MXPA96002271A - Hydraulic cement with accelerated development of high resistance - Google Patents
Hydraulic cement with accelerated development of high resistanceInfo
- Publication number
- MXPA96002271A MXPA96002271A MXPA/A/1996/002271A MX9602271A MXPA96002271A MX PA96002271 A MXPA96002271 A MX PA96002271A MX 9602271 A MX9602271 A MX 9602271A MX PA96002271 A MXPA96002271 A MX PA96002271A
- Authority
- MX
- Mexico
- Prior art keywords
- calcium
- clinker
- cement
- sulfoaluminate
- content
- Prior art date
Links
- 238000011161 development Methods 0.000 title description 14
- 239000011396 hydraulic cement Substances 0.000 title description 13
- 239000004568 cement Substances 0.000 claims abstract description 102
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000011575 calcium Substances 0.000 claims abstract description 67
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 61
- 239000000292 calcium oxide Substances 0.000 claims abstract description 48
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 47
- 235000019976 tricalcium silicate Nutrition 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 235000012241 calcium silicate Nutrition 0.000 claims abstract description 19
- 238000005755 formation reaction Methods 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 18
- 235000011132 calcium sulphate Nutrition 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000006703 hydration reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 13
- 239000010440 gypsum Substances 0.000 claims abstract description 13
- JHLNERQLKQQLRZ-UHFFFAOYSA-N Calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 12
- 229910001653 ettringite Inorganic materials 0.000 claims abstract description 11
- 230000036571 hydration Effects 0.000 claims abstract description 10
- 239000001175 calcium sulphate Substances 0.000 claims abstract description 5
- 238000003801 milling Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 32
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 29
- 235000015450 Tilia cordata Nutrition 0.000 claims description 29
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 29
- 239000004571 lime Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 19
- 229910052925 anhydrite Inorganic materials 0.000 claims description 13
- 238000007792 addition Methods 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 229910052904 quartz Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 235000011116 calcium hydroxide Nutrition 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000011398 Portland cement Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- SMYKVLBUSSNXMV-UHFFFAOYSA-J aluminum;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-J 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- -1 sulfate ions Chemical class 0.000 description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 239000011405 expansive cement Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000003111 delayed Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 241000562356 Polietes Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000036462 Unbound Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000295 complement Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 230000001066 destructive Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- NTGONJLAOZZDJO-UHFFFAOYSA-M disodium;hydroxide Chemical compound [OH-].[Na+].[Na+] NTGONJLAOZZDJO-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000001131 transforming Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Abstract
The present invention relates to a method for the manufacture of cements based on calcium sulfoaluminate, which consists in the formation of a clinker by means of the calcination of the raw materials at temperatures above 1200 ° C, in such a way that the clinker produced has a high content of calcium sulfoaluminate, tricalcium silicate and dicalcium silicate and, during or prior to the milling stage, add to the clinker thus produced and with the aforementioned basic components, optimal quantities of calcium oxide or hydroxide and calcium sulfate in order to activate said clinker. In this milling a temperature of approximately 100 to 125 ° C must be observed and a sufficient time to convert the gypsum into hemihydrate, which will ensure that the calcium sulphate present in the as-adrested product is able to react quickly during the hydration of the cement, giving rise to to the formation of ettringite, requiring for this the presence of a pH higher than 12. Of course, also claimed as a novelty activated cement, resulting from the method of calcination and grinding of the invention.
Description
HYDRAULIC CEMENT WITH ACCELERATED DEVELOPMENT OF HIGH RES? STEWaAS
FIELD OF THE INVENTION
The invention object of the present application is related to the production of cements that develop predistobile high resistances in short times, more particularly the invention provides a method for producing such cements as well as the cement itself.
BACKGROUND OF THE INVENTION
Hydraulic cements are known that constitute materials composed by oxides and defined chemical compounds belonging to inorganic chemistry and that base their use in the chemical reaction of said oxides and other constituents of cement with water, to form hydrated compounds that agglutinate, resulting in a mass that develops more or less rapid mechanical resistances. Within the general expression of "hydraulic cements", there are on the market cements of the aforementioned type capable of developing mechanical strengths very quickly, which are well known as "aluminous cements". Said aluminous cements are essentially constituted by calcium aluminate of formula CaO.Al2O3 and minor amounts of calcium aluminoferrite 4CaO.Al2? 3.Fe2? 3 as well as traces of another calcium aluminate of formula 12CaO.7Al2O3. The invention object of this application is not related to the aluminous cements but to the cements based on the calcium sulfoaluminate compound of the formula 4CaO: 3Al2O3.SO3. The oldest mention of calcium sulfoaluminate-based cements was made in a French patent granted, in the year 1936, to the company Poliet et Chausson in Paris, whose invention originated in the research work of Henry
