Materials for Civil Engineers

Chapter 3- Portland Cement

Waleed Zeiada, Ph.D.

Assistant Professor
Civil & Environmental Engineering
 Cement
Cement

Polymeric Mineral

Glues and adhesives Non-Hydraulic – Not Water Resistant

− Epoxies − Gypsum based
− Resins − Lime
− Quicklime

Bitumens
− Asphalt (from crude Hydraulic – Water Resistant
oil refinery) − Portland cement (Types I-V)
− Tars (from coal − Blended cement (Furnace slag
distillation) cement)
 Early History and Development
 Use in antiquity
 Egyptians (3000 BC) used lime
and gypsum mortar (mostly in
pyramids)
 Assyrian and Babylonians (1800
BC) used clay to bind stones
 Greeks and Romans (27 BC) used
lime with volcanic ash in many
structures (Colosseum, Pantheon,
etc.)

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Portland Cement History and Development
 Modern Development
 1756, John Smeaton – Repeated Failures of
Eddystone Lighthouse, Coast of Cornwall,
England
o Mix of lime, clay and crushed slag, and water
 1824, Joseph Aspdin – Took out a patent for
"Portland Cement,"
o Fired fine ground clay and limestone until the
limestone was calcinated
o Derived name from the its similarity to the highly
desired stone that was quarried on the Isle of
Portland in Dorset, England
 1854, Isaac Johnson – Modern Portland cement
o Used higher temperatures (1400 to 1500C)
o Clinkering occurs and produces very reactive
cement 4
 Cement Raw Materials
 The elements used in cement production are mainly Ca, Si, Al, Fe
 For convenience we represent these in a short-hand or “Cement
Notation”
Oxide Cement Composition
Material
Notation Notation in PC
Calcium Oxide
(limestone) CaO C 60-67%
Silica (Silicon Dioxide) SiO2 S 17-25%
(clay, sand, fly ash)
Alumina (Aluminum Trioxide) Al2O3 A 3-8%
(clay, fly ash)
Iron Oxide Fe2O3 F 0.5-6.0%
(iron ore)
Sulfate SO3- S’ 1-3%
( gypsum)
Alkalies K2O+Na2O -- 0.2-1.3%
 Cement Manufacturing
1. Crushing and grinding of raw materials
 Calcium Oxide
 Silica & Alumina
2. Heat and melt in a furnace at 1400-1650oC (2500-
3000oF) which forms cement clinker
3. Add gypsum (delays set time) to clinker and pulverize
to fine powder
 7 x 1011 particles / lb
 Small particles produce a large surface area for more
complete hydration

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 7
http://civildigital.com/cement-manufacturing-process-simplified-flow-chart/
 Major Reactions in the Kiln
 Calcination Reaction (450˚C – 900˚C)– Limestone
or calcium carbonate (CaCo3) gets converted into calcium
oxide (CaO) by releasing of CO2

 Clinkering Reaction
(1400˚C – 1650˚C)–
Many reactions occur
inside the kiln, but the
major and the most difficult
one is the combination of
C2S and CaO to form C3S. Clinker

 Clinkering reaction ends

when all CaO is used up
 Major Cement Minerals
 90-95% of a Portland cement is comprised of the four
main cement minerals, which are C3S, C2S, C3A, and
C4AF

Material Chemical Cement Mineral

Formula Notation Name

Tricalcium Silicate Ca3SiO5 C 3S Alite

Dicalcium Silicate Ca2SiO4 C 2S Belite

Tricalcium Aluminate Ca3Al2O6 C 3A Aluminate

Tetracalcium Aluminoferrite Ca2AlFeO5 C4AF Ferrite

 Major Cement Minerals
 Tricalcium Silicate (C3S):
 Hydrates & hardens rapidly
 Responsible for early strength
 Dicalcium Silicate (C2S):
 Hydrates & hardens slowly
 Contributes to later age strength (beyond 7 days)
 Tricalcium Aluminate (C3A):
 Releases a large amount of heat during first few days
 Contributes to initial strength development
 React very rapidly with the sulfates and cause volume increase
 Tetracalcium Aluminoferrite (C4AF):
 The reactivity of the pure C4AF is much slower than that of the C3A
 Color of hydrated cement (gray) due to ferrite hydrates
 Major Cement Minerals
 The four cement minerals play very different roles in
the hydration process that converts the dry cement
into hardened cement paste

