Cement Data Book Duda Vol1
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According to document D1a the amount of sulphur in the raw mix feed varies between 0.10 and 0.63% by weight, depending on the specific type of raw material used (see pages 77, Table 19). Moreover calculations made by the appellant on the basis of data provided by D1a lead to the conclusion that, at least in the case of raw materials like "unterer Muschelkalk" or "oberer Muschelkalk" the amount of sulphur in the final Portland cement clinker is well above 1.5% by weight, namely 1.9% and 1.75%, respectively. It is established according to various cement standards that the SO3- content in cement is between 2.5 and 4% SO3 (see D10, page 7).
4.1. As far as composition of the raw mix feedstock and the final Portland cement clinker are concerned, D1a gives no details regarding the calciner - kiln system described on pages 26 to 28. Some general information is provided in separate sections of D1a, however. Thus, data regarding the sulphur content of a number of different raw meals can be found in Table 19 on page 77. According to Table 19 the sulphur content, calculated as SO3, varies between 0.10 and 0.63% by weight, depending on the type and the geological age of the raw meal (see page 77, last paragraph). It was not disputed that these contents fall within the range defined in claim 1, "calculated on a LOI free basis". On pages 77 to 80 of D1a the possibility of introducing sulphur-containing components to the feedstock during the burning process is discussed. On the basis of model calculations based on the assumption that the degree of sulphatation is 100%, it is concluded that sulphur may be introduced into the system in a total amount which varies between 3.70 and 7.59 Kg sulphur per 1000 Kg of clinker, again depending on the type and the geological age of the raw meal. According to the appellant's undisputed submissions, this corresponds to sulphur contents of 0.92 and 1.9% by weight in the clinker, calculated as SO3.
Over the years, Portland cement concretes have undergone increasing demands for constructability, cost, quality, and environmental impact. These demands were met, mainly, through changes in the cement composition and the introduction of chemical admixtures. In this sense, through a literature review, the authors sought to create a collection of information on the evolution of these materials and their standards from 1937 to 2020 in Brazil . This work is part of a research project that aims to elaborate a dating protocol for Brazilian concretes. From the review conducted, the authors observed that the absence of systematic records in the Brazilian civil construction sector hinders the attempt to create a chronology of the development of concrete in the country. In addition, we concluded that the knowledge of the evolution of Portland cement and chemical admixtures is relevant information that can assist in concrete dating processes. The reliable comparison data, posteriorly combined with microstructural characterisation techniques, may lay the basis for an effective dating methodology.
On the other hand, given that the technological evolution of concrete reflects, above all, the development of Portland cement and the introduction of chemical admixtures to the matrices , knowledge on how these materials advance over the years can be useful in dating strategies. A database of the evolution of the use and composition of cement and admixtures in Brazil was not found in the literature and can assist researchers of various fields. In this sense, the present work seeks to create a collection of reliable data on the topic in Brazil. This study represents the initial step on the development of a methodology for dating Brazilian concretes.
Figure 1 presents the evolution of consumption of Brazilian Portland cement types according to data from the National Union of the Cement Industry (SNIC), presented at statistical yearbooks published by the Brazilian Institute of Geography and Statistics (IBGE) .
Figure 2 shows trends in the levels of constituents of Portland cements produced worldwide over time. Brazilian cement technology followed the same trends. The graphs were constructed from a series of data collected in books and scientific articles, shown in the Appendix.
Ultimately, no records were found in the Brazilian literature regarding the beginning of the adoption of the other types of admixtures in the country. There was also no data on their production volume and when the first chemical industries were established. Records of when these admixtures were first introduced in the Brazilian concretes can lead to valuable clues as to the age of a concrete element. By identifying the chemical component of the admixture in the cement matrix, the age of the structure can be traced over a narrow range of years. The authors have ongoing initiatives seeking to recognize the type of admixture used in samples taken from hardened concrete.
Estimation techniques such as polygonal, triangular prism, trapezoid, isopach maps, and inverse distance methods are often used in ore or industrial minerals deposit evaluation. These techniques do not express the variability of the deposit and do not allow a determination of the reliability of the estimates. However, geostatistical methods can express a measure of the error associated with the estimates, by finding weighting coefficients for a given mining block, and can also help with data configuration that minimizes the error. This work addresses an application study on the quality and reserve characteristics of the cement raw materials of the Adana Cement Factory in Adana, Turkey, based on the spatial distribution and variability of the chemical components (SiO2, CaO, Al2O3, Fe2O3). The study has been carried out using a geostatistical procedure that is useful for site assessment, characterization, and monitoring situations where data are collected spatially. Directional and omnidirectional experimental variograms of the cement raw material variables showed that neither strong geometric nor severe zonal anisotropy exists in the data. The most evident spatial dependence structure expressing the continuity for omnidirectional experimental variograms were characterized by exponential and spherical variogram models. These models have been used in cross-validation analysis, which proved that these models, their parameters, and kriging parameters are applicable for the study area. Quality contour maps of the deposits at given levels underground were estimated using a kriging interpolation technique. Anomalies such as bullseyes and drift were not observed in the maps that were generated. Kriged maps showed the spatial distribution of quality continuity and variability of the deposits. Grade-tonnage curves and total tonnage estimates in the particular grade were determined using ordinary kriging in order to improve the mining operation and planning. Consequently, local uncertainty and the probability of extreme values occurring are tools of prime importance for the mine planning, the optimum mix of raw materials coming from different quarry stopes.
Geostatistical analysis provides a powerful tool for enhancing the prediction and decisionmaking capabilities of planners and engineers in the cement raw materials industry. Geostatistical methods are useful for site assessment, characterization, and monitoring situations where data is collected spatially. The approach preferred in a geostatistical study is to apply an iterative three-step approach involving:
Two commercial software packages (Isatis and Surfer) were used for the data assessment and interpolation of the quality (grade) and mineral reserve characteristics of the cement raw materials in the study area. The results from the analyses were included as exploratory data analysis, variogram analyses, cross-validation tests, and the quality mapping and tonnage distributions, and three-dimensional views of the study area.
There are several forms of kriging including ordinary, universal, lognormal, outlier restricted, indicator, probability, multi-Gaussian, and disjunctive. Ordinary kriging is a method that calculates point or block values directly from the semi-variogram (or covariogram) relationship without having to provide additional qualifying data or modification of the sample data or kriging results. Several authors (Fytas et al., 1990; Dominy et al., 1997 and Roy et al., 2004) have stated that for grade distributions with a coefficient of variation of less than about 1.5, meaningful semivariograms can be produced. Fytas et al. (1990) explained that parametric geostatistics like ordinary kriging works well in deposits with a coefficient of variation of around one or less. Coefficients of variation of all the variables for the study area are below 0.4 (Table I). Ordinary kriging was chosen as the estimation method to evaluate in this study. The correlation matrix of the cement modulus is given in Table III. The table shows that there is no correlation amongst the modulus. Therefore, co-kriging was not applied to estimate grade and reserves of the cement raw materials.