RU2058952C1 - Portland cement clinker, cement on its base and method for production of corrosion-resistant concrete - Google Patents

Abstract

FIELD: manufacture of building materials efficient use in cement of active mineral additives, mainly, of natural origin, particular, sedimentary pazzolana, in the amount of 30-50% of cement mass without impairing cement strength, and with no increased shrinkage; such cement providing for frost-resistant concrete is applicable like the portland cement for construction purposes, and, more than that, for production of corrosion-resistant concrete with especially high stability of its properties, including fine-grained concrete. SUBSTANCE: portland cement clinker includes alite analog supersaturated with lime up to CaO/CaO/SiO₂ mole ratio of 3.3-3.7 versus 3 in alite, analogs of calcium aluminate and alumoferrites containing additionally oxides of iron and silicon and silicon oxide, and also belite and oxide of calcium in free state with iron oxide impurity. During hydration of such clinker, alite analog in the cement content reacts with water fae faster than cement alite and evolves far more calcium hydroxide reacting with pozzolana more intensite, and resulted calcium hydrosilicates are stronger and feature slow expansion in the course of setting that leads to strengthening the structure due to mild action of expanding agents at minimum content of free calcium hydroxide to provide for optimal corrosion resistance. EFFECT: higher efficiency. 29 cl, 7 dwg, 27 tbl

Description

 The invention relates to building materials, namely to cement technology and its use.

The basis of construction at present, as over the past 150 years, is a Portland cement fine grinding product together with the calcium sulfate component of normal Portland cement clinker (NPK), which includes four main clinker minerals, tricalcium silicate, or alite 3 CaO · SiO ₂ , dicalcium silicate or it whitens 2 CaO · SiO ₂ , tricalcium aluminate 3 CaO · Al ₂ O ₃ and tetra-calcium aluminoferrite 4 CaO · Al ₂ O ₃ · Fe ₂ O ₃ , or according to the accepted notation C ₃ S, C ₂ S, adopted in cement chemistry, C ₃ A and C ₄ AF, respectively [1] In this notation the oxides of the elements are represented by the first letters of their designations from the usual chemical notation, and the digital coefficients are transferred to the lower indices at these letters. The clinker is obtained by firing before sintering at 1450-1500 ^о С a cement raw mix, with particle sizes of 0.5-200 microns, usually composed of three ground components of lime (limestone, chalk, marble, etc.), silicate (clay , sandstone, etc.) and ferruginous (iron ore, pyrite cinders, etc.). By mixing Portland cement with water, building materials harden both in air and in water, cement dough, forming a cement stone, with an additional fine grout (1-5 mm, sand) cement mortar, and with small and large (5-40 mm and more, crushed stone or gravel) aggregates cement concrete.

The main disadvantages of ordinary Portland cement (OPC) are as follows:
the slow speed of its initial hardening in the first day after mixing with water;
the impossibility of introducing into it active mineral additives in an amount of more than 5-15% by weight without loss of both initial and standard, i.e. 28-day strength in standard cement-sand (1: 3 by weight, ratio by weight of amounts of water and cement W / C ≈ 0.4) mortars, as well as in mortars (other compositions) and concrete;
low sulfate resistance, expressed in the loss of more than 25% of the compressive strength of cement-sand (1: 3 by weight) samples for 6 months. storage in 5% aqueous solutions of magnesium or sodium sulfates [2]
Already at the beginning of the 20th century, these drawbacks of Portland cement were obvious [3] and many technical solutions were proposed to reduce them. The first of them was a clinker that did not contain tricalcium aluminate, obtained by V. Michaelis [4]. This clinker contains alite, belite and aluminoferrite, as well as calcium ferrites.

 However, the rate of hydration of alite in the cement made from it is even lower than in the hardening OPC, and, accordingly, the initial and standard strength of the first is significantly lower than the second.

Also known is the clinker proposed by F. Ferrari, in which, to accelerate the hardening of cement that does not contain C ₃ A, the proportion of alite C ₃ S is significantly increased. Ferrari clinker has the following composition in terms of the content of basic minerals, wt. alit 60-70; whites 5-10; tetra-calcium aluminoferrite 25-30 [5-8] The increase in the alite content in the Ferrari clinker really eliminated the delayed increase in the strength of the cement obtained from it at 1-3 days of hardening compared to OPC, while maintaining high sulfate resistance. Ferrari cement has the following advantages:
1) delayed loss of storage strength due to reduced hygroscopicity of calcium aluminoferrites in comparison with tricalcium aluminate C ₃ A;
2) better workability with an equal amount of water in the cement paste, mortar, or concrete compared to an OPC containing C ₃ A;
3) convenient setting time without false setting, even in individual batches, and without a delayed end of setting in a long-stored cement, which is usual for a lying OPC;
4) high aggregate capacity, i.e., the ability to perceive large quantities of aggregates in concrete at a given strength of the latter, which corresponds to the ability to save cement, or to reduce cement consumption compared to OPC, ceteris paribus (this is due to the advantages 1-3);
5) low shrinkage, formally this can be explained by the fact that C ₃ A is characterized by the greatest shrinkage compared to all other minerals of the NPK, but in fact it is due to the absence of a "house of cards" type structure typical of C ₃ A hydration products in hardening Ferrari cement , the latter are visible under an optical microscope in a hardening cement paste, mortar and concrete made of OPC, they consist of calcium hydroaluminates;
6) increased adhesion to steel reinforcement, which can be explained by the large chemical "affinity" for hydrates obtained from Ferrari cement in comparison with those from OPC;
7) reduced heat generation, which reduces initial shrinkage and is especially important for massive structures, in particular hydraulic structures, but also for mortar and concrete compositions made without special selection of aggregate granulometry, that is, when working on natural materials; in Russia, this is almost the entire volume of construction work;
8) high sulfate resistance of hardened dough, mortars and concrete from Ferrari cement, 1.3-1.7 times higher than that for materials at the OPC [5-9]
However, Ferrari clinker is not widespread. The main disadvantage of the Ferrari clinker is its narrow melting range. G. Frenkel [10] noted that due to the high melt flow rate suddenly occurring with increasing temperature during firing of such a clinker, welds appear in the sintering zone of rotary kilns: clusters of dense and difficult to grind clinker.

