ACID ATTACK

Acid attack

ACID ATTACK
• Concrete, containing Portland cement, is highly alkaline and is not resistant to
attack by strong acids or compounds.
• Some weak acids can be tolerated, particularly if the exposure is occasional.

ACI 201.2R-08: Guide to Durable Concrete, Reported by ACI Committee 201

 Acid attack

ACID ATTACK
 Water draining from some mines and  Mountain streams are sometimes
some industrial waters can contain or mildly acidic due to dissolved free
form acids that attack concrete. carbon dioxide.

Rajkumar Hosdodde, 2014. Water Pollution With Constructive Measures With

Special Reference To India. Indian Streams Research Journal, Vol. IV, Issue. III,
DOI : 10.9780/22307850, http://isrj.org/UploadedData/4576.pdf http://www.publicdomainpictures.net/view-image.php?image=18439&picture=stream-in-autumn&large=1

ACI 201.2R-08: Guide to Durable Concrete, Reported by ACI Committee 201

 Acid attack

ACID ATTACK
 Organic acids from farm silage or from manufacturing or processing
industries, such as breweries, dairies, canneries, and wood-pulp mills,
can cause surface damage.
 This can be of considerable concern in the case of floors, even where
structural integrity is not impaired*

http://www.adaklikkoyunankara.com/wp-content/uploads/2013/09/3.jpg http://www.flickr.com/photos/92886069@N00/2158968494

*ACI 201.2R-08: Guide to Durable Concrete, Reported by ACI Committee 201

 Acid attack

SULFURIC ACID ATTACK (H2S)

• Sewage can be collected under conditions that lead to acid formation.

before after

ACI 210.1 R-94 (Reapproved 1999): Compendium of Case Histories on Repair of Erosion-Damaged Concrete in Hydraulic Structures Reported by ACI Committee 210
 Acid attack

ACID ATTACK
Acid attack Decomposition of
Industrial structures
hydration products

Soluble (leach out)

New compounds are generated
(calcium salts) Insoluble (may be distruptive)

• Rate of deterioration is much higher in a flawing solution than in a stagnant solution.

• With acid attack, the permeability of the concrete is of minor importance unlike
sulfate and alkali attacks. On the other hand, acid attack results in the destruction of
pore system.
 Acid attack

ACID ATTACK

Loss of compressive strength after

exposure of Portland cement
mortars exposed to acid solutions
of different concentrations for a
period of 120 days. (From Türkel,
S. et al., Sadhana, 32, 2007, 683–
691.)

Dyer, Thomas, Concrete Durability, CRC Press, 2014.

 Acid attack

RECOMMENDATIONS TO PREVENT ACID

ATTACK
• A dense concrete with a low w/cm provides a degree of protection against mild acid
attack.
• Certain pozzolanic materials, and silica fume in particular, increase the resistance of
concrete to acids (Sellevold and Nilson 1987).
• In all cases, exposure time to acids should be minimized, if possible, and immersion
should be avoided.
• No hydraulic-cement concrete, regardless of its composition, will long withstand water
of high acid concentration (pH of 3 or lower).
• An appropriate protective-barrier system or treatment can be used. ACI 515.1R gives
recommendations for barrier systems to protect concrete from various chemicals.
• Polymer-modified concretes: Polymer components of the resulting cement matrix are
largely unaffected by contact with acids, thus reducing the rate of deterioration.

ACI 201.2R-08: Guide to Durable Concrete, Reported by ACI Committee 201

 Chemical attack

RECOMMENDATION FOR LIMITING

VALUES OF CONCRETE COMPOSITION

BS EN 206:2013-Concrete — Specification, performance, production and conformity

ALKALI-AGGREGATE ATTACK
(AAR)
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

• Two types of AARs are recognized:
• Alkali-silica reaction (ASR): Silica in some agg.
reacts with the alkalis (Na2O, K2O) in Portland
Cement (especially in warm, humid climates)
• excessive expansion
• cracking
• Popouts Severe map-cracking in a median highway barrier affected by ASR.

