larger than -24. Then, iodine is released from AgI following the redox reaction under even more

reducing conditions:

AgI(s) + 1/2H2(g) ↔ Ag(s) + I-(aq) + H+(aq) (2-20)

Although iodine escapes from AgI by reaction (2-20), the dependence on p(H2) is relatively weak

judging from the gradient of the (Ag + AgI) line. Above a log[p(H2), Pa] of about -7, the iodine be-

havior has nothing to do with the AgI system.

The argument on redox reactions suggests that a mixture of Bi 2O3 and Bi5O7I is more stable

than AgI over a wider range of reducing conditions. However, both systems are not stable under

redox environments controlled by a magnetite/hematite buffer shown in Fig. 2-2 which is believed

to mimic deep groundwater that is in contact with minerals comprised of granite [41].

21
 Fig. 2-2. Iodine release behavior in AgI and a mixture of Bi2O3 and Bi5O7I calculated at pH

= 9, as a function of p(H2). Stability limits of water and the magnetite and hematite redox buffer are

represented with dashed lines and dotted lines, respectively [44].

22
 2.2.2 Anion displacement reactions

Iodine release from iodine compounds is also affected by dissolved anions such as chloride,

carbonate/bicarbonate and sulfate, which are relatively rich in granitic groundwater [43]. These ani-

ons limit the hydrolytic stability of AgI and Bi5O7I by replacing I- with themselves. In the case of

AgI, anion displacement scarcely occurs due to the low solubility of AgI. One possible reaction is

the formation of silver chloride in the presence of chlorine anions through the following reaction:

AgI(s) + Cl-(aq) ↔ AgCl(s) + I-(aq) (2-21)

The above displacement reaction is accelerated when the chloride concentration exceeds 10

mmol dm-3 [43]. The equilibrium iodine concentration could increase up to 10 μmol dm-3 at 25 °C,

which is 2 orders higher than the iodine concentration when chloride is not present [41,45]. This

situation is believed to be improved by using a mixed phase of AgCl and AgI as a waste form, in-

stead of AgI alone. The existence of AgCl could suppress the forward reaction in equation (2-21),

resulting in a decrease of the iodide concentration shown in Fig. 2-3. Other anions such as car-

bonate/bicarbonate and sulfate do not significantly affect the iodide release from AgI because the

solubility of silver carbonate and silver sulfate is too high, indicated by the Gibbs free energy data

of these salts [90].

Contrary to the AgI system, Bi5O7I is relatively weak to anion attacks. In particular, car-

bonate and chloride anions are actively involved in anion displacement reactions, in accordance

with equations (2-22) to (2-24):

2Bi5O7I(s) + 5CO32-(aq) + 4H2O(l) → 5(BiO)2CO3(s) + 2I-(aq) + 8OH-(aq) (2-22)

4Bi5O7I(s) + 5CO32-(aq) + 8H2O(l) → 5(BiO)4(OH)2CO3(s) + 4I-(aq) + 6OH-(aq) (2-23)

2Bi5O7I(s) + 5Cl-(aq) + 4H2O(l) → 5(BiO)4(OH)2Cl(s) + 2I-(aq) + 3OH-(aq) (2-24)

The stability of Bi5O7I in terms of the chloride and carbonate concentrations is shown in Fig.

2-4. Susceptibility to these anions should be dealt with seriously given that these anions are fre-

quently encountered in typical granitic groundwater [91,92].

To summarize, anion substitution in AgI is only significant in the presence of chloride ani-

23
ons, and the reaction could be effectively suppressed when a mixture of AgI and AgCl is used in-

stead of only AgI. However, Bi5O7I is unstable in chloride/carbonate-rich conditions, with increased
129
dissolution of iodine. In other words, AgI is a more suitable phase for I than Bi5O7I in terms of

anion displacement reactions.

2.2.3 Complexation reactions

Another factor affecting the iodine solubility of a waste form is the formation of metal-

ligand complexes in solution. Although some bismuth iodide complexes are known to be stable in

acidic and concentrated iodide solutions [93], Bi5O7I seems to be very resistant to bismuth

complexation because bismuth speciation would not occur as shown in equation (2-15). Additional-

ly, bismuth is not expected to be involved in complexation reactions with common groundwater

anions, although the study was restricted to the carbonate case [45].

The most important anion related to silver complexation is chloride. Silver complexes are

formed through the reaction of AgI and chloride, with increased solubility of AgI to approximately

10-5 mol dm-3 in high concentrations of brines [90]:

AgI(s) + 2Cl-(aq) ↔ AgCl2-(aq) + I-(aq) (2-25)

Although AgI is more susceptible to complexation reactions than (Bi5O7I and Bi2O3), iodine

release by complexation reactions is relatively insignificant compared to redox or anion displace-

ment reactions [45].

24
 Fig. 2-3. Equilibrium iodine concentration of AgI and (AgI + AgCl), as a function of the

chloride concentration, calculated using the Gibbs free energy data in Wagman et al.’s document.

Total iodine concentration including AgI(aq) is represented by the dashed line [43,90].

25
Fig. 2-4. Stability diagram of Bi5O7I, represented with the equilibrium iodide concentration

as a function of pH and chloride (a) or carbonate (b) concentration [41].

26
 2.2.4 Thermal stability

Iodine release from thermal decomposition of iodine compounds imposes a serious problem

due to the environmental dispersion of volatilized I2 gas or from iodide dissolution in solutions. AgI

is thermally stable up to 558 °C which is the melting point of AgI. After that, AgI is decomposed

through the following reaction [45]:

2AgI(s) → 2Ag(s) + I2(g) (2-26)

In the case of Bi5O7I, its decomposition in air is reported to start at approximately 500 °C

[44,45,94]. It is transformed to Bi2O3 through a reaction with oxygen:

2Bi5O7I(s) + 1/2O2(g) → 5Bi2O3(s) + I2(g) (2-27)

An oxygen-free environment reportedly induces the decomposition of Bi5O7I to Bi2O3(s) and

BiI3(s) at temperatures higher than 480 °C [95]. Fig. 2-5 shows iodine partial pressures based on the

calculation for (2-26) and (2-27). The iodine partial pressures of AgI increase as the temperature

increases, yet the values suggest that the iodine partial pressure is very low until AgI melts. Bi5O7I

has higher iodine partial pressures than that of AgI at all temperature ranges, and the shaded area

indicates the uncertainty of the iodine partial pressure in Bi5O7I. A low iodine partial pressure is

significantly meaningful when high temperature processing is needed to fabricate durable waste

forms. Given the requirements for the long-term disposal of iodine waste, thermal treatment of io-

dine wastes would be essential. For thermal stability, AgI is a more appropriate iodine phase than

that of Bi5O7I.

27
Fig. 2-5. Iodine partial pressures of AgI and Bi5O7I as a function of temperature [41].

28
 Chapter 3. Novel Synthesis of Bismuth-Based Adsorbents for the
Removal of 129I in Off-Gas

3.1 Introduction
Recently, studies have sought to develop alternative adsorbents and waste forms for 129I in off-

gas [15,19–21,83]. A bismuth-oxide-iodine waste form was investigated to scavenge iodine contained

in iodine scrubbing solutions [46,47,96]. Krumhansl et al. [46,47] successfully separated iodine in the

scrubbing solutions by the precipitation reaction of bismuth iodide (or iodate) compounds using bis-

muth nitrate. Studies on the chemical stability of these precipitates under possible repository condi-

tions have shown that bismuth-iodine-oxides have low solubility in water, with some common ground

water anions, which suggests the possibility of bismuth-iodine-oxides as phases for long-term dispos-

al. Although this study suggested the importance of Bi in iodine waste management, research on Bi to

capture 129I gas has not yet been attempted.

We investigated whether Bi can also be used to trap iodine gas. The gas-solid reactions be-

tween Bi and I2(g) are highly exothermic, as shown in Table 3-1, suggesting that Bi can effectively
129
adsorb I2(g). We aimed to synthesize adsorbents using Bi to capture I in off-gas produced from

spent fuel reprocessing. Interestingly, the changes of the Gibbs free energy involved in iodine reac-

tions between Bi and Bi2O3 are largely different, as shown in Table 3-1, suggesting that the iodine

trapping capacity of Bi is better than that of Bi2O3. Therefore, we attempted to synthesize two types

of adsorbents: one composed of elemental Bi and another composed of Bi2O3. Porous bulky materials

were synthesized to increase the frequency of the gas-solid reaction. A templating synthesis was se-

lected as a strategy to synthesize porous materials, which were fabricated with polyvinyl alcohol

(PVA) as a sacrificial template that was removed by calcination [97–102]. To the best of our
129
knowledge, this work is the first attempt to synthesize adsorbents from Bi to adsorb I-containing

off-gas released from the treatment of spent nuclear fuel. An iodine trapping test was then performed

to examine the removal efficiency of iodine. The surface areas and volumes of the pores in the porous

materials were investigated with Brunauer, Emmett and Teller (BET) instrument and a porosimeter.

The crystalline structure, microstructure and thermal stability of the reaction products were analyzed

with an X-ray diffractometer (XRD), a field emission-scanning electron microscope/energy dispersive

29
spectroscope (FE-SEM/EDS), and a thermogravimetric-differential scanning calorimeter (TG-DSC),

respectively. Our findings strongly suggest that bismuth-based adsorbents can be used to capture io-

dine-containing off-gas released from the treatment of spent nuclear fuel, replacing silver-loaded zeo-

lites.

Table 3-1. Data for Gibbs free energy of formation (∆Gf°) at 298 K related to formation of

various iodine compounds

∆Gf°
Reaction equation Spontaneity
(kcal/mol)

Ag + 0.5I2(g) = AgI -16.06 Spontaneous

Bi + 0.5O2(g) + 0.5I2(g) = BiOI -52.43 Spontaneous

Bi + 1.5I2(g) = BiI3 -33.38 Spontaneous

5Bi + 3.5O2(g) + 0.5I2(g) = Bi5O7I -275.0 Spontaneous

2.5Bi2O3 + 0.5I2(g) = Bi5O7I + 0.25O2(g) -5.87 Spontaneous

2Bi2O3 + 2I2(g) = 4BiOI + O2(g) 5.59 Non-spontaneous

Bi2O3 + 3I2(g) = 2BiI3 + 1.5O2(g) 40.90 Non-spontaneous

30
 3.2 Experimental
3.2.1 Synthesis of porous sorbents

The synthesis of porous materials was conducted by the templating method, in which various

templates such as colloidal crystals or polymers, are infiltrated into the subject materials and then,

subsequently removed by chemical etching or calcination to create porous materials [97–102]. In our

study, we chose PVA (Junsei, Tokyo, Japan) and bismuth (III) nitrate pentahydrate (Bi(NO 3)3∙5H2O,

98%, Sigma-Aldrich, MO, USA) as a template and Bi precursor, respectively. For the Bi precursor

solutions, 100 g of Bi(NO3)3∙5H2O was dissolved in 100 mL of distilled water with the addition of 50

mL of nitric acid (HNO3, 69-70%, Junsei, Tokyo, Japan). The procedure was repeated to synthesize

three identical solutions. For the template solutions, 50, 75, and 100 g of PVA was dissolved in 400,

450, and 500 mL of distilled water, respectively. All of the reagents in this experiment were used

without further purification. The three Bi precursor solutions and each template solution were mixed

and magnetically stirred until transparent yellowish solutions were obtained. The solutions were then

dried at 40 °C for 96 h to obtain gel-type materials, followed by calcination under an air atmosphere

in a thermal furnace to remove PVA. To prevent damage to the pore structure by the rapid volatiliza-

tion of PVA, the heating profile was carefully controlled as follows: the temperature was elevated to

250 °C at a rate of 1 °C min-1, maintained at 250 °C for 3 h, and then elevated to 400 °C at a rate of

1 °C min-1 and maintained at 400 °C for 3 h. The obtained yellow materials were denoted as BP1-O,

BP2-O, and BP3-O, in order of increasing PVA content. A portion of each material was set aside for a

thermal treatment at 310 °C for 12 h in 4% H2/Ar. The resulting gray-black materials were denoted as

BP1, BP2, and BP3, in order of increasing PVA content.

3.2.2 Iodine trapping test

The trapping capacity of I2(g) is one of the most important parameters in determining the per-

formance of adsorbents. The actual trapping of iodine-containing off-gas released from the treatment

of spent nuclear fuel can be realized with an off-gas treatment system: iodine containing gas is re-

leased as off-gas from the oxidation of fuel and captured in the filter media [103]. However, we used

nonradioactive iodine crystals as a source of iodine gas to simplify the tests. Despite the use of solid

iodine, a gas-solid reaction was possible because of the sublimating property of iodine crystals at am-

bient pressures. The specific procedure for the iodine trapping test is described as follows. The initial

31
masses of the adsorbent (~0.3 g) and the iodine crystal (~0.3 g, I2, 99%, DC Chemical, Seoul, Korea)

were measured with a digital balance having a specificity of 10-4 g. Then, the samples were placed in

an alumina crucible, covered with a lid, and reacted at 200 °C for 24 h in air. After cooling below

100 °C, the final mass of the sample was measured again to calculate the adsorbed mass. Because the

atmospheric conditions permit the possibility of reaction between bismuth and O2(g), as well as Bi

and I2(g), the amount of pure iodine in the adsorbed mass was determined by analyzing the reaction

products. For comparison, commercial Bi powder (Bi, 100 mesh, 99%, Sigma-Aldrich, MO, USA)

and AgX (silver-exchanged zeolite, Ag: 35 wt%, granular, 20 mesh, Sigma-Aldrich, MO, USA) were

also tested by the same procedure. For the Bi powder, a similar iodine trapping test was also per-

formed in a tube-type furnace with flowing N2 gas to exclude any oxygen effect.

3.2.3 Characterization

The specific surface areas and mesopores of the samples were analyzed based on N2 adsorp-

tion and desorption with a BET instrument (Trista II 3020, Micrometrics, GA, USA). The macropore

size was measured based on mercury intrusion with a porosimeter (AutoPore N9520, Micrometrics,

GA, USA). The crystalline structure of the samples was investigated from XRD (D8_Advance_A25,

Bruker, Karlsruhe, Germany) with Cu Kα radiation as the X-ray source operated at 40 kV and 40 mA.

The samples were scanned from 5 to 90° of 2θ in 0.01° increments. The microstructure and elemental

composition of the samples were determined with FE-SEM/EDS (SU8010, Hitachi, Tokyo, Japan).

The specimens were coated in a sample coater (Q300T T, Quorum Technologies, East Sussex, UK)

with Pt. The electron beam in the SEM was generated at 15 keV and 10 μA. The thermal stability of

the samples was studied with TG-DSC (Labsys.Evo, Setaram, Caluire, France) from room tempera-

ture to 800 °C at 10 °C min-1 in flowing N2 gas.

3.3 Results and Discussion

3.3.1 Characterization of the as-synthesized adsorbents

Fig. 3-1 shows the optical images of BP3-O and BP3. The samples resulting from the proce-

dure described above had maximum particle sizes of 10 to 15 mm. Many small pores distributed on

the surfaces of the two samples could be detected by visual inspection, indicating that the PVA in the

precursor solution was removed through heat treatment, resulting in the formation of a porous materi-

32
al. The yellow color of BP3-O suggests that the Bi precursor was oxidized and converted into a Bi2O3

crystal. The color was changed to gray-black by hydrogen reduction, indicating the reduction of Bi2O3

to Bi.

The crystalline state of each sample was identified by XRD analysis as shown in Fig. 3-2. As

expected, most peaks in Fig. 3-2 (a) with large intensities were assigned to crystalline Bi2O3. A few

small peaks assigned to Bi were attributed to the incomplete oxidation of the Bi precursor. Contrary

to the XRD pattern of BP3-O, the relative intensities of Bi to Bi2O3 peaks were highly enhanced in

BP3 (Fig. 3-2 (b)), confirming that chemical reduction was successfully performed in BP3. Neverthe-

less, a few Bi2O3 peaks still exist because the reduction process was not perfect.

The microstructures of the samples were examined using FE-SEM. Fig. 3-3 (a) shows an im-

age of a Bi powder sample (denoted as BP0). Large particles of greater than 5 μm and small particles

of 1-2 μm were stacked together. Pores were not found on the surfaces of the particles, and a few

pores of less than 1 μm were found at the boundaries of the particles. On the contrary, many pores

were observed in BP1, BP2, and BP3 with pore sizes distributed within 0.5-2 μm (Fig. 3-3 (b-d));

however, a clear relationship between the pore size and PVA content was not detected.

Structural information on the samples was obtained by N2 adsorption/desorption and mercury

intrusion (see Table 3-2). The measured specific surface areas revealed that the surface areas of the

samples were nearly proportional to the quantity of PVA used, and the surface areas of the synthe-

sized BP samples were approximately 2- to 4- fold larger than that of BP0. These trends were similar

for specific pore volumes. These results suggest that porous materials were successfully synthesized

through calcination of PVA because the space occupied by PVA became pores as the PVA was re-

moved. The size of the mesopore in BP1, BP2, and BP3 was approximately 11 nm, indicating that the

PVA removal by calcination left a void volume with a diameter of approximately 11 nm. The larger

size of the mesopores in BP0 was likely attributed to the pores resulting from interparticle stacking.

33
Fig. 3-1. Optical images of BP3-O (a) and BP3 (b).

34
Fig. 3-2. XRD patterns of BP3-O (a) and BP3 (b).

35
Fig. 3-3. SEM images of BP0 (a), BP1 (b), BP2 (c), and BP3 (d).

36
 Table 3-2. Textural properties of the as-synthesize samples

Sample SSABET, m2/g Vpore, cm3/g Dmeso, nm Dmacro, μm

-3
BP0 0.1882 ± 0.0006 0.71 × 10 15.07 ± 0.05 -

BP1 0.4605 ± 0.0008 1.26 × 10-3 10.96 ± 0.02 7.05

BP2 0.6458 ± 0.0039 1.86 × 10-3 11.55 ± 0.07 6.46

BP3 0.8690 ± 0.0082 2.42 × 10-3 11.16 ± 0.10 6.33

37
 3.3.2 Characterization of the reaction products

Fig. 3-4 shows images of each sample after reaction with the iodine crystal at 200 °C for 24 h.

