Cement – Specification and Performance Hugh Wang Eduardo Caballero CEMEX USA hugh.wang@cemex.com Use of cement: • Cement is ONLY one of the ingredients in any applications – well cementing or construction concreting. • The specified quality parameters of cement are tested without considering other ingredients. • Lessons learned from concrete mixtures - interaction of cement with other ingredients can be critical to performance. Production of quality well cement involves: Grinding Proportioning Chemistry Ca, Si, Al, Fe Mineral C3S, C2S, C3A, C4AF Physical fineness, strength, TT, FF etc Burning Desired clinker characteristics for well cement: Mineral C3S, C2S, C3A, C4AF • Well crystallized alite; • Optimize burning condition in order to minimize f-CaO content; • Generally very low in C3A content – a challenge for kiln operation. Physical properties requirements: Physical fineness, strength, TT, free fluid, etc • Fineness; • Thickening time (TT); • Free fluid (FF). Potential conflicting response: • Fineness vs TT; • Fineness vs FF. Specifications - ASTM vs API : API Ordinary A C ASTM MSR B C D, E, F HSR G H B C SO3, max% 3.5 4.5 3.0 3.5 3.0 3.0 3.0 3.0 3.5 C3S% 48/58 min/max C3A, max% 8 15 C4AF+2C3A max% Blaine, min 280 400 280 400 m2/kg w/c % 46 56 46 56 38 D, E, F 3.0 III: high early strength V: II: H Ordinary MSR Ordinary MSR HSR HSR I: G 3.0 3.0 3.0/3.5D D D 3 4.5 8 15 3.5 D 3.5 D 3 8 5 260 38 5 25 280 400 56 D 48/65 24 44 38 46 2.3 260 44 38 260 48.5 • Fineness: ASTM lowered the limit from 280 to 260 m2/kg; • SO3: ASTM adopted performance based specification; D It is permissible to exceed the values in the table for SO3 content, provided it has been demonstrated by Test Method C1038 that the cement with the increased SO3 will not develop expansion exceeding 0.020 % at 14 days. • C3S: No requirement for MSR and HSR cements. • C4AF+2C3A: 24 API vs 25 ASTM. Mineral calculation – ASTM: Mineral calculation – ASTM: Mineral calculation – API 10A: Mineral calculation – API vs ASTM: When Al2O3/Fe2O3 is C3S = C2S = API ASTM > 0.64 ≥ 0.64 4.071CaO - 7.600SiO2 - 6.718Al2O3 -1.430Fe2O3 - 2.852SO3 C3A = 2.650Al2O3 - 1.692Fe2O3 3.043Fe2O3 C4AF = When Al2O3/Fe2O3 is C3S = C2S = ≤ 0.64 < 0.64 4.071CaO - 7.600SiO2 -4.479Al2O3 -2.859Fe2O3 - 2.852SO3 2.867SiO2 - 0.7544C3S No requirment C3A = C4AF = 2.867SiO2 - 0.7544C3S No requirment 0 3.04Fe2O3 2.100Al2O3 - 1.702Fe2O3 Discussions – ASTM vs API • Minimum blaine 400 m2/kg for API Class-C: if high blaine is intended for early strength, its benefit may be potentially reduced due to the higher water demand. • Minimum blaine for other types of cements should be harmonized with ASTM requirements from 280 to 260 m2/kg;. This will improve thickening time performance. • Why ASTM revised cement SO3 content? – Critical in the mixtures containing supplementary cementitious materials (SCM) and chemical admixtures. Construction industry has gone through the learning process. – Potential incompatibility problems in the mixtures shall be considered when complex components are used in slurry. Energy release rate mW/g Cement hydration rate profile I II III IV V Maximum heat release rate On-set of acceleration stage Conversion of ettringite to mono-sulfate Time in hours