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Current Concerns on Durability of Concrete Used in Nuclear Power Plants and

Radioactive Waste Repositories

Conference Paper · January 2018

DOI: 10.1007/978-981-10-6713-6_111

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 Current Concerns on Durability of Concrete
Used in Nuclear Power Plants and Radioactive
Waste Repositories

Quoc Tri Phung(&), Norbert Maes, and Diederik Jacques

Institute for Environment, Health, and Safety,

Belgian Nuclear Research Centre (SCK∙CEN), 2400 Mol, Belgium
{quoc.tri.phung,norbert.maes,
diederik.jacques}@sckcen.be

Abstract. Nuclear power, to most of us, is mystic and somehow scary, and
despite its drawbacks, is still playing an important role in the world wide energy
supply. However concrete, without mystery as the most widely used materials in
construction, is used as a major constituent for nuclear facilities such as
radioactive waste repositories and nuclear power plants. Concrete is the only
practical material offering a number of advantages including sufficient shielding
against the dangers of radiation, good compressive strength, low cost, easy
building, and retention of radionuclides limiting their dissipation. The assess-
ment of the long-term durability of such concrete structures is of utmost
importance and urgently needed as our knowledge on concrete durability
beyond the basis of an expected several decade service life is limited. Within its
service environment, these structures undergo chemical degradation processes
which are very slow but they significantly change the physical integrity and the
chemical conditions of the structures with the passage of time. Current issues on
durability of these concrete structures include alkali-silica reaction, delayed
ettringite formation, leaching, carbonation, etc. which might be magnified under
severe/accelerated conditions (high temperature, radiation, moisture, cyclic
loading, and acidic environments). These degradations induce an evolution of
the microstructure, cracking and changes in transport properties of concrete
which are still unclear due to the limited experimental timeframe available to
capture these processes. This paper presents an overview on these concerns with
the focus on the long-term chemical degradation aspect and presenting a case
study on Ca-leaching.

Keywords: Concrete durability
Radioactive waste
Nuclear power plant

Chemical degradation
Alkali silica reaction
Leaching

1 Introduction

Despite that renewable energy is steadily going up (e.g. biogas, municipal waste, solar,
wind, hydro), nuclear power still has an important role in the energy supply worldwide
and contributes almost 12% electricity of the world (Pomaro 2016). Nuclear energy is
used by more than 30 countries. More than 25% of the electricity of Europe is nuclear

© Springer Nature Singapore Pte Ltd. 2018

H. Tran-Nguyen et al. (eds.), Proceedings of the 4th Congrès International
de Géotechnique - Ouvrages -Structures, Lecture Notes in Civil Engineering 8,
DOI 10.1007/978-981-10-6713-6_111
1108 Q.T. Phung et al.

power and is generated from 186 nuclear power plants (NPPs) as of 2016. In the United
States 61 NPPs provide about 20% of the electricity supply (Naus 2009). Asia is the
main region in the world where nuclear power is growing significantly. There are 128
operable nuclear power reactors, among them Japan contributes 43 reactors. The
increase of NPPs also entails that considerable amounts of radioactive waste need to be
managed for very long time periods.
In the case of nuclear wastes storage and disposal, a multi-barrier principle is
adopted in order to ensure the safety of people working or living near storage facilities.
Different types of confinement elements, often made from cementitious materials, are
used so that optimal storage conditions are satisfied. These cementitious materials are
envisaged for use both for encapsulation of radioactive waste and as engineered bar-
riers for disposal of radioactive waste, both in near-surface repositories for
low/intermediate active waste and geological/deep repositories for high level long-lived
radioactive waste (see Fig. 1a, b). The role of cement-based materials in these appli-
cations is not only focused on the retention of radionuclides (attributed to its low
transport properties) but also in helping creating beneficial conditions for the waste
package integrity (steel corrosion) because of its high-pH buffering capacity for a very
long period. Concrete is also the first choice for isolation the radioactive materials when
a nuclear disaster happens. Following the 1986 Chernobyl disaster, the whole site of
Chernobyl NPP was encased inside a vast structure known as the sarcophagus made
from 400,000 m3 of concrete to limit radioactive contamination of the environment.
And recently, after the 2011 Fukushima accidence, Japanese engineers was thinking to
burry NPP in thick concrete layers as done at Chernobyl.

(a) (b) Concrete (c)

Concrete

Fig. 1. Concrete used for (a) encapsulation, backfill and construction in low level waste facility,
(b) disposal gallery lining, buffer, end-plug of gallery and backfill in high level waste facility –
Belgian Supercontainer concept (examples of current proposed concepts by ONDRAF/NIRAS
for Belgium, pictures taken from NIRAS (2012) and NIRAS (2011)) and (c) cooling towers in
Tihange-Belgium NPP.