The colors of different samples were different after the experiment was performed under the same

conditions. These colors were assumed to reflect those of bismuth iodine compounds considering that

iodine gas reacted with the bismuth-based materials. Among the many bismuth iodine compounds,

BiI3 and BiOI have been reported to exhibit dark gray and deep orange-red colors, respectively [44].

Therefore, BP0 is believed to mostly contain BiI3, whereas BP3 is believed to mostly contain BiOI.

The other two samples, BP1 and BP2, are presumed to contain a mixture of BiI3 and BiOI. The dif-

ferent red colors shown in BP1, BP2, and BP3 are likely due to the different ratios of BiI3 to BiOI and

the existence of other bismuth iodine compounds.

The characterization of the reaction products was performed with XRD. Fig. 3-5 shows the

XRD peak patterns of the samples after reacting with iodine, which was identified with a pattern fit-

ting software from Bruker. Most peaks in the samples were matched with the peak of BiOI or BiI3,

and very few peaks were matched with Bi2O3, BiO4I, and BiO2. Based on the XRD results, the as-

synthesized samples were determined to capture iodine gas, resulting in BiOI, BiI3, or BiO4I, while

producing some oxidation products such as Bi2O3 or BiO2. The relative ratio of the reaction products

is believed to be related to the pore volume of the samples: as the pore volume increases from BP0 to

BP3, the intensity of BiOI relative to BiI3 also increases.

Thermal stability of the reaction products was investigated with TG-DSC analysis (Fig. 3-6).

In all of the samples, the regions of weight decrease appeared to be divided into five segments from

room temperature to 800 °C. The small decrease of less than 0.5 wt% observed until 100 °C was at-

tributed to the evaporation of adsorbed water. Water did not appear to be adsorbed during the sorption

experiments because the experimental temperature (200 °C) was too high for water to be adsorbed.

Thus, water was believed to be adsorbed between the test and the analysis. Interestingly, the endo-

thermic peaks at 100 °C became more prominent from BP0 to BP3, suggesting that the adsorbent

with the highest surface area is more prone to adsorb water. The decrease from 300 to 410 °C corre-

sponds to the decomposition of BiI3, which is supported by the study of Ye et al., who examined the

decomposition of BiI3 [104]. According to their study, BiI3 is transformed to BiOI or decomposed to

bismuth and I2(g) from 300 to 420 °C. Considering the nitrogen atmosphere applied to our TG-DSC

38
analysis, the transformation to BiOI is practically impossible because of the absence of O2(g) [104].

Therefore, the only reaction involved in this region is provided as follows:

BiI3 → Bi + 1.5I2(g) (3-1)

The cause of the decrease from 500 to 800 °C appears to be complicated; the difference of

gradients implies that the volatilization of at least three different materials was involved. With respect

to the results of the XRD analysis, the candidate materials in this region are BiOI, BiO 4I, Bi2O3, and

BiO2. The thermogravimetric analyses performed by Ye et al. and Yu et al. indicated that BiOI begins

to lose I2(g) by reacting with O2(g) at 350 or 420 °C, respectively [104,105]. However, the proposed

reaction through which BiOI is transformed into Bi5O7I does not fundamentally occur in our inactive

conditions. Instead, we propose a plausible reaction involving BiOI as follows:

BiOI → Bi + 0.5O2(g) + 0.5I2(g) (3-2)

Considering that the weight decrease from 500 to 650 °C is relatively large compared with

those at higher temperature regions, it is reasonable that the decrease from 500 to 650 °C is due to the

decomposition of BiOI. Please note that the amount of BiOI in the samples is larger than that of BiO4I,

Bi2O3, and BiO2 as shown in the results of XRD analysis. According to the thermodynamic calcula-

tion performed with the HSC 6.0 code [65], the changes of Gibbs free energy (ΔG) during the de-

composition of BiOI are provided as follows:

BiOI → Bi + 0.5O2(g) + 0.5I2(g), ΔG = 44.041 kcal (400 °C) (3-3)

BiOI + 0.2O2(g) → 0.2Bi5O7I + 0.4I2(g), ΔG = -3.415 kcal (400 °C) (3-4)

The ΔG in the former reaction is positive, indicating that the reaction is not spontaneous at

400 °C. In contrast, the latter reaction is spontaneous at 400 °C considering the negative ΔG, which

explains why the decomposition of BiOI in our experiment began at 500 °C, not the reported 350 or

420 °C. Interestingly, the TG-DSC analysis demonstrated an increase in the weight ratio of BiOI to

BiI3 from BP0 to BP3 samples, which complies with the increase of the pore volume from BP0 to

39
BP3. Summarizing the results and discussions on the observation of the samples, the XRD and TG-

DSC analyses strongly suggest that the pore state of the sample affects the governing reaction, result-

ing in differences in the reaction products. A detailed discussion of this issue will be addressed in the

following section. Discriminating the causes of weight decrease between the two regions existing

from 650 to 800 °C is not trivial because the information on BiO4I and BiO2 is not well known. How-

ever, we infer that the decomposition of Bi2O3 contributed to the weight decrease from 650 °C based

on the study by Klinkova et al. that revealed that Bi2O3 lost part of its oxygen at temperatures above

300 °C in air [106].

The microstructures of the samples after reaction with I2 were studied with FE-SEM/EDS.

The comparison of the SEM images in Fig. 3-7 and Fig. 3-3 demonstrate that pristine samples disap-

peared during the reaction with iodine, and newly shaped crystals were observed. The identification

of these crystals was possible through quantitative EDS spectra analysis. The EDS analysis of rock-

shaped crystals found in Figs. 3-3- (a) and (d) showed that the crystals consisted of Bi and iodine (Fig.

3-7 (e)); the rock-shaped crystal is BiI3. The EDS spectra with slight deviation of each element in Fig.

7 (f) belong to hexagonal plates in Fig. 7 (b), rod-shaped crystals in Fig. 7 (c), and broken plates and

rosette-shaped crystals in Fig. 7 (d). The hexagonal plates were BiOI crystals; the rod-shaped crystals

were BixOyIz, with x higher than z; and the broken plates and rosette-shaped crystals were crystals

with Bi:I ratios between those of hexagonal plates and rod-shaped crystals. These results are support-

ed by the work of Krumhansl et al. [47], which suggested that BiOI forms platelet-shaped crystals

that become more rod-like as the Bi:I ratio increases.

40
Fig. 3-4. Optical images of BP0 (a), BP1 (b), BP2 (c), and BP3 (d) after reacting with iodine

crystals at 200 °C for 24 h.

41
Fig. 3-5. XRD patterns of samples after reacting with iodine.

42
Fig. 3-6. TGA-DSC profiles of iodine-reacted BP0 (a), BP1 (b), BP2 (c), and BP3 (d) at a rate

of 10 °C min-1 and N2 flow.

43
 Fig. 3-7. SEM images of BP0 (a), BP1 (b), BP2 (c), and BP3 (d) after reacting with iodine,

and representative EDS spectra of BP0, BP1, BP2, and BP3 (e, f) (Pt signal in EDS spectra originated

from Pt coating of samples).

44
 3.3.3 Mechanism of the iodine trapping reaction

The existence of different reaction products, such as BiI3 and BiOI, is likely due to the dif-

ferent concentrations of I2(g) and O2(g) surrounding the outer and inner surfaces of the samples. To

explain the underlying mechanism, we first considered reactions related to the formation of BiI3 and

BiOI:

Bi + 1.5I2(g) → BiI3 (3-5)

Bi + 0.5O2(g) + 0.5I2(g) → BiOI (3-6)

A sample with low pore volume may have relatively more active sites on the outer surface

compared with the inner surface. Accordingly, the frequency of the reaction on the outer surface is

higher than that on the inner surface. In addition, the volatilization of iodine causes concentration of

I2(g) to be higher than that of O2(g) in the air surrounding the outer surface. When O2(g) is first ad-

sorbed onto the outer surface, the surface is oxidized. Then, the formation of BiOI is nearly impos-

sible because the oxidized surface does not react with I2(g), as will be discussed in the following

section. Thus, the reaction facilitating the formation of BiI3 mostly occurs on the outer surface. For

a sample with high pore volume, however, relatively more active sites exist on the inner surface.

Moreover, the concentrations of I2(g) and O2(g) in the air surrounding the inner surface is different

from those in the air surrounding the outer surface. In other words, the O2(g) concentration becomes

higher than the I2(g) concentration because light O2(g) more readily diffuses into the inner surface

compared with I2(g). Therefore, the reaction facilitating the formation of BiOI mostly occurs on the

inner surface. The schematic diagram illustrating this mechanism is shown in Fig.3-8. A possible

concern is the oxidation of Bi by H2O(g) or O2(g) in air, which would compete with the proposed

mechanism. The related reactions and ΔG as calculated by the HSC 6.0 code [65] are provided as

follows:

2Bi + 3H2O(g) → Bi2O3 + 3H2(g), ΔG = 50.367 kcal (200 °C) (3-7)

2Bi + 1.5O2(g) → Bi2O3, ΔG = -107.651 kcal (200 °C) (3-8)

The signs of ΔG suggest that the oxidation of Bi is only possible by O2(g) and not by

45
H2O(g). After O(g) oxidizes Bi, Bi2O3 loses the ability to react with I2(g) as previously addressed,

and thus does not contribute to the formation of BiOI.

Fig. 3-8. Schematic diagram representing the main reactions occurring on the outer and in-

ner surfaces of the samples.

46
 3.3.4 Iodine trapping capacity of the as-synthesized samples

Iodine trapping capacity is one of the most important parameters to assess the feasibility of

adsorbents in actual systems. To determine the iodine trapping capacity, we first measured the ad-

sorbed mass during the trapping test. Then pure mass of iodine in the adsorbed mass was calculated

by considering the ratio of the reaction products. The adsorbed mass was readily measured from the

difference of the sample masses before and after the test. The ratio of the reaction products was cal-

culated from the TG-DSC results. As discussed earlier, the amounts of BiI3 and BiOI correspond to

the loss from 300 to 400 °C and 400 to 650 °C, respectively. From 650 to 800 °C, we assumed that

the loss was attributed to only Bi2O3. This prevents overestimation of the adsorbed mass of pure

iodine. Finally, we could obtain the pure mass of iodine by considering the relative ratio of iodine or

oxygen in the adsorbed mass because the adsorbed mass originated from I2(g) or O2(g) (Table 3-3).

Fig. 3-9 shows the iodine trapping capacity of each sample determined from 5 repetitive experi-

ments. The high deviations of data are believed to be due to the inhomogeneity of the samples; a

violent boiling phenomenon was observed at the end of the sample drying process, which likely de-

creased the homogeneity of the as-synthesized samples. As shown in Fig. 3-9, the mean iodine trap-

ping capacities of the as-synthesized samples were higher than that of commercial AgX despite the

high variability in the data. Bead-type AgX may be responsible for the low performance due to bad

diffusion of I2(g) into the beads; however, an experiment, which we performed with powdered AgX,

has shown the result that the iodine trapping capacity of the powdered AgX could increase to 0.305

g-I/g-AgX, which is still lower than that of the as-synthesized samples. Interestingly, the mean trap-

ping capacities of BP1, BP2, and BP3 were higher than that of BP0, which is likely related to the

surface area. For example, the maximum trapping capacity among the samples was measured at

0.468 g-I/g-sorbent in case of BP2, which is approximately 1.3- and 1.9- fold higher than that of

BP0 and AgX, respectively. Until now, it was unclear why BP2, which has a lower surface area,

showed a higher capacity than BP3. We infer that the accessible surface area in which iodine can

actually react is different from the measured surface area through N2 adsorption. Interestingly, BP1-

O, BP2-O, and BP3-O did not adsorb any iodine; this result can be explained by thermodynamics.

As summarized in Table 3-1, the reactions forming BiOI or BiI3 from bismuth at 200 °C are exo-

thermic, with a ΔG of -52.428 and -33.376 kcal, respectively. These values are much lower than that

of the AgI-forming reaction, which is a possible basis for the high capacity of our samples, despite

47
their low specific surface areas. In contrast, the reactions forming BiOI or BiI3 from Bi2O3 at 200 °C

are endothermic, suggesting that the reactions do not readily occur, which was verified by the ob-

servation that the oxidized samples exhibited no iodine trapping capacity.

Bismuth powder that had reacted with iodine in an N2 atmosphere exhibited an iodine trap-

ping capacity of 0.524 g-I/g-Bi. In this case, all of the adsorbed mass was due to iodine by the for-

mation of dark gray BiI3 as a reaction product. The iodine trapping capacity was approximately 1.4-

fold higher than that of BP0 that had reacted with iodine in air, suggesting that an oxygen-free at-

mosphere is favorable for efficient iodine adsorption.

Process off-gases from the reprocessing of nuclear fuel also contain H2O(g), NOx(g) and

O2(g), as well as volatile radionuclides. The existence of O2(g) due to air-based process off-gases is

not expected to be of serious concern because our experiment showed that the iodine adsorbing per-

formance of our adsorbents is better than that of AgX in an air-based environment. However, exist-

ence of H2O(g) and NOx(g) might affect the iodine trapping capacity of our bismuth-based adsor-

bents. Moreover, the iodine concentrations in real off-gases are very small (on the order of ppmv)

[10], which is different from our experimental conditions. Therefore, further studies are needed to

evaluate if other parameters affect the adsorption performance. Soelberg and Watson performed io-

dine sorbent tests using AgZ and silver-functionalized aerogel in the presence of H2O(g) and NOx(g)

[80]. In this study, they used the process gases that contained I2(g) (1.6-49 ppmv), H2O(g) (1.5

vol%), NO(g) (800 ppmv), and NO2(g) (800 ppmv). We are also planning to establish the process

gas supply system to simulate real off-gases. The gas composition of very low concentration of I2(g)

and other gases is expected to be realized with a specially designed gas supplying system [80]. An-
129
other study on iodine trapping behavior of AgZ that is a baseline adsorbent for I removal is also

planned to compare its performance with our adsorbents.

48
 Table 3-3. Adsorbed mass resulting from the iodine trapping reaction and pure iodine mass

calculated from the relative ratio of iodine or oxygen in the adsorbed mass in different samples

Relative ratio of I or O in the adsorbed mass

Initial Adsorbed Pure I
Sample
I I O O
mass (g) mass (g) mass (g)
(in BiI3) (in BiOI) (in BiOI) (in Bi2O3)

0.305 ± 0.135 ± 0.111 ±

BP0 0.56 0.26 0.03 0.14
0.002 0.018 0.017

0.302 ± 0.155 ± 0.128 ±

BP1 0.51 0.28 0.04 0.18
0.003 0.030 0.027

0.304 ± 0.173 ± 0.142 ±

BP2 0.41 0.32 0.04 0.23
0.002 0.030 0.028

0.302 ± 0.155 ± 0.127 ±

BP3 0.24 0.46 0.06 0.24
0.002 0.035 0.032

49
Fig. 3-9. Iodine trapping capacity of each sample compared with that of AgX beads.

50
 Chapter 4. Bismuth-Embedded SBA-15 Mesoporous Silica for Ra-
dioactive Iodine Capture and Stable Storage

4.1 Introduction
Yang et al.’s recent study [107] investigated iodine confinement within porous bismuth

granules. This study showed a high capacity of bismuth granules for iodine adsorption, suggesting
129
the utility of cheap and non-toxic bismuth to capture I2(g). However, bismuth utilization for io-

dine capture was not efficient due to the low surface area and pore volume of the sorbents produced

by calcination of polyvinyl alcohol. Additionally, stability of the iodine-bearing bismuth compounds

has not been studied for the purpose of long-term disposal.

In the current work, we further investigated the use of bismuth for iodine capture through an

improved synthetic process with SBA-15 mesoporous silica. SBA-15 mesoporous silica, which fea-

tures high surface area as well as adjustable large pores, with the size ranging from 50 to 300 Å with

uniform distribution [108], has been demonstrated to have broad applications in various research

fields. In particular, adsorption of noble or heavy metals from aqueous solutions was shown to be

facilitated by surface functionalized SBA-15 [109–113]. Typically, the surface functionalization

modifies the interior pore surfaces of SBA-15 allowing incorporation of a wide range of functional

groups such as amine, phenyl, and thiol moieties [114]. This observation becomes the basis of our

research. We made functionalized SBA-15s with thiol-groups, followed by bismuth adsorption into

the thiol-functionalized SBA-15. The bismuth-embedded SBA-15 was studied for iodine adsorption,

as the first study of its kind.

In addition, a post-sorption process was developed to enhance the chemical durability of the

sorbents. We observed the iodine-bearing phase was converted into a more stable phase through a

facile heating process. According to Taylor et al.’s research [42], bismuth iodide (BiI3) could be

changed to a more stable bismuth oxyiodide (Bi5O7I) with a thermal process. Their studies also sug-

gested that a mixed phase of Bi5O7I and Bi2O3 is as stable as the well-known AgI phase [40,43,45].

The former is reported to be even more stable in strongly reducing environment that mimics deep

groundwater [43,45].

51
 4.2 Experimental
We aimed at assessing the feasibility of the bismuth-embedded SBA-15 for iodine capture

and long-term storage. Thiol-functionalized SBA-15 was made with 3-

mercaptopropyltrimethoxysilane (MPTMS) as a thiol-group precursor. Bismuth was adsorbed into

the thiol-functionalized SBA-15 with Bi-S bonding. Then, iodine capturing test was performed at an

elevated temperature to examine iodine loadings in the bismuth-embedded SBA-15. Additionally,

the iodine-bearing sorbent was thermally treated with the addition of Bi2O3 to make a more stable

iodine phase. Afterward, basic chemical durability of the samples was investigated through a simple

leaching test.

