Portland Cement

First patent in 1824 by Joseph Aspdin

Portland stone

Portland cement So named because it resembles Portland stone a quarried limestone from Portland (UK) which had an excellent reputation as a building material

Raw Materials for Cement Manufacture

Lime (CaO) Limestone Shale Marl Chalk

Silica (SiO2) Clay Shale Marl Sand

Alumina (Al2O3) Clay Shale Ore refuse

Iron (Fe2O3) Clay Iron ore Mill scale

(Various waste materials and industrial by-products are also used)

These materials are blended in the appropriate proportions and the raw mix is fed into the kiln to make clinker

Raw Materials for Cement Manufacture Clinker + Calcium sulfate

interground to produce Portland cement

Different forms of calcium sulfate may be used: CaSO4 Anhydrite Hemihydrate CaSO4H2O CaSO42H2O Gypsum

Processing Raw Materials

Production begins at the quarry Raw materials primary crusher secondary crusher Each crushed raw materials stored separately

Processing Raw Materials

Production begins at the quarry Raw materials primary crusher secondary crusher Each crushed raw materials stored separately Raw materials proportioned and blended Blended material ground to a powder in mills Homogenized in blending silos Dry Process Fed into kiln

Processing Raw Materials

Production begins at the quarry Raw materials primary crusher secondary crusher Each crushed raw materials stored separately Raw materials proportioned and blended Blended material ground Mixed with a water to form a slurry Blended Fed into kiln Wet Process

Pyroprocessing

Pyroprocessing
Temperature in kiln reaches 1450oC Burning changes raw mix chemical into clinker

Pyroprocessing
Temperature in kiln reaches 1450oC Burning changes raw mix chemical into clinker

More plants have preheater and better recycling of hot gases reduced kiln length

Pyroprocessing
Temperature in kiln reaches 1450oC Burning changes raw mix chemical into clinker Clinker cooled Clinker and gypsum stored separately Fed into grinding mills

Process of Clinker Production

Clinker nodules

Cooling grate

Finishing, Storing (Homogenization) & Transportation

Clinker & gypsum are interground Finished cement is stored (and blended) in silos Shipped by bulk tanker or bags

Finish Grinding
Clinker Combined material

Gypsum

gypsum hemihydrate anhydrite

CaSO4 2 H 2O CaSO4 1 H 2O 2
CaSO4

Combined material

Finish Grinding
Ball Mill

Finished cement

Finish Grinding

Finished cement stored in large silos Final blending of product carried out to improve uniformity Ready for distribution

Transportation & Packaging

~ 100 Mtonnes per annum shipped through U.S.A. Most in bulk by truck, rail, barge or ship Also in waterproof paper bags

Chemical Changes during Pyroprocessing CaCO3 (limestone) 2SiO2Al2O3 (clay, shale) Fe2O3 (iron oxide) SiO2 (silica sand)
~ 1450oC

Kiln

CaOSO32H2O
Finished cement interground

3CaOSiO2 2CaOSiO2 3CaOAl2O3 4CaOAl2O3Fe2O3

Gypsum + Clinker

Main Compounds - Clinker

Chemical Name Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite

Chemical Formula 3CaOSiO2 2CaO SiO2 3CaOAl2O3 4CaOAl2O3Fe2O3

Shorthand Notation C3S C2S C3A C4AF

Mass (%) 50 - 70 15 - 30 5 - 10 5 - 15

Main Compounds - Cement

Chemical Name Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Calcium sulfate dihydrate

Chemical Formula 3CaOSiO2 2CaO SiO2 3CaOAl2O3 4CaOAl2O3Fe2O3 CaSO42H2O

Shorthand Notation C3S C2S C3A C4AF CSH2

Mass (%) 50 - 70 15 - 30 5 - 10 5 - 15 ~5

cement also includes gypsum.

Shorthand Notation
Oxide CaO SiO2 Al2O3 Fe2O3 MgO K2O Na2O SO3 CO2 H2O Shorthand C S A F M K N S C H sulfate carbonate water Common Name lime silica alumina ferric oxide magnesia alkalis

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Typical Chemical Composition of Portland Cement

Oxide Analysis
Oxide %

SiO2 Al2O3 Fe2O3 CaO

MgO K2O Na2O SO3 LOI

20.6 5.07 2.90 63.9

1.53 0.73 0.15 2.53 1.58

90 95% (in main compounds)

Minor compounds Na & K involved in ASR Too much MgO leads to unsoundness SO3 controls setting Too much SO3 may be harmful

+ other trace elements

Compound Composition

Bogue Composition C3S = 4.07C 7.60S 6.72A 1.43F 2.85S C2S = 2.87S 0.75C3S C3A = 2.65A 1.69F C4AF = 3.04F (Only valid when A/F 0.64)

Taylor, H.F.W. 1989. Modification of the Bogue Calculation. Advances in Cement Research, Vol. 2, pp. 73-77.

