CE 6237 Durability of Structures: Concrete

2014‐08‐13
CE 6237
Durability of Concrete Structures
CE 6237 ‐ Durability of Concrete Structures
Course Themes:
• Basic Cement Chemistry & Concrete Technology
• Durability of Reinforced Concrete
• Condition Assessment of Existing Structures
2
Grade Evaluation:
• Assignments 10%
• Journal Club 30%
• Final Exam 60%
• Attendance at lectures is NOT mandatory.
• Attendance at journal club presentations IS mandatory.
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Journal Club (?!)
• Each student will be required to perform two journal club
presentations during the semester.
• This exercise will entail the student choosing a suitable,
previously published journal paper related to the course
themes
• Presenting that paper to the class in a professional manner
as if the student was presenting his own research at a
conference
• with the exception that a short critique of the paper must
also be included.
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To keep yourself up‐to‐date with this course ‐
Please send email to
azmhappy@gmail.com
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Tentative List of Topics:
Basic Cement Chemistry
• Review of basic properties of cement and concrete
• Hydration of individual cement compounds – Macro and Micro
aspects
• Role of admixtures and pozzolans
Properties of Concrete
• Transport Properties ‐ porosity, Ingress of deleterious materials,
permeability etc.
• Cracking
• Volume change – shrinkage
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Durability of Reinforced Concrete
• Leaching & Efflorescence • Extreme heat or fire
• Sulphate Attack exposure
• Acid Attack • Carbonation
• Alkali‐Silica Reaction • Surface wear
• Alkali‐Carbonate Reaction • Sea water
• Freezing & Thawing ‐ salt
scaling, D‐cracking
• Corrosion of steel
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Condition Assessment of Existing Structures
• Inspections Approach and  Destructive testing
types ‐ Sampling Techniques
 Non‐Destructive ‐ Mechanical Tests
Evaluation ‐ X‐Ray Diffraction (XRD)
‐ Penetration Techniques ‐ Scanning Electron Microscopy
‐ Sonic Methods (SEM)
‐ Stress Wave Techniques ‐ Mercury Intrusion Porosimetry
‐ Magnetic Techniques (MIP)
‐ Infrared Thermography

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Lecture‐2
Learning Points:
• Definition of concrete
• Cement Composition
• Cement Types
• Hydration of individual cement compounds
• Microstructure of hydrated cement paste
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Concrete
Definition
Concrete is a particulate composite consisting of dispersed
particles (aggregates) surrounded and bound together by a
continuous matrix (hydrated cement paste).
Ingredients
Portland Cement
Water
Aggregates (Fine & Coarse)
Admixtures
Supplementary Cementing Materials
Other Inclusions
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Concrete Phases
Concrete = Filler + Binder

Portland Cement Concrete = Aggregate + Portland cement paste
(Find and Coarse)
Mortar = Fine aggregate + Paste
Paste = Cement + Water
Concrete exhibits three distinct phases:

Hydrated Cement Paste (hcp)
Aggregates / Inclusions
hcp-Aggregate Interphase (ITZ)
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Typical Oxide Composition of a General-Purpose Portland Cement
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Typical Phases (Compound Composition) of Anhydrous OPC
Various particle size
in anhydrous
cement; laths of
calcium sulphates
dispersed on mineral
grains
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C3S 55%
C2S 32%
C3A 7%
C4AF 4%
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C3S 52%
C2S 30%
C3A 17%
C4AF 0%
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Phase Calculation
Oxide analysis is determined by XRF (X-ray Fluorescence Spectroscopy) and

then the phase calculation is performed by Bogue Calculation (ASTM C 150)
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Characteristics of Hydration of the Cement Compounds
Hydration chemical combination of cement and water.
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Characteristics of Hydration of the Cement Compounds

Degree of hydration
Contribution to strength
Influence of Cement Compounds on Concrete Properties
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Types of Cement (ASTM)
below
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Typical chemical composition and properties

GU MHH, MSR HES LHH HSR
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Strength Development
Type I GU
Type II MHH, MSR
Type III HES
Type IV LHH
Type V HSR
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Applications
Type I – General construction where no special properties are required.
Type III – where rapid strength gain is desirable, e.g.
precast work; concreting at low temperatures.
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Applications
ASTM Type III – not
suitable for thick (> 0.5 m)
concrete, e.g. piers,
abutments etc.
Thermal cracking
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Applications
ASTM Type II and Type IV – Moderate / Low Heat Cement
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Applications
ASTM Type II and Type V – Moderate / High Sulphate Resistant Cement
Sewer pipe Wetting‐drying cycles Marine structure
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Hydration
The setting and hardening of concrete are the result of
chemical and physical processes that take place between
cement and water.
Hydration Products (hydrates) – new solids formed on
hydration.