• Alkali-carbonate reaction (ACR): Carbonates in

aggregate can also react to a lesser extent
(reported mostly in Canada and China)
• ASR is far more widespread than ACR
• Destruction is the same.
Typical surface map-cracking due to ACR.
Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
RECORDED CASES OF ALKALI AGGREGATE REACTIVITY
• During the 1920s and 1930s, numbers of Thomas Stanton of the California
State Division of Highways
concrete structures in California, USA, were
observed to develop severe cracking within
a few years of their construction.
• In 1940, Stanton was able to demonstrate
the existence of alkali-aggregate reaction as
an intrinsic deleterious process between
the constituents of a concrete.
• In 1957, expansive distress in field concrete
due to alkali-carbonate reactivity (ACR) was
first observed by Swenson in Ontario.
• In 1990s, first cases reported in İzmir,
Turkey.
ASR damage in a viaduct foot,
Izmir, Turkey
ACI 221.1R-98:State-of-the-Art Report on Alkali-Aggregate Reactivity Reported by ACI Committee 221
 Alkali-aggregate reaction

RECORDED CASES OF ALKALI SILICA REACTIVITY

Although the number of
cases of serious
deterioration is very small
indeed compared with the
number of concrete
structures that have been
built, no continent, and few
countries of the world, have
no examples of affected
structures.

R.N.SWAMY, The Alkali-Silica Reaction in Concrete, , © 1992 Blackie and Son Ltd, First published 1992
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

• Since the attack is only certain substances, the mechanism is more than
acid attack and similar to sulfate attack.
• Sulfate attack reactive substance is in cement.
• Alkali attack reactive substance is in aggregate.

• Alkali comes mostly from cement

• Other sources of alkalis;
• Mixing water
• Sea water
• Ground water
• Deicing salts
• Some minerals in aggregate such as micas, feldspats, some kind of clays
• Some admixtures (either chemical or mineral)
 Alkali-aggregate reaction

REACTIVE AGGREGATES for ALKALI-

AGGREGATE REACTION
 The reactive forms of silica;  The reactive forms of carbonate;
• Dolomitic limestone

ACI 201.2R-08: Guide to Durable Concrete, Reported by ACI Committee 201

 Alkali-aggregate reaction

REACTIVE AGGREGATES for ALKALI-

AGGREGATE REACTION

R.N.SWAMY, The Alkali-Silica Reaction in Concrete, , © 1992 Blackie and Son Ltd, First published 1992
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

Reactive Aggregate + Alkali GEL
(OH-, Na+, K+ ions)

Gel + Water Deformation

Cracking

• Map cracking is typical but not unique to AAR.

• ‘Pop-out’ of reactive particles has been noted
in certain cases.
• Spalling observed rarely (mostly near joints In certain cases Typical
due to expansion).
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

alkali content
water EXPANSION
temperature
time
 Alkali-aggregate reaction

EFFECT of MOISTURE to ASR

The humidity of air in contact with concrete
undergoing ASR profoundly affects expansion,
with relative humidity below approximately
75% producing little or no expansion and an
increase in expansion with humidity above
this level.

Influence of relative humidity on ASR expansion of mortar bars held for 22

months in sealed glass containers.
(From Olafsson, H. The effect of relative humidity and temperature on alkali expansion of mortar bars.
In P. E. Grattan-Bellew, ed., Proceedings of the 7th International Conference on Concrete Alkali–
Aggregate Reactions, Ottawa, Canada, August 18–22, 1986, pp. 461–465.)

Dyer, Thomas, Concrete Durability, CRC Press, 2014.

 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

Photograph of a Thin Section of Concrete The so-called “alkali-silica gel” will be found
Undergoing ASR (field of view ~ 5 mm) filling cracks within the aggregate particles,
lining or filling voids and fractured surfaces of
the cement paste and the aggregate particles.

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 PESSIMUM EFFECT

• Expansion did not necessarily increase

with an increase in the reactive aggregate
content.
• Such behavior is associated with some,
but not all, highly reactive aggregates.

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

• Occurrence of damage due to ASR is very late (often after more than 5 years, 5-15
years is perhaps most common but some reported examples have not exhibited
distress for 25–40 years post construction).
• Expansion occurs in a much shorter timeframe with ACR (1-2 years).

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

A portion of concrete
road pavement,
Cracking in a sea defence wall of plain concrete
Cape Town.
in Japan.
Length of the pencil is
R.N.SWAMY, The Alkali-Silica Reaction in Concrete, , © 1992 Blackie and Son Ltd, First published 1992 125 mm.
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

Map-cracking in the wing wall of a Longitudinal cracking in a

30-year-old bridge structure Severe relative precast, reinforced concrete
affected by ASR dislocation/misalignment, leading to beam affected by ASR.
loss of clearance and localized
spalling (photo from SHRP C-315
1991).

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

Cracking due to alkali-silica reaction in a In the case of reinforced concrete columns, cracks
column. The cracks form in the direction of tend to be aligned vertically due to the restraint
least resistance thus indicating the path of imposed by the primary reinforcement and the dead
the compression trajectories in this column. load
Yu, C.W., Bull, J.W., Durability of Materials and Structures in Building and Civil Engineering, CRC Press, 2006.
Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

Longitudinal cracking Well-defined crack pattern

Enlargement (red rectangle) of a connected by map cracking in associated with the development of
section of the pavement in left severely damaged concrete ASR in highway pavement; the
figure showing the aligned pavement (photo from SHRP orientation of predominant cracks is
(longitudinal) cracking in pavement C-315 1991). longitudinal, while map- or pattern-
with connecting map cracking. cracking is also identified.

