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    Chapter2 Portland and Blended Cement

    Uploaded by

    OMAR MUKTHAR JAMAL MOHAMED

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    © All Rights Reserved
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    NRMCA CONCRETE TECHNOLOGY MIDDLE East (CTME) PROGRAM STUDENT GUIDE AND NOTES NRMCA ENGINEERING DIVISION Portland and Blended Cement (© NRMCA November 2011 © National Ready Mixed Concrete Association 900 Spring Street, Silver Spring, MD 20910 ‘Phone 301.387.1400 + Fax 301.585.4219 ‘winrnemen.ong NRUCA CoucRETE TecHwaLocy MiDOLE EAST PRogaan Table of Contents SPECIFICATIONS... TERMINOLOGY nnn INDUSTRY FACTS MANUFACTURE. (CEMENT COMPOUNDS... PROPERTIES OF CEMENT COMPOUNDS. 3 ‘TYPES OF PORTLAND CEMENT -ASTMC 130. ‘ EFFECTS ON CONCRETE PROPERTIES 7 PORTLAND CEMENT svn = (ChnUcAL REQUIREMENTS AND EFFECTS OF MNOR CONSTITUENTS 8 DhvsicaL Tests ND REQUIREMENTS 3 AppIrONS 70 PowsLaw Ces 10 UNIFORMITY OF CEMENT - ASTMC917, ‘QUALITY CONTROL OF CEMENT. BLENDED CEMENTS oven SPECIAL CEMENTS... ‘SAMPLE MILL TEST REPORT. ADDITIONAL REFERENCES. REVIEW QUESTIONS.. Leaming Objectives 1. Manufacture of Portiand cement. Properties of the cement compounds and their effect on strength, setting, and heat of hydration ‘Types of cements defined in C 150 and their uses. Mil test report information, uaity contro of cement and C 917 reports. ‘Specifications C 595 and C 1157. Blended and Special cements. NRWCA Gowcmere Tecnwotogy MIDDLE EAST PROGRAM Portland and Blended Cement Specifications A ‘STM C 150/is the Standard Specification for Portland Cement AASHTO M 85 is the equivalent standard in AASHTO and is similar to ASTM C 150. ASTM C 595 is the Standard Specification for Blended Hydraulic Cements ASTM C 1157 is the Standard Performance Specification for Hydraulic Cement Terminology linker > Product from cement kiln Portland Cement > —_—Cllinker + Gypsum > ground to fine powder Cement Paste > Cement + Water Mortar > — Paste + Sand (Fine Aggregate) Concrete > — Mortar + Stone (Coarse Agoregate) ‘Hydraulic cement is one that chemically reacts with water and can set and harden under water (ASTM C 125). The general chemical reaction, called hydration, can be represented by the reaction of the calcium silicates with water to form calcium silicate hydrates, that is the cementitious product that bonds aggregates together and imparts the strength and durability of concrete. Cement + water > C-S-H + calcium hydroxide Calcium hydroxide (hydrated lime) is a byproduct of the hydration reaction that does not provide any benefit. However, it reacts with porzolanic material lke fly ash and silica fame to form additional cementitious (C-S-H) product. NRMCA Concnere TecnnaLocy mipoLe EX Industry Facts In the eatly days, cement was measured in barrels — 1 barrel was 170 kg of cement. ‘One sack of cement is roughly (0.03m’) of loose volume and weighs 42 kg. ‘The US manufacturing capacity is about 110 million meteic tons of cement annually with about 125 cement plants. It is the third largest manufacturer after China and India. The US consumes about 130 million mettic tons at its peak, thereby importing between 25 t0 30%, The blended cement used is about 3% of the total porland and blended cement quantity. The ready mixed concrete industry consumes about 75% of the cement in the US. Worldwide cement consumptions is about 2.8 billion metric tons annually Manufacture Raw Materials. Cement plants are usually located in proximity to limestone quarries as limestone is a primary raw ingredient used in its manufacture. The following is a breakdown of the primary oxides needed to manufacture portland cement and the raw ‘materials that are used in cement manufacture. Tre Sie [Alenia 0 | soe | so aire Fe 10% Tale Chay Aor Limestone | FipAsh | Bauxite ‘Mast Sand Clay Aragonite_|_ Shale Shale 30s($) 6% Gypsum CaS0,2H0 Anhydste CaSO. Leecsin () teshonnd notations Sip ts ‘The ingredient raw materials ate quarried, milled through a primary crusher and secondary crusher to 25 mm size and kept in storage bins or silos. NRUCA