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ICOMTA 2020 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1175 (2021) 012018 doi:10.1088/1757-899X/1175/1/012018

A review of concrete durability in marine environment

W D Pratiwi1, F D D Putra2, Triwulan3, Y Tajunnisa4, N A Husin5

and K D Wulandari6
1,2,6
Shipbuilding Institute of Polytechnic, Surabaya, Indonesia
3
Civil Engineering, Institut Teknologi Sepuluh Nopember, Surabaya, Indonesia
4,5
Civil Infrastructure Engineering, Institut Teknologi Sepuluh Nopember, Surabaya,
Indonesia

E-mail: [email protected]

Abstract. There are many concrete constructions in marine environments. Due to its salinity
content, seawater is aggressive, both towards concrete and reinforcement. Concrete interacts
with seawater which causes deterioration. The chemical attack occurs at least through 3
common mechanisms: sulfate-attack, carbonation, and chloride-induced corrosion of
reinforcement. The chemical resistance of concrete is determined by the porosity and chemical
composition of the concrete. Partly subsitution of cement with supplementary cementitious
materials (SCM) known as an effective way to create the less permeable concrete. Concrete
with fly ash as SCM has excellent potential to be applied to marine construction in Indonesia
because the abundant availability of fly ash in Indonesia and the presence of aluminum species
in fly ash provide an opportunity to increase binding capacity to chloride.

1. Introduction
Concrete is a material that is widely used in marine construction, for examples are docks, piers,
breakwaters, LNG terminals, offshore windmills, and many other structures. The durability of a
structural concrete in a specified marine environment likely to depend upon the structural factor
(geometries, crack) and material factors (mixture components and its composition, curing, etc).
Degradation of reinforced concrete can be classified into: physical (freeze-thaw cycles, fire);
mechanical (erosion, abrasion); chemical; biological (biogen attack); structural (overloading). The
main chemical damage mechanisms of reinforced concrete are caused by sulfate attack, carbonation,
calcium leaching and chloride-induced corrosion.
The hardened cement paste always has capillary pores which decrease in volume as the water to
cement ratio (w/c) drops and the degree of hydration increases. The same is true of concrete, but in
concrete tends to be more porous as the presence of the aggregates. The existence of these capillary
pores creates permeability in concrete. At high porosity, the interconnected pore system connects the
concrete surface to the bulk of concrete. Permeability increases sharply if the porosity exceeds 25%,
which is obtained from the w / c 0.45 and 75% degree of hydration [1].
Concrete permeability causes ions in seawater to enter the structure or vice versa leaching the
constituent components of the concrete to sea water. Four basic mechanisms of the passage of fluid
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ICOMTA 2020 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1175 (2021) 012018 doi:10.1088/1757-899X/1175/1/012018

and ions through concrete are: capillary suction, due to capillary action inside capillaries of cement
paste, permeation, due to pressure gradients, diffusion, due to concentration gradients, and migration,
due to electrical potential gradients [1]. The transport rate of ions or fluid depend on mechanism,
concrete porosity, and the binding of transported substances by the hydrated cement paste as well as
on the environmental conditions.
Many studies have been carried out to improve the impermeable properties of concrete, for
example by adding clay brick powder [2], regulating water to cement ratio [3], fly ash substitution [4–
6] and blast furnace slag subtisution [7].
Concrete exposed to seawater is deteriorated due to chemical and physical interactions. The
chemical failures are majorly caused by sulfate attack, carbonation and chloride-induced corrosion.
While mechanical action and the growth of marine biota affect concrete degradation, however, this
paper is focused on the durability against chemical attack. The main objective of this paper is to study
the chemical breakdown mechanism of concrete and the critical properties of concrete that affect its
resistance. Further research needs to be identified to produce concrete that is resistant to seawater
attacks by taking into account the availability of materials in Indonesia.

2. Sulfate Attack
The aggressiveness of seawater to concrete is influenced by several factors, including the composition
of seawater, climate, waves, and marine zones (immersion, tidal, splash or spray zones). The main
ions present in seawater are Na+, Mg2+, Cl− and SO42-, together with the small quantities of K+, Ca2+,
HCO3- and Br− [8]. The salinity of seawater varies widely, but it can be assumed that an average of
3.5% (35 g / L dissolved salt) [9]. The permeability of the concrete and the compositions of the
hydrated phases of the cement are the main factors of concrete materials governing the sulfate
reaction. The hydration products of the tricalcium aluminate (C3A) are known as the susceptible phase
to sulfate attack [10].
Sulfate ions from the environment attack the concrete and are known as external sulphate attack
(ESA). Sulfate attacks originating from concrete components known as internal sulfate attacks (ISA)
or delayed ettringite formation (DEF) are not included in this paper. External sulfate attack includes all
chemical reactions from external sulfate sources that cause concrete damage regardless of the type of
cation. The sulfate attack mechanisms consists of [8,10]:

2.1. The reaction of sulfates with the constituent components of the cement paste produces gypsum or
is known as gypsum attack. The two common reactions are:
2.1.1. The reaction of sodium sulfate with calcium hydroxide and water result gypsum and sodium
hydroxide.

