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The concept of differential thermal analysis (DTA) came from Le Chateliers pioneering work in 1887 on the heat of decomposition of clays and limestones. Since then the application of DTA has become widespread for material characterization and evaluation. Particularly during the last two decades, DTA has found diverse applications in the cement industry. The ability to detect minor chemical changes and provide relevant analytical information for portland cement, its raw materials, and its hydration products has made DTA one of the foremost analytical methods, along with X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscopy (SEM). The technique is convenient, fast, and accurate, and provides information that is not readily available from other techniques. In addition, it has special applications in monitoring thermal changes in simulations of cement kiln operation. Thermal analysis instrumentation frequently used for such applications is shown in Figure 8.4.1. In addition to the DTA, the following thermoanalytical techniques (Table 8.4.1) are frequently used in analysis pertaining to cement science and manufacturing.
Figure 8.4.1. DSC and TGA equipment frequently used by the cement industry.
*Senior Scientist, Construction Technology Laboratories, Inc., 5400 Old Orchard Road, Skokie, Illinois, U.S.A. **Senior Principal Scientist, Construction Technology Laboratories, Inc.,5400 Old Orchard Road, Skokie, Illinois, U.S.A.
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Table 8.4.1. Thermoanalytical Techniques Frequently Used in Cement Analysis Technique used
Thermogravimetric Analysis Differential Thermogravimetry
Abbreviation
TGA DTG
Common applications
Monitors loss of weight when material decomdecomposes as a function of temperature Examines rate of weight change to increase precision of identifying temperatures at which weight changes occur and separations of multiple weight change events Permits elucidation of rate changes in thermal processes and deconvolution of complex patterns Quantification of heat increments associated with thermal changes
DDTA DSC
Table 8.4.2. Raw Materials in Cement Manufacture (Ramachandran, 1969; Kosmatka, 2001) Materials
Carbonates Aluminosilicates Corrective materials Mineralizers Set regulator Hydraulic blending materials
Sources
Limestone, chalk, marble, sea shell, marl Clay, shale, fly ash, and slate Sand and sandstones, bauxite, iron ore, laterite, mill scale, diatomaceous earth CaF2, Na2SiF6, fluorspar/gypsum Gypsum, anhydrite Natural pozzolanic rocks, blast-furnace slag, fly ash, silica fume, metakaolin
Reviews by Mackenzie (1964), Ramachandran (1969), Barta (1972), Ben-Dor (1983), and Bhatty (1993) have covered several aspects of these applications. The annual worldwide production of portland cement is estimated to be more than 1.6 billion metric tons (PCA, 2002), which requires more than 2.4 billion metric tons of raw materials and some 320 million metric tons of fuel. The major cement producers are given in Table 8.4.3; the Republic of China is by far the dominant producer of portland cement, followed by India, USA, and Japan.
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Table 8.4.3. Major Portland Cement Producers in the World (PCA, 2002) Country
Republic of China India USA Japan South Korea Brazil Germany Italy Turkey Total World
Limestone and clay are the most common sources of lime (calcium oxide) and silica respectively, required in cement making. Secondary sources of lime such as chalk, marl, and shell deposits are also used when available. Other sources of silica are silt, shale, quartz sand, and fly ash. The presence of alumina and iron-bearing minerals in the raw mix is also required to ensure the presence of some liquid phase in the burning zone, as well as essential for clinker nodulization and for improving the burnability of the raw mix. The dual Table 8.4.4. Typical Oxide Analysis goals of raw mix design are to provide a composition of Cement that is burnable and to produce cement that is Oxides Wt, % consistent with market demands. The composition CaO 60 67 corresponds roughly to the range of values shown in SiO2 17 25 Table 8.4.4, leading to the compound compositions Al2O3 38 shown in Table 8.4.5. Thermal analysis has been Fe2O3 0.5 6.0 frequently employed in characterizing raw materials MgO 0.1 4.0 to ensure compositional quality and detect the presAlkalis 0.2 1.3 SO3 24 ence of any deleterious impurities therein.
