Construction and Building Materials 24 (2010) 878–884

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Construction and Building Materials

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Durability and strength evaluation of high-performance concrete

in marine structures
Hosam El-Din H. Seleem a, Alaa M. Rashad a,*, Basil A. El-Sabbagh b
a
Building Materials Research and Quality Control Institute, Housing & Building National Research Center, HBRC, Cairo, Egypt
b
Raw Building Materials Technology and Processing Research Institute, Housing & Building National Research Center, HBRC, Cairo, Egypt

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

Article history: The aim of this research work is to investigate the seawater resistance of concrete incorporating silica
Received 30 September 2009 fume (SF), ground granulated blast furnace slag (GGBS) and metakaolin (MK) as an addition to cement
Received in revised form 9 January 2010 in binary and ternary combinations. Permeability of different mixtures was measured. Strength deterio-
Accepted 15 January 2010
ration ratios (SDR) were determined after 3, 6 and 12 months of exposure to synthetic seawater. Chloride
Available online 12 February 2010
ion concentrations (chloride ingress) at the surface layer and at the core of tested specimens were deter-
mined after 6 and 12 months of exposure. The mineralogical compositions of all mixtures before expo-
Keywords:
sure and after exposure to synthetic seawater for 12 months at the surface layer and at the core of
Pozzolan
Marine
tested specimens were investigated by X-ray diffraction (XRD). The results indicate that the binary com-
Permeability bination of cement-SF proves to be the most effective pozzolana to resist seawater attack. The ternary
Durability combination of cement-SF–MK came in the second place. The ternary combination of cement-SF–GGBS
came in the third place. The binary combination of cement-MK came in the fourth place. The binary com-
bination of cement-GGBS came in the fifth place. The ternary combination of cement-MK–GGBS came in
the sixth place. Finally pure cement came in the last place.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Concrete Exposed to marine environment is susceptible to at-
tack by the simultaneous action of a number of physical and chem-
ical deterioration processes. For instance, the chemical action of
seawater constituents on cement hydration products, alkali-aggre-
gate expansion (when reactive aggregates are present), crystalliza-
tion pressure of salts within concrete if one face of the structure is
subject to wetting and others to drying conditions, frost action in
cold climates, corrosion of embedded steel in reinforced or pre-
stressed members, and physical erosion due to wave action and
floating objects.
Oceans make up 80% of the surface of the earth; therefore, a large
number of structures which are exposed to seawater either directly
or indirectly could be classified as marine structures (coastal or off-
shore structures). Docks, harbors, break-waters, and concrete plat-
forms for airports, power plants, waste disposal facilities and oil
storage tanks are some examples of marine structures.
Most seawaters are fairly uniform in chemical composition [1],
which is characterized by the presence of about 3.5% soluble salts
* Corresponding author. Mobile: +2 0128527302; fax: +202 33351564, +202
33367179.
E-mail addresses: alaarashad@yahoo.com, alaarashad@hotmail.com (A.M. Ra-
shad).
by weight. The ionic concentration of Na+ and Cl are the highest.
However, from the standpoint of aggressive action to cement
hydration products, sufficient amounts of Mg2+ and SO2 4 are pres-
ent. In spite of this fact, it is a common observation [1] that even
when a high C3A Portland cement has been used and large amounts
of ettringite are present as a result of sulfate attack on the cement
paste, the deterioration of concrete is not characterized by expan-
sion; instead, it most likely takes the form of erosion or loss of the
solid constituents from the mass. Identically this view is consistent
with the hypothesis that alkaline environment is necessary for
swelling of ettringite by water adsorption. The fact that the pres-
ence of uncombined calcium hydroxide in concrete can cause dete-
rioration by an exchange reaction involving magnesium ions was
known as early as 1818 from investigations on disintegration of
lime-pozzolan concretes by Vicat [2].
From long term studies [3] of Portland cement mortars and con-
cretes exposed to seawater, the evidence of magnesium ion attack
is well established by the presence of white deposits of Mg (OH)2,
also called brucite, and magnesium silicate hydrate. In seawater,
well-cured concrete containing large amounts of slag or pozzolan
in cement usually outperform reference concrete containing only
Portland cement, partly because the former contain less uncom-
bined calcium hydroxide after curing. The implication of loss of
lime by cement paste, whether by magnesium ion attack or by
CO2 attack, is obvious.