Na2SO4+Ca(OH)2 + 2H2O → CaSO4.H2O + 2NaOH (1)

2.1.2. The reaction of MgSO4 with Ca(OH)2 produce gypsum and magnesium hydroxide.

MgSO4 + Ca(OH)2 + 2H2O→ CaSO4.2H2O + Mg(OH)2 (2)

The gypsum produced by those reactions is believed to damage concrete by increases in overall
solid volume. In addition, the reduction of Ca(OH)2 lead to depasssivation of reinforcing steel as
decreasing the alkalinity of pore solution. Magnesium hydroxide (eq. 2) has very low solubility so it
tends to form deposits on the concrete surface. These deposits can protect the next attack if the
construction is submerged [8,10].

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ICOMTA 2020 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1175 (2021) 012018 doi:10.1088/1757-899X/1175/1/012018

2.2. Expansion occurs due to the formation of ettringite (called a sulfoaluminate attack), include two
reactions:
2.2.1. Gypsum reacts with calcium aluminate hydrate plus water to form ettringite and calcium
hydroxide.

3(CaSO4.2H2O) + 4CaO.Al2O3.19H2O + 8H2O

→ 3CaO.Al2O3.3CaSO4.32H2O + Ca(OH)2 (3)

2.2.2. The reaction of sodium sulfate with calcium monosulfoaluminate, calcium hydroxide and
water produce ettringite and sodium hydroxide.

2Na2SO4 + 3CaO.Al2O3.CaSO4.12H2O + 2Ca(OH)2 + 2H2O

→ 3CaO.Al2O3.3CaSO4.32H2O + 4NaOH (4)

The formation of ettringite (eq. 3, 4) causes volume expansion, hence generate the cracks [11–13].
However, interactions with chloride prevent ettringite from forming [8].

2.3. Decomposition of calcium-silicate-hydrate, calcium aluminatehydrate, calcium

monosulfoaluminate, resulting in the loss of cementing properties (paste cohesion, paste-to-
aggregate bond, strength, and durability
The reaction of MgSO4 with calcium aluminate hydrate
2.3.1. Forms gypsum, magnesium hydroxide and aluminum-hydroxide.

3MgSO4 + 3CaO.Al2O.36H2O + 6H2O →

3(CaSO4.2H2O) + 3Mg(OH)2 + 2Al(OH)3 (5)

2.3.2. The reaction between magnesium sulfate and calcium monosulfoaluminate hydrate produce
gypsum, magnesium hydroxide, and aluminum hydroxide.

3MgSO4 + 3CaO.Al2O3.CaSO4.12H2O + 2H2O →

4(CaSO4.2H2O) + 3Mg(OH)2 + Al2O3.3H2O (6)

2.3.3. The reaction of magnesium sulfate and calcium silicate hydrate result gypsum, magnesium
hydroxide and silica gel.

3MgSO4 + 3CaO.2SiO2.nH2O + zH2O →

3(CaSO4.2H2O) + 3Mg(OH)2 + 2SiO2.xH2O (7)

2.3.4. Magnesium sulfate reacts with calcium silicate hydrate and calcium hydroxide to form
magnesium silicate and gypsum.

4MgSO4 + CaO.SiO2.H2O + (4 − x) Ca(OH)2.nH2O →

4MgO.SiO2.8H2O + 4CaSO4.2H2O (8)

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ICOMTA 2020 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1175 (2021) 012018 doi:10.1088/1757-899X/1175/1/012018

2.4. Thaumasite sulfate attack, namely sulfate attacks together with carbonate to produce thaumasite
Thaumasite is a pulpy soft mass and has no binding ability. This attack often occurs at low
temperatures (<10oC)

3Ca2+ + SiO23- + CO32- + SO42− + 15H2O →

3CaO·SiO2.CO2·SO3·15H2O (9)

2.5. Salt recrystallization

The ions present in the environment have penetrated the concrete and then react with various
possibilities as mentioned above. When the ions, generally sodium and sulfate, reach the surface then
recrystallization occurs. This recrystallization often happens when the concrete experiences changes in
temperature and humidity, for example in areas that subjected to drying-wetting cycles or tidal zones.
Some authors classify it as a physical attack, however, disallowed by the other since the process
involves chemical reactions [8].

