KR20150144744A - Lower heat processed calcium sulphates for early strength cements and general use - Google Patents

Abstract

The present invention relates to increasing the initial and final strengths of cements classified under EN and ASTM as Portland or CEM cements, and also employing all of the clinker cements and calcium sulphates for optimization of coagulation and production The present invention relates to any kind of new cements for simply cementing new cements by simply processing the new methods for forming new cements and by incorporating calcium sulphate resources used for complexing and optimization of new methods. New calcium sulfate resources are obtained by employing lower heat and these inputs are arranged at different dewatering levels, which can be most efficient for their chosen use. These different dehydration levels are called intermediate phases of dehydrated or semi-hydrates or are referred to as monohydrates. The present invention clarifies the well-defined concept of reactivity that was not defined by the existing scientific basis. As a result, cements with initial strengths much higher than known can be produced.

Description

LOWER HEAT PROCESSED CALCIUM SULPHATES FOR EARLY STRENGTH CEMENTS AND GENERAL USE.

The present invention relates to a main set of coagulation optimization for all cements, including cements and clinkers under the standards EN or ASTM, to obtain an excellent increase in early strength and an increase in final strengths To a specific method of incorporating calcium sulphates as a tool. A new cement product was obtained. The second set of products is a new type of gypsum that can be used for all applications where known gypsum is used. And third, by using new calcium sulphates, a high strength pozzolan lime binder is obtained. To begin with the first aspect; Although the mechanisms of action have not yet been fully elucidated, it is conceivable that calcium sulphate affects the strength development (increase) of cements by affecting the microstructures of calcium silicate hydrates. What is generally needed is the introduction of a sufficient amount and type (sorts) of calcium sulphate to balance the reactivity of the aluminate phases. In this way, premature hydration of the silicate phases can be provided and the porosity of the system is reduced.

Cement minerals reactions are associated with four minerals; It relates to calcium silicate minerals (C ₃ S and C ₂ S), calcium aluminate / ferrite minerals (C ₃ A and C ₄ AF), and reactions with additional sulfate ions should be mentioned. Hydration of sulphates is basically necessary to limit the formation of ethene zeit around the C ₃ A and C ₄ AF hydration processes and to prevent their breakage in relation to water. In this way their reactivity is being reduced (retarded) and allowing more silicate phases to gain early strength and thus reducing the porosity of the system. Calcium salts reduce the concentration of Ca (OH) ₂ in the liquid phase of the cement paste to provide a silicate of potassium silicate phases to obtain intensities and prevent its settling by separating from the solution. If, after the discharge of the sulphates, no adequate sulphate hydration is provided, the aluminate concentration may increase due to ongoing C ₃ A and C ₄ AF hydrates. Monosulfate in the curing paste, when combined with sulfate ions, can be converted to ethene zeite and volume expansion and cracking can occur. The greater the solubility of the hemihydrate, the faster the formation of ethene zite in the early stages of hydration, whereas the formation of C ₃ A is slower. By reducing the solubility of the aluminates in the sulphate retention conditions, the heat released is reduced and this stage is where sulphates are discharged and early strengths are formed or determined. Aluminate phases contribute to initial strengths and can directly affect final strengths. In time sequence, the main strength factor is the silicate phase, C ₂ S is generated in time, but the C ₃ S hydration rate is clearly higher and provides a faster build up of strength. Although the discussion focuses more on calcium silicates, it is known that other phases are also important. If the validation and disclosure of existing knowledge continues, the effects of calcium sulphate on cement hydration concentrate on false set and instant set discussions. Advantageous applications provide cooling precautions to maintain the dehydration level to a certain amount of the semi-hydrates considered as part of the scheme considered to be controllable and even to the desired amount at which a soluble anhydrite can be formed, Is the inclusion of 3-5% of natural gypsum stones or natural gypsum and gypsum that coexist in nature with clinkers at the prescribed stage of the process. The primary measure of effectiveness may be the amount of SO ₃ (content). Generally acceptable industrial processes are also available. Calcium sulfate optimization studies constitute one of the major research areas of the cement sector and include designing the initial and final strengths desired, rheology, workability, coagulation time, etc. closest to existing requirements. These are similar series of studies in thousands of cement factories. The parallel and in-situ acquisition of calcium sulfate resources with clinker grinding is complex. It is contemplated that forming the semi-hydrates and soluble gypsum in the high temperature environments of the grinding will provide more soluble sulphates to control the preliminary (initial) activity of the aluminates. If, for cooling, suitable devices for controlling water spray fail to achieve false coagulation, initial cement hydration, loss of rheology and fluidity can occur and strength losses can also occur. The formation of 40-50% semi-hydrates and soluble gypsum is allowed as an optimal range. The purpose is to obtain the calcium sulfate content which can control the optimum strengths and the drying shrinkage (and expansion), otherwise an excess of SO ₃ can cause excessive swells. The imported cement standards are limited to the maximum amount (content) of SO ₃ . Although primarily SO ₃ content, the solubility parameter is important as one of the fundamental factors for general tolerances. Half hydrates and soluble gypsum have higher solubility and should be used for this reason. Solubility is also allowed as a measure of reactivity. There is no clear view about the activity wave. On the other hand, there are some expressions that although the semi-hydrates and soluble gypsum are more soluble, they have a smaller hydration activity than the natural gypsum stones, i.e. the latter provide sulfate ions that are faster than the half-hydrates . As noted, the hydration process involving calcium sulphates may also not be fully described.

