Master ID-RIMS

Alexandra BERTRON

Master ID-RIMS

Durability of concrete:
standards,
deterioration phenomena,
and performances
Prof. Alexandra BERTRON
INSA Toulouse – Dép. Génie Civil
LMDC
[email protected]
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Context
Alexandra BERTRON

• Durability of concrete structure is a huge economic, societal and

environmental challenge:
 Economic & societal:
 Cost of repair itself
 Interruption of structure service, production tool, etc. during the repair work
 Potential injury and consequences to human health of structure failure
 Environmental (repair or rebuild):
 Use of natural resources
 Greenhouse gas emission
production of materials, repair work
 Energy consumption

Angst M&S 2018

• Designing cement-based materials and structures that perform well in
(naturally) aggressive environments, and extending their service-life
requires:
 Understanding deterioration and resistance mechanisms
 Quantifying deterioration kinetics
 Kinetics of concrete deterioration
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 Content
Alexandra BERTRON

• Introduction: Concrete structures in their environment: attacks and

pathologies
 Bridges (decks, pillars, abutments/supports/retaining walls)
 Soft water management structures (dams, canals, water towers, etc.)
 Marine structures and buildings in coastal zones
 Agricultural structures (silos, farm/breeding buildings, methane
digesters, etc.)
 Sewer systems (pipes, manholes, WWTP)
 Tunnels, etc.

• Standard environment
 Cement standardisation EN 197-1 & 197-5
 Classification of aggressive environments and recommendations in EN
206, FD P 18-011
 Principles
 Lacks

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Content
Alexandra BERTRON

• Reminders: cements, hydration, microstructure of cement paste and

reactive transfer.

• Exogenous and endogenous attacks: mechanisms, performance of

concrete
 Leaching: pure water, acids
 Carbonation
 Sulfates
 Natural waters: Sea water (sulfate, magnesium, carbonate), Soft water
(magnesium, carbonate)
 Biological attacks: sewage systems (biogenic acid), agricultural
environments, WWTP, biocolonisation
 Freeze-thaw and de-icing salts
 DEF and AAR

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 Alexandra BERTRON

CONCRETE STRUCTURES IN THEIR

ENVIRONMENT
 Bridges (decks, pillars, abutments)
 Soft water supply structures (dams, pipes, water tower)
 Marine structures
 Agricultural structures (silos, farm buildings, biogas plants, etc.)
 Sewer systems (pipes, WWTP)
 Tunnels, etc.

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Concrete structures in their environment

Alexandra BERTRON

• Physico-chemical attacks on concrete can reduce the service lifespan of structures

 Bridges

• Bridge decks, pier caps, and abutments

• Cantilever and segments De-icing salts
Chloride (corrosion) sea spray Vinci
CO2 (carbonation => corrosion)

• Pier cap/pillar
Humidity on massive
structures (DEF*)
Kentucky Transportation Center
Chloride + other ions
in sea water: Mg2+, SO42-, CO32-
CO2 Godart & Divet 2013

TSA**

*Delayed Ettringite Formation

** Thaumsite Sulfate Attack (with carbonates)

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 Concrete structures in their environment
Alexandra BERTRON

Buttresses
 Dams, soft water pipes

Thomas et al. 2017

Rosenqvist et al. 2017

• Walls, columns/pillars,
buttresses
Water (leaching)
Soft water (Mg2+, CO32-, etc.)
Freeze-thaw
ASR: alkali-silica reaction
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Concrete structures in their environment

Alexandra BERTRON
Alexandra BERTRON
Bertron
 Structures in coastal zones

Emerged zone:
• CO2 (carbonation, corrosion)
• Chloride by sea sprays (corrosion)
Submerged zone:
• Mg2+, sulfate, carbonate
Most intense deterioration in the tidal zone

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 Concrete structures in their environment
Alexandra BERTRON

 Agricultural/breeding/farm plants, silos, buildings

• Slatted floors: • Silos: organic acids, CO2
• Surface: organic acids
• Subface: H2S
Bertron

Bertron

• Biogas systems:
• Immersed: CO32-, NH4+, organic acids
• Gas phase: H2S, CO2
Koenig & Dhen

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Concrete structures in their environment

Alexandra BERTRON

 Wastewater networks Waste water treatment plants

• Organic acids
Sewer pipes, manholes • Ammonium (nitrification)
H2S => Sulfuric acid • CO2
“Biogenic acid attack” • H2S (gas phase)

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 Concrete structures in their environment
Alexandra BERTRON

 Tunnels (shotcrete)

Seepage groundwater flowing

from cracks in shotcrete
Karacic et al 2018
Chemical attack
• Magnesium
• Chloride Galan et al 2019
• Sulfate Sulfate, TSA Sintering (carbonate)
• Carbonate Oslofjord
Ettringite, TSA, leaching, corrosion, sintering of drainage systems subsea tunnel
(Norway)
Microbial activity (Fe, Mn, S-metabolizing microorganisms)
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Alexandra BERTRON

REMINDERS: CEMENT AND CEMENTITIOUS

MATRIX
 Anhydrous cement
 Main hydrates
 Microstructure of cementitious matrix
 Basics of reactive transfer

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 Cement manufacturing
Alexandra BERTRON

• Cement is a hydraulic binder, in the form of a fine mineral powder, which hydrates with water.
Cement is the fundamental component of concrete: it allows the transformation of a non-cohesive mix into a solid
body (setting, hardening)

