Materials for Civil and

Construction Engineers
Binding Materials and Portland
Cement

[Link]. M.Süheyl Akman, Yapı Malzemeleri, 1987

Dr. Osman Nuri Oktar, Ders Notları
Doç. Dr. Halit Yazıcı, Yapı Malzemeleri Sunumu
 Binding Materials
Binding materials are materials used for the purpose of holding
solid particles (such as sand, gravel, crushed etc.) permanently
together in a coherent mass.
For example: Gypsum, lime, cement, bitumen.

Binding materials mixed with water first became a viscous liquid,

dough-like material, then they solidify and gain strength by
hardening over time.
Binders that can set only in air are called "non-hydraulic binder"
(e.g. lime),
Binders that can set in both air and water are called "hydraulic
binders" (e.g. gypsum, cement, water lime).

2
 Binding Materials
Setting: The solidification and hardening of binding materials by
their transition from the liquid phase to the solid phase irreversibly
is called “setting”. This process is not just a physical event. It is a
physicochemical event.
Setting occurs when mixing with water begins. In practical terms,
reaching a certain level of hardening is called “initial setting time".
This level is defined by a standardized test (e.g. Vicat test for
cement).

Hydration is the name of the chemical process when water

combines with a solid material, preserving its H2O composition. H2O
molecules take place in the crystal structure formed as a result of
this reaction.

3
 Gypsum
•One of the oldest binding materials.
Throughout the history it is mainly used for
plastering with different application techniques;
9000 BC: Çatalhöyük gypsum-lime plaster,
350 BC: Ancient Greece - Rome, gypsum
plastering on walls and wood,
1890: USA, first use of double-sided cardboard
and gypsum (gypsum board)
1900s: in fire insulation of wooden buildings in
Europe
79 AD Pompei

Doç. Dr. Halit Yazıcı, Yapı Malzemeleri Sunumu 4

 Gypsum
•It is generally used with fibers against tensile stresses.
•The raw material of gypsum is gypsum stone in nature.
Gypsum is a naturally occurring calcium sulphate mineral
(CaSO4.2H2O) that contains 2 moles of water.

5
 Gypsum
Production: It is produced in three stages.
•Grinding gypsum rock
•Calcination
•Grinding the output product

6
 Gypsum
•Grinded gypsum rock (raw gypsum) turns into hemi-
hydrate gypsum when heated to 190 0C.
CaSO4.2H2O ----- > CaSO4.1/2H2O + 3/2H2O
raw gypsum hemi-hydrate (plaster of paris)
Set very quickly with water
even with the moisture in air

•T~330 0C→ CaSO4 (solving anhydrite) No hydration property

•T>600 0C→ dissolving anhydrite Floor Gypsum:

• has late setting time,
• has higher strength compared
• ~1000-1200 0C → CaSO4 → CaO + SO3 with plaster of paris,
• can be used in mortars.
floor gypsum

7
 Gypsum
•Setting of gypsum occurs through the reverse reaction of
the production reaction.
•CaSO4.1/2H2O + 3/2H2O ----- > CaSO4.2H2O
gypsum (powder) gypsum (solid)

•If excessive water is used during this reaction, excess

water evaporates and pores are formed. This situation
decreases the strength and durability.

8
 Gypsum
•The physical cause of setting is crystallization, the chemical
cause is hydration. Hydration means getting hydrate water to
its molecular structure.
•The hydration of the gypsum occurs very fast, in about 3-15
minutes. In practical terms, it may be necessary to delay or
accelerate setting.
Setting retardants: weak acids, additives such as glue, talc
Setting accelerators: Cl, Sulphate salts
•The faster the hydration, the larger the crystals and the lower
the strength.
9
 Gypsum
Stukko
•Gypsum + water with gel / water with glue  Stukko,
•Stronger comparing to gypsum,
•Generally used in interior decoration material.
Keene Cement
•Gypsum, produced from gypsum stone , grinded and heated with alum
•Sulfoaluminates (x CaO. y Al2O3. z Ca SO4) will formed,
•Provides high strength and durability,
•It is not deformed under water effect.

