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Cmsrrucrion and Buikliing Morerials, Vol. IO, No. 7, pp. 515-519.

1996
Copyright 0 1996 Elsevier Science Ltd
ELSEVIER
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Resistance of cement mortars containing
heavy metal oxides exposed to long-term
repeated action of chloride solution
V. Zivica
institute of Construction and Architecture, Slovak Academy of Sciences, Dubravska 9,
84220 Bratislava, Slovakia
Received 6 November 1995; revised 22 April 1996; accepted 26 April 1996
The subject of the paper is the study of the long-term repeated action of NaCl solution on cement
mortars containing PbO, ZrO, and Cr,O,. According to the obtained results, mortars containing
these heavy metal oxides have significantly lower resistance compared with plain mortar. The
resistance of mortars exposed to repeated action of chloride solution decreases in the order of
oxides: PbO, Cr,O, and ZrO,. The reason for mortar degradation, including disturbing the PbO steel
corrosion inhibition effect, seems to be the induced leaching chloride corrosion. Copyright 0 1996
Elsevier Science Ltd.
Keywords: cement mortar; heavy metal oxides; chloride solution
Certain heavy metal oxides (MeO,) used as admixtures
in concretes can inhibit reinforcement corrosion
induced by chlorides. Our results have confirmed
the inhibition effect of the oxides PbO, Cr,O, and
Zr0,2,3.
The practical employment of MeO, inhibitors
requires understanding of their action on the
properties of concrete. Our results show that adding the
mentioned oxides below 4% of cement mass influences
positively the cement hydration, development and qual-
ity of the created pore structure and its strength. In pre-
vious works, including ours, the inhibition effect of
MeO, admixtures has been observed under conditions
of adding chloride admixtures into concrete. However,
in practice the concrete reinforcement corrosion is
caused very frequently by chloride solutions. Usually
such events are the results of a long-term repeated
attacking of concrete pavements and bridges by chlor-
ide solutions (RACR) from the application of chloride
deicing salts.
RACR conditions produce a dynamically varying com-
plex process. One of its considerable features is the ren-
ovation of the acting solution and the possibility of
increasing the chloride concentration in an attacked
concrete structure and of intensifying the reinforcement
corrosion. The diffusing chlorides can cause the modifi-
cation and decomposition of hydrated phases in hard-
ened cement paste of the attacked concrete, including
the decrease of its strengthb. This means that the chlor-
ide solutions can, besides the embedded reinforcement,
also attack the concrete cover. Further, the possibility
of repeatedly washing off in water soluble products of
the decomposition and of developing leaching of the
attacked composite represents next the considerable
process being exercised in RACR.
The following three types of chloride concrete corro-
sion are known:
515
The leaching type, represented by solving and
leaching the components of hardened cement paste
in concrete, and by a hydrolytic decomposition of
hydration cement products.
The expanding type, represented by expansion and
development of cracks in concrete, caused by for-
mation of the voluminous reaction product of
calcium-aluminate hydrates with chlorides,
C,A.CaCl,. lOH,O, known as Friedel salt.
The physical type, represented by the development
of cracks in surface layer of concrete, caused by an
expansion action of chloride salt crystallization in
the concrete capillaries. This destruction process
depends significantly on the surrounding tempera-
ture, relative humidity and on the surrounding air
flow velocity. Obviously, the intensity of this type
of corrosion will significantly depend on the cli-
matic conditions of the concrete structure.
The conditions for RACR are evidently present
where the concrete is treated by deicing chloride
salts. In this case leaching and physical corrosion
represent the main concrete destruction factors. A
study of concrete pavements damaged by deicing
chloride salts has confirmed the dominant destruct-
ing role of leaching corrosion. Our results show
that PbO admixtures in concrete can inhibit the cor-
rosion of concrete reinforcement caused by chloride
516 Resistance of cement mortars containing heavy metal oxides: V. Zivica
Table 1 Experimental conditions
Test specimens
composition
Mortar cement: sand 1:3, w/c 0.5, 1 and 4% of
PbO, Cr,O,, ZrO, from the mass of cement,
control mortar without metal oxides admixture.
24 h at 95% RH, 20C in the moulds. after
demoulding 6 days at 50% RH, 20C applica-
tion of epoxide coating on the surface of the
test specimens, except their top surface, 20 mm
edge mortar cubes were used.
Curing Wetting top surface without epoxy coating
of the test specimens by 0.5 ml of 20%
NaCl solution.
Curing of the wetted test spectmens at 95%
RH and 20C for 7 days.
Drying of the wetted test specimens at 60C
for 5 days.
Regular repeating of the steps 1 to 3.
Materials used Portland cement CEM 1 42.5 according_toCSN
PENV 197-1, silica sand according to CSN 72
1208.
Properties
studied
Bulk weight, compressive strength, pore
structure using mercury porosimetry (high pres-
sure mercury porosimeter mod, 2000. macro-
porosimeter unit 120. Erba Science Milano).
content of bound water using thermogravi-
metry (Q derivatograph, MOM Budapest).
admixture. But this inhibition effect was not
observed under the RACR conditions. The inhibition
effect was obviously inhibited by the induced leach-
ing chloride corrosion.