The present invention seeks to contribute to these deficiencies by approaching from observing the behaviors of the calcium sulphates themselves as an important consideration factor. At each dewatering level, different calcium sulfate forms are obtained and have different activities or behaviors. That is to say only referred to as gypsum, can be used for each phase, such as wet gypsum stones, dry (2.0 mol. Water) gypsum, 1.9, 1.8, 1.7 ,, molecular water gypsum stones Can provide different clinker calcium sulfate reactions (interactions). According to the previous descriptions, the half-hydrates are defined by reducing the molecular water to 0.5-0.8. Do they have to consider more than this extent as dehydrates, even though they show different features? No particles are dehydrated in conventional industrial practice. Although we can assume that the clinker can be cooled to a certain extent and then ground, conventional scale mills still generate heat to undesired levels. Some mills that do not produce excessive heat are also available. In addition, the basic factor is to determine which of the gypsum stones or sandstone is selected for grinding. The present invention provides descriptions and new products and new methods for solving and describing related matters. The cements of the present invention provide first order high initial strengths equal to or higher than the second order strengths of known plant cements. Even at the same fineness, very high (high) strength (ultra) cements are obtained without requiring ultra fineness. In many applications, the final intensities are also kept at high levels. The present invention acquires all of these only by introducing calcium sulphates. By virtue of this property, the present invention can be applied to all known cements and also to cements which require the use of calcium sulphates in the future.

The early strength factors of today's cements are of decisive importance. These areas are important optimization areas that consider expansion, shrinkage, hydration temperature, and the chemical composition of chemical additives. Due to the construction of high-rise buildings, it is often necessary to use dependable and sustainable molding, pouring and de molding cycles, using pre-cast sector systems, and having convenient flow, And provides exceptional first, second and third day compressive strengths due to the demand for high-speed manufacturing tracks and moldings that have sufficient working time but provide this without significant expansion or contraction, Continue to provide and are also increasingly required in the cement / concrete market. There are different sequences (processes) that require speed from feed molding to feed feed. The present invention clearly demonstrates that calcium sulphates are associated with these fast demand processes. There is some mention in the literature that calcium sulphates can affect initial strengths, but these are not actually described or categorized by the demands of industrial applications. When we continue the pragmatic approach, the contribution to environmental factors is also evident, under the initial generation of robbers. With this approach, a method is being obtained for obtaining the highest initial intensities, by reducing the use of clinkers to some extent and by using higher calcium sulfate contents. According to the outbreaks discovered with these approaches, a 2.0 molecular water bearing gypsum appears to be desirable, although the invention's external humidity is dried in combination with natural pumice grinding. While existing documents are employed to illustrate the above, some valid aspects have been determined; When we examine the hydration process of calcium sulphate with water only, the half-hydrates and soluble salts are at least three times more soluble, but this ability begins to change, while the heat begins to approach 50 ° C or above 50 ° C It is known that the comparative solubility of the hemihydrate to the hydrate decreases. Initiation of heating increases the diffusion rate and also increases the reaction rate. When the heat of the mixed water exceeds 100 캜, the reaction can not proceed and the dissolution rates of the monohydrates and hydrates are the same. We think that this gypsum hydration information includes an effective theory of cement hydration. If enough calcium sulphate is available to prevent permanent instant coagulation actually being supplied by the semihydrates, it is clear that a beneficial hydration process has begun. One must be careful that this should not be excessive so as not to cause erroneous coagulation or excess ethene zit formation problems. Knowledge implies that the half-hydrate and soluble anhydrate dissolve in the first 60 minutes. On the other hand, the high-temperature calcined siltstone begins to dissolve after 60 minutes and the natural siltstone begins to dissolve after 24 hours. That is, a good distribution of jobs (jobs) can be provided. Also, if the calcium sulfates of the present invention are employed, the semi-hydrates may be required in very small amounts. In other words, we can assume that sufficient solubility is obtained by increasing the cement hydration heat. According to some studies, at the end of the day, the solubility of gypsum stones and siltstones are all melting, but the siltstones dissolve more slowly, their hydration is slower (both rates are considered in parallel) the same in that they provide more than 26.5% CaSO _4. If we synthesize the matter, the following explanation can be obtained. At the first times (in the first 60 minutes), the half-hydrates may first be dissolved, so that some half-hydrates may be implemented to prevent instant coagulation. However, if instant coagulation does not exist and your gypsum provides sufficient solubility, anti-hydrates may not be required. It is known that if high heat calcined anhydrite is present in the calcium sulfate system, they may be soluble after 60 minutes. The present invention places dehydrated gypsum stones in a major role and defines them according to their dehydration levels. Dehydrated gypsum can also be dissolved (starting from the first time) at an increased dissolution rate due to the heat of hydration due to the heat of hydration, and in many cases is sufficient solely to complete the process (may be sufficient). The amount of assigned gravels that can be dissolved after 24 hours adopts a good role for the completion of later stages of crude steel formation, as the demand for calcium sulphate is also apparent and the like. As a result, the main role in hydration driving is dehydration and hemihydrate, and natural limestone has partial roles. Another important finding of the present invention is that monohydrate gypsum also has the ability to displace dehydrated gypsum for hydrates which can provide high initial strengths. In addition, monohydrates are more economical solutions by substituting the half-hydrates when such use is employed. As such, the findings of the present invention and existing knowledge are being considered and are being construed to be combined for the sake of explanation. As expressed by many cement chemists, the area of effect of calcium sulphates on strength is a complex area. Though calcium sulphates can affect the rate of hydration, basically there is a difference in the binding capacity of the hydrates formed when more potential strength changes (differences) are observed. The present invention explains how the use of calcium sulfate methods directly affects the development of strengths and how it affects cement hydration. The existing scientific imperfection or grayness of the existing activity power becomes clear. Gypsum, semihydrate and anhydrate are processed (obtained) according to known applications. According to the present invention, the gypsum concept is a special field that is insufficiently defined. This arbitrary gypsum (or hydrated calcium sulfate) concept consists of many gypsums with various types of features that have been altered and uncontrolled and substantially defined, which complicate matters and make it difficult to explain. Although some uncomfortable compressive strengths were obtained under these conditions, they were never close to the results of the invention. In the same way, the semi-hydrates can also be defined according to the remaining molecular water levels, which also have differences. The main difficulty in preparing the optimum gypsum content studies is that you are against a myriad of gypsum plaster. For this reason, the problem remains so far in practical approaches.