Table 8.4.5. Typical Compound Composition of Ordinary Portland Cement Chemical name
Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Calcium sulfate dihydrate (gypsum)
Chemical formulae
3CaO SiO2 2CaO SiO2 3CaO Al2O3 4CaO Al2O3 Fe2O3 CaSO4 2H2O
Cement notation
C3S* C2S C3A C4AF CSH2
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Tricalcium silicate (C3S) is the major phase with a significant impact on the setting and early strength properties of cement, whereas tricalcium aluminate (C3A), being the most reactive compound, has the highest initial impact on the early hydration behavior of cement. Thermal analysis has routinely been used in monitoring the hydration characteristics of the individual cement components, as discussed in a later section of this chapter.
Limestone
It is critical that limestone (CaCO3) is of adequate quality to permit proper raw feed formulation. The presence of excessive Mg contamination in limestone often leads to inferior clinker that forms potentially less durable cements. DTA techniques can detect impurity in a limestone, enabling adjustments to be made in the formulation of the raw mix. DTA plots for limestone, dolomite, and iron-bearing limestone used in cement raw feed are given in Figure 8.4.2. The x-axis shows the temperature to which the sample is subjected, and the y-axis shows the heat change, H, endothermic (heat consumption) or exothermic (heat release) during the analysis.
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MgCO3
CaCO3
Temperature, C
Figure 8.4.2. DTA plots showing typical peaks for important carbonaceous raw materials used in cement manufacture.
An endothermic peak between 850C and 950C results from the decomposition of CaCO3 in air with the evolution of CO2 and is accompanied by a weight loss. The presence of notable amounts of MgCO3 as a contaminant in limestone, however, produces an additional endothermic peak. Dolomite exhibits two endothermic peaks. The first peak around 750C is caused by the decomposition of MgCO3, and the second peak around 900C is caused by the decomposition of CaCO3. If dolomite is present as a contaminant, the peaks will be shifted slightly (Ramachandran, 1969). In carbonate rocks, dolomite can be estimated by using DTA, even in amounts as low as 0.3% (Bensted, 1978). Pure magnesite, MgCO3, is identified by an endothermic peak around 700C due to its decomposition and release of CO2, whereas brucite-bearing limestones show an endothermic effect around 475C, as a result of dehydroxylation; brucite is the mineral name of magnesium hydroxide, Mg(OH)2. Iron-bearing limestones show an additional endothermic peak between 350C and 400C possibly attributable to dehydration of hydrated iron oxides. The presence of quartz in limestone is determined, and can be quantified, by a reversible endotherm at 575C corresponding to the transformation of to quartz.
Clays
Clays, shales, slates, and schists provide ingredients such as SiO2, Al2O3, Fe2O3, and alkalies that take part in the formation of the essential phases silicates, aluminates, and the melts in cement clinker. The most desirable clay minerals for cement making are kaolinite, which is a hydrous aluminum silicate Al4Si4O10(OH)8, and low-alkali montmorillonite, essentially Al4Si8O20(OH)4nH2O with the substitution of Mg for part of Al (Read, 1970). These clays contain mainly Al2O3 and SiO2, with a low alkali content, and also satisfy other requirements in formulating the kiln feed mix. Kaolin is preferred over pure quartz because kaolin is already naturally finely divided and easy to burn, whereas
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the use of quartz involves expensive and abrasive grinding and may require extra energy for burning. Natural clays may require less kiln thermal energy due to the presence of some natural fluxes. DTA has been effectively used in identifying clay minerals, as reported by Mehta (1964) and Ramachandran (1969). Typical DTA plots of several clay minerals kaolinite, montmorillonite, illite, chlorite, and gibbsite are given in Figure 8.4.3. A highly crystalline kaolinite mineral shows a characteristic endothermic peak due to dehydroxylation between 550C and 600C, and an exothermic peak around 1000C due to phase transition (devitrification of glass) in forming mullite or -Al2O3 nucleation. A poorly crystalline kaolinite often shows an additional small endothermic peak at about 100C due to loss of free water. Montmorillonite clays definitely show an endothermic peak around 100C as a result of dehydration, followed by another peak between 600C and 700C due to loss of lattice water. Another endothermic peak noted at about 900C is due to lattice breakdown, and a final exothermic peak at 955C is due to a phase transition in which a spinel is formed. The thermal analyses are typically quick to identify the presence of any unwanted inorganic and organic contaminations in clays that would otherwise potentially cause processing, operational, and environmental problems during cement manufacture. The presence of quartz in clay minerals is determined by DTA. Since the endothermic peak of to quartz is overlapped by the dehydroxylation peak, it can be observed without interference in the exotherm, during cooling, caused by the transformation of to quartz.