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Compound Composition
Oxide Analysis
Oxide %

Calculated Phase Composition C3S = 4.07(63.9) 7.60(20.6) 6.72(5.07) 1.43(2.90) - 2.85(2.53) = 58.1

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 LOI

20.6 5.07 2.90 63.9 1.53 0.73 0.15 2.53 1.58

C2S = 2.87(20.6) 0.754(58.1) = 15.6 C3A = 2.65(5.07) 1.69(F 2.90) = 8.5 C4AF = 3.04(2.90) = 8.8 Bogue Composition: C3S C2S C3A C4AF 58% 16% 9% 9%

Fineness of Portland cement (PC) Surface area (SA) controls rate of hydration SA increases with fineness Fineness carefully controlled Typically particle sizes are between 1 to 100 microns with an average size of 10 microns (finer for Type HE Type III) 1 kg of PC has ~ 7,000,000,000,000 particles 1 kg of PC has a surface area of ~ 400 m2 (~ 550 m2 for Type HE) It is usual to measure the surface area of the cement rather than its particle size distribution Surface area measured by: Blaine air-permeability apparatus Wagner turbidemeter

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Density
Range= 3100 to 3250 kg/m3 Average = 3150 kg/m3 (196 lb/ft3) Not indicator of quality Used for mixture proportioning calculations

Relative density (specific gravity) = 3.15

Bulk Density
Bulk density of cement varies between 830 kg/m3 (52 lb/ft3) and 1650 kg/m3 (103 lb/ft3).

Cement Hydration Reactions

2C3S 2C2S C3A 2C3A 3C3A C4AF + + + + + + 11H 9H + + + + C3S2H8 C3S2H8 3CSH2 C6AS3H32 CH 2CH + + 3CH CH C6AS3H32 3C4ASH12 C4AH13 C6AFH12

26H 4H 12H 10H

= you will not be tested on these equations

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For the purposes of this course:

Cement + water C-S-H + CH + other phases

Alumino-ferrite phases: Ultimate fate of sulfates impact on durability (esp. sulfate attack) dealt with in CE5503

Calcium-silicate hydrate: The glue that holds things together and is mainly responsible for strength and impermeability

Calcium hydroxide: Little cementitious properties easily leached involved in some deterioration processes represents approx 25% of hydration products

Properties of Fresh Concrete Setting & Hardening

The setting and hardening of portland cement can be explained using a simple model showing unhydrated cement grains dispersed in water. Time starts when the water is first added to the cement. At this point the cement paste is fluid
Modified from Young et al, 1998

Cement Water

Time Addition of water

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Properties of Fresh Concrete Setting & Hardening

A chemical reaction occurs between the water and cement the reaction is called hydration

Modified from Young et al, 1998

Cement Water Hydration products

Time Addition of water

Properties of Fresh Concrete Setting & Hardening

Volume of hydrates > volume of unhydrated cement Increase in solid volume Decrease in original water-filled space Eventually the hydration products will connect adjacent grains and a continuous solid network is formed.
Modified from Young et al, 1998

Cement Water Hydration products

Time Addition of water

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Properties of Fresh Concrete Setting & Hardening

This is referred to as initial set

Modified from Young et al, 1998

Cement Water Hydration products

Time Addition of water Initial set

Properties of Fresh Concrete Setting & Hardening

Rigidity

Between the addition of water and just before initial set occurs the paste has little rigidity its still fluid. If the rigidity of the paste was plotted against time there would be only a small increase during this period which is sometime referred to as the dormant period.
Modified from Young et al, 1998

Time
Cement Water Hydration products

Dormant Period Addition of water Initial set

Time

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Properties of Fresh Concrete Setting & Hardening

Rigidity

Plastic Material (Handling Period)

During this period the paste is still plastic and the concrete can still be handled

Modified from Young et al, 1998

Time
Cement Water Hydration products

Dormant Period Addition of water Initial set

Time

Properties of Fresh Concrete Setting & Hardening

Rigidity Transition (Setting) Plastic Material (Handling Period)

As more hydration products are formed and the solid matrix becomes more dense and rigid.