Lossier, known to date cements based on the calcium sulfoaluminate compound as Lossier cements. For the year 1941 the aforementioned French company made on demand "expansive and non-shrinking cements", produced from a clinker obtained by the calcination of a mixture of suitable composition, formed from gypsum, ferrous bauxite and limestone. In 1958, in the United States, Klein presented a paper at the 60th Annual Meeting of the ASTM, which stated that a compound not precisely identified, but that appeared to correspond to an anhydrous calcium sulfoaluminate, was the cause of the behavior of these expansive cements, practically since then said expansive cements based on calcium sulfoaluminate are known as Cements K by the ASTM and are governed by the specification C-845: expansive hydraulic cements. The aforementioned expansive cements were manufactured in a more or less empirical way until the Fifth International Congress of Cement Chemistry, held in Tokyo in 1968, the works of several authors coincided in pointing out that the main component of these cements It constitutes the calcium sulfoaluminate with the formula 4CaO.3Al2O3.SO2. According to the teachings of the prior art for obtaining such expansive cements, the clinker based on calcium sulfoaluminate was mixed with Portland clinker as well as granulated slag from blast furnaces, to obtain a "controlled expansion" product. It is since then that cement researchers realized that calcium-sulfoaluminate clinker-based cements produced cements with early strengths and higher than those obtained with the use of only Portland cement, as for example is clearly stated in the patent. North American No. 4,957,556 by Hassan Kumbargi Regarding the invention of Kumbargi and in accordance with the teachings that derive from it, it is practically impossible to determine with certainty the cement setting by the Vicat method, since such setting is extremely fast what greatly complicates the handling of concrete produced with this cement, even though the use of citric acid as a retardant of the setting is recommended. Another problem presented by the cement produced according to the Kumbargi patent is that the development of the resistance of the same is unpredictable and even when the compression resistances offered are obtained in some cases, much lower resistance is often obtained, of course , this problem derives basically from the materials that make up the Kumbargi cement defined in the respective North American patent. Also with respect to the Kumbargi patent, in columns 3 and 4, it is emphasized that calcium sulfoaluminate is not thermodynamically stable and decomposes when heated in the industrial furnace at temperatures above 1200 ° C. On the other hand, in said Kumbargi patent, column 5, it is clearly established that due to the thermodynamic properties of calcium sulfoaluminate it is very difficult, if not impossible, for the clinker resulting from the calcination of the raw materials producing of the cement contains calcium sulfoaluminate, tricalcium silicate and dicalcium silicate, for which reason it is established in said patent that it is necessary to mix with the clinker thus produced and a hydraulic clinker containing tricalcium silicate and dicalcium silicate. Finally, with respect to the Kumbargi patent, it is doubtful that the compression resistances mentioned there are real, particularly under the assumption that by using the ASTM-C-109 method or the EN 196-1 method, the latter being the norm of the European community, the values of such resistances are not obtained, without also being clear the real value of said resistance since in the context of the patent in question the resistance of the cement produced according to the Kumbargi method is compared against the resistance of Portland cement. Going even deeper into the problem of resistance measurement developed by Kumbargi cement, it is not exactly clear what method it uses to determine the different cement setting ages, allowing to believe that such measurements are equivalent to those made in respect of cement. to the Portland cements, announcing it in any case as being equivalent, which is not the case, since the value of the mechanical strength of any type of hydraulic cement is not an absolute value such as the specific gravity or chemical composition, since the values of this resistance basically depend on the method used for its evaluation. The mechanical strength in the case of hydraulic cements is a function of the ratio of cement and the relationship of cementrarena and when any of these relationships are changed, the results between the measurement methods are not comparable. According to the ASTM method, the ratio of cemento.arena is 1: 2.75 and the relation aguaxemento is of the order of 0.49 for Portland cements. In the case of the Kumbargi patent, a one-to-one ratio of cementorarena is used and, of course, it is not clear what ratio of aguaxemento uses, however, it is a real fact that Kumbargi cement has much greater resistances than the obtained by the Portland cements, but the determinations made by the ASTM method are not comparable. OBJECTIVES OF THE INVENTION It is therefore a main objective of the invention to obtain a cement based on calcium sulfoaluminate in whose manufacturing process the raw materials are clinkerized at temperatures above 1200 ° C, without decreasing the sulfoaluminate content of calcium in the clinker, because it decomposes. It is yet another object of the invention to obtain a cement based on calcium sulfoaluminate containing, in addition to an adequate amount of calcium sulfoaluminate, tricalcium silicate and dicalcium silicate, thereby eliminating the need, according to the teachings of Kumbargi., the one that must mix the sulfoluminous clinker with a hydraulic clinker containing tricalcium silicate and dicalcium silicate. It is yet another objective of the invention to produce a clinker by using a clinkerization oven provided with preheater and precalciner and in whose composition the calcium sulfoaluminate, tricalcium silicate and dicalcium silicate are present, in addition to other components in smaller proportion, such as result of a single calcination operation in an industrial furnace. It is still a further objective of the present invention, a method for the preparation of a cement based on calcium sulfoaluminate, with better handling characteristics and rapid development of its strength, all as a result of the composition of the clinker and, as a Subsequent or simultaneous stage to the grinding other components are incorporated, obtaining in this way a cement with very high and fast resistances, with better control of setting time and particularly with the guarantee that the resistances that are developed are always within the parameters control, prefixed.
