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Adsorption of Gaseous Radioactive Iodine

Using Bismuth-Incorporated Mesoporous Silica
(Ph.D Defense)

Dept. of Nuclear and Quantum Engineering

Jae Hwan Yang
(Supervisor: Man-Sung Yim)
2015. 11. 17 Tue.

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 Outline

 I-129 overview
 Literature review
 Results of the dissertation
 Summary and conclusion
 Outcomes

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 Generation of I-129

 Composition of spent nuclear fuel (SNF)

Refueling (PWR):
18-24 months

(Source: GAO analysis of DOE data)

 Fission yields of iodine isotopes (%/fission)

I-127 I-129 I-131 I-133 I-135

Half-life stable 1.57x107 y 8.02 d 20.8 h 6.57 h

(Gori nuclear power complex in Korea ) Fission
yield
0.115 0.706 2.878 6.59 6.39
(Source: IAEA data)

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 Generation of gaseous I-129
 Volatilization of SNF during reprocessing

3H, 14C, 85Kr, 129I

(129I phases in off-gas: I2, CH3I, HI…)

(source: U.S. NRC webpage) Block flow diagram for aqueous head-end processing
(from R. Jubin, “Spent Fuel Reprocessing”, ORNL)

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 Problems related with I-129

 Very long half-life

- 129I:1.57×107 y, 3H: 12.3 y, 14C: 5730 y, 85Kr: 10.76 y
 One of the main dose contributors
- β- decay, 5~10 keV after 10,000 y
 Negative health effects related to thyroid diseases
 Dispersion of I-129 is strictly regulated Annual dose
- <5mCi/GWy, 40 CFR 190 (Sv/yr)
 High mobility
- I- predominates in aqueous solutions
- hardly adsorbed on silicate surfaces Receptor
well
 Currently no long-term disposal scheme
Groundwater

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 EPR regulations (40 CFR 190.10)
(a) The annual dose equivalent does not exceed 25 millirems (mrem) to the whole
body, 75 mrem to the thyroid, and 25 mrem to any other organ of any member
of the public as the result of exposures to planned discharges of radioactive
materials, radon and its daughters excepted, to the general environment from
uranium fuel cycle operations and to radiation from these operations.

(b) The total quantity of radioactive materials entering the general environment
from the entire uranium fuel cycle, per gigawatt-year of electrical energy
produced by the fuel cycle, contains less than 50 000 Ci of 85Kr, 5 mCi of 129I,
and 0.5 millicuries combined of 239Pu and other alpha emitting transuranic
radionuclides with half-lives greater than one year.

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 NRC regulations (10 CFR 20)
The total effective dose equivalent to individual members of the public from the
licensed operation does not exceed 0.1 rem (1 mSv) in a year, exclusive of the
dose contributions from background radiation, from any medical administration
the individual has received, from exposure to individuals administered
radioactive material and released under § 35.75, from voluntary participation in
medical research programs, and from the licensee’s disposal of radioactive
material into sanitary sewerage in accordance with § 20.2003

Isotope Air (Ci/m3) at Water (Ci/m3)

site boundary
3H 1.0 × 10-7 1.0 × 10-3
14C 3.0 × 10-5 -
85Kr 7.0 × 10-7 N/A
129I 4.0 × 10-11 2.0 × 10-7
(from R. Jubin, “Spent Fuel Reprocessing”, ORNL)

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 What DF is needed to meet the regulations?
 Decontamination factor (DF)
* DF = (Input contaminant conc.)/(Output contaminant conc.)
550 3.1
mrem/y sorbent mrem/y
DF = 550/3.1 = 177.4

(R.T. Jubin et al., INL/EXT-12-25410, 2012)

MEI: a hypothetical individual who could
potentially receive the maximum possible
dose of radiation from a given event or
process

(R.T. Jubin et al., INL/EXT-12-25410, 2012)

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 Estimation of DF
 Assumptions for analysis
- Fuel type: LWR (UOX)
- Burn-up: 60 GWd/tIHM
- Size of plant: 1000 t/y

Required DF Required DF
Isotope - 100% allocation of dose - 10% allocation of dose
limit to volatiles limit to volatiles
3H
1.9-1 38-1
14C
1 1
85Kr
7-1 7-1
129I
190 (99.5%) 570 (99.8%)
(R.T. Jubin et al., Advances in off-gas treatment for used nuclear fuel processing, 2014)

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 Outline

 I-129 overview
 Literature review
 Results of the dissertation
 Summary and conclusion
 Outcomes

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 Separation technology of I-129 (1)
 Wet scrubbing
(1) Alkaline scrub (1–2 M NaOH)
 Chemical reaction: 3I2 + 6OH- ↔ 5I- + IO3- + 3H2O
 Captured iodine resides as NaI, NaIO3, and NaOI.

