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Danish experience
S.CHATTERJEE, Z.FRDS and N.THAULOW
Abstract
In Denmark research on alkali-silica reactivity and preventive measures has
been carried out in two distinct phases. In the first phase, flint and opaline
limestone were identified as the main reactive components in Danish aggregates.
Suggested preventive measures were the use of low-alkali cement and/or the
use of aggregates containing less than 2% reactive components. At this stage
the basic assumptions were that the alkali content of concrete is determined by
that of its cement and the alkalis are evenly distributed.
The second phase of research, on the other hand, assumed that a real-life structure
may acquire extra alkalis from its environment and there is always a concentration
distribution of alkalis in it. An accelerated test method of storing mortar prisms in a
saturated NaCl solution at 50C was devised. New and detailed mechanisms have
been proposed for alkali-silica reaction and the associated expansion.
As regards the preventive measures, the following innovations have been
made:
(1) The assumptions of a constant and uniform distribution of alkali in a
concrete structure have been dropped.
(2) The environment to which a structure may be exposed has been classified
as regards its severity.
(3) The acceptance criteria of aggregates, both fine and coarse, have been
made very strict, and have been collated with the environmental classes.
(4) The permissible total alkali content of a concrete mix has been collated
with the environment to which the concrete would be exposed.
(5) A fly ash Portland cement has been introduced to the Danish market.
components in one or another size fraction, i.e. there is always a risk of ASR. It
is hardly surprising that the first description of the effects which could be
attributed to ASR was reported by Poulsen in 19141, long before Stantons
work in the 1940s. However, systematic research on ASR did not start until
Nerensts report in 19512. The research on ASR in Denmark can be broadly
divided into two phases-that carried out before the 1970s and that afterwardswith fairly clear differences in their research philosophies.
the concrete roads. Since non-reactive granite was used as coarse aggregates and
the cement contained about 0.6% Na2O eq. alkali, it was inferred that the
extensive reaction was a result of an interaction between the de-icing salt NaCl
and reactive silica present in the sand, i.e. NaCl acted as an accelerator. This
inference was then verified by laboratory experiments31. The above road
investigation also revealed that the cement-stabilised sub-base of the roads
(containing about 6% cement) though it used the same reactive sand as the
roads, suffered no ASR. A subsidiary investigation indicated that this absence of
ASR in the sub-base may be because of absence of free Ca(OH)2 in the subbase
material32. At about the same time, the electron probe microanalytical technique
was applied to determine the chemical composition of alkali-silica gel33. A high
content of CaO in the gels analysed, up to 20%, was found. The gel was
analysed in situ within the cracks at known and increasing distances from the
perimeter of the original reacted particle. The CaO content of the gel increased
with increasing distances. This paper, which remained somewhat dormant for a
time, played a very important role in the elucidation of the ASR mechanism.
The explicit assumptions of this second phase of research were that the reallife structures often receive alkalis from outside sources, e.g. from the
groundwater, from de-icing salt, etc., and that there is nearly always a
concentration gradient of alkalis in any structure.
Most of the subsequent research in Denmark could be treated as a followup
to the above-mentioned three papers. The subsequent research could be
divided into the following subgroups:
(1) That directed to the elucidation of mechanisms of ASR and attendant
expansion.
(2) That directed to the development of methods for the measurement of the
expansion capacity of reactive aggregates.
(3) That directed towards the development of preventive methods.
Beside these systematic studies, there were some isolated studies of the effects
of ASR on reinforced concrete beams, life expectancy of a structure suffering
from ASR reaction, occurrence of ASR in swimming pools, etc.
in prisms made with slag Portland cement. The X-ray diffraction diagram of the
prism made with slag Portland cement and stored in an NaCl bath showed that
prisms contained no Ca(OH)2 but had substantial amounts of Friedels salt,
indicating that NaOH had formed in those prisms by the following reaction:
4CaO+Al2O3+2NaCl+13H2O=3CaOAl2O3CaCl212H2O+2NaOH
A point to note is that no expansion occurred in spite of this extra NaOH
formation. This confirmed the importance of crystalline Ca(OH) 2 in the
expansive ASR.