A typical NPP uses a number of concrete-based structures to provide foundation

support and shielding as well as containment functions. Concrete structures also
function as spent and new-fuel storage pools and cooling towers (Fig. 1c). Under its
service environment, these concrete structures undergo chemical degradation processes
which are usually very slow but important for the long-term durability assessment.
Chemical degradation is typically the result of alteration of the cement matrix miner-
alogy caused by interaction with its environment. The interaction disturbs the equi-
librium between the pore solution of the cementitious materials and the solid phases of
 Current Concerns on Durability of Concrete 1109

the cement matrix which results in dissolution and/or precipitation of minerals. The
degradation is a function of many factors including the constituent materials, its
location (e.g. coastal, inland or underground for waste disposal), climatic conditions
(e.g. temperature and moisture), and the presence of external agents (e.g. sulfates and
chemicals). The chemical degradation of cementitious materials is mostly followed by
alteration of the microstructure and, thereby, its transport properties. The most common
chemical degradation processes include chloride ingress, sulphate attack, alkali-silica
reactions, carbonation and Ca-leaching. The operating licenses for commercial NPPs
are typically issued for 40 years and can be renewed for additional 20 years with no
limit to the number of renewals. Therefore, the concrete structures in NPPs need to be
reliably designed for ages longer than 60 years. For waste disposal facilities, the service
life of concrete structures is directly related to the time necessary for the waste’s
radioactivity to decay, which typically exceeds hundreds or thousands of years (Jac-
ques et al. 2013). It is, therefore, necessary to explain how concrete will degrade, and
how the properties evolve in the long-term. With this research, we aim at giving an
overview on these concerns with the focus on the long-term chemical degradation
aspect and presenting a case study on Ca-leaching in accelerated conditions.

2 Concrete Degradation in Nuclear Related Structures

2.1 Road Ahead to Ensure Concrete to be a Durable Material

for Nuclear Related Structures
Many environments are highly aggressive due to various chemical components. In such
environments, concrete is subjected to processes of chemical degradation. Common
chemical degradation processes are sulfate and chloride attacks, alkali silica reaction
(ASR), leaching and carbonation (Fig. 2a). Depending on the roles of structures, the
expected life span and the environments to which the concrete structures are exposed,
different chemical degradation processes are considered. For concrete used in con-
tainment buildings of NPPs designed as the physical barrier against radioactive material
release to the outside environment, potential degradation is reinforced corrosion and
nuclear radiation induced cracking which breaks down its function to ensure the leak
tightness and structural integrity. Other concrete structures (e.g. the reactor building,
spent fuel pools, cooling towers) provide support and shielding functions and they
undergo chemical degradation under different mechanisms depending on its sur-
rounding working environments. For example, the spent fuel pools are exposed to
“aggressive” water (e.g. borated or demineralized water), elevated temperatures and
radiation, while the cooling towers may be susceptible to ageing due to their specific
service conditions (e.g. freeze-thaw action, carbonation). Degradation surely affects the
ability of these concrete structures to meet functional and performance requirements
and reduce its expected service life.
Concrete degradation can be caused by external or internal attacks. The external
attack can be reduced by designing thick cover, elements which allows ensuring a
relative long expected life span of 100 years. However, the internal attack can cause
destruction in short time scales regardless of structure thickness. The internal attack
1110 Q.T. Phung et al.

50 100s 1000s 100,000s Years

(a) Concrete
years
Concrete

(b)

Sulfate EFt
attack

Chloride
attack

ASR

90 years
Leached zone
Leaching
Sound zone

Carbonation

Low High

Chemical degradation

Fig. 2. Typical concrete degradation in relation to roles of concrete structures (a) and proposed
Belgian repository concrete structure under coupled effects by chemical, physical and mechanical
degradation processes (b) (NIRAS 2007)