0950-0618/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2010.01.013
 H.E.H. Seleem et al. / Construction and Building Materials 24 (2010) 878–884
It should be noted that in permeable concrete, the normal
amount of CO2 present in seawater is sufficient to decompose the
cementitious products eventually [4]. The presence of thaumasite
(calcium silicocarbnate), hydrocalumite (calcium carboaluminate
hydrate), and aragonite (calcium carbonate) has been detected in
cement pastes derived from deteriorated concretes exposed to sea-
water for long periods.
The deleterious effect of seawater on concrete could be allevi-
ated by proper inclusion of pozzolans. Cabrera and Nwaubani [5]
measured the effective chloride diffusion coefficients of Portland
cement (PC), PC-15% pulverized fuel ash (PFA), PC-15% metakaolin
(MK) pastes using a chloride diffusion cell. The pastes of water/bin-
der (w/b) ratio 0.4 were moist-cured (100% RH) for 60 days before
being placed in the cell. Both the PC–MK and the PC–PFA pastes
gave lower chloride diffusion coefficients than the PC paste, and
the former gave particularly low values. Zhang and Malhotra [6]
measured the resistance to chloride penetration of PC concrete
and PC-10% MK concrete. The concrete of w/b ratio 0.4 was
moist-cured for 28 and 91 days prior to being subjected to electri-
cal conductivity measurements in compliance with the ASTM
C1202 test. The PC–MK concrete showed significantly lower con-
ductivity values than the PC concrete. In much more detailed stud-
ies, Thomas et al. [7] and Hooton et al. [8] determined the chloride
penetration resistance of concrete of w/b ratios 0.3 and 0.4 contain-
ing 0%, 8% and 12% replacement of PC with high-reactivity MK
(HRM). Data were presented in the form of apparent diffusion coef-
ficients calculated from chloride concentration-depth profiles after
28, 90 and 140 days exposure to 1.0 mol/1 NaCl solution. Two more
recent publications [9,10] extend these periods to 365 and
1095 days. The apparent diffusion coefficients were reduced on
increasing the exposure time and on decreasing the w/b ratio and
showed marked decreases with increasing HRM content. In addi-
tion, the authors determined the chloride binding capacity of ce-
ment paste with and without 8% HRM by exposing dried paste
samples to various concentrations of NaCl solution and determin-
ing the amount of chloride removed from solution on establish-
ment of equilibrium. For up to a 1-M solution concentration, the
binding capacities of the two pastes were similar but above this
concentration the binding capacity of the HRM paste increased at
a much greater rate with increased solution concentration than
did the pure PC paste. Coleman and Page [11] have also estab-
lished, from analysis of the pore solution of cement pastes made
up with chloride containing water (2, 8 and 20 g/l) and cured for
up to 101 days, that MK, when used as a partial cement replace-
ment, produces a significant increase in chloride binding capacity
of the paste. This is attributed to the reaction products formed
from the pozzolanic reaction of MK with the calcium hydroxide
(CH).
Leng et al. [12] have shown that the chloride ion diffusion coef-
ficient of concrete decreases with increasing replacement of PC
with PFA. The decrease was attributed to changes in pore size
distribution, increased CSH gel formation and increased alumina
levels enabling more chloride to be fixed as Friedel’s salt
(C3ACaCl210H2O). Papadakis [13] has demonstrated that increas-
ing cement replacement by FA in mortar exposed to NaCl solution
produces (relative to the equivalent PC mortar) decreasing chloride
concentrations. This applies at all depths in the mortar, except for a
thin surface layer. The increased chloride concentrations in the
surface layers, in mortars containing pozzolan, are attributed to
the increased chloride binding capacity of these mortars. This is a
result of the higher CSH content, which can bind Na+ ions and their
accompanying Cl ions, especially when the CSH has a reduced cal-
cium/silica ratio. Torii et al. [14] determined the apparent diffusion