Known clinker Frenkel composition, different from the composition of the Ferrari increased values of the coefficient of saturation of lime: KH 1, p 0.7-0.9, an average of 0.8 and n 1.9-2.2 [10] when the values of KH according to the formula [ 11] equal to C (1.65A + 0.35F): 2.8. According to Frenkel’s observations, contrary to the calculations of Bogg [2] Kinda [11] with p values of 0.7-0.9 in Portland cement clinker, C ₃ A is still practically absent and, therefore, the advantages characteristic of clinkers of the Ferrari composition are preserved, and the narrow the melting range is significantly expanded.

25 years after the work of Frenkel, Italian researchers V. Cirilli and C. Breezy [12] showed that the reason for the absence of C ₃ A in the Frenkel clinker was an increased MgO content.

Another technical solution consists in a method for producing clinker by co-firing in a rotary kiln of two raw mixtures of normal, coming from the cold end, and highly iron, injected from the hot end. The presence of a highly active aluminoferrite phase in the clinker obtained, approaching in composition to three-calcium ferrite C ₃ F, which was reported by E. Gzhemek (1967) at a lecture in Moscow, namely C ₃ (F _0.9 A _0.1 ) [13 ] The absence of silica in the composition of this aluminoferrite phase was established using the selective chemical-analytical method, which has the standard name for rational chemical analysis in Russia.

The method of rational chemical analysis of Portland cement clinker was almost simultaneously developed in Russia [14] and Japan [15] and was further modified several times without changing it in essence. First, acting on a sample of ground clinker with a solution of a weak acid, which forms stable surface complexes with aluminum and iron oxides, calcium silicates are dissolved, the solid residue is treated with a solution of calcium aluminates and calcium aluminoferrites with solutions of proton-releasing substances, for example, sugars that selectively dissolve calcium aluminates, crystallizing with a molar excess of oxygen, actively reacting with a proton. The last solid residue is an aluminoferrite base. Alite and belite from a separate sample are separated by a phenolic-based solvent, which does not affect belite, removing alite in the solution, which removes calcium during the reaction with phenolic hydroxyl. The Portland cement clinker of industrial production in the composition of the main phases, as established by this method, contains a significant amount of impurities and, at the same time, these phases remain mainly consistent with stoichiometric compositions [3] Impurities alter the activity of the main phases of the clinker in the hydration and hardening processes after mixing with cement water obtained from these clinkers [16]
These well-known technical solutions as a whole have not gained distribution due to the required excessive fuel consumption and / or the currently extremely high clinker cooling rate which is not currently realized under industrial conditions, which also ultimately leads to excessive energy costs.

 Therefore, over the past 30 years, efforts have continued to improve the Ferrari-Frenkel clinker under various industrial conditions. These experiments, repeatedly repeated in different countries, showed that there is another significant drawback of this clinker: the hydration rate and strength of the cement obtained from it decrease when FeO appears in the clinker, i.e. its quality is very sensitive to the composition of the furnace atmosphere and the mode burning fuel in a rotary kiln. Attempts to obtain high-quality Ferrari-Frenkel clinker in powerful rotary kilns with a capacity of more than 70 t / h have been unsuccessful due to the FeO impurity in clinkers and the reduced hydration and hardening rate of cements made from them. Ultimately, it is the latter drawback that determines their small distribution in comparison with the CDD and the OPC, despite the 8 advantages of the former described above.

 To mitigate this drawback, several clinker formulations have been proposed along with technological firing impurities.

 Known technological methods [17] for introducing a small amount of calcium sulfate mineralizer into the raw material mixture and firing it in MgO lined furnaces, are recommended to improve the quality and reduce the sensitivity of the ferrite phase to the composition of the furnace atmosphere.

 However, as the experiments showed, to stabilize the quality of the Ferrari-Frenkel type clinker, introducing a calcium sulfate mineralizer into the raw material mixture and contacting the MgO containing furnace lining was not enough.