commonly causes ASR cracking and internal sulfate attack induced delayed ettringite
formation (DEF). To ensure durability and avoid internal attack, the selection of
concrete constituents is essential. More care in the selection and characterization of
aggregates will help to avoid ASR which can cause important degradation decades after
construction is completed. Some structures (e.g. cooling towers) are subjected to
degradation due to their relatively thin covers and severe environments (e.g. high
humidity, freeze-thaw cycling and varying temperatures). Common external degrada-
tion mechanisms for these concrete structures are freeze-thaw, ice formation, carbon-
ation and corrosion due to acidic water chemistry and corrosion from aggressive marine
environments. Freezing and thawing of water in concrete causes extensive cracking
and/or spalling resulting in loss of concrete integrity and an increase of permeability
that allows water to reach and corrode rebar while chloride attack because vicinity of a
marine environment or using municipal water (high chloride content) for cooling can
seriously corrode the rebar and generate cracks. In general, the safety-related concrete
structures in NPPs are designed to be robust enough to bear both internal and external
attacks. However, as the nuclear power plants age, degradation incidences are starting
to occur at an increasing rate, primarily due to environmental-related factors, which
causes one-fourth of all containments to experience corrosion (IAEA 2016). This is
perhaps due to the fact that there is only a little or no data on long-term concrete
performance for concrete in NPPs, even though they are largely built of concrete!
Operations in the nuclear power industry certainly produce a wide variety of
radioactive wastes. Over the last 60 years, more than 350,000 tons of high-level nuclear
waste has been produced over the world and must be deposited for thousands of years
in a safe place. And on the journey to find a suitable solution, underground repositories
have been chosen by many countries, in which concrete is considered as a useful
material (see Figs. 1a, b and 2b) for these repositories with extremely long-term service
life. Therefore, the assessment of the long-term performance of such concrete structures
is of utmost importance. The role of cement-based materials in these applications is not
only focused on the retention of radionuclides (attributed to its low transport properties)
but also in helping creating beneficial conditions for the waste package integrity (steel
corrosion) because of its high-pH buffering capacity for a very long period. Within its
 Current Concerns on Durability of Concrete 1111

service environment, these structures undergo coupled degradation processes (Fig. 2b)
which might significantly change the physical integrity (e.g. transport and mechanical
properties) and the chemical condition (e.g. pH) of the structures in the long-term. In
many cases, the disposal facility is attacked by aggressive water, which will induce
chemical disequilibrium and dissolution of cementitious solid phases by processes such
as Ca-leaching and carbonation. The chemical degradation of cementitious materials is
mostly followed by alteration of the microstructure and, thereby, transport properties.
The transport properties such as permeability and diffusivity are the key parameters to
evaluate whether the concrete still retains its function as a barrier against the transport
of radionuclides and other hazardous products out of the disposal system. Moreover,
the heat generated during the repository life may accelerate the chemical processes. The
alteration of chemical properties will in turn induce changes in the cement
microstructure and consequently changes in mechanical performance and transport
properties (permeability, diffusion (Patel et al. 2016)) of concrete structures. Therefore,
a systematic approach is needed to establish the relationship between multiple pro-
cesses at multiple scales, which would provide knowledge of long-term safety of
radioactive waste disposal and suggestions on how safety functions of the repository
components can be improved in terms of material and structure designs. Although a lot
of effort has been spent on studies concerning the use of cement-based materials in such
structures, the evolution of the microstructure and transport properties under chemical
degradation over long time periods (up to thousands of years) is still unclear due to the
limited experimental timeframe available to capture these processes.
The predisposal waste management is to produce waste packages suitable for
storage, transportation and final disposal. For decades, the nuclear industry has used
cement-based materials (CBM) to immobilize low- and intermediate-level short-lived
and long-lived radioactive waste originating from the operation of nuclear power plants
and from the chemical reprocessing of spent fuel. Compared with other solidification
techniques, the cementation technique is relatively simple and inexpensive. Moreover,
CBM shows many advantages such as easy supply, good self-shielding and high
alkalinity, which allow to precipitate and thus confine many radionuclides. One could
expect that this practice would result in a stable waste form that is well compatible with
the final disposal site, there are, however, many examples that show that this is not
always the case. Specific issues have been addressed, such as the gel-formation
attributed to ASR in the concrete operational waste of the nuclear power plant of Doel,
Belgium (Federal Agency for Nuclear Control (FANC) 2014), the limitation of adverse
cement–waste interactions which may affect the quality of the resulting solidified waste
form, or the understanding and prediction of long-term properties of the waste pack-
ages and cement barriers. There is also a need for safe processes minimizing the
production of secondary wastes.
In the following sub-sections, the authors will briefly address some current con-
cerned degradation mechanisms of CBM in nuclear related structures.

2.2 Alkali Silica Reaction and Delayed Ettringite Formation

ASR is a deleterious reaction between the silica (from aggregates) and alkalis in pore
solution or portlandite (CH) (solid phase) in the presence of water to form ASR gel
1112 Q.T. Phung et al.