• Manufacturing of cements:
 5 steps :
1. Extraction of raw materials. For clinker: CO2
 Limestone: CaCO3 (80 %)
 Clay: SiO2, Al2O3, Fe2O3 (20%) CaCO3 CaO
heat
2. Raw matter crushing fuel
3. Heating (in cement kiln, up to 1450°C)
4. Cement grinding
5. Addition of gypsum (setting regulator) Supplementary
and/or SCM and mixing (/ co-grinding) cementitious
materials (SCM)

cement kiln

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Supplementary cementitious materials (SCM)

Alexandra BERTRON

What?
Waste or co-product of other industries
- Blast furnace slag - Fly ash (siliceous, calcareous) Slag
- Silica fume - Burnt shale
- Pozzolana (natural, calcined) - Limestone

Why?
Cement manufacture:
• Lower CO2 emissions (less CaCO3 burnt for the binder, local
resources => less transport)
• Lower energy consumption
• Lower consumption of raw matter (in case of waste, co-product
of another industry)
In some cases, higher durability of cementitious materials
Reduction of global warming potential (GWP) of concrete
mixes with various degrees of clinker replacements with
respect to reference concrete produced from OPC
Angst CCR 2023
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 Composition of cements
Alexandra BERTRON

• Chemical composition of common cements:

 Binder = clinker + calcium sulfate + other possible compounds: slags, fly ashes, limestone
fillers, silica fume, etc.
 Cement chemistry = oxide chemistry
Cementitious notation: Lime (CaO) C
Typical clinker analysis (oxide weight%)

Silica (SiO2) S
Alumina (Al2O3) A
Ferrite (Fe2O3) F
Water (H2O) H

 Clinker is composed of 4 main anhydrous phases: Epoxy resin

Winter

Compound Formula Cement Mass

notation (%)
Tricalcium silicate or alite Ca3SiO5 C3S 50-70

Dicalcium silicate or belite Ca2SiO3 C2S 15-30

Tricalcium aluminate or celite Ca3Al2O6 C3A 5-10

Tetracalcium aluminoferrite or brownmillerite Ca4Al2Fe2O10 C4AF 5-15

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Hydration of cement
Alexandra BERTRON

• Hydration of cement:
 Reaction with water
 Complex reaction mechanisms occurring simultaneously at different speeds:
i. dissolution of anhydrous cement
ii. formation of supersaturated solution
iii. hydrate precipitation
 Hydrates precipitate on preferential germination sites (surface of anhydrous grains).
 Hydrates are little/in-soluble compounds. Their precipitation leads to setting and progressive hardening.
 Hydration is an exothermic process.

Bishop et al. 2003 Chem. Mat.

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 Main hydrates of the cement matrix
Alexandra BERTRON

Portland cement + water → Cx(Aw)SyHz + Ca(OH)2 + Ettringite + (CxAHy) + Fe-bearing phases

C-S-H or C-(A-)S-H
- 60 to 70% of hydrates Portlandite CH
- Strength - 20 to 25% of hydrates
- Porous structure - Basic: pH > 12 Ettringite
- Soluble: 1.2 g/l - needles
- not harmful

CxSyHz or (CaO)x(SiO2)y(H2O)z

Cx(Aw)SyHz or C-A-S-H for cement with Al-SCM 3CaO. Al2O3.3CaSO4.32H2O

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The microstructure of cement paste

Alexandra BERTRON
Anhydrous residual grain C-S-H
• Hydrated cement paste contains:
 Hydration products (hydrates)
 Residual anhydrous grains (there are always anhydrous grains left)
 Capillary pores partially filled with water (depending on humidity)
 Air voids.

Ca(OH)2 Capillary
• The microstructure of cement paste results from the granular nature of cement.
The formation of hydrates around the anhydrous grains progressively fills intergranular space  capillary porosity

• Porosity comprises: Hg porosimetry

 Capillary porosity Hydrates’ pores

 Hydrates’ porosity Capillary pores

• Capillary porosity is involved in durability properties:

 Volume => resistance and durability
 Connectivity => durability Pore diameter (nm)
 Size (diameter) => durability

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 Reactive transfer in cementitious materials
Alexandra BERTRON

• The durability of cementitious materials, which are porous and reactive materials, exposed to aggressive
agents is related to reactive transfer:
 Transfer of chemical species inside the matrix (through porous network)
 Reactivity of cementitious phases with the chemical agents

• Mass transfer phenomena:

In saturated conditions, 2 main transfer phenomena within the porous network of cementitious materials: diffusion &
permeation
 Diffusion: mass transfer driven by concentration gradients
 Molecular diffusion: 1st and 2nd Fick’s laws in 1D system
 Ion diffusion: Nernst-Planck relation)
 Permeation: mass transfer of a gas, a liquid or vapour, driven by pressure gradient through a solid (Darcy law)
• Kinetics of diffusion and permeation depends on:
 the porous network characteristics (tortuosity)
 the moving species itself
 The environmental conditions (temperature, pressure)

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Reactive transfer in cementitious materials

Alexandra BERTRON

• Chemical stability of hydrates

Depends on phase’s solubility and on chemical conditions (pH, alkaline concentration, temperature,
etc.).
Reaction of dissolution and precipitation of phases have their own kinetics.