Calcium sulfate resources were simply defined as gypsum stones and were basically evaluated according to their SO ₃ levels and solubilities and impurities, and their different properties specify different behaviors according to different dewatering levels and how based on these new cements We did not in-depth evaluate the core of the invention to explain whether products are available. According to the present invention, the effect of calcium sulphates on cement hydration and high strength production is important. This is provided by dehydrates, monohydrates and hemihydrates. Especially when the compressive strengths of the first and second days are taken into account, the strengths obtained by dehydrated dehydrates, monohydrates and semi-hydrates in some manner can not be obtained by other known gypsum stones. In the context of the present invention, many experiments have been performed. In these experiments, random aggregate calcium carbonate stones of 0-5 mm size were used as aggregates. In all experiments, the cement dosage was 450 kg / m ³ and the water and cement ratio was 0.37-0.40. Cements and clinkers from different factories were tested. To illustrate the results with specific examples; When the 42.5 R cement of a particular plant is compared to the cement of the invention made of the clinker of the specific cement as the ground for the same fineness, the compressive strengths of the second day were 20-22 MPa, but the latter obtained 29-32 Mpa. Chemicals or polishing aids were not employed in these formulations. When the cements of the present invention in the tests are described; External humidity drying and dehydrated gypsum stones are polished and mixed. The effect of all dehydration levels is felt; The dehydration realized heat was considerably lower than the usual practice, and different low heating levels were tested. Many dehydration steps have been tested and studied simultaneously with the heat factor. These aspects can be explained in the following paragraphs. Much higher initial strengths were adopted than those of their own prepared to use clinkers of different factories and 42.5 R cements. The cements of the present invention obtained relatively apparently high first day intensities that could go to 25 MPa samples. The strengths of factory 42.5 R cements of the second day are obtained by the cements of the present invention or surpass those of many samples only at the first day. It is clear that this capability can provide cost reduction and speed increase for all uses. Thereafter, compressive strengths were also measured, and it is evident that although the cushioning has decreased, the cements of the present invention apparently resulted in higher compressive strengths. Other intermediate phases, also called major intermediate phases, also have higher results than factory cements, although not as much as the previous one, and all are desirable for factory brands.

The present invention finds that the external (initial) humidity of the gypsum stone raw material has a significant impact on the reaction quality of the final calcium sulfate input to be mixed with the clinker. When the external humidity is polished after drying, the reaction capacity of the gypsum (calcium source of yellow sand) increases considerably. The external humidity should preferably be reduced to zero or at least about 1% prior to the grinding process to obtain a competent calcium sulfate source. At each increment of humidity by as much as 0.2% by weight, a measurable reduction in compressive strength was observed. The natural gypsum raw material was ground on the same powder as the Portland cement 42.5 R brands. The present invention is based on the fact that the drying and dehydration of molecular water in a dense high temperature mill and the dehydration of the molecular water of already dried gypsum stones in less hot mill environments result in different products, Lt; RTI ID = 0.0 > hydration. ≪ / RTI > Further dewatering in a controllable manner also results in different products, if induced to reduce outside humidity before gratings, which are highly desirable instruments. The loss of 1 wt% of the molecular water is positive, and additional steps are also studied in detail. After a 2-2.5% loss, the gray area is reached, where the intensities may indicate a decrease.

The basic approach of the present invention is based on the evaluation of the different calcium sulfate resources depending on their reactivity power obtained in dependence on their dehydration level under lower thermal conditions. The findings are validated with XRD measurements. Experiments have been carried out with the adoption of lower optimum calcium sulfate and SO ₃ rates, which allows to obtain higher first days and early compressive strengths. These calcium sulfate products are produced by heating gypsum stones under different heat and heating periods and are polished to 3500-4000 brains at fixed grinding time. The samples were generally heated at 105 ° C and their external humidity was induced and ground. Depending on the batch amount, aggregate particle size, and mixing conditions, the selected grinding process, heat setting, and environment can result in a loss of molecular weight of 2% to 2.5% molecular weight from dry, -13 loss). The XRD measurements of these products yielded a ratio of 16% -25% half-hydrates. The cement reaching the highest premature compressive strengths was obtained by the calcium sulfate product with 21% -26% half-hydrates as above. These XRD-reading half-hydrate emitters lie above computational water loss results that are physically measured. At an additional 0.70% dehydration level, this XRD reading and physical calculation difference continued in a decreasing manner. Compressive strengths obtained with cement using this phase product are higher than those of the Portland cements on the market but lower than the previous case of the cement of the present invention. In a further step of dehydration to a weight of 0.5% -0.7, these calcium sulfate products which increase again as the XRD readings and physical calculations are closer to the difference, and which use the cement, are very close to the first case (with only 5-10% Which gives rise to higher intensities. The XRD measured half-hydrate ratio is 33% -35%. The optimum calcium sulfate content also increased by 4-5%. At the next further dehydration levels, the XRD readings and calculations were again closer, and the half-hydrate ratios were read in the 40% -50% range. Depending on these calcium sulfate products, the previous compressive forces may not be obtained again. The highest compressive intensities were registered with the first high XRD read difference - where the ratio of the half-hydrates is in the range of 21% to 26%. The second high difference range is obtained by products which are 30-34% on the formation of the half-hydrates Loses. These products are named by us as intermediate phases of dehydrated intermediate dehydrates. The second range of gypsum stones resulting from the calcium sulfate resource is when the XRD semi-hydrate ratio begins to approach 60%. Here too, the XRD readings of the semi-hydrates are in excess of those of the calculated results for physical molecular water losses. The slight difference is smaller than that of the case of the first mentioned dehydrated product. These points are what we call as the 1.20 molecular water dehydrate phase for the monohydrate phase. The monohydrate phase (molecular water 1.00) named by us is suitable for forming high compressive strength cements in a conspicuous manner and the difference tends to increase, but the half-hydrate according to XRD is about 70% and the physical water loss Still high. When the semi-hydrate phase begins to form in the 78% XRD readings, the half-hydrate (0.90 molecules of the semi-hydrates) begins to approach the physical loss and they become equal when the readings are in the 80% range. These points are what we nominate as the 0.80 molecular water hemhydrate phase. Up to this point, the optimum minimum content of calcium sulfate resources according to the present invention was in the same range, but following these points, the content ratios were lower. In a different way, the anti-hydrate ratios from these points of XRD reading are lower than those of the physical water loss calculation. When we become half-molecule water half-hydrates, this difference in readings becomes more apparent. The half-hydrates are 89%, the soluble gypsum is 6% and the dehydrated water is 2%. When dehydration continues at the same heat level, 47% soluble solids are formed, the dehydrate is lower than 28% and the dehydrate is increased to 23%. This is a structure similar to that of natural limestone stones. It is the point at which the XRD reading difference is minimized. When the same dewatering level is repeated at 170 占 폚, a similar beaded product is obtained for a 0.5 molecule water hemihydrate. However, since the water loss is high, it is clear that the reading difference is relatively large. When this is taken into account for the strenght development capability, a high jump of the first moment and the reading difference is the products for obtaining the highest intensities. And then follows the low region until a second jump point where good results are resumed is obtained. Following these points are high-strength products. After point, the XRD reading difference disappears and XRD shows less hemi-hydrates than the physical molecular water loss. Good results can also be obtained by these. However, after the jump point where this difference becomes apparent, (overdispersed) products do not produce good products. Products with the external humidity dried, 1.5% -2.0% additional dewatering realized, the 1.75-1.80 molecular water product and the 3.0% -3.5% dehydrated approx 1.63 molecular water products are the most efficient These are economical options. This is followed by additional dehydration products starting from 1.20 molecules of water and going down there. By detailed scientific research, all theoretical options and images can be achieved. It is important to recognize that the 40-50 half-carbohydrate ratio considered to be a widely deployed practice remains inefficient.