The theoretical process of cement hydration has been
developed through the study of the hydration of pure
compounds (C3S, C3A, etc).

It is assumed that the hydration of each compound takes place
independently. However, this assumption is not truly valid
since:
1. Compounds are not pure
2. Interaction between hydrating compounds takes place
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Hydration
Two primary mechanisms:

• Through solution ‐ involves dissolution of anhydrous
compounds to their ionic constituents, formation of hydrates
in solution, and eventual precipitation due to their low
solubility

• Topochemical or Solid‐state hydration ‐ reactions take place
directly at the surface of the anhydrous cement compounds
without going into solution
Hydration of Calcium Silicates
The hydration reactions of C3S and C2S are similar:
2C3S + 11H → C3S2H8 + 3CH

Tricalcium water C-S-H calcium
silicate hydroxide
2C2S + 9H → C3S2H8 + CH
Dicalcium water C-S-H calcium
silicate hydroxide
C-S-H (calcium silicate hydrate) – poorly crystalline, amorphous

material that forms as very small particles (< 1 µm).
Calcium hydroxide – highly crystalline material with fixed composition.
C3S hydration
: Initial dissolution
Induction or
Acceleration Deceleration
dormant period
period period Steady state
Calorimetric Study – Rate of heat evolution
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C3S hydration
Gartner, E., Young, J., Damidot, D., and Jawed, I., 2002, "Hydration of Portland cement", Structure and performance of cements, V. 13,
pp. 978‐970.
C3S hydration
• The initial rapid reaction is due to dissolution of a small proportion of C3S,
forms a metastable hydrate layer of C‐S‐H(m) about few nm thick,
strongly bonded to C3S substrate and form a very effective barrier against
further rapid C3S dissolution.
• Formation of the surface hydrate is extremely rapid; an equilibrium is set
up between the aqueous phase and the C‐S‐H(m) phase within less than
30 seconds of wetting; Ca2+ dissolution levels off at this time.
• It does not exist as an independent phase but rather as a surface hydrate
stabilized by the underlying C3S. Stage I hydration kinetics are controlled
by the C‐S‐H(m) layer.
• However, the metastable C‐S‐H layer is more soluble than solution‐
precipitated C‐S‐H(s). Even then the solution is very unsaturated with
respect to C3S itself at any times!
C3S hydration
• Not all the initial C‐S‐H necessarily forms on C3S surface; an appreciable
amount might migrate and deposit on other available surfaces during stage I,
and may be in a more stable form, C‐S‐H(s).
• Due to high initial silica concentration produced in solution, SiO2 can diffuse
away from the C3S more rapidly during stage I than any other time in the
hydration process.
• Despite the presence of C‐S‐H(m) layer, the Ca2+ and OH– ions continue to go
into solution at a steady (but declining rate) clearly implies that the layer is not
perfect barrier against continued C3S dissolution.
• The net process in stage I & II could be as follows:
C3S + H2O  C‐S‐H(m) + 1.3 Ca2+ + 2.6 OH–

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C3S hydration
Gartner, E., Young, J., Damidot, D., and Jawed, I., 2002, "Hydration of Portland cement", Structure and performance of cements, V. 13,
pp. 978‐970.
Hydration of Tricalcium Aluminates
The hydration reaction of C3A alone is:
C3A + 21H → C4AH13 + C2AH8
These hydrates are not stable and convert to:
C4AH13 + C2AH8 → 2C3AH6 + 9H

Hydrogarnet
This reaction occurs very quickly and is commonly referred to as flash set.
Gypsum is added during the manufacture of cement to provide a delaying
mechanism.
The hydration reaction of C3A with gypsum present is:
C3A + 3CS̅ H2 + 26H → C6AS̅ 3H32
Gypsum Ettringite (AFt)
Once all of the sulphate ions (from gypsum) are consumed:

2C3A + C6AS̅ 3H32 + 4H → 3C4AS̅ H12
Ettringite (AFt) Monosulphoaluminate (AFm)
Essentially, this delays C3A hydration in order to avoid flash set problems.
• AFt denotes the phases related to ettringite – calcium aluminum trisulfate
(C3A ∙ 3CS ∙ 32H2O), with the F indicating the possible substitution of iron for
aluminum in the structure. This phase forms when the concentration of
sulfate ions in solution is relatively high and has a morphology of hexagonal
rods.

