Wednesday, March 25, 2015

Portland Cement
Chapter 2
Fundermentals of Civil Engineering Material
建 筑 材 料 基 础
2.1 Introduction

‹ Definition: “Cement is a crystalline compound of calcium

silicates and other calcium compounds having hydraulic
properties” (Macfadyen, 2006).
‹ Portland cement was patented by Joseph Aspdin in 1824
and was named after the limestone cliffs on the Isle of
Portland in England. (Kosmatka et al.)

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History

‹ Lime and clay have been used as cementing material

on constructions through many centuries.
‹ Romans are commonly given the credit for the
development of hydraulic cement, the most
significant incorporation of the Roman’s was the use
of pozzolan-lime cement by mixing volcanic ash from
the Mt. Vesuvius with lime.
‹ Best know surviving example is the Pantheon in
Rome

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History

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Types of Cement

‹ Cements are considered hydraulic because of their ability

to set and harden under or with excess water through the
hydration of the cement’s chemical compounds or minerals
‹ There are two types:
9 Those that activate with the addition of water
9 pozzolanic that develop hydraulic properties when the
interact with hydrated lime Ca(OH)2
‹ Pozzolanic: any siliceous material that develops hydraulic
cementitious properties when interacted with hydrated lime.

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Types of Cement

‹ Portland Cement
9 Limestone + Sand + Clay + Iron ore +
heat(1500 C) = PC Clinker + Grinding = PC
powder
9 Hydraulic Cement – hardens in air and under
water
9 Types I, II, III, IV and V
• IA and IIA – blended with air-entraining
agents
• White Portland Cement

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Blended Cements

‹ Blended Cements
9 Type IP or P – Portland Pozzolan Cement
• Moderate heat and moderate sulfate
resistance
–Class C Fly Ash – 15 to 40%
–Class F Fly Ash – 15 to 25% (FDOT)
9 Type IS or S - Portland Blast Furnace Slag
Cement
• Low Heat (FDOT)
–25 – 70%

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Other Types of Cement

‹ High Early Strength Cements - RR

9 Calcium Sulfoaluminate – Rapid Set
9 Calcium Aluminate Cements- Cement Fondu
9 Magnesium Phosphate – SET-45
‹ Oil-Well Cements
‹ Acid Resistant Cements
9 Silicate based
9 Sulfur

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2.2 Production
RAW MATERIALS:
The fundamental chemical compounds to produce cement clinker are:
¾Lime (CaO)
¾Silica (SiO2)
¾Alumina (Al2O3)
¾Iron Oxide (Fe2O3)

Raw materials used in the production of clinker cement

Fly ash: by-product of burning finely grounded coal either for industrial application or in
the production of electricity

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Clinker compounds in Type I portland cement

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SOURCES OF CaCO3
Sedimentary deposits of marine origin (limestone)
Marble (metamorphosed limestone)
Chalk
Marl
Coral
Aragonite
Oyster and clam shells
Travertine
Tuff

LIMESTONES
Originate from the biological deposition of shells and skeletons of plants and animals.

Massive beds accumulated over millions of years.

In the cement industry limestone includes calcium carbonate and magnesium carbonate.
Most industrial quality limestones is of biological origin.

The ideal cement rock 77 to 78% CaCO3, 14% SiO2, 2.5% Al2O3, and 1.75% FeO3.
Limestone with lower content of CaCO3 and higher content of alkalis and magnesia
requires blending with high grade limestone

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Sources of argillaceous minerals

Argillaceous mineral resources:

Clay and shale for alumina and silica
Iron ore for iron

Other natural sources of silica are and alumina are:

Loess, silt, sandstone, volcanic ash, diaspore, diatomite, bauxite

Shales, mudstones, and sandstones are typically interbedded with the

limestone and were deposited as the inland waters and oceans covered the
land masses. Clays are typically younger surface deposits

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 PROCESSING

Lime
Lime
Clay
Clay
Ironore
Iron ore
Grinding mill Grinding mill
kiln cement

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 USES
Uses

Main use is in the fabrication of concrete and mortars

Modern uses
Building (floors, beams, columns, roofing, piles, bricks, mortar, panels, plaster)
Transport (roads, pathways, crossings, bridges, viaducts, tunnels, parking, etc.)
Water (pipes, drains, canals, dams, tanks, pools, etc.)
Civil (piers, docks, retaining walls, silos, warehousing, poles, pylons, fencing)
Agriculture (buildings, processing, housing, irrigation)

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PRODUCTION

Data in thousand metric tons

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2.3 Composition and Hydration of Portland Cement

Shorthand
Compound Formula Fraction(%)
Notation

Tricalcium silicate 3CaO·SiO2 C3S 37~60%

Dicalcium silicate 2CaO·SiO2 C2S 15~37%

Tricalcium aluminate 3CaO·Al2O3 C3A 7~15%

Tetracalcium aluminoferrite 4CaO·Al2O3·Fe2O3 C4AF 10~18%

Gypsum CaSO4·2H2O CSH2 5%

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2.3 Composition and Hydration of Portland Cement

