CE2155 Structural Mechanics and Materials

How long does concrete last?

Materials – 2. Cement

Instructor: GENG Guoqing, Dr., Assistant Professor

Email: ceegg@nus.edu.sg
(please identify yourself as a CE2155 student)

Office: E1A #02-17E

Previously in Introduction

Three requirements of construction material

• Performance
• Availability (economical)
• Sustainability
Admixture

Cement
Coarse
Aggregate
Fine
Aggregate

Concrete

Air
Water
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2. Cement - outline

Portland cement (the most commonly used cement)

• Manufacturing & composition
• Hydration

Supplementary cementitious material (SCM)

• Classification & composition
• Hydration

Standard related to cement

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Portland Cement

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Portland Cement – composition

Raw materials
• 2/3 Limestone/chalk/marl (CaO)

• 1/3 Clay/shale (SiO2, Al2O3)

Cement notation

Alite
Belite

S SO3
(Mindess et al 2003) C CO2
CaCO3 CC 5
Portland Cement – manufacturing

Fineness is critical! 6
Portland Cement – manufacturing

Cement manufacturing contributes to ~8% yearly anthropogenic CO2 emission!

1. Burning fossil fuels:
C + O2  CO2 + heat
2. Decomposition of limestone:
CaCO3  CaO + CO2

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Portland Cement – hydration

Hydration - reaction with water

• Calcium silicates (C3S, C2S)
H = - 500 J/g

H = - 250 J/g

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Portland Cement – hydration

C-S-H, ( ~ C3S2H8 ) CH, ( Ca(OH)2, Portlandite )

• Volume: 50% to 60% of cement paste • Volume: 20% to 25% of cement paste
• High Surface (100 to 700 m2/ g) ----> High Van • Low Van der Walls force,
der Walls Force -----> Strength. • Problems with durability and strength
• Main contributor to the concrete strength

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Portland Cement – hydration

Tricalcium aluminate (C3A)

• C3A reacts with water VERY FAST, leading to flash set.

2C3A + 21H  C4AH13 + C2AH8

• To slow it down, we need sulphate ions (supplied by gypsum).

• Gypsum (CaSO4•2H2O, or CSH2) is important to avoid flash set.

• Too much gypsum will affect setting and hardening.
• The amount required increases with C3A content.

Wait a minute, can we use the fast setting property of C3A?

Yes, fast repair!

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Portland Cement – hydration

C3A hydration slowed down by gypsum:

H = - 1350 J/g

or, AFt

• Ettringite is stable hydration product only while there is an

sufficient supply of sulphate

Sulfate attack:
When gypsum is completely consumed
External sulfate enters
concrete and converts
AFm back to AFt.
Monosulphoaluminate
Why not a problem at
or, AFm early age? 11
Portland Cement – hydration

Ferrite Phase C4AF

• Forms similar hydration products to C3A, but less reactive
AFt
AFm

• Reactions are slower and involves less heat.

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 The rate of hydration during the first few days
Portland Cement – hydration
C3A > C3S > C4AF > C2S

(Mindess et al 2003)

C3A C3S Gypsum completely consumed; C3S provides most of the early strength (in the first 3-4 weeks).
C3A + Ettringite  monosulfate Both C3S and C2S contributes to ultimate strength.
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Portland Cement – hydration

initial setting final setting & initial hardening

(Mindess et al. 2003)

Stage 1 – dissolution Stage 2 – induction (dormant) Stage 3 – Acceleration

Stage 4 – Deceleration Stage 5 - Steady
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Portland Cement – types

Type of Portland Cement (ASTM)

Type I – ordinary portland cement (OPC)
• Most commonly used in construction
Type II – Modified cement
• Moderate sulphate resistance
• Moderate heat of hydration
Type III – Rapid hardening portland cement
• Used for obtaining high early strength, cold
weather concreting, precast concrete
Type IV – Low heat portland cement
• Used for mass concrete, hot weather
concreting
Type V – Sulphate resisting portland cement
• Used in situation where ground water or
soil have high sulphate contents

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Portland Cement – types concrete made with different cements

Strength Heat release

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(Adapted from Concrete Manual, 8th ed. Bureau of Reclamation, Denver, Co, 1975)
Portland Cement – microstructure
Cement paste after hydration
aggregate ITZ
Interfacial transition zone
Porosity
Gel pores (< 10 nm) – space between C-S-H
foils/particles; regarded as an intrinsic part of
the C-S-H.
Capillary pores (> 10 nm) – remnants of
water filled space that exists between the
partially hydrated cement grains. Capillary
pore system is the interconnected network of
pores through which bulk water flow & ion
diffusion occur easily.
paste
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Supplementary Cementitious
Material (SCM)

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Supplementary Cementitious Material (SCM)

also called ‘mineral admixture’

Primary purposes of adding SCM in concrete

• To replace cement (economical, technical and environmental consideration)
• To improve the workability of fresh concrete
• To reduce heat and early temperature rise
• To enhance the durability of hardened concrete

Current practice
• blended cements
• added in concrete mixers as supplementary cementing materials

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SCM – Pozzolanic material

Definition
siliceous or siliceous and aluminous materials which, in themselves, possess little or
no cementitious value but which will, in finely divided form and in the presence of water, react
chemically with calcium hydroxide at ordinary temperature to form compounds possessing
cementitious properties.