10
 Gypsum
•Advantages of gypsum:
•1. Energy efficient: Less energy required during gypsum production
compared to other building materials such as lime and cement.
For example, while it is necessary to increase the heat to 900 oC and
1500 oC in lime and cement productions, gypsum can be obtained at
150-200 oC.
•2. Healthy: It is a material that does not produce bacteria.
•3. Provides thermal insulation: It presents thermal insulation properties
because of it’s microscopic pores inside.
•4. Provides sound insulation: It transmits sound less than other plaster
materials such as cement and lime
•5. Resistant to fire: Flammability class A, Non-flammable
•6. Balancing the moisture: Absorbs indoor moisture quickly
11
 Gypsum
•Disadvantages of gypsum:
1. The water resistance of gypsum is not good. It is not
recommended to be used in places exposed to weather conditions.
2. The adherence of gypsum with silica (generally the main
substance of sand) is weak. It has high adherence to brick and
stone but does not adhere well to wood.
3. It has a corrosive effect as it creates an acidic environment. Iron
and steel cannot be used as reinforcement together with gypsum.
4. Increases in volume during setting (except Keene cement)

12
 Gypsum
•Places of Use:
1. Mold Plasters, Porcelain, Ceramic, Tile mold plasters
2. Plasters Used in Medicine: Dentistry, Orthopedics
3. Building Sector:
Plastering: Perlite plaster, Machine plaster
Satin surface finishing plaster
Paper Mache production, mixed with paper pulp
Ceiling and partition wall production, Gypsum board
Glue (gypsum board, wallboard, drywall)
Construction chemicals

13
 Gypsum

Doç. Dr. Halit Yazıcı, Yapı Malzemeleri Sunumu

14
 Gypsum
•Relevant standards:

•TS EN 13279-1, Gypsum binders and gypsum plasters - Part 1:

Definitions and requirements

•TS EN 13279-2, Gypsum binders and gypsum plasters - Part 2:

Test methods

•ASTM C 22-28-36-59-471-472

15
 Lime
It is a very old binding material.
It is a non-hydraulic binder (set and harden with the effect
of air), not water resistant and its strength is low.

Raw materials
-Calcium carbonate (CaCO3) contained stones,
i.e. Limestone, Chalk ---> contains less amount of clay and silica,
with white color

-Calcium and Magnesium carbonate (CaCO3. MgCO3)

contained stones,
i.e. Dolomite ---> contains magnesium carbonate with dark-color and
relatively high strength.
16
 Lime
Production: It is produced in two stages

1-Calcination (Burning) Process:

+900 0C
CaCO3 -------- > CaO + CO2
quicklime (burnt lime) (If CO2 can not be moved away, the
reverse reaction will start.)
2-Slaking (Quenching) Process:
Released heat can be +400
•CaO + H2O ------------------- > Ca (OH)2 0C during this reaction.

(formed by hydration) slaked lime

The slaking process is done by spraying water in factories. The

output material is fine-grained and called hydrated lime.

17
 Lime
If T> 550 0C, reverse reaction will start.

Ca (OH)2 --------------- > CaO + H2O

To prevent this, water is sprayed in regular period of time till to the

end of the process in modern facilities.

18
 Lime
Hardening of lime takes place in 3 stages:
-Drying,
-Crystallization : in Ca(OH)2 form
-Carbonation : Combines with CO2 in the air and carbonates
Drying and crystallization are temporary, when mixed with water,
lime softens again, but the actual hardening is as a result of
carbonation.
•Ca (OH)2 + CO2 -------- > CaCO3 + H2O
•This reaction happens very slowly and the presence of CO2 is
essential. Therefore, lime is a “non-hydraulic binder"
19
 Lime
Lime Mortar:
Lime + Sand (low strength, high porosity, easy to process, not
resistant to water, dissolving.) Today, it is not used as a binder
alone, it is used by mixing with cement.
Hybrid Mortar:
Lime + Cement + Sand (higher strength, resistance to crack
formation, used in masonry and plastering, it is not resistant to
water). If lime is added to the plaster and masonry mortar, a mortar
will be obtained that does not adhere to the trowel, but adhere to the
wall and does not crack easily.

