Progress in Nuclear Energy 85 (2015) 375e383

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Progress in Nuclear Energy

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Technetium transmutation in thin layer coating on PWR fuel rods

Bin Liu a, b, *, Liming Huang c, Jing Tu d, Fang Liu a, b, Qiong Cao a, b, Rendong Jia a, Xiang Li a,
Jin Cai a
a
School of Nuclear Science & Engineering, North China Electric Power University, Beijing 102206, China
b
Beijing Key Laboratory of Passive Safety Technology for Nuclear Energy, North China Electric Power University, Beijing 102206, China
c
China Nuclear Power Design Co., Ltd., Shenzhen, Guangdong 518045, China
d
Northwest Institute of Nuclear Technology, Xian, Shanxi 710024, China

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

Article history: Based on the EFTTRA-T2 experiment results, we study the transmutation characteristics of pressurized
Received 4 February 2015 water reactors (PWR) after coating a thin layer of Tc-99 on the fuel rods. Our calculation shows that for
Received in revised form the same Tc-99 loading amount, the effect on the PWR keff after coating Tc-99 on the PWR fuel rods is
21 July 2015
much less than that of the homogeneous addition of Tc-99 to uranium dioxide nuclear fuel. If we just coat
Accepted 22 July 2015
0.2lc (0.0065 mm) thickness Tc-99 on PWR fuel rods, the total Tc-99 coating amount is about 291.37 kg,
Available online 5 August 2015
this is approximately equivalent to the 4 PWR Tc-99 annual outputs, and the system keff merely decreases
to 0.98530.
Keywords:
Technetium
Loading Tc-99 to the PWR is equivalent to introducing extra poisons to PWR system to control excess
Transmutation reactivity, some control poisons like boric acid concentration in primary coolant or burnable poison rods
Thin layer coating in fuel assemblies are needed to be removed to keep the reactor in criticality. As Tc-99 coating thickness
PWR increases from 0.05lc to 0.2lc, no matter which substitution pattern is used, B16/12 or C16/12, the
system keff variations are almost the same and can return to criticality again after removing corre-
sponding burnable poison rods from fuel assemblies. For coating 0.15lc or 0.2lc thickness on the fuel rods
of PWR, the system keff is slightly below the criticality either in B16/12 or C16/12 substitution pattern,
we may reduce the concentration of the boric acid slightly to let the system in criticality again.
Our calculation results indicate that the optimal coating thickness of Tc-99 on PWR fuel rods is
probably between 0.15lc to 0.2lc, i.e. 0.00488e0.0065 mm.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction One of the most noxious fission products is Tc-99, produced in

Like any other human activities, nuclear power industry also
creates nuclear wastes. During the period of irradiation of the fuel
assemblies in the core of a nuclear reactor, harmful long-lived
fission products and minor actinides are produced by fission and
activation. In order to reduce the amount of the long-lived fission
products and minor actinides which could induce very long-term
radioactivity, people need to study the transmutation techniques
in the thermal reactors (Liu et al., 2013; Takeda et al., 2002; Artisyuk
et al., 2005), fast reactors (Iwasaki and Hirakawa, 1994;
Wakabayashi, 2002) or other neutron sources (Herrera-Martnez
et al., 2007; Beller et al., 2001).
* Corresponding author. School of Nuclear Science & Engineering, North China
Electric Power University, Beijing 102206, China.
E-mail address: Liu_Bin@ncepu.edu.cn (B. Liu).
significant amounts in spent fuel from nuclear reactors: fission of
U-235 by thermal neutrons produces the technetium isotope Tc-99
in a yield of 6.2%, fission by fast neutrons gives a yield of 5.9%
(Konings et al., 1998a). Typical 900 MWe pressurized water reactors
(PWR) discharges about 22 tons of spent fuel per year, thus the
annual output of technetium-99 from a typical PWR is approxi-
mately 66 kg. With a very long half life of 2
105 years, Tc-99
decays by b emission to the stable ruthenium isotope Ru-99. Tc-
99 has the ability to migrate in any kind of material, including the
storage containers, which could, in a worst-case scenario, lead to its
release in the environment during long-term storage. Since tech-
netium is unstable, only minute traces occur naturally in the Earth's
crust as a spontaneous fission product of uranium, it is estimated
that a kilogram of uranium contains 1 ng (1
109 g) of technetium
(Emsley, 2011).
In contrast with the rare natural occurrence, bulk quantities of
technetium-99 are produced each year from spent nuclear fuel

