Durability of concrete

 Introduction
 Physical causes of deterioration
 Chemical causes of deterioration
 Summary

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 Introduction

 Concrete is considered as a relatively durable material. However

ingredients limitations, design and construction practices, and
severe exposure conditions can cause concrete to deteriorate =>
aesthetic, functional, or structural problems
 Measure of success of a designed concrete structure => Time
needed before costly repairs
 Costly repairs could be avoided with good knowledge of
environmental conditions and good concrete proportioning that
would protect it from possible harmful effects => selection of
sound materials and production of high-quality concrete =>
increase in initial cost => might reduce life-cycle costs

2
 Introduction
 Early damage might have occurred within the concrete for many years
before visible signs are apparent => concrete becomes more
vulnerable to other types of degradation => exponential deterioration

Excellent
75% of service life
$1
CONDITION

40% quality loss

Very good spent
here...
Good

…may save up
Fair
40% quality loss to $10 here
Poor

AGE (years)
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 Introduction

 The cause of deterioration of concrete structures could be

divided into 2 categories: physical causes and chemical causes
 Physical causes of concrete deterioration are divided into 2 classes:
surface wear and cracking
 Chemical causes of concrete deterioration are divided into 3 classes: 1)
Hydrolysis (chemical decomposition process that uses water to split
chemical bonds of substances) of the cement paste components by soft
water; (2) Cation-exchange reactions between aggressive fluids and the
cement paste; and (3) Formation of expansive products from certain
chemical reaction

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Deterioration: physical causes

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 Physical causes – surface wear

 It is defined as a progressive loss of mass

from a concrete surface. Three physical
causes can lead to surface wear of concrete:
Abrasion, erosion, and cavitation
 Abrasion is dry attrition: wear of concrete pavement
or industrial concrete floor slabs by vehicular traffic

 Erosion: wear by abrasive action of fluids containing

solid particles in suspension: hydraulic structures:
canal lining, pipes
 Cavitation: Cavitation is a process in which the
pressure in the fluid decreases to a level below the
ambient pressure thus forming 'vacuumholes' in the
fluid. When the pressure increases (due to sudden
change in direction for example), these
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'vacuumholes' implode, and damage the concrete
 Physical causes – cracking
 Volume changes due to:
 Temperature and humidity gradient
 Thermal cracking: In general solids expand on heating and contract on
cooling. The associated strains depend on the coefficient of thermal
expansion and on the temperature drop or rise. In massive concrete
structures, considerable rise in temperature could be registered due to poor
dissipation of heat produced during the cement hydration. Cooling of the
concrete to the ambient temperature, would result in thermal shrinkage.
Thermal shrinkage strains, when restrained, induce tensile stresses. Since
concrete is weak in tension, cracks will develop
 Plastic shrinkage: this is the reduction of volume in freshly placed concrete.
A variety of causes contribute to plastic shrinkage including, bleeding or
sedimentation, absorption of water by subgrade or forms, and rapid water
loss by evaporation
 Drying shrinkage: it is caused by the removal of water from small capillary
pores and that adsorbed on the surface of the C-S-H from the HCP mainly by
exposing concrete to low relative humidity conditions. At 30% relative
humidity, most of the adsorbed water is lost 7
 Physical causes – cracking
 Volume changes due to:
 Crystallization pressure of salts in pores
 Crystallization of a salt solution can occur only when the concentration of the
solute exceeds the saturation concentration at a given temperature. The
pressure from the salts crystallizing into the concrete pores will result into
stresses that will cause the concrete to deteriorate
 Structural loading
 These are the cracks induced by any type of structural loading (live load,
dead load, impact load, cyclic load, etc.)
 Exposure to temperature extremes
 Fire: Concrete is incombustible and does not emit fumes on exposure to
high temperature. Concrete is able to retain sufficient strength for
reasonably long periods at temperatures of the order of 700 to 800°C.
Decomposition of concrete ingredients on heating and development of
internal stresses from the gaseous decomposition products are the main
deterioration mechanism in concrete due to fire 8
 Physical causes – cracking
 Exposure to temperature extremes
 Freeze/thaw
 It is the process by which water inside the concrete
voids expands from freezing temperatures, which
cause the concrete to crack and deteriorate.
Freeze/thaw damage can take several forms including
scaling, popout, and D-cracking. Scaling refer to the
flaking or peeling off of the finished concrete surface.
It occurs mainly in concrete slabs in the presence of
moisture and deicing chemicals. Popout refer to the
breaking out of porous types of aggregates (cherts,
sandstones, and limestones for example) from the
concrete surface due their freezing. D-cracking refers
to the cracks adjacent and parallel to the joints in
concrete slabs due to the repeated freezing and
thawing of aggregate particles
 The mechanisms of frost action on concrete are still
being researched, but the common reported
mechanisms are: Hydraulic pressure, Osmotic
pressure, and capillary effects 9
 Physical causes – cracking
 Exposure to temperature extremes
 Freeze/thaw
 Hydraulic pressure: When water freezes, its volume increases by 9%. This means that
if water is inside a concrete capillary void, the void has to dilate by 9% or to force the
amount of excess water out through the boundaries or some of both effects. During
this process hydraulic pressure is generated. To reduce these pressures, researchers
have shown that escape boundaries should be provided at 0.08 to 0.01 mm from the
capillary voids. This is the reason for using air entrainment in concrete mixes
 Osmotic pressure: Water in the capillary voids is not pure, it contains several soluble
substances such as alkalies, chlorides, calcium hydroxides. Solutions with different salt
concentration will freeze at different temperatures below the freezing point. The
existence of local salt concentration gradients between capillaries will induce osmotic
pressure
 Capillary effect: While water in large cavities turn into ice, water in small gel pores will
stay as liquid water in a supercooled state. It is reported that water in gel pores does
not freeze above -78°C. Therefore, migration of water from small pores to large
cavities will occur. The new supply of water in the capillary voids increases the volume
of ice, which causes internal pressure