coefficients from chloride distribution profiles in PC concrete and
concrete containing PC replaced with 30% PFA, at w/b ratios of
0.45, 0.55 and 0.65. The chloride concentration-depth profiles were
879
determined after 8 months and 2 years exposure to sea shore. For
all the concretes, Friedel’s salt and ettringite were present in the
surface layers, and particularly for concrete containing mineral
admixtures CH was absent in the surface region and was replaced
with brucite and calcite. The mineral admixtures reduced the level
of chloride penetration into the concrete and were effective in
reducing chloride ingress. Their effects were much more pro-
nounced than the effect of reducing w/c ratio on these aspects, par-
ticularly at long exposure periods. This suggests that chloride
binding plays a dominant role in reducing the apparent chloride
diffusion coefficient.
Both MK and PFA, when used as partial cement replacement,
have been shown to reduce the strength retardation experienced
by concrete or mortar exposed to seawater. Bose et al. [15] pro-
duced mortar prisms with 0% and 30% replacement of PC with
MK, moist-cured them for 28 days and immersed some in seawater
and some in distilled water, some at 20° C for 180 days and some at
30° C for 90 days. Relative to water-cured mortar, the seawater-ex-
posed specimens showed reduced strength, but the retardation in
strength was much less for the MK mortars. This was attributed
to increased pore refinement and reduced permeability for these
mortars. Kumar [16] investigated the percentage loss in strength
(strength deterioration factor (SDF)) of marine exposed concrete
relative to equivalent water-cured concrete for concrete prepared
with 0%, 10%, 20% and 30% PFA replacing types I, II and V PC bind-
ers. After 1 year of exposure, concrete with PC replacement of up to
20% PFA for types I and II cement resulted in much lower SDFs. This
was not the case with type V cement, even though type V cement
has a much lower C3A content (1.9%) than type I (9.5%) cement, and
hence a lower chloride binding capacity. This indicates that in a
marine environment type I cement blended with pozzolan will
produce more durable concrete than type V cement.
It was stated [17] that measurement of chloride diffusion coef-
ficients to predict chloride penetration in concrete can be mislead-
ing due to the continued formation of hydration products which
leads to pore refinement and pore blocking. Also, the calculated
chloride diffusivities are in practice ‘‘apparent” because no account
was taken for the effect of chemical binding on the transport of
chloride ions. Therefore it is much more realistic to measure chlo-
ride penetration depth under the intended exposure conditions.
2. Experimental program
2.1. Materials
The employed sand is natural siliceous and has a fineness mod-
ulus of 2.47. Its particle size distribution lies within the range of
medium grading zone according to the classification of the Egyp-
tian Standard Specification ES 1109/2002. The coarse aggregate is
a crushed basalt stone; 40% of its particles in the size range of
10–14 mm, and the rest of its particles are finer than 10 mm size.
Ordinary Portland cement (CEM I: 42.5N) of Blain surface area
3250 cm2/gm, complies with the Egyptian Standard specifications
ES 4756-1/2007 is used through this work at a constant content
of 400 kg/m3.
Three types of pozzolanic materials were employed, i.e. silica
fume (SF) containing about 95% SiO2, ground granulated blast fur-
nace slag (GGBS), and metakaolin (MK). Silica fume (SF) was used
as received from the supplier, but the other two types were spe-
cially processed before use. Kaolin was heated at about 850 °C
for 2 h then brought out the furnace at Lab temperature to cool
down rather fast, thereby enables the formation of amorphous
glassy phases with pozzolanic nature (metakaolin). The ground
granulated blast furnace slag was delivered in the form of water
quenched fine grains. The slag was then finely ground in a labora-
880 H.E.H. Seleem et al. / Construction and Building Materials 24 (2010) 878–884