• The AFm phases are isostructural with calcium aluminum monosulfate (C3A ∙
CS ∙ 12H2O). The phases have a hexagonal plate morphology.
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The balance of C3A and gypsum is critical !!
The balance of C3A and gypsum is critical !!
Formation of Hydration Products from C3A
Kawada et al. 1967.
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Hydration of Ferrite Phase
Hydration of OPC
Heat of hydration
Hydration of OPC
Mechanism of hydration
• Immediately upon contact with water, rapid dissolution of ionic species
gets under way
• Alkali sulfates dissolves completely within seconds contributing K+, Na+
and SO42– ions;
• C3S dissolves congruently and a layer of C‐S‐H(m) precipitates at the
cement particles; Since the C/S ratio of the C‐S‐H(m) (~1.7:1) thus formed
is always lower than that of the C3S (3:1), hydration of C3S is always
associated with a simultaneous liberation of Ca(OH)2, which increase the
Ca2+ and OH– concentration in the liquid phase. Silicate ions also enter the
liquid phase although concentration remains very low.
• Only about 2 – 10% of the C3S is hydrated in the pre‐induction period.
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Hydration of OPC
• C3A phase dissolves very rapidly and reacts with Ca2+ and SO42– ions present
in the liquid phase. However, the aluminate concentration do not last long
and in a matter of seconds there is precipitation of an aluminate hydrate
layer on the cement particle surface. This layer is composed of poorly
crystalline ettringite (AFt). Only about 5 – 25% C3A hydrates in the pre‐
induction period.
• Ferrite phase reacts similar to C3A and yields AFt.
• Only a small fraction of C2S reacts in the pre‐induction period and
contributes less but similar products as of C3S.
Hydration of OPC
Ca(OH)2 Concentration and Nucleation
• Hydration of C3S is always accompanied by liberation of Ca(OH)2.
1. The solution became supersaturated with respect to CH within minutes
however, solid CH is not precipitated even after its concentration in the
liquid phase had reached and exceeded the saturation level due to a
poisoning of the surface of CH nuclei by silicate ions (Odler et al. 1979).
2. The solution remaining undersaturated with respect to CH throughout
stage I and II (Young et al. 1977) and its concentration in the liquid phase
rises slowly during stage II (Taleb 1985) and reaches a maximum close to
the end of induction period. Ca(OH)2 begins to nucleate at the end of
stage II (Young et el. 1972, Wu and Young 1983)
Hydration of OPC
• Nucleation of a “second‐stage C‐S‐H” terminates the induction period and
accelerates the hydration – renewed hydration of C3S and C2S starts –
Crystalline CH starts to precipitate – Formation of secondary AFt –
reduction of SO42– concentration.
• After the concentration in the liquid phase declines, the AFt phase react in
a through‐solution reaction with additional aluminate phase to give
monosulfate (AFm)
2C3A + C3A ∙ 3CS ∙ H32 + 4H  C3A ∙ CS ∙ H32
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Hydration Kinetics
Hydration Kinetics
Formation of hydration products with time
Maekawa, K., Ishida, T., and Kishi, T., "Multi‐scale modeling of structural concrete", Taylor & Francis,
New York, USA, 2009.
Hydration Kinetics
Relative Volume of Hydration Products
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0 – 3 hours
Microstructure of HCP
The term macrostructure is generally used for the gross structure,

visible to the human eye. The limit of resolution of the unaided
human eye is approximately one-fifth of a millimeter (200 μm).
The term microstructure is used for the microscopically magnified

portion of a macrostructure.
Physical Properties of Hydration Products
Porosity
Porosity is another major component of HCP. All pores are not created equal,
there is a wide range of sizes.
Capillary pores – remnants of water‐filled space that exists between the
partially hydrated cement grains.
Gel pores – intrinsic part of the C‐S‐H
Classification of Pore Sizes in HCP
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Porosity
Porosity of HCP is a vital contributor to physical, mechanical and durability
properties.
Influence of Pore Sizes on Properties of the HCP
Water in HCP
Capillary Water – water present in voids larger than about 5 nm.
‐ Water that exists in voids > 50 nm, removal does not cause any volume change ‐ free
(bulk) water
‐ Water held by capillary tension in small capillaries (5 to 50 nm), which on removal
may cause shrinkage of the system.

Adsorbed water – physically adsorbed onto the surface of solids in the hcp. Up to six
molecular layers of water (15 °A) can be physically held by hydrogen bonding; can be
lost by drying to 30% RH – mainly responsible for the shrinkage of the hcp on drying.