Stage I: dissolution Stage III: acceleration Stage V: steady Stage II: induction (dormant) Stage IV: deceleration Cement hydration heat release – strength indication Incompatibility: uncontrolled early hydration Power (mW/g) 4 3 2 1 0 0 Cmt 4 8 12 Time (h) Cmt+24%C-FA 16 20 24 Cmt+24%C-FA+WR&Retarder 0 Energy (J/g) 44 88 132 176 220 Incompatibility: slow strength development 0 Cmt 4 8 Cmt+24%C-FA 12 16 Time (h) 20 24 Cmt+24%C-FA+WR&Retarder Well cement examples: SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O TA00 20.53 4.08 6.63 65.45 0.81 0.94 0.12 TA01 20.30 4.04 6.59 65.39 0.80 1.41 0.14 TA03 19.95 3.95 6.51 65.00 0.78 2.35 0.13 TA05 19.62 3.84 6.42 64.68 0.77 3.31 0.13 C3S TA00 TA01 TA03 TA05 70.51 70.94 70.00 69.23 K2O f-CaO 0.41 0.40 0.40 0.39 0.35 C2S C4AF+C2F 4.32 3.34 3.08 2.72 19.85 19.69 19.36 18.99 Hydration rate at 23˚C (73˚F) 5 Power (mW/g) TA03 TA05 3 2 0 1 7 TA00 13 Time (h) TA01 TA03 19 TA05 25 380 Hydration heat at 23˚C (73˚F) 60 Energy (J/g) 140 220 300 TA05 1 10 TA00 19 28 37 46 Time (h) 55 TA01 TA03 TA05 64 73 Hydration rate at 38˚C (100˚F) TA03 Power (mW/g) 9 6 TA05 3 0 1 7 TA00 13 Time (h) TA01 TA03 19 TA05 25 390 Hydration heat at 38˚C (100˚F) 40 Energy (J/g) 110 180 250 320 TA05 1 10 TA00 19 28 37 46 Time (h) 55 TA01 TA03 TA05 64 73 Example: cement and fly ash combination 6 100 5 80 4 60 3 40 2 20 1 0 0 0 Class-C 35 Consistency (Bc) 70 105 Pressure (kpsi) Consistency (Bc)Temp (°F) 120 140 Time (min) Temperature(F) Pressure(kpsi) Well cement with 50% Class-C fly ash (C-FA) 6 100 5 80 4 60 3 40 2 20 1 0 0 44 Consistency (Bc) 88 132 176 • Viscosity increase 220 Time (min) Temperature(F) Pressure(kpsi) 26 5 22 4 18 3 14 2 10 1 6 0 0 20 Class-C+50% FA 40 60 80 100 120 140 Time (min) Consistency (Bc) Pressure(kpsi) 160 Pressure (kpsi) Consistency (Bc) 0 Class-C+50% FA Pressure (kpsi) Consistency (Bc)Temp (°F) 120 120 6 100 5 80 4 60 3 40 2 20 1 0 0 46 138 184 230 26 5 22 4 18 3 14 2 10 1 6 0 Time (min) Temperature(F) Pressure(kpsi) 0 20 Class-C+50% FA 40 60 80 100 120 140 Time (min) Consistency (Bc) Pressure(kpsi) 160 Pressure (kpsi) Consistency (Bc) 92 Consistency (Bc) 0 Class-C+50% FA +1.5% Gypsum Pressure (kpsi) Consistency (Bc)Temp (°F) Well cement with 50% C-FA and 1.5% gypsum Viscosity profile comparison 80 60 • Gypsum addition eliminates high viscosity during early stages 40 20 0 0 Class-C 46 230 26 Class-C+50%FA+1.5% gyp 22 138 92 Time (min) Class-C+50%FA 184 Consistency (Bc) Consistency (Bc) 100 18 14 10 6 0 20 40 60 80 100 120 140 160 Time (min) Class-C Class-C+50%FA Class-C+50%FA+1.5% gyp SO3: Supply - Demand Rule SO3 supply SO3 demand If SO3 supply is greater than demand If SO3 supply is greater than demand If SO3 supply is less than demand If SO3 supply is less than demand Recommendations • In order to make well cement more robust for slurry mixtures containing SCM and chemical admixtures, the cement SO3 needs to be optimized. • The 280 m2/kg blaine requirement needs to be revised to 260 m2/kg, this will help to improve thickening time. • The minimum blaine 400 m2/kg for Class-C cement may be eliminated by specifying the strength requirement. • Harmonize cement mineral phase calculation to reflect lasted advance in understanding cement chemistry.