tory ball mill, the fraction passing 100 lm sieve is used through water and about two thirds of it was added to the mixer and mix-
this work. Table 1 outlines the chemical compositions of the em- ing operations continued until the mixture became homogenous
ployed pozzolanas. The used high-range water reducer (HRWR) is after about 120 s. Sand was added to the wet mixture and mixing
of modified sulphonated naphthalene base, and complies with further continued to assure complete homogeneity. Coarse aggre-
ASTM C-494 Type F. gate was subsequently added to the rotating mixer and mixing
continued for further 120 s. Finally the rest of water containing
2.2. Mixes features HRWR was added and mixing continued for another 60 s until
the mixture became homogenous. A sample of fresh concrete
As it well known, durability issues are of main concern for sea was extracted for consistency measurement (slump test). At the
structures. Therefore, concrete mixes for such structures or at least same time the oiled steel molds of different specimens were filled
the elements exposed to marine environment should preferably be in approximately three equal layers, and mechanically vibrated on
rich in cementitious materials. Also, the water-to-cementitious a shaking table. After 24 h the specimens were demolded and
materials (w/cm) ratio should be as low as possible. These precau- cured in water till the age of testing.
tions are normal for production of low permeability concrete
which is the main key to durability.
3. Methods of investigation
Based on the above-mentioned considerations, a summary of
the main features of the designed concrete mixtures shown in
The current work aims to investigate the ability of the proposed
Table 2 are as follows:
concrete mixes to long last against aggressive marine environment.
Evaluation was done via the following tests:
- The employed cement content is 400 kg/m3 and a constant (w/
Compressive strength of the water-cured specimens in comparison
cm) ratio of 0.32 is adopted for all mixtures.
with that of the synthetic seawater-exposed specimens. For this pur-
- An appropriate level of flowabiliy is acquired by employing
pose, seven groups of companion three cubes with 15 cm side
high-range water reducer (HRWR) at a dosage of 2.0% from
length were cast for each mixture. The first four groups were
the cementitious materials weight.
water-cured till the age of testing at 28 days, 3 months, 6 months,
- The coarse aggregate (basalt) to sand ratio is 1.5 by weight.
and 12 months. The other three groups were initially cured for
- Each of the three pozzolanic materials was employed as an
addition to cement with a ratio of 20% by weight. 28 days, and then immersed in synthetic seawater till the age of
testing at 3 months, 6 months, and 12 months. The strengths of
The pozzolanic materials were employed either in binary blends the seawater-exposed specimens were compared with that of the
water-cured specimens, and the retained strengths were evaluated
with cement in the first group of mixtures or in ternary blends in
the second group. for the different exposure periods. The composition of the syn-
thetic seawater was 30 g/l NaCl, 6 g/l Mg Cl2, 5 g/l MgSO4, 1.5 g/l
CaSO42H2O and 0.2 g/l KHCO3.
2.3. Specimen preparation
Permeability. Three half-cylinders, 15 cm diameter and 15 cm
length, were prepared from each mixture. The outside cylindrical
Mixing operations of the concrete mixtures sequenced as fol-
perimeters (lateral faces) of the specimens were painted with
lows: all the fine materials i.e. cement and pozzolanas were care-
epoxy resin. The other two opposite faces were sanded to have
fully mixed in a drum mixer. The HRWR is premixed with the
clean surfaces. The specimens were positioned in the permeability
cells of the testing apparatus. The water is forced to flow from one
Table 1 face to the other under 30 bar pressure continued for at least 24 h.
Chemical composition of cementitious materials. The permeated water is collected in a 100 ml graduated flask. The
Oxide Silica fume Blast furnace slag Metakaolin Cement formula for calculating the permeability coefficient (Darcy coeffi-
cient) is:
SiO2 94.5 30.38 58.52 20.39
Al2O3 1.03 9.05 35.54 5.6
cc  h
Fe2O3 0.78 3.82 1.15 3.43 K¼ ðm2 =Pa SÞ
CaO 1.1 45.88 1.24 63.07 Atp
MgO 0.46 5.39 0.19 2.91
Na2O 0.27 0.52 0.25 0.38 where cc is the permeated water (m3), h is specimen height (m), A is
K2O 0.43 0.31 0.05 0.35
specimen surface area (m2), t is permeation time (seconds), p is
SO3 0.08 1.78 0.06 0.7
C3A – – – 9.04 hydrostatic pressure (Pa).
LOI 1.31 1.41 2.74 2.06 Fig. 1 shows schematic description of the employed water per-
meability apparatus.

