CEMENT

Uses of Portland Cement in Concrete

Buildings Bridges Pavements Concrete block buildings

Other Uses of Cementitious Materials

Mortar for masonry Grout (protection, leveling, bonding, ...) Shotcrete Cement board Soil Stabilization Railroad ties, countertops, moldings...

Portland Cement History

Egyptian Pyramid of Cheops (3000 B.C.)

First Calcareous Cement (CaO based) Calcined gypsum

Roman and Greek Projects First Hydraulic Cements (100 B.C.)

calcined limestone and clay

History of Cement

2000 B.C.: Egyptians used cement in mortar when making Pyramids 27 B.C.: Roman cement made of lime and volcanic ash 1756: Smeaton rebuilt Eddystone Lighthouse 1824: Joseph Aspdin discovered and patented Portland cement

Portland Cement History

Rotary Kiln

Ransome (1886), Edison (1909) U.S. (1910-1940)

Gypsum and Air-Entraining Admixtures

Cement is a Manufactured Material

Portland Cement Gypsum+Portland Cement Clinker (pulverizing) Portland Cement Clinker Calcareous & Clayey Materials (burning) Paste P.C. + Water
Mortar P.C. + Water + Sand Concrete P.C. + Water + Sand + Gravel

RAW MATERIALS OF P.C.

1)

Calcareous Rocks (CaCO3 > 75%) Limestone Marl Chalk Marine shell deposits Argillocalcareous Rocks (40%<CaCO3<75%) Cement rock Clayey limestone Clayey marl Clayey chalk

2)

3)

Argillaceous Rocks (CaCO3 < 40%) Clays Shales Slates Portland cement is made by mixing substances containing CaCO3 with substances containing SiO2, Al2O3, Fe2O3 and heating them to a clinker which is subsequently ground to powder and mixed with 2-6 % gypsum.

CLINKER

GYPSUM

PRODUCTION STEPS
1)

2)

3) 4)

Raw materials are crushed, screemed & stockpiled. Raw materials are mixed with definite proportions to obtain raw mix. They are mixed either dry (dry mixing) or by water (wet mixing). Prepared raw mix is fed into the rotary kiln. As the materials pass through the kiln their temperature is rised upto 1300-1600 C. The process of heating is named as burning. The output is known as clinker which is 0.15-5 cm in diameter.

5)

Clinker is cooled & stored.

Clinker is ground with gypsum (3-6%) to adjust setting time.

6)

7)

Packing & marketting.

~100C free water evaporates. ~150-350C loosely bound water is lost from clay. ~350-650Cdecomposition of claySiO2&Al2O3 ~600Cdecomposition of MgCO3MgO&CO2 (evaporates) ~900Cdecomposition of CaCO3CaO&CO2
(evaporates)

~1250-1280Cliquid formation & start of compound formation. ~1280Cclinkering begins. ~1400-1500Cclinkering ~100Cclinker leaves the kiln & falls into a cooler. Sometimes the burning process of raw materials is performed in two stages: preheating upto 900C & rotary kiln

CHEMICAL COMPOSITION OF P.C.

Portland cement is composed of four major oxides (CaO, SiO2, Al2O3, Fe2O3 90%) & some minor oxides. Minor refers to the quantity not importance.

Common Sources for Raw Materials

Lime

(CaO) - Limestone, shale Silica (SiO2) -Clay, sand, shale Alumina (Al2O3) - Clay, fly ash, shale Iron (Fe2O3) - Clay, iron ore

Portland Cement Production

5/8 rock 1/5 1/10 1/20 1/20

CaO Limestone or calcareous

SiO2 Clay or argillaceous rock Al2O3 Clay or Ore Fe2O3 Clay or Ore CaSO4*2H2O Gypsum

Shorthand Chemistry
C = CaO S = SiO2 A = Al2O3 H = H2O S = SO3 F = Fe2O3

Clinker: artificial mineral containing:

C3S tricalcium silicate C2S dicalcium silicate C3A tricalcium aluminate C4AF tetracalcium aluminoferrite

Clinker Micrographs

Finish Grinding

Interground with ~5% Gypsum 95% material must pass #325 Sieve

How are Portland Cements different? Four Main Compounds

Tricalcium Silicate (C3S)

Dicalcium Silicate (C2S)

Tricalcium Aluminate (C3A)

Tetracalcium Aluminoferrite (C4AF)

C3S

Tri Calcium Silicate

3CaO.SiO2 -Alite
Provides Early strength development

70% reacts by 28 days

Usually present at 40-70%

If >65% difficult to burn

C2S

Dicalcium Silicate

2CaO.SiO2 -Belite
Provides late strength development 30% reacts by 28 days

Present at 20-40%
Under-burning can result in higher C2S contents in cement

C3A

Tricalcium Aluminate

3CaO.Al2O3 -Celite
Provides heat generated in hydration (10 to 15 F per 100 lb. cement) High C3A not as resistant to sulfate attack Little contribution to strength

