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

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Raw Materials for Cement Manufacture Clinker + Calcium sulfate

interground to produce Portland cement

Different forms of calcium sulfate may be used: • • • CaSO4 Anhydrite Hemihydrate CaSO4·½H2O CaSO4·2H2O Gypsum

Processing Raw Materials
• • • Production begins at the quarry Raw materials → primary crusher → secondary crusher Each crushed raw materials stored separately

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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 3 .

Pyroprocessing Pyroprocessing • • Temperature in kiln reaches 1450oC Burning changes raw mix chemical into clinker 4 .

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 5 .

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 6 .

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 7 .

barge or ship Also in waterproof paper bags 8 .A. Most in bulk by truck.S. rail.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.

70 15 .Chemical Changes during Pyroprocessing CaCO3 (limestone) 2SiO2•Al2O3 (clay.Clinker Chemical Name Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Chemical Formula 3CaO•SiO2 2CaO• SiO2 3CaO•Al2O3 4CaO•Al2O3•Fe2O3 Shorthand Notation C3S C2S C3A C4AF Mass (%) 50 . shale) Fe2O3 (iron oxide) SiO2 (silica sand) ~ 1450oC Kiln CaO•SO3•2H2O Finished cement interground 3CaO•SiO2 2CaO•SiO2 3CaO•Al2O3 4CaO•Al2O3•Fe2O3 Gypsum + Clinker Main Compounds .30 5 .15 9 .10 5 .

15 ~5 … cement also includes gypsum.70 15 .10 5 . 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 10 .Cement Chemical Name Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Calcium sulfate dihydrate Chemical Formula 3CaO•SiO2 2CaO• SiO2 3CaO•Al2O3 4CaO•Al2O3•Fe2O3 CaSO4•2H2O Shorthand Notation C3S C2S C3A C4AF CSH2 Mass (%) 50 .Main Compounds .30 5 .

11 .W. 73-77.04F (Only valid when A/F ≥ 0.73 0.75C3S C3A = 2.87S – 0.60S – 6. Modification of the Bogue Calculation.43F – 2. H.72A – 1. pp.65A – 1.90 63.9 1.64) Taylor.F.” Advances in Cement Research. 1989.15 2.69F C4AF = 3.53 1.85S C2S = 2.53 0.07C – 7.58 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 = 4.07 2. 2.Typical Chemical Composition of Portland Cement Oxide Analysis Oxide % SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 LOI 20. Vol.6 5.

72(5.2.6) – 0.5 C4AF = 3.07 2.73 0.000.90 63.754(58.07) – 1.90) = 8.000 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 12 .87(20.90) = 8.07) – 1.6 5.85(2.69(F 2.6 C3A = 2.000.43(2.07(63.04(2.15 2.000.53) = 58.60(20.65(5.1 SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 LOI 20.1) = 15.90) .53 1.9) – 7.9 1.Compound Composition Oxide Analysis Oxide % Calculated Phase Composition C3S = 4.8 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 ~ 7.6) – 6.58 C2S = 2.53 0.

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 13 .

At this point the cement paste is fluid Modified from Young et al. 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. 1998 Cement Water Time Addition of water 14 . Time starts when the water is first added to the cement.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.

1998 Cement Water Hydration products Time Addition of water 15 . 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.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 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 – it’s still fluid. Modified from Young et al.Properties of Fresh Concrete – Setting & Hardening This is referred to as initial set Modified from Young et al. 1998 Time Cement Water Hydration products Dormant Period Addition of water Initial set Time 16 . 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.

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. 1998 Time Cement Water Hydration products Dormant Period Addition of water Setting Initial set Final set Time 17 .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. Modified from Young et al.

Modified from Young et al.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. 1998 Time Cement Water Hydration products Dormant Period Addition of water Setting Initial set Final set Time 18 .

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 19 .

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 • • 20 .

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 21 .

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 22 .

90 Young et al.60 W/CM 0.30 0.40 0.70 0. with degree of hydration 23 . ∴ Rate decreases with time (i.e.80 0.50 0.e.… with decreasing W/CM 50 100% Hydration 40 Capillary Porosity (%) 30 20 10 0 0. 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 0 1 3 7 14 Age (days) 28 Hydration becomes diffusion controlled – i. rate depends on how fast water can diffuse through the layer of hydrated material that surrounds the cement grain.

Simplified Model of hydrated cement paste after Powers (1958) • • • • Capillary pores 10 – 10.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 μm 10 μm 100 μm 1 mm 10 mm Adapted from Mehta & Monteiro.000 nm Contribute to mass transport (i. 1993 24 .

Stone Test Specimens Structures 10mm 100 m 1m 10 m 100 m 1 km 10 km 100 km 25 .