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Microstructure, chloride migration and corrosion near the transition zone

between substrate and repair concrete

Conference Paper · November 2005

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Microstructure, chloride migration and corrosion near the transition zone between substrate
and repair concrete
P. Skoglund, M. Kalinowski & J. Trägårdh
Swedish Cement and Concrete Research Institute, CBI, Sweden

ABSTRACT: In 1992 reinforced and patch repaired concrete specimens were made at the Swedish Cement
and Concrete Research Institute (CBI). The substrate concrete in the specimens had w/c ratios of 0.50 and
0.70. A chloride content of 1.0 % of the cement weight was mixed into the substrate concrete in order to study
the extent and nature of chloride migration into the repair concrete. The repair concrete had a w/c ratio of 0.40
in all specimens and the concrete cover was 16 mm. The specimens have been exposed to outdoor climate at
CBI since 1992. In the present investigation, which started 2004, rebar corrosion was observed near the transi-
tion zone in both the substrate concrete and the repair concrete. The characteristics and microstructure of the
transition zone between the repair concrete and the substrate concrete was studied with different microscopic
techniques. The transition zone is mainly composed of a 50-100 µm thick layer of carbonated portlandite and
is more porous than the substrate concrete and the repair concrete. Thin-section analysis shows that the sub-
strate concrete near the transition zone is carbonated to 2.6 mm depth in the specimen with a w/c ratio of 0.70
and to 1.6 mm depth in the specimen with a w/c ratio of 0.50. The high porosity of the transition zone pro-
vides a pathway for CO2-diffusion with successive carbonation of the substrate concrete. The repair concrete
showed little carbonation.

1 INTRODUCTION mixed into the substrate concrete. The repair con-

crete in the patch repair had w/c ratio of 0.40 in
1.1 Background both specimens. The specimens have been exposed
Concrete repair due to reinforcement corrosion to outdoor climate (CBI, Stockholm, Sweden) for
caused by chlorides is common in Sweden espe- 12 years.
cially in parking structures, bridges and swimming
pools. Chloride contaminated concrete is very
common in damaged structures that needs concrete Substrate
repair. Where reinforcement intersects the transi- Concrete
tion zone between concretes there may be a risk of
future damages caused by corrosion initiated by in-
creased chloride concentrations near the transition
zone, Nagataki et al (1996). The increased concen- Reference steel
trations of chloride ions near the transition zone
could be explained by differences in electrochemi-
cal potentials between concretes.