(2) Mercurex process (0.4–14 M Hg(NO3)2+HNO3)

 Chemical reaction:
- I2: 6I2 + 6Hg(NO3)2 + 6H2O ↔ 5HgI2 + Hg(IO3)2 + 12HNO3
- CH3I: 2CH3I + Hg(NO3)2 ↔ HgI2 + 2CH3NO3

(3) Iodox process (20–23 M HNO3)

 Chemical reaction:
- 2CH3I + 4H(NO3) ↔ 2CH3NO3 + I2 + N2O4 + 2H2O
- I2 + 4H2O ↔ 2I+ + 2NO3- + N2O4 + 2H2O
- I+ + 3HNO3 + NO3- ↔ IO3- + H+ + 2N2O4 + H2O

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 Separation technology of I-129 (2)
 Summary on wet scrubbing
 Wet scrubbing techniques demonstrate high efficiency of iodine removal
(DF: 102-104).
 Most methods were developed into lab or pilot scale, and alkaline scrub was
deployed at full scale.
 Iodine is trapped into a liquid solvent, which must undergo additional
processing prior to permanent disposal of the iodine.
 Maintenance costs are another problem due to the use of highly corrosive
liquids.
 Solid sorbents
 Adsorption column operations are generally simplistic in design, resulting in
a more reliable system with lower maintenance costs.
 The primary adsorbent materials tested include activated charcoal and
various forms of metal loaded alumina silicates.

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 Separation technology of I-129 (3)
 Activated carbon ( <3500 m2/g)
 Extensively used to control 131I at reactors.
 Generally impregnated with KI or organic
amines to improve the performance.
- CH3131I + K127I → CH3127I + K131I
- R3N + CH3131I → R3N+CH3131I-
 Exhibits poor iodine retention at high temp.
 Has a relatively low ignition point.
(http://www.activatedcarbonindia.com)

 The presence of NOx gas in the gas stream

adversely affects the media performance.

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 Separation technology of I-129 (4)
 Macroreticular resin (Amberlyst XAD series)
 Resins attract molecular species due to their
relative hydrophobicity or hydrophilicity.
 Generally functionalized acrylic esters or
polystyrene with di-vinyl benzene cross-linking.
 Quite effective for removal of elemental iodine or
organic iodide at 25-50 ℃
 Highly porous and acid resistant, facilitating
rapid mass transfer.
 Reasonably stable in feed streams containing NOx.
 Adversely affected by moisture.
 Iodine removal efficiency greatly reduced at
temperatures above 50 ℃.

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 Separation technology of I-129 (6)
 Solubility of various iodides
Iodide Solubility (g/100 mL, 20 ℃)
AgI 3х10-7
BiI3 7.761х10-4
CuI 4.2х10-3
HgI2 6х10-3
PbI2 7.56х10-2
CdI2 84.7
LiI 167 (at 25℃)
NaI 178.8
BaI2 221
(Source: wikipedia)

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 Separation technology of I-129 (7)
 Silver nitrate impregnated substrates (Europe and Japan)
 Elemental iodine is removed by
- AgNO3 + I2 → AgI + INO3
- 2INO3 + AgNO3 → AgIO3 + 3NO2 + 0.5I2
- INO3 ↔ NO2 + 0.5O2 + 0.5I2
 Alkyl iodide is removed by
- AgNO3 + RI → RNO3 + AgI
 Silica and alumina have been used to bind the silver nitrate.
 Silver nitrate impregnated amorphous silicic acid (AC-6120, German)
- Surface area: 65-110 m2/g, pore size: 20-40 nm, grain size: 1-2 mm, Ag: 8-12 wt%
- Optimal operating temperature: 150 ℃ (DF: 100-500)
- Used at WAK reprocessing plant in Karlsruhe from 1975 to 1992.
 Silver nitrate impregnated alumina (AgA, Japan)
- Tested for treating off-gas streams at the Tokai reprocessing plant (Ag: 24 wt%)
- Optimal operating temperature: 150 ℃ (DF: 250)