http://dx.doi.org/10.1016/j.pnucene.2015.07.015
0149-1970/© 2015 Elsevier Ltd. All rights reserved.
376 B. Liu et al. / Progress in Nuclear Energy 85 (2015) 375e383
rods, which contain various fission products. Due to its high fission
yield and relatively high half-life, technetium-99 is one of the main
components of nuclear waste. Its decay, measured in becquerels per
amount of spent fuel, is dominant at about 104e106 years after the
creation of the nuclear waste. The long half-life of technetium-99
and its ability to form an anionic species makes it (along with I-
129) a major concern when considering long-term disposal of high-
level radioactive waste (Kloosterman and Li, 1994). Current disposal
options for nuclear wastes favor burial in geologically stable rock.
The primary danger with such a course is that the waste is likely to
come into contact with water, which could leak radioactive
contamination into the environment. The anionic pertechnetate
and iodide are less able to absorb onto the surfaces of minerals so
they are likely to be more mobile (Wang et al., 2012). By comparison
plutonium, uranium, and cesium are much more easily to bind to
soil particles. For this reason, the environmental chemistry of
technetium is an active area of research. An alternative disposal
method, nuclear transmutation, also has been demonstrated at
different countries to reduce the long term radioactivity of the
technetium-99. Nuclear transmutation is the conversion of one
chemical element or isotope into another. In other words, atoms of
one element can be changed into atoms of other element by
transmutation. This occurs either through nuclear reactions, or
through radioactive decay. Nuclear transmutation can occur
through various natural processes, or it may be artificially induced
by human intervention. In transmutation of the technetium in the
depleted reactor fuel the intention is to convert the technetium into
stable ruthenium isotope.
After Tc-99 capture a neutron, Tc-99 becomes Tc-100, decaying
to the stable isotope Ru-100 with a half-life of 16 s (Yang et al.,
2004). The neutron-capture cross-section of Tc-99 in the thermal
energy range is 19 b (Rochman et al., 2008; Gunsing et al., 2001),
and there are several strong resonance absorptions in the epi-
thermal energy range (Gunsing et al., 2000; Gruppelaar et al., May
1992).
Several institutions have made significant progress in the
experimental research of transmutation of the technetium-99 in
the world wide. A burnup of 0.67% of technetium-99 for 10 days
was achieved in Hanford Fast reactor (USA) using a metal-hybrid
moderated environment of the target (Wootan et al., 1991). A
burnup of 16e18% for 579.3 days of irradiation was achieved in the
Petten high flux reactor (Holland) which has a thermal flux of
2
1014 cm2 s1 (Konings et al., 1998a; Konings and Conrad, 1999).
More than 100 technetium targets (discs with a diameter of 6 mm
and thickness of 0.3 mm were irradiated in the SM-3 high flux
reactor (Russia) at RIAR (Kozar' et al., 2002). The flux of thermal
neutrons was 1.2
1015 cm2 s1 in the neutron trap inside the
target at the beginning of the irradiation and increased to about 15%
when the technetium-99 burnup achieved 70%. The epithermal
neutron flux in the neutron trap was 1.1
1014 cm2 s1 and
changed insignificantly during irradiation. The transmutation rate
achieved in the SM-3 reactor permits 50% conversion of
technetium-99 into ruthenium-100 in 150 days (Peretroukhine
et al., 2004).
Although thermal reactors, fast reactors, subcritical reactor and
other neutron sources all can be used to transmute the technetium
into stable ruthenium isotope, only the technology of thermal re-
actors and fast reactors is mature, furthermore the majority of
commercial reactors in operation in the world are PWR reactors, so
to study the technetium transmutation characteristics in the PWR
reactors are very important in the point of technetium trans-
mutation. Probably, the commercial PWR reactors are the only
choice to transmute the nuclear wastes in large scale. As techne-
tium has relatively large thermal neutron capture cross sections,
when technetium is introduced in the PWR reactors within the fuel,
the initial reactivity of the PWR reactor decreases, as the PWR re-
actors in operation, the consumption of the technetium and fuel
may lead to the increase of the reactivity, this means that techne-
tium act as the burnable poisons in the PWR reactors in some sense.
This is one of distinct advantages to transmute the technetium in
the PWR reactors.
In this paper, we study the technetium transmutation charac-
teristics in the pressurized water reactors. We use the MCNP code
to simulate the effects after adding technetium-99 transmutation
material to the pressurized water reactor core. In simulation
calculation the technetium-99 is introduced to the pressurized
water reactor core in two different ways. One is to mix the
technetium-99 to the uranium dioxide nuclear fuel homoge-
neously, this means all the fuel rods have technetium trans-
mutation material; the another way is that we study the effects to
the system keff after coating different thickness technetium trans-
mutation material to the PWR fuel rods. We also calculate the
possible reduction of the concentration of the boric acid in the
coolant of the PWR reactors and removal of the number of the
burnable poison rods after coating different thickness technetium
transmutation material to the fuel rods of pressurized water
reactor.
2. The loading pattern of technetium transmutation in
thermal reactor
To illustrate the reasons why we propose to transmute techne-
tium in thin layer coating on the PWR fuel rods, we introduce some
details about the EFTTRA-T2 experiment of technetium trans-
mutation thermal neutron field (Konings and Conrad, 1999). In
EFTTRA-T2 experiment, technetium target diameter is 4.8 mm,
length is 25 mm. The target is irradiated in the 2
1014 cm2 s1
thermal neutron flux for 579.3 days, the total thermal neutron
fluence is 8.742
1025 m2, the measured technetium-99 trans-
mutation rate is 15e18% on the pellet average. Electron probe
microanalysis showed an increase from 16% ruthenium in the
centre to 30e40% ruthenium near the rim of the pellets. Metallo-