1.2 Specimens
Reinforced concrete specimens, 250x100x55 mm,
with concrete repairs (Fig. 1) were made in 1992 at Repair
Swedish Cement and Concrete Research Institute Reinforcement concrete
(CBI) in Stockholm. The aim of the project was to
study reinforcement corrosion in patch repaired
specimens. In this present investigation two speci-
mens, 33R and 43R, were investigated. The con- Figure 1. Reinforced concrete specimen with
crete cover is 16 mm in both the specimens. The concrete repair.
substrate concrete in the two specimens in this in-
vestigation had w/c ratio of 0.70 (33R) and 0.50
(43R) and 1.0 % chlorides of cement weight were
1.3 Aim
The aim with this present investigation is to study
microstructure, chloride transport and carbonation
in the transition zone between substrate concrete
and repair concrete in two field stored specimens
after 12 years.
2 METHODS
2.1 Preparing of specimen before analysis
From the concrete samples, 10 mm thick slices
were cut out with a precision saw (Fig. 2). To pre-
vent the chlorides to be “washed out” during the
sawing process no cooling water was used. The
cuts were directed so the transition zone between
the substrate and repair concrete was located in the
middle of the slices and 25 mm of concrete on both
sides of the transition zone was included. The cuts
were tangent to the rebar steel so its surface was
exposed. Subsequently, the slices were fractured
perpendicularly to the transition zone. This prepa-
ration technique is believed to produce the least al-
tered surfaces for the purpose of chemical analysis.
Rebar
Substrate
concrete
50 mm
Transition Repair
zone concrete
Figure 2. Specimen slice with rebar attached to the
concrete.
2.2 SEM-EDS analysis
The amounts of chloride ions in the samples was
analysed using a scanning electron microscope
(SEM) equipped with energy dispersive spectrome-
ter (EDS). All the EDS-analyses were carried out
on the fractured surfaces. The analytical results are
presented as wt % of chloride ions (Cl-). All the
EDS-analyses were carried out in the cement paste
and the beam was focused to point analyses. As the
chloride ions are not evenly distributed in the ce-
ment paste on the micro-scale, two to six EDS-
analyses were done at every distance. The amount
of chloride ions shown in Figures 3, 4 and 5 repre-
sent mean values of several analyses made at the
same distance from the transition zone. EDS-
analyses on rebar steel (Fig. 5) were carried out as
area analyses. The analysed areas are 655x90 µm
in dimension. Distance in Figures 3, 4 and 5 shows
the distances between the analytical points (or are-
as as in Fig. 4) and the transition zone. Distances
marked with a negative sign (e.g., -1) correspond
to analyses located in the substrate concrete. Dis-
tances with a positive sign (e.g., 1) correspond to
analyses done in the repair concrete.
2.3 Microscope analysis
Thin-sections for light microscopy were prepared
with an epoxy resin containing a fluorescent dye.
The polarizing light microscope has a fluorescent
light mode which increases the contrast in the ce-
ment paste. The thin-sections were prepared per-
pendicularly to the transition zone between sub-
strate concrete and repair concrete. The thin-
sections enabled a study of the density of the ce-
ment paste from the substrate concrete towards the
transition zone and into the repair concrete as well
as calcite formation due to carbonation.
2.4 Corrosion analysis
The specimens and the reinforcement were studied
ocularly. After the rebars have been separated from
the concrete, the reinforcement corrosion was stud-
ied under a stereomicroscope. Some samples were
prepared (Fig. 2) with the rebar attached to a slice
of concrete showing the transition zone between
substrate concrete and repair concrete (Figs. 6 and
7). This enabled an analysis of how the corrosion
products were located in relation to the transition
zone.
The chloride content in the corrosion products
was measured along a profile on the mantle surface
of the rebar with SEM-EDS equipment. The profile
transected the transition zone. Due to the strong
correlation between the amount of chlorides de-
tected on the rebar surface and the corrosion inten-
sity, a picture of how the amount of corrosion
products varied across the transition zone was ob-
tained. The result is shown in Figure 5.
2.5 Carbonation analysis
The depth of carbonation from the transition zone
and into the substrate concrete and the repair con-
crete was measured in a polarizing light micro-
scope.
 3 RESULTS ride concentrations are between 1.8 and 3.6 wt %
at 4 mm depth into the repair concrete.
3.1 Chloride profiles
33R Surface of reinforcement
In Figure 3, the chloride profile across the transi- Substrate Concrete - Repair concrete
tion zone for 33R is shown. The content of chlo-
3,6
rides in the substrate concrete is low, almost 0 wt
3,2
%, between 0 and 6 mm from the transition zone. 2,8
Corroded steelarea

Between 6 mm and 16 mm distance from the tran- 2,4

Substrate Repair

Cl- (vikts%)
Concrete Concrete
sition zone, the concentrations of chlorides lie be- 2,0
tween 1.8 and 2.2 wt %. At larger depths than 16 1,6
Transition
mm into the substrate concrete the concentrations 1,2 Zone

