Module III:

Materials for Civil and

Construction Engineers
Chapter 6: PCC
Lecture 19, 20 – Cement manufacturing, chemistry,
types and properties

1
Learning Objectives of Concrete Block
• You will be able to classify cement types and identify underlying phases
and minerals
• You will be able to relate cement chemistry/composition to concrete
performance
• You will be able to interpret cement and concrete properties in relation
to performance of structures
• You will be design a concrete mixture for performance
• You will be able to summarize critical steps in batching, mixing, and
transportation of concrete
• You will be able to identify critical steps and issues during placing and
finishing of concrete
2
What is Concrete?
In its simplest form, concrete is a mixture of coarse and fine
aggregates bound together with cement “glue” created by mixing
water and hydraulic cement

Source: FHWA – Toward Sustainable Pavement Systems (2015)

Hydraulic cement is a terminology for all
cementitious materials (CM)
Hydraulic cement used today is NOT pure Portland cement
defined by AASHTO M85 and ASTM C150
Cementitious Materials

Hydraulic Cements Pozzolans or materials with

pozzolanic characteristics
Portland cement
Blended cement
Supplementary Cementitious Ground granulated blast furnace GGBF slag
Materials (SCMs) (GGBF) slag Class C fly ash
Class C fly ash Class F fly ash
Natural pozzolans (calcined clay,
calcined shale, metakaolin)
Silica fume 4
Definitions
• Cementitious materials – all cements and pozzolans
• Hydraulic cement – material that sets and hardens by a series
of nonreversible chemical reactions with water (hydration
process)
• Portland cement – a specific type of hydraulic cement
primarily composed of hydraulic calcium silicates (C-S-H)
• Pozzolan – finely divided material that reacts with cement and
water to form cementitious compounds
• Supplementary cementitious materials (SCM) – cements and
pozzolans other than portland cement 5
Primary Markets High-rise buildings

Pavements

Bridges
Low-rise buildings
Turning Point
• 18th century – John Smeaton
• Use of hydraulic cement versus Non-
hydraulic cement
• An impure, soft limestone containing clay
minerals made the best hydraulic cement

Source: PCA
Joseph Aspdin patented portland cement
(1824)
The name came from the resemblance to
limestone quarried from the Isle of Portland
(England), which had been used as a premier
building stone since Roman times.

Portland cement is a fine powder Source: PCA

Essentials of Quality Concrete
• Suitable materials and proportions
• Materials characteristics
• Water-cementitious materials ratio
• Adequacy of curing
• Design-Workmanship-Environment

Source: PCA
Cement Raw Materials (LISA G.)
• Lime (Calcium) (CaO) (~65%)
– Limestone, shale
• Iron (Fe2O3) (~3%)
– Clay, iron ore, blast furnace dust
• Silica (SiO2) (~21%)
– Clay, sand, shale Quarried limestone

• Alumina (Al2O3) (~6%)

– Clay, fly ash, shale, bauxite
• Gypsum (CaSO4.2H2O) (~3%)
10
Source: PCA
Manufacturing Process Step-By-Step
Aerial View of Cement Plant
1. Raw meal preparation
2. Proportioning and
grinding
3. Clinker production
4. Finish grinding

Bags stored for small jobs Trucked in bulk for big jobs
Source: PCA
1. Raw Meal Preparation
Selected raw materials are transported from the quarry and
crushed to the size of a typical gravel.

Source: PCA
2. Proportioning and Grinding
Blend the proportions of the raw materials for the desired
chemical composition and grind

Source: PCA
3. Pyroprocessing: Clinker Production
Ground raw materials are fed into preheater and then upper end
of a rotary kiln for calcination to take place and clinker production

Source: PCA
Balancing Inputs-Outputs in Cement
Production
• We start with ~1600 kg raw
material to obtain 1000 kg
cement
• Where does the raw meal go?

Calcination:
CaCO3 -> CaO (free lime) + CO2
~553 kg CO2 per 1000 kg cement
production due to calcination

15
Chaote (2003) – Energy and emission reduction opportunities for the cement industry
Cement Kiln
Raw materials reach approximately 1450 C in a 20-25 ft in
diameter and 150-300 ft long kiln rotating 1-3 times per min

Source: PCA
Final product from the kiln is Clinker
Clinker in the size of marbles or coarse sand is formed through
chemical reactions by burning raw materials in the kiln

This particular clinker is about 20 mm

diameter.