Interlayer water – water associated with the C‐S‐H structure. A monomolecular water
layer between the layers of C‐S‐H is strongly held by hydrogen bonding. Can be lost only
on strong drying (i.e., below 11% RH) and causes considerable shrinkage by collapse of
the C‐S‐H structure.

Chemically combined water – integral part of the structure of various cement hydration
products. This water is not lost on drying; it is evolved when the hydrates decompose on
heating.
Influence of Paste Components on Paste Properties
Component Strength Deformation Durability

Provides major Water loss from
Very insoluble..
cohesive force but is micropores causes
C‐S‐H Water in micropores does not freeze
intrinsically weak shrinkage (on drying)
(50‐60%) and has low mobility (low
because of micro‐ and creep (on loading)
permeability).
porosity. at room temperature.
Blocks capillary pores and hence
lowers permeability, But slowly
Dimensionally stable.
CH Contributes by leached by water, causes
Restrains C‐S‐H
(20‐25%) reducing porosity. efflorescence and increases
deformations.
permeability. Carbonates , and is
dissolved by acids.
Not significant.
C4ASH12 Causes sulfate attack by reforming
Reduces total Minor effect.
(10‐15%) ettringite and causing expansion.
porosity.
Renewed hydration may cause
Unhydrated Significant only in Retains C‐S‐H
autogenous healing of internal
cement low‐porosity paste. deformations.
microcracks.
Total porosity is the Fine pores (< 50 nm) Porosity influences permeability and
Capillary
major factor contribute to shrinkage diffusivity. Large pores increase
pores
influencing strength and creep. water flow through concrete.
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0 – 3 hours
C–S–H Model
Intrinsic porosity between the calcium
silicate sheets is filled with additional
calcium ions and water molecules.
P : Isolated capillary pores – bulk
water – menisci created
M : Micropores – menisci cannot form
– layers kept apart by disjoining force
– disappears below RH 50%
I : Interlayer pores – forms when
micropores approach closely.
0 – 3 hours
0 – 3 hours
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Microstructure Development 0 – 3 hours
10 min hydration; Gelatinous Dried fractured surface after
appearance with short rods of 1h hydration; Many short
AFt rods (scanned by HVEM – rods of AFt rods.
wet process);
• The gelatinous layer is probably an amorphous colloidal product, rich in alumina
and silica, but also containing significant amounts of calcium and sulfate
• Exact composition varies with the composition of the underlying grain surface.
Scrivener et al. 1984, 1983; Dalgleish et at. 1982a, 1982b.
• After 3h of hydration, the
amount of C‐S‐H formed is
sufficient for this phase to
be identified on fracture
surfaces.
• When the cement paste is
dried (for SEM etc.), the
gelatinous layer collapses
2h of hydration; 3h of hydration; Spiky
and shrinks back on to the
Gelatinous appearance outcorps of dried C‐S‐H
with AFt rods. (wet surface of grains and, the with AFt rods. (dry
scanning ‐ Ion‐beamed AFt rods also fall back onto scanning – SEM)
thinned section, STEM)
the surface of grains.
Microstructure Development
3 – 12 hours
• However, the separation may occur as little
as 5 hours hydration.
• The separation is thought to occur
because the C‐S‐H nucleates outside the
gelatinous layer formed earlier, on a
framework of AFt rods.
• Separation indicates that the formation of
Separation of the C‐S‐H shell C‐S‐H occurs by through‐solution
from the dark anhydrous
core, after 12 h hydration mechanism
The growth of C‐S‐H between the cement grains bonds the paste together,
causing the paste to set after about 3 to 4 hours of hydration.
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The growth of C‐S‐H
between the cement
grains bonds the paste
together.
Initial mix
90 days
3 – 12 hours
Fracture surface SEM at time of setting
24 h hydration, undried in the
environmental cell of HVEM;
Crumpled foil with rods of AFt
24 h hydration, Fracture surface
SEM; ‘Rossettes’ of dried fibrillar
C‐S‐H and long rods of AFt from
the secondary reaction of C3A
• In undried state, C‐S‐H has a filmy foil‐like morphology, which dries to a fibrillar
morphology (Type I) where there is plenty of space and to a honey‐comb
morphology (Type II) where space is more restricted.
• The hollow space in the dried section (right fig.) was most likely filled with a highly
concentrated or colloidal solution in wet state.
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• After about 16 hours, a renewed growth of AFt occurs with long rods growing
through the C‐S‐H layer. This micro‐structural changes correspond to the shoulder
on the main heat evolution peak in the calorimetric curve.
Pratt et al. 1983.
After about 12 to 18 hours, the bond of the outgrowing C‐S‐H becomes strong
enough for fracture to occur through the hydrate shell, such that the separation
between them and the anhydrous core can be seen on fracture surfaces.
Pratt et al. 1983.
Unhydrated section of polymineralic grain.
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~ 10 min. Some C3A reacts with calcium sulfate in
solution. Amorphous, aluminate‐rich gel forms on
the surface and short AFt rods nucleate at edge of
gell and in solution.
~ 10 h. Reaction of C3S to produce outer
product C‐S‐H on AFt rod network
leaving a gap (1 μm) between grain
surface and hydrated shell.
~ 18 h. Secondary hydration of
C3A producing long rods of
AFt. C‐S‐H inner product starts
to form on inside of shell from
continuing hydration of C3S.
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1‐3 days. C3A reacts with any AFt inside shell forming hexagonal plates
of AFm. Continuous formation of inner product reduces separation of
anhydrous grain and hydrated shell.
~14 days. Sufficient inner C‐S‐H has formed to fill in the space between
grain and shell. The outer C‐S‐H has become more fibrous.
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~ Years. The remaining anhydrous material reacts by a slow solid state
mechanism, to form additional inner product C‐S‐H.
Volume Changes During Hydration
Initial mix
90 days
With the progression of hydration, water that separates individual cement
grain is replaced by solid hydration products. This happens because ……
This happens because, the hydration products occupy a greater specific volume
than the original cement compounds, owing to their lower specific gravity.
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C-S-H and CH will either grow around solid particles or stop growing
when they hit an obstacle.
Thus, there is no increase in total bulk volume of the paste due to