200
400
600
800
1000
1200
1400
Temperature, C
Figure 8.4.3. DTA plots for typical clays used in cement manufacture.
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Shale
As mentioned above, shale is also a common material which, like clay, can be used as a silica, alumina, and iron source in cement manufacture. Thermal analysis has been frequently used in characterizing the mineral composition of shale. Since shale has a mineralogical composition very similar to many clays, the thermal analysis results are similar. In some plants, the terms shale and clay are essentially interchangeable. Other argillaceous materials of interest are the slates and schists. They also provide the necessary silicates, aluminates, and some iron for the kiln feed mix design.
Sand
Most sands are largely quartz. The principal thermoanalytical feature of quartz is the aforementioned to transition at 575C, which can be quantified. The quartz content of raw materials, or potential raw materials, is very important with respect to raw mix burnability; characterization using thermal analysis is a useful adjunct to a microscopical characterization.
Iron Ore
Thermal analysis can be used with iron-bearing materials to characterize reduced iron species and hydrates. Reduced iron species will oxidize when heated in a DSC in air; this exotherm can be quantified to determine how much reduced iron is present. The endotherm resulting from the dehydration of hydrates such as goethite, or decarbonation of limonites, can be used to quantify the amount of such mineral phases in the iron ore of interest. Thermal analyses (TGA and DSC) can also determine the amount of moisture and the temperature at which it is released from iron hydrates to assess their impact on the raw feed thermal behavior, especially during their passage through the preheater stages.
Mill Scale
Mill scale is usually principally iron metal, together with small amounts of iron oxides. The mode of generation of this material often dictates that it contain variable amounts of oils, which are organic and can cause emissions of hydrocarbons or carbon monoxide from the stack. DSC is a powerful tool in identifying the quantity of any such oil, and the temperature at which it is volatilized and/or burned. This information will aid plant personnel in deciding whether a given mill scale source is compatible with plant operations and/or environmental requirements.
Gypsum
Gypsum is added to clinker during the finish milling, primarily to regulate the setting properties of cement. Thermal analysis is often used to determine the presence of hemihydrate (also known as plaster) in gypsum. It is critical to know the degree of conversion of gypsum to plaster, as an excess of plaster may cause the phenomenon known as false set, while too little dehydration can cause
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quick setting behavior. In the field, inadequate amounts of gypsum, or especially plaster, in a cement to be used with fly ash and/or admixtures in concrete can cause erratic setting and strength development. A typical gypsum DTA plot is shown in Figure 8.4.4 for a crucible with a pinhole in the lid. Dehydration of gypsum gives rise to an endothermic peak around 150C (decomposition of gypsum to plaster) and another at 200C (dehydration of plaster to soluble anhydrite, -CaSO4).
Plaster Gypsum
20
70
120
270
320
370
Fly Ash
Lately, fly ashes rich in unburned carbon are being considered as economical materials having additional benefits in supplementing fuel. Applications of thermal analysis (both TGA and DSC) have contributed greatly to characterizing the intrinsic fuel value of such ashes. The techniques have also been used to determine the existence (if any) of volatile organics and their temperature of release in the cement kiln, helping to avoid any emission problems. Figure 8.4.5 shows a DSC
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plot of a fly ash rich in unburned carbon. A large exotherm around 600C confirms release of heat attributed to carbon. The vertical axis is heat released in J/g.
50
150
250
350
650
750
850
Figure 8.4.5. DSC plot for fly ash with significant unburned carbon content.