graphic examinations showed no change in the microstructure
compared to the unirradiated material.
Based on above EFTTRA-T2 experiment results we can conclude
as the technetium-99 transmutation target irradiated in the reactor,
the strong spatial self-shielding effect in the epithermal neutron
energy region drastically enhances the transmutation rate in the
surface region and hampers the neutron capture reaction of the
technetium-99 atoms outside surface region of the transmutation
target. The transmutation rate of technetium-99 in the surface re-
gion of the transmutation target is strikingly higher than that of
inner region of the transmutation target. For a commercial thermal
reactor, its thermal neutron flux is much lower than that of the high
flux thermal reactors used in the EFTTRA-T2 experiment. The
thermal neutron flux of a typical pressurized water reactor in the
steady state operation condition is about f0 ¼ 1
1014 cm2 s1, if
the radius of the transmutation target is the same as that of fuel rod,
i.e. R ¼ 0.4095 cm, for 579.3 days irradiation in the PWR, from the
results of EFTTRA-T2 experiment we can predicate that the trans-
mutation rate of the technetium-99 on the transmutation target
average is much lower than that of in the high flux thermal reactor.
It is obviously that the low neutron flux is the main factor to hinder
the people use PWR to transmute the LLFP and other nuclear
wastes. Nevertheless, majority of commercial reactors in operation
in the world are PWR reactors and only thermal reactor technology
such as PWR is mature technology. Based on the experiment results
of EFTTRA-T2 we know that the transmutation rate in the surface
region of the cylindrical transmutation target is much higher than
that of the inner region of the cylindrical transmutation target, if we
 B. Liu et al. / Progress in Nuclear Energy 85 (2015) 375e383
just use the surface region of cylindrical transmutation target to
transmute the technetium-99, the overall transmutation rates will
much higher than transmutation rate on the transmutation target
average. This encourages us to study the transmutation character-
istics of PWR after coating a thin layer of technetium-99 to the fuel
rods. Following in this paper, we will study the effects to PWR
reactor after coating different thicknesses of technetium-99
transmutation material on PWR fuel rods.
3. The technetium transmutation in PWR core
We establish a PWR technetium transmutation core by using
MCNP code (Briesmeister, April 2000). MCNP code has criticality
calculation feature for critical systems (Liu et al., 2010). We use
MCNP code to study the technetium transmutation characteristics
in the pressurized water reactors as a thin layer technetium-99
coats on the fuel rods with different thicknesses.
3.1. The PWR core configuration
The PWR core consists of the fuel assemblies, control rods and
water which acts as both the coolant and moderator with boric acid
dissolved in it. We simulate reactor core of China Guangdong Daya
Bay 900 MW pressurized water reactor (Su and Yang, 2005) to
study the technetium transmutation characteristics. Fig. 1 depicts
the structure of China Guangdong Daya Bay 900 MW PWR core
which includes the pattern of the fuel assemblies with different
enrichments. Table 1 lists the key parameters of the fuel assemblies
of this 900 MW PWR which is the same as a typical PWR.
All fuel assemblies are the typical 17
17 PWR fuel assemblies,
every fuel assembly has 264 fuel rods, 24 control rod guide tubes
and 1 neutron detector guide tube. There are three kinds of
different fuel assemblies in the core which are labeled by A, B and C
with U-235 enrichments 1.8%, 2.4%, 3.1% respectively. The numbers
of the fuel assemblies in three different enrichments are 53, 52 and
52; these make the total 157 fuel assemblies in this 900 MW PWR
Fig. 1. Cross sectional arrangement of 900 MW PWR core.
377
Table 1
Parameters of the fuel assemblies of 900 MW PWR.
Parameter Value
Pin pitch (cm) 1.24
Pin diameter (cm) 0.95
Cladding thickness (cm) 0.057
Fuel pellet radius (cm) 0.4095
Active assembly height (cm) 365.8
reactor core. One third of the fuel assemblies are replaced with
fresh fuel for every refueling. There are no burnable poison rods in
the 53 fuel assemblies with enrichment 1.8% (labeled A). For the 52
fuel assemblies with enrichment 2.4% (labeled B), 12 fuel assem-
blies have 16 burnable poison rods, 40 fuel assemblies have 12
burnable poison rods. For the 52 fuel assemblies with enrichment
3.1% (labeled C), 8 fuel assemblies have 16 burnable poison rods, 8
fuel assemblies have 12 burnable poison rods, other 36 fuel as-
semblies, which are on the periphery of the reactor core, have no
burnable poison rods at all. As all the burnable poison rods
distribute in the 2.4% and 3.1% enrichment fuel assemblies, we use
B16 to denote the fuel assemblies which have 16 burnable poison
rods and B12 to denote the fuel assemblies which have 12 burnable
poison rods in all the fuel assemblies with 2.4% U-235 enrichment.
Likewise, we use C16 to denote the fuel assemblies which have 16
burnable poison rods and C12 to denote the fuel assemblies which
have 12 burnable poison rods in all the fuel assemblies with 3.1% U-
235 enrichment, see Fig. 1 for details.
Based on the parameters in Table 1, we use MCNP code
(Briesmeister, April 2000) to establish a model to study the tech-
netium transmutation characteristics in the China Daya Bay
900 MW PWR under two different technetium transmutation
material loading patterns. For the easy calculation, we assume all
the control rods are completely withdrawal from the PWR core in
MCNP simulation calculation. The initial reactivity is 1.01042 in
criticality. The initial concentration of the boric acid in the coolant
is 705 ppm. The abundance of boron-10 in boric acid is 30%.
378 B. Liu et al. / Progress in Nuclear Energy 85 (2015) 375e383
4. The effects after loading technetium to the PWR core
4.1. Material property of technetium
Technetium-99 is silver-gray, radioactive metal. It occurs natu-
rally only in very small amounts. Its melting point is 2250  C which
is much higher than the operation temperature within the PWR
core and its boiling point is 4877  C (Haynes, 2015), so in practice
there is no limit on its temperature when irradiated in the PWR. It is