4.2.1 Synthesis of bismuth-embedded SBA-15

The procedure for synthesizing thiol-functionalized SBA-15 followed a typical procedure as

described elsewhere [115]. For a typical synthesis, a micellar solution was prepared by dissolving 4

g of Pluronic P123 (EO70-PO20-EO70, Mw = 5,800, Sigma-Aldrich, St. Louis, MO) into 125 g of

1.9 M HCl solution. Then, (41-x) mmol (x = 11.5, 14, or 20) of tetraethylorthosilicate (TEOS, 95%,

Sigma-Aldrich) was added and magnetically stirred at 40 °C. Since the early addition of MTPMS

ruins mesostructural orderings [115], the solution was stirred for 3 h prior to the addition of

MPTMS to give a sufficient pre-hydrolysis time. After that, x mmol (x = 11.5, 14, or 20) of

MPTMS was added into the solution and stirred for 20 h at 40 °C to complete the sol-gel reaction.

The resultant mixture was poured into a PTFE bottle, which was tightly sealed and kept for 24 h at

100 °C. In another case, the process was conducted at 120 °C for 72 h to examine the effect of hy-

drothermal condition. The hydrothermally treated mixture was filtered to recover a solid product,

and the solid was dried at 40 °C for 24 h. Surfactants within the solid product were removed by a

solvent extraction [114], i.e., 3 g of the solid sample was mixed with 800 mL of ethanol and re-

fluxed for 24 h. Finally, the thiol-functionalized SBA-15 was obtained after drying at 40 °C for 24

h. Pristine SBA-15 as a reference was synthesized by the same procedure except for a slight modifi-

cation: MPTMS was not used (x = 0) and the total reaction time after the addition of 41 mmol of

TEOS was 24 h.

For bismuth adsorption into the thiol-functionalized SBA-15, the samples were impregnated

52
into bismuth solution at a ratio of 1 g: 100 mL for 6 h. The bismuth solution was made by dissolving

BiCl3 (98%, Kanto Chemical Co., Kagaku, Japan) into boiling MeOH at a ratio of 5 g: 100 mL.

Since BiCl3 is fairly hygroscopic, it is readily hydrolyzed to form an insoluble bismuth oxychloride

(BiOCl). The clear bismuth solution was obtained after filtering BiOCl precipitation. After the im-

pregnation was completed, the yellow-turned sample was separated from the solution, and dried at

40 °C for 24 h. In a previous study [107], it was demonstrated that iodine adsorption was signifi-

cantly affected by bismuth oxidation state. Thus, some portions of the bismuth-impregnated samples

were thermally treated at 250 °C for 6 h in 4% H2/Ar atmosphere. The samples at different synthesis

stages and MPTMS molar ratios were named as shown in Table 4-1.

53
 Table 4-1. Sample names at different synthesis stages and MPTMS molar ratios

MPTMS/(MPTMS+ Synthesis stage

TEOS) (molar ratio) Thiol- Bismuth-impregnation Heat-treatment in

functionalization 4%H2/Ar
0.28 SBA-15-SH1 Bi-SBA-15-SH1 Bir-SBA-15-SH1

0.34 SBA-15-SH2 Bi-SBA-15-SH2 Bir-SBA-15-SH2

0.34 SBA-15-SH2Aa Bi-SBA-15-SH2Aa Bir-SBA-15-SH2Aa

0.49 SBA-15-SH3 Bi-SBA-15-SH3 Bir-SBA-15-SH3

a
These samples were made with hydrothermal treatment at 120 °C for 3 days.

54
 4.2.2 Iodine adsorption experiments

Iodine adsorption of the as-synthesized samples was studied in static air with a specially de-

signed device (Fig. 4-1). 2 g of nonradioactive iodine crystal (I2, 99%, DC Chemical Co., Seoul,

Korea) as an iodine source was put into the bottom of the alumina reaction vessel. Porous alumina

disk (pore size: < 1 mm) and sheet were then placed above the iodine crystals to avoid direct contact

between the samples and the iodine crystals. After that, 0.1-0.2 g of the as-synthesized samples was

placed on the porous sheet, and the reaction vessel was covered with an alumina lid. Because iodine

crystal actively transforms to I2(g) above its boiling point (182.8 °C), thermal reaction was per-

formed at 200 °C for 6 h under a static air condition. After the reaction, the device was cooled in a

convection oven at 40 °C to prevent any moisture trapping during the cooling process. Blank exper-

iments without sample and I2 were also performed under the same conditions for quality control

purposes. Another experiments without I2 were also performed under the same conditions for SBA-

15 and Bi-SBA-15-SHx (x = 1, 2, or 3) to observe the effect of the residual P123 loss during the

reaction. The effects of the device and residual P123 loss were subtracted when iodine capturing

capacity was determined. For comparison, iodine capture was also performed with silver-exchanged

zeolites (AgX, Ag: 35 mass%, granular, 20 mesh, Sigma-Aldrich) under the same experimental

conditions except the process temperature at 150 °C. It is found that 150 °C is the optimal tempera-

ture for AgX that enables the maximal iodine adsorption [9]. The mass gain during the experiment

was measured with a digitalized balance that has a resolution up to 0.1 mg. Iodine capturing capaci-

ty of the as-synthesized sample (CI) was then determined with Eq. (4-1) where ∆m and ms are the

mass gain and the initial mass of sorbent, respectively.

CI (mg-I/g-sorbent) = ∆m/msⅹ1000 (4-1)

It is worth noting that the capturing efficiency might be decreased in the presence of H2O(g) and

NOx(g) due to the competitive adsorption, which could occur in real off-gas trapping conditions

[10].

55
Fig. 4-1. A schematic of the apparatus for iodine capturing experiment in steady air.

56
 4.2.3 Chemical durability test

A post-sorption process was developed to make chemically durable iodine-bearing materials.

1 g of the iodine-trapped Bir-SBA-15-SH2A (denoted as Bir-SBA-15-2A-I) was prepared and com-

pletely mixed with 4.1 g of Bi2O3 (99.9%, Sigma-Aldrich) by a mortar. The powder mixture was put

into an alumina crucible, followed by the sequential heat-treatments with three steps: 250 °C,

400 °C, and 500 °C for 3 h, respectively. Then, the sample was named the chemically durable io-

dine phase (CD-IP). For comparison, different samples such as Bir-SBA-15-2A-I, AgI (99.9%,

Sigma-Aldrich), and SnI4 (99.999%, Sigma-Aldrich) were also prepared. Then, chemical durability

of each sample was studied with a leaching test. The testing method was similar to the Product Con-

sistency Test (PCT) protocol [116]. First, each powder sample was poured into a polypropylene

(PP) bottle and deionized water was added at a mass ratio of 1:10. Notice that a sieving procedure,

which the PCT test standard designates to select particles within 74-150 μm range, was omitted

since the sample powders were very fine, with the sizes of the particles being less than 74 μm. The

tightly sealed bottle was kept at 90 °C for 7 d to induce elemental leaching from the sample. The

elemental concentration in leachate was then analyzed with the inductively coupled plasma atomic

emission spectroscopy (ICP-AES). Fractional loss of iodine (FL,I) was calculated with Eq. (4-2),

where ∆m and m is the iodine loss into the leachate and the initial mass of iodine in the specimen,

respectively.

FL,I (mass%) = (∆m/m)ⅹ100 (4-2)

4.2.4 Characterization

The degree of mesostrucutral arrangement was studied with the patterns of small angle X-

ray scattering (SAXS) obtained from an Empyrean (PANalytical B.V., Almelo, Netherland) XRD

system. 2θ was scanned from 0.3° to 3° with a 0.013° step size and 50 s dwell time. The structural

parameters on the surface areas and pores were obtained from nitrogen adsorption and desorption

isotherms at 77 K measured using a Trista II 3020 (Micrometrics Instrument Co., Norcross, GA)

system. Prior to the measurement, all samples were degassed at 100 °C in a vacuum. Brunauer-

Emmett-Teller (BET) [117] and Barrett-Joyner-Halenda (BJH) [118] theory were used to calculate

the specific surface areas and pore sizes/volume from the isotherms, respectively. Surface function-

57
alization was studied using a Fourier-transformed infrared (FT-IR) spectra obtained from a FT-IR

4100 (Jasco Inc., Tokyo, Japan) system. Powder samples were pelletized with a KBr binder prior to

the measurement. The mass ratios of the sulfur in the samples were measured using a FLASH 2000

(Thermo Fisher Scientific Inc., Waltham, MA) elemental analyzer. A powdered X-ray diffraction

(XRD) technique was used to conduct the phase analysis. The XRD patterns were gathered using a

D8_Advance_A25 (Bruker Co., Karlsruhe, Germany) equipment operated at 40 kV and 40 mA with

Cu Kα radiation. 2θ scan was conducted at 5-70° with a 0.02° step size and 0.02 s dwell time. The

sample morphology and particle size were studied using an SU8010 (Hitachi Ltd., Tokyo, Japan)

field-emission scanning electron microscope (FE-SEM). Powder specimens loaded onto carbon tape

were coated with platinum, and the samples were irradiated with an electron beam operated at 15

kV and 10 μA. A quantitative elemental analysis was conducted using the energy dispersive spectra

(EDS) with a silicon drift X-ray detector. The operating voltage and current for EDS were 20 kV

and 20 μA, respectively. Transmission electron microscopy (TEM) images and selected area diffrac-

tion (SAD) patterns were taken using a JEM-2100F (JEOL Ltd., Tokyo, Japan) electron microscope

operating at 200 kV. Specimens that were sparsely dispersed in ethanol were dropped on 300 mesh

copper grids and completely dried prior to the measurement. A thermogravimetric analysis (TGA)

of the samples was performed using a Labsys.Evo. (Setaram, Caluire, France) equipment from room

temperature to 800 °C at a heating rate of 10 °C min-1 in flowing Ar gas.

4.3 Results and Discussion

4.3.1 Sample characterization

In this study, the bismuth-embedded SBA-15 was developed through three phases. The opti-

cal images of the samples made at different phases are shown in Fig. 4-2. In the first phase, the thi-

ol-functionalized SBA-15 (Fig. 4-2(a)) was synthesized by co-condensation process with MPTMS

and TEOS as a thiol and silica precursor, respectively. Thiol-functionalization within the samples

could be confirmed by the FT-IR spectra (Fig. 4-3). The weak peaks at 2580 cm-1 found in Fig. 4-3

(b)-(d) were assigned to the vibration of the mercaptan groups (-SH) [114], suggesting the success-

ful thiol-functionalization onto the surfaces of SBA-15-SH1, SBA-15-SH2, and SBA-15-SH3. The

strong peaks at 2900 cm-1 found in Fig. 4-3 (b)-(g) were attributed to the C-H stretching vibration of

the propyl (-CH2CH2CH3) chains attached to the thiol groups. The amount of thiol groups loaded

58
onto the samples was estimated with the measurement of sulfur ratio (mass%). Measurement

showed about 80 % of the added MPTMS was used for thiol-functionalization onto surfaces of

SBA-15 (Table 4-2). The as-made thiol-functionalized SBA-15s were white granules with amor-

phous shape and the size distributions of 2-5 mm. In the second phase, bismuth was adsorbed in the

thiol-functionalized SBA-15. Upon immersing in the prepared bismuth solution, the granules imme-

diately turned yellow (Fig. 4-2(b)), suggesting the adsorption of bismuth in the granules. This was

also illustrated with the disappearance of the IR peaks at 2580 cm-1 in the bismuth-adsorbed samples

(Fig. 4-3(e)-(g)), indicative of thiol-bond breakage by the bismuth adsorption. Studies on the ad-

sorption of noble or heavy metals such as Au, Pt, Pd, and Hg by the thiol-functionalized SBA-15

indicate that thiol groups effectively react with these metals through metal-sulfur bonding [109–

112]. Thus, it is assumed that bismuth was anchored on the surfaces of the samples with Bi-S bond

formation. In the third phase, the specimens were thermally treated at 250 °C in 4%H2/Ar flow, to

turn to dark brown granules as the final bismuth-embedded SBA-15 (Fig. 4-2(c)).

59
Fig. 4-2. Images of (a) SBA-15-SH1, (b) Bi-SBA-15-SH1, and (c) Bir-SBA-15-SH1.

60
 Fig. 4-3. The IR spectra of different samples: (a) SBA-15, (b) SBA-15-SH1, (c) SBA-15-

SH2, (d) SBA-15-SH3, (e) Bi-SBA-15-SH1, (f) Bi-SBA-15-SH2, and (g) Bi-SBA-15-SH3.

61
Table 4-2. Comparisons of the calculated and measured mass ratios of sulfur in several

samples to estimate the MPTMS utilization for thiol-functionalization

Sample Scalc (mass%, Smeas (mass%,

Smeas/Scalc
calculated) measured)a
SBA-15-SH1 11.1 8.9 ± 0.1 0.80 ± 0.01

SBA-15-SH2 12.8 10.2 ± 0.2 0.79 ± 0.01

SBA-15-SH3 16.2 13.4 ± 0.2 0.83 ± 0.01

a
These data were obtained from an elemental analyzer.

62
 The attachment of thiol groups within the samples affects mesostructure of the samples,

which is presented in the SAXS patterns (Fig. 4-4). The pristine SBA-15 made without MPTMS

showed three clear peaks that were assigned to d100, d110, and d200 spacings, indicative of typical

p6mm hexagonal symmetry of SBA-15 [108]. Peak intensities were substantially decreased with the

increased MPTMS concentration, consistent with the result of Margolese et al.’s study [115]. More-

over, peaks assigned to higher order (110) and (200) reflections disappeared at the SBA-15-SH2,

suggesting that the mesostructural orderings were gradually decreased as the MPTMS concentration

increased. For the SBA-15-SH3, no peaks were observed, presumably due to complete collapse of

pore structures.

The decreasing tendency of mesostructural ordering is consistent with that of structural pa-

rameters. The characteristic feature revealed from nitrogen adsorption and desorption isotherms is

that specific surface areas of the samples were significantly diminished as the MPTMS concentra-

tions increased (Table 4-3). It is likely that replacement of TEOS by MPTMS decreased the open

porosity of the samples originated from the distortion of mesostructural ordering and micropore

connectivity [119]. The adsorption isotherm for SBA-15 shown in Fig. 4-5 corresponded to the type

IV isotherm with a noticeable capillary condensation, a characteristic of mesoporous materials with

large pore size [119,120]. In addition, the shape of H1 hysteresis loop in SBA-15 suggests that the

narrow distribution of pore size, as well as the formation of channel-type pores [120]. The adsorp-

tion isotherms for the other samples were also type IV isotherms associated with mesoporous mate-

rials, yet hysteresis loops shifted to the left indicating pore size decrease. The measurement of pore

diameter in thiol-functionalized samples such as SBA-15-SH1, SBA-SH2, and SBA-SH3 shows that

the pore sizes were expanded compared to that of SBA-15 (Table 4-3) which is contradictory to

general expectations: the pore diameters at the highest volume fraction in these samples are smaller

than that of SBA-15 shown in the inset of Fig. 4-5. This seemingly unreasonable result is likely to

be related with large pores present in the samples containing thiol-groups. In other words, the pre-

sented data does not exactly show the pore diameter of the intra-particle because large pores at-

tributed to the inter-particle spaces also contribute to the determination of pore diameters. This con-

tribution appears to be more significant as the amount of thiol-groups increases. As revealed in the

SEM images in Fig. 4-6, the particles become shorter and more agglomerate as the functionalization

proceeds. It is also worth noting that the surface area and pore volume of SBA-15-SH2A are higher

63
than those of SBA-15-SH2, suggesting that high temperature and long duration for hydrothermal

reaction are beneficial to create high surface area and large pore volume. Interestingly, the surface

areas of the bismuth-embedded SBA-15s (after heat-treatment) were remarkably increased com-

pared to those of the thiol-functionalized SBA-15s. It is thought to be attributed to the extended

open porosity due to the removal of residual P123 during thermal treatment.

Micrographs of the pristine SBA-15 or thiol-functionalized SBA-15s were shown by SEM

(Fig. 4-6). The SBA-15 material mostly consisted of aggregated rod-like particles within a size

range of 1-1.5 μm, which is consistent with the morphology found in a typical SBA-15 [108]. The

general trend shown in the micrographs was that the lengths of rod-like particles were shortened,

and the particles were aggregated to form a large lump as the MPTMS concentration increased. In

particular, rod-type particles were not observed in SBA-15-SH3 at all owing to a strong agglomera-

tion of individual particles. The morphology observed in SBA-15-SH2 was similar to that of Bi-

SBA-15-SH2 (Fig. 4-6 (c), (e)), indicating that bismuth adsorption within the samples does not in-

duce microstructural changes. In contrast with Bi-SBA-15-SH2, needle-like particles were observed

in a micrograph of Bir-SBA-15-SH2 (Fig. 4-6). These crystals formed with thermal elevation at

250 °C were identified using Bi2S3 or S based on the results of an XRD analysis shown later. It is

reasonable that the crystals are assigned to Bi2S3 when considering the low-melting temperature of S

(115.2 °C).

The microstructure of SBA-15 revealed by TEM (Fig. 4-7(a)) illustrates that channel-type

pores were hexagonally arranged with the honeycomb shape, which is common in typical SBA-15

samples [108]. It is also shown that the pore structure was not ruined when the MPTMS ratio was

increased up to 0.34 (Fig. 4-7 (c)). However, it was observed that the pore structure collapsed when

MPTMS was excessively added as shown in Fig. 4-7 (d), which was also expected from the results

of SAXS analysis. In contrast, bismuth adsorption in the thiol-functionalized SBA-15 as well as

thermal treatment at 250 °C did not affect the pore structure (Fig. 4-7 (e), (f)). Note that the SAD

pattern of Bi-SBA-15-SH1 (Fig. 4-7 (e)), as well as that of SBA-15 and the thiol-functionalized

SBA-15s, revealed the amorphous nature of the samples. Upon heat treatment at 250 °C, the period-

ic dot pattern, presumably by Bi2S3, appeared in Bir-SBA-15-SH1 (Fig. 4-7 (f)). This indicates that

very small particles were made with Bi-S bond formation that crystalline nature was not observed

until these particles were sufficiently agglomerated with heat-treatment.