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Chemical causes

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 Chemical causes – Hydrolysis of the HCP
components
 Soft water from rain or from melting of snow and ice tend to
hydrolyze or dissolve the calcium-containing products of the
hydrated cement paste, especially calcium hydroxide. Leaching of
calcium hydroxide for the HCP will induce reduction of strength of
concrete over time. Once the calcium hydroxide reaches the
concrete surface, it will interact with carbon dioxide (CO2) to form
precipitation of white crusts of calcium carbonate. This is known
as efflorescence

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 Chemical causes – Cation-exchange reactions
between aggressive fluids and the HCP
 Based on cation exchange, there are 3 types of deleterious
reactions that can occur between chemical solutions and the
components of the HCP
 Formation of soluble calcium salts: The cation-exchange reaction between
the acidic solutions and the constituents of the HCP give rise to soluble
salts of calcium. Hydrochloric, sulfuric, or nitric acids may be present in
effluents of the chemical industry. Acetic or lactic acids are found in many
food products. Carbonic acid is present in soft drinks.
 Formation of insoluble and nonexpansive calcium salts: Oxalic, tartaric,
humic, hydrofluoric, or phosphoric acids.
 Chemical attack by solutions containing magnesium salts: Bicarbonate of
magnesium is frequently found in groundwater, seawater, and some
industrial effluents. Magnesium ion attack is very detrimental to concrete
since it attacks the Calcium-silicate-hydrates (CSH) by replacing its calcium
ions with magnesium ions
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 Chemical causes – Formation of expansive
products
 Alkali-Silica reaction
 Alkali-Silica Reaction (ASR) in concrete refers to the chemical reaction
involving alkali ions (sodium and potassium), hydroxyl ions, and some
siliceous constituents. Three requirements must be met for the reaction to
occur: reactive forms of silica in the aggregate, sufficient alkalies, and
moisture. Almost all rocks contain some silica (with the exception of pure
limestones and dolomites). The more soluble the silica, the faster the
alkali-silica reaction occurs. The most harmful alkali-reactive rocks are
opaline cherts, chalcedomic cherts, quartzose cherts, siliceous limestone,
and siliceous dolomites