also a very dense material at high temperature, a mass of
technetium-99 weighs 11.5 times as much as an equal volume of
water, so it can occupy smallest space in the reactor core and its
parasitic absorption cross section is also relatively small (Lu et al.,
2011). EFTTRA-T1 (Konings et al., 1998a) and EFTTRA-T2 (Konings
and Conrad, 1999) experimental results indicate that metal tech-
netium has good stability at high temperature and good resistance
to radiation damage which enable it to be irradiated in PWR for
very long time. There is no gaseous element produced during
technetium irradiated in the reactor.
4.2. Homogeneous mixing of Technetium-99 with PWR nuclear fuel
After adding the technetium transmutation materials to the
uranium dioxide nuclear fuel homogeneously, technetium-99 is
diluted by uranium dioxide nuclear fuel; therefore the spatial self-
shielding effect in the epithermal neutron energy region of tech-
netium metal is reduced to the minimum. On the other hand, the
technetium has high thermal conductivity; its thermal conductivity
is about 50 W/mK at the reactor steady state operation tempera-
ture. After technetium-99 mixed with uranium dioxide nuclear
fuel, it will increase the thermal conductivity of the uranium di-
oxide nuclear fuel, the thermal conductivity of the uranium dioxide
without technetium is just 2.5 W/mK in the temperature range
from 1000 to 2000  C. Study shows that technetium-99 does not
react with the cladding materials of PWR fuel rods (Yang et al.,
2004). We calculate the variations of PWR keff after adding tech-
netium 0e2% of total uranium dioxide nuclear fuel to PWR core. In
our MCNP simulation calculation, we just use the metallic Tc mix-
ing with uranium dioxide nuclear fuel homogeneously in MCNP
input file for easy calculations. When people try to build a real
transmutation PWR reactor, we believe Tc should be in oxide form
or other compound form, for example TcO2.
The red (in the web version) curve in Fig. 2 shows the effects on
keff of the PWR core after adding technetium-99 to the uranium
Fig. 2. Effects on keff after introducing technetium-99 to PWR.
dioxide fuel homogeneously. From Fig. 2 we can see that addition of
technetium to the uranium dioxide fuel homogeneously can affect
keff of the PWR significantly. Even 1.0% homogeneous addition of
technetium-99 to the nuclear fuel can reduce keff of the pressurized
water reactor drastically. Technetium-99 has relatively large cap-
ture cross section in the thermal neutron regions and the spatial
self-shielding effect is reduced to the minimum after adding tech-
netium to uranium dioxide fuel homogeneously, so it consumes a
lot of thermal neutrons, this makes the thermal neutrons decrease
after adding technetium to the core of the pressurized water
reactor, this is also an important reason that causes the decrease of
keff of the pressurized water reactor after adding technetium.
In addition to reducing the initial reactivity significantly, the
uniform distribution of technetium in the uranium dioxide nuclear
fuel may also affect the lifetime of a fuel loading. In order to in-
crease the allowable initial core fuel loading, it is usually to load
into the PWR core high neutron absorption cross section burnable
absorb materials to compensate for excess reactivity during the
early stages of the PWR core life. If these burnable absorb materials
(poisons) match the time behavior of the excess fuel reactivity as it
decreases over PWR core life appropriately, these burnable absorb
materials allow larger initial fuel inventories without a corre-
sponding increase in control requirements. Burnable poisons thus
possess a number of advantages, they increase core lifetime
without any decrease in control safety, reduce the amount of con-
trol rod control requirements, and if distributed in a proper fashion,
can also improve core power distributions.
As technetium has relatively large capture cross sections in the
thermal neutron region, adding technetium in the uranium dioxide
nuclear fuel can partially compensate for excess reactivity during
the early stages of the PWR core life. This means that technetium
can replace some burnable absorb poisons in the pressurized water
reactor. However, the uniform distribution of technetium in the
uranium dioxide fuel leads to the initial change in reactivity very
high due to the rapid depletion of the technetium, this technetium
loading pattern results in a reactivity mismatch (Duderstadt and
Hamilton, 1976). This mismatch will be less severe for a poison
with a small absorption cross section. As technetium have relatively
large capture cross sections in the thermal neutron region, the
reactivity rise due to the relatively rapid depletion of technetium
will be greater than which can be handled by the available me-
chanical control in the PWR. Except to reducing the initial reactivity
significantly, mixing technetium in the uranium dioxide nuclear
fuel homogeneously may also bring the control difficulties in the
pressurized water reactor. Thus based on the simulation calculation
results and above arguments, for the transmutation of technetium
in the pressurized water reactor, it is obviously not feasible to mix
the technetium to the uranium dioxide fuel homogeneously.
4.3. Thin layer coating of Technetium-99 on PWR fuel rods
The uniform distribution of technetium-99 in the uranium di-
oxide fuel not only can lead to the initial change in reactivity very
high due to the rapid depletion of technetium-99, but also result in
a reactivity mismatch (Duderstadt and Hamilton, 1976). Study
shows that the technetium-99 transmutation rate in PWR within
one fuel cycle is not very high no matter with which technetium-99
loading patterns; people need to recycle the technetium-99 to
transmute again in PWR after discharged from the previous fuel
cycle (Setiawan and Kitamoto, 2001). To avoid the problems of the
homogeneous mixing of technetium-99 with PWR nuclear fuel, we
explore the transmutation characteristics of coating a thin layer
technetium-99 on PWR fuel rods.
Base on EFTTRA-T2 (Konings and Conrad, 1999) experimental
results we know that the transmutation rate in the surface region of
 B. Liu et al. / Progress in Nuclear Energy 85 (2015) 375e383 379