(e.g., calcium potassium silicate hydrate, calcium sodium silicate hydrate). The amount
of ASR gel varies depending on the reaction temperature, type and proportions of the
reacting materials, gel composition, gradation of aggregates, and other factors, among
them silica content and the internal structure of aggregate are the most important.
Swelling of this gel leads to stress development and potentially, cracking of concrete.
ASR is a major durability problem of concrete including dams and hydraulic structures,
pavements, bridges, and recently NPP concrete structures, while there is no feasible
method available to stop the reaction. It has long been known that irradiation affects
concrete properties. Nuclear irradiation (especially neutron irradiation presented later in
Sect. 2.3) can significantly increase the reactivity of silica-rich aggregates. DEF is a
special case of internal sulfate attack. It occurs when internal or external sulfates react
with anhydrous or hydrated calcium aluminates after hardening inducing cracking in
hardened concrete. DEF is a result of high early temperatures (above 70–80°C) in
concrete which prevents the normal formation of ettringite or the decomposition of
ettringite that has already formed. Use of cements having high sulfate from gypsum)
and aluminate (C3A) content can highly lead to DEF. The extent of DEF development
is also dependent on water presence in concrete and the temperature. Elevated tem-
perature, which is the case for concrete in nuclear related structures, increases potential
for damage due to DEF.
During in-service inspection of the concrete engineered structures, extended
degradations by ASR (Fig. 3a) of concrete apparent on the external surface of the
secondary containment building of the Tihange 2 reactor were observed (Federal
Agency for Nuclear Control (FANC) 2013). Typical degradation depths were 3 to
5 cm. DEF was also sometimes observed in association with ASR. DEF is also a high
risk for cemented wastes containing high sulfate content. Seabrook NPP in the U.S.
also appears to be significantly suffering from ASR in localized zone of its subbase-
ment (Saouma and Hariri-Ardebili 2014) (Fig. 3b). Some NPPs in Japan, France and
Canada also reported ASR related degradation.

2.3 Nuclear Radiation Damage

Concrete structures used as biological shields in NPPs and radioactive waste storage
facilities are subjected to two types of radiation, gamma and neutron (William et al.
2013). Neutron radiation is the emission of neutrons; gamma rays are a special form of
photon radiation. There are two types of interactions between nuclear radiation and the
internal structure of concrete: geometric changes of solid phases and phase transfor-
mations resulting in changes in properties of concrete. Gamma rays have an insignif-
icant effect on hydrated phases and aggregates of concrete but significantly influence
the pore solution (Kontani et al. 2014). Water in the concrete can be decomposed by
gamma rays by a process called radiolysis and can be converted to hydrogen, oxygen,
and hydrogen peroxide which may react with the cement paste. Water can also be
removed from the concrete by evaporation due to heat generated by gamma radiation
resulting in shrinkage of cement paste (Fig. 3d). Neutron and gamma radiation can lead
to an increase in concrete temperature up to 250°C (Fillmore 2004) inducing significant
impacts on the mechanical and radiation-shielding properties of concrete. It also has
been shown that as the gamma radiation dose increases the concentration of calcite
 Current Concerns on Durability of Concrete 1113

(a) (b) (c)

(d) Ȗ -irradiated (e) (f)

Sound zone Leached zone

Fig. 3. ASR at containment building of Tihange NPP (a) (Federal Agency for Nuclear Control
(FANC) 2013), Seabrook NPP (b) (Saouma and Hariri-Ardebili 2014) and cemented waste drum
from Doel NPP (c) (Federal Agency for Nuclear Control (FANC) 2014); Effect of c-radiation of
dose 290 MGy on microstructure cement paste (d) (Lowinska-Kluge and Piszora 2008); Changes
in microstructure and mineralogy due to leaching (e); Carbonation of a concrete cooling tower at
a coal-fired electrical generation plant in the southwest U.S. (f).

increases resulting in carbonation of the concrete (Vodák et al. 2011). For neutron
irradiation, the neutrons have more influence on the solid phase by scattering or
ejecting neutrons than on the water phase. Under neutron radiation, the internal
structure of some aggregates can be converted from an ordered crystalline structure to a
disordered structure, resulting in a decrease in specific gravity and an increase in
volume. Experimental studies have shown that the reactivity of silica-rich quartz can be
significantly increased by exposure to nuclear radiation. As a result, irradiation can
produce ASR in concretes containing aggregates that are typically nonreactive.