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Figure 8.4.6. Limestone quarry showing layers of material that may have chemical variation as well as organic contaminants.
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Figure 8.4.7. Shale deposit with overburden organic impurities with potential environmental significance.
DSC plots of selected limestone and shale samples acquired from various depth locations of the same quarries are given in Figures 8.4.8 and 8.4.9. Exothermic peaks below 350C indicate the presence of organic species that could be released earlier in the back end of the kiln and would most likely report to stack emissions, either as hydrocarbons or as CO. Deeper limestone has much higher peaks at lower temperatures (around 350C and less), and would therefore be expected to represent greater emission problems. Likewise, shale 1 would be expected to experience more severe emission problems owing to its low temperature peaks.
Limestone: 6m deep
50
150
250
550
650
Figure 8.4.8. DSC plots showing organic impurities with potential emission problems in limestones. Low temperature peaks suggest presence of organics with potential emission-related impact.
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Shale 1
Shale 2
50
150
250
350 Temperature, C
450
550
650
Figure 8.4.9. DSC plots showing organic impurities in shales, with potential emission impact.
CLINKERING REACTIONS
DTA or DSC can readily be used to closely simulate the conditions existing in the rotary kiln during clinkering (Pope and Judd, 1977). The level and rate of heating of the samples as well as the atmospheric conditions in DTA or DSC can within limits be adjusted to those of the kiln, thereby confirming these techniques (and also TGA) as powerful tools for characterizing not only the raw materials but also the finished product. The formation of clinker results from a series of thermochemical reactions that take place when the kiln feed is heated through different stages in a rotary kiln. Since thermal analysis can be used to determine the heat generated or absorbed in chemical reactions, it is also appropriate for following the clinkering process. As is already known, some of the reactions involved during clinkering are endothermic while others are exothermic. Ignoring all process heat losses, the net theoretical requirement of heat for converting kiln feed to 1 kg of clinker is close to 420 Kcal. With respect to minerals formation, the sequence of processes during gradual heating of a kiln feed, as simulated by a DTA run (Gouda, 1981) is shown in Figure 8.4.10. The plot clearly shows the stage of dehydration caused by the loss of moisture in the raw feed at about 400C, followed by decarbonation at 740C and 850C resulting from the decomposition of dolomite and limestone involving loss of carbon dioxide. This is followed by devitrification of clay-derived glass, exothermic belite formation between 1100C-1270C, liquid formation between
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Dehydroxylation 450C
Belite Ferrite
Figure 8.4.10. DTA plot showing a sequence of phase formation in a typical cement raw feed.
1250C-1300C, and alite formation above this temperature. The region beyond 1300C may also reflect the crystal growth. If the sample is subsequently cooled, the exotherm attributable to the crystallization of melt may be seen. In certain cases, it may also be possible to discern small endotherms attributable to the volatilization of alkali and/or sulfur compounds. The major reactions and the heat exchange involved during the clinkering of kiln feed, as reported by Hondoo (1999), are summarized in Table 8.4.6.
Table 8.4.6. Reactions and Heat Exchange During Clinkering (Hondoo, 1999) Temperature, C
100 450-500 850-950 >900 900-1200 1250-1280 >1280
Clinkering reactions
Dehydration, loss of free moisture Dehydroxylation, release of bound water Decarbonation, release of CO2 from limestone, dolomite, carbonates Crystallization of dehydrated clay products Reaction between lime and clay products, and formation of belite Melt formation and liquid phases aluminates and ferrites Further formation of liquid phase, alite formation and completion of clinkering, possible alkali/sulfur volatilization Crystallization of melt
Heat exchange
Endothermic Endothermic Endothermic Exothermic Exothermic Endothermic Endothermic overall Exothermic
Cooling
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High-temperature DTA can be used to determine the temperature of clinker melt formation, belite formation, alite formation, and crystallization of the clinker interstitial phase, as well as the evaporation of volatile materials such as alkali salts. This technique is particularly valuable when applied to exercises optimizing raw mix design for burnability and fuel economy. For example, if a kiln feed contains two types of silica (quartz and clay mineral derivation), belite may form in two different temperature ranges. The clay-derived silica may react at much lower temperatures than the quartz. Such a raw material mix might generate two separate belite exotherms. These could have a significant influence on the desired flame profile to obtain optimum clinkering. An example of a DTA for a white clinker production process is shown in the Figure 8.4.11 (Chrom , 1974). Typical exothermic y and endothermic peaks identified during the clinkering of a clinker raw feed are given in Table 8.4.7.