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 Chemical causes – Formation of expansive
products
 Alkali-Silica reaction
Reaction
1 Release of alkali ions from the cement during
hydration
2 Initial hydrolysis of siliceous fraction of the
aggregate in the highly alkaline pore solution
K(Na)OH+SiO2  K2O(Na2O)-SiO2-H2O
(amorphous alkali-silicate gel)
3 Swelling of alkali-silicate gel by imbibition of
water
4 Liquefaction of alkali-silicate gel by further
imbibition of water
Result
Increases the concentration of
hydroxide ions in the pore
solution
Destroys aggregate integrity
Causes localized swelling,
internal pressure, and cracking
Expulsion of liquid gel through
the cracks
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 Chemical causes – Formation of expansive
products

 Alkali-Silica reaction
 Step 1 is controlled by the alkali content of the cement
 Step 2 is probably rate determining and depends on the exact form of silica
in the rocks
 Step 3 is the critical reaction causing extensive damage to the concrete; the
gel goes from an amorphous solid to a semi-solid to a liquid state (step 4)
as water is taken into the structure.
 Step 4 does not further damage but provides a useful diagnostic symptom
 Steps 3 and 4 are sensitive to the presence of moisture and will not occur if
the concrete is kept dry
 Control of this reaction must be taken at step 1; either by avoiding reactive
aggregates or by keeping the alkali content of the cement low [less than
0.6% equivalent Na2O (Na2O+0.65K2O)]

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 Chemical causes – Formation of expansive
products

 Alkali-Carbonate reaction
 Alkali-carbonate reactivity describes several different reactions which may
take place between carbonate rock aggregate particles and the cement
paste of Portland cement concrete. The composition of the carbonate rock
involved determines which type of reaction occurs. The only form of ACR
known to be harmful to concrete is the "dedolomitization" reaction which
may take place between argillaceous (clay-rich) dolomitic limestone
aggregate particles and the high pH of the pore fluids in cement paste.
 In the first phase of dedolomitization, pore solutions with a high pH break
down dolomite to form calcite, brucite and carbonate ions:

CaMg(CO3)2 + 2 OH-  CaCO3 + Mg(OH)2 + CO32-

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 Chemical causes – Formation of expansive
products

 Alkali-Carbonate reaction
 Excess carbonates in solution react with lime to produce additional calcite
and regenerate the hydroxides that drive the first phase of the reaction
series:
CO32- + Ca(OH)2  CaCO3 + 2 OH-
 The net reaction will proceed until either dolomite or Portlandite is
exhausted:
CaMg(CO3)2 + Ca(OH)2  Mg(OH)2 + 2 CaCO3
 During dedolomitization, considerable expansion occurs locally, at the rims
and in the zones surrounding reactive aggregate particles, where calcite
and brucite are deposited. Because of this, ACR often leads to a loss of
bond between aggregate particles and cement paste

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 Chemical causes – Formation of expansive
products
 Sulfate attack
 Sulfates in soil or seawater (primarily sodium sulfate, magnesium sulfate,
and calcium sulfate) can react with calcium hydroxide and aluminates in the
cement gel to produce compounds that have volume greater than the initial
volume, which causes expansion and cracking in concrete

Chemical reaction Relevant factor in Control strategy

concrete
1 SO42- (external)  SO42- (internal) Permeability Low w/c, pozzolan
and/or slag addition
2 Ca(OH)2 + SO42-  CH2+ 2 OH- Ca(OH)2 content pozzolan and/or slag
addition
3 C4AH12+CH2  C6A3H32 C3A content of cement Type II or V cement

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 Chemical causes – Formation of expansive
products
 Corrosion of embedded steel in concrete
 Corrosion of reinforcing steel in concrete structures is known to be one of
the principle causes of their deterioration. Corrosion of steel is initiated
when the iron oxide film around the steel starts to disintegrate. This thin
layer usually makes steel passive to corrosion in a high alkaline
environment (pH>11.5)
 Two phenomena are known to destroy this passive layer; carbonation and
chloride ion intrusion.
 Concrete, with alkalies in its pore system and 20% by weight solid calcium hydroxide, has
an alkalinity above 12. However, when the alkalies and most of the calcium hydroxide are
carbonated (react with carbon dioxide, CO 2) or neutralized by acidic solutions, the pH of
concrete may drop to less than 11.5, which causes carbonation-induced corrosion.
 Chloride-induced corrosion, on the other hand, involves the diffusion of chloride ions
through the concrete pore water system to the vicinity of the steel. These ions take part
in an electrochemical process that produces rust (Fe 2O3). The transformation of metallic
iron to rust induces expansion stresses in concrete, which results in cracks and spalls