64
 The results of the XRD analysis were consistent with the above discussion that the bismuth-

adsorbed specimens (before heat-treatment) consisted of amorphous structures, evidenced by broad

peaks as exhibited in Fig. 4-8. Diffraction peaks corresponding to crystalline structures appeared

only after the bismuth-loaded samples were thermally treated, indicative of crystalline growths trig-

gered by thermal activation. Most peaks were identified with Bi 2S3 (JCPDS no. 17-0320) and S8

(JCPDS no. 86-1278). There were also some minor peaks, but these could not be identified within

the existing reference peaks. The XRD results suggest that, contrary to our intention, reduction of

the bismuth-loaded samples with heat-treatment was not achieved. After iodine capture, prior peaks

disappeared and new peaks were found that matched BiI3 (JCPDS no. 07-0269).

65
 Fig. 4-4. Small angle X-ray scattering (SAXS) patterns of (a) SBA-15, (b) SBA-15-SH1, (c)

SBA-SH2, and (d) SBA-15-SH3. Inset is a part of the SAXS patterns that are vertically magnified

by 12 times.

66
 Table 4-3. Structural parameters for various samples revealed by N2 adsorption and desorp-

tion isotherms

SBA- Bir- Bir- Bir-

SBA- SBA- SBA-
SBA-15 15- SBA- SBA- SBA-
15-SH1 15-SH2 15-SH3
SH2A 15-SH1 15-SH2 15-SH3
SaBET
2
637 215 153 232 51 429 368 223
(m /g)
VbBJH
3
0.88 0.35 0.31 0.40 0.10 0.36 0.32 0.12
(cm /g)
DcBJH
6.34 6.93 8.75 6.85 9.37 5.80 6.00 4.05
(nm)
a
This sign indicates the surface area determined from BET theory.
b
This sign indicates the pore volume determined from BJH theory with adsorption isotherms.
c
This sign indicates the pore size determined from BJH theory with adsorption isotherms.

67
 Fig. 4-5. N2 adsorption and desorption isotherms and pore size distributions (inset) of SBA-

15 (■), SBA-15-SH1 (●), SBA-15-SH2 (▲), SBA-15-SH2A (◆), and SBA-15-SH3 (▼).

68
 (a) (b)

(c) (d)

(e) (f)

Fig. 4-6. SEM images of different samples: (a) SBA-15, (b) SBA-15-SH1, (c) SBA-15-SH2,

(d) SBA-15-SH3, (e) Bi-SBA-15-SH2, and (f) Bir-SBA-15-SH2.

69
Fig. 4-7. TEM images and SAD patterns (insets) for (a) SBA-15, (b) SBA-15-SH1, (c) SBA-

15-SH2, (d) SBA-15-SH3, (e) Bi-SBA-15-SH1, and (f) Bir-SBA-15-SH1.

70
 Fig. 4-8. The XRD patterns for different samples: (a) Bi-SBA-15-SH1, Bir-SBA-15-SH1,

and Bir-SBA-15-SH1-I, (b) Bi-SBA-15-SH2, Bir-SBA-15-SH2, and Bir-SBA-15-SH2-I, (c) Bi-

SBA-15-SH3, Bir-SBA-15-SH3, and Bir-SBA-15-SH3-I, (d) Bi-SBA-15-SH2A, Bir-SBA-15-

SH2A, and Bir-SBA-15-SH2A-I.

71
 4.3.2 Iodine adsorption experiments

Fig. 4-9 exhibits the results of the iodine adsorption test for various samples conducted at

200 °C (or 150 °C for AgX) in steady air. The bismuth-embedded SBA-15s demonstrated effective

capture of iodine with the highest capacity of 540 mg-I/g-sorbent for Bir-SBA-15-SH2A. Compared

to the results of AgX, our new sorbent accomplished 1.7 times higher capacity than that of the cur-

rent baseline sorbent. It was also shown that the capacity was increased as the bismuth concentra-

tion in the samples increased (Table 4-4). The pristine SBA-15 showed a substantially low capacity.

The high data fluctuation is likely to be attributed to the removal of captured water within the SBA-

15. The results strongly suggest that iodine capture is mostly dependent on bismuth, not SBA-15.

However, the capacity was not directly proportional to the bismuth mass ratio (Table 4-4 and Fig. 4-

10). Unlike the linear relation between the mass ratios of sulfur and bismuth, the iodine capturing

capacities of Bir-SBA-15-SH2 and Bir-SBA-15-SH3 were nearly identical, although the bismuth

mass ratio changed (Fig. 4-10). This is attributed to the noticeably reduced surface area of the mate-

rials (Table 4-3) due to the collapse of pore structure (Fig. 4-7), resulting in the lowered accessibil-

ity to iodine binding sites. By the same token, the improved iodine capture of Bir-SBA-15-SH2A is

related with higher surface area of SBA-15-SH2A than that of SBA-15-SH2. These results indicate

the accessible surface area is pivotal for iodine capture. It is worth noting that less iodine was ad-

sorbed with Bi-SBA-15-SHs (before heat-treatment) than Bir-SBA-SHs (after heat-treatment). Yang

et al. [107] demonstrated the iodine adsorption with bismuth was significantly affected by the oxida-

tion state of bismuth. However, the XRD phase analysis revealed that the crystal within the sorbents

after heat-treatment was Bi2S3, not Bi, suggesting that there was no change in the oxidation state of

bismuth during the heat-treatment adopted in this study. It could be hypothesized that residual P123

inside the samples prior to heat-treatment blocked the pore entrance, reducing accessible binding

sites. It is reported that residual P123 remains approximately 6 % within SBA-15 after solvent ex-

traction [115].

72
 Fig. 4-9. Iodine capturing capacities in static air for (a) SBA-15, (b) Bi-SBA-15-SH1, (c) Bi-

SBA-15-SH2, (d) Bi-SBA-15-SH3, (e) Bir-SBA-15-SH1, (f) Bir-SBA-15-SH2, (g) Bir-SBA-15-

SH3, (h) Bir-SBA-15-SH2A, and (i) AgX (tested at 150 °C).

73
 Table 4-4. Mass ratios of sulfur, bismuth, and iodine, and iodine capturing capacities in io-

dine-bearing samples

Sample Capacity (mg_I/g-

S (mass%)a Bi (mass%)b I (mass%)
sorbent)
Bir-SBA-15-
8.9 ± 0.1 9.9 ± 1.7 26.6 ± 1.7 414 ± 24
SH1-I

Bir-SBA-15-
10.2 ± 0.2 15.7 ± 3.9 31.1 ± 1.2 501 ± 16
SH2-I

Bir-SBA-15-
13.4 ± 0.2 28.8 ± 4.7 32.0 ± 0.1 502 ± 2
SH3-I

a
These were the data of thiol-functionalized SBA-15s before bismuth adsorption.
b
These data were obtained from an SEM-EDS.

74
Fig. 4-10. Graphs on the relation of mass ratios between (a) sulfur and bismuth and (b) bis-

muth and iodine capturing capacity.

75
 4.3.3 Adsorption mechanism

Yang et al. [107] explained that the effective iodine adsorption with the bismuth-based

sorbents was due to the affinity of bismuth for iodine. In other words, chemical adsorption (chemi-

sorption) of iodine occurs as the chemical reaction between bismuth and iodine produces thermody-

namically stable compounds. The thermodynamic accounts for iodine capture could also be applied

in this study. It is different from the prior study that Bi 2S3 instead of Bi was involved in the iodine

capture. The XRD phase analysis (Fig. 4-8) revealed that BiI3 was a primary compound that was

made by iodine capture with the bismuth-embedded SBA-15s. Although the iodine capturing test

was performed under static air, other compounds such as BiOI or Bi 2O3 were not found unlike the

previous study. In terms of thermodynamics, the formation of BiOI or Bi2O3 is also favorable at 473

K as represented by the negative values of ∆Gf° when Bi2S3 reacts with I2(g) in the presence of

O2(g) (Table 4-5). However, thermodynamic calculations showed the chemical reaction that in-

volves Bi2S3, I2(g), and O2(g) to form BiI3 and SO2(g) was most stable with ∆Gf° = –523.2 kJ mol-1

at 473 K, which was significantly lower than that related with reactions to form BiOI or Bi 2O3. It is

worth noting that the small mass loss up to 100 °C shown in the TGA results (Fig. 4-11) suggests

that physical adsorption (physisorption) of iodine also occurs, although chemisorption is a main

process.

76
 Table 4-5. Chemical reactions related to iodine adsorption with Bi2S3 in static air, as well as

Gibbs free energy of formation (ΔGf°) at 473 K

reaction ΔGf°a
chemical reaction spontaneity
product (kJ mol-1)

0.5Bi2S3 + 1.5I2(g) = BiI3 + 1.5S BiI3 -71.2 spontaneous

0.5Bi2S3 + 0.5I2(g) + 0.5O2(g) = BiOI + 1.5S BiOI -151.0 spontaneous
0.5Bi2S3 + 1.5I2(g) + 1.5O2(g) = BiI3 + 1.5SO2(g) BiI3 -523.2 spontaneous
Bi2S3 + 1.5I2(g) + 1.5O2(g) = Bi2O3 + 3S + 1.5I2(g) Bi2O3 -313.8 spontaneous
a
These data were calculated with the HSC Chemistry 6.0 code.

77
 Fig. 4-11. TGA data for various samples: curves for the samples prior to iodine capture are

presented with a dashed line. Curves for bismuth-embedded SBA-15 are shown with a solid line.

78
 4.3.4 Chemical durability analysis

Chemical durability of waste forms is a crucial factor that determines whether the waste

forms could be safely disposed of for a long time or not. Radionuclide dissolution to groundwater

would lead to a deleterious impact on human body along with groundwater transport. In this regard,

studies are needed to develop iodine sorbents with improved chemical durability, along with effec-

tive iodine capture capability. However, not much is known about the chemical stability of the re-

cently developed sorbents [13,14,19,121,122]. This study performed a preliminary assessment of

chemical durability of the bismuth-embedded SBA-15 after iodine capture, as well as other iodine-

loaded materials, with a simple leaching test. The leaching test followed the protocol of PCT test

developed for powdered specimens in hot aqueous media, which provides severe environment for

elemental leaching, aiming at estimating the chemical durability of specimens with a short-term test.

As shown in Fig. 4-12 and Table 4-6, the fractional loss of iodine was 7.88 mass% in Bir-SBA-15-

SH2A-I; after the post-sorption process, the loss was significantly decreased to 0.29 mass%. It is

attributed to the change of iodine-bearing phase from BiI3 to Bi5O7I as revealed from the XRD pat-

terns (Fig. 4-13, 4-14). This result indicates that BiI3 as a final waste phase for 129I may not be ade-

quate due to a considerable loss of iodine that could occur at repository sites. The iodine loss should

be mitigated either by addition of other getter materials to the mix and/or via stronger chemical

bonding of the iodine. In this sense, the post-sorption process introduced in this study could be a

plausible scheme for iodine stabilization: the formation of stable phase (Bi 5O7I) through the chemi-

cal reaction between Bi2O3 and BiI3. The chemical durability is expected to be further enhanced

with the use of binding materials for waste forms [17,30], as well as optimization of the process

conditions. AgI, which is made by iodine chemisorption with silver-exchanged zeolites or silver-

functionalized silica aerogels, also showed a remarkably low fractional loss of iodine. However, the

loss from SnI4, measured at 89.8 mass%, was strikingly high. SnI4 is the iodine compound formed

through iodine captured within the Sn2S3-based chalcogels [20,21]. This result indicates that iodine

capture with the Sn2S3-based chalcogels may not be adequate from a waste form standpoint, alt-

hough these sorbents achieved a high iodine removal efficiency. Encapsulation with binding materi-

als would provide a physical barrier to block the groundwater contact, improving chemical durabil-

ity to some degree. Therefore, when considering disposal criteria for chemical durability, the stabi-

lizing treatment to form stable iodine phases could be included as a requirement.

79
Fig. 4-12. Fractional iodine loss for various samples revealed by the PCT test.

80
 Table 4-6. Fractional iodine loss at different samples calculated from iodine concentrations

in leachates obtained by ICP-AES

I amount in 10 I fraction in unit Fractional loss

Concentration
Sample mL solution gram sample (mass%,
(ppm)
(g, A) (B) A/Bⅹ100)

1.63 × 10-4 ±
CD-IP 16.3 ± 1.6 0.060 0.27 ± 0.02
1.15 × 10-5
Bir-SBA-15- 2.59 × 10-2 ±
2590 ± 233 0.329 7.88 ± 0.71
SH2A-I 2.33 × 10-3
9.70 × 10-5 ±
AgI 9.7 ± 0.2 0.541 0.02 ± 0.00
1.73 × 10-6

4
7.28 × 10-1 ±
SnI4 7.28 × 10 ± 950 0.24 89.8 ± 1.2
9.50 × 10-3

81
 Fig. 4-13. The XRD patterns for (a) the initial mixture sample composed of BiI3 and Bi2O3,

(b) the heat-treated sample at 250 °C for 3h, (c) the heat-treated sample at 400 °C for 3h, and (d) the

heat-treated sample at 500 °C for 3h.

82
Fig. 4-14. The XRD patterns for (a) Bir-SBA-15-SH2A-I and (b) CD-IP.

83
 4.4 Implications for Waste Management
129
One of the most serious challenges in the management of I is to provide very long-term

stabilization and isolation. As gaseous releases from reprocessing facilities to the environment is the
129
primary pathway of I release, efficient capture and stabilization of I2(g) have been the focus of

iodine waste management to satisfy the environmental regulations [5,123]. Recent efforts have been

made to improve iodine loadings within sorbents [15,18,20,21,48]. However, in-depth research on
129
stabilization of iodine-bearing sorbents is still needed to guarantee the long-term safety of I-

incorporated waste in spite of a few related studies [17,30,124].

A previous study suggested the use of bismuth for iodine capture [107]. Relatively low price

and environmentally benign property [39] of bismuth are advantages over silver that has been wide-

ly used for iodine capture. Moreover, a fairly simple process that neither requires complicated nor

expensive systems could be beneficial for industrial applications. However, bismuth could not be

fully utilized for iodine capture due to the significantly low surface areas as well as small pore vol-

ume of the sorbents. The bismuth-embedded SBA-15, as shown to provide high surface areas and

porosity in this study could prove to be useful for industrial applications. Additionally, this study

demonstrated that, through a facile thermal process, chemical durability of the iodine-bearing

sorbents could be significantly improved. These findings open the possibility of long-term effective

management of 129I2(g) through the use of bismuth-embedded SBA-15. Of course, it should be men-

tioned that the PCT test used in this study is designed to predict the short-term behavior of waste

forms deposited in a deep repository. In particular, the leaching solutions would be saturated in a

short time given the high surface areas of sample powders. As a consequence, great care should be

taken in the use of these results for the prediction of long-term behavior. Further work is needed to

predict the long-term behaviors of the bismuth-embedded SBA-15 under various conditions of deep

groundwater (i.e., at different pH, redox potentials, and dissolved anion concentrations).

Performance of the bismuth-embedded SBA-15 is expected to be further enhanced with the

optimization of the synthesis process. The MPTMS ratio determines bismuth adsorption in the

sorbents that is correlated with iodine capture. However, excessive addition of MPTMS spoils the

pore structure of SBA-15, decreasing the bismuth utilization. In addition, it was observed that the

bismuth-embedded SBA-15 became less robust with higher MPTMS ratio. This phenomenon would

be of serious concern when considering that densely packed sorption beds by fragmented sorbents

84
could cause severe pressure gradients in the flow stream [125]. Some portion of sorbents could also

be lost along the flowing air. Thus, determination of the optimal MPTMS ratio is required to im-

prove industrial applicability. Hybrid sorbents with porous polymer such as polyacrylonitrile could

be a remedy to strengthen mechanical properties [21]. To examine the effect of pore structure, other

mesoporous silicas with different pore structures [126,127] might be studied for iodine adsorption.

The heat-treatment condition could also affect the iodine loadings. Higher temperature is advanta-

geous to completely remove residual P123. However, higher temperature would cause agglomera-

tion of Bi2S3, lowering the utilization of bismuth. Considering the low melting temperature

(271.4 °C) of elemental bismuth, temperature lower than 270 °C would be desirable. Finally, a

study is planned to examine the removal efficiency of I2(g) in flowing air with significantly low io-

dine concentrations under the presence of other gases (e.g., NO, NO2, and H2O). This would simu-

late the actual off-gas stream and help to determine the optimized synthetic process for the applica-

tion of the bismuth-embedded SBA-15.

85
 Chapter 5. Glass Composite Waste Forms for Iodine Confined in
Bismuth-Embedded SBA-15

5.1 Introduction
Volatile fission products such as 129I, 3H, 14C, and 85Kr are released as gaseous phases during

the head-end process of spent nuclear fuel [123]. Among them, proper management of 129I has been

a challenging issue due to its very long half-life (1.57 × 107 y) and high environmental mobility [2].
129 129
The special features of I have led to develop various sorbents to effectively separate I2 vapor

from off-gases [10]. Currently, silver-exchanged zeolites, known as Ag-faujasite (AgX) or Ag-
129
mordenite (AgZ), are most commonly used for I capture [9,13,14]. Iodine could be effectively

sequestrated by formi ng a stable iodine compound (AgI) within zeolites. However, a significant

portion of iodine is weakly bound inside zeolite pores [38], which will pose easy desorption of
129
I2(g) during thermal elevation. In addition, the physisorbed iodine is much vulnerable to release

during long-term storage of 129I due to the increased solubility of elemental iodine in water [3]. The-

se problems must be overcome for safe and long-term management of 129I.

