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Putting Bogue Back in Vogue

Today the Bogue equations are most often cited for their shortcomings rather than their usefulness, but their contribution to cement chemistry and especially raw mix design are invaluable. The Bogue equations provide a simple and convenient method to find out the final composition of a clinker, which tells us a lot about its likely behavior. Technically, they indicate the potential composition since not all of the reactions that occur in the kiln will go to completion and since the cement phases are not ideal compounds. Plant chemists have used these equations for years, sometimes adjusting them based on their own raw materials and their own experience. You cant make cement if you dont know all about your raw materials. An oxide analysis of the raw materials is the first step, which provides input for a wide variety of ratios and moduli that relate oxide compositions to one another. These include: LSF (lime saturation factor), SM (silica modulus or ratio), AR (alumina-to-iron ratio), and other lesser-used formulas like the hydraulic modulus. So just how do you come up with a raw mix proportions from an oxide analysis? Thats the basic principle behind raw mix design and one of the pioneers that put Bogue back in vogue was Clyde Moore. His important contribution to raw mix design was made in a landmark paper titled, Chemical Control of Portland Cement Clinker1. Moore selected what he considered were the three most critical control parameters:

Silica ratio

Alumina-iron ratio

Lime factor

The silica ratio represents the burnability of a raw mix. The burnability impacts how much energy is put into the system. As the ratio of silica to alumina plus iron increases, it becomes harder to burn harder to combine the raw materials into the phases we want. As the ratio decreases, the tendency for fluxing (the ability of the solid materials to become liquid) increases, and the combining reactions become easier. Another consideration is that silica present as quartz is generally more difficult to combine than silica present as silicates. The alumina-to-iron ratio is important because it controls the potential C3A/C4AF ratio in the finished cement, which is important because of sulfate resistance, heat generation, and admixture compatibility issues. The lime saturation factor controls the potential C3S to C2S ratio in the finished cement. C3S governs the early age strength development while C2S governs the later age strength. Moores Method Moore discovered that Kinds formula (which defines a modulus based upon the lime, alumina, iron, and silica amounts) can be further refined into what he defined as the lime factor. The importance of the lime factor is that it includes all four of the ingredients necessary for clinker production. But Moore went

a step further. He used this new lime factor along with the silica ratio and alumina-iron ratio to come up with a simple resource for raw mix design. By substituting the three moduli (lime factor, silica ratio, and alumina-iron ratio) into the Bogue equations and performing some basic algebra, Moore was able to define the four clinker phases by specifying just three control parameters. The key to Moores method lies in recognizing that most plants obtain their raw materials from just one source. Even if there is some variation, any difference can be distributed proportionally among the four clinker phases. The advantages to Moores method are impressive: The four clinker phases (C3S, C2S, C3A, C4AF) are defined by just three parameters. Equations can be derived directly for each of the phase compositions in terms of the control parameters. The ratios of oxides can be used either on a clinker basis or on a raw-feed basis since the ratios are independent of loss on ignition. Theres no need to think in terms of potential clinker phases in the kiln feed where the clinker phases do not yet even exist. The relative error in the lime factor is less than the relative error calculated in C3S content from the oxide analysis. Theres an easy check on the real lime factor through the use of XRD. Moore developed a variety of examples to illustrate his method, including the design of a raw mix when three materials are available by using two parameters, such as the lime factor and silica ratio. Todays manufacturing environment uses rapid, in-stream sampling and analysis coupled with computerized proportioning to make almost continuous process improvements. It is a far cry from the matrix methods that helped Moore develop his quantitative relations between chemical control parameters and clinker phases. Moores method may indeed seem simplistic. But the real benefit is that Moores method makes raw mix design intuitively obvious for the new process engineer or plant chemist. Its a great teaching tool because it incorporates the basics. The information in this newsletter was obtained primarily from PCAs Control of Portland Cement Quality by Clyde Moore and his original work 1. Chemical Control of Portland Cement Clinker, Ceramic Bulletin, Vol. 61, No. 4, 1982, pages 511 to 515. Silica ratio = SR or SM = SiO2/Al2O3 + Fe2O3 Alumina-iron ratio = AR = Al2O3/Fe2O3 Lime factor = C (1.65A + 0.315F)/S Lime saturation factor = LSF = 100(CaO + 0.75Mg) / (2.85SiO2) + (1.18Al2O3) + (0.65Fe2O3) For MgO below 2% Lime saturation factor = LSF = 100(CaO + 1.5Mg) / (2.85SiO2) + (1.18Al2O3) + (0.65Fe2O3) For MgO above 2%

Bogue Equations for Potential Composition C3S = 4.071C 7.6S 6.718a 1.43F C2S = -3.071C + 8.6S + 5.068A + 1.079F C3A = 2.65A 1.692F C4AF = 3.043F

(above equations only valid when A/F 0.64 ) Illustrative Example: Percentage of oxide as per Oxide Analysis Calculated Compound Composition