• Primary reaction: amorphous SiO2 reacts with CH from

cement hydration.
SiO2 + Ca(OH)2 + H2O  C-S-H

• May reduce early heat evolution & early strength, but

not long-term strength.

• Reduce porosity and permeability, increase durability.

aggregate ITZ paste

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SCM – Pozzolanic material

Natural Pozzolans (Where was the term “Pozzolan” come from?)

History contains many references to ancient concrete,
including in the writings of the famous Roman scholar
Pliny the Elder, who lived in the 1st century A.D. and
died in the eruption of Mt. Vesuvius in A.D. 79. Pliny
wrote that the best maritime concrete was made from
volcanic ash found in regions around the Gulf of Naples,
especially from near the modern-day town of Pozzuoli.

Volcanic ash: SiO2 (and Al2O3)

+  C-S-H
Quicklime: CaO

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SCM – Pozzolanic material

By-product materials

Fly ash – inorganic, non combustible residue

of powdered coal after burning in coal-burning
power plants.
Class F fly ash
produced from bituminous coals
(SiO2+Al2O3+Fe2O3)  70%
Class C fly ash
produced from lignitic and sub-bituminous coals
(SiO2+Al2O3+Fe2O3)  50%

1-300 μm; sphere shape (good for fluidity)

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SCM – Pozzolanic material
Rice husk ash
By-product materials

Silica fume – a by-product in the manufacture of

Silicon metal and alloys .

extremely fine size 10-100 nm: good reactivity, but

paste becomes sticky.

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SCM – Ground Granulated Blast-Furnace Slag (GGBFS)

By-product in the manufacture of iron, obtained by rapid cooling (quenching) the

molten slag using water to form calcium aluminosilicate glass, followed by grinding.

Typical composition
CaO = 35-45%, SiO2 = 32-38%, Al2O3 = 8-16%,
MgO = 5-15%, Fe2O3 <2%, sulfur = 1-2%

GGBFS reacts slowly with water, strength development too slow

• Slags can be activated by Portland cement
• In slag-cement blends, slag also shows pozzolanic behavior
• Products of slag hydration: mixture of C-S-H and AFm (monosulphoaluminate)

Portland Type C Type F SiO2

cement Slag Fly Ash Fly Ash (silica fume, RHA)

Cementitious Pozzolanic
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SCM – effect on workability

Heat of hydration (when substitute cement with SCM)

• Reduce the overall heat of hydration
Substitution vs Addition ?
• Reduce the rate of heat liberation
• Reduce temperature rise in concrete

Workability
• Improve cohesiveness: fly ash and silica fume are particularly beneficial due to their spherical shape
• Addition of fly ash allow ratio of water/(cement + mineral admixture) (w/cm) to be reduced while
maintaining good fluidity
• Adding silica fume makes cement paste sticky

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SCM – effect on strength development

• May reduce early-age strength

• Develop very good strength over a long term
• More reactive pozzolanic materials such as silica fume will reduce
setting time and contribute to early strength

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(Mindess et al 2003)
SCM – effect on durability

• Increase C-S-H & reduce CH leads to more homogenous microstructure

SiO2 + Ca(OH)2 + H2O  C-S-H
• Improve pore structure, reduce overall porosity & pore size
• Increase sulfate resistance
• Reduce chloride diffusion

Blended cement OPC+SCM on-site blending

Advantage Blended in factory, thus better quality control Flexible with changing the portion of SCM and OPC

Disadvantage No flexibility with the portion of SCMs Need experts/lab tests to guarantee the quality

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Standard of Cement

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Standard – ASTM vs BE-EN
ASTM
Portland C 150 – Spec for Portland
cement cements
Blended C 595 – Spec for blended
cements hydraulic cements
C 1157 – Performance Spec for CEM III – blastfurnace cem
blended hydraulic cements
Mineral C 618 – Spec for coal fly ash
admixtures and raw or calcined natural
pozzolans for use in concrete
C 989 – Spec for GGBFS for
use in concrete and mortars
C 1240 – Spec for silica fume
used in cementitious mixtures
BS-EN
197-1: 2000
CEM I – Portland cement
197-1: 2000
CEM II – Portland comp. cem
CEM IV – pozzolanic cem
CEM V – composite cem
450-1: 2005 Fly ash for concrete –
Definition, spec, and conformity
criteria
15167-1: 2006 Ground granulated
blast furnace slag for use in
concrete, mortars, and grouts
13263-1: 2005 Silica fume for
concrete 29
Standard – BE-EN

N – ordinary early strength

R – high early strength 30
Reading material

Zongjin Li, 2011. Advanced concrete technology. Hoboken, New Jersey: John Wiley & Sons, Inc.

Section 2.2.2.1, 2.2.2.2, 2.2.2.3, 2.2.2.5, 2.3.4

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