When dehydration heat, dehydration level, heating process time, and particle size distribution of the heated material are taken into account, the preliminary discovery was that these reactivity powers were high in products in the 90-120 ° C range. However, for large-scale operations, relatively low heat 90-100 占 폚 operations may require a timeout and result in a much higher ratio of anti-hydrates in XRD versus those processed at 105 占 폚 -120 占 폚, Which may not be effective in the cement hydration process. The formation of industrial processes in low heat becomes very difficult and the results may also be inadequate. Similar problems occur with very high dewatering levels. For products that require slightly lower dewatering, higher heat up to 135 占 폚 gives good results. For high levels of dehydration, this heat may also be excessive. The heat increases after 1% dewatering level control difficulties have been issued. The heating process is generally performed for a longer period of time, and the mentioned rows become product rows. Even in the case of drying only the external humidity, the highest heat levels prevent the formation of the required molecular structure. Low heat and long process times provide the formation of the required molecular structure. It was as successful as low heat treatment products by any one of the products obtained at the high 170 ° C heat level. In high heat treated products, during the same fixed grinding time, the particle size becomes finer due to the scattering of certain crystals, and the structure and unit volume become larger. Above 135 캜, these effects have been observed and become more apparent as the heat level increases. According to the existing literature, these types of structurally destroyed products have a higher degree of reactivity when the reactivity is measured simultaneously or together with the heat level of the reaction. However, these products can not achieve high compressive strength levels obtained by non-scattered (ruptured) structural products. The present invention assigns a reaction power concept. If demonstrated by the experiments carried out, calcium sulfate products were obtained below 105 ° C in the dehydrated or semi-hydrated class, all with the same unit volume and weight. However, additional dehydration cracking of the crystals begins and the volume increases. At 135 ° C operations, some cracking may start in an early fashion and may increase as the dewatering level increases. At higher temperatures of 170 캜, this becomes more apparent. First, the dewatered products after being polished may be first dehydrated to a certain level and then show structural change and volume increase compared to the gypsum stone aggregate to be polished. This is the result of inflations, surface enlargement, and cracking on a particular size. Another observation is that a much finer specific size distribution is obtained when wet gypsum stones are polished in a period of time of dried gypsum stones. To obtain a similar distribution, a polishing time of less than 20-25% is required. This is due to the abrasive characteristics of the wet stones and the crystal cracks of the wet product. Although drying of wet stones in the low heat term is only intended to be drying of external humidity, some unavoidable formation of the half-hydrates occurs. For example, if drying of 2.5% of the external humidity is done in a very long time to 90 ° C heat, the level of semi-hydrates reaching 40% can be obtained and the desired calcium sulphate phase may not be obtained. If 105 ° C is selected, this is assured and the desired response power can be obtained and the level of anti-hydrates can be at 20. Exactly the same operation is done below 135 ° C, the semi-hydrate level can reach the 25% range and the reactivity power is very close to the previous one. At temperatures above 140 ° C, even for dry purpose operations only, volume increases and reactivity power losses become apparent. The rows of the polishing operation must be calculated in parallel. During the polishing operation, the removal or reduction of the external humidity is important and it may be a minimum requirement to obtain a minimum humidity level of 1-1.5%. It is desirable to maintain the dewatering level in the polishing step in the range of 2% -3% without generating very high heat of polishing. As such, the required response power products are obtained. The calcium sulfate resources of the present invention can be used to obtain the best premature compressive strength production at low ratios or at high ratios to the clinker due to economic and environmental reasons.