As a summary of the advantages provided by the invention object of this application, the following may be mentioned: a) a clinker is produced which, in accordance with the teachings of the prior art, was not possible to produce. b) the total chemical composition of the clinker produced allows it to be conveniently activated by other components during a subsequent grinding process c) through the process of obtaining the cement of the invention it is possible to produce in a totally controlled and predictable way a cement that develops quickly very high mechanical resistance. d) the cement object of this application has characteristics that allow the elaboration of concrete pavements that can be opened to the traffic of heavy trucks in no more than 8 hours after its construction, application that is clearly extended to the laying of runways , repairs of bridges or concrete structures, these applications being given only as illustrative examples, but not restrictive. For simplicity of writing, in the description of the invention object of this application, the abbreviated annotations for the chemical compounds will be used, which is usually used, in a usual way, at a world level in the cement industry: S will serve to identify the SiO2; A for Al2O3 F for Fe2O3 C for CaO M for MgO S for SO3 N for Na2O K for K2O and H for H2O
SUMMARY OF THE DESCRIPTION As mentioned above, the invention of this application consists in obtaining a clinker resulting from the calcination of cement-forming raw materials whose chemical composition had not been possible to obtain industrially, a composition consisting of a high content of calcium sulfoaluminate 4CaO.3Al2O3.SO3 tricalcium silicate 3CaO.SiO2 and dicalcium silicate 2CaO.SiO2, mainly, adding to said clinker, during the grinding stage optimal amounts of calcium oxide or hydroxide (Cal and Calcium hydrated) and some of the different forms of calcium sulphate, natural or industrially produced or as an industrial by-product, the addition of these latter ingredients results in the activation of the clinker. Of course, the addition of the last mentioned ingredients can be done prior to grinding or during grinding, providing sulfoaluminous clinker, lime or hydrated lime and calcium sulfate the necessary fineness to be used as a cement with the essential characteristic of this , consisting of the development of high resistances in very short times. As raw materials for the production of clinker can be used any type of materials normally used in the production of calcium sulfoaluminate-based cements, which properly dosed provide the proper chemical composition to the mixture, which, prior to milling, will be fed to an industrial furnace of those normally known in the cement industry for its calcination at a temperature higher than 1200 ° C, which produces a sulfoaluminous clinker as part of the process for obtaining the cement of the invention . As an example of the raw materials that can be used are those that are usually used in the production of Portland cement, such as limestone, marl, calcareous rocks and any of the natural forms of calcium sulfate, such as gypsum or anhydrite; different clays such as kaolin and alumiand any of the different types of bauxite, if necessary. It is also possible the use of raw materials that are the result of industrial processes as waste, with the only limitation that complies with the provisions related to environmental laws, thus, gypsum obtained as a byproduct of an industrial process, such as the phosphogypsum, obtained marginally in the industrial production of phosphoric acid. The quantities of the raw materials used in the manufacture of the clinker are subject to, after its calcination at temperatures above 1200 ° C, the following percentages are met: 1. The calculated content of calcium sulfoaluminate will preferably be between 20 and 40% of the total weight of the cementitious composition. 2. The calculated content of the dicalcium silicate should preferably be between 10 and 30%. 3. The calculated content of the tricalcium silicate must necessarily be always greater than at least 1%, but preferably between 10 and 30%. 4.- The calculated content of CaSO4 anhydrite will be at least 1%. 5.- In no case the content of the combined lime in the clinker, calculated as total lime minus free lime, will lead to values of C3S outside of that specified in point three. 6.- The content of free lime will preferably be less than 0.5%, but in no case will it be so high that it falls outside of that specified in points 3 and 5. According to the teachings of the invention, it is of utmost importance coexistence in the clinker produced of calcium sulfoaluminate with the dicalcium and tricalcium silicates, for which it is necessary that the temperature in the hottest zone of the furnace be higher than 1200 ° C and that the combination reaction of calcium oxide with the others Oxides are as complete as possible, which means that the control of the furnace operation is carried out by determining the calcium oxide that remains uncoated, a compound known as free lime in the cement industry. For the analytical determination of calcium oxide that remains uncombined, the most recommended method is that described in ASTM-C114: Chemical Analysis of Hydraulic Cement, this method of determination allows precise control of the operation of the furnace, which ensures that the Chemical reactions carried out inside the furnace are carried out in the desired form, thereby ensuring the formation of the prefixed amounts of calcium sulfoaluminate and the dicalcium and tricalcium silicates. Once the clinker has been produced, the optimum quantities of calcium hydroxide and calcium sulfate should be established in the laboratory, which must be dosed to the clinker during its grinding process, in order to obtain the desired compression strengths. The dosage of calcium hydroxide and calcium sulphate to the clinker may be carried out, as already mentioned, before and during the grinding of the materials to a previously fixed fineness, and any of the various existing forms may also be used as calcium sulphate. of this compound, with the only condition that the temperature inside the mill is such that the cement during the grinding process reaches a temperature between approximately 100 and 125 ° C and that the retention time in said mill is sufficiently long to convert the gypsum CaSO2H2O in hemihydrate 2CaSO4.H2O, which ensures that the calcium sulfate present in the cement is able to react quickly during the hydration of the cement and that it develops the strength sought. The presence of the calcium hydroxide added before or during the grinding of the cement as well as that the calcium sulfate is in the cement composition as a hemihydrate, are totally unknown teachings in what is described and claimed in the Kumbargi patent, this being the fundamental reason that the calcium sulfoaluminate-based cement consistently develops the fast resistances sought and that the setting time is more delayed, which facilitates the use of concrete.
DETAILED DESCRIPTION OF THE INVENTION As already stated above, the invention object of this application is particularly related to the industrial, controlled production of a cement based on calcium sulfoaluminate, which predictably develops very high resistances in short times. As a clarification, it is known that the cements of the previous art, based on calcium sulfoaluminate, were classified exclusively according to their expansive characteristics, in the present invention, this expansion characteristic is not relevant. Also by way of clarification, it is made known that when reference is made to a solution, it will be referring to the paste that results from adding water to the cement, in which certain substances are dissolved as a result of cement hydration reactions.