The next investigation addressed the mechanisms by which NaCl and
Ca(OH)2 accelerate the alkali-silica expansion35. In that investigation, prisms
made from reactive sand and Portland cement containing varying amounts of
diatomites were exposed to saturated NaCl solution at 50C. The expansion of
the prisms was measured up until about 1 year, and at the end of that period the
prisms were further examined by petrographic, X-ray diffraction and electron
probe microanalytical techniques. Figure 6.1 shows that the alkali-silica
expansion decreases with the increase in the diatomite content in the cement.
The X-ray diffraction diagrams showed that crystalline Ca(OH) 2 content
decreased with the increase in diatomite in cement.
The most interesting information came from the electron probe
microanalyses of reactive grains and their surrounding pastes. Normalised
major oxide analyses of reacted grains and their surrounding areas are shown
in Figures 6.2 to 6.5. The figures show that (i) the entry of CaO and Na2O into
reacted grains decreases with the increase in diatomite content in cement, (ii)
more CaO and Na2O enter the grains when the prisms are stored in NaCl
solution than when stored in water, (iii) CaO enters reactive grains irrespective
of the nature of the bath, (iv) in samples free of diatomite, SiO2 concentration
Figure 6.1 Expansion characteristics of mortar prisms. Figures indicate moler contents.
Figure 6.2 The distributions of oxides in and around a reactive grain. Mortar prism stored in
water bath. No moler in cement.
Figure 6.3 The distribution of oxides in and around a reactive grain. Mortar prism stored in an
NaCl bath. No moler in cement.
Figure 6.4 The distribution of oxides in and around a reactive grain. Mortar prism stored in
water bath. Cement contains 25% moler.
Figure 6.5 The distribution of oxides in and around a reactive grain. Mortar prism stored in an
NaCl bath. Cement contains 25% moler.
Figure 6.7 A model for the alkali-silica reaction. If the amounts of water, alkali hydroxide and
calcium hydroxide entering the reactive particle are larger than the amount of alkali-silica gel
seeping out, the particle expands and cracks the surrounding cement paste.
concentration, only a limited amount of SiO 2 can diffuse out, but more
materials are pumped in. This generates the pressure necessary for expansion.
Note that according to this hypothesis, the chemical reaction and
accompanied expansion are not directly related.
The above roles of Ca(OH)2 are quite different from that assigned to it in the
hypothesis of Powers and Steinour30. According to the Powers and Steinour
hypothesis the expanding grain should be low in CaO, whereas according to
the newly proposed hypothesis the expanding grain should contain
substantial amounts of CaO. The near universally high content of CaO in gels
can be seen in Figure 6.836.
Figure 6.8 Composition of alkali-silica gel in concrete. Data published in Ref. 20 and
microanalyses in Ref. 36.
Figure 6.9 Expansion characteristics of mortar bars stored in different sodium salt solutions.
Figure 6.10 Expansion characteristics of mortar bars stored in KCl solutions of varying
normality.
maximum tolerable alkali salt solution will be around 0.75 N. After some time,
the concentration in the pore liquid and in the salt bath will be the same. An
estimate of the amount of alkali needed to trigger expansive reaction may be
estimated from the following considerations. Consider a concrete mix
containing 350 kg cement per cubic metre and a water-cement (w/c) ratio of
0.5, i.e. an initial water content of 175 litres. Further assume that, after
hardening, the free water content is 85 litres. The maximum tolerable alkali
content can be calculated as:
estimation, it has been assumed that no alkali salts may migrate from an
outside source and that alkali salt is uniformly distributed throughout the mass
of the concrete mix. If alkali salts migrate from an outside source or local
evaporation takes place at certain parts, then the local concentration of alkali
salt may go above the critical value and give rise to alkali-silica expansion
even though the overall alkali content may be lower than the critical value.
Various practical implications of this newly proposed hypothesis have been
discussed in a paper40.
with the requirement of DS 427, Portland cement and Portland fly ash cement,
2nd Edn, April 1983. In DS 427 there is no regulation of the alkali content of
the cement. However, in May 1986, a new Code of Practice was issued. This is
the so-called BBB (In Danish: Basis Betonbeskrivelsen for
Bygningskonstruktioner)42. This is a fundamental concrete specification to be
used in all public building construction works. A system is set out to prevent
harmful alkali-silica reaction.