Calcium sulfate resources of the present invention were dehydrated at 45-50% and 60-70% and were obtained under 105 ° C heat treatment and analyzed under TGA / DTA analysis. As expected, more dehydrated products went through shape (phase) changes in short time and lower temperatures (123 ° C-133 ° C) and a second shape change occurred in similar rows such as 190 ° C for both. The weight loss occurs mostly until reaching 200 ° C, and this loss mainly starts at 90 ° C to 110 ° C. These are relatively straightforward processes and are consistent with the findings of the present invention.

The Ankara region (Golbasi-Bala-Kochisar), also used by many cement factories, 4-8% impurity-bearing gypsum stones were used in the experiments and were used in the Denizli region 7-8% impurity gypsum The stones were adopted as controls. Each type of gypsum was polished to a fineness similar to that of cement. Clinkers from the Nuk Cement Factory in Hereke were adopted, but other clinkers were also adopted as controllers (Limak / Ankara, Akcansa, Denizli) and the general characteristics of the discoveries were confirmed. Each gypsum phase was formed, i. E. The respective dewatering levels of calcium sulfate were tested to find optimal contents to obtain the best initial intensities. It was found that these optimizations were quite sensitive to changes and even occurred at ± 3% measurable changes in intensities. In the case of the use of a single gypsum source, these optimum content ratios were found to be 10-30% lower than those of the cements produced. These cements can not obtain their nominal strength values with low gypsum content, and the cements of the present invention can act as a wider range of calcium sulfate resource content. The minimum optimum content ratio of treated and polished natural gypsum stones in accordance with the present invention was generally 3.75% for most dehydrated wastewaters (wateggi) (high dehydrated content products, in some cases this was 3.85%), Respectively. The content of clinker was 3.40-3.45% for semi-hydrate wedge products and 3.30-3.35% in some cases. These figures give a preliminary knowledge of SO ₃ content for suspicious locations. Although initial strengths were considered to be more important, samples that did not yield the final strengths of the manufactured cements were not considered.

The present invention defines all of the calcium sulfate resources according to their dehydration levels and according to the molecular species left as a result of dehydration heating and polishing. The column level is a low column range, but the column level can also be specified along with the molecular water. As such, dehydrates start from a 2.0 molecular weight and go down to a molecular range of 1.20 to 1.00. In this range, we nominate the clinker as a range of merchant monohydrate for the calcium sulfate demand and against it. This is an anti-hydrate. We also designate semi-hydrates with these molecular entities. Similar to dehydrated products, there are also many intermediate hemihydrate phases. The effective range for cement is generally in the range of 0.70-0.90.

Due to cost considerations and / or environmental considerations, it may be desirable to include a higher percentage of gypsum for the clinker. The cements of the present invention may be capable of this. A higher content similar to that of many factories, such as 5%, allows a very slight reduction of the initial strengths. In addition, the inclusion of natural limestone in the calcium sulfate fraction is possible because some simple samples are given below. 3.5% dehydrated water + 0.75 natural pumice 24 MPa of the first day, 28 MPa of the second day (Σ 4.25%), 3.25% dehydrated water +1.5% natural pumice 21 MPa of the first day, 27 MPa of the second day 4.75%), 3.3%. Dehydrated water + 1.3% natural pumice can be described on day 21 of the first day and 26 Mpa on the second day. The inclusion of the half-hydrate phases resulted in opportunities such as 0.75% 0.70 molecular water half hydrates + 2.45% dehydrated water +1.65% natural pumice 21 days on day 1 and 30 Mpa (Σ 4.85%) on day 2, Water +2.35% dehydrated water + 1.95% 0.75% semi-hydrates with natural gypsum yields 30.5 Mpa (Σ 5.05%) on day 22 and day two. The use of the hemi-hydrates of the present invention as the most abundant CaSO ₄ source with natural gypsum also yields good results; % 3.2 0.70 Molecule water Half-hydrate + 0.9% Natural viscose gives 21 MPa on the first day and 29 MPa on the second day (Σ 4.1%). Many good alternatives can be obtained. The gypsum produced under high heat under natural gypsum also imparts a desirable adjuvant. These are calcined products at 450 ° C-500 ° C and 850 ° C-100 ° C, and their modifications are treated with alum or borax to make Keene cement, Martins cement, etc., Or using these products in combination with other calcium sulfate resources, produces very high crude steel cements. For example, 3.5% dehydrated water + 0.75% calcined anhydrite is calcined at 20.5 Mpa for the first day and 28 Mpa (裡 4.25%) for the second day, 3.35% dehydrated water + 1% identical The gypsum will be 24 Mpa on the first day and 30 Mpa (Σ 4.35%) on the second day. Higher calcium sulfate content is also possible. For example, 3% dehydrated water + 2% calcined gypsum gives 29.5 Mpa (Σ 5.0%) of the second day. The sole use of the same anhydrate as 5% provides a second strength of 30.5 Mpa. Crude steel cements can be obtained by the inclusion of the semi-hydrates or monohydrates of the present invention. All of the cements of the present invention mentioned above also have at least the same final strengths obtained by the same clinker factory cements of the same class or several times higher and, in some cases, slightly lower. In short, the present invention provides significantly higher initial intensities also having higher final intensities. While providing these key steps, the present invention also finds methods for higher calcium sulfate content for clinker.