C4AF Tetracalcium
Aluminoferrite

4CaO.Al2O3.Fe2O3 -Felite
Governs the color of the cement Present at 1-10% Iron facilitates formation of other compounds-acts as a flux

Little contribution to strength

Oxide CaO

Common Name Lime

Abbreviation C

Approx. Amount (%) 60-67

SiO2
Al2O3 Fe2O3 MgO Na2O K2O SO3

Silica
Alumina Iron-oxide Magnesia Soda Potassa Sulfuric Anhydride

S
A F M N K

17-25
3-8 0.5-6 0.1-4

0.2-1.3
1-3

CaOlimestone SiO2-Al2O3Clay Fe2O3Impurity in Clays SO3from gypsumnot from the clinker

The amount of oxides in a P.C. Depend on the proportioning of the raw materials and how well the burning is done in the kiln. The chemical composition is found by chemical analysis. A typical analysis of O.P.C.
C S A F M N K Free C Total 63.6 20.7 6 2.4 2.1 2.6 0.1 0.9 1.4 99.8

Insoluble residue=0.2 Loss on ignition=1.4

CaO (C), SiO2 (S), Al2O3 (A) & Fe2O3 are the major oxides that interact in the kiln & form the major compounds. The proportions of these oxides determine the proportions of the compounds which affect the performance of the cement. SO3comes largely from gypsum P.C. alone sets quickly so some gypsum is ground with clinker to retard the setting time.

If too much gypsum is included it leads to distruptive expansions of the hardened paste or concrete.
ASTM C 150 SO3 3% in O.P.C.

MgO+H2OMH C+HCH volume expansion & cause cracking. ASTM C 150 M<6% free C < 3%

Alkalies (Na2O & K2O) may cause some dificulties if the cement is used with certain types of reactive aggregates in making concrete. The alkalies in the form of alkaline hydroxides can react with the reactive silica of the aggregate & resulting in volume expansion after hardening. This process may take years. Na2O & K2O 0.6%

Insoluble Residue: is that fraction of cement which is insoluble in HCl. It comes mainly from the silica which has not reacted to form compounds during the burning process in the kiln. All compounds of P.C. is soluble in HCl except the silica. The amount of I.R., determined by chemical analysis, serves to indicate the completeness of the reactions in the kiln. ASTM C 150 I.R. 0.75%

Loss on Ignition (L.O.I.): is the loss in weight of cement after being heated to 1000C. It indicates the prehydration or carbonation due to prolonged or improper storage of cement & clinker. If cement is exposed to air, water & CO2 are absorbed & by heating the cement upto 1000C loose these two substances. ASTM C 150 L.O.I. 3% for O.P.C.

COMPOUND COMPOSITION OF P.C. (OR CLINKER)

Oxides interact with eachother in the kiln to form more complex products (compounds). Basically, the major compounds of P.C. can be listed as:
Name Chemical Formula 3CaO.SiO2 2CaO.SiO2 3CaO.Al2O3 4CaO.Al2O3.Fe2O3 Abbreviations C3S C2S C3A C4AF

Tri Calcium Silicate Di Calcium Silicate Tri Calcium Aluminate Tetra Calcium Alumino Ferrite

The degree to which the potential reactions can proceed to equilibrium depends on:
Fineness of raw materials & their intermixing. The temperature & time that mix is held in the critical zone of the kiln. The grade of cooling of clinker may also be effective on the internal structure of major compounds.

1)

2)

3)

There are also some minor compounds which constitute few %, so they are usually negligible. Moreover, portland cement compounds are rarely pure. For example in C3S, MgO & Al2O3 replaces CaO randomly. C3SALITE & C2SBELITE Ferrite Phase: C4AF is not a true compound. The ferrite phase ranges from C2AF to C6AF. *C4AF represents an average.

Methods of Determining Compound Composition

1)

Each grain of cement consists of an intimate mixture of these compounds. They can be determined by: Microscopy X-Ray Diffraction But due to the variabilities involved the compound composition is usually calculated using the oxide proportions. Calculations (Bouges Equations)

2)

3)

P.C.+waterthe compounds in the cement undergo chemical reactions with the water independently, and different products result from these reactions.
C3S C2S
Slow Low Poor Good

Influence of Compound Composition on Characteristics of P.C.

C3A
Fast Very High Good Poor

C4AF
Moderate Moderate Poor Poor

Rate of Reaction Heat Liberation Early Cementitious Value Ultimate Cementitious Value

Moderate High Good Good

ASTM Type & Name of P.C. C3S

Average Compound Composition C2S C3A C4AF

Type I - O.P.C.
Type II - Modified Type III - High Early Strength Type IV - Low Heat P.C. Type V - Sulfate Resistant P.C.

49
46 56 30 43

25
29 15 46 36

12
6 12 5 4

8
12 8 13 12

General Purpose
For Moderate Heat of Hydration C3S&C3A increased, C2S decreased C2S increased Limit on C3A5%, 2C3A+C4AF25%