Characteristic C3S C2S C3A C4AF

Rate of hydration Fast Slow Very Fast Very Slow
Heat of hydration High Low Very High Very Low
Sulfate resistance Poor Good Very Poor Very Good
Responsible Responsible Responsible
for for for
Short‐term Long‐term Initial
Hardening Hardening strength
development
 Types of PC
Standard Types
 I Normal
 Use for general purposes: buildings, bridges, etc
 II Moderate Sulfate Resistance
 Used for structures exposed to soil or water containing sulfate ions: mat
foundation, retaining walls, etc
 III High Early Strength
 When high early strength is desired (< 7 days): Early opening of highways or
rapid construction projects
 Generates a lot of heat and recommended for cold climate regions
 IV Low Heat of Hydration
 When low heat of hydration is required: massive concrete structures such as
dams and nuclear power plants where higher amount of heat is developed
 Recommended for hot climate regions
 V High Sulfate Resistance
 Used for high sulfate from sea water and soil
Other cement types: for special uses such as colored
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cement
 Typical Compositions of PC
ASTM C3S C2S C3A C4AF Fineness
Common Name
Type (%) (%) (%) (%) (m2/kg)
I General Purpose 55 19 10 7 370
Moderate Sulfate
II 51 24 6 11 370
Resistance
III Early Strength 55 19 10 7 540

IV Low Heat 28 49 4 12 380

High Sulfate
V 38 43 4 9 380
Resistance
 Hydration of Cement
 Drying – Evaporation of water from a system
 Hydration – Chemical reaction with water
 Hydration is an exothermic reaction
 The chemical components (C3S, C2S, C3A) react with
water to form new compounds that will provide the
strength and stability to this network
 Only a certain amount of water is needed to fuel this
reaction
 Water in excess of this minimum amount can lead to
pores in the cured product, but can also help workability
 Chemical reactions depend on both temperature and
time
 Hydration of Cement
 Hydration process is tracked by temperature profile
 Hydration of Cement
 Before Mixing
 Cement particles consists of
calcium silicates and calcium
aluminates
 Calcium Silicates
o Alite (C3S)
o Belite (C2S)

 Calcium Aluminates
o Aluminate (C3A)
o Ferrite (C4AF)

 Gypsum (Calcium Sulfate-CS’)

o To avoid the uncontrolled setting
resulting from the rapid reaction of C3A
with water
 Hydration of Cement
 Stage 1: Mixing/Dissolution
 Last for only short time (<15 min.)
 C3A dissolves rabidly and react with the water and creates calcium aluminate
hydrate (C3AH6)
 Big amount of temperature is released
 If uncontrolled this reaction will occur very fast and permanently harden the
mixture (a bad thing)  FLASH SET
 Providing gypsum (sulfate) controls the reaction by
reacting with some of the aluminate to create
C3A(3CS’)H32, which is known as Ettringite (C-A-S’-H),
then temperature goes down
 Too much gypsum hydrates creates a plaster and
cause FALSE SET
 False set is not as bad as flash set and can be
overcome by additional mixing, but will reduce the
potential strength of the mix.
1. C3A + 6H  C3AH6 + Heat
2. C3A + CS’H (gypsum) + 26H  C3A(3CS’)H32 + Heat
 Hydration of Cement
 Stage 2: Dormancy/ Induction Period
 Last for 2 to 4 hours
 Minimal temperature release
 This stage is mainly controlled by C3S
 Silicates (alite mainly and belite) slowly
dissolve releasing calcium ions, silicate
ions, and hydroxyl ions in solution
 No hardening or setting occurs during
dormancy time
 This stage continues till the solution
becomes supersaturated
 The concrete mix can be transported and
placed
 Hydration of Cement
 Stage 3: Hardening/Acceleration Stage
 Last for 2 to 4 hours
 At supersaturation state, ions combine into
new solid phases and form C-S-H and CH
 C-S-H forms fiber like solids
 CH forms platelets like solids
 Concrete setting starts to occur (initial-
30% and final-70%)
 Heat is generated causing thermal
expansion
 The gel-like C-A-S’-H transforms into
needle-like solids (ettringite) that
contributes somewhat to early strength C3S2H3  Calcium Silicate
Hydrate or C-S-H
 C3S reaction aids mainly in short term
hardening (initial and final setting) CH  Calcium Hydroxide
3. 2C3S + 6H  C3S2H3 + 3CH (lime) + Heat or hydrated lime
 Hydration of Cement
 Stage 4: Cooling/Deceleration
Stage
 Last for several hours
 After final setting, the building of C-S-
H and CH begins to limit the access
of water to unresolved cement
 Silicate reactions slow
 Heat peaks and begin to drop
 Concrete cools and contract
 Cracking can occur
 Hydration of Cement
 Stage 5: Densification/Steady Stage
 Can continue for years
 Start of belite reaction and produce C-
S-H and CH forming a solid mass
 Longer length of this stage gives
concrete greater strength, lower
permeability, and greater durability
 To promote continued hydration,
moisture must be retained as long as
possible
 C2S reaction occurs more slowly and
mainly contributes to long term
strength