When calcium sulfate contents are taken into account, the pumice has 26.5% more CaSO ₄ than dehydrated, and the latter use registers 3.75% optimum content of gypsum stone sauce with 7% impurities, which is 2.48% CaSO ₄ , and in the extreme example it is the same source, but the calcined gypsum is included as 5% meaning 4.65% CaSO ₄ . The content of CaSO ₄ can be doubled. The variation in the SO ₃ level is also similar and varies between 1.15% and 2.46%, i.e. the difference is more than double. The present invention demonstrates that the SO ₃ content (ratio) is not the main actor for determining the level of total SO ₃ as contained in the clinker. As a primary factor in the control of coagulation, note that the lowest rate is taken as providing the highest early strength and this level is lower than known practices. Not identical to it, but not so close, the initial high compressive strength can be obtained by containing twice the amount of SO _3. As a result, we can say that there is no exact correlation between SO ₃ levels and obtaining crude steel. Existing knowledge of the SO ₃ content to be formed as the molecular weight of Al ₂ O ₃ of 0.6 appears to remain uninitiated. Existing solubility-reactivity or reactivity power descriptions are also insufficient. The present invention finds that the main effect is provided that selected phases of calcium sulphates are provided in providing a cement hydration process. That is, the present invention specifies and describes sources of activity powers of calcium sulfate resources. The literature based on or derived from prevailing industry practices also appears to be reconsidered. It is also evident that significant reductions are seen at the SO ₃ levels and also stop the inflations. The basic factor of coagulation management is not the matter of SO ₃ management, but it is to manage the intermediate phase properties of gypsum stones to obtain the highest reactivity power measured by the compressive strength provided by the phase.

Considering the content of other constituents to the clinker, the 5% range of abraded calcareous (calcite) minerals (calcium carbonate) has a first priority. The effect of such on compressive strength has also been tested on the cements of the present invention by treating (-) 10 micron calcite, and a range of 3 to 5% has been found to be appropriate. By adopting 4%, i.e. replacing 4% of the inventive cements by 4% and using 3.75% of the inventive dehydrated cement, the existing compressive strengths were further improved and the 5% 3% on day 4, 3% on day 4 and an additional 5-8% on day 28. On the other hand, it has been found as a net gain, since it has to compensate for the effects on negative environmental and cost conditions. Positive effects for contents exceeding 6% are begun to be apparently reduced. For the cements containing calcium silicates under the present calcium calcium sulfate dehydrates, the results were similar. However, when the half-hydrates are included in the calcium sulfate moiety, different observations begin to occur. When the hemihydrate 0.80 was included in the dehydrated (substituted) at 10%, the compressive strengths decreased. In the case of 4% undifferentiated calcite content, this reduction became more apparent. Alternatively, when 4% of the similar filler was included, the first day strength of 21.9 Mpa dropped to 19.7 when the cement admixture contained 0.90% of the semi-hydrate 0.80 + 2.0% of dehydrated water + 2.4% of the natural and hydrated calcium sulfate reserve cement. The intensity of the second day of mpa fell to 26.5 Mpa. The inclusion of anhydrate makes this negative trend a little slower. This is an interesting and important case, while it does not contribute much to the content of the half-hydrate, but it also showed that the calcium carbonate was fine (-10 microns) and had a reaction during hydration. The plausibility is that it causes calcium hydroxide in the cement paste to increase their concentration and to separate and precipitate from the solution. Although the same effect predominates in the manner of decreasing the half-hydrate ratio to some extent, the decreasing negative effect can be explained by the overloading of calcium sulphate which allows some degree of stabilization and arrangement to be made. These findings can generally affect the widespread industry practices of using excess half-hydrates with 5% lime stone. The inclusion of rock gravels reduces the negative effects. All the experiments mentioned so far have been carried out by adopting clinkers from various factories and although the values were different; Obviously, the compression initial strengths obtained by the application of the present invention were clearly higher for all shades.

The cements of the present invention obtain their very high premature compressive strengths under normal hydration heat producing conditions and expansion and contraction. Coagulation initiation and termination are normal at the limits for known cements. For cements with lower SO ₃ levels than also known, the expansions are readily at their limits. Although highly precisely reduced SO ₃ is introduced, the high and significant expansion predicted by existing knowledge does not occur. These are important advantages. In practice, standards do not limit the SO ₃ maximum level. All effects produced by the inclusion of activators, water cutters (reductants), chemical additives, ash, fillers, etc. have been tested for cements of the present invention and additions to those of known cements . Cement particle size effect studies are similar to this. The effects on the intensities of the intergral gypsum, which were of very fine size and constituted the ultrafine portion of the gypsum, were compared with the separately polished cement-size gypsum yielding better strengths. As such, the present invention also cures other deficiencies of existing systems. When the clinkers were finely ground, results similar to those of known cements were obtained and higher intensities were obtained. The water requirements of new cements were lower than those of brand plant cements. This also helped to reduce the porosity and increased the strength. When examined from an industry perspective, it is clear that targets and methods can be realized by employing known industrial methods. The first requirement is that the heat level should not be so high that it does not cause high speed or excessive dehydration of gypsum stones. Many types of heating processes can be employed including instantaneous heating. For proper heating, a homogeneous particle size may be preferred, wherein the particle size of the mixture may not be mixed with very large size and very small particles. Polishing and cooling plaster resources may be mixed with the cooled clinker by either dozing, weighing, or mechanical missing methods. In special mills that do not produce excess heat, interblending can be realized. However, in this selection one must know that the gypsum particle size can be much finer to form the finest parts of the cement mixture. Even if the gypsum stones are separately polished, the mill should be constructed so as not to cause excessive high-speed dehydration. Since the gypsum part of the cements is in the range of 3-6%, large scale mills may not be needed. Economical operations can be provided by providing specially scaled, abrasive form from special plants and gypsum required in cooler form. Intergrinding in which the clinkers are sufficiently cooled can also be employed. Clinkers and calcium sulfate (gypsum) parts can be supplied to the two components to be mixed in concrete redemix plants. As a result, a set of most flexible alternatives can be designed to choose the most appropriate one.

The present invention resides in the ability to actually solve mixed practices that are based primarily on their own practices by merely describing and modifying the underlying prior knowledge. Plans and calculations are actually easily managed. The findings of the present invention are also intended to illustrate the structures and phases and behaviors of calcium sulphates and it is believed that adopting them in uses or industries other than the cement sector by simply taking the solutions found throughout the basic findings It becomes easier.