2.4 Ca-Leaching
Leaching (Phung et al. 2014) is a process of ion extraction from solid compounds by
dissolution. In cement based-materials, leaching of calcium, also called decalcification,
is of utmost importance because of the high calcium (Ca) content in cement compared
to other potentially leachable ions (Fe2+, Al3+, Mg2+, etc.) and the high solubility of the
aqueous Ca-controlling phase portlandite. Ca-leaching is one of the most serious
degradation processes in concrete and reinforced concrete structures for the very
long-term (nuclear waste disposal system) or in hydro structures (dam, bridge, water
tank) but it has only been studied since the 1980s despite the long history of concrete.
The reason is that leaching of concrete is an extremely slow process under normal
conditions (few mm leaching front in a hundred years). However, the lifetime of civil
concrete structures is normally under one hundred years and that is too short to see the
effects of leaching degradation. Leaching of concrete structures in NPPs have been
observed even on dry surfaces of structures (Tcherner et al. 2017) which cause local
reduction in alkalinity of concrete leading to corrosion of reinforcement and embedded
parts. Leaching of cement-based materials also changes its properties such as an
1114 Q.T. Phung et al.

increase in porosity (see Fig. 3e) and transport properties and detrimental effects on
properties related to long-term durability. One might intuitively presume that leaching
alters the cementitious materials to a material with coarser microstructure and higher
transport properties. And this presumption is confirmed by literature. However, to what
extent the microstructure and transport properties are modified, is still questionable,
especially on the long-term.

2.5 Carbonation
Carbonation (Phung et al. 2015a) is a chemical degradation process through the
reaction between Ca2+ and CO32− ions. In most cases, it is believed that the driving
force behind the carbonation is diffusion of CO2. However, it depends on the condi-
tions of carbonation, in the case of concrete used for underground waste disposal
purposes, concrete is almost fully saturated and subjected to a high hydrostatic pressure
and the surrounding environment may contain a high dissolved CO2, a combination of
diffusion and advection should be taken into account. Carbonation results in a pH
decrease which accelerates the corrosion of reinforcing bars in concrete (Fig. 3f)
because of dissolution of the thin oxide passive layer protecting the steel bars from
corrosion. On the other hand, carbonation also results in beneficial effects. It is gen-
erally believed that carbonation decreases transport properties and refines pore structure
and increase strength of Portland cement-based materials. Furthermore, in recent years,
there is considerable interest in applying carbonation of cement-based materials for
solidification and stabilization of radioactive waste. There are many factors influencing
carbonation: chemistry of hydration products, free water content, internal relative
humidity, pore structure, CO2 partial pressure and external conditions where carbon-
ation occurs (e.g. ambient relative humidity, temperature, CO2 concentration and
applied pressure). In general, the higher the CO2 concentration, the quicker the car-
bonation proceeds. However, up to a certain concentration, the carbonation may not
increase because the retention process resulting from porosity reduction and releasing
water overwhelms the effect of higher concentration. Increasing temperature will speed
up the carbonation process because the reaction and penetration of CO2 occurs faster.
The core reaction in carbonation is the reaction between dissolved CO2 and portlandite.
Therefore, the more portlandite is present in the hydration products, the higher the
degree of carbonation. Water plays an important role in the carbonation process.
Carbonation does not occur without water. It is a catalyst in carbonation reaction even
though this reaction releases water. However, water can fill the pores and prevent CO2
gas to penetrate into the concrete pore network. In fact, carbonation reaches the highest
efficiency at an internal relative humidity between 50–70%.
Under irradiation conditions, carbonation of concrete can be accelerated due to
elevated temperature, this phenomenon is known as radiation-induced carbonation
(Vodák et al. 2011). The phase transformation in this type of carbonation is similar to
the natural carbonation reaction in concrete. However, the natural carbonation reaction
takes place at the surface layer of concrete, where CO2 comes from the environment
and penetrates into the concrete through diffusion, whereas the radiation-induced
carbonation occurs in the concrete that has been irradiated and thus is not a
diffusion-limiting reaction. Another major difference between the two types of
 Current Concerns on Durability of Concrete 1115

carbonation reaction is that the natural carbonation reaction can produce an increase in
concrete strength as mentioned above, whereas the radiation-induced carbonation
produces a decrease in the strength of the concrete as the result of a succession of
chemical reactions, starting with radiolysis of water and terminating in the formation of
calcite crystals (William et al. 2013). It is evidenced during repairing of concrete
structure of secondary containment of reactor building of Tihange 2 reactor that a
deeper than expected and extended carbonation front was developing on the whole
structure (Federal Agency for Nuclear Control (FANC) 2013).

