C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S
CEMENT TECHNOLOGY CEMENT TECHNOLOGY
Cement Chemistry Cement Chemistry C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Cement Process - Key Trends Capital Intensive, ~$200/t, 1mtpa, ~$200,000,000 Environmental Pressure (ISO 14001) Quarry Dust Noise SOx, NOx, CO 2 , VOC Leachates ~15% of capital is for environmental protection. Energy intensive 0.1-0.2 tonnes of coal per tonne of cement 100-130 kWhs per tonne of cement Relatively low price commodity , say $40-100/tonne C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Cement Process Raw material extraction (or procurement) Proportioning Grinding Blending Drying - Preheating - Calcining - Sintering Cooling Cement Grinding Cement Storage Cement Despatch C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Raw Material Source of Limestone or Chalk, CaCO3 CaO Shale or Clay Al 2 O 3 .Fe 2 O 3 .SiO 2 Iron Oxide Fe 2 O 3 Bauxite Al 2 O 3 .Fe 2 O 3 Sand SiO 2 Slag CaO (Al 2 O 3 .Fe 2 O 3 .SiO 2 ) Raw Materials Figure 3. C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Compound Formula Shorthand Molecular Weight Water H 2 O H 18.02 Carbon Dioxide CO 2 C 44.01 Lime (Calcium Oxide) CaO C 56.08 Magnesia MgO M 40.31 Silica SiO 2 S 60.09 Titania TiO 2 T 79.90 Alumina Al 2 O 3 A 101.96 Ferric Oxide Fe 2 O 3 F 159.70 Phosphorus Pentoxide P 2 O 5 P 141.94 Sulphur Trioxide SO 3 S 80.06 Soda Na 2 O N 62.00 Potash K 2 O K 94.20 Calcium Carbonate CaCO 3 CC 100.09 Magnesium Carbonate MgCO 3 MC 84.32 Sodium Carbonate Na 2 CO 3 NC 106.01 Calcium Sulphate CaSO 4 CS 136.14 Potassium Sulphate K 2 SO 4 KS 174.26 Principal Compounds and Shorthand Notation Figure 2. C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Mineral Shorthand Name Formula Formula Typical Range Tricalcium Silicate C 3 S Alite 3CaO.SiO 2 Ca 3 SiO 5 60% 30-70% Dicalcium Silicate C 2 S Belite 2CaO.SiO 2 Ca2SiO4 20% 5-40% Tricalcium Aluminate C 3 A Aluminate 3CaO.Al 2 O 3 Ca 3 Al 2 O 5 10% 5-15% Calcium Aluminoferrite C 4 AF Ferrite 4CaO.Al 2 O 3 .Fe 2 O 3 Ca 4 Al 2 Fe 2 O 10 8% 5-15% Figure 9. What is cement? - Clinker Minerals C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Limestone Shale S 3.3 A 0.7 F 0.2 C 53.5 S 52.8 A 14.2 F 8.7 C 1.0 Raw Meal Raw Mill Coal Ash Kiln S 13.2 A 3.4 F 1.9 C 43.0 S 51.7 A 26.4 F 9.5 C 1.6 Clinker S 20.9 A 5.6 F 3.0 C 65.7 Figure 4. Process Chemistry C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S 0 1 2 3 4 5 6 7 8 9 0 2 4 6 8 10 12 14 16 Movement of Material R e l a t i v e
W e i g h t 700 800 900 1000 1100 1200 1300 1400 1500 0 2 4 6 8 1 0 1 2 1 4 Quartz CaCO 3 Free Lime C 2 S C 3 S Temperature Deg C C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Principal Cement Properties Silicates Aluminate Ferrite Alkalis, Total and water soluble Sulfate, Clinker and Cement Forms of Sulfate Fineness, Blaine, Residues, Particle Size Distribution Surface Properties, Carbonation, Pre-hydration, LOI Free Lime Clinker Crystallography, Thermal History Cement Composition, Slag, Fly Ash, Pozzolan, Limestone Minor Components, MgO, Cl , F, P2O5 C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Silicates Main Phase Present Typically 70-80% total silicates Alite (C3S) and Belite (C2S) Strength providing phases Higher LSF means higher C3S Higher C3S:C2S gives higher early strength at same 28 day strength Actual v Potential Bogue differences due to Free Lime Crystallography also important C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Aluminate/Ferrite Interstitial Phases Important for clinker formation C3A content and crystallography strongly influences concrete water demand C3A:SO3 interaction important Important in Flash/False Set behaviour C4AF main cause of colour C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Alkalies Potassium (K2O) and sodium (Na2O) salts As sulfates or in solid solution Alkali:Sulfate balance in clinker is important Total and water soluble contents important Higher clinker sulfate content produces a higher water soluble level Higher total alkali levels reduce 28 day strength Higher levels of water soluble alkalies increase early strength C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Water Soluble Alkalis 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 0.1 0.3 0.5 0.7 0.9 1.1 Clinker Eq. Na2O C l i n k e r