GoncaeTe TecHwotoay MinoLe Exet Paoanaw Portland snd Blended Cement ‘The raw matetials are passed through a final crushing stage to make up very fine powders. Raw feed composition is continuously monitored and blended to get the desired raw feed composition that is important to the cement being produced. The raw feed should be of constant composition, finely divided and well balanced. Dry Process ~ In this process, grinding and blending is done with dry raw materials. Blending of dry materials is less effective relative to producing uniform blend and composition but the process requires less energy to fire the materials in the kiln, Heres ining ts Poem Tpmeged Garton ‘rag ae ‘Wet Process ~ In this process, grinding and blending of raw materials is done in slurry form, thereby the raw feed is more homogeneous. Cement manufactured using wet process has higher energy requirements and raw materials require longer kiln residence time to remove the water. Wet process plants are generally older and represent about 30 percent of the US cement producing capacity. eee to 12 teal : = erga Ue Ye) > Raf Sryenminiioose oma LQ Sryommieate 89 Sempre Sep 3: After blending, the ground raw materials are fed into the upper (feed) end of a rotary kiln, or into a preheater tower. The raw mix passes through the kiln at a ate controlled by the slope and rotational speed of the kiln. The kiln is a large rotating cylinder on an incline, lined with refractory brick, about 6 m in diameter and 180 m in length, rotating at 60 to 200 rounds per hour. Burning, fuel (powdered coal, oil, or gas, sometimes supplemented with alternative fuels such as tires) is forced into the lower (discharge) end of the kiln, Residence time of the raw feed in the kiln is approximately 2 to 2 ¥2 hrs for wet process; 1 to 1 Yrs for dry. Hottest temperature in the kiln isin the range of 1400 to 1600°C. A portion of feed melts in the kiln and the raw materials convert into cement compounds. Exiting the kiln at the lower end are grayish-black pellets called clinker, which are predominantly the size of 12.5 mm diameter nodules. Clinker is moved to stomge or directly to final grinding. The production capacity of modem cement plants exceeds 5000 tons per day. NRMCA Concneré TecnnoLogy MiDoLE EAs Proonan Tn modem systems, the raw materials are fed into a preheater tower where waste gases from kiln pre-heat the raw feed and a pre-calciner (fash furnace) that calcines (reduce CaCO, to CaO) the raw feed, thereby using some of the waste energy. os, eeniapacoee! Step 4: ‘The clinker is cooled and conveyed to storage or to the finish grinding process. Finish grinding is done in ball mills. Air separators are used to te-circulate coarse material back to the ball mill. During finish grinding a small amount of about 5% of gypsum (CaSO,2H,O) is added to regulate the setting time of the cement. Some manufacturers replace anhydrite (CaSO) for some of the gypsum. The clinker is ground so that most of it passes through a No. 325 mesh (45 micrometer) sieve. This fine gray powder is portland cement. Average size of a cement grain is about 10 jum (0.01 mm), = oer Finished cement is stored in silos until shipped in bulk by road, ral, or barge. Some of the product is bagged. Cement received by the customer may be bleaded from Afferent production lots. NRUCA Cononere Teenwovoey MIDDLE Exst Paoonau Cement Compounds During the buming process, the raw ingredients combine to form four principal cement compounds that make up about 90% by mass of the cement. The following ate the primary compounds, the notations used, and the approximate amounts present in finished portland cement. As indicated earlier, gypsum is added during finish grinding. “Compound —_ NststionAmoune, “Tricalcium Siieate (Alte) Dicaleium Silicate Belite) cs Tecalcium Aluminate GA ‘Tetracalcium Aluminoferste (Ferite) CAF ‘Gypsum cS Shorthand Notation: C=CaO; A = ALOy S = SiO F = Fe,O, 5 = SO, H = H,0;C§ Jn the presence of water, the principal compounds in cement chemically react with water in /ydration reactions to form new compounds that form the glee in