20
 Lime
•Places of Use:
In production of plasters, mortars
As stabilization material on roads/highways
As an additive in bituminous mixtures
In production of aerated concrete
In production of sand-lime brick
In whitewash applications

21
 Lime

•Relevant standards:

•TS 30 -31-32-2848-4022-11669
•ASTM C 5-25-50-51-110-141-207

22
Pozzolans (Trass)

23
 Pozzolans (Trass)
The efforts of human beings to produce binders that can also set in
water and do not dissolve with the effect of water date back to
ancient times.
It has been observed that this feature is partially achieved when
soils containing active silica (SiO2) are mixed with lime.
•The name pozzolan comes from the Puzzuoli town in Italy
•Ancient Romans produced a hydraulic binder by mixing hydrated
lime with soil (predominantly volcanic ash)
Grinding the burnt clay (brick) and mixing with lime were widely
used in Ancient Egypt and Asia Minor, i.e. Khorasan mortar.
Ottomans used it widely.
•Nowadays, the word pozzolan covers a broad range of artificial and
natural materials

24
 Pozzolans (Trass)

Pozzolan: Inorganic materials, either natural or artificial,

which harden in water when mixed with Ca(OH)2 (lime) or
with materials that can release Ca(OH)2 (such as Portland
Cement)

25
 Pozzolans
•Reacts with Calcium Hydroxide

Good Bad
2C3S  6H 
 C3S2 H 3  3CH
Fast

2C2S  4 H Fast

 C3S2 H 3  CH

C3S  H Fast

 C  S  H  CH

Pozzolan  CH  H Slow
 C  S  H

Pozzolanic reaction is low compared to hydration

Early strength is low.
 Pozzolans (Trass)
Pozzolans consist of SiO2 and small amounts of Al2O3.
When mixed with water, they turn into mud and return to
their original state after drying. However, when mixed with
lime, they become binding and turn into a water-insoluble
calcium silicate salt.
Active silica + Lime ------ > Calcium Silicate
(hydraulic binder)
In order to be more successful for the pozzolan-lime
composition,
 pozzolan should be ground very finely,
 the environment should be wet,
 the necessary long time should pass.

27
 Pozzolans must be in powder
form to start reactions.

•Pozzolans

Natural Pozzolans Artificial pozzolans

• Volcanic materials (pumice, • Fly ashes
trass, tuff, volcanic ash, • Blast furnace slags
zeolit, santorin earth…) • Silica fume (microsilica)
• Calcined clay
• Calcined shale, opaline • Obtained by burning
shale materials which contain SiO2.
• Crystal structured SiO2 turn
• Metakaolin to amorphous structure
• Diatomaceous earth during burning.
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
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 Pozzolans (Trass)

•Pozzolans can be also added to cement.

•It is important that pozzolans to bind lime, in terms of
cement. Thus, the lime that soluble in the cement with the
effect of water becomes insoluble and the cement
becomes more resistant to chemical effects.
•Pozzolanic cements are used especially in marine
structures.

29
 Supplementary Cementitious Materials
•Fly Ash (FA)
most commonly used pozzolan in CE structures
by-product of the coal industry
Class N, F, and C
increases workability and extends the hydration
process
•Ground granulated blast furnace slags (GGBFS,BFS)
By-product of iron and steel making
used as a cementitious material in concrete and in
cement production.
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
30
 Supplementary Cementitious
Materials (Cont.)
•Silica Fume
By-product of the production of silicon metal or
ferrosilicon alloys
increases strength and durability
reduces concrete corrosion induced by deicing or
marine salts

•Natural Pozzolans
 Not cementitious, but react with calcium hydroxide to
form compounds possessing cementitious properties
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
31
 Definition of Cement
•EN 197-1
Cement is a hydraulic binder, i.e. a finely ground inorganic material
which, when mixed with water, forms a paste which sets and
hardens by means of hydration reactions and processes and which,
after hardening, retain its strength and stability even under water.
•TS EN 197-1
Çimento su ile karıştırıldığında hidratasyon reaksiyonları ve
prosesler nedeniyle priz alan ve sertleşen bir hamur (pasta)
oluşturan ve sertleşme sonrası suyun altında bile dayanımını ve
kararlılığını koruyan, inorganik ve ince öğütülmüş hidrolik
bağlayıcıdır.

32
 Portland Cement
•PC is named after the limestone & chalk cliffs on the Isle of
Portland, where it was first made in the early 1800s.
•Joseph Aspdin obtained the patent for Portland cement on
1824.