the transmutation target is much higher than that of the inner
region of the transmutation target. If we just use the surface region
of transmutation target to transmute the technetium-99, the
overall transmutation rates will be much higher than trans-
mutation rate on the transmutation target average. This encourages
us to study the transmutation characteristics after coating a thin
layer of technetium-99 on the fuel rods of the PWR which we
believe can achieve a higher technetium-99 transmutation rate in
the commercial PWR reactors.
As shown in the Fig. 3, the geometrical configuration of
technetium-99 transmutation target is exactly the same as the fuel
rods of the PWR, we just slightly reduce the diameter of the fuel
pellet of the PWR and coat a thin layer of the technetium-99
transmutation material on PWR fuel pellet, the final diameter of
the technetium-99 transmutation target is exactly the same as the
fuel rods of the PWR. By this means, the structure of the PWR is not
modified at all. Technetium-99 has a highest neutron capture cross
section 4400 b at energy 5.6 eV, the corresponding mean free path
of neutron capture is lc ¼ 0.0325 mm. We calculate the variations of
the PWR keff, total technetium-99 loading amount and technetium-
99 to fuel ratio after coating technetium-99 on the PWR fuel rods in
the thicknesses of 0.05lc, 0.1lc, 0.15lc, 0.2lc, 0.4lc, 0.6lc, 0.8lc, 1.0lc
respectively. The calculation results are listed in Table 2.
From the calculation results listed in Table 2 we can see clearly,
as technetium-99 coating thickness increase from 0.05lc to 1.0lc,
the loading amount of technetium-99 also increase, but the keff of
PWR core decrease significantly. When the coating thickness of
technetium-99 reach to one mean free path of technetium-99 at
neutron energy 5.6 eV, which is equal to 0.0325 mm, keff of PWR
core drops to 0.92156. This indicates that coating a thin layer of
technetium-99 to the fuel rods of PWR can drastically affect system
keff. We also calculate the total technetium-99 loading amount and
the corresponding number of annual PWR technetium-99 yield, see
Table 2 for the detail.
From Table 2 we can see, if we just coat 0.20lc thickness
technetium-99 on PWR fuel rods, this equals to 0.0065 mm thick-
ness of technetium-99 coating, total technetium-99 coating
amount is 291.37 kg, this is approximately equivalent to the 4 PWR
technetium-99 annual outputs, the system keff merely decreases to
0.98530. So we conclude that the optimal coating thickness of
technetium-99 on PWR fuel rods is probably between 0.15lc to
0.2lc, i.e. 0.00488e0.0065 mm.
The black curve in Fig. 2 shows the effects on keff of the PWR
core after coating different thickness of technetium-99 to the PWR
fuel rods. From Fig. 2 we can see that addition of technetium to the
uranium dioxide fuel homogeneously can affect keff of the PWR
significantly. In comparison of the two curves in the Fig. 2 we find
that for the same technetium-99 loading amount, the effect on keff
of the PWR core after coating technetium-99 to the PWR fuel rods is
much less than that of the homogeneous addition of technetium-99
to uranium dioxide nuclear fuel. In other words, the curve of the
thin layer technetium-99 coating is more flatten than the curve of
the homogeneous addition of technetium-99 to uranium dioxide
nuclear fuel. This comes from the facts that coating a thin layer of
the technetium-99 on PWR fuel rods prevents the technetium-99
from admixture with the uranium dioxide nuclear fuel thor-
oughly, the initial keff drops much slower than the homogeneous
addition of technetium-99 to uranium dioxide nuclear fuel. In
addition, even coating 1.0lc thickness of the technetium-99 on
PWR fuel rods, the spatial self-shielding effect is negligible, so the
transmutation rate of the technetium-99 can get to highest point.
Therefore, compared to the homogeneous addition of technetium-
99 to uranium dioxide nuclear fuel, a thin layer coating of
technetium-99 to the PWR fuel rods have unique advantages in
transmutation of technetium-99 within the PWR, it can avoid the
spatial self-shielding effects and initial keff of PWR to drop too fast.