3 Case Study on Leaching

3.1 Experiments
Experiments were performed on cement pastes made from cement, tap water and
limestone fillers (LS). Type I OPC cement (CEM I 52.5 N) was used. LS used had a
CaCO3 content of 98.30%. Superplasticizer Glenium 27 was added to the mix with
content of 0.5% w.r.t. mass of cement. In order to investigate the effects of LS, three
sets of cement pastes were cast in a temperature-controlled room of 21 ± 1°C: sample
C0 with w/p ratio of 0.425, 0% of LS replacement; C10 with w/p ratio of 0.375 and
10% of LS replacement, and C20 with w/p ratio of 0.325 and 20% of LS replacement.
The material compositions used in this study are relevant (but without coarse aggre-
gates) for the composition used within the Belgian Supercontainer concept which is a
proposed reference design for disposal of high-level waste and spent fuel (Bel et al.
2006). Note that all samples had quite similar w/c ratios of 0.415 ± 0.01. The leached
samples are named C0-L, C10-L, C20-L, respectively. Cement pastes were cured for 28
days under sealed conditions then sawn into 25 mm thick slices. In order to accelerate
the leaching, the saturated cement slices were immersed in 6 M ammonium nitrate
solution. After leaching, a number of post-analysis techniques including scanning
electron microscopy (SEM), XRD/QXRD, mercury intrusion porosimetry (MIP), and
N2-adsorption were used to characterize the microstructural and mineralogical changes.
The leached depth was determined by phenolphthalein spraying. The effect of leaching
on permeability was quantified with the permeability setup as discussed in (Phung et al.
2013).

3.2 Modelling
A one-dimensional diffusion-based transport model (Phung 2015; Phung et al. 2016)
was developed to simulate leaching of saturated hardened cement paste in contact with
an aggressive NH4NO3 solution with a concentration of 6 mol/l. The model was based
on a macroscopic mass balance for Ca in aqueous and solid phases and the changes of
Ca equilibrium with different NH4NO3 concentrations were taken into account. The
proposed model only considered the degradation of portlandite and calcium silicate
hydrates (C-S-H) which are the main hydrated phases in typical CEM I Ordinary
Portlandite cement. The hydration during leaching was not taken into account in the
model because of the short experimental duration.
1116 Q.T. Phung et al.

3.3 Selected Results and Discussion

We only presents some selected results, the reader is referred to (Phung 2015) for more
experimental and modelling details/results. Figure 4a shows a good agreement between
the predicted leached depths with the measured ones. The modelling results show that
within the investigated duration (28 days), the propagation rates of degraded depth and
Ca-leached amount were almost in direct proportion to the square root of time.
Higher LS addition resulted in slower degradation rate. Figure 4b compares the
porosity of leached and reference samples determined by the combined MIP and N2-
adsorption method (Phung et al. 2015b). In the range of 3 nm–100 μm, the porosity of
leached samples hugely increased, from 68% up to 159% compared to the porosity of
reference samples. Despite different initial porosities, the porosities of all leached
samples were quite similar. The higher LS replacement, the larger porosity increases.
Such a large porosity increase is not only due to the decalcification of CH but also due
to partial decalcification of the C-S-H system. In all leached samples, the cumulative
pore volume curves exhibited two ranges of significant porosity increase. The first
range was situated in the 60 nm – 500 nm pore sizes corresponding to CH dissolution.
The second ranges was smaller than 10 nm corresponding to C-S-H (and other phases)
dissolution. In contrast, reference samples exhibited only one significant pore volume
increase stage. Portlandite profiles (normalized to the initial content) after 28-day
immersion in NH4NO3 solution are shown in Fig. 4c. The CH content suddenly
increased after the degraded front. Sample with higher LS replacement exhibits a
steeper jump of CH content at the front. Figure 4c also shows that the predicted
portlandite profile for samples C0 and C20 are in line with the profiles determined with
quantitative X-ray diffraction measurements on powder, especially for sample without
limestone fillers.
The specific surface areas (SSA) determined by the BET method of the leached
samples significantly increased (Table 1). The SSA of samples C0 and C10 increased
with a factor of 5 after 28-day of leaching. For the samples with the highest LS
Normalized portlandite content

1.0
(a) (c)
Porosity, %

45
10
9
Measured C0 Predicted C0 40 (b) Ref. C0 Leached C0-L 0.9
0.8
Predicted C0
Measured C0
Degraded depth, mm

Measured C10 Predicted C10 35 Ref. C10 Leached C10-L Predicted C10
8 0.7
7 Measured C20 Predicted C20 30 Ref. C20 Leached C20-L Predicted C20
0.6 Measured C20
6 25
5 0.5
20 0.4
4
3 15 0.3
2 10 0.2
1 5 0.1
0 0 0.0
0 1 2 3 4 5 0.001 0.01 0.1 1 10 100
Square root of tesƟng Ɵme, (days)0.5 Pore diameter, µm 0 0.005 0.01 0.015 0.02 0.025
PosiƟon, m