 Example of stability data of some hydrates

pH of
Hydrates pK = -log(Keq)
dissolution
Portlandite 5.2 12.5

pK = 5.84(C/S) + 2.02 [FUJ 81]

C-S-H pK = 14.75(C/S) + 0.083 [GLA 87] ∼ 10.5 – 8.8
C/S: C-S-H molar ratio

Ettringite 43.9 10.6

Thermodynamic data for C-A-S-H not well known

(but C-A-S-H are more stable than C-S-H when pH )

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 Alexandra BERTRON

STANDARDS
 Ordinary cement composition: EN 197-1 & 197-5
 Classification of aggressive environments and recommendations on concrete design EN 206, FD
P 18-011 & other documents

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Standard environment of concrete

Alexandra BERTRON

 European/French standard for cements: 197-1 & 197-5

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 Common cements as defined by EN 197-1 & 197-5
Alexandra BERTRON
 27 + 5 common cements according to EN 197-1 & 197-5
Common cement = clinker + SCM + minor additional constituent (sulfate – setting regulator)
EN 197-1
EN 197-5

Portland-
composite
cements

Composite cements

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Common cements: EN 197-1

Alexandra BERTRON
Alexandra BERTRON

 Principle of standardised designation

EN 197-1

SR

Type of
common
cement

Composition classes

Nature of SCM

28 day strength class

Short term strength

CE marking

Additional patterns SR 0: C3A = 0 %

Complies with french standard CEM I SR 3: C3A ≤ 3 %
SR 5: C3A ≤ 5 %

CP: limited content of sulfides (for CEM III-SR: no requirement on C3A content
prestressed concrete)
CEM IV-SR: C3A of the clinker ≤ 9 %

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 Concrete environment: Exposure classes according to NF
EN 206 / FD P 18-011
Alexandra BERTRON

No risk - X0 Cl sea water- XS

Carbonation - XC
Freeze thaw+salt- XF

Chloride - XD

Chemical attack - XA

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Exposure classes NF EN 206 and FD P 18-011

Alexandra BERTRON

• Map of freezing and salting in France

Freeze-thaw + salts - XF
Freezing zones Salting zones

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 Standards vs. aggressive environments to concrete
Alexandra BERTRON
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Standards: lacks in XA class definition

 pH is the main classification parameter for acidic media.

No mention of the acids’ nature, no mention of organic acids.
The acids’ aggressiveness depends on their properties and EN 206
those of their salts.
Bertron M&S 2014, Bertron and Duchesne 2013

 Concentration limits of some aggressive chemicals are very

different from one standard to another, and sometimes are not
suitable (NH4+, Mg, etc.) and/or not experience-based (H2S)
Giroudon et al. M&S 2021, Rosenqvist et al. CCR 2017

 Effect of biofilm not considered/mentioned

Bertron M&S 2014, Voegel et al. 2021, Giroudon et al. JEM 2021
FD P 18-011
 Relation between the environmental conditions and the
aggressiveness?

More research is needed!

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Exposure classes NF EN 206 and FD P 18-011

Alexandra BERTRON

• FD P 18-011

Chemical attacks - XA

Latest revision: June 2022

Some limitations…

And some lacks /

missing criteria:
Organic acids,
microbial activity,
T°C…
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 Exposure classes NF EN 206 and FD 18-011
Alexandra BERTRON

• Chemical attacks: cement selection as a function of the exposure class

FD P 18-011

Renovation in progress

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Recommendations on concrete composition and properties

Alexandra BERTRON

• NF EN 206/CN

Please note the table’s foot-notes – see EN 206

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 Exposure classes: other documents
Alexandra BERTRON

• Documents to assist in the selection of exposure classes

Guide LCPC-EFB

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Exposure classes: other documents

Alexandra BERTRON

• Documents to assist in the selection of exposure classes

Guide LCPC-EFB

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 Alexandra BERTRON

OVERVIEW OF CONCRETE ATTACK

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Concrete in its environment(s)

Alexandra BERTRON

• Concrete material is:

 multi-phasic (solid, liquid, gas phases)
 porous
 highly alkaline and reactive
 composite (cement paste & aggregates)

• In its environment, mostly neutral or acid, it undergoes chemical and/or physical attacks with more or less
deleterious impact:
 on mechanical, physical and chemical properties of the material / structure,
 which in turn may impact the aesthetic & safety of structures, health of occupants, and/or induce economic and
environmental issues

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 Overview of attacks on concrete
Alexandra BERTRON

Exogenous attacks Endogenous attacks

• Chemical and/or physical actions: • Chemical and physical actions:
 Carbonation  Delayed ettringite formation (DEF)
 Leaching (dams, potable water pipes,  Alkali-aggregate reaction (AAR)
river structures, etc.)  Pyrite aggregates attack
 Acid attack (organic and mineral acids):  Thaumasite sulfate attack (in some
agricultural environments, acid rains, cases)
sewers
 External sulfate attack: soils, sewers
 Attacks by saline solutions: magnesium
(sea, natural water), ammonium
 Biological attacks (sewer, agriculture,
etc.)
 Freeze-thaw and/or de-icing salts

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General mechanisms of chemical attack

Alexandra BERTRON

• Mechanisms of concrete alteration when exposed to chemical environments:

 Reactive transfer: combination of
 Mass transfer (diffusion/permeation) through porous network of aggressive species and/or cementitious cations,
 Chemical reactions:
 dissolution of cementitious phases driven by different mechanisms as a function of the aggressive species
 precipitation (or not) of secondary phases (which may then transform again). The precipitation of these phases depends on:
their intrinsic stability (solubility products)
the local chemical conditions (pH, concentration of chemical species)
 In turn:
 Dissolution of cementitious phases creates porosity, lower mechanical strength
 Precipitation of secondary phases, if so, may create:
 either partial clogging of the porosity (e.g. calcite, calcium oxalate)
 or additional voids/cracks in case of expansive phases (e.g. ettringite)
 changes transfer properties

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 General mechanisms of chemical attack
Alexandra BERTRON

Ettringite M-S-H
Porous Aqueous
material medium K+ Mg2+
SO42-
Mg2+ Al3+ 2+
Ca Ca2+

Si4+
Ca2+ NH4+ Ca2+
NH4+ Calcite HCO3- Ca2+

HCO3-
Ca2+
SO42- Na+

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Prominent role of water

Alexandra BERTRON

Water is essential to chemical attack, since:

 it acts as a solvent for aggressive agents, and participates in the chemical reactions (e.g.
hydrolysis)
 it helps to transport the aggressive agents, the cementitious ions, and their reaction products.

Depending on the case, most favourable conditions to the attack occur:

 Either in fully immersed or 100% RH conditions (most aggressive aqueous environments) – e.g.:
DEF
 Or on certain RH ranges: e.g. for carbonation, the 50-70% RH range
 Or in cyclic wetting-drying (especially for exogenous attacks with expansive salts, such as sulfate
attack)

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 General mechanisms of chemical attack
Alexandra BERTRON

 Strong gradient of composition between the environment and the cementitious material.
 Progressive alteration of the cementitious matrix with creation of chemical and
mineralogical zonation within the matrix
Case of pure water attack
Pâte de ciment CEM I lixiviée
Alteration (dissolution) fronts eau pure 114 jours 72°C

Aggressive Decalcified Decalcified Decalcified

medium C-S-H C-S-H C-S-H
(pure
water)

Degraded material Sound material Kamali et al. 2008

From Adenot 1992, 1996

 Kinetics of alteration front progress is generally governed by mass transfer kinetics since:
Kinetics of mass transfer
<<
Kinetics of chemical reactions
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General mechanisms of chemical attack

Alexandra BERTRON

• Overview of mechanisms and impact

Regourd et al. 1981

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 Parameters influencing the attack aggressiveness
Alexandra BERTRON

• Material’s related parameters

Chemical and mineralogical composition of the cementitious matrix
Porous network characteristics
Aggregate mineralogical nature

• Environmental parameters:
The aggressive agent:
 Its chemical nature, its concentration and the way the structure is exposed to it
 directly conditions the alteration mechanisms
 Its physical nature: gas, liquid or solid (an indispensable step is the solubilisation of the aggressive species)
Hygrothermal conditions and their possible cyclic evolutions:
 Humidity (optimal conditions depend on the pathology); wetting-drying cycles
favours salt precipitation and thus damage
 Temperature, weather conditions
Mobility of the aggressive species or medium
Combination of chemical attack and other stresses: mechanical, thermal…
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Alexandra BERTRON

EXOGENOUS ATTACKS
 Leaching by pure water and acids
 Carbonation
 Sulfate attack
 Natural waters: soft water, seawater, underground water attack (magnesium, sulfate, etc.)
 Biodeterioration & biocolonisation
 Freeze-thaw and de-icing salts

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 Alexandra BERTRON

EXOGENOUS ATTACKS
 Leaching by pure water and acids
 Carbonation
 Sulfate attack
 Natural waters: soft water, seawater, underground water attack (magnesium, sulfate, etc.)
 Biodeterioration and biocolonisation
 Freeze-thaw and de-icing salts

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Leaching of concrete: inventory of situations

Alexandra BERTRON

• Types of structure exposed to leaching: dams, pipes & conduits, waste water treatment plants, external concrete
walls, agricultural structures (silage silos, etc.), fertilizer production plants, etc.

Acids

Urban activities Industrial processes Natural occurences

Acid rains Chemical Agro-industry

Soils Waters
Gaseous pollution industries… Sewage systems

Strong: HNO3, HCl, H2SO4… Weak: acetic, oxalic…

Leeman et al. CCR 2010, Sand et al. IBB 1997, Williams et al. 1997…
Water

On-site Laboratory
Natural (glacier, rain water, lakes, rivers) and Leaching by pure water: long-term behaviour
drinking or waste waters in nuclear waste repository, dams…

NH4NO3 Kinetics acceleration: in replacement of pure water Carde et al. CCR 1997, Bernard et al. CMS
2008, Schneider et al. 1998, 2005…
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 Mechanisms of cementitious materials’ leaching
Alexandra BERTRON

• Pure water, pH 7

Two phenomena:
 Diffusion of ion species (Ca2+, OH-, K+, Na+,
Mg2+, Al3+, etc.) because of concentration
gradients between the highly alkaline
interstitial solution and the external neutral,
demineralized or so, medium

 Dissolution of the Ca-bearing cementitious

phases by hydrolysis to maintain local
equilibrium

Concrete pipe for potable water supply

Berthomier 2019

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Mechanisms of cementitious materials’ leaching