5. Technetium-99 partial substitution for control poisons

Based on previous section analyses we can conclude that no

Fig. 3. The configuration of the Tc-99 transmutation rod after a thin layer Tc-99
coating on fuel pellet.
matter which way the technetium-99 loading to PWR, a homoge-
neous addition of technetium-99 to uranium dioxide nuclear fuel or
coating a thin layer of the technetium-99 on PWR fuel rods, the
initial reactivity of the PWR reactor will drop, the different is just
the extent of keff drop of two different loading patterns. This re-
minders us that the technetium-99 behaves as control poisons in
some sense in the thermal reactors (Liu et al., 2013, 2014; Hu et al.,
2015). Therefore, after loading technetium-99 transmutation ma-
terial to PWR, some control poisons should be removed from the
PWR core to keep the reactor in criticality, that is technetium-99

Table 2
The calculation results of coating Tc-99 on PWR fuel rods.

Coating Inner radius of fuel Inner radius of Tc-99 Outer radius of Tc-99 Total Tc-99 loading Equivalence number Tc/(Tc þ UO2) keff Standard
thicknessa rods (cm) coating (cm) coating (cm) amount (kg) of one PWR Tc-99 (weight %) Variation deviation of keff
annual outputb

0 0.409500 0.409500 0.409500 0 0 0 1.01042 0.00022

0.05lc 0.409338 0.409338 0.409500 72.89 1 0.0895 1.00338 0.00054
0.10lc 0.409175 0.409175 0.409500 145.74 2 0.1789 0.99700 0.00047
0.15lc 0.409013 0.409013 0.409500 218.57 3 0.2682 0.99014 0.00059
0.20lc 0.408850 0.408850 0.409500 291.37 4 0.3575 0.98530 0.00021
0.40lc 0.408200 0.408200 0.409500 582.28 8 0.7141 0.96638 0.00021
0.60lc 0.407550 0.407550 0.409500 872.73 12 1.0699 0.94976 0.00021
0.80lc 0.406900 0.406900 0.409500 1162.7 17 1.4248 0.93472 0.00021
1.00lc 0.406250 0.406250 0.409500 1452.23 22 1.7789 0.92156 0.00020

Note.
a
lc ¼ 0.0325 mm, is the technetium-99 mean free path of neutron capture at neutron energy 5.6 eV.
b
Typical 900 MWe PWR discharges about 22 tons of spent fuel per year, roughly 5% of that are fission products and roughly 6% of those is Tc-99, therefore the annual output
of technetium-99 from a typical PWR is approximately 66 kg.
380 B. Liu et al. / Progress in Nuclear Energy 85 (2015) 375e383
can partially substitute for control poisons in the PWR, either
burnable control rods or boric acid in the coolant. This is one of
distinct advantages to transmute the technetium-99 in the PWR
reactors, we may reduce the concentration of the boric acid in the
coolant of the PWR reactors and increase the negative temperature
coefficient of the thermal reactors, all these measures can drasti-
cally reduce the possibility of the critical accident in a fuel cycle. We
may also just remove some burnable control rods from the PWR
core and reduce the negative impacts on the PWR operation. In
other words, loading technetium-99 transmutation material to
PWR does not consume extra neutrons; technetium-99 trans-
mutation material just consumes the neutrons which absorbed by
the removed control poisons.
5.1. Technetium-99 partial substitution for boric acid
In a typical PWR reactor, very slow but ultimately very large
changes in reactivity is made by adjusting the boric acid concen-
tration which dissolved in the coolant. Such soluble poisons or
chemical shim have several advantages. Since the poison distribu-
tion is uniform and independent of the amount of reactivity being
controlled, the fuel loading can be more easily distributed to yield a
uniform power distribution. Chemical shim control reduces the
mechanical control rod requirement quite considerably.
However, chemical shim control does have several disadvan-
tages. Since the rate at which reactor operator can inject or with-
draw appreciable amount of boric acid from the coolant is quite
small, the reactivity insertion rates are correspondingly small.
Hence boric acid is only used to compensate for relatively slow
reactivity changes. Chemical shim control can have a major effect
on the moderator temperature coefficient of reactivity. In PWR, this
effect on the moderator temperature coefficient of reactivity is
usually quite negative, since the injection of the boric acid to the
coolant means that the decrease in coolant density, this further
leads to a decrease in neutron moderation and hence reactivity.
However if a soluble poison is present, a decrease in coolant density
will also lead to a decrease in poison concentration, a positive
reactivity effect. Therefore, our desire for a negative temperature
coefficient will limit the amount of boric acid allowed in the pri-
mary coolant.
As technetium-99 behaves as control poisons in some sense in
the thermal reactors (Liu et al., 2013, 2014; Hu et al., 2015), after
loading technetium-99 transmutation material to PWR, we may
reduce the boric acid concentration in the coolant to compensate
some the reactivity decrease induced by addition of technetium-99.
This denotes that technetium-99 can partially substitute for boric
acid in the PWR coolant and increases the negative temperature
coefficient of the PWR; this can reduce the possibility of the critical
accident in a fuel cycle of PWR.
Table 3
Substitution of Tc-99 for Boric acid.
Tc-99 coating Boric acid concentration vs keff (CB/keff)
thickness
The keff after coating a thin layer Tc-99 on PWR fuel The boric acid concentration after readjusting keff to
rods
0 705 ppm/1.01042
0.05lc 705 ppm/1.00338
0.10lc 705 ppm/0.99700
0.15lc 705 ppm/0.99014
0.20lc 705 ppm/0.98530
0.40lc 705 ppm/0.96638
0.60lc 705 ppm/0.94976
0.80lc 705 ppm/0.93472
1.00lc 705 ppm/0.92156
To study the actually amount of the boric acid concentration in
the coolant can be reduced after coating a different thickness of
thin layer of technetium-99 on PWR fuel rods, we readjust the boric
acid concentration in the PWR coolant to let the reactor to return
criticality and calculate reduced boric acid concentration in the
coolant. The calculated results are listed in the Table 3.
From the results listed in the Table 3 we can conclude, under the
initial boric acid concentration 705 ppm, as the technetium-99
coating thickness increases the total technetium-99 loading
amount increases, and the system keff decreases correspondingly.
Likewise, we can also let the PWR keff return criticality by read-
justing the boric acid concentration in the coolant of PWR. The
more technetium-99 is loaded to the PWR, the more boric acid
concentration need to be reduced from the coolant. For instance,
when the coating thickness of technetium-99 is 0.2lc, 149 ppm
boric acid concentration must be reduced from the PWR primary
coolant to let the PWR return criticality. As a result, we may say that
loading the technetium-99 to the PWR is equivalent to introducing
extra poisons to PWR system to control excess reactivity; some
control poisons like boric acid concentration in primary coolant
need be removed to keep the reactor in criticality. This once again
indicates that technetium-99 can partially substitute for boric acid
in the PWR primary coolant to increase the negative temperature
coefficient of a PWR; the reduction of the boric acid concentration
in the primary coolant can reduce the possibility of the critical
accident in a fuel cycle of PWR. This is definitely one of distinct
advantages to transmute the technetium-99 in the PWR reactors.
5.2. Technetium-99 partial substitution for burnable poisons
The lifetime of a given PWR core fuel loading is generally
determined by sufficient excess reactivity to permit startup and full
power operation. Of course the amount of fuel loaded into the PWR
reactor will depend in part on the excess reactivity that can be
conveniently compensated for by the reactor control elements. In
order to increase the allowable initial core fuel loading, it is com-
mon to load into the core burnable poisons characterized by high
neutron absorption cross sections that compensate for excess
reactivity during the early stages of the PWR core lifetime. People
choose such burnable poisons used in the PWR because they burn
out somewhat faster than the fuel burnup, so that later in PWR core
life they contribute negligible negative reactivity. Burnable poisons
thus possess several advantages. They increase PWR core lifetime
without any decrease in control safety, reduce the amount of con-
trol rods requirement, and can improve PWR core power distri-
bution if distributed in PWR core in a proper way.
Our previous conclusion reveals that after introducing
technetium-99 into PWR core, it can behave as control poisons in
some sense in the PWR reactors. Except partially substitute for
The reduced boric acid concentration
(CB)
criticality
662 ppm/1.01039 43 ppm
621 ppm/1.01059 84 ppm
589 ppm/1.01028 116 ppm
556 ppm/1.01045 149 ppm
443 ppm/1.01042 262 ppm
345 ppm/1.01069 360 ppm
258 ppm/1.01029 447 ppm
174 ppm/1.01075 531 ppm
 B. Liu et al. / Progress in Nuclear Energy 85 (2015) 375e383 381