4. 2C2S + 4H  C3S2H3 + CH (lime) + Heat

Primary Products from Cement Hydration
C3S2H3  Calcium
Silicate Hydrate or C-S-H
(fiber like)

CH  Calcium Hydroxide
or hydrated lime
(platelets like)

C3A(3CS’)H32 
Ettringite or C-A-S’-H
(Needle like)
 Calcium Silicate Hydrate
 Forms from reaction of C2S and C3S

 High specific surface (250 – 450 m2/gram)

 Leads to strength through Van Der Waals forces

which are magnified due to large surface area

 Since Van Der Waals forces are responsible for

holding cement together the tensile strength will be
much lower than compressive strength
Hydration of Cement
 Mass-Volume Relationships
 Specific gravity of Portland cement varies from 3.10
to 3.20 (3.15 is the most common value)
 Dry unit weight of cement varies between 52 and 103
lb/ft3
 Water-Cement Ratio (w/c)
 The ratio of the weight of water to that of cement

 The most important property of hydrating cement

 Lower w/c = better hardened PCC properties

 Strength, stiffness, durability, bond between
reinforcement, permeability, volume change from wetting
and drying, etc.
 Lower limit of w/c is approximately 0.25-0.15, below this
ratio there is not enough water to fully hydrate the cement

 Higher w/c = more desirable fresh PCC properties

 Increased workability
 Effect of W/C Ratio on Compressive Strength

Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc. 27
 Fineness
 Smaller cement particles have more surface area to react with
water (2 to 90 μm – 10 μm aveg.)
 Fineness controls the rate of hydration (heat & strength gain)
 Too fine is more expensive and can be harmful
 Surface area measured indirectly (cm2/g)
 Wagner Turbidimeter – Measures sedimentation rate
suspended in kerosene - finer settles slower

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Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
 Properties of Hydrated Cement
 Setting or Stiffening: change from plastic to solid (initial
and final)
 Initial set: Occurs when the paste begins to stiffen
considerably
 Final set: Occurs when the cement has stiffened to the point
at which it can sustain some load
 Not the same as hardening, which is strength gain after set
 Handling, placing, & vibrating must be completed before
initial set
 Finishing between initial and final
 Curing after final set
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 Tests for Initial and Final Set
 Setting tests are used to characterize how a particular cement paste sets
 Penetration of weighted needle

Vicat Gillmore

 The Vicat frame consists of a metal stand  The apparatus consists of two horizontal arms
with a sliding rod and a needle which carry two weighted steel needles
 Total test weight of 300 g  The initial needle 2.12 mm dia., weighs 113 g
 A cement paste is molded and placed in a  The final needle 1.06 mm dia., weighs 453,6 g
moist cabinet and allowed to start setting  A consistent cement pat with a flat top is made
 Periodic penetration tests are performed  The Gillmore needle is applied lightly to the
on this paste by allowing a 1-mm Vicat cement specimen surface
needle to settle into this paste  The process is repeated until the pat resist the
 Initial set occurs when needle penetrates force of the needle without any noticeable
after 30s - 25 mm (1 inch) into paste indentation
 Final set occurs when there is no visible  The initial needle gives the initial setting time and
penetration the final needle gives the final setting time
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc. 30
 Compressive Strength of Mortar
 ASTM C109
 Average of three 2" mortar cubes (cement, water, and sand)
 Minimum values for different cement type at different ages
 Compressive strength of concrete cannot be accurately
predicted from cement strength