SiO2 20.6 Al2O3 5.07 Fe2O3 2.90 CaO 63.9 MgO 1.53 K2O 0.73 Na2O 0.15 SO3 2.53 LOI 1.58

C3S = 4.07(63.9) 7.60(20.6) 6.72(5.07) 1.43(2.90) - 2.85(2.53) = 58.1 C2S = 2.87(20.6) 0.754(58.1) = 15.6 C3A = 2.65(5.07) 1.69(2.90) = 8.5 C4AF = 3.04(2.90) = 8.8 Bogue Potential Composition: C3S: 58% C2S: 16% C3A: 9% C4AF :9%

Lime Saturation Factor The LSF is a ratio of CaO to the other three main oxides. Applied to clinker, it is calculated as: LSF=CaO/(2.8SiO2 + 1.2Al2O3 + 0.65Fe2O3) Often, this is referred to as a percentage and therefore multiplied by 100. The LSF controls the ratio of alite to belite in the clinker. A clinker with a higher LSF will have a higher proportion of alite to belite than will a clinker with a low LSF. Typical LSF values in modern clinkers are 0.92-0.98, or 92%-98%. Values above 1.0 indicate that free lime is likely to be present in the clinker. This is because, in principle, at LSF=1.0 all the free lime should have combined with belite to form alite. If the LSF is higher than 1.0, the surplus free lime has nothing with which to combine and will remain as free lime. In practice, the mixing of raw materials is never perfect and there are always regions within the clinker where the LSF is locally a little above, or a little below, the target for the clinker as a whole. This means that there is almost always some residual free lime, even where the LSF is considerably below 1.0. It also means that to convert virtually all the belite to alite, an LSF slightly above 1.0 is needed. The LSF calculation can also be applied to Portland cement containing clinker and gypsum if (0.7 x SO3) is subtracted from the CaO content. (NB: This calculation (ie:

0.7 x SO3) does not account for sulfate present as clinker sulfate in the form of potassium and sodium sulfates) and this will introduce a slight error. More particularly, it does not account for fine limestone or other material such as slag or fly ash in the cement. If these materials are present, calculation of the original clinker LSF becomes more complex. Limestone can be quantified by measuring the CO2 content and the formula adjusted accordingly, but if slag or fly ash are present, calculation of the original clinker LSF may not be conveniently practicable.) Silica Ratio (SR) The silica ratio (also known as the Silica Modulus) is defined as: SR = SiO2/(Al2O3 + Fe2O3) A high silica ratio means that more calcium silicates are present in the clinker and less aluminate and ferrite. SR is typically between 2.0 and 3.0. The silica ratio is sometimes called the silica modulus. Alumina Ratio (AR) The alumina ratio is defined as: AR=(Al2O3/(Fe2O3) This determines the potential relative proportions of aluminate and ferrite phase in the clinker. An increase in clinker AR (also sometimes written as A/F) means there will be proportionally more aluminate and less ferrite in the clinker. In ordinary Portland cement clinker, the AR is usually between 1 and 4. The above three parameters are those most commonly used. A fourth, the 'Lime Combination Factor' (LCF) is the same as the LSF parameter, but with the clinker free lime content subtracted from the total CaO content. With an LCF=1.0, therefore, the maximum amount of silica is present as C3S.

Hydraulic modulus

Its the ratio between percentage of lime to percentages of combination of alumina, iron oxide and silica. The hydraulic modulus to be maintained between 1.7 to 2.3.

If hydraulic modulus was more than 2.4, then the concrete made from the cement has expansion and shrinkage problems even at normal or high/low temperatures ie., the cement loses its volume stability. Also the clinker is hard to burn resulting increase in fuel consumption. The cement liberates more heat when mixed with water (more heat of hydration) resulting chances of cracking if not cured properly. The cement has lower initial strength and so the setting and strengthening of concrete takes time resulting increased time to demould /remove concrete frame work. The cement also loses the property of resistance to chemical attack. So that kind of cement cannot be used at construction of bridges as cement was exposed to water/sea water.The cement cannot be used at places where it was exposed to water, ice ,salt and chemicals.

hydraulic modulus of raw mix is less than 1.7, then the resulting cement will have lower strength. Hydraulic modulus was used for compositional effect of ash replacement on calcinations. It was also used to predict hydraulic activity on strength development. If you are using flyash or any other ash, you must monitor hydraulic modulus compulsory to avoid strength and expansion problems. So monitor hydraulic modulus while producing special cements and flyash added cements like PPC cements as these cements are exposed to salt,

water, chemicals and ice. Hydraulic modulus was not used in most of the cement plants nowadays as only lime saturation factor, alumina modulus and silica modulus are used mostly. After the discovery of lime saturation factor, the usage of hydraulic modulus was declined as hydraulic modulus not applies for varying conditions and materials under modern cement manufacturing process.