In the previous research, a novel approach for iodine capture was studied with Bi-based

sorbents [107,128]. It was shown that iodine gas could effectively be captured within Bi-embedded

SBA-15. The high performance of our sorbent is attributed to the fundamental affinity property be-

tween Bi and I2(g), being demonstrated by the large values of Gibbs free energy of formation (∆Gf0)

[128]. The use of SBA-15 mesoporous silica also significantly decreased the physical adsorption of

iodine, resulting in chemisorption of iodine as the main capturing mechanism: the captured iodine

was present as BiI3 [107]. The newly developed Bi-embedded SBA-15 is expected to be feasible to

sequestrate 129I2(g) given the environmentally benign characteristic and low price of Bi.
129
The cradle-to-grave management for I ought to cover fabrication of chemically durable

waste forms and their safe storage in casks with very long-term integrity. Basic principle for making

chemically durable waste forms is to incorporate or encapsulate radioactive waste with binders

composed of glasses, glass composite materials or ceramics [129]. Chemical durability of waste

forms could be significantly enhanced when fine waste particles are homogeneously dispersed with-

in binding matrices. Conventionally, vitrification has been performed to make nuclear waste glasses

86
containing high level waste [130,131]. This technology has several advantages as a method to im-

mobilize waste materials into glass matrices: a wide range of waste can be vitrified because the

open glass structure can incorporate many elements; significant volume reduction is expected due to

the small volume of the final waste form; vitrified waste forms can be stable for many years due to

the high chemical durability of glass [131]. Currently, borosilicate glass is the material of choice.

However, vitrification is not appropriate to incorporate halogen-containing wastes because halogen

elements are insoluble to silicate-based glasses due to their large ionic sizes and polarizability [132],

as well as high volatility at the processing temperatures (1050-1150 °C). Retention ratio, defined as

the mass fraction remaining in the melt relative to the original concentration, is reported ~20% for

the case of iodine in the low-activity glass [132]. Even further, iodine solubility in borosilicate glass

is known to be low ranging 0.1-1 wt% [132,133]. Thus, another technology based on different bind-

er materials is needed to efficiently immobilize halogen-containing wastes.

The present study aims to fabricate dense and durable monolithic waste forms for Bi-

embedded SBA-15 after capturing iodine gas. Our previous study has shown that BiI3 within Bi-

embedded SBA-15 could successfully be transformed into chemically durable Bi 5O7I by using a

facile thermal process with the addition of Bi2O3 [128]. The result of elemental leaching test exhib-

ited that iodine loss from Bi5O7I was decreased by more than 10 times than that from BiI3. This

suggests that a chemically durable waste form could be fabricated using iodine-bearing Bi-

embedded SBA-15 by selecting proper binder materials to induce stabilization from BiI3 to Bi5O7I.

In this sense, Bi-containing binders that could activate transformation of iodine phase would be

candidate materials for the present study. Another consideration is that processing temperature

should be sufficiently low to minimize iodine loss during waste form fabrication. Therefore, our

strategy is to use low-temperature sintering glasses that contain bismuth oxide as binder materials

[17,30].

Herein, we present the fabrication of glass-composite waste forms for iodine-bearing Bi-

embedded SBA-15 by using low-temperature sintering glasses. Details of materials synthesis and

characterization for the waste forms were described. In addition, chemical durability of the new

waste forms was investigated following protocols of the standard Product Consistency Test (PCT)

[116].

87
 5.2 Experimental
5.2.1 Preparation of Bi-embedded SBA-15

Preparation of Bi-embedded SBA-15 was through the modification of SBA-15 with thiol-

groups. Details of the procedure to synthesize thiol-functionalized SBA-15 could be found else-

where [114]. Typically, 16 g of Pluronic P123 (EO70-PO20-EO70, Mw = 5,800, Sigma-Aldrich, St.

Louis, MO) was added into 500 g of 1.9 M HCl solution and magnetically stirred to make a micellar

solution. To the solution, 108 mmol of tetraethylorthosilicate (TEOS, 95%, Sigma-Aldrich) was

added and vigorously stirred at 40 °C for 3 h. Then, 56 mmol of MPTMS (3-

mercaptopropyltrimethoxysilane) was added and the stirring reaction continued for another 20 h.

The mixture was moved to a polytetrafluoroethylene bottle after the reaction, tightly sealed, and

kept at 100 °C for 24 h. The aged material was filtered to separate solid from liquid, and the solid

was dried at 40 °C for 24 h. To remove P123 inside the solid, 3 g of the solid and 800 mL of ethanol

was mixed and refluxed for 24 h. After drying at 40 °C for 24 h, thiol-functionalized SBA-15 was

obtained.

For Bi incorporation, the thiol-functionalized SBA-15 was soaked into BiCl3 solution at a

ratio of 1 g: 100 mL for 6 h. To make BiCl3 solution, BiCl3 (98%, Kanto Chemical Co., Kagaku,

Japan) was added into methanol at a ratio of 5 g: 100 mL and reflux was performed. It is worth not-

ing that BiCl3 is readily hydrolyzed to form bismuth oxychloride (BiOCl) that is an insoluble com-

pound when it contacts with methanol. Thus, BiOCl precipitate should be filtered to obtain clear

BiCl3 solution. The sample turned to yellow upon completion of Bi incorporation. Finally, the solid

was heat-treated at 250 °C for 6 h in 4% H2/Ar atmosphere to remove residual P123 present inside

the sample pores.

5.2.2 Iodine capturing experiments

Iodine capturing experiment was performed using a specially designed device as described

elsewhere [128]. At first, 5 g of nonradioactive I2 crystal (I2, 99%, DC Chemical Co., Seoul, Korea)

was placed at the bottom of reaction crucible. Then, an alumina plate with small holes (<1mm) and

an alumina sheet were put above the I2 crystal. About 2 g of Bi-embedded SBA-15 filled the reac-

tion crucible. Iodine capturing reaction was performed at 200 °C for 6 h under air atmosphere be-

cause the generation of I2(g) is greatly activated above the boiling point of iodine (182.8 °C). The

88
increased mass was measured by a balance at the completion of the experiment.

5.2.3 Waste form fabrication

Low-temperature glasses were produced as binders for the waste forms. The target glasses

were commercial glasses composed of Bi-Zn-B and Bi-Zn-Si-Al (EG2998 and EG2922 at Ferro

Corporation) [17,30,134,135]. For the synthesis of each glass, powders of Bi2O3, ZnO, B2O3, SiO2,

and Al2O3 were homogeneously mixed at the designated ratios and melted at 1200 °C for 1 h. After

cooling to room temperature, the synthesized glasses were crushed to make fine powders. The Bi-

Zn-B glass and the Bi-Zn-Si-Al glass were denoted as LGC1 (low-temperature glass composition1)

glass (equivalent to the composition of EG2998 at Ferro Corporation) and LGC2 (low-temperature

glass composition2) glass (equivalent to the composition of EG2922 at Ferro Corporation), respec-

tively.

To fabricate waste forms, Bi2O3 powder was also added to the glass powders as a stabiliz-

ing additive to promote reaction between Bi2O3 and the iodine compound within Bi-embedded

SBA-15. Total six samples with different waste loadings were prepared and the samples composi-

tions were presented in Table 5-1. The prepared powders were sufficiently mixed for homogeniza-

tion using a pestle. Then the powder mixtures were cold pressed to become pellets with a diameter

of 8.8 mm under uniaxial pressure of 300 MPa (Fig. 5-1(a)). Zinc stearate dispersed in ethanol was

used as a lubricant. The pellets were heated at 600 °C (heating rate: 10 °C/min) for 2 h in air, to

complete the glass composite waste forms (Fig. 5-1(b)).

89
 Table 5-1. Sample compositions prior to heat-treatment

Sample Mass fraction (%)

Glass type
name Wastea Ib Bi2O3 Glass

LGC106 6.2 2.6 20.4 73.4

LGC113 13.2 5.6 26.0 60.7 LGC1
LGC119 19.0 8.0 24.9 56.1
LGC206 6.2 2.6 20.4 73.4
LGC213 13.2 5.6 26.0 60.7 LGC2
LGC219 19.0 8.0 24.9 56.1
a
Waste means Bi-embedded SBA-15 after iodine capture (denote Bi-SBA-15-I).
b
Mass ratio of I was calculated by considering the percentage of I within Bi-SBA-15-I.

90
 Fig. 5-1. Images of (a) pelletized samples before sintering (LGC106, LGC113, LGC119,

LGC206, LGC213, and LGC219 from the left) and (b) glass composite samples after sintering

(LGC106, LGC113, LGC119, LGC206, LGC213, and LGC219 from the left).

91
 5.2.4 Elemental leaching test

The short-term corrosion behavior of the glass composite waste forms was studied in ac-

cordance with the protocol of PCT. The glass composite samples were crushed and only the parti-

cles of 75-150 μm were selected by a sieving process. 1.5-2.0 grams of the crushed samples were

then mixed with 15-20 mL of deionized water (DIW) in polypropylene bottles. After being sealed

tightly, the bottles were placed in an oven at 90 °C for 7 days for elemental leaching. The leachates

were filtered and analyzed by ion chromatography (IC) for iodide detection or by inductively cou-

pled plasma atomic emission spectroscopy (ICP-AES) for detection of other ions. The normalized

leaching rate of each element (NRi) was calculated using Eq. (5-1).

NRi = Ci/(fi∙SA/V∙t) (5-1)

where Ci is concentration of element, i, in the leachate (mg/L), fi is mass fraction of ith ele-

ment prior to the leaching test (unitless), SA/V is the sample surface area (SA) divided by leachant

volume (V), where SA was assumed to be ~1000 m-1 (density of our samples and borosilicate waste

glass were ~4.9 g/cm-3 and ~2.7 g/cm-3, respectively, and the SA/V of general borosilicate waste

glass was ~2000 m-1. The SA/V of the samples was estimated to be about half (1000 m-1) of the

SA/V of borosilicate waste glass) [136], and t is the duration for the leaching test (day). Test was

also performed using NaCl, Na2CO3, Na2SO3, and NaF solutions with 0.005 M concentrations in-

stead of DIW to investigate the effect of dissolved anions in the leaching solutions, which is allowa-

ble in the protocol of PCT-B method [116].

5.2.5 Characterization

Measurement of thermogravimetric analysis (TGA) was performed using a Mettler Toledo

TGA/DSC1 1100 SF system. Sample powders were loaded onto the alumina crucibles and heated at

a rate of 10 °C/min. Air gas flowed into sample chamber at a rate of ~50 mL/min. Phase analysis of

each sample was conducted using powder X-ray diffraction (XRD) measurements. The XRD pat-

terns were collected using a Bruker D8_Advance_A25 equipment, operating at 40 kV and 40 mA

using Cu Kα radiation. Microstructural images were obtained by a field-emission scanning electron

microscope (FE-SEM) system (of Hitachi SU8010). Each sample was coated with platinum prior to

92
the measurement. Electron beam was generated using 15 kV of voltage and 10 μA of current.

5.3 Results and Discussion

5.3.1 Characterization of samples

It is essential to identify iodine phases within the samples because the chemical state of io-

dine is closely related with the chemical durability of waste forms. Thus, XRD analysis was per-

formed to reveal crystalline structures within the iodine bearing Bi-embedded SBA-15 (Bi-SBA-15-

I). As shown in the result of XRD measurement (Fig. 5-2), most peaks of the sample were in ac-

cordance with those of the reference BiI3 (JCPDS #07-0269). Several peaks around 25°, 32° and 37°

indicate that Bi2O3 and Bi5O7I are also present as minor compounds. This result suggests that most

iodine exists as BiI3 within Bi-SBA-15-I. Our target is stabilization of BiI3 through the fabrication

of waste forms.

After sintering, it was measured that the crystalline structures inside the glass composite

waste forms were totally different from those of Bi-SBA-15-I as shown in Fig. 5-3. The result of

XRD illustrates that iodine phases within the samples are composed of BiOI, BI5O7I, and BiI3. The

presence of BiI3 as shown in Fig. 5-3(a) even after sintering at 600 °C for 2 h might seem at odds

according to the report that BiI3 completely transforms to BiOI by heat-treatment at 350 °C for 2 h

[104]. It is presumed that the LGC1 glass captured volatilizing iodine and reacted to form BiI3. This

could be supported by Sava’s study [17]: BiI3 was formed by the reaction of evolving iodine with

the low-sintering glass (EG2998) after sintering at 500 °C for 1 h. It is worth noting that BiI3 was

not found in the LGC2 samples, indicating that LGC2 hardly reacted with iodine gas. This differ-

ence is thought to be related with the relatively high softening temperature of LGC2 (505 °C) com-

pared to that of LGC1 (440 °C). In addition, it should also be mentioned that the major peaks in the

samples were dependent on glass type: the main peaks in the LGC1 samples (denoted the LGC1

series) and the LGC2 samples (denoted the LGC2 series) are BiOI and Bi 5O7I, respectively. The

effect of glass type will be discussed later along with the thermal analysis of the samples.

The surface morphologies of the samples were characterized by FE-SEM (Fig. 5-4 and Fig.

5-5). In Fig. 5-4, the images at low magnification demonstrate that the structure becomes more po-

rous as the waste fraction increases. In addition, the comparison of Fig. 5-4 and Fig. 5-5 illustrates

that more densified and homogenized structure was developed in the LGC1 series. This difference is

93
due to the lower glass transition temperature of LGC1 than that of LGC2 [17]. The images of LGC1

series at high magnification (Fig. 5-4(d)-(f)) showed that crystalline structure is mostly composed of

plate-like particles. In contrast, irregular and rod-like particles were more frequently found in the

images of LGC2 series at high magnification (Fig. 5-5(d)-(f)). The rod-like particles correspond to

Bi5O7I crystals [137]. The morphological difference between LGC1 and LGC2 series is related with

the difference of major compounds as evidenced by the XRD results (Fig. 5-3).

Mass loss during sintering was measured by TGA (Fig. 5-6). Note that the samples for the

analysis were the powder mixtures prior to sintering and the heat-treatment condition in this analy-

sis was the same with the sintering condition to simulate the sintering. Then the declining behavior

of TGA curves indicates that volatile compounds are lost from the samples as sintering proceeds. It

is observed that there are four distinctive regions with different curve gradients: the loss from the

room temperature to 250 °C originated from weakly captured water as well as the physically bound

iodine within micropores of Bi-SBA-15-I [128]. It is noticeable that the shape of curves from

250 °C in the LGC1 series is quite different from that of the LGC2 series. The thermal loss after

250 °C until 380 °C was attributed to the transformation and decomposition of BiI3 as shown in the

following reactions [104]:

2BiI3 + O2(g) = 2BiOI + 2I2(g) (5-2)

2BiI3 = 2Bi(g) + 3I2(g) (5-3)

The relatively gentle slopes found in the LGC1 series are likely to be related with the cap-

ture of volatilizing iodine that leads to the formation of BiI3 (2Bi + 3I2(g) = 2BiI3). Judging from the

XRD result that BiI3 was only found in the LGC1 series (Fig. 5-2), the LGC2 glass seems inappro-

priate to capture iodine escaping from Bi-SBA-15-I in contrast to the LGC1 glass. From 380 to

450 °C in the LGC1 series, mass loss occurs with the transformation reaction given as [104]:

5BiOI + O2(g) = Bi5O7I + 2I2(g) (5-4)

The curve slope in the LGC1 series dramatically increases after 450 °C that is near the glass

softening temperature of LGC1 (440 °C). In this region, decrease of mass is likely due to decompo-

94
sition of Bi5O7I to BiOI (Bi5O7I = BiOI + 2Bi2O3), followed by the volatilization of Bi2O3 (Fig. 5-7).

In the LGC2 series, however, the reaction (4) that transforms BiOI to Bi5O7I continues until 500 °C

that is around the glass softening point of LGC2 (505 °C). After 500 °C, the LGC2 series also show

similar behavior as the LGC1 series, which is the volatilization of Bi2O3. It is speculated that volatil-

ity of Bi2O3 is activated after the glass softening point. After all, different degrees of reactions in

two series led to the difference of crystalline structures between the LGC1 and the LGC2 series as

exhibited in the XRD results (Fig. 5-3).

Iodine mass ratio in each glass composite sample was characterized by X-ray fluorescence

(XRF). XRF measurement on the BiI3 standard sample displayed that the mass ratios of Bi and I

measured by XRF are nearly equivalent to the calculated values (Table 5-2), suggesting that quanti-

tative analysis of elements by XRF is fairly reliable. The mass fraction of iodine in each sample be-

fore and after the sintering, as well as the iodine retention ratio reflecting iodine loss, is presented in

Table 5-3. It was found that the iodine mass ratios in the LGC1 series were apparently higher com-

pared with those in the LGC2 series. In addition, the retention ratio of iodine showed decreasing

tendency as the waste fraction increases irrespective of glass type. The first observation is attributed

to the re-capturing effect of evolving iodine during the sintering process by the LGC1 glass to form

BiI3 compound, as mentioned above. The second phenomenon is related with the relative ratio of

additive (Bi2O3) to I by mass (Table 5-1): the higher ratio of Bi2O3 to I (e. g., LGC106 and

LGC206) might contribute to diminish iodine loss by the formation of thermally stable phase

(Bi5O7I) through the following reaction:

BiI3 + 7Bi2O3 = 3Bi5O7I (5-5)

This result suggests that the iodine volatility is dramatically affected by compositional ad-

justments of glass and the additives in the case of glass composite waste form for Bi-embedded

SBA-15.

95
Fig. 5-2. XRD pattern for Bi-embedded SBA-15 after iodine capture, revealing that most io-

dine within Bi-embedded SBA-15 exists as BiI3.

