CIVL 111 Construction Materials

Prof. Zongjin Li Department of Civil Engineering

Chapter 4 Portland Cement

Portland cement is a type of binder that glue individual filler particles together to form into concrete. A binder can be classified as organic and inorganic binder.
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Chapter 4 Portland Cement --Organic binder

Epoxy Asphalt

: Resin + hardener : Petroleum asphalt original form or cutbacks

Gasoline

Cutbacks =

Kerosene + original asphalt Diesel

Chapter 4 Portland Cement --Inorganic binder

Use water for mixing Nonhydaulic cement: cannot harden in water examples: Gypsum and Lime Hydraulic cement: can harden in water examples: Hydraulic lime, Pozzolan cement, Portland cement

Chapter 4 Portland Cement --Inorganic binder

Gypsum

Gypsum plaster boards

Chapter 4 Portland Cement --Inorganic binder

Natural gypsum, CaSO4.2H2O Heated to about 130-160C, it loses a part of water of crystallization, is known as half-hydrate gypsum (plaster of Paris) CaSO4.0.5H2O ) At about 200C, gypsum loses all its water of crystallization, turn out into anhydrate gypsum. Gypsum-based items should be used only in dry state and in premises of not more than 60% relative humidity

Chapter 4 Portland Cement --Inorganic binder

Raw material: Limestone CaCO3 Shell, coral, chalk Manufacture: burning limestone at a temperature of about 900~1000Clime stone is decomposed to CaO and CO2

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Chapter 4 Portland Cement --Inorganic binder

CaO+H2OCa(OH)2 Ca(OH) 2+CO2+nH2O=CaCO3+(n+1)H2O

Make

mortar for laying masonry and plastering Added to cement mortar to increase plasticity and workability Mix with mud and sand, used for foundation of building, pavement or ground Strengthen soft ground Ski resistance for road
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Chapter 4 Portland Cement --Portland cement

Portland cement is major binder for civil engineering. 4.1 Manufacture of Portland cement 4.2 Chemical composition 4.3 Hydration 4.4 Types of Portland cement 4.5 Porosity of harded cement paste and the role of water 4.6 Basic tests of Portland cement
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Chapter 4 Portland Cement --Portland cement

1756 John Smeaton (England) used lime +pozzolans for construction of Eddystone Lighthouse 1776 James Parker (England) patented hydraulic cement (lime + clay) (1813 Vicat France) 1824 Joseph Aspdin (England) Patented Portland cement 1845 Isaac Johnson burned the first batch of cement

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4.1 Manufacture of Portland cement

Raw materials: Main materials: Limestone(CaCO3) (1000oC) CaO + CO2 Clay(600oC) SiO2 + Al2O3 + Fe2O3 + H2O Additional materials Aluminium & Iron (Al2O3 + Fe2O3) Gypsum (2CaSO4 2H2O)

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4.1 Manufacture of Portland cement

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4.1 Manufacture of Portland cement

Limestone(CaCO3) (1000oC) CaO + CO2 (100) (56) (44) One ton cement contains about 620kg CaO So that CO2 = 620 x 44 / 56 = 487kg Fuel burning produces CO2 450kg One ton cement produces one ton CO2!!

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4.1 Manufacture of Portland cement (3)

Limestone Clay Iron Ore, Bauxite

High temperature (1450oC)

3CaO SiO2 2CaO SiO2 3CaO Al2O3 4CaO Al2O3 Fe2O3

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4.2 Chemical composition (1)

Abbreviation CaO = C Al2O3 = A H2O = H Examples: Ca(OH)2 = CH

SiO2 = S Fe2O3 = F SO3 = S

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4.2 Chemical composition (2)

Major compounds
Compounds Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Oxide C3 S C2S C3A C4AF Color white white white/ grey black Percentage 50% 25% 12% 8%
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4.2 Chemical composition (3)

Minor components

Gypsum, MgO, and alkali sulfates Gypsum: To avoid flash set (barrier effect).
Alkalies

(MgO, Na2O, K2O, free lime) : Increase pH value upto 13.5

- Soundness problem - Alkali aggregate reaction
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Potential Problems

4.2 Chemical composition

MgO:

limited to 4-5%, Free-lime: behaves similarly with MgO SO3: typically <3.5%, if excessive, expansion Alkalis (K2O and Na2O): Limit content 0.6%