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

ATTACK by ALKALI-AGGREGATE REACTION

 Alkali-aggregate reaction

EFFECT of ASR to MECHANICAL

PROPERTIES

Lower Bound of Residual Mechanical

Properties for ASR-Affected Concrete
Specimens, Expressed as a
Percentage of Values Obtained for
Unaffected Concrete at 28 Days (ISE

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

PRECAUTIONS FOR PREVENTING ALKALI-

AGGREGATE REACTION
Methods for minimizing the risk of damaging ASR include one or more of the following:
 Avoid utilization of reactive aggregates (perhaps the most obvious and certain way to avoid damaging)
 Minimize reactivity if a reactive aggregate must be used
• Minimize alkali content of P.C.
 equivalent alkali (Na2O + 0.658K2O) < 0.6% is recommended*
• Reduce cement dosage
• Keep concrete as dry as possible
• Replacement of PC partly by fly ash, slag, silica fume, rice husk ash (Pozzolans).
• Use suitable chemical admixtures such as lithium salts and other salts such as barium salts,
sodium silica fluoride, and alkyl alkoxy silane (chemical admixture use to inhibit the ASR has not
been widely employed by the construction industry).
• W/C Strength Porosity Permeability Mobility of alkali ion
Pore alkali concentration
*ASTM C150/C150M − 12: Standard Specification for Portland Cement
**ACI 201.2R-08: Guide to Durable Concrete, Reported by ACI Committee 201
 Alkali-aggregate reaction

PRECAUTIONS FOR PREVENTING ALKALI-

AGGREGATE REACTION
Other methods for minimizing the risk of damaging ASR include one or more of the
following:
• Air entrainment (accomodating the reaction products)
• Reduce the alkali content of admixture
• Sealing of concrete
• Coating of aggregate

• For alkali-carbonate rock reactive (ACR) aggregates, avoidance or reduction in

proportion of the reactive phases is the only recommended practice**

*ASTM C150/C150M − 12: Standard Specification for Portland Cement

**ACI 201.2R-08: Guide to Durable Concrete, Reported by ACI Committee 201
 Alkali-aggregate reaction

EFFECT of SCMs to ASR

• One of the most efficient means of controlling ASR in concrete
containing reactive aggregates is the appropriate use of
supplementary cementing materials (SCM).
• Such materials include pozzolans (e.g., fly ash, silica fume, calcined
clay, or shale) and ground-granulated blast furnace slag.
• The potential use of pozzolans to control ASR dates back as far as the
discovery of ASR, having been reported in the first major publication
on the phenomenon (Stanton 1940).

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EFFECT of SCMs to ASR

• Thomas (2011) showed that almost any SCM can be used to control ASR
provided it is used at a sufficient level of replacement. The amount
required varies widely depending on, among other things, the following:
• The nature of the SCM (especially mineralogical and chemical composition); more SCM is
required as its silica content decreases or as its alkali and calcium content increase,
• The nature of the reactive aggregate; generally, the more reactive the aggregate, the higher
the level of SCM required,
• The availability of alkali within the concrete (i.e., from the portland cement and other sources);
the amount of SCM required increases with the amount of available alkali,
• The exposure conditions of the concrete; concrete exposed to external sources of alkali may
require higher levels of SCM.

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EFFECT of SILICA FUME to ASR

• Low amount (up to 10%) expansion
• High amount expansion (due to the silica in silica fume)

• +air entrainment If CaO/SiO2 ratio of C-S-H ≤ 1.2

SF (%) Expansion 1. C-S-H can accommodate Na2O and K2O in the
structure, reducing hydroxyl ion concentration.
Without air With air
2. Silica fume forms microcystalline hydrosilicates
entrainer entrainer
containing alkalis similar to alkali-silica gels.
0 1.05 0.48 Expansion of this product does not deteriorate
6 0.85 0.45 concrete because the cement is plastic at that
12 0.62 0.28 moment.
 Alkali-aggregate reaction

EFFECT of FLY ASH to ASR

• Usually F type (low CaO content) fly ash is
used in the literature.

Effect of fly ash replacement level

on expansion of concrete (Shehata
and Thomas 2000)
Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EFFECT of FLY ASH to ASR

• The alkali content of fly ash is
important. Higher the alkalis the
lower the expansion reducing
effect.