Fundamentally, the rapid development of resistances in the cement of the invention is based in particular on the formation of the chemical compound, so-called Etringite, whose formula is C3A.3CaSO4.32H2O, and whose conditions of formation will be detailed with precision in the description of the invention that is subsequently offered and that is the result of the chemical reaction between calcium sulfoaluminate, calcium sulfate and calcium hydroxide, when the cement is hydrated. It is of vital importance, as it derives from the teachings of the invention that Etringite is produced from the first moments of the hydration of the cement, being essential for it that it is in solution necessary quantities of the 2+ 2 calcium ions: Ca , the sulfate ions: SO4"and the hydroxyl ions OH". Said amounts must be sufficient to form a supersaturation of the respective ions in the solution that forms the cement paste, the calcium and sulfate ions react with the calcium sulfoaluminate to form the ettringite and the hydroxyl ions will maintain a pH greater than 12. , which will allow the formation of the ettringite. From the above-mentioned briefly, some of the restrictions of the clinker composition are derived and that are established as derivatives of this invention, which can be summarized as follows: 1.- all the aluminum oxide present in the clinker it must be found as sulfoaluminate, in order to guarantee the maximum formation of Etringite in the shortest possible time, starting from a single compound during the hydration of the cement by the development of a single chemical reaction. If tricalcium aluminate existed in the clinker, Etringite, derived from the reaction of tricalcium aluminate with calcium sulfonate, could be formed, but both the reaction rate and the chemical equilibrium would change as two compounds compete simultaneously at different speeds for the sulfate ion
2. - to ensure that all the aluminum oxide present is found as sulfoaluminate in the clinker, a slight excess of SO3 must be foreseen, that is, there must be a minimum of anhydrite, therefore all the SO3 that can react with the aluminum oxide will form sulfoaluminate. If there is an excess of aluminum oxide, deficiency of the sulfate ion will form tricalcium aluminate, a compound that is undesirable to be present in the cement, as explained in the previous paragraph. 3.- In order to ensure that the formation of Etringite occurs quickly, it is necessary to maintain a highly alkaline medium, this is a pH at least equal to or greater than 12, which is guaranteed by the presence of the OH "ions" coming from of the addition of hydrated lime during grinding or before cementing it in. Additionally, the Ca ions present also by the addition of hydrated lime help to maintain the supersaturation of calcium ions, necessary for the rapid formation of Etringite. presence in the clinker of free lime is a contribution to the amount of calcium ions present in the cement hydration solution and also a factor to maintain a high pH value in the same, but the speed to pass solution will also depend on several factors, for example, the calcination temperature of the clinker leads to calcium oxide during calcination to a state of lower reactivity (lime burned to death) than a well burned lime. In the clinker, the grains of free lime are of different sizes and are generally surrounded by other chemical compounds as part of the clinker, so their availability to react is not immediate. In fact, it is not known exactly how fast and how long the residual free lime will start to react in the clinker, this being the reason why it is established that the free lime in the clinker (calcium oxide) must be maintained at a minimum level, this is at a value of less than 0.5%, in addition to ensuring the maximum possible formation of dicalcium and tricalcium silicate 4.- if as a result of calcination the value of free lime exceeds
0. 5%, this factor must be corrected during the clinker activation tests, in any case the excess of free lime should be avoided, as it is clear from what is described in the previous paragraph, since the excess of free lime can cause also the following problems: a) There may be an undesirable and uncontrolled expansion during the hydration of the cement that would be the result of the hydration and extemporaneous reaction of said free lime. In the event of the above, the formation of the Etringite would be delayed, causing the retardation of the destructive expansion of the cement. b) The calculation of the compounds can lead to a negative value for the tricalcium silicate, which alters the chemical equilibrium conditions that are desired with the specific chemical composition of the invention, and the cement produced will tend to fall within of the specification and problems of the behavior of the Kumbargi cements, therefore, and due to the problems analyzed above, the free lime should not reach a value such that a tricalcium silicate negative is obtained. In addition to the characteristics described above with respect to the chemical composition of the clinker, it is very important that the operating conditions of the furnace are adequate to obtain the formation of the compounds that are intended, within certain quantity parameters. Within the operational parameters of the furnace, the temperature reached by the material in its hottest zone must be above 1200 ° C and, preferably, it must be between 1200 ° C and 1500 ° C. An additional feature of the furnace operation is that it must be operated in such a way that the material remains at the maximum temperature for the time necessary for the free lime content resulting in the clinker to be less than 0.5%. The chemical composition of the produced clinker will be evaluated by any method of chemical analysis used in the cement industry, for example, by X-ray fluorescence, however, in case of discrepancy of results, the method that should be used will be that described in ASTM-C-114: Chemical Analysis of Hydraulic Cement. For the determination of the free lime content during the furnace operation, the recommended and most convenient analytical method is that described in ASTM-C114: Chemical Analysis of Hydraulic Cement-94, section 27. 1.- The chemical analysis expressed in percent in mass, will be expressed in moles, for which the percentage of each oxide will be divided by its molecular weight: Moles of silicon oxide SiO2 =% SiO2 / 60.07 Moles of aluminum oxide Al2O3 =% Al2O3 / l 01.96 Moles of ferric oxide Fe2O3 =% Fe2O3 / l 59.69 Moles of total calcium oxide CaO (t) =% CaO (t) /56.08 Calcium oxide moles CaO (x) =% CaO (x) /56.08 Moles of sulfuric anhydride SO3 =% SO3 / 80.06 2.