Table 2
Investigated concrete mixture.

Mix designation Ingredients/m3

CA/sanda ratio Cement (kg) MK (kg) SF (kg) GGBS (kg) Water (l) HBW (Rb)
Mc Control 1.5 400 – – – 128 0.02
Mk First group 80 – – 153.6 0.02
Mf – 80 –
Mgs – – 80
Mk-f Second group 80 80 – 179 0.02
Mk-gs 80 – 80
Mf-gs – 80 80
a
Coarse bazalt aggregate to sand by weight.
b
Ratio from cementitious materials weight.
 H.E.H. Seleem et al. / Construction and Building Materials 24 (2010) 878–884 881

80

Compressive Strength (MPa)

70 28 day 3 month 6 month 12 month

60
50
40
30
20
10
0
Mc Mk Mf Mgs Mk-f Mk-gs Mf-gs
Mixture Identification

Fig. 2. Compressive strength of the continuously cured specimens till the age of
testing.

a marginal increase in concrete strength over that of the control

Fig. 1. Water permeability apparatus (a) and permeability cell (b).
The content of chloride ions Cl in the surface layer and inside
the seawater-exposed specimens was measured for two exposure
periods (6 and 12 months). For this purpose, representative sam-
ples were collected from the surface layer (about 30 mm thick)
of the crushed concrete cubes of each mix (three companion spec-
imens) after completion of the compression test. Another samples
were collected from inside the specimens (about 50 mm thick
core). The samples were ground to a very fine powder that passes
(150 lm) sieve, then subdivided to produce representative sub-
samples of about 75 lm fineness. The samples were prepared, trea-
ted, and tested in accordance with BS 1881: part 124 [18]. The
chloride contents were calculated as a percentage of the concrete
mass to the nearest 0.01%.
A mineralogical study by the X-ray diffraction Technique (XRD) to
identify the formed phases during exposure to seawater. It was found
appropriate to test the 12 months exposure specimens rather than
the other exposure periods. Test samples are collected from the
surface layer and from inside the specimens as outlined in the last
mentioned ion concentration test.
specimens. At 1 year age, the strength of the pozzolan mixtures
were higher than that of the control mixture by about 24.4%,
57.4%, 15%, 44.6%, 8.3%, and 30.3% for MK, SF, GGBS, MK–SF, MK–
GGS, and SF–GGS combinations, respectively.
Fig. 3 shows compressive strength values of the seawater-ex-
posed specimens for different periods. The corresponding strength
deterioration ratios (SDRs) are plotted on the same graph. SDR is
defined as the ratio of the strength lost relative to the strength of
the continuously cured specimens at the same age. As could be ob-
served, SDR increases with age increasing for all mixtures except
for the mixture containing GGBS as the reduction in strength de-
creased from about 5.3% at 3 months to about 3.0% at 12 months.
The last SDR is the least one, which appreciate GGBS as the most
efficient in retaining strength in marine environment. On the other
hand, PC–SF mixtures exhibited relatively higher strength values at
all ages than all other mixtures. Obviously, SF although not effi-
cient as GGBS in retaining strength, nevertheless owing to its con-
tribution in progressively enhancing the strength could be
considered as the most appropriate in marine environment as long
as strength values is the evaluation criterion.
4.2. Permeability
It is intuitive to believe that permeability has an effect on the
concrete durability. That is because; it measures the ability of del-
eterious ions and salts to penetrate into the concrete. Due to the
increasing conscious of the significance of permeability to durabil-
ity of concrete exposed to aggressive waters, some countries [1],
e.g. Norway specifies the maximum permissible permeability for
off-shore structures, k 6 1016 m2/Pa S.
Permeability measurements outlined in Table 3 show that all
kinds of pozzolanic materials are efficient in reducing concrete per-

80 25
Compressive Strength (MPa)

4. Test results and discussion 3 month 6 month 12 month

70 SDR 3m SDR 6m SDR 12m
20
4.1. Compressive strength results 60
50 15
SDR %

Fig. 2 illustrates the strength progress over time of the investi- 40

gated concrete mixtures continuously cured in tap water till the 30 10
age of testing. The cited values are the average of three companion
20
cube specimens. As could be seen, the control mixture experienced 5
less strengths than the other mixtures containing pozzolans at all 10
ages. The mixture Mf with 20% silica fume possessed the highest 0 0
Mc Mk Mf Mgs Mk-f Mk-gs Mf-gs
values of strength. The results of the mixture (Mk-f) with the ter-
Mixture Identification
nary blend cement-metakaolin–silica fume are the second in order.
The blend metakaolin-ground granulated blast furnace slag caused Fig. 3. Compressive strength of the seawater exposed specimens.
882 H.E.H. Seleem et al. / Construction and Building Materials 24 (2010) 878–884

Table 3
Permeability and chloride concentration.