The new calcium sulfate resources of the present invention can be employed for other applications as the second step of the invention of fortification of ash-burnt lime binders. The inventor has another. The invention is useful for many applications that do not require structural strengths such as initial strengths to be used in many applications and mortars, fillers, low simple high rise buildings, block making, lean concrete, (S) to obtain economical and environmentally friendly phosquimone binders which give rise to ultimate strengths which may be sufficient for the use of quicklime. Initial strength is quite sufficient. These are high volcanic ash (s) containing binders. A very typical sample is the new 1.5% calcium sulfate of the present invention containing 76.5% Trass, 22% Lime, + 87% Half-hydrate and having a molecular weight in the range of 0.80. Strengths are 10.7 Mpa in the seventh day and 15.3 Mpa in the 28th day. Another version at 0.90 molecular water gets 12.1 Mpa from the seventh day and 17 Mpa at the 28th day. 14.2 Mpa on the seventh day and 23.5 Mpa on the 28th day when the polycarboxylate type extender / water cutter is used. On the 28th day with NaOH activator, go to 25 Mpa. These are very high numbers sufficient for the product to be available in the market. One can easily remember that structural works of up to 30 years were carried out with 22.5 MPa concrete. UN Habitat states that 50-60% of the works in which Portland cements are used do not require the structural strengths given by these cements. In this case, however, the Portland cement industry alone accounts for 7-8% of the world's CO ₂ emissions. It should be noted that the new calcium sulphates can also be used in many different formulas and also for many Pseudo-Lime / Pseudo-Limestone Cements.

Another use of the calcium sulphates of the present invention is in the area of calcium sulfate binders. They can be used for many tasks where market-shaped anti-hydrates are used. Useful are more anti-hydrate contents, including those starting from the monohydrate range. Their difference from market products is that they require more water for their hydration and more aggressive properties (fast settling - high temperature). This can provide more product acquisition by the use of more water. The porosity increases the volume of the product and allows less calcium sulfate products to be used. These are durable and strong products such as anti-hydrates in the market. It is possible to obtain stronger products by inclusion of appropriate water cutter additives to reduce porosity and increase density. It is also clear that since these products are not dehydrated to the range of 0.5-0.55 molecules of water on the market, less energy can be used for the same amount of product and fewer raw materials are required for the same volume. When products are dehydrated at 170 ° C to the same dehydration, they are not useful. Applicable new products are stronger. They may be used for partial or complete substitution of alpha alcohols and Type II high temperature dehydrated anhydrides. These new calcium sulfate binders can be used to perform all applications (casting, sheets, screed, render, etc.) that can be performed by known calcium sulfate ducts. All known production techniques can be applied to new products.

Claims (38)