1290C
1380C
1400
1450
1500
Peak type
Exothermic Endothermic Endothermic
Phase formation
Belite Formation Transition of Belite, and melt formation
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B H
Alite peaks
Figure 8.4.12. DTA plots for raw mixes showing variation in burnability.
As can be seen, the position and intensity of endothermic peaks due to alite formation (around 1370C) are critical in determining the burnability of the raw feeds. Raw feed A appears to have better burnability because alite formation with this feed takes place at a lower temperature of 1350C as compared to 1375C for both B and C feeds. The data also suggest that the alite formation reaction occurs more easily for feed A, and that the heat requirement for raw feed A to convert to clinker may be lower than either B or C.
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Ampian and Flint (1973) have used DTA and TG techniques to monitor the effects of mineralizers such as fluosilicates on the formation of C3S from C2S and free lime. They estimated the extent of these effects by measuring the free lime content from the corresponding reactions and substantiating the results using X-ray diffraction data. The technique of DTA has also been used by Viswanath and Ghosh (1983) to study the effect of mineralizers on the burnability of a cement plant raw mix. Fluoride, calcium fluorides, and phosphogypsum were used as mineralizers for a hard-burning raw mix, with a lime saturation factor (LSF) of 84 and alumina to iron ratio (A/F) of 1.35. The DTA plots are shown in Figure 8.4.13a-d.
1270C
1300C H
1355C
1330C Temperature, C
(a)
1230C
(b)
Temperature, C
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1165C
1230C
1345C
1140C
0.4% Fluoride
1230C Temperature, C
1320C
(d)
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KCl, K2SO4, Na2SO4, and CaSO4-K2SO4 double salts. In addition, mixtures of these salts may melt at especially low temperatures. As a result, they condense on lower-temperature refractory surfaces and also cause plugging problems in suspension preheaters. Chen (1982) also emphasized the application of DTA in the identification of spurrite (2CaOSiO2 CaCO3), a needle-like compound that forms during the clinker-burning process and adversely affects the raw meal flowability. Janko (1985) examined and evaluated the composition of ring formation in the kiln and quantified spurrite formation using the TGA and SEM techniques. Figure 8.4.14 shows thermal analysis peaks for both calcite from recarbonation of lime and spurrite formed in a kiln ring.
6 4 H 2 0 Weight loss, % -2 -4 -6 -8 400 TGA plot Corresponding weight loss DSC plot 760C Calcite 800C Spurrite
600
800 Temperature, C
1000
1200
Figure 8.4.14. DSC and TGA plots showing calcite and spurrite peaks with corresponding weight losses.
Preheater/Precalciner Performance
Thermal analysis can be of use in monitoring preheater/precalciner performance in a cement operation. By subjecting the feed from individual stages of the preheater to DSC/TG analyses, the degree of calcination can be quantified from the weight loss due to decarbonation of uncalcined limestone in the kiln feed. The data can be used to establish the temperature profile of the preheater. The same approach can also be used for product from the calciner, to monitor its performance by quantifying the degree of calcination. Figure 8.4.15 shows two hot meals from the fourth stage of a preheater at a cement plant, taken at two separate occasions. The peaks and weight loss clearly indicate improved calcination in the second sample relative to the first sample: i.e., A is more calcined than B.
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-6
-8
Hot meal B
-10
Figure 8.4.15. DTA plots of two separate hot meals A and B taken from fourth stage of preheater.