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 Separation technology of I-129 (8)
 Summary on silver nitrate impregnated substrates
 High decontamination factors for elemental and organic iodides
at elevated temperature (150 ℃) and high utilization of silver
 High resistance to NOx
 Organic contaminants negatively affect the performance
 Removal efficiency is significantly reduced by high humidity.
 The cost of the silver nitrate adsorbents is reported to be 3 to 10
times less than silver zeolites.

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 Separation technology of I-129 (9)
 Silver-exchanged zeolites (e. g., AgX, AgZ)
 Faujasite (3.5Na2O∙3.5Al2O3∙17SiO2∙32H2O)
 Mordenites (Na2O∙Al2O3∙10SiO2∙6H2O)
 Mechanism: chemisorption + physisorption
 Chemisorption: Ag2O + I2 ↔ 2AgI + 0.5O2
 High portion of physisorption (I2): >40 wt%
- Thermally unstable
- Readily soluble in water (fatal to long-term disposal) FAU
 High price of silver (643 USD/kg, 2014)
 Toxicity of silver (regulated by EPA)

We need an another sorbent for 129I(g) capture!

LTA
(http://www.iza-online.com)

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 Separation technology of I-129 (10)
 Other metal loaded zeolites
 Various metals were investigated for the  Thermodynamic data at 298 K
capture of iodine. Oxide ∆Gf°, Iodide ∆Gf°,
 (Pb, Cu, Cd, Mn, Pd, Tl, Hg) exchanged kJ/mol kJ/mol
zeolites have been evaluated as possible PbO* -187.9 PbI2* -173.6
alternatives to silver based adsorbents. Cu2O* -147.9 CuI* -69.4
 Although some showed promise for * CdI2*
removing elemental iodine, all were shown CdO -228.5 -201.3
# MnI2#
to have unsatisfactory removal efficiencies MnO -363.0 -262.8
and/or low loading capacity for methyl PdO# -83.5 PdI2# -90.4
iodide. Tl2O* -143.5 TlI* -125.5
 Metals exchanged with sodium exist as
HgO* -58.6 HgI2* -102.2
oxide forms in the zeolites.
Ag O * -11.3 AgI * -66.3
 These oxide forms are thermodynamically 2

more stable than the corresponding metal *Strachan et al., PNNL-20807, 2011
#Calculated by HSC chemistry 6.0
iodides.

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 Study on bismuth-iodine-oxides (1)
 Bismuth oxyiodides for I-129 waste forms
 Extensively studied by P. Taylor et al. to judge their potential as candidate waste
forms for I-129
 Stabilities in terms of thermodynamics and kinetics of various compounds
containing bismuth and iodine were studied.
 Considering groundwater intrusion into waste forms dissolves radiotoxic
isotopes, one of the most important parameter to evaluate long-term stability of
waste forms is hydrolytic stability.
 Mixture of Bi2O3 and Bi5O7I was proposed a promising waste form.
- Bi5O7I(s) + OH-(aq) ↔ 5/2Bi2O3(s) + I-(aq) + 1/2H2O(l), KI,1 = {I-}/{OH} = 10-3.39±0.20
- 5/4BiOI(s) + OH-(aq) ↔ 1/4Bi5O7I(s) + I-(aq) + 1/2H2O(l), KI,2 = {I-}/{OH} = 103.49±0.18
- 1/2BiI3(s) + OH-(aq) ↔ 1/2BiOI(s) + I-(aq) + 1/2H2O(l), KI,3 = {I-}/{OH} = 1010.0±1.0
 Iodine release is decreased by using a mixture of Bi2O3 and Bi5O7I.
- log{I-}= log{OH-}−3.4±0.2 (at 25 ℃) → log{I-}= −10.4±0.2 (at neutral pH and 25 ℃)
 Iodine dissolution from (Bi2O3+Bi5O7I) is even lower than that from AgI near neurtal pH.
- AgI: log{I-}= −8.0±0.5 (at most pH and 25 ℃)
 Comprehensive understanding on hydrolytic stability is obtained by examining other
factors.