of chloride ions lie between 0.6 and 0.7 wt %. In 0,8

the repair concrete the concentrations of chloride 0,4

ions near the transition zone varies between 0.4 0,0

-15 -10 -5 0 5 10 15 20 25
and 1.3 wt % up to a distance of 20 mm from the Distance (mm)
transition zone. Figure 5. Chloride profile on the mantle surface of the rein-
In Figure 4 the chloride profile across the transi- forcement crosscutting the transition zone in 33R.
tion zone for 43R is shown. Between 3 mm and 25
mm in the substrate concrete the concentrations of
chloride ions lie between 1.1 and 3.0 wt %. In the 3.2 Carbonation
repair concrete the chloride concentration near the From the thin-sections the depth of carbonation
transition zone is about 0.4 wt % (0 to 8 mm near the transition zone was analyzed by a polariz-
depth). ing light microscope. The substrate concrete was
carbonated to 2.3 mm depth from the transition
zone in specimen 33R (w/c ratio 0.70) and to 1.6
33R Chloride profile
mm depth from the transition zone in 43R (w/c ra-
3,2 tio 0.50). In both specimens the repair concrete had
2,8
Substrate Repair 0-0.1 mm carbonated cement paste from the transi-
2,4 Concrete Concrete tion zone.
Cl (weight %)

2,0
Transition
Zone 50 mm Rebar
1,6
3.3 Corrosion
1,2
-

0,8
The two field specimens, 33R and 43R, showed no
visual cracking due to reinforcement corrosion.
0,4
Corrosion was observed on the reinforcement in
0,0
-25 -20 -15 -10 -5 0 5 10 15 20 25
the area near the transition zone (Figs. 6 and 7).
Distance (mm) Figure 5 shows a chloride profile along the mantle
surface on the rebar crosscutting the transition zone
Figure 3. Chloride profile across the transition zone in 33R. in specimen 33R. As can be seen in the diagram,
the chloride contents on the rebar surface increase
43R Chloride profile near the transition zone and continue to show high
concentrations about 5 mm into the repair concrete.
3,2
Substrate Repair
The high level of chloride concentrations on the
2,8
Concrete Concrete rebar surface corresponds with the visually ob-
2,4
served distribution of corrosion products. In this
Cl- (weight %)

2,0
Transition case the corrosion products are mainly located on
1,6 Zone
the repair concrete side of the transition zone. The
1,2 corrosion products have two colours, black and or-
0,8 ange.
0,4

0,0
-25 -20 -15 -10 -5 0 5 10 15 20 25
Distance (mm)

Figure 4. Chloride profile across the transition zone in 43R.

The chloride profile on the surface of the rein-

forcement in 33R (Fig. 5) shows that that the chlo-

Figure 6. Corroded steel area in the transition zone. Main
corrosion is in the repair concrete.
Slices from the two field specimens slices were
cut out perpendicular to the transition zone. The
cuts were placed on either side of the rebar in such
a way that the pieces included it (see Figure 2). On
these pieces it was possible to examine how the
corrosion products were located in relation to the
transition zone. It was observed that the bulk of the
corrosion products were located on different sides
of the transition zone when the pieces were rotated
around the rebar. Consequently, the corroded parts
of the steel was embedded in the repair concrete on
one side of the sliced piece and on the substrate
concrete on the other side (Figs. 6 and 7). In one
case, the corroded part of the steel ended sharply at
the transition zone (Fig. 7).
Figure 7. Corroded steel area in the transition zone. Main
corrosion is in the substrate concrete. Same piece as in Figure
6.
3.4 Microstructural observations from light
microscopy
The carbonation of the substrate concrete resulted
in a denser cement paste near the boundary to the
repair concrete. At the same time the cement paste
becomes more crystalline due to calcite formation.
This is shown in Figure 8 and 9. Immediately near
the transition zone the substrate concrete becomes
even denser, which is shown as a 0.1-0.2 mm dark
rim along the transition zone between the concretes
in Figure 8 (33R, w/c ratio 0.70). In sample 43R
(w/c ratio 0.50) the dense rim was however not de-
tected. The repair concrete did not show any signif-
icant carbonation (about 0-0.2 mm).
The transition zone itself is mainly composed of a
50-100 µm thick layer of carbonated portlandite
(minute calcite crystals). This zone is more porous
than both the substrate concrete and the repair con-
crete and it resembles the type of transition zone
which often occurs between large aggregates and
cement paste (ITZ) (Trägårdh 1999). The high po-
rosity of the transition zone between the concretes
makes it a pathway for CO2-diffusion with succes-
sive carbonation of the substrate concrete as a con-
sequence. The same type of transition zone also
envelopes the rebar steel along its extension.
The transition zone comprised a zone of weak-
ness resulting in a poor adhesion between the con-
cretes. The adhesion to the repair concrete was
found to be somewhat stronger in the specimen
where the substrate concrete had a w/c ratio 0.70
(33R) compared to a w/c ratio 0.50 (43R).
Figure 8. Thin-section of the transition zone between sub-
strate concrete (left) and repair concrete (right). Specimen
33R. Picture taken in fluorescent light, 100 X magn.