3. Chloride-Induced Corrosion of Concrete Reinforcement

Chloride-induced corrosion is assumed as the foremost origin of reinforced concrete damage. Many
studies have been carried out to determine the values for critical chloride content (Ccrit) in reinforced
concrete, i.e. the chloride concentration value on the surface of reinforcing steel which causes
corrosion initiation. According to European standards, EN 206-1, Ccrit value is 0.2 or 0.4% by weight
of cement, depending on the type of cement [14]. In contrast, some experiment state the higher value,
for example Kwon [15] reported Ccrit of 2.5%. The Ccrit value is the most decisive input parameter in
the service life probability modelling.
Chloride from the environment, which is absorbed on the concrete surface enters the deeper zone
by diffusion. The diffusion coefficient is the main parameter to describe the diffusion process that
occurs.
The mechanism of chloride attack on reinforcing steel occurs in the following steps [1].
(i) Chloride ion penetrates the oxide film on the steel surface at the defect site. The penetration of
chloride ion is stronger than other ions, therefore termed as the aggressive ion.
(ii) Chloride ion is adsorbed on the metal surface. At the same time, dissolved oxygen and
hydroxyl ion are adsorbed on the metal surface;
(iii) The ferrous-cation formed from corrosion reacts with chloride ions to form a soluble complex
of iron chloride. This compound leaving the metal surface attacks the protective layer of
Fe(OH)2 so that corrosion continues.
The Ccrit value is influenced by the pH of the concrete or concentration of hydroxyl ions in the pore
solution, steel potential, and the presence of voids on the steel/concrete interface. The concentration of
hydroxyl ions depends on the type of cement mixture. The risk of corrosion attack increases when the
[Cl-]/[OH-] ratio increases to a certain value. However, several authors have shown different critical
values [1].
The substitution of cement with SCM has two-fold effects. The first has the effect of reducing
porosity, and the second increases the binding capacity of chloride. The binding capacity behaviour for
cement paste with metakaolin, silica fume, fly ash, and slag substitution has been studied. The highest
binding capacity is found in pastes with metakaolin. This fact can be understood since the formation of
Friedel's salt (FC3A.CaCl2.10H2O) requires aluminium, while metakaolin is a mineral with a high
aluminium content. The use of fly ash with different calcium content did not show a significant

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ICOMTA 2020 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1175 (2021) 012018 doi:10.1088/1757-899X/1175/1/012018

difference. However, apart from the type of mineral, the w/c factor also plays an important role. The
increase in binding capacity due to mineral substitution was detected at w/c 0.5, while at w/c 0.3, the
binding capacity change was only slightly. It is suspected that an increase in w/c provides the
availability of free Al for the formation of Friedel's salt [16].
In another study, concrete with 56 and 58% fly ash was exposed to the marine environment for 24
years. It was found that the cement substitution with fly ash resulted in resistance to chloride ion
penetration. However, to get the best results, it is necessary to take synergic steps of SCM substitution,
low w/c ratio (not more than 0.4) and sufficient cover depth. [6].
The combination of chloride and magnesium sulfate attack was studied on the three kinds of mortar
made of Portland cement, sulfate resisting cement and a blended of 50% OPC -50% slag. Substitution
with slag prevents the formation of brucite (Mg(OH)2 ) hence there are no protective properties on the
surface [17].

4. Carbonation
Carbonation take places when carbon dioxide in the environment infiltrates into the concrete to react
with calcium hydroxide giving calcium carbonate:

CO2 + Ca(OH)2 + → CaCO3 + H2O (10)

Reduction of Ca(OH)2 causes an increase in porosity and causes a decrease in pH. Under normal
conditions, the pH of the concrete pore solution is in the range 13-14 so that the reinforcing steel is in
a passive state. In the case of carbonization, the pH can drop close to neutral.
Water to cement ratio (w/c) is the main factor controlling the resistance against carbonation of
normal concrete. When chloride ions ingress and carbonation occur at the same time in concrete,
chloride ions become soluble due to the deterioration of cement hydrates caused by carbonation. In
addition, the chloride bound in the form of calcium chloroaluminate hydrate is released into the pore
solution so that it becomes more aggressive [1].
Carbonation is affected by moisture. In both completely dry and wet environments, carbonation
does not occur. In marine structures, the splash zone and above water are at risk of carbonation
attacks. The condition for the attack is getting worse if there is chloride from both concrete
components and the environment [1].
Research to determine the resistance of concrete to gas and water permeability was carried out on
high-volume fly ash (HVFA). A 50% fly ash mixture by mass and a water-to-binder ratio of 0.4 is
obtained to have water and gas permeability lower than normal concrete, provided that fly ash has a
fairly low LOI (loss on ignition), 3.5% and high refinement (19% retained) on a 45 μm sieve [18].
The leaching resistance of concrete is sensitive to w/c and the paste composition. The concrete
undergoes leaching due to the presence of portlandite in the paste. Furthermore, the leached concrete
is susceptible to sulfate attack. High C3S cement substitution with 30% FA had an increased impact
on leaching resistance and sulfate attack. Substitution of cement with 62% GGBS (ground granulated
blast-furnace slag) gives the best results [12]. However, different results were found by Ashish [19],
the slag substitution of 20% affected increasing durability, but an increase in substitution of 40% or
more resulted in a decrease in durability.