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 Study on bismuth-iodine-oxides (2)
 Redox reactions
 Iodine dissolution from (Bi2O3+Bi5O7I) is nearly
independent on p(H2) until log[p(H2), Pa]=−8,
suggesting strong resistance to reducing conditions.
 More reducing conditions lead to reduction of
(Bi2O3+Bi5O7I) that becomes extremely dependent

Reducing
on p(H2).
- Bi5O7I(s) + OH-(aq) + 15/2H2(g) ↔ 5Bi + 8H2O(l) + I-(aq)
 In AgI, resistance to redox conditions is relatively
weak: iodine dissolution became dependent on p(H2)
above log[p(H2, Pa)]=−24
- AgI(s) + 1/2H2(g) ↔ Ag(s) + I-(aq) + H+(aq)
 In summary, (Bi2O3+Bi5O7I) is more stable than
AgI over a wider range of reducing conditions. (Taylor and Lopata, AECL, TR-350, 1985)
However, both systems are not stable under redox
environment controlled by magnetitie/hematite
buffer, which is believed to be similar with the
granite groundwater.

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 Study on bismuth-iodine-oxides (3)
 Anion displacement reactions
 Iodine dissolution is affected by anions such as
chloride, carbonate and sulfate, which are
relatively rich in granite groundwater.
 In AgI, carbonate or sulfate does not significantly
affect the iodide dissolution.
 Chloride anions can increase iodine dissolution,
but (AgI+AgCl) suppress the reaction.
- AgI(s) + Cl-(aq) ↔ AgCl(s) + I-(aq) (Taylor and Lopata, AECL, TR-350, 1985)
 Bi5O7I is relatively weak to the anion attacks.
2Bi5O7I(s) + 5CO32-(aq) + 4H2O(l)
→ 5(BiO)2CO3(s) + 2I-(aq) + 8OH-(aq)
4Bi5O7I(s) + 5CO32-(aq) + 8H2O(l)
→ 5(BiO)4(OH)2CO3(s) + 4I-(aq) + 6OH-(aq)
2Bi5O7I(s) + 5Cl-(aq) + 4H2O(l)
→ 5(BiO)4(OH)2Cl(s) + 2I-(aq) + 3OH-(aq)
 To summarize, AgI is more resistant to anion (Taylor et al., ASTM STP 1033, 1989)
displacement reactions than Bi5O7I.

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 Study on bismuth-iodine-oxides (4)
 Complexation reactions
 Iodine solubliity can be affected by formation of metal-ligand complexes.
 In AgI, silver complexes are formed by the reaction of AgI and chloride.
- AgI(s) + 2Cl-(aq) ↔ AgCl2-(aq) + I-(aq)
 Bi5O7I is known to be very resistant to complexation reactions.

 Thermal stability
 Decomposition of AgI is activated after 558 ℃.
- 2AgI(s) → 2Ag(s) + I2(g)
 Bi5O7I is reported to be thermally stable up to ~500 ℃.
- 2Bi5O7I(s) + 0.5O2(g) → 5Bi2O3(s) + I2(g)
 Inert air reportedly induces decomposition of Bi5O7I at 480 ℃.
- 3Bi5O7I(s) → 7Bi2O3(s) + BiI3(s)
 Thermal stability of AgI is higher than that of Bi5O7I.

(Taylor et al., ASTM STP 1033, 1989)

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 Study on bismuth-iodine-oxides (5)
 Summary on bismuth-iodine-oxides
 Bismuth iodine compounds were studied to evaluate the potential
as waste forms for I-129.
 Studies on iodine behavior in various conditions suggest that
(Bi2O3+Bi5O7I) could be a promising candidate waste form.
 Currently, there is no definite winner between AgI and
(Bi2O3+Bi5O7I).