Adapted from Fig. 1.2,

Lea's Chemistry of Cement
and Concrete
by Peter Hewlett
ISBN: 0750662565

British Patent 5022 (21 October 1824) granted to Joseph Aspdin

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
33
 Portland Cement
•There are many types of cement, but portland cement is
so prevalent that in construction cement is always
assumed to mean portland cement.
•This choice of name was applied because of that time
Portland stone had a high reputation for high quality and
durability

34
 •Cement paste = cement + water
Glue (or binder) that bonds aggregates together to
make concrete
•Mortar = cement paste + sand
•Concrete = cement + water + sand + coarse aggregates:
Portland cement (7.5% - 15% of volume)
Water
Aggregates (60% - 75% volume)
Air voids (1% - 15% of volume)
Sometimes admixtures
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
35
 6.1 Cement Production
1. Crushing and grinding of raw materials
Calcium Oxide (calcareous material)
 limestone, chalk, or oyster shells
Silica & Alumina (argillaceous material)
 clay, shale, blast furnace slag
2. Heat and melt in a kiln at 1400-1650oC (2500-3000oF)
which forms cement clinker
Clinker: consist of limestone+clay+iron ore
size of walnut
(C, Si, Al, Fe, N, K….)

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
36
 6.1 Cement Production
3. Add gypsum (delays set time) to clinker and pulverize to
fine powder
15 x 1011 particles / kg
 small particles produce a large surface area for
more complete hydration

• Gypsum is added to clinker in

order to adjust setting time.

• ≈ 3% of clinker by weight

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
37
 Virtual cement plant tour: [Link]
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
38
 Dry process or wet process?
-More homogeneous mixture is obtained in wet process. However
fuel consumption is higher.
-In the wet process of cement manufacture , the grinding and
homogenization of the raw mix is carried out in the form of a slurry
containing 30 to 40% water.
-Modern cement plants favor the dry process, which is more energy
efficient than the wet process because the water used for slurrying
must subsequently be evaporated before the clinkering operation.

39
41
 Data obtained from chemical
analysis of Portland Cement
•Main compounds can be determined
CaO: 60-67%
SiO2: 17-25%
Al2O3: 3-8%
Fe2O3: 0.5-6%
MgO: 0.1-4%
Na2O+K2O: 0.2-1.3%
SO3: 1-3%

43
 6.2 Chemical Composition of PC
•Calcination in the kiln changes molecular structure of ingredients.

•Main compounds: •Minor compounds: small

percent but can have strong
tricalcium silicate
influences:
(C3S=3CaO.SiO2)
magnesium oxide
dicalcium silicate titanium oxide
(C2S=2CaO.SiO2) manganese oxide
tricalcium aluminate sodium oxide
(C3A=3CaOAl2O3) potassium oxide

tetracalcium aluminoferrite •Alkalis (Na2O, K2O) react with

(C4AF=4CaO.Al2O3.Fe2O3) silica causing disintegration &
expansion of concrete
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
44
 Abbreviations for Oxides and
Clinker Compounds
•CaO: C SiO2:S Al2O3:A Fe2O3:F
•MgO:M SO3: S H2O:H

C4ASH12 Ca4Al2(OH)12.SO4.6H2O (Monosulphate:AFm)

C6AS3H32 Ca6Al2(OH)12.(SO4)3.26H2O (Ettringite:AFt)

45
Composition of Portland Cement

Compound Usual Range by

weight (%)
C3S 45-60
C2S 15-30
C3A 6-12
C4AF 6-8

46
 Kinetics and Reactivities of PC
Components
•The rate of hydration during the first few days is in the order of
C3A > C3S > C4AF > C2S.

C3A
Aluminate
C3S
C4AF
Rates of
C2S
hydration of the
four main
chemical
components of
PC.
 Kinetics and Reactivities of PC
Components
• C3A hydrates rapidly
but its strength is low

• C3S contributes to
strength at early
ages

• C2S contributes to
strength at later ages

Strength development over time of the four

main chemical components in PC.
 Influence of Compound Composition on Characteristics of
P.C.

Relative comparison:
C3S C2S C3A C4AF

Rate of Reaction Moderate Slow Fast Moderate

Heat Liberation High Low Very High Moderate

Strength at Early Ages Good Poor Good Poor

Strength at Later Ages Good Good Poor Poor

• MgO and SO3: Causes volume increase with free lime and it will increase the
cracks
• Na2O and K2O: These alcali oksits react with active silicas (aggregates may
contain active silicas) and produce a gel. Volume of this gel increase slowly but
in big proportions when swelling. Thus a thick network of cracks may be
observed in concrete.
• Insoluble residue: Used to find insoluble parts of cement in HCl. This result
shows us if the reactions in rotary kiln is sufficient enough.
• Loss on ignition: Volatile substances (H2O, CO2) evaporate in 1000 0C. Cement
is deteriote if contact with air and this test may be used to determine the quality
of cement