Alexandra BERTRON

• Pure water, pH 7

 Chemical and mineralogical zonation of the matrix

From the inward to the outward: Dissolution fronts From Adenot 1992, 1996

i. Ca(OH)2 - less stable hydrate

of the matrix, is dissolved first Aggressive
medium
ii. Then, C-S-H are progressively decalcified (pure
Decalcified Decalcified
C-S-H C-S-H
Decalcified
C-S-H
water)
iii. AFm and Aft dissolve successively
iv. Outer layer:
At pH 7: hydrogarnet, hydrotalcite, Fe & Al-substituted C-S-H Degraded material Sound material

At lower pH: silica gel containing Al and Fe

Pavlik CCR 1994, Faucon et al. CCR1996

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 Mechanisms of cementitious materials’ leaching
Alexandra BERTRON

• Leaching process controlled by:

• the thickness
• the diffusion resistance of the degraded layer

• Fick's law  degraded thickness d= a*t1/2 (Carde et al. 1996)

.

Linear relationship between weight loss and added acid as a Berthomier 2017, CEM III paste
function of the square root of time for cement-based material pH 7
subjected to leaching (Adenot and Buil 1992)

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Alexandra BERTRON
Pure water ↘ mass and alkalinity
Le Bellego et al. JEM 2002
Leaching by Strong acids ↗ porosity and permeability Sellier et al. NED 2011
NH4NO3 ↘ strength and rigidity, ↗ creep…

Leaching of Ca(OH)2 ↑porosity > 0.2 µm

Creates more porosity than C-S-H
Leaching of C-S-H ↑porosity < 0.2 µm
Haga et al. CCR 2005

Mostly responsible for the

loss of strength Porosity due to leaching of hydrates
Carde et al. 1999

Young’s Modulus can decrease

by more than 80 %
CH C-S-H
Gérard 1996
Stora et al. CCR 2009 - Multi-scale
homogenization approach
Jain et al. CCC 2005
- volume fractions of CH and C–S–H leached
determined indirectly from thermal analysis
- measured increase in porosity 48 48
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 Mechanisms of cementitious materials’ leaching
Alexandra BERTRON

• Classification of the attack:

 Leaching matches A and BI pathways

 Consequences are: loss of alkalinity, loss of mass, loss of strength of the matrix

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Mechanisms of cementitious materials’ leaching

Alexandra BERTRON

• How to improve the resistance of cementitious matrices to leaching

(pH 7 or slightly acidic): 26°C

 Acting on the composition:

 Chemical: reducing Ca content, increasing Al and Si amounts
 Mineralogical: reducing Ca(OH)2 content, lowering C/S in C-S-H, favouring C-A-S-H
(higher chemical stability than C-S-H)
 Latent hydraulic additions (LHA) such as slags
=> produce more stable C-A-S-H
=> stable residual anhydrous grains 85°C

 Pozzolanic additions: fly ashes, silica fume, metakaolin (similar consequences

as LHA)
 Slag- and MK-based geopolymers

 Acting on the porous network:

 Reducing total porosity, reducing average porosity size, Increasing tortuosity of Kamali et al. CCR 2008
porous network thanks to SCM

CEM III, CEM V, CEM II with pozzolanic additions are recommended

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 Degradation by acids
Alexandra BERTRON

• Attack by mineral and organic acids:

• Reactions: general case

Other secondary
Acid + Cementitious phase Salt + phase(s)

HNO3 Ca(OH)2 Ca(NO3)2.4H2O

HCl CaCl2.6H2O Silica gel
+ (CaO)x.(SiO2)y.(H2O)z +
H2SO4 CaSO4.2H2O Al-Si Gel
CH3COOH (CaO)x.(Al2O3)z.(SiO2)y (H2O)w Ca(CH3COO).2H2O
… … Very porous,
low
Dissolution Precipitation mechanical
or not… strength
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Degradation by acids
Alexandra BERTRON

• Very different mechanisms and kinetics for acids with highly vs. slightly soluble Ca-salts

Acid Ca-salt Solubility in water (g/L) (0°C)

Nitric Ca(NO3)2.4H2O 2660
Hydrochloric CaCl2.6H2O 2790 Highly soluble Ca-salts

Acetic Ca(CH3COO).2H2O 400

Sulfuric CaSO4.2H2O 1.75 Slightly soluble Ca-salt

 Sulfuric acid: produces gypsum (precipitates at the surface) and ettringite (in the inner zones) which
creates cracks

• Deterioration kinetics for different acids

Pavlik, CCR 1994

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 Degradation by acids
Alexandra BERTRON

• Degradation by strong acids and organic acids with soluble calcium salts:
HNO3, HCl, acetic acid and other volatile fatty acids
Deterioration mechanisms are similar to those by pure water, with more rapid kinetics,
and more drastic decalcification of the cementitious matrix in the outer layer

Aggressive
medium Decalcified Decalcified Decalcified
C-S-H C-S-H C-S-H
Pure water

pH 7
Degraded material Sound material
From Adenot 1992, 1996

Aggressive
2 3
medium:
Decalcified1Decalcified Decalcified
Decalcified
Acid with C-S-HSi-Al gelC-S-H C-S-H
C-S-H
soluble Ca-
salts

pH < 7
Degraded material Sound material
Adapted from Bertron et al. 2004, 2005, 2007
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Degradation by acids
Alexandra BERTRON
• Degradation by strong acids and organic acids with soluble calcium salts: Agricultural environments
HNO3, HCl, acetic acid and other volatile fatty acids