hardened concrete that binds aggregates together. The calcinm silicates, C,S and C,S, which constitute about 75% of the weight of cement, hydrate to form the compounds calcium silicate hydrate (C-S-H) and calcium hydroxide. The strength and other properties of hydrated cement are due primarily to the C-S-H. In the absence of sulfites, CyA reacts with water to form calcium aluminate hydrates in a rapid reaction. ‘Gypsum is interground with clinker to conteol the hydration of C,A. C,A, gypsum, and water combine to form ettringite, a calcium sulfoaluminate hydrate and this reaction delays the setting of concrete so that there is sufficient time to handle and place it. (CAP may also react with water to form calcium aluminoferrte hydrates. ‘Properties of Cement Compounds ‘The primary properties of these cement compounds when cement hydeates follows: Alite - C,S hydeates rapidly and is essentially sesponsible for inital set and ealy age strength development. Its hydration contebutes to the heat of hydsation. In general, cements containing higher percentages of C,S content will have higher eatly strength and higher heat of hydration. Belite - C,S hydiaces and hardens at a slower sate and contributes largely to strength at Inter ages. Aluminate - C,A liberates a luge amount of heat during the first few days of hydration and hardening. It has minor contribution to early age strength. If early age hyciation of this compound is uncontrolled by insufficient quantities of gypsum the cement can have flash setting characteristics. Cements with low percentages of C,A will have lower heat of hydration and will be more resistant to deterioration in exposures containing sulfates (sulfate resistance). 3.Ca0Si0, NRMCA Concmere Tecuwo.eay Mile Exsr Proanan ration Strength Development 100 Rate of Hydrat cS q| \z i 2 5 4 8 2A + Gypsum GAF + Gypsum © 2 49 6 0 10) 7 ™ ‘Ymenf2, 8% 100 Time, Days Ferrite - C,AF acts like a fux and reduces clinkering temperatures during cement manufacture, This compound hydrates relatively slowly and does not contribute much to strength. This compound is responsible for the color of cement. White cement has very litle iron in the raw feed and thereby very low percentage of C,AF. Sulfate - ($O,) controls setting time by regulating C,A hydration. The amount added to cement during finish grinding will affect the strength and shrinkage of the cement and the cement manufacturers add amounts that will be optimized for strength. Calcium sulfate in cement can be in essentially three forms: Gypsum — CaSO, 2H,0 Calcium sulfate hemihydrate (plastet}~ CaSO,12H,0. This form exists when gypsum dehydrates due to high temperatures in the grinding mill. Cements with predominantly this form of calcium sulfate can have false setting characteristics in short mixing cycles. ‘This false setting occurs as the plaster converts to gypsum. Calcium sulfate anhydsite ~ CaSO, This form has a lower solubility in water compared to the other forms of calcium sulfite. ‘The form of calcium sulfate in the cement at the time of use in concrete will influence setting characteristics and admixture performance. “Types of Portland Cement-ASTM C150 Type Use Requirements 1__| General Purpose Biasic minimum requirements TL _| Moderate Sulfite Resistance | Max CsA TQ | Moderate Heat of Hydration | Max CA = 8% CS 4.75 CsA S100; Max fineness 450 m/e Tt_| Figh Basly Serena 183 day stxengh Kens TY _| Low Heat of Hydration 78 28 day strength limits V__| High Sulfite Resistance Max GA = 5% NRMGA Goncaere TechwoLocr MiDDLE EAcT Progam Check chemical and physical requirements and limits (standard and optional) in Tables 1 ehrough 4 in ASTM C 150 ‘The table below reflects the typical composition and fineness of C 150 Portland cements - Values are averages of a recent PCA survey of portland cements marketed in Noxth America in 2004. Type | GS | GS | GA | CAF Blaine, m?