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 State of the art (1)
 On-going efforts to develop new sorbent for I-129
 The Department of Energy
(DOE) Fuel Cycle Research
and Development (FCRD)
Program has supported R&D
on iodine control and iodine
waste forms for the past several
years.
 The Off-Gas Sigma Team was
formed in 2009 within the
Separations and Waste Forms
Campaign to establish a team
of researchers from various
DOE sites to focus on R&D of
emission control and waste (Soelberg, INL/EXT-12-27075, 2012)
forms for volatile radionuclides.

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 State of the art (2)
 Chalcogenide-based aerogels (chalcogels)
 Chalcogels include anions such as S, Se, Te.
 Synthesized by an aggregation of simple binary
nanocrystals (e.g., CdS, ZnS, PbS, CdSe) or a
chemical linkage between chalcogenido clusters
(e.g., Ge4S104-) and metal ions (e.g., Pt2+) that
promote interlinking of the structural units.
 Chalcogels have selective affinity for specific
ionic species.
 According to HSAB principle, I2(g) is a soft
Lewis acid and (Te, S, Se) are soft Lewis base.
 Iodine loading capacity (2390 mg_I2/g_sorbent)
and removal efficiency (>99.8%) are excellent.
 Se is a toxic element controlled by the EPA.
 Se and Te-based chalcogels are air-sensitive.
 Iodine-sorbed chalcogels are thermally
decomposed at higher than 150 ℃.
(Riley et al., RSC advances, 2011)

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 State of the art (3)
 Silver-functionalized silica aerogels
 Silica aerogel is functionalized with thiol
group by using supercritical CO2 solvent.
 Silver ions are bound to sulfurs in the thiol
group, forming silver nanoparticles through
reduction of silver ions.
 Silver content: ~35 wt%
 Sorption capacity: ~832 mg_I2/g_sorbent
(AgZ: ~120-150 mg_I2/g_sorbent)
- Chemisorption(AgI): ~412 mg_I2/g_sorbent
- Physisorption: ~420 mg_I2/g_sorbent
 Demonstration of consolidation
- Hot uniaxial pressing in air
- 1200 ℃ for 30 min under 29 MPa
- Iodine retention: 92.1%
(Strachan et al., PNNL-20807, 2011)

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 State of the art (4)
 Metal-organic framework (MOF)

(Sava et al., I&EC, 2012)

 MOFs consist of metal centers linked with organic

building blocks.
 Very high surface areas (<3500 m2/g) and facile
functionalization
 Various applications for gas capture (I2, Kr, CO2, H2)
 Sorption capacity: ~1500 mg_I2/g_sorbent
(I2 molecules are physically bound into the frameworks)
 Relatively weak I2 binding: mass loss at 100-240 ℃

(Chapman et al., JACS, 2011)

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 Outline

 I-129 overview
 Literature review
 Results of the dissertation
 Summary and conclusion
 Outcomes

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 Bismuth-Embedded SBA-15
 Bismuth for iodine capture
 Reaction tendency in thermodynamics
ΔGf°
chemical reaction spontaneity
(kJ mol-1, 298.15 K)
Ag + 0.5I2(g) = AgI -66.3 spontaneous
2Bi + 3I2(g) = 2BiI3 -177.9 spontaneous
 Low price (24 USD/kg, 2014): 27 times less than Ag price (643 USD/kg, 2014)!
 Environmentally benign character: non-toxic element
 SBA-15 mesoporous silica
Zeolites Mesoporous silica

 Mesostructure: 2-D hexagonal (p6mm)

 Tunable pore size: 5-30 nm

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 Synthesis of sorbent
 Procedure
1. SBA-15: TEOS (Si source) + P123 (SDA) in acidic media
2. Thiol-functionalization: MPTMS
3. P123 removal: solvent extraction with EtOH
4. Bi adsorption: impregnation into Bi solution (BiCl3+MeOH)
5. Heat-treatment: 250 ℃ for 6h (4% H2/Ar) SBA-15-SH Bi-adsorbed Heat-treated

TEOS MPTMS

Tetraethyl ortholsilicate Mercaptopropyl trimethoxysilane

Thiol-
functionalization Bi incorporation

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 Confirmation of surface modification
 Fourier-transformed infrared spectroscopy (FT-IR)

(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, (g) Bi-SBA-15-SH3

 Weak peak near 2550 cm-1: stretching vibration of S-H bond.