Source: PCA
Kiln Reactions
1. First stage is water removal from the powder at 700 C
2. Calcination starts (700-900 C) CaCO3 → CaO (free lime) + CO2
3. CaO and Silica reaction to form first calcium silicates (C2S:belite)
Kiln Reactions
4. Calcination is completed and material becomes sticky. CaO continues to
react with silicates to form small C2S crystals (1150-1200 C)
5. Liquid phase forms and fee CaO and expanding crystals of C2S forms a
new phase called C3S (alite)
Kiln Reactions
6. Temperature peaks. C2S continues to react with the free CaO to form more alite
increasing size and amount of C3S (1350-1450 C)
7. Nodules form as the liquid agglomerates crystals together forming clinker
8. Upon cooling C3A and C4A crystals form
4. Finish Grinding (final stage)
Clinker is rapidly cooled and then pulverized into a fine material
with gypsum and sometime limestone (up to 5% by mass)
Gypsum regulates setting time of concrete
• Without the addition of gypsum, flash setting would occur and
concrete cannot be placed
• Use of sulfates also improves shrinkage and strength development
Cement Chemist’s Shorthand
A = Al2O3 - alumina
C = CaO - calcium oxide (aka free lime)
F = Fe2O3 - ferric oxide
H = H2O - water
M = MgO - magnesia
S = SiO2 - silica
S! = SO3 - sulfate
Primary Phases
• The following four phases make up
85-90% of cement by mass
– Tricalcium silicate – C3S (50-70%)
– Dicalcium silicate – C2S (10-25%)
– Tricalcium aluminate – C3A (10%)
– Tetracalcium aluminoferrite – C4AF Source: PCA
(15%) Lighter color angular crystals
• Gypsum, limestone and other of Alite-C3S

grinding aids make up the rest Rounded darker crystals

are Belite-C2S
What does each phase do?
• C3S = 3CaO·SiO2 Calcium Silicates
– Hydrates and hardens rapidly and is largely responsible for initial set and early
strength
• C2S = 2CaO·SiO2 Calcium Silicates
– Hydrates and hardens slowly, contributing largely to strength increase at ages
beyond one week
• C3A = 3CaO·Al2O3 Aluminates
– Liberates a large amount of heat during the first few days of hydration and
hardening
• C4AF = 4CaO·Al2O3· Fe2O3 Aluminates
– Resulting from the use of iron and aluminum raw materials to reduce the
clinkering temperature during cement manufacture.
Hydration
• Hydration is the reaction between water and cement
• New products are formed = hydration products
• Aggregates are glued together by the hydration products

Source: PCA
Stages of Hydration, Setting, Hardening
• Unhydrated cement grains are
dispersed in water (plastic material)
• Hydrated products grow and start
filling space between adjacent grains
to form a continuous solid network
(initial set to final set)
• Finally, calcium-silicate-hydrate forms
dense, bonded aggregations
between the crystalline phases and
the remaining unhydrated cement
grains (rigid material)
Source: PCA27
Hydration Reactions
Hydration of calcium silicates:
Moderate Rate
C3S + H2O → C-S-H + 3CH + 500 J/g

Slow Rate
C2S + H2O → C-S-H + CH + 260 J/g

Calcium Silicate Hydrate Calcium Hydroxide

• Heart of concrete • Weak and soluble
• Very strong and dense
1. Calcium-Silica-Hydrates (C-S-H)
• Principle hydration product
• Occupies 50-60% of total hydrated cement paste (HCP)
• Non-crystalline, amorphous phase
• Very strong and dense

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2. Calcium Hydroxide (CH)
• Occupies 20-25% of total HCP volume
• Crystalline with plate-like prisms
• Lower strength due to weak Van der Walls

Source: PCA 30
Other Reactions
Hydration of aluminates
Very Fast Rate
C3A + Gypsum+ H2O → Ettringite + Heat

A source of sulfate Forms seconds after water is added

• Needle shaped crystals

C3A + Ettringite + H2O → MSH + 1350 J/g

Monosulfate hydrate
• Plate shape crystals
3. Ettringite (Calcium Sulfoaluminate Hydrate)
• Rapidly forms with water addition when
sulfates are present (i.e. gypsum)
• Ettringite slows the reaction of remaining
C3A and allows for dormant period for
placement
• If too much ettringite is formed, early Source: PCA

stiffening called false set may occur

• False set can be recoverable with additional
mixing
32
4. Calcium Monosulfoaluminate
(monosulfates)
• Occupies 15-20% of total HCP volume
• Plate-like crystals
• Little contribution to strength
• However, presence affects:
– Setting
– Rate of hardening
– Long-term stability
Source: PCA

33
Flash setting vs. False setting
• Too much ettringite formation (false setting)
– Can be recovered with additional mixing
– Placement problems
• Too little gypsum and cements high in C3A (flash setting)
– Permanently sets too fast
– Very undesirable
• Too much gypsum, long delays in setting
• Therefore, amount of gypsum needs to be carefully regulated

