CEMENT and CONCRETE RESEARCH. Vol. 12, pp. 87-92, 1982. Printed in the USA.

0008-8846,/82/010087-06503.00/0 Copyright (c) 1982 Pergamon Press, Ltd.

DAMAGE OF CONCRETE SLEEPERS BY CALCIUM CHLORIDE

L. Berntsson and S. Chandra

Division of Building Materials
Chalmers University of Technology
S-412 96 GSteborg, Sweden

(Refereed)
(Received Sept:. 14, 1981)

ABSTRACT
High strength concrete sleepers damaged by calcium chloride have
been studied here. Chloride content is estimated at different
depths qualitatively by the classical wet method and quantita-
tively by ion selective electrodes. The samples were analyzed
by x-ray diffraction spectroscopy and were studied under micro-
scope. The damage of concrete is attributed to be a combined
effect of chemical, mechanical and physical processes. Calcium
chloride is found to be very detrimental to concrete. Special
care should be taken for its use.

En undersSkning har utfSrts med avsikt att fSrklara anmgrk-

ningsv~rt allvarliga skador p~ sliprar av hSgh~llfast betong.
Genom anv~ndning av olika analysmetoder, s~som v~tkemisk ana-
lys, jonselektiva elektroder och rSntgendiffraktometri kunde
bl a konstateras att kalciumklorid nyttjats som tSsalt. Skade-
mekanismen utgSres sannolikt av en kombination av kemisk, fysi-
kalisk och mekanisk p~verkan. Kalciumklorid i koncentrerade
18sningar har konstaterats ge upphov till kemisk nedbrytning
av betong under kort rid, varfSr sErskild f~rsiktighet ~ir att
rekommendera vid anv~ndning av kalciumklorid p& oskyddad
betong.

Introduction
Sleepers of high strength prestressed concrete used for crane tracks have
shown severe damage within a couple of years service. The type of damage under
this work was studied mainly from the practical point of view considering
physical, mechanical and chemical effects on concrete material.
Much of the research work on the influence of salts on the durability of
concrete has been done in the laboratory scale. It is a common trend to use
deicing salts for melting ice and snow on roads and streets during wintertime.
7
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L. Berntsson, S. Chandra

The most used deicing salt in Sweden is rock salt because of its low price.
This salt contains mainly sodium chloride. Calcium chloride has some advan-
tages in comparison with the other deicing salts, such as efficiency at
extremely low temperature and creation of high icemelting rate. The most
common use of calcium chloride is as a dust binder on roads because of its
hygroscopic character. Other use is as an accelerating admixture in con-
crete (I). Normally the calcium chloride used is of technical quality and
contains about 90% calcium chloride.
Materials and methods
The composition of concrete for sleepers and its compressive strength are
shown in table I.
Table I
Concrete Composition and Compressive Strength

Standard portland cement 465 kg/m 3

Sand (granite 0-4 mm) 880 "
Gravel (granite 4-16 mm) 810 "
W/C 0,45
Compressive strength
(cylinder ~ 67 mm) > 60 MN/m 2
Air content 1,5 %

Mean value of chloride content in concrete sleepers from the surface to

10 mm down as well as at the depth of 45-55 mm was estimated qualitatively by
the classical wet chemical analysis and quantitatively by ion selective
electrodes. The samples were taken out by dry boring. The material was
thoroughly grounded to get homogeneity. 5 g of material was used in the ana-
lysis. The concentration of free chloride ions was determined and the results
are shown in table II. The samples were also analyzed by X-ray diffraction
spectroscopy.
Table II
Chloride Ion Concentration as Measured by Ion Selective Electrodes

Sample C1 mol/l C1 % by weight C1 % by weight

in concrete of cement

SL-I 4.90"10 -4 0.035 0.2

SL-2 1.48-10 -4 0.011 0.06

SL-I is from 1 - 1 0 mm down the surface

SL-2 is from 45-55 mm depth in concrete measured from the surface
Specimens were cut and polished for photography and for microscopic
studies. The micrographs are presented in the figures I-6.

Results and discussions

The concentration of chloride ions decreases with depth into concrete.
Near the surface the free chloride content was found to be 0.2% of the
Vol. 12, No. i 89
CHLORIDE, CHEMICAL CORROSION, PHYSICAL PROCESSES, MECHANICAL DAMAGE

FIG. i
Polished surface of
high strength concrete

FIG. 2
SEM-photo from concrete
near the surface of
steel reinforcement bar

FIG. 3
Crystals inside an air-
pore in the zone of
corroded concrete
90 Vol. 12, No. i
L. Berntsson, S. Chandra

FIG. 4

S u r f a c e on a g g r e g a t e
with precipitated
crystals

i 14

FIG. 5

R e p l i c a of an a g g r e g a t e
in the cement paste

FIG. 6

Precipitated crystals
on the wall of an air-
pore at about 70 m m
d e p t h from the c o n c r e t e
surface
Vol. 12, No. i 91
CHLORIDE, CHEMICAL CORROSION, PHYSICAL PROCESSES, MECHANICAL DAMAGE