calcium silicate hydration. It only occupy the volume, initially occupied
by mix water.
Ettringite, however, may develop crystal growth pressure in limited

space conditions.
In unhardened paste, ettringite will make additional room by pushing

aside obstructing cement grains.
In hardened paste, a volume expansion will ensue, which will induce

internal stresses that may crack and damage the paste.
1 cm3 of cement will occupy about 2.1 cm3 of space when fully hydrated
(Powers and Brownyard Model)
w/c = 0.5
For complete hydration (α = 1), w/c ratio should not fall below 0.42.
Compressive strength is proportional to gel/space ratio.
(Powers and Brownyard Model)
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CE 6237 Durability of Structures: Concrete

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2014‐08‐13

Concrete = Filler + Binder

Concrete exhibits three distinct phases:

Typical Oxide Composition of a General-Purpose Portland Cement

Typical Phases (Compound Composition) of Anhydrous OPC

Typical Phases (Compound Composition) of Anhydrous OPC

Typical Phases (Compound Composition) of Anhydrous OPC

Oxide analysis is determined by XRF (X-ray Fluorescence Spectroscopy) and

Characteristics of Hydration of the Cement Compounds

Hydration ­ chemical combination of cement and water.

Characteristics of Hydration of the Cement Compounds

Influence of Cement Compounds on Concrete Properties

Types of Cement (ASTM)

Types of Cement (ASTM)

Typical chemical composition and properties

Types of Cement (ASTM)

Sewer pipe Wetting‐drying cycles Marine structure

The hydration reactions of C3S and C2S are similar:

2C3S + 11H → C3S2H8 + 3CH

C-S-H (calcium silicate hydrate) – poorly crystalline, amorphous

Calcium hydroxide – highly crystalline material with fixed composition.

Calorimetric Study – Rate of heat evolution

The hydration reaction of C3A alone is:

C3A + 21H → C4AH13 + C2AH8

These hydrates are not stable and convert to:

C4AH13 + C2AH8 → 2C3AH6 + 9H

Once all of the sulphate ions (from gypsum) are consumed:

The balance of C3A and gypsum is critical !!

The balance of C3A and gypsum is critical !!

Formation of Hydration Products from C3A

The term macrostructure is generally used for the gross structure,

The term microstructure is used for the microscopically magnified

Classification of Pore Sizes in HCP

Influence of Pore Sizes on Properties of the HCP

Component Strength Deformation Durability

Thus, there is no increase in total bulk volume of the paste due to

Ettringite, however, may develop crystal growth pressure in limited

In unhardened paste, ettringite will make additional room by pushing

In hardened paste, a volume expansion will ensue, which will induce

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Hydration chemical combination of cement and water.