Mix designation Permeability (K  1010), cm/s Chloride Cl concentration (%)

6 months 12 months
Surface layer Inside specimen Surface layer Inside specimen
Mc Control 2.36 0.1 0.09 0.5 0.48
Mk First group 1.16 0.08 0.01 0.37 0.1
Mf 0.884 0.04 0.01 0.06 0.03
Mgs 1.47 0.1 0.06 0.5 0.16
Mk-f Second group 0.78 0.08 0.03 0.14 0.04
Mk-gs 1.31 0.08 0.04 0.35 0.12
Mf-gs 0.92 0.04 0.01 0.2 0.04

meability. Meanwhile, silica fume is the most efficient in this re- chloride to be fixed as Friedel’s salt and the increased CSH due
gard. That could be attributed to its ultra fineness and activity to the pozzolanic reaction.
(higher values of amorphous components) which lead to the for- - Ground granulated blast furnace slag is of less efficiency than
mation of intense pozzolanic reaction products within the capillary the other employed pozzolans regarding chloride penetration
pore spaces and as a consequence, finer and more segmented pore resistance. This result is further confirmed by permeability
system is produced. As could be seen, three mixtures passed the results.
Norway acceptance criterion mentioned above; namely Mf, Mk-f,
and Mf-gs, which is an evidence of the efficiency of silica fume It is clear from the above discussion that all types of pozzolans
either alone or in combination with other kinds of pozzolan in pro- could be utilized in increasing the concrete resistance to chloride
ducing impermeable concrete. Evidently, the ternary blend Port- penetration. Apparently, the most pronounced contribution in this
land cement-metakaolin–silica fume (Mk-f) is superior to all regard is experienced by silica fume.
other mixtures in producing impermeable concrete.
4.4. Interpretation of XRD results
4.3. Resistance to chloride penetration
The coarse aggregate of the employed concrete mixtures is
The resistance to chloride penetration is governed by two fac- crushed basalt stone; it has a cryptocrystalline structure with some
tors: firstly, the permeability of concrete mixtures, which is a func- amount of volcanic glass and is composed of plagioclase and
tion of the pore size distribution. Secondly, the chloride ion binding
capacity of the cementitious paste, which increases [9–14] with
increasing CSH gel formation and increased alumina levels en-
abling more chloride to be fixed as Friedel’s salt (C3ACaCl210H2O)
The chloride ion concentration measurements for the concrete
mixes exposed to synthetic seawater till 6 months and 12 months
age are presented in Table 3. Measurements are made at two loca-
tions for each specimen: at the surface layer and at the core (inside
specimen). It is generally noted for the pozzolan-concrete mixtures
that, the chloride concentration at surface layer is several times
that inside the specimens. With age increasing from 6 to
12 months, the concentration at the surface layers more inten-
sively increased than inside the specimens. On the other hand,
the control specimens assumed different pattern as the chloride
ion concentrations are almost the same inside and at the surface
layer of the specimens at both of the exposure periods.
Comparing all mixtures, the following remarks could be drawn:

- Silica fume (mixture Mf) is the most efficient in prohibiting

chloride ingress inside the specimens as well as at the surface
layer. The last one indicates a relatively low chloride binding
capacity and therefore efficiency is attributed to the enhanced
pore size distribution.
- Silica fume in combination with other pozzolans (mixtures Mk-
f and Mf-gs) caused a significant reduction in chloride concen-
tration inside the concrete specimens comparable to that of
the preceding case, but chloride concentration at the surface
layer is relatively higher due to increasing the chloride binding
capacity of these mixtures.
- The metakaolin mixture (Mk) exhibited a relatively low chlo-
ride concentration inside the specimens, i.e. high penetration
resistance. At the surface layer, the chloride concentration is
relatively high due to increasing the chloride binding capacity.
This is a result of the increased alumina level that enables more Fig. 4. XRD patterns of concrete mixtures before exposure to synthetic seawater.
 H.E.H. Seleem et al. / Construction and Building Materials 24 (2010) 878–884 883

augite. These minerals are normally found in the X-ray diffracto-

grams; plagioclase [Na–Al–Si–O–Ca–Al–Si–O] and augite [(Ca, Fe,
Mg) SiO3] but they do not affect interpretation of the results. The
X-ray diffractograms of all mixtures before exposure to the syn-
thetic seawater are shown in Fig. 4. As could be seen, the reduction
in the calcium hydroxide (CH) diffraction peaks (main peak at
2h = 34.1) is obvious for all pozzolan-concrete mixtures except
for ground granulated slag mixes because the slag contains a rela-
tively high amount of CaO as shown in Table 1. A neighbour peak
identifies calcium aluminates (C3A) appeared at 2h = 34.45 for
pozzolans containing alumina, i.e. metakaolin and granulated slag.
The Stratlingite mineral (C2ASH8) is formed in a minor amount in
some pozzolan mixtures; meanwhile it is more recognized in the
Mk-f mixture. It was reported [19] that the formation of Stratling-
ite is favorable due to its stability and relatively high strength.
Fig. 5 shows the diffraction patterns of the samples collected
from the core (inside) of the specimens after 1 year of exposure
to synthetic seawater; the identified mineral compounds are to a
great extent similar to those of the corresponding specimens be-
fore exposure (Fig. 4), except for the following:

 The reduction in the CH is more pronounced than before

exposure.
 The formed cementing phases (C2S and C3S) are slightly
increased.
 The Stratlingite mineral is formed in a considerable amount in
the metakaolin mixtures especially the Mk-f mixture.
 The brucite (magnesium hydroxide) mineral is recognized in the
control mixture which implies that an exchange reaction took
place in the form of loss of lime by magnesium ions attack.

Fig. 6. XRD patterns of concrete mixtures after 1 year of exposure to synthetic

seawater-samples from the surface layer.

The X-ray diffractograms of samples collected from the surface

layer of the specimens after 1 year of exposure to synthetic seawa-
ter are shown in Fig. 6. The Comparison between the diffracto-
grams of the different mixtures reveals that: CH is almost
disappeared from all mixtures except for those containing ground
granulated slag.

 New compounds are formed; magnesium hydroxide or brucite

(Mg (OH)2), magnesium silicate hydrate or seplolite
(Mg2Si3O82H2O) and they were more pronounced in the con-
trol mixture.
 Friedel’s salt (C3ACaCl210H2O) is formed in almost all mixtures,
especially the metakaolin mixes and the granulated slag mixes,
which indicate increasing the binding capacity of chloride ions
on the surface layer of these mixes. On the other hand, this min-
eral compound is hardly noticed in the mix Mf due to the effi-
ciency of silica fume in consuming the free calcium hydroxide
and the non availability of alumina.
 The ettringite mineral is formed in the control mix, while it is
hardly noticed in the pozzolan-concrete mixes.