/lg seats tS 5 388 7 | |» it aT Fr a 348 Ww Not Widely Avaable v [=[= [3s] s a I $80 Efects on Concrete Properties Cements that guin strength rapidly will typically have a lower ultimate strength. ‘Strength guin characteristics of cement are related to composition and fineness. Higher initial strength of Type III cement is primarily related to the higher fineness. Heat of hydration of cement is related to the amount of C,A and C,S - the greater the quantity, the higher the heat generated. Also cements that ate ground finer will have a higher rate of hydration and generate more heat. Type I cement, in conjunction with fly ash and slag, is typically used for mass concrete where lower heat of hydration is required. ical Concrete Stren ical Temperature Rise Ayr a oe 1p IV, 4 80 z g z a 00 3 i : bao é 5 & é 20 Detressing eis acsa 7 ° 71438080 a IM rr 7” “Time, Days Tunes Days NRUCA Gowcnere Tecnvatoay MiDDLe East Proasam Portland sad Blended Cement Portland Cement Chemical Requirements and Effects of Minor Constituents ASTM C 150 has several requirements for portland cements and these characteristics are reported on a mill test report. A sample mill test report is provided at the end of these notes. What follows isa brief discussion of these requirements and implications to the cement quality and its performance in concrete. ‘+ Composition -ASTM C 114 } ‘The oxides are measured on the finished cement by chemical or other analytical methods > Compounds are calculated from oxides using the Bogue equations in the appendix of ASTM C 150 ‘* Alllis are the sum of sodium and potassium oxides and are reported as Na,O equivalent (Na,O + 0.658 K,O). Itis an optional requirement in ASTM C 150 bots Bequendy sported Cement with higher alkali content set and gain strength faster. These cements are also mote effective with pozzolans and slg as they react with these ‘materials faster } Higher alkali-lower AEA dosage for same air- air content is less stable. > Potential for deleterious expansive cracking due to alkali-aggregate reactivity with potentially reactive aggregates. An optional alkali limit of max 0.60% is often specified or fly ash and/or slag are used with these aggregates, ‘© Free Lime (not required to report) and MgO. > Both react with water to form larger volume reaction products which is called “unsoundness and causes expansion of concrete > Only MgO present in a certain form called peticlase is a problem. Max limit of ‘MgO in portland cement is 6.0% ‘* Loss on Ignition LOD - ASTM C 114 - 3% max. Loss of weight when oven- dry cement is heated to a temperature of 950°C. LOI increases due to: > Pre-hydrated cement due to extended storage time > Carbonated free lime > Water of crystallization from gypsum * Insoluble Residue - ASTM C 114 - 0.75% max. where a cement is dissolved in acid and the un-dissolved postion is the insoluble sesidue. IR increases due to > Unburnt raw material > Contamination from storage ot interground gypsum © SO,~There are maximum limits on the amount of sulfate in the cement these vary from 2.3 to 4.5% depending on the cement ‘Type and the amount of C,. ‘The cement manuficturer is allowed to exceed the maximum when the optimum SO, required for the cement is close to or exceeds the limit and it has NRUCA Concnere TecunoLocy MiDOLE EAST Procaau Porciand and Blended Coment been demonstrated by ASTM C1038 that the cement will not cause expansion due to the additional sulfate. Optional Chemical requirements as listed in ‘Table 2 of ASTM C 150 can be invoked by the purchaser. The optional requirements that can be invoked include limits on C,A and the equivalent alkali content. Physical Tests and Requirements ‘* Air Content - ASTM C 185 - Max 12%, This limit is to ensure that the cement does not have contaminant materials that will entrain ar in concrete, ‘* Fineness ~‘Two methods are used. Typically Blaine values are reported > ASTM C 204 - Blaine - Min 280 m‘/kg. > ASTMC 115 - Wagner - Min 160 m’/kg While there is no definite relationship between fineness measured by these methods, ‘an approximate conversion that can be used: Blaine fineness ~ 1.8 (Wagner fineness) * Autoclave Exp. - ASIM C 151 - Max 0.80% > Checks for unsoundness or expansion potential, typically from free lime and ‘MgO © Compressive Strength - ASTM C 109 > 50 x 50 mm cubes, standard