S O 3
. 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.1 0.6 0.5 0.4 0.7 0.3 0.2 Eq. Water Soluble Na2O Clinker SO3 =0.84% Eq. Na2O =0.66% Eq. Water Soluble Na2O ~0.44% TIS MS004. C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Sulfate Present in clinker and as added calcium sulfate Forms of sulfate important Influences: Water Demand Setting behaviour Early strength Later strength Shrinkage Flash/false set behaviour Silo Set C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Fineness Measured as Air Permeability, Blaine or SSA, m 2 /kg or cm 2 /g Residues, e.g. Alpine 45 micron Particle Size Distribution, e.g. laser diffraction, sedimentation Higher SSA provides higher early strength, shorter set time Higher residues reduce 28 day strength Higher grinding efficiency provides a narrower psd C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Cement Fineness SSA = 350 m 2 /kg 99% < 90 microns 85-95% < 45 microns 6-10% < 2 microns Gypsum SSA = 1000-1200 m 2 /kg 1% gypsum = 10-12 m 2 /kg 1% SO3 = 30 m 2 /kg <2 microns = ~50% of SSA Gypsum = ~15% of SSA 50 Billion (50,000,000,000) particles per gram C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Surface Properties Degree of pre-hydration/carbonation can be expected to influence Strength development Setting Characteristics Water Demand Flowability (Packset) Use of clinker stored outside can change SSA/strength relationship LOI is a guide, 1% can equate to 4 mpa C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Cement Composition Clinker, Gypsum, but also Blast Furnace Slag Fly Ash Pozzolana Limestone . Levels and quality will influence water demand setting strength SSA v kWh/tonne relationship C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Alite Sizes, Typically 15-100 microns Smaller (<40) - better strength Larger (>60) - less reactive Burning Temperature Lower - better crystal sizes Cooling Regime Faster - smaller crystal size Crystal Impurities Purer crystals - less reactive Reduction Loss of SO3, Flowability problems Raw Feed Fineness Coarser - difficult combinability Raw Feed homogeneity Siliceous - lower strength Calcareous - better strength Heterogeneity - difficult combinability Porosity Lower - difficult grindability Clinker Microstructure Characteristics C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Influences on Clinker Microstructure Raw feed Chemistry Raw Material Mineralogy Raw Feed Fineness Burning Regime - Atmosphere, Temperature Fuel Type and Fineness Cooling Studied by Microscopic Examination C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Influences of Minor Components M g O Expansive Behaviour Fluoride Mineralisation, Setting and Late Strength Chloride Process, Setting, Early Strength, Corrosion P 2 O 5 Setting, Belite Stabilisation (v. high levels) Strontium Belite Stabilisation Barium Belite Stabilisation Heavy Metals e.g. Pb, Zn on environment and setting Transition Metals e.g. Cr, V, Mn on colour C E M E N T A D D I T I V E S C E M E N T A D D I T I V E S Parameter Unit Incremental change 2d 28d MPa MPa SSA m2/kg +10 0.30 0.30 45-micron residue % +1 -0.35 -0.40 Eq. Na 2 O % +0.1 0.80 -1.70 LOI % +1 -0.50 -3.00 C3S % +1 0.35 0.10 Free Lime % +1 0.50 -1.50 SO3 % +0.1 0.50 0.10 C3A % +1 0.50 1.00 Effect on strength Figure 12. Some Rules of Thumb