 It confirms thiol-functionalization to the surface of SBA-15.
 Disappearance of that peak suggests that formation of Bi-S bond.

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 Pore information
 N2 adsorption/desorption isotherms (BET/BJH method)

 Structural parameters
SBA-15 SBA-15-SH1 SBA-15-SH2 SBA-15-SH3
SBET (m2/g) 637 215 153 51
VBJH (cm3/g) 0.88 0.35 0.31 0.10
DBJH (nm) 6.34 6.93 8.75 9.37

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 Mesostructural arrangement
 Small angle X-ray scattering (SAXS)
(100) (a) SBA-15, (b) SBA-15-SH1
(c) SBA-SH2, (d) SBA-15-SH3

(110)
(200)

Random pore (110) (200)

structure

 2-D hexagonal (p6mm) pore structures

 Mesostructural ordering is collapsed when too much MPTMS is added.

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 Microstructural images
 Scanning electron microscopy (SEM)
(a)
SBA-15 (b)
SBA-15-SH1

Rod-like particles
(1-1.5 μm)

(c)
SBA-15-SH2 (d)
SBA-15-SH3
Agglomeration of rods

Bi-incorporation does not (e) (f)

Bir-SBA-15-SH2
Bi-SBA-15-SH2
disturb structure Needle-like particles
(Bi2S3)

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 Microstructural images
 Transmission electron microscopy (TEM)
SBA-15 SBA-15-SH1

SBA-15-SH2 SBA-15-SH3
Random pores in
SBA-15-SH3

Bir-SBA-15-SH1 Ordered pore channels

Bi-SBA-15-SH1
even after Bi incorporation
and heat-treatment

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 Iodine capturing experiment
 Experimental conditions
 Sorbent mass: 2-3 g
 I2 source: I2 granule (nonradioactive)
 I2 mass: ~4 g
 Reaction device: Al2O3
 Reaction: 200 ℃ for 6 h
 Atmosphere: static air
 Mass check: digital balance (4 digit)
 Capacity(CI, mg-I/g-sorbent): CI = ∆m/mi×1000
(Unit: mm)

< a schematic for iodine capturing experiment>

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 Performance test result
(f) (g)
Iodine capturing capacity (mg-I/g-sorbent) 600
(a): SBA-15
(b): Bi-SBA-15-SH1
500 (e) (c): Bi-SBA-15-SH2
(d) (d): Bi-SBA-15-SH3
400 (b) (c)
(e): Bir-SBA-15-SH1
(h) (f): Bir-SBA-15-SH2
300
(g): Bir-SBA-15-SH3
(h): AgX
200

100
(a)
0
(AgX was tested at 150 ℃)
 Very small adsorption by SBA-15
 High iodine loading: Max. ~600 mg-I/g-sorbent
 Not linear relation between Bi and I capture
 Iodine capture benefitted from high surface area.
 Chemisorption is a main mechanism, with minor physisorption.

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 Phase analysis
 X-ray diffraction technique (XRD)
BiI3

Bi2S3

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 Thermodynamic consideration
 Gibbs free energy of formation (ΔGf°) at 473 K

reaction ΔGf°
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

Formation of BiI3 is most favorable among several

reaction products!

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 Thermal stability
 Thermogravimetric analysis (TGA)

Thiol group
decomposition

BiI3 volatilization
Moisture adsorption

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 Stabilization by phase transition
 Phase transformation from BiI3 to Bi5O7I
Reaction: BiI3 + 7Bi2O3 = 3Bi5O7I

 Procedure
Chemically durable
Powder preparation
(I trapped sorbent : Bi2O3 = 1:4)
Mixing Heat-treatment at 500 ℃ iodine phase
(CD-IP)

CD-IP
BiI3 was successfully transformed to Bi5O7I!

Bir-SBA-15-SA2-I

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 Chemical durability
 Elemental loss of different samples (90 ℃, 7 days)

Improved chemical durability

by phase transition!