50
 Bogue formulas
•The mineralogical compositions of Portland Cements
containing no secondary materials may be calculated by
using Bogue formuleas
a)

51
 Bogue formulas
•b)

52
 Alkali-Silica Reactivity

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
53
 6.3 Fineness
•Smaller cement particles have more surface area to react with
water
fineness controls the rate of hydration (heat & strength gain)
too fine is more expensive and can be harmful
•Surface area measured indirectly (cm2/g)
Blaine test – Measures air Wagner Turbidimeter – Measures
permeability against known sedimentation rate suspended in kerosene -
standard material finer settles slower

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
54
 FINENESS OF CEMENT
Fineness : indicates average particle size

Particle size Fineness

Hydration rate
Heat of Hydration
Water requirement
 6.4 Specific Gravity

•Gcement  3.15 gr/cm3

Measured for cement particles without air voids

•Bulk unit weight (weight required to fill a container) is

highly variable.

•Cement should not be measured by volume.

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
56
 6.5 Hydration
•Chemical reaction of cement with water
•“Hardening” – is not setting or drying
Drying = evaporation = no water
– stops reaction

•Mechanisms:
Through-solution: dominates early stage of hydration
Topochemical: solid-state reaction at cement surface
•Hydration rate: aluminates > silicates  needs balance

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
57
 Hydration
•Cement + Water  Hydration products + Heat

•Main hydration products :

CSH
CH
AFm, AFt
 •Hydration of C3S & C2S:
produces C-S-H (calcium-silicate-hydrate)  makes
paste strong
•Primary Chemical Reaction Chemical reactions that
harden cement paste
Fast in the beginning but is long term (decades in
dams)
Causes heat, which can be a problem if there’s too
much
•Structure development in cement paste

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
59
 Hydration Products of Cement
Hydrations of pure cement compounds:
•The mechanism of hydration of the cement as whole is very
complex and has not been fully understood yet.
•So far, the only approach to studying the hydration of Portland
cement is to investigate the reaction mechanism of individual
compounds separately.
•This assumes that the hydration of each compound takes place
independently and no interaction occurs. Although this
assumption is not valid completely, it helps to understand the
chemistry of hydration.

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Silicates
•2C3S + 11H→C3S2H8 + 3CH
•2C2S + 9H→ C3S2H8 + CH

The principal hydration product is Another product is CH,

C3S2H8, calcium silicate hydrate, or calcium hydroxide (lime).
C–S–H (nonstoichiometric).
• Although C3S and C2S produce the same hydration products, their reaction
rates are very different;
• C3S reacts very fast at the early stage, releases more hydration heat, and
contributes most to early age strength of concrete.
• C2S reacts very slowly, releases less heat, and contributes minimally to early
age strength of concrete. C2S contributes the most to the long-term strength
of concrete.
Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Silicate Hydrate
(C-S-H)
C-S-H is an amorphous, colloidal (with very small
particles) material with variable chemical and physical
structure.
It is the major phase,
Occupies 2/3 of the paste volume,
Microporosity associated with this phase is about 25%,
Huge surface area
Forms a continuous matrix,
Small crystals of calcium hydroxide (CH),
embedded within
Smaller crystals of calcium sulfoaluminate hydrates,
the C-S-H matrix
Some unhydrated residues of the original cement grains

CSH provides the strength of hardened cement

paste, therefore, strength of concrete.
 Calcium Silicate Hydrate
(C-S-H)
Its average composition has a CaO/SiO2 (C/S) ratio of
1.5-1.7,
However, the C/S ratios of individual particles may vary
over 1-3,
C-S-H has considerable quantities of impurity oxides,
alumina and sulfur,
Its water content is variable,
Water associated with C-S-H ranges from:
chemically bound water
weakly bound water to the surface through van der Waals
 Calcium Silicate Hydrate
(C-S-H)
Chemically bound water is represented by the formula
3CaO.2SiO2.H2O and obtained after very strong drying
in vacuum (D-drying),
When water is removed from C-S-H, its physical
structure changes considerably,
C-S-H is a metastable, particularly saturated “xerogel”
similar to silica gel formed by precipitation from solution,
The way of removing water influences the microstructural
changes [if more gentle drying is used, then structural
rearrangements are much less, and the material more
closely approximates to the original xerogel structure].
 Calcium Hydroxide (C-H)
•Another hydration product is CH, calcium hydroxide.
•CH is formed in solution by crystallization and occupies about
20-25% in the hardened cement paste (hcp).
•This product is a good crystalline with a plate shape in most
cases.
•Size of the crystals depends on the amount of space available.
•Much lower surface area than CSH
•Does not contribute much to strength
•Dissolves easily with water