34
Heat of Hydration

Rapid
Plastic & strength and
Continuous strength
Workable modulus
gains development
Hardened Cement Paste
• Identify phases…
Hydration Products Relative Volumes
Relative Reactivity of Cement Phases
C3A > C3S > C4A > C2S

Source: PCA

Overall” has a composition of 55% C3S, 18% C2S, 10% C3A, and 8% C4AF
Less
workable
mixes
0.4
Water to Cementitious
Lower
strength

Materials Ratio
(w/c)

39
Water is a key ingredient for pastes and
concrete
• Makes the concrete plastic and workable
• Phases in clinker chemically reacts with water
• Amount of water added controls durability and strength

No more water than is absolutely necessary to make the

concrete plastic and work should be used.

40
Significance of Water
• Cement paste cylinders of
equal mass and equal
cement content, but mixed
with different water to
cement ratios
– Which one has higher w/c?
– Why are volumes different?
– Which one has lower
strength?

Source: PCA
Advantages of Optimal Water Content
• Increased compressive and
flexural strength
• Lower permeability and
increased water tightness
• Increased durability and
resistance to weathering
• Better bond between concrete
and reinforcement
• Less volume change from Ten cement-paste cylinders with water-cement ratios
Source: PCA

wetting and drying from 0.25 to 0.70 and equal amount of cement.

Increased water dilutes the effect of the cement paste,

increasing volume, reducing density, and lowering
strength.
Types of Portland Cement
• Cements are manufactured to meet ASTM C150/AASHTO M
85
– Type I: Normal
– Type II: Moderate sulfate resistant
– Type III: High early strength
– Type IV: Low heat of hydration
– Type V: High sulfate resistant
Type I
General purpose suitable for standard applications

Source: PCA
Type II
• Necessary protection against moderate
sulfate attack
• Structures exposed soil or groundwaters with
sulfate concentrations higher than normal but
not too severe
• Type V is for conditions with severe sulfate
concentrations

Source: PCA
Sulfate Attack Protection
Mechanism:
• Sulfate in soil or water permeates in concrete and reacts with
hydrated C3A phases
• As a result, paste expands and cause cracking
Solution:
• Type II and V cements has low C3A (less than 8%)
• Use low water/cement ratio to achieve low permeability to
prevent sulfate attack

46
Type III
• Provides strength at an earlier period than
normal
• Cold weather concrete, fast track paving,
and rapid form removal for precast
concrete

Source: PCA
Type V
• Used in concrete exposed to severe sulfate environments

Source: PCA
Rating: Poor Rating: Good
Type V, w/c = 0.65 Type V, w/c = 0.37
Composition Statistics
Blaine
Limestone
Type C3S C2S C3A C4A Fineness
content
m2/kg

I 57.5 13.0 9.3 7.6 375-440 3.4

II 59.1 12.7 6.4 10.3 305-471 3.1

III 58.0 13.6 7.3 9.2 365-723 3.0

IV 42.2 31.7 3.7 15.1 319-362 -

V 59.2 14.6 4.1 11.6 302-551 3.2

Compressive Strength

Source: PCA
Blended Hydraulic Cements

Silica fume Calcined clay

Slag

Blended cement
Fly ash
Clinker

Portland cement Gypsum

Source: PCA
Blended Hydraulic Cements
• Produced by intergrinding clinker or blending cement with two
or more types of fine materials (supplementary cementitious
materials [SCM])
• ASTM C595/AASHTO M 240
– Type IS (X): Portland blast-furnace slag cement
– Type IP (X): Portland-pozzolan cement
– Type IL (X): Portland-limestone cement
– Type IT (AX)(BY): Ternary blended cement

(X), (Y): Mass percentages of SCMs

Subcategories to produce special
cements
• A- air-entraining
• MS- moderate sulfate resistant
• HS- high sulfate resistant
• MH- moderate heat of hydration
• LH- low heat of hydration
• R- resistant to alkali-silica reactivity
Physical Properties of Cement
• Compressive strength • Consistency
• Setting time • Heat of hydration
• Early stiffening • Loss on ignition
• Particle size and • Density and relative
fineness density
• Soundness • Bulk density
Compressive Strength
• 50 mm cubes are tested

Source: PCA
Compressive Strength
Fineness
• Blaine air permeability test – ASTM C204
• Cements with finer particles have more surface area in square
meters per kilogram of cement.
Setting Time
• Measures the time penetration resistance of a needle is reached
• Initial set at 3.5 MPa and final setting at 27.5 MPa

Source: PCA
Consistency
• Relative mobility of a freshly mixed cement paste
• Mixed to reach to a consistency defined by 10 1 mm

Source: PCA