Successful example: The Nant-y-

Moch Dam in 2011 – No Symptoms
of ASR after 50 Years – Constructed
with Reactive Aggregate and 25%
Fly Ash

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EFFECT of SLAG to ASR

• Molten slag glassy(amorph)
• Controls alkali-aggregate reaction as follows;
• Dilution effect
• Pozzolanic action
• Entrapment of alkalis in the C-S-H phase
• Changes the CaO/SiO2 ratio of the C-S-H phase
• Reduce permeability

• Alkali content of slag is also important

• A result 60% should be used
 Alkali-aggregate reaction

EFFECT of SCMs to ASR

• Figure shows the expansion of concretes
at 2 years as a function of the type and
amount of SCM used;
• Silica fume and metakaolin are the most
efficient with regards to reducing the
expansion at 2 years, followed by low-
calcium fly ash.
• Slag, high-calcium fly ash, and high-alkali
fly ash were less efficient and had to be
used at significantly higher replacement
levels to control expansion to below
0.040% at 2 years.

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EFFECT of SCMs to ASR

• The amount of SCM required to prevent damaging ASR expansion generally falls in
the ranges below (modified from Thomas and Folliard 2007).

Required levels
of SCM

• However, the level of SCM required may exceed these values under exceptional
conditions (e.g., extremely reactive aggregate, high alkali availability in concrete –
including alkali contribution from aggregates, concrete exposed to high
concentrations of alkali in service, critical structure with extended service life).
Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EFFECT of LITHIUM to ASR

• The ability of lithium to control deleterious
expansion due to alkali-silica reaction (ASR) in
mortar and concrete was first demonstrated by
McCoy and Caldwell (1951).
• LiCl, Li2CO3, LiF, Li2SiO3, LiNO3, and Li2SO4 were
the most promising and could virtually eliminate
the expansion when they were used at sufficient
levels of replacement. LiNO3 is considered to be
the most efficient form for suppressing ASR.
• It is somewhat paradoxical that lithium
compounds are effective suppressants of ASR as
lithium is an alkali metal like sodium and Photograph Showing Topical Application of
30%-LiNO3 Solution to Concrete Pavement
potassium. in Idaho

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EFFECT of LITHIUM to ASR

• The precise mechanism by which lithium controls ASR is not known, although many
theories have been put forward (Feng et al. 2005).
• The simplest and most commonly used explanation is that lithium salts will react
with reactive silica in a similar way to sodium and potassium salts, but the reaction
product is an insoluble lithium- silicate with little propensity to imbibe water and
swell. The lithium silicate forms around reactive aggregate particles and protects the
underlying reactive silica from “attack” by alkali hydroxides.
• The amount of lithium required to control expansion was a function of the
availability of other alkalis (Na + K) in the system, reactivity could be effectively
suppressed when the lithium-to-sodium-plus-potassium molar ratio was greater
than 0.74, i.e., [Li]/[Na+K] > 0.74.

Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

USE of COATINGS or SEALERS TO ASR

• Silicone-based products have been used most commonly as mitigation
measures for not only ASR, but also to help reduce the ingress of water
(to enhance frost resistance) and external chlorides (to reduce the rate of
corrosion of reinforcing steel).

Topical Application of 40%-Silane

Reduction in Cracking of Highway Barriers
Solution (solvent-based) to ASR-Affected
in Canada, after Application of Silane
Highway Barrier in Massachusetts
Thomas, M.D.A., Fournier, B., Folliard, K.J., Alkali-Aggregate Reactivity (AAR) Facts Book, U.S. Department of Transportation Federal Highway Administration, 2013.
 Alkali-aggregate reaction

EVALUATING AGGREGATES FOR POTENTIAL

ALKALI-AGGREGATE REACTIVITY
• There is no need to laboratory tests for AAR If satisfactory field
performance can be demonstrated
• However, the concrete examined should be at least 10 years old
• Otherwise, several tests can be conducted to determine AAR such as;
For ASR For ACR
• Petrographic examination (ASTM C295) • Rock cylinder method (ASTM C586)
• Mortar bar test (ASTM C227) • Chemical composition (CSA A23.2-26A)
• Quick chemical method (ASTM C289) • Concrete prism test (ASTM C1105)….
• Accelerated mortar bar test (ASTM C1260)
• Concrete prism test (ASTM C1293)

Damaged ASR test specimen

 Alkali-aggregate reaction

EVALUATING AGGREGATES FOR POTENTIAL

ALKALI-AGGREGATE REACTIVITY

Canadian general procedure

for evaluating aggregates
and determining risk of
AAR damage.

ACI 201.2R-08: Guide to Durable Concrete,

Reported by ACI Committee 201