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Hydroxide (C-H)
•Keeps the pore solution alkaline (pH > 12) and it is good for
corrosion protection of steel.
•From a durability of concrete point of view, CH may lead to
leaching due to its solubility, carbonation due its reaction with
carbon dioxide, alkali aggregate reaction due to its high pH
value, or sulfate attack due to its reaction with sulfate. Hence, in
contemporary concrete technology, there has been a trend to
reduce amount of CH in concrete as much as possible.
•However, a minimum amount of CH is needed to keep the high
alkali environment in concrete.
Calcium Sulfoaluminate Hydrates

• Calcium Sulfoaluminates do not contribute

much for strength.

• If only C3A hydrates : C3A + 6H  C3AH6

• This reaction is very fast  Flash setting
• To prevent flash setting, gypsum is added during the
production of cement.
 Calcium Sulfoaluminate Hydrates
•10-15% (by volume) of cement paste
•The primary initial reaction of C3A with water in the presence of
a plentiful supply of gypsum is;
Tricalcium
aluminate + gypsum + water → ettringite

• C3A + 3CSത H2+ 26H →C6ASത 3H32

The 6-calcium aluminate trisulfate-32-hydrate, is usually called

calcium sulfoaluminate hydrate and more commonly
ettringite, which is the name of a naturally occurring mineral of the same
composition. The nickname of ettingite is AFt.

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Sulfoaluminate Hydrates
•The effect of ettringite on concrete strength can be evaluated in
two cases.
•In case 1, ettringite is formed before the paste has hardened
and gained strength due to hydration of C3S. It will contribute to
the early strength development of concrete since the needle-
shaped crystals can work as reinforcement for the surrounding
C–S–H, and the expansion is not so significant.
•In case 2, if ettringite is formed after the concrete has
DANGER

hardened and free space has been occupied by other hydration

products, it will make its space to grow by breaking the hardened
hydration products and hence create cracks and volume
instability.

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
 Calcium Sulfoaluminate Hydrates
•The ettringite is stable as long as there is sufficient gypsum
available and at a temperature lower than 60℃. If all the
gypsum is consumed before the C3A has completely hydrated
or the temperature rises to above 60℃, it can be broken down
during the hydration of the conversion to monosulfoaluminate:

•2C3A + C6A Sത 3H32 + 4H →3C4ASത H12

Tricalcium
+ ettringite + water → monosulfoaluminate
aluminate

• Monosulfoaluminate is also called tetracalcium aluminate

monosulfate-12-hydrate. Its nickname is AFm.
• Monosulfoaluminate is the stable phase in mature concrete
 Calcium Sulfoaluminate Hydrates
•When monosulfoaluminate is brought into contact with a new
source of sulfate ions, ettringite can be formed again:
ത 12 + 2CSH
•C4ASH ത 2 + 16H → C6ASത 3H32
Monosulfo
+gypsum + water → ettringite
aluminate

•Sulfate attack is mainly the result of the reaction of

monosulfoaluminate with sulfate ions (from sea water or salty soil).
This reaction causes internal volume expansions, which lead to
internal microcracking and hence overall concrete deterioration.
•Therefore, C3A is limited for concretes to be exposed to sulfates.
•If C3A < 5%  Sulfate resisting cement
 Calcium Sulfoaluminate Hydrates
•The hydration products of C4AF are similar to those of C3A.
However, the reaction rate of C4AF is slower than that of C3A.
When reacting with gypsum, the following equation applies:

ത 2+ 21H → C6(A, F)Sത 3H32 + (F, A)H3

•C4AF + 3CSH

Tetracalcium Ferric-aluminum
aluminate hydrate hydroxide

•The expression C6(A, F)Sത 3H32 indicates that iron oxide and alumina
occur interchangeably in the compound.

Li, Z., Advanced Concrete Technology, John Wiley Sons, Inc., Hoboken, New Jersey, 2011.
Components of Hardened Cement Paste

Portland cement after 24 hours hydration time

CSH
CH
Ettringite
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
77
Cement Hydration
Cement Hydration
Cement Hydration
Cement Hydration
Cement Hydration
Porosity

Minutes Hours Days

 Heat of Hydration
Hydration process of cement is accompanied by heat
generation (exothermic).