Effect of the pH
Z. 2
Zone 1
Zone 3

CEM I pastes exposed to pH 4

and pH 6 acetic acid solutions

pH 4 pH 6

Adapted from Bertron et al. 2004, 2005, 2007

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 Attack of organic acids
Alexandra BERTRON
• Degradation by organic acids with little soluble calcium salts: Agricultural environments
Volatile fatty acids
12 Citric pH 4
More aggressive

Degraded layer depths (mm)

11
10
9 Succinic
Immersion 8
of CEM I pastes 7
Acetic  Reference acid
6
in organic acids 5
4
[acid] = 0.28 M 3 Malic
2
1
Tartaric
0 Oxalic Less aggressive
0 50 100 150 200 250 300 350
(pH 0.85)
Time (days)
pH: not enough to
characterize the
aggressiveness of
an acid solution

Properties of Ca-
salts of the acids
are crucial (molar
Bertron & Duchesne 2013
Larreur-Cayol et al. CCR 2011
volume, solubility…)

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Attack by organic acids

Alexandra BERTRON

• Degradation by organic acids with little soluble calcium salts:

Volatile fatty acids

Bertron M&S 2014

Diagram of parameters influencing the
aggressiveness of organic acids on the cement
matrix

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 Leaching tests for concrete
Alexandra BERTRON

• Pure water & strong acids: => Standardisation in progress (GEF 8,

 Semi-dynamic leaching test with constant pH Perfdub)

pH probe

Demineralized
pH, T°C, water
added acid
HNO3 0.25 M pH volume
regulator Ca(OH)2
indicator

 Concrete specimens: diam 8 cm, height 3 cm

 pH = 5.5 or 5.0 ± 0.1 for class XA1, pH = 4.5 ± 0.1 for class XA2, pH = 4.0 ± 0.1 for class XA3
Ammonium Pure water
nitrate
 Criteria for concrete durability assessment: Accelerating factor =
between 30 and 300
 Ca leaching
Leaching under saturated conditions
 (Acid consumption)
(Perlot 2005; Perlot et al. MCR 2007)
 (Degraded layer depth: phenolphtalein)

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Alexandra BERTRON

EXOGENOUS ATTACKS
 Leaching by pure water and acids
 Carbonation
 Sulfate attack
 Natural waters: soft water, seawater, underground water attack (magnesium, sulfate, etc.)
 Biodeterioration & biocolonisation
 Freeze-thaw & de-icing salts

01/10/2024 58
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 Preamble
Alexandra BERTRON

• Carbonation is the natural reaction of CO2 in air with the Ca-bearing phases in the cementitious
matrix
formation of calcium carbonate within the cementitious matrix
intrinsically a rather favourable phenomenon: it clogs the porosity and reduces the permeability of
concrete.

• Nevertheless, carbonation reduces the pH of the matrix from 12 to

13.5 to values < 9
 Steel is no longer passivated at such pH
• In the case of thin or porous cover concrete, corrosion can initiate
quite rapidly
• Carbonation is one of the two main factors of steel corrosion in
concrete, with chloride penetration

Angst et al. RTL 2020

Master ID-RIMS Unauthorized reproduction prohibited

General mechanism of concrete carbonation

Alexandra BERTRON
• Schematic diagram of carbonation reactions
Solid
phase

Gas
phase
Pore of
concrete

Liquid
phase

Solid
After (Thiery, 2006)
phase C-S-H

Calcite Aragonite Vaterite Amorphous carbonate

Master ID-RIMS Unauthorized reproduction prohibited
 Consequence of carbonation on concrete microstructure and properties
Alexandra BERTRON

• Volume and size of porosity of carbonated concrete < those of sound concrete
 Molar volume of products (calcite and carbonated C-S-H) > molar volumes of reactants (Ca(OH)2 and C-
S-H)
Calcite occupies a part of initial capillary porosity
 Distribution of porosity size: significant 
of main pore mode in the range 30-60 nm

• Mechanical strength and Young’s modulus of OPC concretes increase after carbonation
Carbonation is not in itself harmful to OPC based concretes

! For slag-based concretes, mechanical strengths decrease (increase of porosity) !

Manns & Wesche 1968, Smolczyk 1968, Matsusato ICCC 1992, Xiao et al CBM 2002

De Ceukelaire et al. 1993, Castellote et al CCR 2008, Bier et al. 1987, ACI special pub. 1989, Puertas et al JMS 2006
Pihlajavaara M&S 1968, CCC 1974, Patel et al M&S 1988, Papadakis et al ACI Mat J 1991, Morandeau et al 2014
Master ID-RIMS Unauthorized reproduction prohibited

Measurement of carbonation depth

Alexandra BERTRON

•  of concrete pH to values < 9 can  corrosion of steel (no longer passivated, see Pourbaix Diagram)
• Phenolphthalein*/Tymolphtalein indicator (transparent) turns to violet/blue when pH > 9.5
• Very simple and suitable test to detect carbonation
*carcinogenic compound
• But be careful, violet coloured zones do not mean sound zones To be used in a hood or with a mask

Ordinary concrete
Ca(OH)2 is
dissolved

UHPC
Rozière 2007
Kashino 1984

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 Influence of relative humidity on carbonation
Alexandra BERTRON