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 Chemical causes – Formation of expansive
products
 Corrosion of embedded steel in concrete
 The chloride ion reaches steel through cracks in concrete or through
diffusion in the concrete pore water. The passive steel layer will be
destroyed and therefore steel starts to corrode, when the threshold level,
ranging from 0.6 to 0.9kg acid-soluble chloride ion per cubic meter of
concrete, is reached
 In the anode (corroding site), several chemical reactions take place. The
first reaction involves a change of iron into iron ion:
Fe  Fe2+ + 2e-
 This iron ion complexes with the chloride ion to form iron chloride complex:
Fe2++2Cl-  FeCl2
 Iron chloride complex reacts with water and the hydroxyl ion to form iron
hydroxide:
FeCl2+H2O+OH-  Fe(OH)2+H++2Cl-

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 Chemical causes – Formation of expansive
products
 Corrosion of embedded steel in concrete
 Iron hydroxide reacts with oxygen ion to form rust and water:
4 Fe(OH)2+2 O-  2 Fe2O3 + 4 H2O
 Rust, being several times larger than iron, induces expansion stresses in
concrete that lead to cracks and spalls
 In the cathode (non-corroding site), hydroxyl ion is formed from the
reaction of oxygen, water, and the electrons released from the
transformation of iron into iron ion:
O2 + 2 H2O + 4e-  4 (OH)-
 This hydroxyl ion diffuses through the concrete pore water and reacts, as
described above, to form iron hydroxide.
 Chloride ion content, as noted in the above chemical reactions, greatly
affects the rate of corrosion

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 Chemical causes – Formation of expansive
products
 Corrosion of embedded steel in concrete

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 Summary
Description Cause Involved Symptoms
components
Surface wear Abrasion, erosion, HCP and Loss of mass
cavitation aggregates
Thermal cracking Internal stresses from HCP (aggregates) Localized cracking
and shrinkage restrained contractions
Physical causes

Crystallization of a Internal stresses due to salt HCP Localized cracking

salt solution crystallization
Structural loadings External applied loads Concrete Cracks
Frost attack Freezing of water in pores HCP Scaling and spalling at
surface
D-cracking-popout Freezing of water in pores Aggregate Fine crack pattern at joints-
loss of aggregate
Fire damage Decomposition of HCP HCP (aggregate) Cracking and spalling
products and development
of internal stresses
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 Summary
Description Cause Involved Symptoms
components
Alkali-Silica Reaction of siliceous Aggregate Coarse map-cracking with
aggregates by alkali ions viscous fluid erupting

Alkali-Carbonate "dedolomitization“ of Aggregate Loss of bond between

argillaceous dolomitic aggregate particles and
Chemical causes

limestone cement paste

Sulfate attack Reaction of paste
components with sulfates
Rebar corrosion Rusting of steel
Hydrolysis Dissolution and leaching of
CH
Acid attack Dissolution by acids
HCP General cracking and
softening
Reinforcement Cracks with rust stains
above location of
reinforcement-delaminated
areas
HCP white crusts of calcium
carbonate
HCP (aggregate) General etching of surface

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 Summary
 For concrete to be attacked rapidly, aggressive agents must be able to
enter the concrete easily because surface attack is slow. Thus the ease
with which water can flow into and through concrete (carrying with it
dissolved reactants) is of great importance. This is measured by the
permeability coefficient, Kp, determined by D’Arcy’s law:
dq h
 Kp A
dt x
 Where dq/dt is the rate of flow, Dh is the pressure head, x is the
thickness through which flow occurs (Dh/x is the pressure gradient),
and A is the area
 The use of low w/c ratios and provision for extended moist curing can
lower Kp drastically
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 Summary
 Aggressive agents can penetrate into the concrete by a diffusion-
controlled process. This could be diffusion of ions in solution or gases
which diffuse through vacant pores or through pore solution in
saturated pores
 The diffusion process can be described by Fick’s law:
dc dc
 D
dt dx
 Where dc/dt is the rate of diffusion, dc/dx is the diffusion gradient, and
D is the diffusion coefficient
 The use of low w/c ratios and provision for extended moist curing can
lower D drastically

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