About 50% of this heat is liberated within 1-3 days

& 75% within 7 days.

By limiting C3S & C3A content heat of hydration can

be reduced.
 Heat of Hydration
-Hydration of cement is an exothermic (heat released) reaction

Stage I: Rapid Heat Evaluation (<15 min.)

Stage II:Dormant Period (important for transportation) (2-4 hours)
Stage III: Accelarating State (begins with intial set) (4-8 hours)
Stage IV: Deceleration State (no longer workable) (12-24 hours)
Stage V: Steady state
 Stage 1

• The first stage is a very short one,

and the heat liberated there is due
mainly to the wetting and early
dissolution of the cement
Stage 2

The induction period is

characterized by negligible
reaction rates, which allows the
paste to maintain its fludity
 Stage 3
• The rapid reaction rates at the
beginning of Stage 3 is mainly due to
the onset of hydration of the C3S
phase.
• About the time of the initial rise in
rates, there is already sufficient
buildup of hydration products to lead
the initial setting
• While final setting has occured before
hydration has reached the peak
marking the end of stage 3.
Stage 4

• The arrow marking the C3A hydration

in stage 4 indicative of the time when
gypsum is depleted and now C3A
begins a more rapid reaction.
 Stage 5

• Finally, in stage 5, all of the reaction

proceed more slowly as the hydration
products fill in the pore space
between cement grains.
Interpretation of Calorimetry
Curve
 HYDRATION as a summary
•Is the chemical combination of cement and water to form
hydration products
•Takes time
•May not proceed to 100% completion

Formation of hydration products over time leads to:

•Stiffening (loss of workability)

•Setting (solidification)
•Hardening (strength gain)
 6.6 Voids in Hydrated Cement
a) Interlayer hydration space
space between atomic layers
shrinkage if humidity <11%
b) Capillary voids
w/c ratio too high
decrease strength and increase permeability
c) Trapped voids
large pockets caused by handling
decrease strength and increase permeability
d) Entrained air
microscopic bubbles caused by admixtures
increases durability
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
93
 6.7 Properties of Hydrated Cement
Setting
•Stiffening: change from plastic to solid (initial and final)
not the same as hardening, which is strength gain
handling, placing, & vibrating must be completed
before initial set
finishing between initial and final
curing after final set
•False Set: premature stiffening within a few minutes
due to humidity in cement during storage
remix without adding water
•Quick set & flash set are different – cannot be fixed
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
94
Flash-Set: is the immediate stiffening of cement paste in a
few minutes after mixing with water. It is accompanied by
large amount of heat generation upon reaction of C3A with
water.

 Gypsum is placed in cement to prevent flash-set. The

rigidity can not be overcome & plasticity may not be regained
without addition of water.

 Amount of gypsum must be such that it will be used upto

almost hardening. More gypsum will cause undesirable
expansion after hardening.
 SETTING TIMES
Cement+water

time = 0  like a liquid

Initial
setting Final
time = t1  starts to stiffen
setting

time = t2  starts to harden

(complete loss of
plasticity)
 Tests for Initial and Final Set
•penetration of weighted needle

Vicat Gillmore
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
97
 Soundness
Ability to retain its volume after
setting
•Expansion after setting is
measured in the autoclave test at
420oF & 295 psi

Frame for measuring

length of sample
before and after Autoclave
autoclave conditioning

Sample molds
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
98
 Soundness
•Le Chatelier ring

Le Chatelier Method:
1) 24 hours in water: Effect of free CaO can be determined.
2) 4 h boiling: Effects of both free CaO&MgO can be determined.
 Compressive Strength of Mortar
ASTM C109
•Average of three 2" mortar cubes
•Proportional to compressive strength of cylinders
•Compressive strength of concrete cannot be accurately
predicted from cement strength

Mold Compression
Prepare sample test Typical failure
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
100
 6.8 Water-Cement Ratio
•The most important property of hydrating cement
•Water needed for hydration, w/c = 0.22-0.25
•Extra water is needed for workability but causes voids
Decreases strength
Decreases durability
Decreases bond between successive layers
Decreases bond between concrete and rebar
Increases permeability
Increases volume change from wetting and drying