Figure 9. Carbonation from the transition zone and 2-2,5 mm
into the substrate concrete (left). The repair concrete to the
right is left uncarbonated. Specimen 43R. Polarised light, 50
x magn.
4 DISCUSSION
A substantial part of damages in concrete construc-
tions are caused by chloride initiated reinforcement
corrosion. One important step in a concrete repair
is the removal of the deteriorated concrete. Rec-
ommendations and requirements in Sweden
(SNRA Publ. 2002:47. 2002) say that concrete
with higher chloride content than 0.30 wt % of ce-
ment at the reinforcement should be removed. It
costs a lot of time and money to remove all this
concrete. Often there are higher concentrations of
chlorides behind the reinforcement than 0.30 wt %.
One question which often arises is: can concrete
with relatively high content of chlorides be left in
the structure? Are chloride ions migrating from
the contaminated substrate concrete into the repair
concrete? In this investigation it is shown that
chlorides from the contaminated substrate concrete
have moved into the repair concrete. In specimen
33R (w/c ratio 0.70 in substrate concrete) the level
of chlorides is about 1.0 wt-% at a depth of 20 mm
into the repair concrete. Specimen 43R (w/c ratio
0.50 in substrate concrete) has 0.1-0.3 wt-% chlo-
rides at a depth of 25 mm into the repair concrete.
The investigation shows that chloride ions can
move into a repair concrete which is of good quali-
ty and reach levels higher than required for chlo-
ride initiated reinforcement corrosion.
The carbonation analysis with light microscope in
thin sections shows that the substrate concrete in
the transition zone has been carbonated during
these 12 years but almost not the repair concrete.
This means that the transition zone must have been
porous so the air could penetrate the specimen. The
low carbonation in the repair concrete may be ex-
plained by the low w/c ratio.
The chloride transport may be affected by the po-
tential difference between the two materials.
There may also be a potential difference when the
substrate concrete has carbonated but not the repair
concrete.
The reinforcement was corroded in the area near
the transition zone. In the sample slices across the
transition zone, corrosion was observed in the sub-
strate concrete on one side and in the repair con-
crete on the other side. This sort of corrosion spiral
was observed in both specimens and is probably
caused by electrochemical phenomena. An earlier
investigation (Gu, 1994) has observed that corro-
sion occurs in the denser matrix with the conclu-
sions that surface corrosion reactions appear in ar-
eas covered by denser matrix regions and the effect
of matrix heterogeneity on reinforcing steel corro-
sion is dependent on the level of oxygen and chlo-
ride ion concentration at the cement-steel interfac-
es.
The SEM-EDS analysis on the surface of the re-
inforcement in specimen 33R showed that the level
of chlorides was highest in the area where the cor-
rosion was located.
The carbonated zone near the transition zone has
almost no detectable chlorides. Immediately behind
the carbonation zone the concentration of chlorides
in the substrate concrete was far higher than the
background value of 1.0 wt-%. Between 8 mm and
16 mm into the concrete the concentration of chlo-
rides decreased to background values.
Tutti (1982) found that: Carbonating concrete
does not have at all the same capacity for binding
chlorides as does non-carbonated concrete. This
means that the equilibrium which occurs between
the free chloride and bound chloride is displaced so
that the free chloride increases in the pore solution.
In a concrete which was homogeneous from the
beginning, a difference in concentration is gradual-
ly built up for the chlorides with the greatest con-
centration at the surface. The difference in concen-
tration leads to a diffusion process. In popular
terms one might say that the carbonation process
ploughs the chlorides into the concrete. A chloride
level at the reinforcement which was acceptable
from the beginning can thus become too high be-
fore the carbonation front reaches. This observa-
tion is similar to the results in this present investi-
gation.
Byfors (1990) writes about two possible explana-
tions why carbonated concrete cannot bind as
much chloride as uncarbonated concrete: One ex-
planation for this may be that calcium carbo-
aluminate is formed in the carbonated concrete.
This compound is similar to Friedl’s salt. It may
thus be a question of an exchange reaction in this
compound. Another possible explanation may be
chloride transport as a consequence of moisture
transport in the carbonated concrete. Which expla-
nation that describes the observations in our spec-
imens is not investigated so far.
5 CONCLUSIONS 7 REFERENCES