Known Portland cement clinker, including the sum of calcium silicates of alite and belite types, calcium aluminate and calcium aluminoferrite in mass parts in the ratio (78-93) :( 0-2) :( 7-20), characterized in that as calcium aluminoferrite it contains a solid solution from the series with extreme members of C ₄ AF C ₂ F, and as a calcium silicate of the belite type α 'and β -C ₂ S. To prevent the latter from becoming hydraulically passive γ-C ₂ S and the formation of FeO, this clinker burned by rapid heating in a furnace of a fluidized bed, fed from below y, and discharged from the upper part of the fluidized bed equipped with a water cooled chute refrigerator fluidized bed where quenched from 1500 ^{° C} to 1000-1100 ^{° C} [18] An advantage of this clinker relating to the composition of the clinker-type Ferrari, is the presence of highly active, during hydration of the cement prepared from it, aluminoferrite phase containing a solid solution of variable composition, due to rapid cooling, and, in addition, due to the absence of C ₃ A reduced cement exothermy in the initial stage of the hydration process ui.

Firing such a clinker in a conventional rotary kiln is difficult due to the generally low content of the sum of the minerals of the melt (C ₄ AF + C ₃ A) up to 22 wt. against 22-27% in CDD, and requires a long time of sintering at a temperature higher than 1500 ° ^C. As a result, admixture of FeO, inevitable in this situation, would accelerate the conversion of α 'and β-C ₂ S in the hydraulically passive γ-C ₂ S with sprinkling of clinker and a significant decrease in strength and its growth rate in cements made from it. This disadvantage eliminates the present invention.

Considering the specifics of cements and methods for their production on the basis of clinkers of the Ferrari-Frenkel type, cements of the Ferrari-Frenkel type are obtained, as a rule, by finer grinding of the corresponding clinkers compared to the OPC [6-9] This is primarily due to the need to compensate for the delayed initial hydration of aluminoferrite phase compared with C ₃ A during the first three days of hardening of cement by increasing the content of fine fractions of 0.3-5 microns in cement [9]
An analogue of the invention in terms of composition and production of cement from clinkers with phases of variable composition is cement based on clinker containing rhombohedral alit modification (RC ₃ S), belite, tricalcium aluminate and aluminoferrite phase, as well as 1.5-6 wt. free calcium oxide CaO [19, p. 140] crushed together with gypsum to a specific surface of more than 3200 cm ² / g [19, p. 149, Table 69] characterized by standard strength (at the age of 28 days) of more than 55 MPa.

The disadvantage of this cement is due to the fact that clinker, including rhombohedral alite (RC ₃ S), requires low supersaturation of the melt with lime during roasting, and this is possible only when using highly reactive feed mixtures for clinker roasting, characterized by the activation energy of alite formation during roasting less than 840 kJ / mol [33, p.146] To obtain such raw material mixtures, a very fine grinding of them is necessary.

 This disadvantage is also eliminated by the invention in its part related to the composition of cement and its production.

Known methods for the manufacture of corrosion-resistant concrete based on cement with a reduced content of tricalcium aluminate, as well as aggregates and water [20 and 21] Their corrosion resistance in natural waters, or sulfate solutions containing more than 5000 mg SO ₃ ion / l, is determined by the low content in the hardened concrete generated during the hydration of tricalcium aluminate, calcium hydroaluminates which when penetration sulfate solutions reacted with sulfate ions to precipitate in the solid phase ettringite 3 SaOAl ₂ O ₃ · CaSO ₄ xx 3 32 H ₂ O and velicheniem volume, leading to the expansion of pores and occurrence of cracks, which enhances penetration into the concrete corrosive ambient agents. In addition, calcium hydroxide, which is released, in particular, from hydroaluminates during phase transitions, reacts with a sulfate ion penetrating from the outside to form gypsum CaSO ₄ · 2H ₂ O, which also expands the pores [22]
There are also known methods of manufacturing corrosion-resistant concrete based on cement, in which tricalcium aluminate is completely absent [23 and 24] However, in order to avoid difficulties associated with the manufacture of such cement, it is considered advisable to use cements with a limited content of tricalcium aluminate to 5-6 wt. what is currently set as a standard in standards for sulfate-resistant cement in many countries [25 and 26]
In addition, there are known methods for increasing the corrosion resistance of concrete based on cement containing an aluminate phase, in which calcium hydroxide-binding active mineral additives, in particular natural pozzolans introduced into the cement composition are used [27]
The disadvantage of these technical solutions is that they do not compensate for the shrinkage that intensifies when active mineral additives are added to cements or to hardening concrete based on these cements.

 The invention in terms of a method of manufacturing corrosion-resistant concrete helps to eliminate this drawback.