Mold Compression
Prepare test Typical failure
sample 31
Mamlouk/Zaniewski, Materials for Civil and Construction Engineers, Third Edition. Copyright © 2011 Pearson Education, Inc.
 Mixing Water
 Any potable (drinkable) water can be used

 If fresh water isn't available, we may allow some

impurities if we still obtain a reasonable concrete mix
 Example: seawater may be used for plain concrete,
but not for reinforced

 Acceptable Criteria (ASTM C94)

 Average 7-day comp. strength of mortar cubes ≥ 90%
of strength of those made with fresh water
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 Admixtures
 Commonly used to improve properties of fresh and
hardened concrete (Chemical and Minerals)
Chemical Admixture Minerals Admixture

Left to right  antiwashout admixture, Left to right  Fly Ash, Slag Cement,
shrinkage reducer, water reducer, Silica Fume, Natural Pozzolans
foaming agent, corrosion inhibitor, and
air-entraining admixture
 Chemical Admixtures
1. Air entertainer
2. Water reducer
(Plasticizer)
3. Retarder
4. Hydration controller
5. Accelerator
6. Specialty admixtures
Left to right  antiwashout admixture,
shrinkage reducer, water reducer, foaming
agent, corrosion inhibitor, and air-
entraining admixture
 Air Entrainers
 Functionality: AEA Structure
Produce tiny, dispersed
air bubbles with
identical surface Hydrophilic Hydrophobic
Group Group
charge into the
concrete so that they Stabilized Bubble

will separate from each

other and won’t form
large air pockets (0.01
to 1 mm)
Air Bubble
 Sources: salts of wood
resins and salts of
petroleum acids
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 Air Entraining Admixtures
 Applications:
 Recommended for all concrete exposed to freezing
 Water expands as it freezes causing internal stress that
cracks the hardened cement paste and greatly reduces
durability
 Air entrainer provides space for the water to go as it
expands
 Improve workability, resistance to de-icing
chemicals, sulfates, & alkalis
 Decreases strength by about 20% but can be
compensated with lower w/c ratio
 Entrained vs. Entrapped Air
 Entrained air = tiny and
well distributed and
complete separate air
bubbles Thin section of concrete
with air voids dyed blue

 Aids in freeze thaw and

chemical scaling resistance
 Entrapped air =
interconnected pockets of
air in PCC system.
 Allow water to enter system
and promotes freeze thaw
failures
 Water Reducing Admixture
 Functionality: Without WRA
Cement Particles
Neutralize surface
charges in cement and
prevent clumping
 Types:
 Mid-range water With WRA
reducer
 High range water
reducer
 Plasticizer
 Superplasticizer
 Water Reducers
 Applications: Increase mobility of cement particles
and Improves workability – measured with slump test

Normal
No water water reducer
reducer

High-range
Mid range water reducer
water (Superplasticizer)
reducer

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 Three Ways to Use Water Reducers
1. Improve workability using same w/c ratio
2. Increase strength using lower w/c ratio
3. Reduce cost at same w/c ratio by reducing both
water & cement
Compressive
Cement Strength (Mpa)
content Water/Cement Slump
kg/m3 Ratio (mm) 7 day 28 day
Base mix 300 0.62 50 25 37
Improve
300 0.62 100 26 38
consistency
Increase
300 0.56 50 34 46
strength

Reduce costs 270 0.62 50 25.540 37.5

 Plasticizer (Superplasticizer)

 High-range water reducers used same as above:

 Increase slump from 3" to 9"
 Reduce water by 12 - 30% at same slump
 Lasts only 30 - 60 min. with rapid loss of workability
 High strength concrete (10,000 to 12,000 psi)
 Added at the jobsite

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 Mineral Admixtures

1. Fly Ash

2. Silica Fume

3. Slag Cement

4. Natural Pozzolans
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 Fly Ash
 Most commonly used pozzolan in CE structures
 By-product of the coal industry
 Silica glass compound (Silica, alumina, iron oxide,
and lime)
1 μm to more than
100 μm in diameter
 Increases workability
 Extends the hydration
process

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 Silica Fume-Microsilica
 Byproduct of the production of silicon metal in the
electric arc furnace
 5% and 10% by mass of the total cement
 Less than 1 μm in diameter, average diameter of
about 0.1 μm
 decreases permeability
level
 Increases strength and
durability
 Reduces concrete
corrosion
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