Admixed chlorides of 1 wt % of cement in labora- Bro 2002, SNRA, Vägverkets allmänna tekniska
tory made substrate concretes (w/c ratio 0.70 and beskrivning för nybyggande och förbättring av broar
0.50) were found to migrate into a denser repair (SNRA´s general technical descriptions for new
concrete (w/c ratio 0.40). The concentrations of bridges and reconstruction of bridges), Publ. 2002:47,
chlorides reached relatively high levels in the re- Vägverket, Borlänge, 2002. (In Swedish).
pair concrete. In the case where the substrate con- Gu P, Fu Y, Xie P, Beaudoin, Effect of uneven
crete had a w/c ratio of 0.70, the chloride concen- porosity distribution in cement paste and mortar on
trations in the repair concrete reached about 1 wt reinforcing steel corrosion, Cement and Concrete Re-
%. search, Vol. 24, No. 6, pp. 1055-1064, 1994.
Near the transition zone the substrate concretes Tutti K., Corrosion of steel in concrete, CBI Research,
have been carbonated due to a porous transition 4.82 1982 Swedish Cement and Concrete Research
zone to about 2.3 mm (w/c ratio 0.70) and 1.6 mm Institute, Stockholm, 1990.
(w/c ratio 0.50). The repair concrete showed little Trägårdh J., Microstructural teatures and related
or no carbonation (0 – 0.2 mm depth). properties of self-compacting concrete, Proceedings
The carbonated zone in the substrate concretes of the First International RILEM Symposium, RILEM
contained low concentrations of chlorides. Behind Proceedings PRO 7, Stockholm, 1999.
the carbonated zone the chloride concentrations Nagataki S. et al, Macro-cell corrosion on embedded
reached high levels of 2 – 2.5 wt %. This has earli- bars in concrete members with joints, Durability of
er been reported in the literature (Tutti, 1982). At Building Materials & Components, 7, Volume 1, Pre-
greater depths the concentrations decreased to diction, Degradation & Materials, E&FN Spon, Lon-
background values of about 1 wt %. don, 1996.
A chloride profile along the mantle surface of the Byfors K., Chloride initiated reinforcement corrosion
rebar steel showed high chloride concentrations, Chloride binding, CBI-report 1:90, Swedish Cement
about 3.5 wt %, at the transition zone between the and Concrete Research Institute, Stockholm, 1990.
concretes. Corrosion was concentrated to this zone.
A section of about 6-7 mm of the steel was corrod-
ed.
It was observed that the bulk of the corrosion
products were located on different sides of the
transition zone when the rebar was rotated. Con-
cequently, the corroded part of the steel was em-
bedded in the repair concrete on one side of the
steel and on the substrate concrete on the other
side.
The gathered data in this study suggest that dif-
ferences in electrochemical potentials between
concretes were established and that these differ-
ences have been the driving force for corrosion and
chloride concentration at the transition zone.
It is the authors view that the potential for corro-
sion in the transition zone needs to be considered
in patch repair work.

6 ACKNOWLEDGEMENTS

We would like to thank the Swedish construction

industry's organization for research and develop-
ment, SBUF, for financial support.
The authors also wish to thank Mårten Janz at the
Swedish Cement and Concrete Research Institute
for valuable discussions and Professor Johan
Silfwerbrand at the Swedish Cement and Concrete
Research Institute for reading the manuscript.

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