The closest to the invention in terms of clinker composition is Portland cement clinker, which includes non-stoichiometric crystals of three-calcium silicate of variable composition in the form of alite, two-calcium silicate in the form of belite, calcium aluminate and calcium aluminoferrite, characterized in that to accelerate the hydration and hardening of the alite phase and clinker in general produced after mixing thereof with water of cement clinker contains tricalcium silicate, alite composition in the form of (2,8-3,2) xx CaO · SiO ₂ at a content therein domains nesteh ometrii wt. (2.8-2.95) CaO · SiO ₂ 50-80; (2.96-3.05) Ca · SiO ₂ 10-25; (3.06-3.2) xx CaO · SiO ₂ 10-25 [28] In general, this clinker contains, by weight. Alite 33-71; whites 15-35; tricalcium aluminate 4-14; tetra-calcium aluminoferrite 10-18. It is obtained by roasting the raw material mixture, the chemical composition of which, expressed in the oxide form in the four main components, is in the following limits (wt.) Without taking into account losses during calcination (pp): SiO ₂ 19-25; Al ₂ O ₃ 3.5-9; Fe ₂ O ₃ 3-9; CaO 65-68. The non-stoichiometric alitic phase is obtained in clinker by replacing part (30%) of the lime component in the raw material mixture with Ca (OH) ₂ or by using other technological methods, for example, blowing ground limestone from the hot end of a rotary kiln by replacing it with 30% of the lime component, fed from the cold end of the furnace, which allows CaO with a higher activity in the alitogenesis reaction to be obtained as a part of the calcined material as compared to CaO formed during the decarbonization of the calcareous component in conventional oh cement raw mix. Alite containing 70-80% of the phase (2.8-2.95) CaO · SiO ₂ , 10-18% of the phase (2.96-3.05) CaO · SiO ₂ and 12-20% of the phase (3.06 -3.2) CaO · SiO ₂ , in the composition of cement made from this clinker, after 1, 3, 7 and 28 days of hardening, it reaches a 3-5% greater degree of hydration compared to alite in the composition of the OPC, and prepared from the first cement has an initial strength (at 1 day old) of 2-5. and the standard strength (at 28 days of age) is 5-12 MPa higher than the OPC ceteris paribus.

The disadvantage of this clinker is that it is not possible to produce it using the conventional technology adopted in the cement industry for the production of NPK and OPC, since either double burning of 30% of the known component of the raw material mixture or its injection in the specified quantity from the hot end is necessary rotary kiln in such a way that it falls into the periphery of the fuel flame, as previously proposed in [29]
The invention is devoid of this drawback. Obtained according to the invention by firing in a traditional rotary kiln, a Portland cement clinker, comprising non-stoichiometric crystals of variable calcium tricalcium silicate, dicalcium silicate, calcium aluminate and calcium aluminoferrite, is characterized in that it contains a composition component (3.3-3.7 as a tri-calcium silicate of variable composition) ) CaO · SiO ₂ as a phase idiomorphic to alite, as a calcium aluminate a component of composition 2 (3СаО · Al ₂ O ₃ ) · Fe ₂ O ₃ · (1.5-3) SiO ₂ , as a calcium aluminoferrite, a component of composition ( 4,5-6 ) CaO · Al ₂ O ₃ · (1-3) Fe ₂ O ₃ · SiO ₂ , and, in addition, additionally contains free calcium oxide CaO in the following ratio, wt.

Composition Component (3.3-3.7) x
x CaO · SiO ₂ as a phase,
idiomorphic alite 60-85
Dicalcium silicate 0.05-6
Component composition 2 (3CaO x
x Al ₂ O ₃ ) · Fe ₂ O ₃ · (1.5-3) SiO ₂ 0.05-6
Composition Component (4.5-6) x
x CaO · Al ₂ O ₃ · (1-3) Fe ₂ O ₃ · SiO ₂ 10-25
Calcium Free Oxide
CaO 3-18
In an embodiment of the invention, the free calcium oxide in the proposed clinker contains Fe ₂ O _{3 of} more than 1%, preferably 5-28.5 wt.

To obtain a clinker of a given composition, a raw mix with calculated characteristics corresponding to the following concentration of basic oxides in it, wt. loss on ignition (p.p.p.) 35-39; SiO ₂ 12.6-14.2; Al ₂ O ₃ 0.5-2.5; Fe ₂ O ₃ 2.1-5.5; CaO 44.5-48. When firing this raw mix prepared by wet or dry methods in conventional rotary kilns, Portland cement clinker is obtained without taking into account the dust of the following chemical composition, expressed in terms of the content of basic oxides, wt. SiO ₂ 14.5-21.2; Al ₂ O ₃ 1-3.8; Fe ₂ O ₃ 3.3-8.5; CaO 69.7-79. The clinker should be designed for an excess content of free calcium oxide at an average level of 10%, although in fact it can differ from the calculated one both in the direction of decrease and increase. This excess of calcium oxide reduces the activation energy of alitogenesis in any raw material mixture of the above chemical composition to a level below 840 kJ / mol. Ultimately, this leads to an increase in the C / S ratio in the alite phase of the clinker and supersaturation of clinker melt remaining after crystallization of the alite.

The invention in terms of clinker composition consists in the fact that it contains an idiomorphic alite phase of a non-stoichiometric composition corresponding to the formula (3.3-3.7) CaO · SiO ₂ , supersaturated with lime not only with respect to normal alite in the NPK with a CaO / SiO ₂ molar ratio close to 3 and not exceeding 3.17 [3] but also with respect to alite, which is part of nonequilibrium clinkers, for example, obtained according to the proposal [28] where the CaO / SiO ₂ does not exceed 3.2. It is known that the structure of the alite crystal lattice does not allow even in the presence of calcium in the internodes to contain more than 3.17 mol of CaO for each mol of SiO ₂ [3] Therefore, the alite type phase with the formula established experimentally using the method of rational chemical analysis of clinker in which CaO / SiO ₂ 3,3-3,7, it is necessary to consider as a result of the formation of additional subepitaxial CaO monolayers inside naturally formed 3 CaO · SiO ₂ crystals from the melt. This is precisely how the excess of CaO in belite was considered in [30], which increases the molar ratio of CaO / SiO ₂ from a value of 2 for the stoichiometric phase of belite to 2.2–2.7.