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
101
 w/c Ratio w/c Ratio
Air Entrained Concrete Non-air Entrained Concrete
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
102
 6.9 Types of PC
Standard PC types
• I Normal
• II Moderate Sulfate Resistance
 Type I/II is both normal & moderate sulfate resistance
• III High Early Strength
 becoming cheaper & more common
 we can strip forms earlier and speed up production
• IV Low Heat of Hydration
 for large, massive pours to control heat of hydration
• V High Sulfate Resistance
Other cement types: for special uses
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
103
 Type IV Moderate and
Low Heat Cements

Portland, Blended,
and Other Hydraulic
Cements
109
EN 197-1 : Cement- Part 1: Compositions, specifications and
conformity criteria for common cements

110
 TS EN 197-1 : Çimento - Bölüm 1: Genel çimentolar -
Bileşim, özellikler ve uygunluk kriterleri
Ana Bileşenler (Kütlece % olarak)
Minör
Çimento Yüksek Kalker Kalker İlave
Adı Notasyon Silis Doğal Endüstriye Silisli Kalkersi Pişmiş
Tipi Klinker Fırın (Kireç (Kireç Bileşenle
Dumanı Puzolan l Puzolan Uçucu Kül Uçucu Kül Şist
K Cürufu Taşı) Taşı) r
D P Q V W T
S L LL
CEM I Portland Çimento CEM I 95-100 - - - - - - - - 0-5
Portland Cüruflu CEM II/A-S 80-94 6-20 - - - - - - - - 0-5
Çimento CEM II/B-S 65-79 21-35 - - - - - - - - 0-5
Portland Silis
CEM II/A-D 90-94 - 6-10 - - - - - - - 0-5
Dumanlı Çimento
CEM II/A-P 80-94 - - 6-20 - - - - - - 0-5
Portland Puzolanlı CEM II/B-P 65-79 - - 21-35 - - - - - - 0-5
Çimento CEM II/A-Q 80-94 - - - 6-20 - - - - - 0-5
CEM II/B-Q 65-79 - - - 21-35 - - - - - 0-5
CEM II/A-V 80-94 - - - - 6-20 - - - - 0-5
Portland Uçucu Küllü CEM II/B-V 65-79 - - - - 21-35 - - - - 0-5
CEM II
Çimento CEM II/A-W 80-94 - - - - - 6-20 - - - 0-5
CEM II/B-W 65-79 - - - - - 21-35 - - - 0-5
Portland Pişmiş Siştli CEM II/A-T 80-94 - - - - - - 6-20 - - 0-5
Çimento CEM II/B-T 65-79 - - - - - - 21-35 - - 0-5
CEM II/A-L 80-94 - - - - - - - 6-20 - 0-5
Portland Kalkerli CEM II/B-L 65-79 - - - - - - - 21-35 - 0-5
Çimento CEM II/A-LL 80-94 - - - - - - - - 6-20 0-5
CEM II/B-LL 65-79 - - - - - - - - 21-35 0-5
Portland Kompoze CEM II/A-M 80-94 6-20 0-5
Çimento CEM II/B-M 65-79 21-35 0-5
CEM III/A 35-64 36-65 - - - - - - - - 0-5
Yüksek Fırın Cüruflu
CEM III CEM III/B 20-34 66-80 - - - - - - - - 0-5
Çimento
CEM III/C 5-19 81-95 - - - - - - - - 0-5
CEM IV/A 65-89 - 11-35 - - - 0-5
CEM IV Puzolanik Çimento
CEM IV/B 45-64 - 36-55 - - - 0-5
CEM V/A 40-64 18-30 - 18-30 - - - - 0-5
CEM V Kompoze Çimento
CEM V/B 20-38 31-50 - 31-50 - - - - 0-5

111
 S: Granulated Blast Furnace
Slag
P: Natural Pozzolana
Q:Natural calcined Pozzolana
V: Siliceous fly ash
W: Calcareous fly ash
Strength T: Burnt shale
Used
admixture
class L: Limestone
Amount of
D: Silica fume
admixture
Portland Limestone Cement
A: Low admixture
B: High admixture
C: Very high admixture

Strength classes:R32.5,
→ Yüksek erken mukavemet
42.5, 52.5 özelliğini
R: High early gösterir
strength (rapid)
N: Ordinary
N → Yüksek erken mukavemet early strength
özelliği olmadığını (normal)
gösterir
[Link]

113
114