Kiln Buildups
The formation of many buildups in rotary kilns results from the volatile components contained in the raw materials. The alkalies, typically derived from the minerals illite, orthoclase, muscovite, sodalite, and/or scapolite, generate volatile alkali sulfates and chlorides in the hottest part of the kiln. The volatiles are swept together with the combustion gases toward the colder regions of the kiln system where they condense. The buildups are highly undesirable, as they may narrow the feed inlet, increase pressure drop through the preheater, reduce gas flow, and ultimately require shutdown to remove the accretions, thereby increasing kiln downtime and causing serious production losses. Thermal analyses (DTA/TGA) have been routinely used by Hondoo and Agharwal (1989) to identify the mineralogical composition of the buildups and thereby elucidate the underlying reaction mechanism. The buildups were taken from different stages of a dry kiln plant with cyclone preheaters and subjected to DTA analysis. The samples of buildups were taken from 1) the blades of the induced draft fan, 2) top of the stage-4 cyclone, 3) bottom of the stage-4 cyclone, and 4) coatings from the calcination zone. The DTA plots are shown in Figure 8.4.16. A summary of data interpretation is given in Table 8.4.8.
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Figure 8.4.16. DTA plots showing buildups from different locations of cement operation.
Table 8.4.8. Mechanism of Kiln Buildups from DTA Data (Hondoo and Agharwal, 1989) Sample location
Buildup from draft fan blades
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Stored clinker
Dehydroxylation
Decarbonation
Weathered clinker
200
800
1000
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occur. The appearance of peaks and the associated weight losses in weathered clinker as compared to the original clinker gives a relatively better measure of the damage to the clinker from improper storage or prolonged weathering.
Plaster Gypsum
20
70
120
270
320
370
Figure 8.4.18. DSC plot showing gypsum and plaster in a finished ground cement.
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Syngenite Gypsum H
Plaster
20
70
120
170
320
370
420
Figure 8.4.19. DSC plot showing gypsum, plaster, and syngenite in a finished ground cement.
Silo Set
If cement transferred into a silo is very hot, and if the exterior walls of the silo are cool, water transfer can occur from the hot silo interior to the cooler exterior, forming syngenite, and creating the phenomenon known as silo set. Syngenite (CaSO4 K2SO4 H2O) is a needle-like crystalline substance that can hinder cement flowability significantly. Thermal analysis is also helpful in discovering and quantifying the syngenite in cement. This material is formed by the transfer of water from gypsum to potassium sulfate, often occurring in cement silos during storage. Figure 8.4.19 has already shown the existence of syngenite in cement.
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2C2S + 4H2O Ca(OH)2 + C3S2H3 C3A + 3CaSO4 2H2O + 26H2O C6A 3H32
(Ettringite)
Generally, C3S2H3 is calcium-silicate-hydrate of an approximate composition, and Ca(OH)2 is calcium hydroxide. In common cement notations, C3S2H3 and Ca(OH)2 are also termed C-S-H and CH respectively. The rate of reaction and the formation of the hydration products are dependent upon the composition of the cement. These determine most of the physical properties of the hydrated system, such as the heat of hydration, setting times, tendency toward abnormal stiffening, admixture compatibility, compressive strength, and durability-related properties such as expansion and alkali-silica reactivity. Thermal analysis can provide both qualitative and quantitative information on the hydration characteristics of cement, based on the rate of formation of the hydration products. The data can be related to the composition and quality of cement to project its potential engineering behavior.
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17 Days Hydrated iron oxide CaCO3 Ettringite H Monosulfate Ca(OH)2 CSH 45 Days
200
800
1000
Figure 8.4.20. DSC plots of cement pastes hydrated for different curing times.
Generally, the peak temperatures vary with the techniques used, but their positions relative to each other remain unchanged. It will be noted that the endotherms for C-S-H and ettringite are close together, and separation may become an issue. If so, the sample can be treated with acetone and heated to 45C for 4 hours prior to testing. This treatment eliminates the C-S-H endotherm, allowing an interference-free determination of the ettringite endotherm.
Peak C
105 115 140 165 195 390 480 750
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(5)
where the factor 0.41 corrects for the water loss equivalent to that of decarbonation, assuming that the carbonate is formed by carbon dioxide reaction with calcium hydroxide from hydration. A selection of calculations of chemically-bound water and its relationship to the degree of hydration of cement paste is shown in Table 8.4.10.