boric acid in the PWR primary coolant to increase the negative Table 5
temperature coefficient of the PWR, we are confident to believe Burnable poison rod substitution pattern after coating Tc-99 on fuel rods.

that technetium-99 can also be used to substitute for burnable Tc-99 Substitution keff Standard Removed
absorb rods to control the excess reactivity of PWR. China Guang- coating pattern deviation burnable
dong Daya Bay 900 MW pressurized water reactor use borax glass thickness of keff poison rods

as the burnable poisons. Table 4 lists its material composition. 0.05lc B16/12 1.00600 0.00051 48
There are three different fuel assemblies in the core of China C16/12 1.00482 0.00057 32
0.1lc B16/12 1.00093 0.00052 48
Guangdong Daya Bay 900 MW pressurized water reactor which are
C16/12 0.99975 0.00053 32
labeled by A, B and C with U-235 enrichments 1.8%, 2.4%, 3.1% 0.15lc B16/12 0.99516 0.00055 48
respectively. See Fig. 1 for details. For the layout of the fuel as- C16/12 0.99325 0.00051 32
semblies with 16 and 12 burnable poison rods, see Fig. 4 for details. 0.2lc B16/12 0.98762 0.00021 48
C16/12 0.98637 0.00022 32
As all the PWRs are well designed, and the PWRs are pretty
mature technology, we should try to modify the structure of PWRs
minimally when introduce the technetium-99 to PWR core for
transmutation. After introducing technetium-99 into PWR core, it
can behave as control poisons in a way, so we need to remove some poison rods from fuel assemblies. The removed burnable poison
burnable poison rods from PWR core to let the PWR return criti- rods for two different substitution patterns are quite different
cality. This indicates that coating thin layer of technetium-99 because the enrichment difference in the two different fuel as-
transmutation material on the fuel rods can also partially substi- semblies. For B16/12 (2.4% enrichment fuel assemblies) substi-
tute for burnable poison rods in PWR core. We remove 4 burnable tution pattern, the removed burnable poison rods are 48, whereas
poison rods from the fuel assemblies of B16 or C16, so the total for the C16/12 (3.1% enrichment fuel assemblies) substitution
numbers of burnable poison rods in fuel assemblies of B16 or C16 pattern, the removed burnable poison rods are 32. There are 16
become 12. Then we calculate the system keff after coating different removed burnable poison rod differences between the two
thickness of technetium-99 transmutation material on PWR fuel different substitution patterns. As the B16 and C16 fuel assemblies
rods. The calculated system keff is listed in Table 5 after coating are in the different location of reactor core and with the different
different thickness of technetium-99 transmutation material on the fuel enrichment, above results indicate that when people use the
PWR fuel rods and removing 4 burnable poison rods from the fuel technetium-99 transmutation materials to substitute the burnable
assemblies of B16 or C16. poison rods, the locations of the substituted burnable poison rods
Table 5 lists the system keff and removed burnable poison rods of are also an important factor. For coating same amount of the
two different substitution pattern as technetium-99 coating transmutation materials on the fuel rods of PWR, the substituted
thickness increases from 0.05lc to 0.2lc. We can see from Table 5 burnable poison rods are different for removing burnable poison
that as technetium-99 coating thickness increases from 0.05lc to rods from the fuel assemblies in different locations of reactor core.
0.2lc, no matter which substitution pattern we use, B16/12 or From Table 5 we also can see, after coating 0.15lc or 0.2lc
C16/12, the system keff variations are almost the same and can thickness to the fuel rods of PWR, the system keff is slightly below
return to criticality again after removing corresponding burnable the criticality either in B16/12 substitution pattern or the
C16/12 substitution pattern; we may reduce the concentration of
the boric acid slightly to let the system in criticality again. If the
technetium-99 coating thickness on PWR fuel rods is thicker than
Table 4
0.40lc, the system keff drops too much (see Table 3 for details),
Material composition of burnable poisons.
simulation calculations show that system keff is unable to return to
Nuclei B-10 B-11 O-16 Al-27 Si-28 criticality just by removing burnable poison rods from the PWR
Ratio 0.0140 0.0568 0.6530 0.0077 0.2685 core either by B16/12 substitution pattern or C16/12