① 2(3CaO⋅SiO2) + 6 H2O = 3CaO⋅2SiO2⋅3H2O + 3 Ca(OH)2

C-S-H gel
② 2(2CaO⋅SiO2) + 4 H2O = 3CaO⋅2SiO2⋅3H2O + Ca(OH)2
C-S-H gel
③ 3CaO⋅Al2O3 + 6 H2O = 3CaO⋅Al2O3⋅6H2O

④ 4CaO⋅Al2O3⋅Fe2O3 + 7 H2O = 3CaO⋅Al2O3⋅6H2O

+CaO⋅Fe2O3⋅H2O

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3CaO⋅Al2O3 + Ca(OH)2 + 12 H2O = 4CaO⋅Al2O3⋅13H2O
The C3A compound, without the presence of gypsum, would react
vigorously with water to produce in a short time a large amount of
hydration products, which can cause setting within a few minutes.

4CaO⋅Al2O3⋅13H2O + 3 (CaSO4⋅2H2O) + 14 H2O =

3CaO⋅Al2O3⋅3CaSO4⋅32H2O + Ca(OH)2
However, in the presence of gypsum, the C3A compound reacts to
form ettringite, which builds up as a layer on the C3A particle and
prevents rapid hydration:

3CaO⋅Al2O3⋅3CaSO4⋅32H2O + 2（3CaO⋅Al2O3）+ 4 H2O =

3(3CaO⋅Al2O3⋅CaSO4⋅12H2O)
Once the gypsum is depleted, ettringite and C3A react further and
monosulfoaluminate is the stable phase in mature concrete.

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Degree of hydration (%)

3 days 7 days 28 days 3 months 6 months

C3A 71.8 76.4 79.7 88.3 90.8

C3S 33.2 42.3 65.5 92.2 93.1

C4AF 64.3 66.0 68.8 86.5 89.4

C2S 6.7 9.6 10.3 27.0 27.4

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Development of structure in the cement paste

1 2 3

1—cement particle；
2—water;
3—gel；
(a) (b) 4—crystal；
3 4 5 6 5—unhydrated cement；
6—pore

(c) (d)
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2.4 Properties of Portland Cement

‹ Specific Gravity
9 About 3.15
9 Determined according to ASTM C188
‹ Fineness
9 Maximum size of the cement particles is
0.09mm
9 85%~95% of the particles are smaller than
0.045mm
9 Measured by determine the percent passing the
0.045mm sieve(No. 325)

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2.4 Properties of Portland Cement

‹ Setting
9 Initialsetting: more than 45 minutes
9 Final setting: less than 10 hours

Final
setting
C-S-H
Initial formation
setting

time
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Measurement of setting time

Influence factor of setting

Testing pole
① content of C3A
② fineness of cement；
③ water to cement ratio；
④ content of mineral
admixture。

mould

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‹ Strengthof cement
9 Actually the term is measured by the
compressive strength of mortar
9 Size 40x40x160mm cement mortar prisms
9 Mixture proportion (by weight)
• Cement: Water: Sand = 1 : 0.5 : 3
9 Cured in water at 20℃±2℃
9 Tested at 3 and 28 days

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Strength Requirement (GB175-2007)

Compressive strength Flexural strength

（MPa） （MPa）
Types
3d 28d 3d 28d

42.5 17.0 42.5 3.5 6.5

42.5R 22.0 42.5 4.0 6.5

52.5 23.0 52.5 4.0 7.0

52.5R 27.0 52.5 5.0 7.0

62.5 28.0 62.5 5.0 8.0

62.5R 32.0 62.5 5.5 8.0

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‹ Volume stability
9 f-CaO
9 CaSO4

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Hydration heat

Hydration Heat，J/g

Compound C3 S C2 S C3 A C4AF

3d 240 50 880 290

Hydration
Heat
28d 377 105 1378 494

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 Cement 300kg/m3
Temperature adiabatic
Rise(℃)

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40 6m
30 3m
2m
20

10
1m

0 2 4 6 8 10 12 14
age(d)
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2.5 Blended Cements and Mineral Admixtures

‹ In modern concrete technology, there is increased

use of concretes in which the cementitious phase
is a blend of portland cement and a mineral
admixture.
‹ Content can be in the range of 20%~70%
‹ Can be added as a separate ingredient to the
concrete in the mixer or can be blended with the
cement in plant.

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‹ Pozzolans

9 Volcanic ash
9 Fly ash
9 SiO2 + Ca(OH)2 + H2O → C-S-H
‹ Blast furnace slag
‹ Silica Fume

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Thank you for your attention!

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