- From the content of total moles of calcium oxide, CaO (t), the content of moles of free calcium oxide, CaO (x), will be subtracted, this value will be considered as combined calcium oxide: CaO ( c) 3.- It is considered that all the aluminum oxide content, Al2O3, is combined as calcium sulfoaluminate 4CaO.3Al2O3.SO3. 4.- The moles of SO3 and CaO that are found to form calcium sulfoaluminate, 4CaO.3Al2O3SO3: moles of SO3 combined in the sulfoaluminate are calculated: SO3 = molesAl2O3 / 3 moles of CaO combined in sulfoaluminate: CaO (l) = moles Al2O3 * (4/3) 5.- The molar content of calcium sulfoaluminate in the clinker will be equal to the number of moles of SO3 in the calcium sulfoaluminate. 6.- The content of ahydrite, CaSO4, in the clinker, will be equal to the surplus of moles of SO3: moles of anhydrite: CaSO = total moles of SO3-SO3 in calcium sulfoaluminate. CaO in anhydrite = CaO (2) = moles of SO3 in anhydrite. 7.- All Faith ^ will be considered as 2CaO.Fe O3. 8.- Calculate the CaO necessary to form 2CaO.Fe2O3: moles of CaO in 2CaO.Fe2O3: CaO (3) = moles of Fe2O3 * 2. 9.- Calculate the remaining moles of calcium oxide without combining at this time: CaO moles that remain unbound: CaO (4) = CaO (c) -CaO (l) -CaO (2) -CaO (3). 10.- Calculate the molar ratio CaO (4) / SiO2. If this ratio is less than 2, the clinker is out of specification. Finish the calculation. 11.- The calcium oxide found as C2S will be: CaO (5) = mole of SiO2 * 2. 12.- The content in moles of C3S will be: CaO (4) less CaO in C2S: moles of
C3S = CaO (4) -CaO (5). 13.- The content of C2S will be equal to the total content of moles of SiO2 minus the moles of C3S. 14. Finally, to transform the results of the calculation of compounds to percentages by mass, the value obtained for each compound will be multiplied by its molecular weight: percentage of calcium sulfoaluminate. 4 CaO. 3 Al2O3. S O3, moles of
4CaO.3Al2O3.SO3 x 610.26. Percentage of anhydrite, CaSO4, moles of CaSO4 x 136.14.
Percent ferric calcium, 2CaO.Fe2O3, moles of 2CaO.Fe2O3 x 271.85. Percentage of tricalcium silicate, C3S, moles of C3S x 228.3. Percentage of dicalcium silicate, C2S, moles of C2S x 172.23. The coexistence in the clinker at the outlet of an industrial furnace of both calcium sulfoaluminate and dicalcium and tricalcium silicates can be checked by different analytical methods, for example, by means of optical microscopy or by scanning electron microscopy. The coexistence of the aforementioned compounds by means of X-ray diffraction can also be proven, however, although any of these methods can be used as a complementary control, it is not essential that they be used for the control of the process, which should focus on the control of free lime by the aforementioned analytical method. It is recommended that the chemical composition of the clinker be controlled from the grinding of the raw materials, carefully controlling the composition of the raw flour, stage of the process during which the dosage of the different materials, such as limestone or marl, is also generally carried out. clays, kaolins, bauxites, gypsum, etc., this being the usual way of controlling the clinker composition in the cement industry. It is evident that for the production of the clinker, different materials that result as waste or industrial by-products in other industries can be used without any problem, for example, sand can be used for casting molds, phosphogypsum, etc. The method of grinding the raw materials can also be carried out by any method normally used in the cement industry, that is, by the use of ball mills, vertical mills, roller presses or some combinations of such equipment. The furnace used for the production of the clinker can also be any type of oven normally used for the production of clinker for Portland cements, as for example, it can be used without any restriction straight kilns, preheater kilns of any of the different types of cyclones or grill, ovens with preheater and precalciner, etc. Likewise, any type of existing systems for clinker cooling, which are common in the cement industry, may be used in the kiln discharge, among which the grate or planetary coolers may be mentioned. Once the clinker is produced, it must be evaluated and tested in the laboratory by activation tests by the addition of calcium oxide or hydroxide and some form of calcium sulfate. The clinker produced industrially will not necessarily result, when ground to any fineness, in a cement capable of rapidly developing high resistances, generally this is not the case. The rapid development of high resistances will result from the adequate chemical composition of the clinker, but in addition to the adequate chemical composition of the cement that allows the rapid formation of ettringite crystals, which will be formed by the reaction of calcium sulfoaluminate with calcium hydroxide. and with calcium sulfate. Contrary to what was established by Collepardi and Turriziani in 1972, this reaction will depend on the concentration of the SO3 'and OH "ions in the solution (solution will be understood as the paste formed by the addition of water to the cement). The availability of these ions in the solution will depend the time of formation of the ettringite crystals and, therefore, the development of the high resistances, for this reason it is important the adequate dosage of Ca (OH) 2 without depending on the appearance of this compound as a function of free lime or the generation of Ca (OH) 2 a
from the hydration of C3S, as proposed by Kumbargi in his Patent No. 4,957,556. whose reaction speed for this purpose is practically impossible to calculate or predict. Something similar happens with the presence of SO3 ions in the solution, whose behavior is erroneously evaluated in laboratory tests by adding gypsum directly to the clinker and without taking into account the actual behavior of these materials in industrial practice, as it is common practice that the presence of SO32 ions are calculated in the laboratory as deriving from gypsum and not as hemihydrate. During industrial grinding, the temperature of the materials in the grinding circuit should be raised to temperatures between 100 and 130 ° C. Under these temperature conditions, the CaSO4.2H2O gypsum loses half a molecule of water and becomes a hemihydrate: 2CaSO4.H2O, whose dissolution and equilibrium rate of saturation of SO3 is different from gypsum and anhydrite, this being the cause of the inadequate dosage of the amount of SO3, it being necessary to add gypsum to the clinker to optimize the development of its resistances, so that and according to the