cement weight. This agrees with limits cited by Schorr (2). He reported a
limit of 0.2% CI- referred to the weight of cement for prestressed concrete
and 0.4% CI- for normally reinforced concrete. These limiting values for the
chloride concentration are referred to the corrosion of reinforcement and not
to the damage of concrete itself.
Figure I shows the photo of a specimen of not corroded concrete in a
sleeper. The airpore volume is estimated to be 1.6%. Figure 2 is a cut section
photographed by SEM. This shows clearly spherical airpores of different sizes
in the cement paste. Figure 3 shows well grown crystals in an airpore. The
length of the crystals is 50-60 ~m and the thickness about 1.5 ~m. Crystalli-
zation has concentrated between the aggregate surface and the cement paste in
the neighborhood of the corrosion zone. Figure 4 shows an aggregate particle
with crystals on its surface. On the top righthand side corner of the pic-
ture there is a contact crack between the particle surface and the cement
paste. A replica of a sand particle in the cement paste is shown in figure 5.
Its contact zone is totally covered with crystallized products. Another type
of crystals on the walls of airpores outside the corrosion zone is shown
in figure 6. The length of the crystals is about 2-3 ~m.
The damage of concrete studied here seems to have connection with chemi-
cal attack. Deformations caused by moisture movement, temperature (thermal
gradient:), freezing and thawing and mechanical stresses (caused by crane
movement:) are also acting upon the material in the practice. Lawrence and
Vivian (13) have reported that strong calcium chloride solution has given a
severe damage on cement mortar, not only during drying and wetting cycles,
but also during continuous storage in strong calcium chloride solution (i.~.
30%). Chlorides are found in the structure of cement paste in concrete. A
complex is formed when hydrated C3A reacts with calcium chloride. The damage
because of complex salt formation seems to be due to expansion and shows
similarity with sulfate attack. Precipitated salt can be seen from the micro-
graphs presented. Similar results are reported by K~hl (4) and Biczok (5).
X-ray diffraction analysis from the specimen near the concrete surface
has shown vaterite (a metastable form of calcium carbonate), calcium chloride
hydrate and monochlorohydrate with traces of Friedels salt (C3A CaCI2 IOH20 )
with some unidentified peaks. In the sample from 50 mm depth under the con-
concrete surface more Friedels salt, monochlorohydrate, calciumhydroxide and
vaterite were detected. Monochlorohydrate is present in both the cases, i.e.
near the surface as well as deep into concrete. It shows its stability both
in Portland cement - H20 system and in Portland cement - CaCI2-CO2-H20 system.
The phenomenon is well discussed by Chatterji (6). According to Richartz (7)
and the literature cited by him, Friedels salt forms on the surface of c~on-
crete in the first hand, but it is not stable during carbonation and forms
hydrargillite and metastable ~aterite. It seems that the presence of chloride
ions influences the formation of vaterite. In some other sample there was
comparatively less effect of carbonation so that a bigger amount of Friedels
salt was present.
It has been pointed out that concentrated solutions of calcium chloride
have shown that the severity of damage on Portland cement concrete increased
with decreasing temperature. The breakdown seems to be due to some comple
formation at a temperature below room temperature, for example 5C (6).
In combination with frost damage, the effect is more complicated with
both physical and chemical phenomena involved. Salt like chloride is no~
chemically damaging the concrete under normal conditions, but can cause sew~re
damage by frost action specially at low salt concentration. Tht~ frost
mechanism has been described by Lea (8), Browne & Candy (9) and Fa~er]und (I0).
92 Vol. 12, No. 1
L. Berntsson, S. Chandra

Conclusions
High strength concrete with compressive strength of more than 50 MN/m 2
has been observed to be severely damaged in a very short time by calcium
chloride.
The chloride concentration decreased with the depth of concrete. Com-
plexes have been formed with calcium chloride and cement paste. The damage
due to this appears to be similar as due to sulfate attack.
The damage of concrete is attributed to be a combined effect of chemical
reaction between calcium chloride and cement paste due to the mechanical
stress developed by load and physically due to freeze-thaw cycles.
As a practical conclusion calcium chloride is very detrimental to con-
crete, especially when it is exposed to the atmosphere all the time. Special
care should be taken for its use.
Acknowledsements
The authors are grateful to B. Hedberg for his help in taking the micro-
graphs, to miss B. Lendheim for preparation of the text and to A. Lampinen
for reproduction of micrographs.
References
I. V.S. Ramachandran, Calcium Chloride in Concrete Science and Technology.
Applied Science Publishers htd, London (1976).

2. K. Schorr, Chloridkorrosion in Stahlbeton. Betonwerk+Fertigteil-Technik,

3, pp. 150-152 (1981).

3. M. Lawrence and H.E. Vivian, The Action of Calcium Chloride on Mortar and
Concrete. Australian Journal of Applied Science, II, 4 (1960).

4. H. KHhl, Zement-Chemie, Band Ill. Verlag Technik, Berlin (1952).

5. I. Bicz6k, Concrete Protection. Akad~miai Kiad6, Budapest (1972).

6. S. Chatterji, Mechanism of the CaCI 2 Attack on Portland Cement Concrete.

Cement and Concrete Research, 8, pp. 461-468 (1978).

7. W. Richartz, Die Bindung von Chlorid bei der Zementerh~rtung. Zement-Kalk-

Gips, 10 (1969).

8. F.M. Lea, The Chemistry of Cement and Concrete. Edward Arnold Ltd, London
(1970).

9. F.P. Brown and P.D. Cady, Deicer Scaling Mechanism in Concrete. Durability
of Concrete. ACI Publication SP 47-6, Detroit (1975).

10. G. Fagerlund, RILEM Recommendation: The Critical Degree of Saturation

Method of Assessing the Freeze/thaw resistance of concrete. Materials and
Structures, 10, 58 (1977).