96
 Fig. 5-3. XRD patterns for the glass-composite waste form samples (after sintering): (a)

samples made with LGC1 binder (LGC1 series), and (b) samples made with LGC2 binder (LGC2

series).

97
 Fig. 5-4. Microstructural images of LGC1 series provided by SEM: (a) LGC106, (b)

LGC113, (c) LGC119 at low magnification; (d) LGC106, (e) LGC113, (f) LGC119 at high magnifi-

cation.

98
 Fig. 5-5. Microstructural images of LGC2 series provided by SEM: (a) LGC206, (b)

LGC213, (c) LGC219 at low magnification; (d) LGC206, (e) LGC213, (f) LGC219 at high magnifi-

cation.

99
Fig. 5-6. TGA for each sample powder mixture (before sintering) during heating at 600 °C

for 2 h (heating rate: 10 °C/min) in air.

100
Fig. 5-7. TG-DSC analysis of Bi2O3 powder from 30 to 1000 °C in air (heating rate:

10 °C/min).

101
 Table 5-2. Comparison of the calculated and measured mass ratios for Bi and I by using BiI3

standard sample

Element Calculation (mass%) XRF (mass%)a Deviation (mass%)

Bi 35.42 34.76 0.66

I 64.58 65.24 0.66
a
XRF measurement was performed on a pelletized sample that is made by pressing powder

mixed with a polymer binder. Thus, the XRF results included other elements (e. g., C and O) and we

normalized the mass ratio of Bi and I by excluding others.

102
 Table 5-3. Comparison of iodine mass ratio in each sample before and after sintering, as

well as retention ratio of iodine obtained by considering iodine volatilization during heat-treatment

I mass ratio (%)

Retention ratio
Sample name Initial Glass-composite I loss (%)
(Ri)
mixture waste forma

LGC106 2.6 2.5 4.3 0.96

LGC113 5.6 2.9 49 0.51
LGC119 8.0 2.7 66 0.34
LGC206 2.6 1.6 41 0.49
LGC213 5.6 1.9 67 0.33
LGC219 8.0 1.7 79 0.21
a
I mass ratio for each sample was measured by XRF.

103
 5.3.2 Chemical durability studies

Waste forms are destined to be emplaced in underground repositories where contact with

groundwater is expected. In the aqueous media, radionuclides are released from glass waste forms

along with glass corrosion through processes such as ion-exchange, dissolution of the glass network,

condensation of hydrated silica, and precipitation of alteration products [138]. Then, the dissolved

radionuclides become mobile, making the isolation of radionuclides challenging. Therefore, evalua-

tion on chemical durability of waste forms is essential to assess the radiological and environmental

safety aspect of waste forms.

As a first step to study chemical durability of our samples, the product consistency test

(PCT) was performed to examine the behavior of radionuclide dissolution and glass degradation at

an early phase. Normalized leaching rates for different elements comprising waste forms were ob-

tained and presented in Fig. 5-8. Comparison of two data sets on LGC106 and LGC206 indicates

that elements in LGC106 have relatively low leaching rates (Fig. 5-8(a)): Bi and Zn, which are glass

formers for LGC106. The measured leaching rates of LGC106 were 0.5-1 order of magnitude lower

than those for LGC206. The observed low leaching rates of Bi are related with the insoluble proper-

ty of the element [139]. The leaching rates of Si are relatively high compared to other elements as it

is known as a sparingly soluble element [140]. This is likely attributed to the leaching from Bi-

embedded SBA-15 where the bonds around Si are presumably weaker than those within the glass

network. The significant difference in the leaching rates between Al and B is expected to originate

from the solubility difference between Al and B, not from the difference of matrix durability: Al and

B are known to be sparingly and significantly soluble elements, respectively [140]. The higher du-

rability of matrix elements in LGC106 is due to the lower glass transition temperature of LGC1

[17], resulting in a denser and more homogeneously mixed structure as revealed in the SEM analy-

sis (Fig. 5-4, 5-5). Being consistent with the behavior of glass formers, leaching rates of iodine for

LGC106 and LGC206 were 7.8×10-3 and 1.7×10-2 g/m2∙day, respectively. There could be two ex-

planations to this result: first, the LGC1 glass was less corroded, resulting in limited diffusion of

water molecules into iodine compounds; second, dissolution of iodine was different due to the pres-

ence of different iodine phases in two samples. As evidenced by the XRD analysis, main iodine

compounds in LGC1 and LGC2 series were BiOI and Bi5O7I, respectively. According to Taylor et

al.’s study on hydrolytic stability of various bismuth iodine compounds, hydrolysis reactions of a

104
few compounds at 25 °C are given as follows [41,43]:

Bi5O7I + OH-(aq) ↔ 2.5Bi2O3 + I-(aq) + 0.5H2O(l), logK1 = log[I-]/[OH-] = -3.39±0.20 (5-6)

1.25BiOI + OH-(aq) ↔ 0.25Bi5O7I + I-(aq) + 0.5H2O(l), logK2 = log[I-]/[OH-] = 3.49±0.18 (5-7)

0.5BiI3 + OH-(aq) ↔ 0.5BiOI + I-(aq) + 0.5H2O(l), logK3 = log[I-]/[OH-] = 10.0±1.0 (5-8)

Comparison of the equilibrium constants indicates that Bi5O7I has much stronger hydrolytic

stability than BiOI or BiI3. The high hydrolytic resistance of Bi5O7I over BiI3 was confirmed by

Yang et al. who illustrated that iodine dissolution from Bi5O7I was much less than that from BiI3

[128]. However, it is not clear whether Bi5O7I is more advantageous than BiOI. The BiOI-

dominated LGC106 exhibited lower leaching rate than the Bi5O7I -dominated LGC206. One possi-

bility is that the effect of restrained water diffusion by the densified glass phase was stronger than

that of increased dissolution of iodine phase. Another possibility is that the thermodynamic equilib-

rium for the hydrolysis of Bi5O7I and BiOI has not yet been reached. In other words, iodine dissolu-

tion from Bi5O7I might be higher than that from BiOI if hydrolysis of Bi5O7I is kinetically favored

and the current data only show the leaching behavior at the intermediate stage. Krumhansl and

Nenoff performed leaching study on various bismuth oxyiodides and their tentative conclusion was

that BiOI was a more appropriate waste phase than Bi5O7I due to lower solubility [47]. Because our

leaching study shows only a limited aspect of chemical durability in a short period, a more compre-

hensive study is needed to acquire better understanding of the leaching behavior.

Leaching rates are also presented with respect to the waste loading ratios in the LGC1 series

(Fig. 5-8(b)). Dissolution of matrix elements such as Bi, Zn, and B was not affected by the waste

fraction. However, it seems that there is some correlation between the waste fraction and the leach-

ing rates of I and Si. Increased leaching rates of I and Si at high waste fraction (i.e., LGC119) are

most likely to be due to evenly distributed surface pores of 0.1-0.3 μm shown in Fig. 5-4(c), through

which water molecules could readily diffuse into iodine phases. This suggests that waste fraction

should be limited not to deteriorate chemical durability of the glass waste forms. It is not clear why

LGC113 displays less iodine leaching rate. It is speculated that the amount of less soluble iodine

phase is relatively large with LGC113.

Typical anions found in common groundwater are Cl-, HCO3-, SO42-, and F- [47,141]. These

105
groundwater anions could affect the iodine behavior in aqueous solutions through anion exchange

reactions [41,43]. Fig. 5-9 shows the leaching rates of LGC106 obtained by the PCT tests using var-

ious solutions. Compared to the leaching rate of I (7.8×10-3 g/m2∙day) in DIW, the release of I in-

creased in anion containing solutions. This suggests that these anions are involved with anion ex-

change reactions with iodide (I-), which might have enhanced iodine leaching from bismuth

oxyiodides. The result shows that the effect of CO32- is higher than that of Cl-, in accordance with

the literature data [142]: CO32- has higher anion exchange preference than Cl-. The anion exchange

tendency of sulfite is known to be similar to that of chloride [47], which is in agreement with our

result. Although there is no data on anion exchange preference for fluoride (F -), this study suggests

that the fluorine effect on iodine release is less than that of other anions such as chlorine, carbonate

or sulfite.

Thermodynamic analysis also provides some insights on the potential waste forms composed

of bismuth oxyiodide. Susceptibility to chloride reaction is quantified by equilibrium constants in

the following reactions [47]:

BiOI + Cl- ↔ BiOCl + I-, K1 = [Cl-]/[I-] = 10-1.02 (5-9)

2Bi5O7I + 5Cl- + 2H2O ↔ 5Bi2O2(OH)Cl + 2I- +3OH-, K2 = [Cl-]5/[I-]2[OH-]3 = 1014.3 (5-10)

The value of K1 in Eq. (5-9) indicates that I- concentration will be 10 times higher than Cl-

concentration at the equilibrium condition. In this regard, the comparison between K 1 and K2 sug-

gests that BiOI is much more susceptible to chloride reaction than Bi 5O7I by ~15 orders of magni-

tude. Likewise, the effect of carbonate could be quantitatively evaluated using the following [43]:

0.8Bi5O7I + HCO3- +0.6H2O ↔ (BiO)4(OH)2(CO3) + 0.2OH- + 0.8I-;

K3 = [HCO3-]/[I-]0.8[OH-]0.2 = 10-1.58 (5-11)

The significantly low K3 compared to K2 means that iodine release from Bi5O7I is much

more significant in the HCO3- containing solutions than the Cl- containing solutions. To summarize,

Bi5O7I is advantageous over BiOI in the groundwater environment where chloride is a dominant

anion. However, iodine leaching from Bi5O7I is expected to be significantly increased when

106
groundwater contains high concentration of carbonate.

Fig. 5-8. Comparison of leaching rates obtained from the results of PCT-A test in different

samples: (a) LGC106 and LGC206; (b) LGC106, LGC113, and LGC119.

107
 Fig. 5-9. Iodine leaching rates from LGC106 when deionized water (DIW), 0.005 M solu-

tions of NaCl, Na2CO3, Na2SO3, and NaF were used as leachant (leaching solution), respectively.

108
 5.3.3 Implications of this study

Fabrication of waste form to immobilize radioactive I (129I) is important for 129I management

for efficient capture and long-term geologic isolation. Considering the potential hazards of iodine

due to its high solubility and mobility in groundwater, it is required to stabilize iodine by preparing

a phase with low solubility. In this respect, bismuth oxyiodides were studied as a candidate waste

phase [41,43,47]. In our previous study, a new sorbent composed of bismuth was developed and the

capture efficiency for gaseous iodine was studied [107]. Successive work studied Bi-embedded

SBA-15 mesoporous silica that improved bismuth utilization for iodine capture by using a substrate

with high surface areas [128]. A preliminary study on chemical durability also suggested that iodine

incorporated in Bi-embedded SBA-15 could be stabilized to a less soluble phase through a thermal

process.

This study addresses fabrication and characterization of waste forms for Bi-embedded SBA-

15. One of the challenging issues in the fabrication of iodine waste forms is to minimize iodine vo-

latilization during heat-treatment. Lowering process temperature is necessary to minimize iodine

loss. Accordingly, use of low-temperature sintering glasses was examined in this study. However,

iodine volatilization during the sintering process could not be controlled. The iodine volatility

showed large fluctuations among different samples. Results also suggested that adjustment of glass

compositions and additive fractions could dramatically diminish iodine volatilization. Regarding the

iodine volatilized from the process, off-gas trapping system to re-capture volatilizing iodine ought

to be prepared in actual applications of waste form fabrication, given that the complete exclusion of

off-gas is impracticable. Utilization of specially designed sealed vessels to contain pelletized sam-

ples might also decrease iodine evolution through the elevation of the system pressure within the

vessel [133].

The reported mass ratios of iodine in typical glass waste forms are significantly low because

iodine is highly immiscible with glassy materials [131–133]. In this regard, the glass composite

waste form proposed in this study is a reasonable option for iodine stabilization: crystalline iodine

compounds could be readily dispersed into a vitreous phase, which improves iodine loading in the

waste form. Encapsulation of stable iodine phase within glassy network may also be advantageous

to increase chemical durability compared to dissolution of iodine into glassy phase. In this study, the

observed low leaching rates of iodine in the range of 10-3-10-2 g/m2∙day may be due to incorporation

109
of stable iodine phases into low-temperature sintering glasses. It is expected that development of a

more durable waste forms could be possible through process optimization. However, a more com-

prehensive leaching study covering extended testing periods is needed as the PCT leaching test per-

formed in this study only revealed the initial leaching behavior of our waste forms. It is also noted

that susceptibility to particular groundwater anions might restrict universal application of bismuth

oxyiodides as final iodine phases. It is also necessary to investigate the iodine behavior in leaching

solutions with various pH and redox potentials to obtain comprehensive understanding on the waste

forms in the groundwater environment.

110
 Chapter 6. Conclusions of This Dissertation

Bismuth-based adsorbents were synthesized from Bi(NO3)3∙5H2O and PVA as a Bi precursor

and sacrificial template, respectively. The characterization of the reaction products revealed that the

ratio of the reaction products was related to the pore volume of the samples. The iodine trapping

capacity demonstrated that the capacities of the as-synthesized samples were greater than those of

AgX beads and Bi powder. The high removal efficiency of the as-synthesized samples is believed to

be due to the high thermodynamic stability of the reaction products. Because of their high perfor-
129
mance and low cost, bismuth-based adsorbents are expected to be utilized as adsorbents of I in

off-gas as an alternative to silver-loaded zeolites.

Efficient capture and stabilization of iodine gas was demonstrated with the bismuth-

embedded SBA-15. Bismuth was readily incorporated into the surfaces of SBA-15 that was modi-

fied with thiol-groups. The as-synthesized sorbents could effectively capture iodine gas with the

maximal loading capacity of 540 mg-I/g-sorbent, which was attributed to the strong reaction ten-

dency of bismuth sulfide with iodine gas, as well as high surface area and porosity of SBA-15. The

large pores within SBA-15 minimized physical adsorption of iodine, enabling chemical binding to

be the main capturing mechanism. Furthermore, it was shown that the iodine inside the bismuth-

embedded SBA-15 could be stabilized with a facile post-sorption process, suggesting that the newly
129
developed sorbent have the potential for stable iodine capture as well as long-term disposal of I.

Given the environmentally benign character and low price of bismuth, industrial application of the

bismuth-embedded SBA-15 appears feasible.

Glass composite waste forms were studied to stabilize iodine confined in Bi-embedded

SBA-15. Low-temperature sintering glasses and Bi2O3 were used as binders and a stabilizing addi-

tive, respectively. During the sintering process, BiI3, which is the major iodine phase present in Bi-

embedded SBA-15, was effectively transformed to more chemically durable Bi 5O7I and BiOI. Io-

dine losses observed in different samples were significantly fluctuated, suggesting that glass compo-

sitions and the mass fraction of Bi2O3 affect iodine volatility. Elemental leaching rates revealed by

the PCT test indicated that the glass composed of Bi-Zn-B was more favorable than the one com-

posed of Bi-Zn-Si-Al because iodine phase could be strongly encapsulated by the densified matrix.

111
Groundwater anions such as chloride, carbonate, sulfite, and fluoride generally increased iodine

leaching rate by anion exchange mechanisms. Among these anions, the anion exchange preference

for carbonate was the highest: the iodine leaching rate was ~3 orders of magnitude higher than that

of the deionized water case. Nevertheless, the leaching rates of iodine measured in the present study

ranged 10-3-10-2 g/m2∙day, which is quite satisfactory considering the rigorous conditions of the PCT

test. This dissertation study shows the possibility of using glass composite waste form for iodine

through the confinement of stabilized iodine phase in Bi-embedded SBA-15.

112
 References

[1] Gao, "Nuclear Fuel Cycle Options", GAO-12-70, United States Government Accountability
Office, 2011.

[2] P. Lind, W. Langsteger, M. Molnar, Thyroid. 8 (1998) 1179-2109.

[3] D.O. Campbell, A.P. Malinauskas, W.R. Stratton, Nucl. Technol. 53 (1981) 111-119.

[4] E.H.P. Cordfunke, R.J.M. Cornings, J. Nucl. Mater. 152 (1988) 301-309.

[5] U.S. EPA. 40 CFR 190, Environmental Protection Agency: Washington, D.C. (2012).

[6] R.T. Jubin, N.R. Soelberg, D.M. Strachan, G. Ilas, FCRD-SWF-2012-000091, INL/EXT-12-
25410, Idaho National Laboratory (2012).

[7] R.T. Jubin, "Spent Fuel Reprocessing", Oak Ridge National Laboratory, 2009.

[8] D.W. Holladay, ORNL/TM-6350, Oak Ridge National Laboratory (1979).

[9] IAEA, "Treatment, Conditioning, and Disposal of I-129", TR-276, International Atomic
Energy Agency, Vienna, 1987.

[10] D.R. Haefner, T.J. Tranter, INL/EXT-07-12299, Idaho National Laborary (2007).

[11] T.R. Thomas, B.A. Staples, L.P. Murphy, J.T. Nichols, ICP-1119, Idaho National Laborary
(1977).

[12] D.T. Pence, F.A. Duce, W.J. Maeck, ICP-1006, Idaho National Laborary (1972).

[13] K.W. Chapman, D.F. Sava, G.J. Halder, P.J. Chupas, T.M. Nenoff, J. Am. Chem. Soc. 133
(2011) 18583-18585.

[14] T.M. Nenoff, M. A. Rodriguez, N.R. Soelberg, K.W. Chapman, Microporous Mesoporous

113
 Mater. 200 (2014) 297-303.

[15] D.M. Strachan, J.Chun, J.Matyas, W.C. Lepry, B.J. Riley, J.V. Ryan, P.K. Thallapally,
FCRD-SWF-2011-000378, PNNL-20807, Pacific Northwest National Laboratory (2011).

[16] J. Matyas, G.E. Fryxell, B.J. Busche, K. Wallace, L.S. Fifield, Proc. Ceram. Eng. Sci.:
Ceram. Mater. Energy Appl. 32 (2011) 23.