The parameters used in this system are as follows:
Alkali content of the concrete
Reactivity of the aggregate
Environmental conditions.
6.3.2.1 Cement and its requirements. The cement falls into one of four groups
of alkali content:
EA extra low-alkali
LA low-alkali
MA medium-alkali
HA high-alkali
>
The alkali contributions of the cement and all other alkali sources in the mix
are summed up as eq. Na2O kg/m3 of concrete.
6.3.3 Experimental results with fly ash and fly ash cement
The effect of fly ash on the expansion due to ASR of mortar or concrete
samples can be evaluated either by the use of closed systems in which the total
alkali content of the systems does not change with time, which is the case
when testing is carried out according to, for example, ASTM C441 or the
modified ASTM method or by the use of open systems in which samples are in
contact with an alkali salt solution, as is the case with the so-called NaCl bath
method. The evaluation can also be carried out by an accelerated test method
or by a long-time storage method 4649. In Denmark both open and closed
systems as well as accelerated and long-time storage methods have been used
to evaluate fly ash or Portland fly ash cement systems.
In normal circumstances (closed systems), the use of a Danish Portland
cement, which has an alkali content of less than 0.8%, in conjunction with a
reactive aggregate does not give rise to any destructive ASR. However, in an
open system, in which alkali salts from an outside source can migrate into a
structure, destructive ASR can develop very quickly.
It is common practice (in Denmark) to use either a low-alkali Portland
cement or a pozzolanic cement (Portland fly ash cement) as a safety factor
against ASR.
In recent years papers50,51 have been published by the Nordic Concrete
Research, from which it appears that:
(1) Long-time storage tests show that addition of fly ash to concrete
mixes has no adverse effect even if its alkali content is as high as
2.34% Na 2O eq.
(2) Accelerated tests according to ASTM show that the addition of fly ash,
even of high alkali content, to Portland cements reduces expansions due
to ASR.
(3) Accelerated tests with unlimited supplies of alkali salt show that the
addition of fly ash to Portland cement reduces, at least, the rate of
expansion and perhaps also the ultimate expansion. Therefore, the use of
the Portland fly ash cement reduces the risk of expansion due to ASR even
in an open system in which alkali salts from an outside source may
penetrate into a concrete structure. For the case of a moderately reactive
sand, this reduction in expansion by using Portland fly ash cement may
make the sand acceptable for concrete-making.
(4) In an open system the use of a low-alkali sulphate-resistant Portland
cement has very little advantage over an ordinary Portland cement. The
most promising results are obtained with the use of Portland fly ash
cement (Figures 6.11 to 6.13).
Figure 6.11 Expansion characteristics of sand-cement mortar bars stored in a saturated NaCl
bath at 50C (ordinary Portland cement compared with low-alkali sulphate-resistant cement
and with Portland fly ash cement (Danish standard cement).
Figure 6.12 Alkali-silica test. Expansion characteristics of mortar bars of Nymlle sand together
with low-alkali cement and Portland fly ash cement.
Figure 6.13 Alkali-silica test. Expansion characteristics of mortar bars of Kallerup sand together
with low-alkali cement and Portland fly ash cement.
6.4. Conclusions
Denmark is a small country with many of its aggregate sources containing
alkali-reactive components. This has led to extensive research programmes on
ASR, on both its fundamental aspect and its avoidance in concrete structures.
As regards the preventive measures, the following innovations have been
made:
(1) The assumptions of a constant and uniform distribution of alkali in a
concrete structure have been dropped.
(2) The environment to which a structure may be exposed has been classified
as regards its severity.
(3) The acceptance criteria of aggregates, both fine and coarse, have been
made very strict, and have been correlated with the environmental classes.
(4) The permissible total alkali content of a concrete mix has been correlated
with the environment to which the concrete would be exposed.
(5) A fly ash Portland cement has been introduced to the Danish market.
It is hoped that as a result of the above innovations the incidence of ASR will
be very much restricted in the future.
References
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14 November 1950 to 15 February 1951 (in Danish). The Danish National Institute of
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