 Alite-type phase crystals in the proposed clinker have exactly the same external shape and faceting as normal alite in NPK with a distinct crystallization of phases. Therefore, the term “idiomorphic” was used in the description to characterize this phase supersaturated with lime as compared to alite in the NPC, but the values of its refractive index when studied under an optical microscope are higher than that of alite in the NPC, which indicates an increased content of lime in it along with the method rational chemical analysis. This phase supersaturated with lime in the proposed clinker after grinding and mixing with water interacts with the latter much faster than normal alite in the NPK, namely, the degree of hydration of 80% at room temperature is achieved in the supersaturated phase in the proposed clinker in 16-18 hours in micropreparations with water-solid the ratio (W / T) is about 10, while for alite in the NPK in the same drugs only for 1-2 months; The supersaturated phase reaches 100% hydration in 3–7 days in micropreparations and in 21–30 days in hardened stone from a test of normal density, while alit in NPK in about 6–12 months in micropreparations and in 10–12 years in a stone from dough normal density under the conditions that, before interacting with water, the proposed clinker and NPK are ground until they completely pass through a N 006 sieve with 60 μm cells, and during water storage of cement stone. This difference of the indicated phase, which is the most important element of the unexpectedness inherent in the invention, from which the fields of its application arise, allows us to consider this phase as a new clinker mineral, idiomorphic and, judging by powder X-ray diffraction patterns structurally close to alite, but superior to it in terms of saturation lime, and hydration rate. This gives reason to distinguish this mineral from normal alite, to call it hyperalite ("superalit").

The difference between this mineral and the known alite [28] is quite obvious, in which, on the contrary, calcium deficiency in comparison with the stoichiometric CaO / SiO ₂ 3 ratio accelerates phase hydration by 5-10% in the hardening stone within 1-28 days, and the degree of hydration reached 80% by the end of this time, which is higher than the usually known level of 60-70% [3] but significantly lower than that of hyperalite.

 In the clinker according to the invention, the value of KH according to V.A. Kind [11] loses its meaning as a measure of the limiting content of lime and retains its value only as an integral indicator of the relative content of lime.

Similarly, experiments show that the remaining components of the proposed clinker, with the exception of the 2CaO · SiO ₂ Belite formed mainly in solid-phase reactions, also differ in chemical composition from phases in the NPC. They include significant amounts of silica, and the aluminate phase, in addition, a significant amount of iron oxide. The appearance of the crystals of these phases in polished sections under an optical microscope is almost similar to that observed in their analogs in the well-known clinker.

Moreover, both the analog component of tricalcium aluminate having the composition 2 (3 CaO · Al ₂ O ₃ ) · Fe ₂ O ₃ · (1.5-3) SiO ₂ , and the analog component of the aluminoferrite phase of the known clinker having the composition ( 4,5-6) CaO · Al ₂ O ₃ · (1-3) Fe ₂ O ₃ · SiO ₂ , in contrast to hyperalite, interact with water much more slowly than their analogues in the well-known Portland cement clinker. So, the degree of hydration of calcium aluminoferrites in known clinkers is 1 month later. hardening of the test of normal density of 20-35% [2] against 5-15% of the analog component in the proposed clinker. After 1 day, the degree of hydration of tricalcium aluminate in the test of normal density from ground samples of known clinker is 65-70% [3], whereas in the proposed clinker, after 1 day, the degree of hydration of the calcium aluminate analog component does not exceed 20-25%. This affects the phase the composition of the products during hydration and hardening of cement from the proposed clinker.

The free calcium oxide present in the proposed clinker contains iron oxide Fe ₂ O ₃ , which changes its structure and the rate of hydration of the quenching with water. In the proposed clinker, as shown in one of the examples below, powder X-ray diffraction patterns show almost no CaO reflexes, which is thus almost X-ray amorphous. Such a situation is possible if free CaO in the presence of an impurity of Fe ₂ O ₃ up to 10% is a solid solution of calcium ferrites in CaO of the limiting composition CF _0.1 . Therefore, despite the CaO content in the proposed clinker is much more than 2% allowed according to [2] or 2.5% according to [19] according to the criterion of uniformity of volume change, cement prepared by joint grinding of the proposed clinker to a specific surface above 4000 cm ² / g, determined by the method of breathability, with a calcium sulfate component, in particular, two-water gypsum, is characterized by the uniformity of the volume change of the test with the content of free calcium oxide in the proposed clinker up to 18%
In addition, the proposed clinker, despite such a significant amount of free calcium oxide, is resistant to carbonation by atmospheric carbon dioxide in the presence of air moisture due to an impurity in CaO of iron oxide. From the thermodynamic point of view, the reaction of siderite formation of FeCO ₃ from FeO and CO ₂ due to the large Helmholtz free energy is more preferable than the reaction of the formation of calcite CaCO ₃ from CaO and CO ₂ . Due to the low content of CO ₂ in the atmosphere (0.04%), the binding of carbon dioxide to siderite reduces its concentration in the pores, and as a result, CaO remains stable. After two years of storage, the proposed clinker is scattered into particles of 0.5-1 mm in size, each of which remains non-carbonated and as if just burnt, while the scattering is associated with unrestricted hydration of CaO + H ₂ O __ → Ca (OH) ₂ . Thus, the behavior of the proposed clinker during storage is also completely different compared to the known one, which, in the presence of free lime, quickly carbonates during storage in the open air.