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4.3 Hydration (1)

The chemical and Physical processes between portland cement and water. Hydrations of pure cement compounds Calcium silicates 2 C3S + 11 H C3S2H8 + 3 CH 2 C2S + 9 H C3S2H8 + CH C3S2H8 (C-S-H) : 50-65% small Size CHCa(OH) 2 : 20-25% pH value 12
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C-S-H gel

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CH(platelike crystals

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4.3 Hydration (2)

Tricalcium

aluminate C3A + 3 (CSH2) + 26 H C6AS3H32 Ettringite Barrier around C3A : Slows down the hydration of C3A. Needle shaped crystal with large volume expansion. Effects of concrete 1. Forms earlier : Good 2. Forms later : unsoundness a. Aggressive b. High crystal pressure ~240MPa
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AFt(ettrigite)

C-S-H

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4.3 Hydration (3)

Kinetics

and Reactivities Hydration rate order : C3A > C3S > C4AF > C2S Reactivities:

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4.3 Hydration (4)

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4.3 Hydration (5)

Calorimetric

curve of Portland cement

2. Induction 1. Initial Period hydrolysis

3. Acceleration

4. Deceleration

5. Steady Stage

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4.3 Hydration (6)

Five

stages

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4.3 Hydration (7)

Ca2+ C3S
STAGE I

C-S-H C3S
STAGE II (Dormant Period)

CH

C3S

C3 S

+
STAGE V

STAGE III

STAGE IV

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New Understanding

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New Understanding
0.88 0.87 0.86 0.85 0.84 0.83 0.82 0.81 0.80 0.79 0.78 0.77 0.76 0.75 0.74 0.73 0 20 40 60 80 100 120 140 160 180 200 220
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P0.3 P0.4

Electrical resistivity (.m)

L(t(l),(l)) M(t(m),(m)) M(t(m),(m)) L(t(l),(l)) P0.5

M(t(m),(m)) II

L(t(l),(l)) III

Time (min)

4.3 Hydration (8)

Volume Change
Cement Compound Compound C3S C2S C3A CSH2 Portland Cement C2AH8 C3AH6 1950 2520+ 165 150 Density (kg/m3) 3150 3310 3030 2320 3150 Molar Volume* (10-6m3) 72.4 52.4 89.1 74.2 Compound C-S-H CH C6AS3H32 C4ASH12 C4AH13 Hydrated Compound Molar Density Volume* (kg/m3) (10-6m3) 2000# 153 2240 1780 1950 2060 33.2 727 313 265

* Gram Molecular Weight divided by density # Value depends on the water content of C-S-H, which is related to how much intrinsic porosity is included in the structure. The number used was determined for material of composition C3S2H4 which has been dried to 11% rh. + In cement the A in C3AH6 is partially substituted bt F and S, which raises the density to close to 3000kg/m3
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4.3 Hydration (9)

Setting and hardening Setting : Losing plasticity and starting solidification. Initial setting: ~2 hours after mixing. Final setting: ~5-10 hours after mixing. Hardening: Process of gain of strength.

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4.4 Types of Portland cements (1)

ASTM Type I Type II Type III Type IV Type V BSI OPC (ordinary) --RHPC LHPC SRPC

OPC -----Ordinary portland cement RHPC ---Rapid Hardening P.C. LHPC --- Low Heat P.C. SRPC --- Sulfate Resistance P.C.

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4.4 Types of portland cements (2)

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4.4 Types of portland cements

Applications:

Type I --- General purpose Type III --- High early strength Type IV --- Mass concrete (dam, pile) Type V --- Ocean structure

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4.4 Types of portland cements (3)

The temperature rise for the different types of cement

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4.4 Types of portland cements (4)

The strength rise for the different types of cement

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4.5 The role of water (1)

Hydration & Workability Three types of water i. Chemically reacted water ii. Absorbed water iii. Free water

a.

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4.5 The role of water (2)

iii

Hydration process
Water

Gel pores

ii

Evaporable water

Unhydrated cement

Hydration products (gel)

i

Total Solid volume

--- degree of hydration

=0
Fresh paste

0.25

0.50 (a)

0.75

1.0
Complete hydration Capillary pores Gel pores

Increasing hydration

Influence of w/c on formation of Capillary pores

Pores empty

Hydration products (gel)

w/c = 0.30

0.40

0.50 (b)

0.60

0.70
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Increasing w/c ratio

4.5 The role of water (3)

b.