Fig. 4. Leached depth (a), porosity increase (b) and portlandite content of leached samples (c)

replacement C20, the SSA increased up to 15 times. Such an huge increase cannot only
be attributed to portlandite dissolution but also to dissolution of C-S-H. The gel pores
of C-S-H which have a higher SSA compared to micro/mesopores became more easily
accessible by nitrogen after leaching. Leaching seriously increased the porosity in the
mesopore region for all leached samples as shown in Table 1. The largest increase in
porosity was for sample C10 of which the porosity increased almost 3 times.
 Current Concerns on Durability of Concrete 1117

Interestingly, the average pore diameter determined by BJH method decreased after
leaching for all compositions. Rather than a refinement of the pore structure of the
leached materials, this reduction indicates an opening of initially inaccessible gel pores.
Sample S5L (the highest LS replacement) exhibited the largest decrease in average pore
diameter, which could be the reason for obtaining the highest SSA increase (relative
values) due to leaching.
Figure 5 shows the XRD patterns for leached and reference samples. It is clearly
observable that CH was completely dissolved in all leached samples. There are two
intense peaks of CH for the reference samples which totally disappear after leaching.

Table 1. N2-adsorption results of leached and reference samples – “L” denotes leached sample
C0 C0-L C10 C10-L C20 C20-L
2
BET surface area, m /g 30.6 145.8 34.8 182.3 5.5 86.7
Porosity (BJH), % 13.0 23.8 9.2 26.1 5.4 21.2
BJH adsorption average pore 11.6 7.8 9.5 7.3 15.8 6.8
diameter (4 V/A), nm

Except for C-S-H, which cannot be detected, the most visible phases in the XRD
patterns of the leached samples are calcite, ettringite and unhydrated cement which
indicate that they are hardly degraded by the NH4NO3 solution. No new crystalline
phases were observed as for leaching in deionized water. This underpins the statement
that leaching in NH4NO3 results in same end-products, as obtained for “natural”
leaching.
Intensity

Intensity

Intensity

Ref. C0 Ref. C10 Ref. C20

Leached C0-L Leached C10-L Leached C20-L

Portlandite

Portlandite Brownmillerite
Brownmillerite EƩringite
Portlandite
EƩringite
Calcite
Calcite Brownmillerite
Belite EƩringite

Calcite

0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Position, 2LJ Position, 2LJ Position, 2LJ

Fig. 5. XRD patterns of reference and leached samples taken in the first 3 mm depth from the
exposed surface

SEM images (Fig. 6) show, similar to the MIP and N2 adsorption measurements, an
increase in pore sizes and porosity after leaching. Some big pores with diameter up to
about 10 μm were observed in most of the leached samples which can be attributed to
the portlandite dissolution. The dissolution of C-S-H mainly contributes to the increase
of pore volume in the micropore to low mesopore range which is difficult to detect by
SEM. Micro cracks were observed in all leached samples. Decalcification of C-S-H
induces polymerization shrinkage, especially when the Ca/Si ratio is lower than 1.2. In
addition, leaching induces a significant loss of mechanical properties. As a
1118 Q.T. Phung et al.

consequence, decalcification shrinkage could generate tensile stresses around rigid

particles (e.g. limestone fillers, unhydrated cements) which results in cracking.

(a) (b) (c)

Micro cracks

Fig. 6. SEM images of reference (a) and leached (b) samples C0 - field width of 128 μm, and
segmented image showing the increases in porosity (in black) of leached sample C0 (c)

The evolution of composite permeability during leaching is shown in Fig. 7a.

Longer immersion time in ammonium nitrate solution results in larger permeability
coefficient. The change in composite permeability is larger during the first leaching
stage when portlandite is still present in the sample. In the second leaching stage, the
rate of permeability increase is slower because C-S-H decalcification has a smaller
effect on the porosity increase. The intrinsic permeability of samples leached during 28
days increased around one order of magnitude depending on LS replacement as shown
in Fig. 7a. Sample C0 without LS exhibited the largest increase in permeability, while
sample S2L with the highest LS replacement exhibited the smallest increase. The extent
of permeability increase is correlated with the porosity and PSD after leaching
(Fig. 4b). Permeability change over the depth is shown in Fig. 7b. After 28 days of
NH4NO3 immersion, the permeability increases for more than 2 orders of magnitudes
near the exposed surface which is much higher than the increase of composite per-
meability because it is controlled by the permeability of “sound” zone.