Modified from Young et al, 1998

Time
Cement Water Hydration products

Dormant Period Addition of water

Setting Initial set Final set

Time

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Properties of Fresh Concrete Setting & Hardening

C-S-H bridging the gap between cement grains Rigid structure develops

Photomicrograph courtesy of Lafarge

Properties of Fresh Concrete Setting & Hardening

Rigidity Transition (Setting) Plastic Material (Handling Period)

Paste transforms from a fluid to a solid.

Modified from Young et al, 1998

Time
Cement Water Hydration products

Dormant Period Addition of water

Setting Initial set Final set

Time

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Properties of Fresh Concrete Setting & Hardening

Rigidity Transition (Setting) Plastic Material (Handling Period) Rigid Material

Solid material with mechanical properties such as strength and stiffness.

Time
Cement Water Hydration products

Dormant Period Addition of water

Setting Initial set Final set

Hardening

Time

Properties of Fresh Concrete Setting & Hardening

Rigidity Transition (Setting) Plastic Material (Handling Period)
Final Set Initial Set Modified from Young et al, 1998

Rigid Material

Time
Cement Water Hydration products

Dormant Period Addition of water

Setting Initial set Final set

Hardening

Time

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Setting Time

Initial Set

Time from moment water is added until the paste ceases to be fluid and plastic Time from moment water is added for the paste to acquire a certain degree of hardness

Final Set

Setting Time

Vicat Needle ASTM C 191 Standard Test Method for Time of Setting of Hydraulic Cement by Vicat Needle Initial set occurs when needle penetrates 25 mm (1 inch) into paste Final set occurs when there is no visible penetration

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Properties of Fresh Concrete Setting & Hardening

Penetration resistance (MPa)

40

6000

Penetration resistance (psi)

30

Final set

4000

20 2000 10 Initial set 0 0 2 4 6 8 0

Time (hours)

W/CM = 0.33 by mass Volume of Water Volume of Cement

W/CM = 0.61 by mass

=1

Volume of Water Volume of Cement

=2

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Original water-filled spaces: Capillary Porosity Low W/CM: Low capillary porosity Small pores poorly connected Low permeability High strength High W/CM: High capillary porosity Large pores - well connected High permeability Low strength

Capillary Porosity decreases with age (degree of cement hydration) and

100

Degree of hydration Degree of Hydration (%)

60

50 50 40 Capillary porosity 30

Capillary Porosity (%)

0 0 20 20 30 40 50 60 Curing time (days)

20

Young et al. 1998

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 with decreasing W/CM

50 100% Hydration 40 Capillary Porosity (%)

30

20

10

0 0.30 0.40 0.50 0.60 W/CM 0.70 0.80 0.90

Young et al. 1998

Concrete will continue to gain strength as long as:

Strength (MPa)

40

100 Degree of hydration (%)

some unhydrated cement remains concrete remains moist Temperature is above freezing The 28-day strength is used to characterize a concrete mix Maximum strength and 100% hydration approached asymptotically

30

75

20

50

35MPa (5000 psi)

25

10

0 1 3 7 14
Age (days)

28

Hydration becomes diffusion controlled i.e. rate depends on how fast water can diffuse through the layer of hydrated material that surrounds the cement grain. Rate decreases with time (i.e. with degree of hydration

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Simplified Model of hydrated cement paste after Powers (1958)

Capillary pores 10 10,000 nm Contribute to mass transport (i.e. permeability & ionic diffusion Smaller pores (10-50 nm) contribute to drying shrinkage at higher RH

C-S-H gel contains approx 26% porosity Very small gel pores < 10 nm Little contribution to mass transport Contribute to drying shrinkage and creep

Dimensional Range of Solids and Pores in Hydrated Cement Paste

Interparticle spacing between C-S-H sheets Entrapped air void

Hexagonal crystals of Ca(OH)2

Entrained air bubbles Capillary Voids Cement grains Sand & stone

1 nm

10 nm

100 nm

1 m

10 m

100 m

1 mm

10 mm

Adapted from Mehta & Monteiro, 1993

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Stone

Test Specimens

Structures

10mm

100 m

1m

10 m

100 m

1 km

10 km

100 km

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