The factors 4.11 and 1.68 are stoichiometric factors for hydroxylation and decarbonation, respectively. The first term of Equation (6) gives the amount of free CH formed during hydration. The second term of the equation refers to the carbonate formed from carbon dioxide reaction with CH. Calculated values of CH for a Type I cement are also given in Table 8.4.10 (Bhatty and Reid, 1985).
Table 8.4.10. Estimated Calcium Hydroxide in Cement Paste (Bhatty and Reid, 1985) Curing time, days
1 3 7 28 120 200
Degree of hydration, %
29.90 45.95 55.43 73.14 78.21 83.57
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cements. Full hydration of a cement paste can be achieved by accelerating the process at elevated temperature and pressure. In DTA or DSC patterns, comparing hydration products of the portland cement with those of the blended cement, the C-S-H peak will be enhanced and the calcium hydroxide peak correspondingly diminished, as demonstrated in Figure 8.4.21.
Blended cement
200
800
1000
Figure 8.4.21. DSC plots for pastes made with portland vs. blended cements.
(7)
After all the gypsum is used up, the ettringite reacts with unreacted C3A to form monosulfate according to the following equation: 2C3A + C3A C H32 + 4H 3(C3AC H12)
(Ettringite) (Monosulfate)
(8)
Study of these two forms of calcium sulfoaluminate hydrates has been of interest for their role in cement chemistry which has been investigated for many years. DSC, sometimes in conjunction
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with X-ray diffraction, has been an invaluable tool in quantifying ettringite and other sulfoaluminate hydrates in cement hydration products.
In a cement paste, the hemihydrate rehydrates back to gypsum and forms a semi-rigid crystalline matrix. As earlier described, DTA/DSC analysis of cement gives peaks for dehydration of gypsum and hemihydrate at 160C and 210C respectively. Using the peak heights and the areas under the peaks, the proportions of gypsum and hemihydrate in cement are quantified. The data on gypsum and hemihydrate are used to assess the potential for false set. Similarly, any potential for flash set in cement can be estimated by the amount of gypsum or plaster present. Flash set occurs due to lack of available sulfate to properly control the hydration of C3A. Using the same DTA/DSC and the quantification method, any lack of gypsum and/or plaster in cement is quantified, and the potential for flash set can be assessed. X-ray fluorescence (XRF) is a technique to determine total sulfate in cement and can be used to supplement DTA/DSC data (Broton, 2002). Figure 8.4.22 shows DSC plots of a normal cement and one with a false setting tendency. The distribution of sulfate forms in the cements and their actual false set behavior as determined with the mortar false set test (ASTM C 359 specification) to verify the findings are shown in Table 8.4.11 below.
Table 8.4.11. DSC and ASTM C 359 Data for Normal and False Set Cements Cement types
Gypsum Plaster Syngenite Initial penetration 5 min 8 min 11 min Remix
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Normal cement
100
200 Temperature, C
300
400
(10) (11)
When the supply of gypsum for reaction is exhausted, the ettringite transforms to monosulfate of the type C3(A,F)CH12. DTA and TGA techniques have also been used to monitor the hydration of the ferrite phase.
CONCLUSIONS
Thermal analysis techniques, TGA, DTA, and DSC in particular, have found multiple uses in studying the fundamental characteristics of cement and cementitious materials. Lately, thermal techniques have found diverse applications in the analyses of cement raw materials for improving processing parameters at the plant, such as formulating the optimum kiln feed mix design, assessing potential environmental compliance, and monitoring calcination behavior during the clinkering operation. The techniques have also found vital applications in clinker and cement characterization. The processes of cement hydration, setting, and strength properties have been
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monitored successfully and improved by their applications. Thermal techniques are being employed routinely for troubleshooting material, operational, and product problems in cement manufacturing with the objectives of improving the process of cement manufacturing and the efficacy of the present techniques for cement evaluation.
REFERENCES
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