Iodine phase in
chalcogel

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 Waste form fabrication for stable storage
 Glass composite waste form
Powder preparation
Mixing
Pelletizing at 300 MPa
Sintering at 600 ℃
Sample Mass ratio (%) Glass
name Bi-SBA-15-I I Bi2O3 Glass identification
LGC106 6.2 2.6 20.4 73.4
LGC1
LGC113 13.2 5.6 26.0 60.7
(Bi-Zn-B glass)
LGC119 19.0 8.0 24.9 56.1
LGC206 6.2 2.6 20.4 73.4
LGC2
LGC213 13.2 5.6 26.0 60.7
(Bi-Zn-Si-Al glass)
LGC219 19.0 8.0 24.9 56.1

Pelletized samples Sintered samples

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 Characterization
 Phase identification of glass composite waste forms

Iodine phases in glass composite waste forms are mostly composed of

Bi5O7I and BiOI, in contrast to BiI3 phase in the sorbent.

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 Characterization
 Microstructural images of glass composite waste forms
LGC106 LGC113 LGC119

• Structure becomes less dense

Low as waste fraction increases.
magnification LGC206 LG213 LGC219 • Densification was better when
(ⅹ5,000) Bi-Zn-B glass was used.

LGC106 LGC113 LGC119

• Plate and rod-like particles are

High mixtures of BiOI and Bi5O7I.
Magnification LGC206 LG213 LGC219
(ⅹ18,000)

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 Thermal stability
 Iodine loss during thermal process

I mass ratio (%)

Retention ratio
Sample name Initial mixture Glass-composite I loss (%)
a (Ri)b
waste form
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
aImass ratio for each sample was measured by XRF.
bRetention ratio is defined by the initial fraction divided by final fraction.

Iodine volatility is significantly affected by the ratio of Bi2O3 to I

within waste forms, as well as glass composition.

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 Chemical durability
 Product consistency test (PCT) (ASTM C1285-14, 90 ℃, 7 days)
• Normalized leaching rate: LRi (g/m2∙day) = Ci/(fi∙SA/V∙t)
- Ci: elemental concentration in solution (ppm)
- fi: elemental fraction (unitless)
- SA/V: sample surface area divided by leachant volume
- t: test duration (day)
 Effect of glass composition (LGC1 vs LGC2)
More efficient diffusion of
water into iodine phases

Range of leaching rates for

various borosilicate waste forms

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 Chemical durability
 PCT leaching result
 Effect of waste fraction
More efficient diffusion of
water into iodine phases

Range of leaching rates for

various borosilicate waste forms

Higher fraction of stable

iodine phase (Bi5O7I)

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 Chemical durability
 PCT leaching result
 Effect of dissolved anions

Range of leaching rates for

various borosilicate waste forms

Common groundwater anions (e.g., Cl-, CO32-, SO32-, F-) increase

I- release by anion exchange reactions.

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 Outline

 I-129 overview
 Literature review
 Results of the dissertation
 Summary and conclusion
 Outcomes

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 Summary and conclusion
 Baseline sorbent for I-129: AgZ
 Limit of AgZ: physisorption, high price and toxicity of Ag
 First study of bismuth for iodine capture
 First study of bismuth-embedded SBA-15 for iodine capture
 Successful incorporation of bismuth onto thiol-functionalized SBA-15
 Chemisorption of iodine (BiI3)
 Low toxicity and price (24.3 $/kg-Bi vs 643 $/kg-Ag, 2014)
 Effective iodine loading (Max. 600 mg-I/g-sorbent)
 Glass composite waste form using low-temperature glasses and Bi2O3
 Chemical durability of iodine due to stabilization by phase transition (from BiI3
to Bi5O7I and BiOI) and encapsulation by glassy network
 Bismuth-embedded SBA-15 could be a breakthrough toward long-term disposal
of I-129 waste.

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 Outline

 I-129 overview
 Literature review
 Results of the dissertation
 Summary and conclusion
 Outcomes

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 Outcomes
 Published papers
1. J.H. Yang et al., “Novel synthesis of bismuth-based adsorbents for the removal
of 129I in off-gas”, J. Nucl. Mater. 457 (2015) 1-8.
2. J.H. Yang et al., “Bismuth-embedded SBA-15 mesoporous silica for
radioactive iodine capture and stable storage”, J. Nucl. Mater. 465 (2015) 556-
564.

 Submitted paper
1. J.H. Yang et al., “Glass composite waste forms for iodine confined in bismuth-
embedded SBA-15”, J. Nucl. Mater., under review.

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