 The siderite mechanism for inhibiting the carbonation of the proposed clinker is proved by the siderite crystals visible under an optical microscope on the surface of the particles of crumbling clinker mentioned above, which, with a practically zero degree of hydration of the aluminate and aluminoferrite phases of this clinker and a slight degree of hydration of hyperalite, could be formed only from free FeO impurity in the oxide .

 With a hyperalite content of 60-85% by weight, the proposed clinker is characterized by optimal strength indicators in the composition of cement obtained by joint or separate grinding with a calcium sulfate component. With a lower content of this component, the properties of clinker cement according to the invention approach the properties of clinker cement according to the prototype, and with a higher content of the said component, the strength of cement according to the invention slightly decreases at 28 days of age compared to its optimal content. The dependence of the strength of pure clinker cement on the content in the clinker of the analog component of tricalcium aluminate is small, but with an increase in its amount in excess of 6%, the properties of the clinker approach the known one, lime supersaturation of the alite analogue ("hyperalite") decreases, and its hydration rate, accordingly, decreases. The dependence of the strength of pure clinker cement based on the proposed clinker on the content of the analog component of calcium aluminoferrite shows an optimum in the range of its content of 10-25% almost regardless of the amount of "hyperalite". If the content of calcium aluminoferrite analogue is increased in excess of 25%, then the standard (28-day) cement strength is reduced due to a decrease in hyperalite content. When the amount of calcium aluminoferrite analogue is less than 10%, sintering of the raw material mixture during firing of the proposed clinker is significantly difficult and fuel consumption increases, and the quality of the resulting clinker decreases as a result of the appearance of vustite FeO in it.

(C₁₂A₇+CA)+CF+

и
C_4,5AFS

(C₆AF₂)+

(C₂AS)+

CS.The above does not mean that the compositions of calcium aluminate and calcium aluminoferrite analogues described above, which simultaneously include 4 main oxides of CaO, Al ₂ O ₃ , Fe ₂ O ₃ and SiO _2, cancel one of the main conclusions of J. Rankin and F. Wright [2] in the CaO system Al ₂ O ₃ Fe ₂ O ₃ SiO ₂ quaternary chemical compounds. This does not mean a return to the many old hypothetical phases, which were considered characteristic of Portland cement clinker. The presented compositions completely follow from the data of rational chemical analysis and mean that the component chemically reacting to standard reagents, like alit, has stoichiometry corresponding to composition C _3.3-3.7 S, and the components chemically reacting in the proposed clinker to standard reagents as calcium aluminate and calcium aluminoferrite, respectively, are characterized by compositions 2 (C ₃ A) · FS _1.5-3 and C _4.5-6 AF _1-3 S. In other words, in addition to the external structural similarity, they have commonality with their counterparts in the NPK chemical behavior. Structurally, they are either block-epitaxial formations of impurity oxides in the matrix of the idiomorphic “initial” phase, or they are complex intergrowths of phases, which may have the following character to explain the observed chemical compositions:
for analogs alita
C _3.5 S __ → C _0.5 + C ₃ S;
for analogs of aluminate and calcium aluminoferrite from many possible options
2 (C ₃ A) FS

(C ₁₂ A ₇ + CA) + CF +

and
C _4,5 AFS

(C ₆ AF ₂ ) +

(C ₂ AS) +

CS

 These variants are consistent with the chemism and idiomorphism of the observed phases.

Let us consider in more detail the process of obtaining the proposed clinker in order to explain the reason for the formation of supersaturated phases: an alite analogue with lime, analogs of calcium aluminate and calcium aluminoferrite with silica, and the second and free calcium oxide with iron oxide. The proposed clinker is obtained by roasting in an oxidizing medium (more than 1% O ₂ in the exhaust gases) of raw mixtures characterized by KH values according to V.A. Kind 1.16-1.5 and p 0.15-0.8, and the higher the KH , the lower should be the alumina module p. The structure of the clinker melt resulting from the firing of such mixtures differs significantly from the known one. The structure of the clinker melt in the NPC [31] is based on the ring structures of (AlO ₄ ) ^5- tetrahedra joined through 5-membered or 6-membered rings through bridging oxygen atoms, which form a connected network in the bulk of the melt. Calcium cations are located on the periphery and in the geometric centers of the rings, while iron atoms replace either the aluminum in the tetrahedra, being in quadruple coordination (Fe ^IV ), or the calcium between them, in sixth coordination (Fe ^VI ). In this melt, the solubility of silica (SiO ₂ ) is realized by pair substitution of aluminum with silicon and calcium prior to the ionic reaction
2Al ³⁺ Si ⁴⁺ + Ca ²⁺ , (1) flowing with the opening of aluminum rings, especially the more stressed of them 5-membered. This despite the increased tension of bonds in such rings requires an increase in energy consumption for firing.