sand, w/e = 0.485 > Minimum strength limits are specified for different cement Types in C 150 ‘© Setting ‘Time -'Two methods are used. ‘Typically Vicat values are reported. > ASTMC 191 - Vicat Test Minimum initial set should be between 45 and 375 min > ASTMC 266 - Gillmore Test Initial set should be greater than 60 min; Final set should not exceed 600 min Optional Physical Tests as listed in ‘Table 4 of ASTM C 150 can be invoked by the purchaser. © False Set ASTM C 451 Ealse set results in stiffening of concrete without significant heat generation. It is caused by the presence of plaster (CaSO, Y H,O) in cements that converts to gypsum (CaSO,2H,0) when contacted with water. Gypsum converts to plaster dne t0 high ‘temperature in the finish mill. Continued mixing will overcome stiffening due to false set. For this reason false set is typically not observed in ready mixed operations. ‘Flash set is another form of premature stiffening caused due to insufficient sulfate (SO) to contol C,A hydration. Flash set is accompanied by heat generation and cannot be overcome by additional mixing. It may be also caused by incompatibility with chemical admixtures. NRMCA Concrete TecHwoLoay MiDoLe EAsr Procnan © Heat of Hydration ASTM C 186 ‘The heat of hydration is required to be conducted for ‘Type II (MH) cements but there is no limit. ASTM C186 is a dated test and cumbersome to perform. A new test based on isothermal calorimetry is being standardized and heat of hydration limits based on this standard will be proposed in the Future. Sulfate Resistance - ASIM C 452 ‘This test evaluates whether the cement is susceptible to sulfate attack. An optional ‘expansion limit at 14 days of 0.040% is indicated for Type V cement. Other Tests © Optimum SO, - ASTM C 563 ‘Test method used by the cement manufacturer to optimize the gypsum to be added based on a I-day strength evaluation. © Calcium Sulfite Expansion ASTM C 1038 > When the SO, content exceeds the C 150 limits, this test can evaluate whether the excess sulfate might cause damaging expansion, Additions to Portland Cement ASTM C 150 allows for certain additions to be made to the finished cement during manufacture © Water or calcium sulfate can be added during manufacture. ‘The limits on the loss on ignition and sulfur trioxide (SO,) control the quantity that can be added. As discussed before the calcium sulfate is added to control the hydration of C\A. Processing additions are those that facilitate the manufacture. They can be added in accordance with ASTM C 465 which is a process by which the properties of the cement with the processing addition is compared properties of cement without the addition to demonstrate that the addition does not adversely affect the properties of the cement. Grinding aids and pack set inhibitors, which improve flowability of cement powder, are the commonly used processing additions. ASTM C150 limits a maximum of 1% for organic sand 5% for inorganic processing additions. The latter has to be evaluated for a specific plant and material in accordance with ASTM C465. ‘¢ Airentmaining admixtures for the air entraining cements. These ate rarely used nowadays. ‘* Limestone additions are allowed to up to 5% by mass of cement. The limestone should be naturally occurring and should be a relatively pure limestone with at least 70% by mass of one ot more forms of calcium carbonate. The loss on ignition and insoluble residue limits will control the quantity of the limestone addition, Limestone additions provide environmental 10 land Sed Blended Cement NRMCA Concrete TeeHNoLoay MiaoLE E benefits to the cement manufacturer in terms of fuel consumption and carbon. dioxide emissions per ton of finished cement. Uniformity of Cement - ASTM C 917 ASTM C 917 is a standard that provides for the cement manufacturer to test and ‘eport the uniformity of cement from one source, based on strength. Typically C 917 evaluation is only conducted for the primary product from a cement plant or terminal. For C 917 strength tests, cement is sampled prior to shipping, Mill certificate tests are from production