[17] D.F. Sava, T.J. Garino, T.M. Nenoff, Ind. Eng. Chem. Res. 51 (2012) 614-620.

[18] C. Falaise, C. Volkringer, J. Facqueur, T. Bousquet, L. Gasnot, T. Loiseau, Chem. Comm.

49 (2013) 10320-10322.

[19] B.J. Riley, J. Chun, J. V. Ryan, J. Matyáš, X.S. Li, D.W. Matson, S.K. Sundaram, D.M.
Strachan, J.D. Vienna, RSC Adv. 1 (2011) 1704-1715.

[20] B.J. Riley, J. Chun, W. Um, W.C. Lepry, J. Matyas, M.J. Olszta, X. Li, K.
Polychronopoulou, M.G. Kanatzidis, Environ. Sci. Technol. 47 (2013) 7540-7547.

[21] B.J. Riley, D.A. Pierce, J. Chun, J. Matya, W.C. Lepry, T.G. Garn, J.D. Law, M.G.
Kanatzidis, Environ. Sci. Technol. 48 (2014) 5832-5839.

[22] L.L. Burger, R.D. Scheele, K.D. Wiemers, PNL-4045, Pacific Northwest Laboratory, 1981.

[23] M.J. den Exter, 21094/03.61576 FAI/ME/JY, Nuclear Research and Consultancy Group,
2004.

[24] K.J. Schneider, A.M. Platt (Eds.), BLWL-1900, Pacific Northwest Laboratory, 1974.

[25] R.D. von Dincklage, Atomkernenerg. Kerntech. 38 (1981) 225-228.

[26] L. Werme, P. Sellin, N. Kjellbert, SKB TR 92-26, Swedish Nuclear Fuel and Waste
Management Corporation, 1992.

[27] N-Y. Ko, J. Jeong, K-S. Kim, J. of Nucl. Fuel Cycle and Waste Technol. 12 (2014) 191-198.

114
[28] R. Fuge, C.C. Johnson, Environ. Geochem. Hlth. 8 (1986) 31-54.

[29] M. Sazarashi, Y. Ikeda, R. Seki, H. Yoshikawa, J. Nucl. Sci. Technol. 31 (1994) 620-622.

[30] T.J. Garino, T.M. Nenoff, J.L. Krumhansl, D.X. Rademacher, J. Am. Ceram. Soc. 94 (2011)
2412-2419.

[31] T. Sakuragi, T. Nishimura, Y. Nasu, H. Asano, K. Hoshino, K. Iino, Proc. Mater. Res. Soc.
Symp. 1107 (2008) 279.

[32] Y. Watanabe, T. Ikoma, H. Yamada, Y. Suetsugu, Y. Komatsu, G.W. Stevens, Y. Moriyoshi,

J. Tanaka, ACS Appl. Mater. Interfaces 1 (2009) 1579-1584.

[33] E. Maddrell, A. Gandy, M. Stennett, J. Nucl. Mater. 449 (2014) 168-172.

[34] T. Nakazawa, H. Kato, K. Okada, S. Ueta, M. Mihara, Proc. Mat. Res. Soc. Symp. 663
(2001) 1-8.

[35] D.M. Strachan, H. Babad, Int. Symp. Ceram. Nucl. Waste. Manage. 11 (1979) 349-353.

[36] G.P. Sheppard, J.A. Hriljac, E.R. Maddrell, N.C. Hyatt, Proc. Mat. Res. Soc. Symp. 932
(2006) 775-782.

[37] M. Yim, TR-110096, Electric Power Research Institute (1998).

[38] R.T. Jubin, R.M. Counce, "Retention of iodine and nitrogen oxides in reprocessing plants",
in: W.R.A. Goossens, G.G. Eichholz, D.W. Tedder (Eds.), "Treatment of Gaseous Effluents
at Nuclear Facilities", Harwood Academic Publishers, London, 1991, pp. 103-178.

[39] U.S. EPA. 40 CFR 261, Environmental Protection Agency: Washington, D.C. (2012).

[40] P. Taylor, V.J. Lopata, TR-350, Atomic Energy of Canada Limited, 1985.

[41] P. Taylor, V.J. Lopata, D.D. Wood, H. Yacyshyn, ASTM STP 1033, American Society for
Testing and Materials, Philadelphia, 1989.

115
[42] P. Taylor, D.D. Wood, V.J. Lopata, AECL-9554, Atomic Energy of Canada Limited, 1988.

[43] P. Taylor, V.J. Lopata, Can. J. Chem. 64 (1986) 290-294.

[44] P. Taylor, V.J. Lopata, Can. J. Chem. 66 (1988) 2664-2670.

[45] P. Taylor, AECL-10163, Atomic Energy of Canada Limited, 1990.

[46] T. Nenoff, J.L. Krumhansl, A. Rajan, Mater. Res. Soc. Symp. Proc. 1043 (2008) 1043-T12-
05.

[47] J.L. Krumhansl, T.M. Nenoff, Appl. Geochemistry 26 (2011) 57-64.

[48] X. Hou, V. Hansen, A. Aldahan, G. Possnert, O.C. Lind, G. Lujaniene, Anal. Chim. Acta
632 (2009) 181-196.

[49] L.E. Trevorrow, G.F. Vandegrift, V.M. Kolba, M.J. Steindler, ANL-83-57, Argonne
National Laboratory, 1983.

[50] A. Chesney, J.P. Goumondy, P. Miguel, A. Lesure, "Radioactive Effluents from Nuclear
Fuel Reprocessing Plants", Proc. CEC SEM., (1977) 447.

[51] W. Hebel, G. Cottone (Eds.), "Management Modes for Iodine-129", EUR 7953, Harwood
Academic Publishers, 1982.

[52] L.L. Burger, R.E. Burns, PNL-3186, Pacific Northwest Laboratory, 1979.

[53] R.T. Jubin, ORNL/TM -6607, Oak Ridge National Laboraty, 1979.

[54] R.T. Jubin, ORNL/TM-10477, Oak Ridge National Laboratory, 1988.

[55] C.B. Shivayogimath, M.N. Hiremath, B. Lokeshappa, Int. J. Eng. Sci. Innov. Tech. 3 (2014)
201-207.

[56] V.M. Efremenkov, IAEA Bulletin, 4 (1989) 37-42.

[57] T.R. Thomas, B.A. Staples, L.P. Murphy, J.T. Nichols, ICP-1119, Idaho National

116
 Laboratory, 1977.

[58] D.T. Pence, F.A. Duce, W.J. Maeck, ICP-1022, 1973. Idaho National Laboratory, 1973.

[59] W.D. Burch, M.J. Feldman, W.E. Unger, B.L. Vondra, ORNL/TM-5556, Oak Ridge
National Laboratory, 1976.

[60] W.J. Maeck, D.T. Pence, Proc. 11th AEC Air Cleaning Conference CONF-700816 (1970)
607.

[61] D.T. Pence, F.A. Duce, W.J. Maeck, Proc. 12th AEC Air Cleaning Conference CONF-
720823 (1972) 417.

[62] R.D. Ackley, Z. Combs, ORNL-TM-4227, Oak Ridge National Laboratory, 1973.

[63] C.M. Slansky, B.C. Musgrave, B.R. Dickey, K.L. Rohde, ICP-1122, Idaho National
Laboratory, 1977.

[64] W.D. Burch, M.J. Feldman, W.E. Unger, B.L. Vondra, ORNL/TM-5463, Oak Ridge
National Laboratory, 1976.

[65] A. Roine, "Outokumpu HSC chemistry for windows", Pori, Finland, 2002.

[66] For the solubility data, I referred to Wikipedia at World Wide Web.

[67] N. Soelberg, T. Watson, INL/EXT-12-27075, Idaho National Laboratory, 2012.

[68] N. Soelberg, T. Watson, INL/EXT-11-23191, Idaho National Laboratory, 2011.

[69] D.R. Haefner, T.L. Watson, INL/EXT-10-19657, Idaho National Laboratory, 2010.

[70] G.P. Sheppard, J.A. Hriljac, E.R. Maddrell, N.C. Hyatt, Mat. Res. Soc. Proc. 932 (2006)
775-782.

[71] N.C. Hyatt, J.A. Hriljac, A. Choudhry, L. Malpass, G. Sheppard, E.R. Maddrell, Mat. Res.
Soc. Proc. 807 (2004) 359-364.

117
[72] T. Nakazawa, H. Kato, K. Okada, S. Ueta, M. Mihara. Mat. Res. Soc. Symp. 663 (2001) 51-
57.

[73] D.M. Strachan, H. Babad, CONF-790420-21, International Symposium on Ceramics in

Nuclear Waste Management, 1979.

[74] J.G. Wilhelm, J. Furrer, 248, CEC Seminar on Radioactive Effluents from Nuclear Fuel
Reprocessing Plants, 1977.

[75] J.G. Wilhelm, IAEA-SR-72/14, Proc. of' the Seminar on the Testing and Operation of Off-
Gas Cleaning Systems at Nuclear Facilities, 1983.

[76] J.G. Wilhelm, J. Furrer, E. Schultes, CONF-760822, 14th ERDA Air Cleaning Conference,
1976.

[77] J.G. Wilhelm, H. Schuttelkopf, CONF-720823, Proc. 12th AEC .4ir Cleaning Conference,
1972.

[78] J.G. Wilhelm, H. Schuttelkopf, CONF-700816, Proc. 11th AEC Air Cleaning Conference,
1970.

[79] T. Fukasawa, K. Funabashi, Y. Kondo, CONF-960715, Proc. 24th DOE/NRC Nuclear Air
Cleaning and Treatment Conference, 1996.

[80] N. Soelberg, T. Watson. INL/EXT-12-26522, Idaho National Laboratory, 2012.

[81] R.G. Parr, R.G. Pearson, J. Am. Chem. Soc. 105 (1983) 7512-7516.

[82] R.G. Pearson, J. Am. Chem. Soc. 85 (1963) 3533-3539.

[83] D.M. Strachan, J. Chun, C.R. Henager, J. Matyas, B.J. Riley, J.V. Ryan, P.K. Thallapally,
PNNL-20007, Pacific Northwest National Laboratory, 2010.

[84] J. Matyas, R.K. Engler, PNNL-22874, Pacific Northwest National Laboratory, 2013.

[85] H. Li, M. Eddaoudi, M. O'Keeffe, O.M. Yaghi, Nature 402 (1999) 276-279.

118
[86] S. Ma, H.-C. Zhou, Chem. Comm. 46 (2010) 44-53.

[87] P. Taylor, V.J. Lopata, H. Davidson, H. Yacyshyn, RC-437, Atomic Energy of Canada
Limited, 1990.

[88] R.A. Robie, B.S. Hemingway, J.R. Fisher, "Thermodynamic properties of minerals and
related substances at 298.15 K and 1 bar (105 Pascals) pressure and at higher temperatures",
Bulletin 1452, U. S. Geological Survey, Washington, DC, 1979.

[89] C.F. Baes, R.E. Mesmer, "The hydrolysis of cations", Wiley, New York, 1976.

[90] D.D. Wagman, W.H. Evans, V.B. Parker, R.H. Schumm, J. Halow, S.M. Bailey, K.L.
Churney, R.L. Nuttall, "The NBS tables of chemical thermodynamic properties. Selected
values for inorganic and C1 and C2 organic substances in SI units", American Chemical
Society and American Institute of Physics for National Bureau of Standards, 1982.

[91] P. Fritz, S.K. Frape, Chemical Geology 36 (1982) 179-190.

[92] S.K. Frape, P. Fritz, R.H. McNutt, Geochim. Cosmochim. Acta. 48 (1984) 1617-1627.

[93] A.J. Eve, D.N. Hume, Inorg. Chem. 3 (1964) 276-278.

[94] A. Rulmont, Revue de Chimie Minerale. 14 (1977) 277.

[95] E. Marti, H.R. Oswald, H.G. Wiedermann (Eds.), "Thermoanalytical studies on antimony
and bismuth chalcogenide halides", Birkhauser Verlag, Basel, 1979.

[96] J.L. Krumhansl, T.M. Nenoff, US 8,383,021 B1, United States Patent, 2013.

[97] O.D. Velev, E.W. Kaler, Adv. Mater. 12 (2000) 531-534.

[98] L. Ai, H. Yue, J. Jiang, Nanoscale 4 (2012) 5401-5408.

[99] K.K. Han, Y. Zhou, W.G. Lin, J.H. Zhu, Micropor. Mesopor. Mater. 169 (2013) 112-119.

[100] Y. Liu, J. Goebl, Y. Yin, Chem. Soc. Rev. 42 (2013) 2610-2653.

119
[101] A. Stein, B.E. Wilson, S.G. Rudisill, Chem. Soc. Rev. 42 (2013) 2763-2803.

[102] Y.K. Kim, K.P. Rajesh, J.-S. Yu, J. Hazard. Mater. 260 (2013) 350-357.

[103] B.R. Westphal, J.J. Park, J.M. Shin, G.I. Park, K.J. Bateman, D.L. Wahlquist, Sep. Sci.
Technol. 43 (2008) 2695-2708.

[104] L. Ye, L. Tian, T. Peng, L. Zan, J. Mater. Chem. 21 (2011) 12479-12484.

[105] C. Yu, C. Fan, J.C. Yu, W. Zhou, K. Yang, Mat. Res. Bull. 46 (2011) 140-146.

[106] L.A. Klinkova, V.I. Nikolaichik, N.V. Barkovskii, V.K. Fedotov, Russ. J. Inorg. Chem. 52
(2007) 1822-1829.

[107] J.H. Yang, J.M. Shin, J.J. Park, G. Il Park, M.S. Yim, J. Nucl. Mater. 457 (2015) 1-8.

[108] D. Zhao, J. Feng, Q. Huo, N. Melosh, G. Fredrickson, B. Chmelka, G. Stucky, Science 279
(1998) 548-552.

[109] T. Kang, Y. Park, J. Yi, Ind. Eng. Chem. Res. 43 (2004) 1478-1484.

[110] A. Bibby, L. Mercier, Chem. Mater. 14 (2002) 1591-1597.

[111] H. Zheng, D. Hu, L. Zhang, C. Ma, T. Rufford, Miner. Eng. 35 (2012) 20-26.

[112] M.B. Haddada, J. Blanchard, S. Casale, J.-M. Krafft, A. Vallée, C. Méthivier, S. Boujday,
Gold Bull. 46 (2013) 335-341.

[113] D. Pérez-Quintanilla, I. Del Hierro, M. Fajardo, I. Sierra, Microporous Mesoporous Mater.

89 (2006) 58-68.

[114] J.A. Melero, R.V. Grieken, G. Morales, Chem. Eng. 106 (2006) 3790-3812.

[115] D. Margolese, J.A. Melero, S.C. Christiansen, B.F. Chmelka, G.D. Stucky, Chem. Mater. 12
(2000) 2448-2459.

[116] "Standard Test Methods for Determining Chemical Durability of Nuclear, Hazardous, and

120
 Mixed Waste Glasses and Multiphase Glass Ceramics: The Product Consistency Test
(PCT)", C1285-14; American Society for Testing and Materials: Pennsylvania (2014).

[117] S. Brunauer, P.H. Emmett, E. Teller, J. Am. Chem. Soc. 60 (1938) 309-319.

[118] E.P. Barrett, L.G. Joyner, P.P. Halenda, J. Am. Chem. Soc. 73 (1951) 373-380.

[119] R. Ryoo, C.H. Ko, M. Kruk, V. Antochshuk, M. Jaroniec, J. Phys. Chem. B 104 (2000)
11465-11471.

[120] K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquérol, T.
Siemieniewska, Pure Appl. Chem. 54 (1982) 2201-2218.

[121] D.F. Sava, K.W. Chapman, M.A. Rodriguez, J.A. Greathouse, P.S. Crozier, H. Zhao, P.J.
Chupas, T.M. Nenoff, Chem. Mater. 25 (2013) 2591-2596.

[122] J.T. Hughes, D.F. Sava, T.M. Nenoff, A. Navrotsky, J. Am. Chem. Soc. 135 (2013) 16256-
16259.

[123] N.R. Soelberg, T.G. Garn, M.R. Greenhalgh, J.D. Law, R. Jubin, D.M. Strachan, P.K.
Thallapally, Sci. Technol. Nucl. Install. 2013 (2013) 1-12.

[124] T.M. Nenoff, P.V. Brady, T.J. Garino, C.D. Mowry, FCRD-SWF-2012-000172,
SAND2012-6892C, Sandia National Laboratories (2012).

[125] J.J. Chiu, D.J. Pine, S.T. Bishop, B.F. Chmelka, J. Catal. 221 (2004) 400-412.

[126] F. Kleitz, S.H. Choi, R. Ryoo, Chem. Commun. 17 (2003) 2136-2137.

[127] K. Flodstro, V. Alfredsson, N. Kallrot, J. Am. Chem. Soc. 125 (2003) 4402-4403.

[128] J.H. Yang, Y.-J. Cho, J.M. Shin, M.-S. Yim, J. Nucl. Mater. 465 (2015) 556-564.

[129] W.E. Lee, M.I. Ojovan, M.C. Stennett, N.C. Hyatt, Adv. Appl. Ceram. 105 (2006) 3-12.

[130] S. Gin, A. Abdelouas, L.J. Criscenti, W.L. Ebert, K. Ferrand, T. Geisler, M.T. Harrison, Y.
Inagaki, S. Mitsui, K.T. Mueller, J.C. Marra, C.G. Pantano, E.M. Pierce, J. V. Ryan, J.M.

121
 Schofield, C.I. Steefel, J.D. Vienna, Mater. Today 16 (2013) 243-248.

[131] M.I. Ojovan, W.E. Lee, An Introduction to Nuclear Waste Immobilization, Elsevier, Oxford,
2005.

[132] P. Hrma, PNNL-19361, Pacific Northwest National Laboratory (2010).

