Application of thermal analysis to the cement industry

Methods involving heat measurements have been applied in the cement industry for a long time. Differential thermal analysis (DTA) is used to explain the clinkering reactions, but it is a dynamic method which thus does not allow measurements and calculations of the thermal balance of the reactions to be made. In contrast, high temperature microcalorimetry may be used to measure the enthalpy of the clinkering reactions of industrial raw materials. Results obtained by using this technique allow us to determine the thermal profile of clinkering reactions in the kiln and to quantify the heat exchange in the solid material during its burning.Low temperature conduction microcalorimetry gives information on the hydration mechanism of the cement pastes. In this paper, we review the applications of thermal analysis in the cement industry paying special attention to new methods such as high temperature microcalorimetry.

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Zusammenfassung Seit langer Zeit werden in der Zementindustrie Verfahren mit Wärmemessung angewendet. Zur Erforschung der Verschlackungsreaktionen wird DTA verwendet, was jedoch ein dynamisches Verfahren ist und keine Messungen und Berechnungen bezüglich des thermischen Gleichgewichtes erlaubt. Im Gegensatz dazu kann Hochtemperatur-Mikrokalorimetrie zur Messung der Enthalpie von Verschlackungsreaktionen industrieller Rohstoffe dienen. Mit Hilfe der durch diese Methode erlangten Resultate kann das thermische Profil von Verschlackungsreaktionen im Kiln und der Wärmeaustausch im Festmaterial beim Brennen bestimmt werden.Niedertemperatur-Konduktions-Mikrokalorimetrie liefert Informationen über den Hydratationsmechanismus von Zementleim. Unter spezieller Beachtung neuer Methoden, wie z.B. der Hochtemperatur-Mikrokalorimetrie, wird in diesem Artikel ein Überblick über die Anwendungen der Thermoanalyse in der Zementindustrie gegeben.

     

Hypothetical transformation of Ca(OH)<Subscript>2</Subscript> into CaCO<Subscript>3</Subscript> in solid-state reactions of portland cement

Summary Previous study of the hydration and ageing products of two cement pastes created the basis for the postulate of the course of solid-state reactions between the portlandite Ca(OH)₂ and the CO₂ from air in the hydrated and air dry cement. XRD basal spacing d(001) of portlandite exceeded the nominal value and increased with ageing, with the wetting and drying procedure and with carbonate content of the paste, indicating that a part of OH^- ions was gradually substituted by CO₃^2- ions, which are about twice bigger. IR spectroscopy showed a considerable content of portlandite, of CO₃^2- of water and silicates. Also HCO₃^- H₂O and CO₂ in cavities between hexagonal rings and hexagonal hydrates were indicated. By MS (mass spectrometry) in vacuum the evaporation of sorbed water was detected at 100-120°C, of gel water at 350°C of portlandite water at 400°C and of high temperature water between 500 and 700°C, simultaneously with CO₂ escape. Slightly higher peak temperatures were found by the TG test either in air or in argon. From these results and from geometric considerations it is postulated that the solid-state reactions take place on ageing of the cement paste and on its heating: hexagonal portlanditecalcium carbonate hydroxy hydratecalcium carbonate hydratehexagonal vaterite and/or orthorhombic aragoniterhombohedral calcite The analysis of the standard files of the calcium carbonate hydroxy hydrates supports this postulate and indicates a gradual transformation.     

An attempt to improve the pozzolanic activity of waste aluminosilicate catalyst

The so-called pozzolanic activity of waste catalysts from fluidised cracking was investigated. For this purpose a series of cement mixtures with this waste material were prepared and subsequently the pastes and mortars were produced. Waste aluminosilicate catalyst was used both in raw form and after grinding in a ball mill for 60 min. The hydrating mixtures were subjected to the calorimetric measurements in a non-isothermal/non-adiabatic calorimeter. After an appointed time of curing the hydrating materials were studied by thermal analysis methods (TG, DTG, DTA). The pozzolanic activity factors were determined, basing on the compressive strength data. The increased activity of cement — ground pozzolana systems has been thus proved. An accelerated Ca(OH)₂ consumption as well as higher strength were found for materials containing ground waste catalyst, as compared to those, mixed with the raw one. Thus grinding was also proved to result in mechanical activation in the case of the waste catalyst from fluidised cracking. This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigations of the influence of different fly ashes on cement hydration

Investigations of physico-chemical properties of three kinds of fly ash and their influence on cement hydration were performed in this work. Thermal analysis, microcalorimetry, infrared absorption and others were used. It was confirmed that the kind of coal and combustion conditions essentially influence physico-chemical properties of fly ash and in consequence influence cement hydration. Investigated fly ashes show in cement system so-called pozzolanic activity. Fly ash from combustion of brown coal in fluidized furnace revealed better activity compared to other investigated ones. This work is an introduction to more extensive investigation of fly ash activation.     