prior art unpredictable results are obtained. The activation tests in the laboratory, prior to grinding, will therefore be performed on a clinker sample representative of the batch to be milled, with a gypsum sample representative of the batch that will be used and that has been maintained. for at least 24 hours in a laboratory oven at 120 ° C, checking by differential thermal analysis, by thermogravimetry and by X-ray diffraction its transformation into 2CaSO4.H2O hemihydrate and with a representative sample of the hydrated lime batch that is going to be used in grinding. The aforementioned materials will be previously ground to a fineness similar to that expected to be produced by the cement and this fineness will be expressed as a percentage of cement particles less than 45 microns. Once the materials have been fully identified, the optimum content of hydrated lime and emihydrate will be determined, which must be dosed to the clinker for activation. Clinker and hemihydrate mixtures are prepared by varying the contents of added SO3, for example, 3%, 5%, 7% SO3, subsequently dosing for each mixture increasing quantities of hydrated lime from, for example, 1% and in increments of 1% since in this case the variation of the lime content is critical, then a series of samples will be identified as follows: 1.- + 3% SO3 and 1, 2,3,4, 5 and 6% lime hydrated 2.- + 5% SO3 and 1, 2,3,4,5 and 6% hydrated lime, etc. For each of the samples, the compressive strength will be determined using the method ASTM-C109-Standard Test Method for Compressive Strength of Hydraulic Cement Mortars, taking into account only that the water to cement ratio will be adjusted through the use of the flow table and not the constant water to cement ratio specified for Portland cements. The developed resistances can be verified at the ages that are considered convenient, for example hour and a half, three hours, etc., after the mixing water was added and, by this method can be easily related to the resistance that the The same age would develop a reference hydraulic cement, for example, a Portland cement. As an example of the compressive strengths that can be obtained following the teachings of the present invention, the following table is presented below in which the Portland cement resistances are also shown.
Age Cement High Strength MPA Portland Cement Type 1 (MPA) Compression Resistance Compression Resistance 1.5 hours 5.0 Note l 3.0 hours 7.5 Note 1 5.0 hours 10.0 Note 2 24.0 hours 20.0 10.0
Note 1: The mortar cubes do not maintain their shape when being demoulded so they can not even be subjected to the compression test. Note 2: Although the cubes maintained their shape by being demolded, these derail as soon as pressure is applied. It is not even possible to measure any resistance. All the compressive strength results of the previous table are expressed in MPA (Megapascals) and have been obtained by the method ASTM-C-109: Standard Test Method for Compressive Strength of Hydraulic Cement Mortars. As with other sulfoaluminate-based cements, it is possible to retard the setting of the cement of the invention, by the use of organic products such as citric acid, as described in the aforementioned article by Collepardi and Turriziani. Based on the studies carried out by the inventors of the cement hydration reactions, it has been concluded that the rapid development of the strength of the cement of the invention is due to the formation of ettringite crystals, which is present from the moment It starts the addition of water. To this compound is attributed only the rapid development of the cement resistance, since the dicalcium and tricalcium silicates initially only act as stabilizers of the main reaction, due to its slow contribution of Ca calcium ions to the solution, helping this way to stabilize a high pH value, which as previously indicated is essential for the development of the main reaction. Said dicalcium and tricalcium silicates subsequently contribute more slowly and gradually to the development of mechanical resistance, all due to their slower hydration reaction. It agrees with what was established by Collepardi and Turriziani that the main reaction is: C4A3S + 6Ca (OH) 2 + 8 CaSO4.2H2O + 74 H2O = 3 (C3A..3CS.32H2O). However, they maintained that the contribution of Ca (OH) 2 is due to the hydration of the calcium silicates, a reaction that, as already mentioned, takes place too slowly, and therefore Ca ( OH) 2 in a more direct manner, thereby obtaining the rapid resistances of the calcium sulfoaluminate-based cements of the invention, which they never achieved. On the other hand, it is possible to monitor the hydration reactions of the cement object of the present application, by means of techniques that are common for the study of the hydration reactions of other hydraulic cements, being able to consult these techniques in the appropriate bibliography, so it is not considered necessary to include them in the present. Some aspects of this monitoring will be described below using the X-ray diffraction technique. The monitoring of the reaction should begin one minute after the reaction begins, by putting the water in contact with the cement, beginning to be defined in the diagrams diffraction lines that identify the presence of ettringite from that first moment. Over time these lines will be precise and growing, while on the contrary, the lines corresponding to calcium sulfoluminate will decrease in intensity. For the purposes of the present invention, the optimum composition of the invention will be such that in addition to presenting the ettringite lines from the first minute and increasing intensity regularly, the lines identifying the calcium sulfoaluminate should decrease regularly in intensity, to completely disappear. 24 hours after starting the hydration reactions, which indicates the total formation of ettringite based on calcium sulfoaluminate. It is obvious that the actual behavior of the cement may differ slightly from what is described here, but in essence it must be very similar. From the foregoing, it should be clearly noted that what Kumbargi expresses differs completely from the foregoing, since he stated in his patent that the rapid resistance developed by the sulfoaluminate-based cements was due to the reaction of calcium aluminate, such as occurs in aluminous cements. In the calcium sulfoaluminate-based cements there is no presence of calcium aluminate, even more in the present invention, provisions are made for the quantification of the cement composition, to prevent the presence of any of the possible compositions of calcium aluminate, C3A, C12A7, etc.