• Kinetics of carbonation front progression depends on:

 Relative humidity of the environment: determines the concrete water content
 When RH , the fraction of pores filled with water , which disturbs CO2 diffusion.
CO2 diffusion coefficient in water is 10-4 lower than in air (10-12 m2.s-1 vs. 10-8 m2.s-1)
 At the same time, low RH slows down CO2 dissolution, and thus, carbonation process
Carbonation kinetics is maximal when RH is between 40 and 80% (Wierig 1984, Van Balen 1994). Optimal RH is around 65%
(common value in tempered climates)

W/C=0.8
Depth of carbonation (mm)

W/C=0.6
Influence of RH on carbonation depth
(20°C, 16 year-old concrete)
Wierig, RILEM, 1984

Relative humidity (%)

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Influence of concrete composition

Alexandra BERTRON

• Porosity and mineralogical nature of the cement matrix greatly influence the sensitivity to
carbonation
 W/C  Cement content

5 yrs in air 20°C, 50% RH

Schiessl 1976

Venuat & Alexandre 1968

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 Influence of concrete composition
Alexandra BERTRON

 SCM:
 Higher sensitivity to carbonation of cementitious materials with SCM, slag and FA, notably (compared to OPC)
 Carbonation kinetics  with % of slag
Carbonation depth of 50%OPC/50 % slag
≈ 1.5*100%OPC
(but mechanical strengths are lower, discrepancy can be lower when considering similar mechanical strength
concretes)
 Curing conditions greatly impact the performances (especially for SF, for example)

De Ceukelaire et al. 1993, Castellote et al CCR 2008,

Bier et al. 1987, ACI special pub. 1989, Puertas et al
JMS 2006, Litvan & Meyer 1986, , Paillere et al 1986

Effect of clinker replacement on the resistance against carbonation

Angst CCR 2023 (compilation of many research works, see ref.)

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Influence of concrete casting condition: curing

Alexandra BERTRON

• Decreasing curing time  increase of porosity of cover concrete  increase of carbonation kinetics

24h in mould
Meyer 1968

27 days in water
OPC with 70% slag

OPC (12% C3A)

Baron 1987

CEM I concretes, 6 yrs in air after initial Concretes kept 1 yr in air after initial
curing period curing period

Master ID-RIMS Unauthorized reproduction prohibited 66

 Alexandra BERTRON

EXOGENOUS ATTACKS
 Leaching by pure water and acids
 Carbonation
 Sulfate attack
 Natural waters: soft water, seawater, underground water attack (magnesium, sulfate, etc.)
 Biodeterioration & biocolonisation
 Freeze-thaw & de-icing salts

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Introduction
Alexandra BERTRON

• Sulfates can occur from:

 endogenous sources: the cement itself, the aggregates,
 exogenous sources: soils, natural waters, gas, etc.
This chapter will focus on exogenous sulfate attack (but exogenous sulfate concentration adds to
endogenous one)

• Sulfate attack on concrete involve complex physico-chemical phenomena, and

depends on many parameters:
 type of sulfate salts – i.e. nature of cation
 type of cement
 moisture conditions (wet-dry cycles or permanently humid/dry conditions)
 pH of the solution in contact with concrete,
 etc.

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 Introduction
Alexandra BERTRON

• Limited number of real cases, but sulfate attack induces severe consequences on concrete (cracks, spalling,
increase of permeability, loss of strength)

• Sulfate attack has been subject of research for long time

Pending issues:
 Coupling of sulfate attack with other chemical attacks,
 Behaviour of SCM-bearing concretes,
 Crystallisation of salts, etc.

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Origin of sulfates
Alexandra BERTRON

• Endogenous sulfates:
 Setting regulator: calcium sulfate (gypsum, anhydrite, semi-hydrate, etc.)
 Sulfate in clinker (EN 206/NA: the amount of SO3 is limited to 3.5% for SR0 and SR3 and 2.5% for SR5%, +
condition on (C4AF + C3A))
 Aggregates containing natural or artificial sulfates (gypsum, anhydrite, pyrites), the content of sulfate in
aggregates is also limited by standard NF XP P18-545

• Exogenous sulfates (1/2):

 Soils:
 sulfates are nutritive components of plants (average concentration: 0.01 to 0.05% of dry soil)
 In gypseous soils, concentrations can be > 5% placoplatre.fr
(e.g. Paris basin)
 Fertilizers (ammonium sulfate SO4(NH4)2 is very aggressive)
 Iron sulfide (pyrites) can be found in soils
When oxidized, sulfuric acid is formed, and then,
gypsum via reaction with CaCO3

Gypsum carrier (France, 93) – 500000 T/yr

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 Origin of sulfates
Alexandra BERTRON

• Exogenous sulfates (2/2):

 Seepage water: they can be enriched in sulfate when coming into contact with sulfates-bearing soils and
backfill (remblai) (polluted soils in industrial environments)
 Gas: in industrial and urban environments, air can contain sulfur dioxide SO2, from combustion gases, which
can oxidize into H2SO4 (stains on façades, gypsum formation on the surface fixing dusts in suspension in air)
 Sewage network: H2S formed from sulfate reduction in the sediment layer. H2S volatilizes and condensates at
the concrete surface. It is then oxidized into H2SO4 by bacteria (see dedicated chapter)