With a high content of Ca ²⁺ and Fe ³⁺ in the melt formed during the oxidative firing of raw mixtures to obtain the proposed clinker, due to the substitution of iron for silicon and calcium
2Fe ³⁺ Si ⁴⁺ + Ca ²⁺ (2) and a reduced aluminum content do not arise for the formation of bound ring structures. Instead, there are layered clusters that are similar in structure to Ca O Fe O Ca layers in the crystal lattices of solid solutions of a number of calcium aluminoferrites C ₄ AF C ₂ F. Silica also dissolves in such layers, since Ca O Fe groups and Ca O Si groups have approximately equal values of the formation energy, in contrast to the Ca O Al group, which is characterized by an increased value of this energy. The difference in the energies of the Ca О Al and Ca О Si groups is called the Levenstein barrier [32]; it prevents the entry of silica into aluminate rings and aluminum into silicate phases. In the melt, when firing the proposed clinkers, the Levenstein barrier is absent. This leads to an increase in both the dissolution rate and the ultimate solubility of silica, and at the same time, according to the principle of Henri Le Chatelier [33], to an increase in similar parameters for CaO. This allows you to increase the KH of the raw mix.

In fact, the substitution reaction (2) in such a melt should proceed together with intermediate parallel reactions
Fe ³⁺ + e ^- ⇄ Fe ²⁺ ; (3)
O ^2- -e ^- ⇄ O ^- ; (4)
Fe ²⁺ ⇄ Ca ²⁺ (substitution); (5)
Fe ²⁺ + O ^- ⇄ Fe ³⁺ + O ^2- . (6)
This leads to the lack of mobility of the oxygen coordination shells of cations in the known clinker melt, to the facilitation of substitution reactions of type (2), lowering their energy barrier, and to the acceleration of the synthesis reactions of the main phases in the clinker. This explains the increased crystallization ability of the clinker melt mentioned in the description below in the description of the proposed chemical compositions.

 The compositions of the main components of the proposed clinker are also determined by the absence of the Levenstein barrier and the layered structure of the uterine clinker melt, which introduces a new, unexpected effect of spatially oriented ion diffusion in the microscale into the clinker formation process. Along layered clusters, the diffusion coefficients for all melt components should be higher than across. Therefore, the composition of the clinker phases formed during firing depends on the size of the clusters. The larger they are, the lower the rate of transverse diffusion and the less influence on the composition of the clinker phases is exerted by the cooling regime, in contrast to the known aluminoferrite clinkers.

The increase in the firing temperature of the proposed clinker mainly increases the longitudinal diffusion rate and the crystal growth rate of the synthesized clinker phases. This explains the accelerated increase in the size of crystals of calcium silicate of alite type during sintering of this clinker, despite the incompleteness of the transverse diffusion process. As a result, in this component, which includes layers of a nonequilibrium texture in its crystal lattice, there is an excess of CaO equal to (0.3-0.7) CaO per mole of 3CaO · SiO ₂ , i.e. the resulting component acquires the composition (3.3-3.7) · CaO · SiO ₂ . The interlayer supersaturation of this component with lime also leads to a faster decomposition of its structure upon interaction with water, completely changing the rate of its hydration compared to normal alite.

 After mass crystallization of the alite analog and removal of CaO from the melt, the less mobile silica does not have time to completely separate from the melt and remains in excess, this increases the viscosity of the melt and, despite the increased content of iron in it, slows its penetration into the lining of a rotary kiln, normalizing the mode of operation of the latter , on the other hand, this complicates the crystallization of the components of the intermediate substance, causing melt overcooling, which follows from the data of differential thermal analysis (DTA) upon cooling nker. Moreover, the separation in the NPC [9] of the exothermal effects of crystallization of analogues of aluminate and aluminoferrite phases in the proposed clinker becomes less noticeable, as if they crystallized in microvolumes almost simultaneously. In the sections of the proposed clinker, analogues of these phases with conventional etchants are poorly separated, they form a common conglomerate, visible as a light intermediate substance and separated only by reducing substances. The dyeing method with methylene blue dye [34] in this clinker leads to staining, in addition to belite, of all phases, even the alite analog and free calcium, which indicates the presence of excess negative charges [35], the origin of which in each phase is apparently different.

 An admixture of silica in analogues of calcium aluminate and aluminoferrite of calcium, as well as an admixture of iron in an analogue of calcium aluminate, which are contained in larger amounts than are found in known clinkers, apparently contribute to the delayed hydration of these phases in the ground “hyperalitic” clinker after it is mixed with water. An additional factor is the presence in the latter case of increased amounts of calcium hydroxide, which, as is known, slows down the hydration of calcium aluminoferrites.

 The invention in terms of clinker composition becomes clearer from examples of its implementation.