Claims (5)
1. - A method for the production of calcium-sulfoaluminate-based cements that develop high predictable short-term resistance, which consists of subjecting the raw materials to a calcining, in a suitable dosage, to obtain a sulfoaluminate-based cement. calcium, at a temperature above 1200 ° C, in such a way that the clinker produced has a high content of calcium sulfoaluminate, tricalcium silicate and dicalcium silicate and with a free lime content of less than 0.5%; activate the clinker produced by the addition of adequate amounts of calcium oxide or hydroxide and calcium sulfate; grind the resulting mixture, taking care that the temperature in the mill is between 100 and 130 ° C.
2. A method for the manufacture of cements based on calcium sulfoaluminate, according to claim 1, wherein the calcination temperature of the raw materials in the furnace is higher than 1200 ° C and more particularly are between 1200 and 1500 ° C.
3. A method for the production of cements based on calcium sulfoaluminate, according to claim 1, wherein the chemical composition of the clinker obtained from the calcination of the raw materials at a temperature higher than 1200 ° C, is like follows: calcium sulfoaluminate content between about 20 and 40%; Dicalcium silicate content between about 10 and 30%; tricalcium silicate content greater than 1%, preferably between about 10 to 30%; Anhydrite content will be at least 1%; The combined lime content in the clinker, calculated as total lime less lime, shall be such that it does not lead to a value of 3CaO.SiO2 outside the provisions for tricalcium silicate; The content of free lime will preferably be less than 0.5%, but in no case will it be so high that it falls outside the limits for the content of tricalcium silicate and the combined lime content.
4. A method for the production of cements based on calcium sulfoaluminate, according to claim 1, wherein the activation of the clinker by the addition of calcium oxide or hydroxide and calcium sulfate is carried out before or during the grinding step of said mixture. 5.- A cement based on calcium sulfoaluminate, where hydrate said cement develop high predictable resistance in short times by the formation of ettringite under a pH greater than 12, when reacting calcium sulfoaluminate with calcium ions and of sulfate. EXTRACT OF THE INVENTION The invention consists in a method for the manufacture of cements based on calcium sulfoaluminate, which consists of the formation of a clinker by means of the calcination of the raw materials at temperatures above 1200 ° C, in such a way that the clinker produced has a high content of calcium sulfoaluminate, tricalcium silicate and dicalcium silicate and, during or prior to the milling stage, add to the clinker thus produced and with the aforementioned basic components optimum amounts of calcium oxide or hydroxide and calcium sulfate in order to to activate said clinker. In said milling a temperature of approximately 100 to 125 ° C must be observed and a sufficient time to convert the gypsum into hemihydrate, which will ensure that the calcium sulphate present in the product thus obtained is able to react quickly during hydration of cement, leading to the formation of ettringite, requiring for this the presence of a pH higher than 12. Of course, also claimed as a novelty the activated cement, resulting from the method of calcination and grinding of the invention.
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX9602271A MX9602271A (en) | 1996-06-10 | 1996-06-10 | High resistance hydraulic cement with accelerated development. |
| US08/766,666 US6149724A (en) | 1996-06-10 | 1996-12-04 | Hydraulic cement with accelerated high strength development |
| CA002193339A CA2193339C (en) | 1996-06-10 | 1996-12-18 | Hydraulic cement with accelerated high strength development |
| DE69720595T DE69720595T2 (en) | 1996-06-10 | 1997-02-04 | Hydraulic cement with accelerated high strength development |
| ES97500026T ES2196285T3 (en) | 1996-06-10 | 1997-02-04 | HYDRAULIC CEMENT WITH AN ACCELERATED DEVELOPMENT OF HIGH RESISTANCE. |
| EP97500026A EP0812811B1 (en) | 1996-06-10 | 1997-02-04 | Hydraulic cement with an accelerated development of high strength |
| CO97013338A CO4560452A1 (en) | 1996-06-10 | 1997-03-12 | HYDRAULIX CEMENT WITH HIGH RESISTANCE ACCELERATED DEVELOPMENT |
| PA19978428701A PA8428701A1 (en) | 1996-06-10 | 1997-04-25 | HYDRAULIC CEMENT WITH HIGH STRENGTH ACCELERATED DEVELOPMENT |
| BR9700621A BR9700621A (en) | 1996-06-10 | 1997-04-28 | Hydraulic cement manufacturing process with accelerated development of high strengths and the resulting product |
| UY24549A UY24549A1 (en) | 1996-06-10 | 1997-05-08 | HYDRAULIC CEMENT WITH ACCELERATED DEVELOPMENT OF HIGH RESISTANCES |
| ARP970102179A AR004900A1 (en) | 1996-06-10 | 1997-05-22 | A METHOD FOR THE PRODUCTION OF CEMENTS BASED ON CALCIUM SULFOALUMINATE, AND CEMENT PRODUCED WITH SUCH METHOD |