Effect of thermal decomposition processes on the thermal properties of carbon fiber reinforced cement composites in high-temperature range

Thermal conductivity, specific heat capacity, thermal diffusivity and linear thermal expansion coefficient of two types of carbon fiber reinforced cement composites are measured in the temperature range up to 800°C. Thermal conductivity and thermal diffusivity are also determined for the specimens exposed to thermal load up to 800°C before the measurement. Differential thermal analysis (DTA), mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD) are utilized for the assessment of thermal decomposition processes taking place in the high temperature range under consideration. The high temperature thermal properties of the studied materials are found to be positively affected by the application of the high alumina cement and in the case of the Portland cement based composite also by using the autoclaving procedure in the production process. Also, the randomly distributed carbon fibers that can reduce the damage of the pore structure by the thermal decomposition processes are identified as a positive factor in this respect. A comparison of thermal conductivity vs. temperature curves obtained for the specimens pre-heated to different temperatures is found to be a useful tool in the identification of major dynamic effects in the specimens due to the thermal decomposition reactions. The results are in a good agreement with the DTA, MIP, SEM and XRD analyses. The character of the thermal conductivity measurements that in fact includes the effects of convection and radiation into the thermal conductivity coefficient can be beneficial for a simple assessment of the influence of the fire on a dividing structure.     

A Study on the Hydration of Portland Limestone Cement by Means of TG

Subject of this paper is to investigate the hydration process of Portland limestone cement containing 10-35% limestone. Cements, produced by co-grinding of clinker, limestone and gypsum, were hydrated for periods 6 h to 28 d and were studied by means of TG and XRD. The Ca(OH)₂ content of the cements containing limestone is higher than in pure cements, specifically for 10% limestone content and ages more than 1 day. These results are in accordance with the strength development of the studied cements. In earlier ages the Ca(OH)₂ content is slightly lower in the limestone cements and independent of the limestone content. After 1 day curing, the increase of limestone addition causes a relative increase of the non evaporable water. The XRD patterns indicated the presence of carboaluminates in the hydrated limestone cements. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase composition and formation of cobalt-copper cement catalysts

Using x-ray phase analysis, DTA, DTG, and temperature-programmed reduction, we have studied the phase composition and formation of cobalt-copper cement catalysts obtained by chemical mixing of hydroxocarbonates of cobalt (CoHC) and copper (CuHC) with the aluminocalcium cement talyum, consisting of CaAl₂O₄ and CaAl₄O₇, in an aqueous ammonia medium. We have shown that when the components are mixed, exchange reactions occur with development of new phases of cobalt and copper hydroxoaluminates, calcite, gibbsite, Cu(OH)₂, CuO. We found that CaAl₂O₄ is more reactive than CaAl₄O₇. We have obtained data on the change in the phase composition upon thermolysis and reduction in H₂.N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 48–54, January, 1992.     

Synthesis, formulation and evaluation of novel zinc-calcium phosphate-based adhesive resin composite cement

Three novel adhesive oligomers having carboxylic acid and methacrylate groups were synthesized, characterized and used to formulate composite bone cements with newly synthesized zinc-calcium-silicate phosphate. The optimal formulation was determined based on types of oligomer, oligomer/diluent ratio, initiator concentration, and filler level using compressive strength (CS) and curing time (CT) as screening tools. Shrinkage, exotherm and aging of the formed composite cements were also evaluated. Results show that the experimental cement was 186% higher in CS, 16% higher in diametral tensile strength, similar in flexural strength, 56% less in exotherm and 64% less in shrinkage, as compared to conventional polymethylmethacrylate cement. The optimal concentrations for initiators were found to be 1.5% (by weight) for both benzoyl peroxide and N,N^′-dimethyl-p-toluidine. With increasing initiator concentration, diluent content and zinc oxide content in the cement formulation, CS of the cement increased but curing time decreased. Shrinkage and exotherm of the cement decreased with increasing filler level. CS was not proportional to an increase of filler level and CT increased with an increase of filler level. During aging, the cement showed an increase of strength over 24 h and then no change for over nine months. It appears that this novel cement may be a potential candidate for orthopedic restoration if its biological performance is good and the formulation is optimized.     

水泥砂浆在主动围压下的动态力学性能

水泥砂浆等脆性材料的力学性能与所受围压的大小密切相关。为了研究水泥砂浆在围压下的动态力学性能,研制了适于分立式Hopkinson压杆加载的主动围压装置,最大预加载主动围压大于30 MPa。实验得到了水泥砂浆在不同围压、不同应变率下的轴向应力应变曲线,发现材料在围压作用下抗压强度和韧性大大提高并且整体进入了伪塑性,而材料的应变率效应也是显著的。     

玻璃离子水门汀固化反应的红外光谱研究

用红外光谱研究了玻璃离子水门汀固化反应过程,结果显示,表征聚丙烯酸盐的峰强度(～1 413 cm-1)随时间延长而逐渐增加,而硅醇基团,即最强峰(～1 039 cm-1)上的肩峰(950 cm-1),在所观察的周期中仍然存在。因此,玻璃离子水门汀抗压强度随时间延长而增加的原因在于： ①Ca2+,Al3+与聚丙烯酸的固化化学反应在一个相当长的时间内仍在进行;②因玻璃结构分解形成的硅醇基团将长期存在,并在缩合形成硅凝胶的过程中,改变基体与填料间的界面结构和组成,因此对玻璃离子水门汀的长期力学性能也将产生一定的影响。