samples obtained from the grinding mill circuit. Therefore, samples, ‘used for C 917 tests more closely represent the cement the customer gets C917 reports require sampling frequency of about 10 per month and tests for T-day and 28-day strength (ASTM C 109) over a period of time. Reports: ‘Individual strength, running average of 5, and overall average during the test petiod. Standard deviation (comected for testing vatiation) which represents the variability of cement strength over a period from that source. C 917 reports are useful to evaluate the strength level and variability of a cement source, determine periods when strength variations are high, and are useful to evaluate ‘whether concrete strength problems can be attributed to lower strength of cement. Example of aC. 917 Chast ‘This is an example of a C 917 report for the year for 28-day strength (1000 psi = 7 MPa). The average strength and the standard deviation - comected for testing - are reported. pm 2 ® Eom c osm ‘Average = 6170 psi Co. SD. = 310 psi 0 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec| Cement Samples "4 NRUCA Concnere TecuNoLoey MiDoLE Exst Paoonau “The average strength and the standard deviation can be compared with the distribution provided in the Appendix of ASTM C.917. For the sample C917 report, the average 28-day strength was 42.5 MPa. Distribution of C 917 Strength so 4 000 Conipresive Sent, psi 7000 8000 ‘The distribution indicates that about 60% of the cement sources had lower 28-day average strength. Similarly, the distribution indicates from the corrected standard deviation (310 ps) (21 MPa) that about 65% of the cement sources had a lower variability than this particular plant. 100 Distribution of Standard Deviation 90 80 in $00 30 0 100 200 300 400 ~— 500600 Corrected Staridard Deviation, psi Records of concrete strength for the same mix design should be periodically compared, ‘with the trends indicated in a C 917 report. 42 NRMGA Goncnere Tecwnocoar MiooLe Exgr PoogeaM | Quality Control of Cement ‘Some general guidance on monitoring quality and uniformity of cement from cement suppliers are: ‘¢ Maintain relationship with supplier to ensure that changes to product are notified ‘¢ Ask for copies of mill certificates periodically and track changes on mill test reports ‘¢ Ask for ASTM C 917 report - realize it isa past record © Compare strength and standard deviation © Correlate concrete strength problems with cement strength ‘* Sample cement - 5 to 10 kg in air-tight bags. Keep samples for the duration of a project If feasible, test coment for color, temperature, LOL, strength, set time, admixture effects: ‘* Monthly concrete tral baiches are recommended with the primary cement you use. Mortar testing may also be sufficient to evaluate trends in cement strength and setting characteristics 3 NRUCA Concaere TecHwo.ooy MipoLE ExeT P sad Blended Cement Blended Cements ‘Two specifications exist for blended cements. ASTM C 595 provides for blended cements based on prescriptive provisions and the ‘manufacturer indicates quantities of fy ash, natural pozzolans or ground granulated blast furnace slag that can be used in the cement. Blended cement that contains 1 pozzolan and slag or 2 pozzolans are designated as “ternary” blended cements, Type IT. The various Types under C 595 are given below. Optional special characteristics such as “A” for airentraining, “MS” for moderate sulfate resistance; “HS” for high sulfate resistance, “MH” for moderate heat of hydration; “LH” for low heat of hydration; and the use of set modifying or water reducing admixtures can be invoked ‘There are various chemical and physical requirements for the blended cement in C 595. The pozzolan ot slag used in the blended cement needs to meet requirements for strength activity index, fineness and ability to control expansion due to alkali silica reactivity. The quantity of pozzolan or slag used in the cement should be indicated in the type designation. For example Type IP(X) contains ““X” percent of pozzolan by ‘weight; and Type IS(

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