The subject of this paper is the results of a study on the
influence of the admixture of heavy metal oxides on the
resistance of cement mortars against the long-term
repeated action of chloride solution.
Experimental method and materials used
The experimental conditions and the materials used are
presented in Tubles 1 and 2.
Results and discussion
Figures I , 2 and 3 show the relative values of compres-
sive strength of the test mortar specimens being exposed
to chloride solution under the conditions described in
Tuble 1. The presented values are given in percentages
of compressive strength of the test specimens after their
demoulding (the value s). For the purpose of compari-
son, Figures 1, 2 and 3 also give the compressive
strength percentages for test specimens, which were
cured in air (RH ca 50%, 20C).
Figures 1, 2 and 3 also show that the chloride solution
caused a permanent decrease of compressive strength of
the test specimens. This resulted in a significant reduc-
tion of compressive strength compared with the test
specimens, which were cured in air.
The observed decrease of compressive strength shows
that the applied NaCl solution was an aggressive
medium against the MeO, mortars, as well as against
the plain mortar without MeO, admixture. The contin-
uous decrease of the compressive strength is typical for
Table 2 The properties of the used materials
Portland cement, class 400, Ladoe
Chemical composition %I
Loss on ignition 1.07
Insoluble residue I .29
SiO, 20.57
Al,O; 5.84
Fe@, 3.06
CaO 64.42
MgQ
I .50
SO, 2.15
CaO free 0.33
Mmeralogical composition Bogue %
CIA 10.30
C,S 55.66
czs 17.13
C,AF 9.30
CaSO, 3.65
Spec. weight (g. cm )
Spec. surface area (m*. kg )
Normal consistency (A;$
Setting - beginning
end
Sand - according to the standard CSN 721208
3.104
338.2
27.7
3 h 30 min
5h
Mortars w/c 0.5
Without Me0 s = 12.4 MPa
x
200-
840d
s = 24.6 MPa
784 d
c = number of cycles
s = compressive strength (initial value)
d = days of air curing
Figure 1 Relative compressive strength of PbO mortars
leaching corrosion. Such a type of corrosion is also con-
nected with the decrease of bulk weight of the attacked
material. This effect is shown in Tubfe 3. The presented
results show that the decrease of bulk weight of MeO, mor-
tars reached values from 5 to 12% compared with the orig-
inal values. The decrease was 5 and 5.7% for PbO (1 and
4%), 6.6 and 7.3% for Cr,O, and 10.8 and 11.9% for ZrOz
mortar, while for plain mortar the value was just 3.6%.
These results show an increased sensitivity of the
MeO, mortars with respect to chloride leaching corro-
sion in comparison with the plain mortar. They show
simultaneously a variable sensitivity of the tested mor-
tars depending on the kind of added MeO,. It is obvi-
ous that the sensitivity of MeO,. mortars increases in the
order of oxides: PbO, Cr,O, and ZrO?.
Resistance of cement mortars containing heavy metal oxides: V. Zivica
517
Mortars w/c 0.5 (
Without MeO,
s = 12.4 MPa
.i
g 200-
434 d
1
f loo-
15C
:
25c 31c
II I
._
s
3
4% Cr,OJ s = 10.8 MPa -
d 200-
Y2
IDO-
15c 25 c
38 c
I II rrl
c = number of cycles
s = compressive strength (initial value)
d = days of air curing
Figure 2 Relative compressive strength of Cr,O, mortars
iz 200 840 c
2 t;b loo-
i
s = 14.7 MPa
:!
l%zro,
.p 200- 784 d
e
p loo-
E
8
:!
3
4% ZrO,
s = 16.9 MPa
3 200-
434 d
loo-
15 a 25 c
31 c
I II In
c = number of cycles
s = compressive strength (initial value)
d = days of air curing
Figure 3 Relative compressive strength of ZrO, mortars
Also the changes of total porosity of MeO,Y mortars
correspond to the level of their sensitivity. Its values are
given in Table 3.
The leaching process usually causes an increase of
total porosity of the attacked material. This effect can
be observed in ZrO, mortar showing the highest sensi-
tivity; the PbO and Cr,O, mortars have not shown an
increase of their total porosity. This is obviously con-
nected with their decreased sensitivity to leaching cor-
rosion.
The leaching also causes the increase of pore median
in the attacked material. This effect was observed in
PbO mortar (Tub/e 3).
The mortar leaching has also been confirmed by the
decrease of their Ca(OH), content; the corresponding
values are given in Table 3. These values have shown
that the Ca(OH), content decrease was superseding its
temporary increase. This effect was observed at 15
cycles of treatment. This shows a temporary accumula-
tion of the produced Ca(OH), in the attacked mortars.
The mentioned effect is undoubtedly caused by a
hydrolytic decomposition of hydration products of
cement in hardened cement paste in mortars. It is
known that the hydrolytic decomposition is a direct and
inevitable consequence of the leaching, which disturbs
the equilibrium between the Ca(OH), and hydration
products of cement in hardened cement paste. The
described effect indicates its decomposition. The
obtained results show that the final Ca(OH), content in
attacked mortars was significantly lower compared with
the non-attacked mortars permanently cured in air. It is
interesting that the plain mortar showed under the
RACR conditions, on the other hand, a slight increase in
Ca(OH), content. The latter confirms its decreased sen-
sitivity with respect to the chloride attack.