5. Conclusions

1. The compressive strengths of all pozzolan-concrete mixtures

Fig. 5. XRD patterns of concrete mixtures after 1 year of exposure to synthetic
seawater-samples from inside the specimens.
were higher than that of the control mixture at all ages. At
1 year age, the strength of the pozzolan mixtures were
higher than that of the control mixture by about 24.4%,
57.4%, 15%, 44.6%, 8.3%, and 30.3% for MK, SF, GGBS, MK–
SF, MK-GGS, and SF–GGBS combinations, respectively.
884 H.E.H. Seleem et al. / Construction and Building Materials 24 (2010) 878–884
2. The strength deterioration ratio (SDR) increases with age for
all mixtures except for the mixture containing GGBS as the
reduction in strength decreased from about 5.3% at 3 months
to about 3.0% at 12 months, which appreciate GGBS as the
most efficient in retaining strength in marine environment.
3. The silica fume mixture exhibited relatively higher strength
values at all ages than all other mixtures. Obviously, SF
although not efficient as GGBS in retaining strength, never-
theless owing to its contribution in progressively enhancing
the strength could be considered as the most appropriate in
marine environment as long as strength values is the evalu-
ation criterion.
4. All kinds of pozzolanic materials are efficient in reducing the
permeability of concrete far below the control one. Mean-
while, silica fume is the most efficient in this regard. That
could be attributed to its ultra fineness and activity which
lead to the formation of intense pozzolanic reaction prod-
ucts within the capillary pore and as a consequence, finer
and more segmented pore system is produced.
5. The ternary blend Portland cement-metakaolin–silica fume
(Mk-f) is superior to all other mixtures in producing imper-
meable concrete.
6. The chloride concentration at surface layer of pozzolan-con-
crete mixtures is several times that inside the specimens,
while for control mixture the chloride concentration is more
or less the same at both the surface layer and inside the
specimens.
7. Silica fume (mixture Mf) is the most efficient in prohibiting
chloride ingress inside the specimens as well as at the sur-
face layer.
8. The metakaolin mixture (Mk) exhibited a relatively low
chloride concentration inside the specimens, i.e. high pene-
tration resistance. At the surface layer, the chloride concen-
tration is relatively high due to increasing the chloride
binding capacity.
9. Ground granulated slag is of less efficiency than the other
employed pozzolans regarding chloride penetration
resistance.
10. Pozzolanic materials provide a good solution to the problem
of durability of marine structures in terms of strength
retaining, recognized reduction in permeability, and limited
diffusion of chloride ions. The XRD results provide an evi-
dence of the efficiency of pozzolans in consuming free lime
which is a main source of instability and also formation of
stable favorable compounds.
References
[1] Mehta P, Monterio P. Concrete-structures, properties, and materials. 2nd
ed. Prentice-Hall International Series in Civil Engineering and Engineering
Mechanics; 1993.
[2] Vicat LJ. A practical and scientific treatise on calcareous mortars and cements;
1837 [translated by J.T. Smith, London].
[3] Mehta PK. Performance of concrete in marine environment. ACI SP-65; 1980. p.
1–20.
[4] Feld J. Construction failures. New York: John Wiley & Sons, Inc.; 1968. p. 251–
55.
[5] Cabrera JG, Nwaubani SO. The microstructure and chloride ion diffusion
characteristics of cements containing metakaolin and fly ash. In: Malhotra VM,
editors. Sixth CANMET/ACI/JCI international conference on fly ash, silica fume,
slag and natural pozzolans in concrete, Bangkok, Thailand, vol. 1; 1998. p. 385–
40.
[6] Zhang MH, Malhotra VM. Characteristics of a thermally activated alumino-
silicate pozzolanic material and its use in concrete. Cem Concr Res
1995;25(8):1713–25.
[7] Thomas MDA, Gruber KA, Hooton RD. The use of high reactivity metakaolin in
high performance concrete. In: 1st Engineering foundation conference on high
strength concrete, Hawaii; 1997. p. 517–30.
[8] Hooton RD, Gruber K, Boddy AM. The chloride penetration resistance of
concrete containing high reactivity metakaolin. In: Proceedings of the PCI/
FHWA international symposium on high performance concrete, New Orleans,
LA; 1997. p. 172–83.
[9] Boddy A, Hooton RD, Gruber KA. Long-term testing of the chloride-penetration
resistance of concrete containing high-reactivity metakaolin. Cem Concr Res
2001;31(5):759–65.
[10] Gruber KA, Ramlochan T, Boddy A, Hooton RD, Thomas MDA. Increasing
concrete durability with high-reactivity metakaolin. Cem Concr Res
2001;23(6):479–84.
[11] Coleman NJ, Page CL. Aspects of pore solution chemistry of hydrated cement
pastes containing metakaolin. Cem Concr Res 1997;27(1):147–54.
[12] Leng F, Feng N, Liu X. An international study on the properties resistance to
diffusion of chloride ions of fly ash and blast furnace slag concrete. Cem Concr
Res 2000;30(6):989–92.
[13] Papadakis VG. Effect of supplementary cementing materials on concrete
resistance against carbonation and chloride ingress. Cem Concr Res
2000;30(2):291–9.
[14] Troii K, Sasatani T, Kawaura M. Chloride penetration in concretes incorporating
mineral admixtures in a marine environment. In: Malhorta VM, editors. Sixth
CANMET/ACI/JCI international conference on fly ash, silica fume, slag and
natural pozzolans in concrete, Bangkok, Thailand, vol. 2; 1998. p. 701–16.
[15] Bose JL, Kouame K, Pera J. Improvement of concrete durability in tropical
marine environment by adding metakaolin and superplasticizer. In:
Proceedings of the sixth international conference on durability of building
materials and components, Omiya, Japan, vol. 1; 1993. p. 448–57.
[16] Kumar S. Influence of water quality on the strength of plain and blended
cement concretes in a marine environment. Cem Concr Res 2003;30(3):
345–50.
[17] Martin-Perez B, Zibara H, Hooton RD, Thomas MDA. A study of the effect of
chloride binding on service life predictions. Cem Concr Res 2000;30(8):
1215–23.
[18] BS 1881: part 124:1988. British standards institution, testing concrete, part
124. Methods for analysis of hardened concrete; 1988.
[19] Ding J, Fu Y, Beaudoin JJ. Stratlingite formation in high alumina cement–silica
fume systems: significance of sodium ions. Cem Concr Res 1995;25(6):1311–9.