| GT199700067A GT199700067A (en) | 1996-06-10 | 1997-05-29 | HYDRAULIC CEMENT WITH HIGH STRENGTH ACCELERATED DEVELOPMENT |
| CR5560A CR5560A (en) | 1996-06-10 | 1997-06-04 | HYDRAULIC CEMENT WITH HIGH RESISTANCE ACCELERATED DEVELOPMENT |
| PE1997000221A PE90598A1 (en) | 1996-06-10 | 1997-06-10 | HYDRAULIC CEMENT WITH HIGH STRENGTH ACCELERATED DEVELOPMENT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MX9602271A MX9602271A (en) | 1996-06-10 | 1996-06-10 | High resistance hydraulic cement with accelerated development. |
Publications (2)
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|---|---|
| MXPA96002271A true MXPA96002271A (en) | 1998-04-01 |
| MX9602271A MX9602271A (en) | 1998-04-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| MX9602271A MX9602271A (en) | 1996-06-10 | 1996-06-10 | High resistance hydraulic cement with accelerated development. |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US6149724A (en) |
| EP (1) | EP0812811B1 (en) |
| AR (1) | AR004900A1 (en) |
| BR (1) | BR9700621A (en) |
| CA (1) | CA2193339C (en) |
| CO (1) | CO4560452A1 (en) |
| CR (1) | CR5560A (en) |
| DE (1) | DE69720595T2 (en) |
| ES (1) | ES2196285T3 (en) |
| GT (1) | GT199700067A (en) |
| MX (1) | MX9602271A (en) |
| PA (1) | PA8428701A1 (en) |
| PE (1) | PE90598A1 (en) |
| UY (1) | UY24549A1 (en) |
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| CN112960929A (en) * | 2021-03-05 | 2021-06-15 | 北京工业大学 | Method for preparing calcium sulfosilicate-dicalcium silicate-calcium sulfoaluminate system from calcium carbide slag raw material and improving later strength of cement |
| EP4101646A1 (en) | 2021-06-11 | 2022-12-14 | HeidelbergCement AG | Concrete composition for 3d printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3147129A (en) * | 1960-09-27 | 1964-09-01 | Socony Mobil Oil Co Inc | Sulfoaluminate cement |
| GB1067858A (en) * | 1963-08-08 | 1967-05-03 | Chem Prestressed Concrete | Expansive and shrinkage-compensated cements |
| US3251701A (en) * | 1964-07-27 | 1966-05-17 | Chem Prestressed Concrete | Expansive and shrinkage-compensated cements |
| US3857714A (en) * | 1971-08-12 | 1974-12-31 | Chem Prestressed Concrete | High calcium sulfate expansive clinker |
| US3860433A (en) * | 1972-05-30 | 1975-01-14 | Borje W A Ost | Very high early strength cement |
| FR2206275B1 (en) * | 1972-11-13 | 1976-04-23 | Lafarge Sa | |
| US4286991A (en) * | 1980-04-25 | 1981-09-01 | United States Gypsum Company | Very high early strength cement |
| JPS6058183B2 (en) * | 1981-04-02 | 1985-12-18 | 秩父セメント株式会社 | Manufacturing method of hydraulic cement |
| US4419136A (en) * | 1982-02-10 | 1983-12-06 | Rice Edward K | Expansive cement |
| SU1244121A1 (en) * | 1982-11-04 | 1986-07-15 | Ташкентский Ордена Дружбы Народов Политехнический Институт Им.А.Р.Бируни | Method of producing high-early-strength high-strength cement |
| ZA879217B (en) * | 1986-12-09 | 1989-04-26 | Lorenzo Valenti Gian | Hydraulic binders and building elements formed of non-traditional materials |
| DE3778916D1 (en) * | 1987-11-19 | 1992-06-11 | Newmont Mining Corp | METHOD FOR PRODUCING CEMENT-LIKE COMPOSITIONS FROM WASTE. |
| US4957556A (en) * | 1989-06-08 | 1990-09-18 | Hassan Kunbargi | Very early setting ultra high early strength cement |
| DE4204227C1 (en) * | 1992-02-13 | 1993-02-11 | Ivan Prof. Dr. 3380 Goslar De Odler | Portland cement clinker prepn. - by firing mixt. of calcium oxide, silica, aluminium@ and ferric oxide in presence of additive contg. sulphate and fluorine ions |
| DE4227815A1 (en) * | 1992-08-21 | 1994-02-24 | Air Beteiligungs Gmbh | Process for the spontaneous chemical precipitation of sulfates dissolved in water as ettringite and use of this process for the production of a low-chloride, aluminum oxide-containing gypsum anhydrite |
-
1996
- 1996-06-10 MX MX9602271A patent/MX9602271A/en unknown
- 1996-12-04 US US08/766,666 patent/US6149724A/en not_active Expired - Lifetime
- 1996-12-18 CA CA002193339A patent/CA2193339C/en not_active Expired - Fee Related
-
1997
- 1997-02-04 ES ES97500026T patent/ES2196285T3/en not_active Expired - Lifetime
- 1997-02-04 EP EP97500026A patent/EP0812811B1/en not_active Expired - Lifetime
- 1997-02-04 DE DE69720595T patent/DE69720595T2/en not_active Expired - Lifetime
- 1997-03-12 CO CO97013338A patent/CO4560452A1/en unknown
- 1997-04-25 PA PA19978428701A patent/PA8428701A1/en unknown
- 1997-04-28 BR BR9700621A patent/BR9700621A/en not_active Application Discontinuation
- 1997-05-08 UY UY24549A patent/UY24549A1/en not_active IP Right Cessation
- 1997-05-22 AR ARP970102179A patent/AR004900A1/en active IP Right Grant
- 1997-05-29 GT GT199700067A patent/GT199700067A/en unknown
- 1997-06-04 CR CR5560A patent/CR5560A/en not_active Application Discontinuation
- 1997-06-10 PE PE1997000221A patent/PE90598A1/en not_active Application Discontinuation
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