5. Discussion
Marine concrete must be resistant to sulfate attack, carbonation, calcium leaching and chloride
penetration. Physically, low permeability properties are the main requirement for concrete to have

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ICOMTA 2020 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1175 (2021) 012018 doi:10.1088/1757-899X/1175/1/012018

resistance to chemical attack. However, the chemical composition of concrete is also a determinant
besides its permeability.
Permeability is controlled by the w/c ratio and the volume of hydrated cement. The higher the w/c,
the larger the pore volume and the increased permeability. Carbonization and calcium leaching are
attacks against Ca(OH)2 from hydration. Carbonized and calcium leaching concrete has a higher
porosity, making it more sensitive to attack by other chemical species, such as sulfate or chloride.
Moreover, calcium leaching causes a higher supply of calcium ions in the pore solution thereby
increasing the rate of reaction in chemical attack [20].
Concrete with fly ash or GGBS substitution has better permeability than normal concrete.
Mittermayr [21] found that concrete made with CEM IIIB cement (Blast furnace cement), fly ash and
calcium carbonate with low w/c have high resistance to sulfate attack. The use of calcium carbonate,
together with fly ash provides a synergistic effect in increasing cement hydration. Calcium carbonate
chemically reacts with the aluminate in fly ash to form a carboaluminate phase, whereas physically,
the calcium carbonate surface provides an additional site for the C-S-H phase deposition. The
chemical similarity of calcium carbonate and C-S-H enhance the growth of C-S-H calcium carbonate
particles [22,23].
Efforts to reduce pores are also carried out by adding inhibitors based on natural ingredients.
Bambusa Arundinacea is reported to have the ability to replace nitrite and amine-based corrosion
inhibiting admixtures for durable concrete structures due to its pore-blocking effects [24]. Meanwhile,
[25] used silica fume to reduce pores and increase chemical resistance.
The resistance of concrete to chloride attack requires special attention. Sulfate-resistant cement is
usually designed to have a low alumina content. This is because the alumina reacts with the sulfate to
form an expansive ettringite which increases the risk of cracking. On the other hand, alumina is a
species necessary to bind chloride to form Friedel's salt. The binding capacity of a concrete determines
its resistance to chloride. And almost the same as the resistance to sulfate, concrete with SCM has
better properties than normal concrete. If in general, the w/c is designed to a minimum to produce
concrete with small pores, this is not the case with chloride resistant. The value of w/c needed is not
too small, generally around 0.4 to ensure the availability of alumina which is ready to bind with
chloride ions.
The porosity of the concrete is determined by w/c and the hydrated phases. Several studies have
recommended blended cement with GBFS to produce a mixture that is durable in seawater. However,
there is a controversy that says the substitution of GBFS is not suitable for environmental conditions
containing magnesium sulfate and chloride.
Concrete with cement substitution using fly ash is considered suitable for applications in the marine
environment in Indonesia. This is due to the abundant availability of fly ash in Indonesia. In 2020, fly
ash and bottom ash from the steam-power plants in Indonesia be around 13.5 million tons, and only
10% have been used. Another reason is that the substitution of fly ash, with any calcium content, is
thought to be effective in producing concrete that is able to withstand the attack of seawater, especially
chloride. This is because fly ash has an aluminium content for the formation of Friedel's salt so that the
chlorine is bound to the concrete.
The drawback of fly ash is its relatively low reactivity so that the substitution of fly ash at a
relatively high level has an impact on decreasing compressive strength. Selection of fly ash with high
fineness and high morphology [29] provides an opportunity to produce good properties as SCM, as
well as adding activator to increase its reactivity [26–28].

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ICOMTA 2020 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 1175 (2021) 012018 doi:10.1088/1757-899X/1175/1/012018

6. Conclusion
Marine concrete has a risk of chemical degradation against sulfates, carbonates and chlorides
attacks. For reinforced concrete, chloride ion attack is critical since it generates corrosion of the
reinforcement.The chemical resistance of concrete is determined by the porosity and the chemical
composition of the concrete. The aluminium content is required for concrete to increase the binding
capacity against chloride. Concrete with fly ash as SCM has excellent potential to be applied to marine
construction in Indonesia because the abundant availability of fly ash in Indonesia and the presence of
aluminium species in fly ash provide an opportunity to increase the binding capacity to chloride.

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