As a prevailing method of inclusion of gypsum stones on the clinker on the polishing of the clinker while the clinker is cooling, the gypsum enters the composite dehydration sequence, in which the presumed ratio of gypsum is converted to the semi-hydrate and soluble gypsum, Levels and methods that can lead to higher early and final strengths by the inclusion of calcium sulfate resources, which include the inclusion of gypsum stones that are dehydrated at planned ratios by adopting specific heat levels in the range of 90-145 < 0 & A prevailing method of inclusion of gypsum stones, consisting solely or as a main method of inclusion of calcium sulfate into other cementitious components by inclusion in clinker and other components at optimum rates as calcium sulfate resource. The method according to claim 1,
(Gypsum) at lower temperatures than the gypsum calcinations (dehydration) known as < RTI ID = 0.0 > 135 C-145 C for < / RTI > The use of these products to obtain different characteristics besides the calcium sulfate resources known as calcium sulphate resources in the dehydration of cement and in the production of cements is a prevailing method of inclusion of gypsum stones. In order to obtain gypsums according to claims 1 or 2, instead of intergrinding by a still cooling clinker, it may be advantageous in small mills or intergrinding with ridles and / or cooled clinkers that do not generate additional excess heat Of the gypsum stones. 2.0 Molecular water, 1.90, 1.85, 1.70, 1.50, 1.00, 0.80, 0.50 Classification of dehydrated gypsums according to any of the claims 1 to 3 according to their molecular weight, such as molecular water And defining their characteristics and function in relation to their specified molecular water levels. The predominant industrial applications and scientific acceptances are 40% -50%, such as when the reactivity power and the efficiency of calcium sulfate resources are measured according to SO ₃ content and solubility, and the solubility is allowed to resemble hydration and reactivity parameters, Are found to be optimal in a gypsum-containing predominantly intergrating system, which is characterized by a high early strength to obtain cements produced by the inclusion of calcium sulfate resources heated to a certain level and in a particular manner, and In the determination of the fact that the dehydrates obtain a high solubility in the sequence of heat of hydration, it is the use of gypsum having a high wortyge of the dehydrated contents obtained according to any of the claims 1 to 4, The initial and final compressive strengths obtained by direct measurements The method of predicting the inclusion of gypsum stones, wherein the power is also measured. Characterized in that all gypsum according to any of claims 1 to 5 obtain different properties and function according to their respective dewatering levels and their respective optimization ratios and their choice is mainly determined by the response power according to claim 4 Lt; RTI ID = 0.0 > of gypsum < / RTI > stones. For gypsums according to any one of claims 1 to 6, it is generally in the range of 10% -25% and in the range of 21-26% semi-hydrates content for the best results and as a second scientific option 30 (Content) in the range of -20 to -34%, and the higher contents cause a decrease in strength. In order to obtain different activity powers and functions according to any one of claims 1 to 6 when half-hydrates are defined as 0.5 molecule water in the conventional practice, it is preferred to use 0.50-1.0 molecules And providing them with different dewatering levels in the water range. The use of semi-hydrate worty gypsums according to claim 8 for treating cement hydration processes as either singletons or as the most sources, as in any one of claims 1 to 7, predominant method of inclusion of gypsum stones. 9. A process for the preparation of cements according to any one of claims 1 to 9, comprising the steps of: 1.75-1.20 and 1.63 molecular water dehydrates, 1.20 tO 1.00 molecular physical monohydrates and 0.70-1.00 half-hydrates Wherein the highest reactivity is the power of calcium sulphate. For the relatively high initial compressive strength cements and for the inclusion of higher contents of calcium sulphate, the formation of calcium sulphate sources which form the greatest formation of calcium sulphate sources compared to the dehydrates according to any one of claims 1 to 10 A prevailing method of inclusion of gypsum stones, which is the use of dehydrated water. To optimize the cement hydration by using a composition containing low CaSO ₄ and SO _3, the predominant method of the inclusion of the plaster stone adoption of a plaster according to any one of claims 1 to 11, wherein a SO ₃ content of 1.2% below . A cement admixture according to any one of the preceding claims comprising up to 2.8% SO ₃ Wherein the content of the gypsum stones is increased. A prevailing method of inclusion of gypsum stones, the use of the method according to any one of claims 1 to 13 for reducing expansion values lower than those of known cements. Wherein one of the gypsums according to any of claims 1 to 14 nominates or specifies 1.0 molecular gypsum as "monohydrate ". 15. A process according to any one of claims 1 to 15, wherein the cement hydration stabilizer or the optimizer is calcined in the form of a ground in the form of 450 DEG C to 550 DEG C and / or 850 DEG C to 1000 DEG C, An advantageous method of inclusion of gypsum stones, which is the use of gypsum and / or gypsum. The inclusion and treatment of these gypsum stones with alum, borax, etc. is an enhancement of the calcium sulfate resources according to claim 16. A prevailing method of inclusion of gypsum stones, which is the use of calcium sulfate resources alone or in combination with the calcium sulfate resources according to any one of claims 1 to 15. A method of predominantly involving the incorporation of gypsum stones, wherein any of the known calcination methods and the performance of the dehydration processes under low heat according to any one of claims 1 to 15 is carried out. A method of predominantly involving the incorporation of gypsum stones, the method of dehydration according to any one of claims 1 to 19, employing instant thermal methods. 20. The prevailing method of inclusion of gypsum stones, wherein for the dewatering treatments according to any one of claims 1 to 20, the adoption of a uniform heat distribution and a particle size distribution comprising closer particle sizes. For mixing of the clinkers and the calcium sulfate resources according to any one of claims 1 to 21, the mixing of the known dosing and mixing methods including mechanical mixing or blending and grinding with clinker into special devices for cooler conditions Adopter, a prevailing method of inclusion of gypsum stones. 22. A method for reducing porosity formation in cements according to any one of claims 1 to 22 which is a grinding of calcium sulfate resources to a projected particle size close to the polished clinker size and rougher than the polished gypsum in inter- A prevailing method of inclusion of gypsum stones. 23. A process for the production of cement according to any one of the claims 1 to 23, which comprises the steps of applying a mixture of cement admixtures, which are grinding aids, water reducing agents, activators, all kinds of chemicals and mineral additives, The predominant method of inclusion of stones. Claim 1 to micronized calcite of the mixture with claim 24, wherein any one of the preceding for the cement to further improve the compressive strength of, not exceeding 6% ratio of the of the inclusion of (CaC0 ₃₎ or similar minerals or industrial fillers , A prevalent method of inclusion of gypsum stones. While the positive effect of the filler according to claim 25 is negative in the case of the use of the most abundant halide hydrates of calcium sulphate, the preponderance of inclusion of gypsum stones, which does not employ calcite (CaCO ₃ ) fillers in such cases Way. 26. A prevailing method of inclusion of gypsum stones, the inclusion of natural gypsum with them to increase the inclusion of the calcium sulfate fraction in the cements according to any one of claims 1 to 26. A prevailing method of inclusion of gypsum stones, comprising the inclusion of natural gypsum to reduce the negative effects of claim 26. While the phase combinations of gypsum according to the claims are determined by employing the Rietvelt X Ray Dates method, the molecular water loss is not measured simultaneously with these measurements, (And reactivity power) change points (peaks) that are specified by the present invention as an explicit measure of the reaction power determination method under the direct measurement of the reaction power, Gt; of the inclusion of gypsum stones. ≪ RTI ID = 0.0 > [0030] < / RTI > Dehydration above the 135C range causes surface area expansion expansions and rupture of gypsum stone crystals and the predominant knowledge response of these products is poor so that it is dehydrated in lower heat for higher dewatering rates, A prevailing method of inclusion of gypsum stones, which is the use of calcium sulfate resources. A prevailing method of inclusion of gypsum stones, comprising dehydration produced in the grinding process for all dehydration calculations, and providing suitable grinding media. While the formation of 40-50% of the monohydrates is assumed by the most favored applications, it is the cements according to claims 1 to 31 employing low thermal dehydration and high reactivity calcium sulfates and contains 35% to 60% The preferred method of inclusion of gypsum stones, wherein the 40-50% is found to be negative, constituted by adopting anti-hydrate ratios. A prevailing method of inclusion of gypsum stones, the use of cements and methods according to any one of claims 1 to 32 for preparing practical and sustainable calcium sulfate optimization processes and calculations and different cements. A prevailing method of inclusion of gypsum stones, which is the production of cements according to any one of claims 1 to 33 with a single mixture or two components. 34. A prevailing method of inclusion of gypsum stones, wherein the incorporation of the inventive findings according to any one of claims 1 to 34 in the coagulation optimization of cements and binders of all classes, including calcium sulfate resources as a component. 35. A method according to any one of claims 1 to 35, wherein the new cement binders are produced. Use of calcium sulfate resources according to any one of claims 1 to 36 in all areas where calcium sulphates are used. Use of calcium sulphates according to any one of claims 1 to 37 having a molecular weight of less than 1.00 in the activation and strengthening of ash (s) -lime binder cements.