A. Goyns
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General mechanisms of sulfate attack

Alexandra BERTRON

• Two main phenomena are involved (1/2):

1. Leaching of calcium from Ca-bearing phases of the cementitious matrix (CH and C-S-H)
and formation of gypsum (when [Ca2+][SO42-] in solution reaches the gypsum solubility)

Reactions in the case of sodium sulfate Na2SO4:

Portlandite Gypsum
Gypsum
 2 2 4 2 2 → . 2

C-S-H
 3 .2 2.3 2 2 4 9 2 →3 .
6 2 2.3 2
Silica gel Gollop & Taylor CCR 1992
CEM I paste exposed to Na2SO4 sol. 0.25 mM

 increase of porosity  increase of permeability and diffusivity

 increase of aggressive species transfer kinetics

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 General mechanisms of sulfate attack
Alexandra BERTRON

• Two main phenomena are involved (2/2):

2. Formation of ettringite from the reaction of gypsum with calcium aluminate of the
binder (anhydrous phases: C3A and C4AF, Ettringite

hydrates: C4AH13, calcium monosulfoaluminate: 3CaO.Al2O3.CaSO4.12H2O)

Gypsum
 3 . 2 3 3 4.2 2 26 2 →
3 . !" #. # .#
Ettringite
Brown et al. CCR 2004
CEM I+45%S paste exposed to Na2SO4 sol.
 3 . 2 3. 4.12 2 2 4.2 2 16 2 →3 . !" #. # .#

 Cracks due to crystallization pressures  loss of strength and stiffness, increase of

permeability and diffusivity  increase of aggressive species transfer kinetics

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Ettringite formation in concrete

Alexandra BERTRON

• Microstructure of ettringite
Menendez et al. 2013

Stark and Bollman 1999

• Ettringite can be either expansive or non-expansive. Even in big quantity in the cement matrix,
the precipitation of ettringite is not necessarily harmful to concrete

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 Ettringite formation in concrete
Alexandra BERTRON

• Different types of ettringite (classification by AFGC-RGCU GranDuBé 2007):

 Primary ettringite: normal product of cement hydration due to the reaction of C3A with the setting regulator
(gypsum, anhydrite, semi-hydrate) and sulfate in clinker. In some cements (supersulfated cements), ettringite
is responsible for hardening
 Not harmful.
 Secondary ettringite likely to induce swelling, in relation with external sulfate attack for non sulfate resisting
cements
 Harmful
 Secondary ettringite that does not cause expansion.
It results from dissolution/precipitation phenomena because of water percolation in concrete (without
exogenous sulfate ingress)
It is also found in some concrete with high amounts of sulfates such as CEM III concretes (no Ca(OH)2)
 Not harmful
 Delayed ettringite, that may cause expansion or not, following early heating of concrete (internal sulfate
attack)
 Harmful, in general

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External sulfate attack as a function of the associated cation

Alexandra BERTRON

• External sulfate attack aggressiveness greatly varies as a function of the cation nature

5 main cases:
Calcium sulfate
Alkaline (Na and K) sulfate
Magnesium sulfate (see section on sea water attack)
Ammonium sulfate
Sulfuric acid

And the case of thaumasite (TSA)

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 External sulfate attack as a function of the associated cation
Alexandra BERTRON

• Calcium sulfate CaSO4: Gypsum soils

 Found in soils (gypsum and anhydrite), and in groundwater.
These salts are aggressive despite their relatively low solubility in water.
Kinetics of attack lower than that of other sulfate salts.

 Phenomena and consequences:

 Secondary precipitation of monosulfoaluminate and then expansive ettringite.

 Initial increase of mechanical strength

through filling of pores by ettringite

 Continuing production of ettringite

generates pressures and microcracking
with expansion
  of mechanical strength
  of permeability

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External sulfate attack as a function of the associated cation

Alexandra BERTRON

• Sodium and potassium sulfate Na2SO4, K2SO4: Lab tests

 These salts are highly soluble. Their kinetics of attack is high.
Na+ and K+ have moderate specific interaction with the matrix (no/low secondary
precipitation) => Na2SO4 is generally recommended for non-acid external sulfate attack
testing
 Phenomena: see slides 72-73

Soils (fertilizers)
• Ammonium sulfate (NH4)2SO4:
 Found in soils (chemical product used as soil fertilizer/treatment)
 Strong attack of cementitious materials
 Phenomenology: combination of ammonium and sulfate attack:
 Ammonium attack leads to strong leaching of the matrix: see slide 51.
 Sulfate attack translates into the formation of gypsum (from the reaction with Ca released
by ammonium attack)

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 External sulfate attack as a function of the associated cation
Alexandra BERTRON

• Sulfuric acid H2SO4 (1/3): Pyrite aggregates

Sulfuric acid can arise in a variety of contexts:
 Industrial wastewaters
 Sewage networks (from the activity of specific microorganisms – see Biodeterioration section)
 Ground waters:
Oxidation of sulfides , especially pyrite, present in soils or concrete aggregates unstable in the presence of O2
and H2O

Pyrite Ferrous sulfate Sulfuric acid

or pyrrhotite Iron (II) sulfate
or

Ferric sulfate
Iron (III) sulfate

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External sulfate attack as a function of the associated cation

Alexandra BERTRON

Pyrite aggregates

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