[133] B.J. Riley, M.J. Schweiger, D. Kim, W.W. Lukens, B.D. Williams, C. Iovin, C.P. Rodriguez,
N.R. Overman, M.E. Bowden, D.R. Dixon, J. V Crum, J.S. Mccloy, A.A. Kruger, J. Nucl.
Mater. 452 (2014) 178-188.

[134] T.M. Nenoff, P.V. Brady, C.D. Mowry, T.J. Garino, FCRD-SWF-2014-000287,
SAND2014-17380R, Sandia National Laboratories (2014).

[135] T.J. Garino, T.M. Nenoff, J.L. Krumhansl, N.W. Ockwig, "Low Temperature Glass Waste
Forms for Sequestering Radioactive Iodine", U.S. Patent Application SD11202,
#12/727,353, filed March 19, 2010.

[136] W.L. Ebert, ANL-94/34, Argonne National Laboratory (1995).

[137] J. Cao, X. Li, H. Lin, B. Xu, B. Luo, S. Chen, Mater. Lett. 76 (2012) 181-183.

[138] J.D. Vienna, J.V. Ryan, S. Gin, Y. Inagaki, Int. J. Appl. Glass. Sci. 294 (2013) 283-294.

[139] H. Suzuki, N. Komatsu, T. Ogawa, T. Murafuji, T. Ikegami, Y. Matano, Organobismuth

Chemistry, Elsevier, 2001.

[140] S. Gin, P. Jollivet, M. Fournier, F. Angeli, P. Frugier, T. Charpentier, Nat. Commun. 6:6360
(2015).

[141] T. Rango, J. Kravchenko, B. Atlaw, P.G. McCornick, M. Jeuland, B. Merola, A. Vengosh,

Env. Int. 43 (2012) 37-47.

[142] R.P. Bontchev, F. Bonhomme, J.L. Krumhansl, R.C. Moore, 229 ACS National Meeting,
San Diego, CA, March, 2005.

122
 Summary (in Korean)

비스무스를 담지한 메조기공 실리카를 이용한 방사성 요오드 기체의

흡착

핵분열반응으로 생성되는 방사성 요오드 (129I)는 사용후핵연료를 재처리하는

과정에서 기체 상태로 휘발한다. 방사성 요오드는 1.57 × 107 년의 매우 긴 반감기를
가지며 지하수를 따라 용이하게 움직일 수 있는 특성 때문에 엄격한 관리를 필요로
한다. 사용후핵연료에서 휘발하는 방사성 요오드 기체를 흡착하기 위해 많은 연구가
이루어져 왔으며, 현재 은 교환된 제올라이트 (AgX 혹은 AgZ)가 널리 사용되고 있다.
129
그러나 I 의 장기간 처분을 고려할 때 제올라이트 기공 속에 물리적으로 붙잡힌
요오드는 심각한 문제가 될 수 있다. 또한 은의 비싼 가격과 높은 독성으로 인해 은을
기반으로 한 흡착제는 궁극적인 해답이 될 수 없다.
제 3 장에서는 사용후핵연료 재처리 과정에서 발생하는 방사성 요오드를
흡착하기 위해 본 학위논문 연구를 통해 새롭게 개발한 비스무스 기반의 흡착제에
대해 다루었다. 이 흡착제는 폴리비닐알코올 (PVA)를 주형으로 하여 제조한 다공성
물질이다. 이 다공성 흡착제를 사용하여 요오드를 흡착시킨 결과, 상용 제품으로
판매되는 은 교환 제올라이트 (AgX)에 비해 1.9 배 정도 높은 요오드 흡착 성능이
나타남을 확인하였다. 이는 요오드가 포집된 후 비스무스와 반응하여 생성되는
화합물이 열역학적으로 안정하기 때문이다. 또한 시료의 내부 기공 부피가 반응
생성물의 화학적 형태와 밀접한 연관이 있음을 확인하였다.
제 4 장에서는 SBA-15 메조기공 실리카를 지지체로 이용한 비스무스를 담지한
메조기공 실리카의 개발 및 이를 이용한 요오드 기체의 포집과 저장에 관한 연구를
수록하였다. SBA-15 표면에 비스무스가 잘 달라붙을 수 있도록 SBA-15 의 표면을
띠올 (-SH)기를 이용하여 개질하였고, 개질된 표면에 비스무스를 흡착시켰다.
비스무스는 Bi-S 결합을 형성하며 SBA-15 표면에 흡착되었고, 열처리를 하게 되면
Bi2S3 의 형태로 바뀌는 것을 알 수 있었다. 비스무스를 담지한 SBA-15 를 이용하여
요오드를 흡착시킨 결과, 흡착제 단위 질량당 540 mg 의 요오드가 흡착되는 우수한
흡착성능을 확인할 수 있었다. 이는 요오드가 비스무스와 반응하여 열역학적으로

123
안정한 BiI3 를 형성할 뿐 아니라 지지체로 사용한 SBA-1 의 표면적 및 기공도가
매우 높기 때문이다. 게다가 AgX 에 비해 SBA-15 의 상대적으로 큰 기공으로 인해
요오드의 물리 흡착을 효과적으로 배제시킨 채 화학흡착만으로 요오드를 흡착시킬 수
있었다. 다음 단계에서는 요오드를 흡착시킨 후 흡착된 요오드를 화학적으로 안정된
물질로 만들기 위해 후속 공정을 개발하였고, 후속 공정을 통해 흡착된 요오드의 상을
BiI3 로부터 화학적으로 안정된 Bi5O7I 로 전환시킬 수 있었다. 이 결과를 볼 때
비스무스가 담지된 SBA-15 를 이용하면 방사성 요오드를 효율적으로 흡착할 수 있을
뿐만 아니라 안정하게 저장하는 것도 가능할 것으로 판단된다.
제 5 장에서는 비스무스를 담지한 SBA-15 에 요오드를 흡착한 뒤 이를 안정한
형태로 저장하기 위한 고화체 제조와 관련된 연구를 다루었다. 요오드가 흡착된
흡착제에 고화매질로서 저온 소결유리와 안정화 물질로서 Bi2O3 분말을 첨가한 뒤
성형과 소결 과정을 거쳐 glass composite 물질을 제조하였다. 소결과정에서 발생하는
요오드의 휘발 정도는 첨가된 Bi2O3 의 비율 및 유리 조성에 따라 크게 영향을 받았다.
그리고 비스무스를 담지한 SBA-15 에 포함된 주된 요오드 상인 BiI3 는 고화체
내에서 Bi5O7I 와 BiOI 의 혼합상으로 존재하는 것을 확인하였다. Glass composite
물질에 대한 침출특성을 조사한 결과, 요오드의 초기 침출률은 10-3-10-2 g/m2∙ day
정도로 양호하게 나타났는데 이는 안정화된 요오드 상이 유리 구조에 둘러싸여
요오드의 침출이 효과적으로 억제되었기 때문으로 판단되었다. 또한 지하수에
존재하는 음이온들 (Cl-, CO32-, SO32-, F-)이 요오드의 침출에 미치는 영향을 보고자
위의 음이온들이 첨가된 용액을 이용한 침출시험을 진행하였으며, 이 경우 요오드와
음이온과의 교환반응을 통해 요오드의 침출률이 증가한다는 것을 확인하였다. 이
학위논문의 연구결과는 비스무스를 담지한 SBA-15 를 이용하여 요오드를 흡착한 뒤
이로부터 glass composite 고화체를 제조한다면 방사성 요오드를 안정적으로 저장할
가능성이 있음을 시사한다.

핵심어: 방사성 요오드 (129I), 비스무스, 비스무스를 담지한 SBA-15, 화학흡착,

안정화, glass composite 고화체

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 Acknowledgement (감사의 글)

3 년 간의 박사과정을 마치고 감사의 글을 쓰게 되는 이 순간이 정말 오게 되다니

감격스럽지 않을 수 없습니다. 먼저 부족한 제가 박사학위를 받을 수 있도록 성심껏
지도해주신 임만성 교수님께 깊이 감사 드립니다. 제가 박사학위 지도교수로서 임만성교수님을
만나게 된 것은 큰 복이었습니다. 뛰어난 실력과 인품을 함께 갖추신 교수님은 학문적인 부분
외에도 여러 면에서 귀감이 되신 분이십니다. 그리고 논문심사를 맡아주신 이건재교수님,
조성오교수님, 윤종일교수님, 그리고 화학과의 유룡교수님께도 감사 드립니다. 학위논문심사
과정에서 주셨던 날카로운 지적들과 귀중한 조언들을 통해 연구자로서 여전히 부족한 저를 알
수 있었고, 깊이 있고 수준 높은 연구를 위해 어떤 점을 보완해야 하는지 배울 수 있었습니다.
원자력연구원에 재직하는 시간제 학생으로서 직장업무와 병행하는 학업의 어려움을
공감해주시고 최대한의 배려를 해주신 신진명박사님께 깊은 감사를 드립니다. 신진명박사님의
격려와 지지 덕분에 어려웠던 박사과정에서 위로를 얻을 때가 한 두 번이 아니었습니다.
신박사님의 직장과 가정생활에서 언제나 좋은 일만 함께 하시길 기원합니다.
7 년 간의 연구원 생활을 통해 만난 직장동료들께도 감사한 마음을 전합니다. 처음 직장에
들어와 여러 가지로 미숙한 저를 도와주시고 많은 것을 가르쳐주신 강권호박사님,
직장선배로서 어떤 자세로 업무를 감당해야 하는지 몸소 실천하시는 조용준박사님, 인자하고
이해심 많으시며 제가 힘들 때마다 여러 가지 조언해주신 박장진박사님, 오랜 기간의 연구소
경험을 젊은 연구원들에게 전해주고자 애쓰시는 조광훈선생님, 늘 한결 같은 자세로 최선을
다하시는 이재원박사님, 항상 바른 시각으로 사물과 사람을 바라보고자 하시는 이도연선생님,
언제나 유쾌하시고 분위기를 즐겁게 만들어주시는 이영순선생님, 유머감각이 뛰어나시고
든든한 형님 같으신 김영환박사님, 함께 실험하며 큰 의지가 되어주신 이주호박사님, 나이는
어리지만 배울 점 많은 전상채박사님, 남자다운 듬직함과 섬세함을 함께 지닌 이광연씨, 그리고
방사성폐기물 처리의 최고전문가이신 박환서박사님을 비롯한 폐기물 팀원들… 여러분들은 모두
제 인생의 귀중한 스승이라 생각합니다.
원자력연구원의 밀알회에서 만난 김관현장로님과 김계남집사님을 비롯한 여러 신앙의
선배님들께도 감사합니다. 힘들고 삭막한 직장생활 속에서 밀알회 예배는 때로 가뭄의
단비와도 같은 기쁨을 주었습니다. 또 밀알회를 통해 좋은 친구 윤인호를 만나게 되어
감사합니다.
카이스트 핵안보 및 원자력환경연구실의 학생들에게도 고마운 마음을 전합니다. 시간제
학생인 관계로 많은 시간을 함께 하진 못했지만 3 년 동안 정이 많이 들었습니다. 김찬, 하지민,
서영아, 조석기, 정영은, 김교남, 이한얼, 강성우, 유찬우, 고종욱, 김철민, 주지은, 김효임,
김정환, 이주호, Dr. Irfan, Dr. Aznan, Phuon, Than, Sana, Shuchang, 김미령, 최지은선생님,

125
그리고 캐롤선생님. 모두가 너무나 마음이 따뜻하고 똑똑한 인재들입니다. 박사과정 기간 동안
이런 좋은 분들을 만나서 정말 감사합니다. 랩원들 모두 대학원에 입학할 때 세웠던 목표를 다
이루고 장차 사회에서 중추적 역할을 감당할 수 있기를 기원합니다.
대덕한빛교회의 같은 집교회 식구로서 언제나 저를 위해 기도해주시고 섬겨주시는 한용식
장로님, 강남숙권사님께도 감사 드립니다. 장로님과 권사님의 삶을 통해 예수님을 믿는 자의
바른 신앙이 어떠해야 하는가를 지속적으로 배우고 있습니다. 바쁘고 힘들다는 핑계로 모임을
소홀히 여기기도 했지만 집교회 모임의 교제와 중보기도를 통해 위로와 힘을 얻을 때가
많았습니다. 한없이 부족한 저를 인내해주시고 예수님의 마음으로 사랑해주셔서 감사합니다.
직장생활과 박사과정을 병행하며 바쁘고 힘들다는 핑계로 가장 소중한 가족에게 소홀할
때가 참 많았습니다. 일과 학업에 지쳐서 힘겨워할 때 제 아내는 언제나 가장 큰 위로자였고
또 안식처였습니다. 철없는 남편이 스트레스를 마땅히 해소하지 못해서 애꿎은 아내에게
짜증내고 상처를 많이 주었습니다. 그럼에도 불구하고 3 년 간 큰 싸움 한 번 없이 조용히
지나간 걸 보면 아내가 저를 참으로 많이 받아준 것 같습니다. 세상에서 가장 예쁜 정화야,
고맙고 미안하고 사랑해. 이제 평생에 걸쳐 내가 갚아 나갈게.
사랑하는 부모님과 장인어른, 장모님께도 감사의 마음을 전합니다. 저희 가정을 늘
챙겨주시고 걱정해주시는 양가 부모님들. 제가 부모가 되어보니 부모님의 사랑이 얼마나 귀한
것인가를 조금은 알게 됩니다. 아버지, 엄마, 장인어른, 장모님, 낳아주시고 길러주신 은혜에
감사합니다. 항상 건강하시고 행복하세요. 사랑합니다.
박사과정 중에 얻게 된 나의 귀한 보물 수빈, 은빈아! 건강히 태어나서 이렇게 예쁜
모습으로 자라고 있어서 고맙구나. 이제 아빠가 좀 더 좋은 아빠가 되도록 노력할게. 사랑해.
마지막으로 저를 지으시고 지금까지 선하게 제 삶을 인도하신 하나님께 감사 드립니다.
저는 늘 걱정과 두려움에 휩싸여 있었지만 하나님의 은혜로 박사과정을 무사히 마칠 수
있었습니다. 앞으로의 제 삶도 변함없이 신실하게 인도하실 것을 믿습니다. 모든 영광 하나님께
돌립니다.

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 Curriculum Vitae

Name: Yang, Jae Hwan

Date of Birth: 2 Dec. 1979
Place of Birth: Itaewon-Dong, Yongsan-Gu, Seoul, Korea
Current Address: 109-1305, Hanbit Apt., Aueun-Dong, Yuseong-Gu, Daejeon, Korea

Education

2013.3-2016.2: Ph.D. Radioactive Waste Management, Nuclear and Quantum Engineering, KAIST, Korea
2002.3-2004.8: M.S. Biological Physics, Department of Physics, POSTECH, Korea
1998.3-2002.2: B.S. Physics, POSTECH, Korea

Career

2011.3-Current: Senior Researcher, Korea Atomic Energy Research Institute (KAERI)

2008.12-2011.2: Researcher, Korea Atomic Energy Research Institute (KAERI)
2005.2-2008.1: Weather Forecast Officer (1st lieutenant), Republic of Korea Air Force (ROKAF)
2003.3-2004.8: Research Assistant, Department of Physics, POSTECH, Korea
2002.3-2003.2: Teaching Assistant, Department of Physics, POSTECH, Korea

Publications

J.H. Yang, Y.J. Cho, J.M. Shin, M.S. Yim, “Bismuth-embedded SBA-15 mesoporous silica for radioactive
iodine capture and stable storage” J. Nucl. Mater. 465 (2015) 556-564.
J.H. Yang, J.M. Shin, J.J. Park, G.I. Park, M.S. Yim, “Novel synthesis of bismuth-based adsorbents for the
removal of 129I in off-gas” J. Nucl. Mater. 457 (2015) 1-8.
J.H. Yang, H.S. Park, D.-H. Ahn, M.S. Yim, “Glass composite waste forms for iodine confined in bis-
muth-embedded SBA-15” J. Nucl. Mater. Under review.
J.J. Park, J.M. Shin, J.H. Yang, Y.H. Baek, G.I. Park, “Fabrication and performance of fly ash granule fil-
ter for trapping gaseous cesium” Nukleonika 60(3) (2015) 565-570.

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 J.H. Yang, J.M. Shin, J.J. Park, G.I. Park, “Waste form of silver iodide (AgI) with low temperature sinter-
ing glasses” Sep. Sci. Technol. 49(2) (2014) 298-304.
J.H. Yang, J.M. Shin, C.H. Lee, C.M. Heo, M.K. Jeon, K.H. Kang, “Stabilization of Cs/Re trapping filters
using magnesium phosphate ceramics” J. Radioanal. Nucl. Chem. 295(1) (2013) 211-219.
J.H. Yang, J.M. Shin, J.J. Park, H.S. Park, “I-129 waste form using Bi-Zn-P-oxide glass” Energy procedia
39 (2013) 151-158.

Patents

양재환, 신진명, 박장진, 박근일, “방사성 요오드 기체를 포집하는 다공성 포집재의 제조”,
등록번호 10-1512248, 대한민국.
신진명, 양재환, 박장진, 김영자, 박근일, “방사성 세슘이 포함된 세슘 폐필터 세라믹 잉곳
및 이의 제조방법”, 등록번호 8969646, 미국.
박장진, 신진명, 양재환, 박근일, 백영희, “기체상 테크네튬 포집을 위한 고효율 칼슘필터
제조방법 및 이를 이용한 포집방법”, 등록번호 10-1473585, 대한민국.
신진명, 양재환, 박장진, 김영자, 박근일, “방사성 세슘이 포함된 세슘 폐필터 세라믹 잉곳
및 이의 제조방법”, 등록번호 10-1401789, 대한민국.
신진명, 양재환, 박장진, 김영자, 박근일, “방사성 세슘이 포함된 세슘 폐필터 세라믹 잉곳
및 이의 제조방법”, 등록번호 5668112, 일본.

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