Volume hydration products (cement gel) Vg = 0.68 cm3/g of cement Capillary porosity

c.

w Pc = 0.36 c

cm3/g of cement

d.

The gel / space ratio (X)

(including volume of gel X = volume of gel + volume of

= 0.68 0 .32 + w / c

gel pores ) capillary pores

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4.6 Basic tests of Portland cement (1)

Test

standards

ASTM- American Society for Testing and Materials BSI- British Standard Institution GB- Guojia Biaozhun ( Chinese National Standard)

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4.6 Basic tests of Portland cement

a.

Fineness (=surface area/weight): Represent average size of cement grain Typical value of 350 m2/kg Controls rate of hydration

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Fineness

The measure of the mean size of the grains in cement Two methods for testing fineness Sieve method: using 80m sieve, measuring grain size finer than 80m. Percentage retained Blains method (air permeability method): A given volume of air is passed through a bed of standard porosity at a steady diminishing rate and the time (t) required is measured.

S=K t

S is the total of surface area of the particles in unit weight of material

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Normal consistency
Water requirement of cement paste Definition

The quantity of mixing water to form a standard paste for setting and soundness test It depends upon the compound composition and fineness of cement About 24%~30% for Portland cement

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4.6 Basic tests of Portland cement

b.

Normal consistency test: 10 mm-diameter needle under 300g weight sink into 10 mm in30s.

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4.6 Basic tests of Portland cement

c.

Time of setting: Initial setting:

The paste starts to stiffen and lose the consistency after the mixing with water Initial setting time for (ordinary) Portland cement: not earlier than 45min If the initial setting time is not qualified, the cement can not be used in engineering

1mm-diameter needle penetrate 25 mm

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4.6 Basic tests of Portland cement

c.

Time of setting: Final setting: The paste loses completely its consistency and begins to gain strength No obvious penetration of a 1mm-diameter needle Final setting time : not longer than 6.5h for Portland cement

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4.6 Basic tests of Portland cement

d. Unsoundness: Unsoundness results from excessive or unstable volume change after setting Unsoundness may cause cracking of the paste Unsoundness can be caused by slow hydration of MgO, free lime or later formation of entringite due to their crystal growth pressure

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4.6 Basic tests of Portland cement

d. Unsoundness: Unsoundness test Autoclave expansion test (ASTM C151): -24 hour curing of molded cement paste -Remove specimen from mold and measure its dimension -Place specimen in autoclave -Raise steam pressure to 2 MPa in 45-75 minutes -Maintain 2 MPa for 3 h -Cool down and reduce the pressure in 1.5 h -Meaure the dimension again 15 minutes later -Expansion should less than 0.8%
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4.6 Basic tests of Portland cement

Le Chatelier test (BS 4550: Part 3) Procedures: 1. Fill cement paste 2. Immerse in water (20oC) and measure distance of indicator 3. Boil specimen for one hour and measure distance again after cooling 4. Expansion <10mm (Mainly for free lime)

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4.6 Basic tests of Portland cement

e.

Strength Compressive test on 2 cube S/C ratio of 2.75:1 W/C ratio of 0.485

Pressure

Pressure

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4.6 Basic tests of Portland cement

f.

Heat of hydration test. (BS 4550: Part 3: Section 3.8 and ASTM C186) The hydration is a heat release process Mass concrete higher in the interior, lower at the surface Shrinkage cracks may result from stress need to control temperature Temperature difference between surface and the interior should not be greater than 25 C.
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JAF Calorimeter

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4.6 Basic tests of Portland cement

g.

Other experiments Sulphate expansion (ASTM C452) 25x25x285 mm bar: SO3 > 7% sand/(cement + gypsum) =2.75; water/(cement +gypsum) = 0.485; In water at 23 degree; Expansion < 0.045% after 14 days
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4.6 Basic tests of Portland cement

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4.6 Basic tests of Portland cement

Air content of mortar (ASTM C185) From density difference of measured and theoretical calculated Cement S.G. and U.W. S.G. (gravity) --- 3.15 U.W. (unit weight) --- 1000 1600kg/m3

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