Fig. 4. Layout of the fuel assemblies with 16 and 12 burnable poison rods.
382 B. Liu et al. / Progress in Nuclear Energy 85 (2015) 375e383
substitution pattern. This is once again indicates that the optimal
coating thickness of technetium-99 on PWR fuel rods is probably
between 0.15lc to 0.2lc.
Besides, as the two most important control mechanisms,
chemical skim control and the burnable poison control, they have
quite different control characteristics on the reactor core. To change
the concentration of boric acid in the PWR coolant, we can adjust
the system keff gradually and continuously. The burnable poison
rods symmetrically distribute in the fuel assemblies of PWR,
therefore just changing the number of the burnable poison rods in
the PWR we are unable to adjust the system keff gradually and
continuously. In real PWR transmutation core design, to control the
system keff after coating technetium-99 transmutation materials on
the fuel rods of PWR, we need to remove corresponding burnable
poison rods from the PWR core no matter which substitution
pattern we use, then change the concentration of boric acid in the
PWR coolant to let the system keff gradually and continuously to
return criticality.
6. Conclusion
Based on the EFTTRA-T2 experiment result (Konings and
Conrad, 1999; Konings et al., 1998b) we conclude that the trans-
mutation rate in the surface region of the cylindrical transmutation
target is much higher than that of the inner region of the cylindrical
transmutation target, this is because the strong spatial self-
shielding effect in the surface region of the cylindrical trans-
mutation target. This encourages us to study the transmutation
characteristics of PWR after coating a thin layer of Tc-99 on the fuel
rods.
Our calculation shows that the homogeneous mixing of Tc-99
with PWR nuclear fuel can lead to the change of initial reactivity
very high in a fuel cycle, affect the lifetime of a fuel loading and
result in reactivity mismatch. In contrast to the homogeneous
mixing, if we just coat 0.20lc (0.0065 mm) thickness Tc-99 on PWR
fuel rods, the total Tc-99 coating amount is 291.37 kg, this is
approximately equivalent to the 4 PWR Tc-99 annual outputs, the
system keff merely decreases to 0.98530. Therefore, compared to
the homogeneous addition of Tc-99 to uranium dioxide nuclear
fuel, a thin layer coating of Tc-99 on the PWR fuel rods has unique
advantages in transmutation of Tc-99 within the PWRs; it can avoid
the spatial self-shielding effect and initial keff of PWRs to drop too
fast.
Loading the Tc-99 to the PWR is equivalent to introducing extra
poisons to PWR system to control excess reactivity; we need to
remove some control poisons like boric acid concentration from
primary coolant or burnable poison rods from fuel assemblies to
keep the reactor in criticality. For instance, when the coating
thickness of Tc-99 is 0.2lc, 149 ppm boric acid concentration must
be reduced from the PWR primary coolant to let the PWR return
criticality. The reduction of the boric acid concentration in the
primary coolant can reduce the possibility of the critical accident in
a fuel cycle of PWR. This is definitely one of distinct advantages to
transmute the Tc-99 in the PWR reactors.
As Tc-99 coating thickness increases from 0.05lc to 0.2lc, no
matter which substitution pattern we use, B16/12 or C16/12, the
system keff variations are almost the same and can return to criti-
cality again after removing corresponding burnable poison rods
from fuel assemblies. This means after removing 4 burnable poison
rods from the fuel assemblies of B16 or C16, the total numbers of
burnable poison rods in the fuel assemblies of B16 or C16 become
12. But the removed burnable poison rods for two different sub-
stitution patterns are quite different because the enrichment dif-
ference in the two different fuel assemblies.
After coating 0.15lc or 0.2lc thickness on the fuel rods of PWR,
the system keff is slightly below the criticality either in B16/12 or
C16/12 substitution pattern; in this situation we may reduce the
concentration of the boric acid slightly to let the system in criti-
cality again. If the Tc-99 coating thickness on PWR fuel rods is
thicker than 0.40lc, the system keff drops too much, simulation
calculations show that system keff is unable to return to criticality
just by removing burnable poison rods from the PWR core either by
B16/12 or C16/12 substitution pattern. This indicates that the
optimal coating thickness of Tc-99 on PWR fuel rods is probably
between 0.15lc to 0.2lc, i.e. 0.00488e0.0065 mm.
In summary, PWR reactor transmutation is a feasible and
economical way to transmute Tc-99 in large scale, and we can
realize the Tc-99 transmutation in the PWR efficiently and guar-
antee the safe operation of PWR simultaneously.
Acknowledgments
This work is supported by China National 863 Project entitled
“Thermal Reactor Transmutation Technology” under contract
number 2013AA051402. This work is also supported by Beijing
Higher Education Young Elite Teacher Project (Grant No.
YETP0720).
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