Similar relations can also be observed in results of the
bound water content given again in Table 3. The con-
tent of bound water is given by the ignition loss in the
interval of lOO-500C and represents adsorbed and
chemically bound water in mortars or in their hardened
cement paste. The indicated changes in bound water
content were undoubtedly connected with the same rea-
sons of destruction of the hardened cement paste, which
already caused the described changes in Ca(OH), con-
tent. The bound water increase can be obviously con-
sidered as the consequence of accumulation of the gel
decomposition products of calcium-silicates and cal-
cium-aluminate hydrates. The consequent decrease of
bound water is obviously the consequence of the leach-
ing process.
The results presented in Table 3 show that the chlor-
ide content in MeO, mortars was 6 to 43% higher than
that in the plain mortar. The exception was the 1% PbO
mortar, which achieved the same chloride content as the
plain mortar. The increased chloride content in MeO,
mortars is in good correlation with the observed
increased sensitivity of these mortars to leaching chlor-
ide corrosion. At the same time it shows the possibility
of formation in mortars of the interaction products of
chlorides and oxide-metallic components in mortars.
Conclusion
The obtained results give the following information:
The long-term repeated action of chloride solution
can develop a leaching type of chloride corrosion of
cement composite. The latter causes the hydrolytic
decomposition of hydration products in hardened
cement paste of the composite and the degradation
of its engineering properties.
The presence of heavy metal oxides such as PbO,
ZrO, and Cr,O, in the cement composite can
increase its sensitivity with respect to leaching
chloride corrosion.
518 Resistance of cement mortars containing heavy metal oxides: V. Zivica
Table 3 Properties of the test specimens of mortars incorporating MeO,
MeO,
added
(W
Curing
regime
Bulk Total Pore
weight porosity median
(kg m ) W) (rim)
Ignition
loss
(100 to
500C)
(x)
Content Content
of of
Ca(OH): chloride
W)
(X)
PbO
I
PbO
4
Cr,O,
1
Cr,O,
4
ZrO,
I
ZrOz
4
Plain
mortar
Initial
value
15 cycles
56 cycles
784 days AC
Initial
value
15 cycles
33 cycles
462 days AC
Initial
value
I5 cycles
31 cycles
434 days AC
Initial
value
I5 cycles
38 cycles
532 days AC
Initial
value
15 cycles
55 cycles
770 days AC
Initial
value
15 cycles
31 cycles
434 days AC
Initial
value
15 cycles
60 cycles
840 days AC
2114
1993
2206
2142
_
2035
2281
1946
2192
2120
._
1981
2269
2139
1907
2217
2156
I899
2198
2133
_
2056
2231
_
16.4
17.12
18.5
17.4
13.9
21.4
18.03
16.8
20.1
17.6
14.2
19.7
23.8
17.0
18.8
21.7
17.3
19.6
16.0
16.6
261
I52
112
188
168
291
220
414
431
385
484
531
216
388
274
288
448
343
706
476
2.13
2.66
0.83
12.7
4.07 0.93
6.00 _
1.52
8.17
5.71
1.83
8.61
_
2.59 I.17
6.63
1.62 1.86
7.16
7.07
1.65
9.23
_
2.48 1.22
5.81
1.38
5.96
5.38
I .45
1.69
_
5.53
3.42 1.00
6.26
1.34
6.87
5.50
I .98
3.00
8.91
3.42 I .08
7.72
1.50
7.95
8.06
I.61
2.94
_
9.19
4.70 I .34
5.12
1.35
3.06
7.50
1.28
cycle - wetting of test specimens by chloride solution and their drying
AC - test specimens cured at 50% RH and 20C
3. An important factor in developing and intensifying
the induced leaching corrosion is obviously the con-
ditions of the long-term repeated action of chloride
solution. These conditions are inherent to the appli-
cation of the chloride deicing salts to prevent ice
formation on the surface of concrete pavements and
bridges. These are the renewing of the attacking
solution and of the repeating of the leaching. The
physical type of chloride corrosion, which could not
manifest itself under the given experimental condi-
tions, represents the next factor, which can intensify
the destruction effect of developing leaching chlor-
ide corrosion under the conditions in practice.
4. The mentioned conditions enable the development
of the hydrolytic decomposition of hydration prod-
ucts in hardened cement paste, simultaneously
excluding the possibility of formation of the men-
tioned voluminous chloride complex and in this
way also the possibility of the development of
5.
expansion chloride corrosion. The developed
hydrolysis was obviously also the reason for the
mentioned disturbing of the PbO inhibition effect.
The increase sensitivity of PbO, ZrOz and Cr,O,
mortars in an aggressive environment appears to be
an important shortcoming of their engineering
properties. Moreover, this adverse action also
cannot be excluded for oxides of other heavy
metals. Therefore, a further study of the reasons for
this effect would seem to be useful.
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