1.E-17 700
Composite permeability, m 2

(a) CH+C-S-H Only C-S-H 600 (b) C0

Permeability increase, Ɵmes

leaching leaching
500 C10
1.E-18
400 C20
Sharp C-S-H dissolution
Predicted C0 300
1.E-19 Measured C0
200
Predicted C10 C-S-H dissolution
Measured C10
Predicted C20
100
Measured C20 CH dis.
1.E-20 0
0 10 20 30 40 50 60 70 80 90 0 0.005 0.01 0.015 0.02 0.025
Leaching Ɵme, days PosiƟon, m

Fig. 7. Increase of composite permeability over time (a) and predicted permeability profile after
28-day immersion in NH4NO3 (b)
 Current Concerns on Durability of Concrete 1119

In general, mass transport properties are mainly affected by capillary and large
pores. As such, an increase in permeability after leaching is linked to an increase in
capillary pores resulting from portlandite dissolution. In addition, it is hypothesised
here that C-S-H decalcification under accelerated leaching conditions is also an
important factor because it increases the connectivity of different types of pores (gel,
micro and mesopores). Furthermore, the decalcification shrinkage originating from a
polymerization of C-S-H due to lower Ca/Si ratio induces micro cracks as seen in SEM
images.

4 Conclusions and Perspective

In general, majority of concrete structures in NPPs meet their functional and perfor-
mance requirements during their service period However, there are evidences of
concrete degradation where the structures may not exhibit the desired durability
without some forms of intervention. Periodic maintenance, and retrofitting are key
elements to ensure the functions of concrete structures. It is indeed much better if
concrete is well-designed in the beginning with a completely characterized material
property data for long-term performance assessment. In this way, by considering the
time evolution of environmental effects, elevated temperature and radiation, damage
models and acceptance criteria can be developed to assess the current as well as predict
the performance of concrete structures in the long-term. In any cases, the analysis and
modelling of transport properties evolution due to degradation is a vital task as these
properties govern the penetration of aggressive substances responsible for degradation
and the transport of radionuclides transport.
The possibility to assess the service life of structures made of CBM for radioactive
waste facilities is of great practical importance but raises new challenges. Unlike
classical structures, the durability of waste disposal facilities needs to be predicted over
hundreds up to thousands of years because of the long-lived activity of radioactive
waste. Under service conditions, the disposal facility is attacked by aggressive water,
which will induce chemical disequilibrium and dissolution of cementitious solid phases
by processes such as Ca-leaching and carbonation. Moreover, the heat generated during
the repository life may accelerate the chemical processes. The alteration of chemical
properties will in turn induce changes in the cement microstructure and consequently
changes in mechanical performance and transport properties of concrete structures.
Therefore, a systematic approach is needed to establish the relationship between
multiple processes at multiple scales, which would provide knowledge of long-term
safety of radioactive waste disposal and suggestions on how safety functions of the
repository components can be improved in terms of material and structure designs.
Despite advances in this area, a significant amount of work is still needed due to limited
experimental timeframe available to capture these long-term processes. There is still a
long journey to reach the safest but economical solution for radioactive waste storage,
but certainly CBM can be a reasonable choice on that journey.
As most of chemical degradation processes are very slow, accelerated tests are
needed, and which in turn arises a question how to interpret and apply the accelerated
results to the real concrete structures. Accelerated test results might be extrapolated to
1120 Q.T. Phung et al.

the natural environments in which concretes undergo degradation by defining the

degradation stages in terms of the changes in mineralogy (portlandite content, Ca/Si
ratio) or microstructure (porosity, pore size distribution). It is then possible to predict
the other properties (diffusivity, permeability, pH) at the same or similar degradation
stages for leaching under normal conditions. In this sense, the combination of accel-
erated experiments and phenomenological model, for which inputs are obtained from
accelerated tests, could be very useful to identify the comparative parameters and to
predict the long-term behaviour of degraded materials. In this way, it is possible to
imitate long-term naturally degraded cementitious materials in waste disposal by
accelerated experiments. As an example, we have performed an accelerated leaching to
understand the alteration degree of transport properties by establishing the links
between mineralogy, microstructure and transport properties; and clearly describing the
degradation processes/mechanisms by the combination of experiments and modelling.
Results showed that the cement mixture had a significant impact on leaching; a higher
limestone filler replacement resulted in an decreased rate of leaching propagation. The
accelerated leaching highly altered the microstructure of the cement paste to a more
porous material which is evidenced by the increases of specific surface area and total
porosity and by the creation of a coarser pore size. Beside the increase in mesopore
volumes, it is interesting to observe that the micropore volume was altered much more
than the mesopore volume. Probably the leaching of C-S-H with a larger volume
fraction than portlandite, results in a significant modification of the micropore structure.
The changes in microstructures and mineralogy led to a significant increase in transport
properties. The composite permeability increased by one order of magnitude, but the
permeability of degraded zone could increase up to 3 orders of magnitude, which is
much larger compared to the one order of magnitude often considered.

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