PRI me R 1. To obtain the proposed clinker use 3 rotary kilns with a diameter of 3.6 m and a length of 60 m, heated by natural gas with a calorific value of 8000 kcal / kg, with a capacity of 13.5 t / h. The raw material mixture from the chalk component of chalk, the silicate component of clay and the glandular component of pyrite cinders, the chemical composition of which is given in Table 1, is prepared by the wet method by two-stage grinding, first in a self-grinding mill of the Hydrofol type with a diameter of 7.0 m and a length of 2, 3 m, then in two tube mills with a diameter of 3 m and a length of 8.5 m, single chamber, with a fill factor of 0.25 grinding media. The resulting sludge with the help of correcting pools is adjusted to the required chemical composition, averaged in a horizontal pool with a capacity of 6000 m ³ and pumped into the furnace through nutrient devices. The furnaces operate on natural draft through pipes 40 m high without dust precipitation devices and for this reason without dust return. The chemical composition of the raw mix every day is presented in table 2, the average physical characteristics of the raw mix in table 3. The firing of the proposed clinker is carried out at the same productivity as the well-known Portland cement clinker (13.5 t / h), and at the same gas flow rate of 3000 nm ³ / h, despite the increased KH values of the raw material mixture and, accordingly, a larger amount of lime component in it subjected to decarbonation. The reason for the lack of increase in fuel consumption for firing the proposed clinker is to accelerate the sintering process due to the "bulk" mineralizing effect of iron oxide in the clinker melt during the firing of the proposed clinker, in contrast to the "surface-active" mineralizers of known types of fluorides, chlorides, sulfates, which are mainly active in melt layers bordering with solid phases, or, in contrast to the well-known clinker melt containing ring-free mineralizers not containing mineralizers. The effect of accelerating sintering at elevated temperatures, taking into account the energy coefficient, compensates, as follows from these experiments, the additional energy consumption for decarbonization of the increased content of the calcareous component during firing of the raw material mixture to obtain the proposed clinker.

 The chemical composition of the average samples of the proposed clinker for 1 day. Each firing is presented in Table 4, which also compares the results of calculating the potential mineralogical composition of clinker according to V.A. Kind, generalized data of quantitative petrographic analysis performed using an optical microscope with a device for observing in polarizing light in immersion preparations according to a known method [34 ] and also the results of calculating the mineralogical composition using formulas that take into account the actual composition of the main phases of the clinker.

 To derive these formulas, the obtained samples of the proposed clinker (1-4) are subjected to rational chemical analysis.

Rational chemical analysis of the proposed clinker is carried out according to the known method [14] with improvements [38] and relating to the choice of working reagents and indicators. As a selective solvent for determining the amount of calcium silicates and separating them from analogues of the aluminate and aluminoferrite phases of the proposed clinker, a 10% alcohol solution of maleic acid is used, which completely dissolves the sum of the alite and belite analog (solubility 98-99%) and almost does not affect analogues aluminate and aluminoferrite phases of the proposed clinker (solubility not more than 1%). A 0.4% alcoholic mannitol alcohol solution, selectively dissolving the calcium aluminate analog and not affecting (no more than 0.5%) analog of the aluminoferrite phase, is used as a selective solvent for separating the aluminate and aluminoferrite phases between themselves. A 3% alcohol solution of ortho-nitrophenol is used as a selective solvent for the separation between the alite analog and belite, which dissolves the alite analog and does not affect (no more than 1%) white. The determinations are carried out in two parallel samples of the clinker analyzed: in one, the total amount of silicate phases of the alite and belite analogue supersaturated with lime is determined using an alcohol solution of maleic acid, and the total amount of calcium cation extracted from the alite analogue and belite is filtered. In the precipitate after treatment of the clinker with maleic acid, an analogue of calcium aluminate is determined by treating the precipitate with an acetate solution of mannitol. The content of calcium aluminate analog is calculated by the amount of aluminum that has passed into the solution. The content of the aluminoferrite phase analogue is determined by the amount of iron oxide remaining that is insoluble in the acetic acid mannitol solution. In another proposed hitch clinker treated by heating ^to 70-80 C and stirred for 5 hours with a solution of o-nitrophenol is determined amount of alite analog.

 Since in all samples of the first sample in solutions in the form of sol or turbidity, there is no precipitating for 1 h, silicon oxide is detected, its amount is determined in the usual way. Colloidal silica, which is present in alcohol extracts from an analogue of the aluminate phase, is sometimes found in the rational analysis of NPKs; in the proposed clinker, for the first time, it is in this phase in an amount comparable to its other components. The amount of alumina present in the lime-saturated analogue of the alitic phase of the proposed clinker, on the contrary, was rather common for the well-known Portland cement clinkers. At first, it was assumed that the analogue of the alite and belite components of the proposed clinker could contain a significant amount of iron oxide, but these assumptions were not confirmed, the content of iron oxide in these components does not exceed the usual for the well-known Portland cement clinker and may well be associated with inaccurate phase separation, therefore further, the presence of iron oxide in the silicate phases of the proposed clinker is not taken into account when calculating its potential mineralogical composition.

 The results of rational chemical analysis for two out of four clinker samples are presented in Table 5. They indicate that the main phases of the proposed clinker have the chemical composition described above in the description of the invention.

With this in mind, Table 6 shows the derivation of formulas for calculating the mineralogical composition of the proposed clinker, taking into account the actual composition of the main components from Table 5. The starting points are as follows:
1) approximately 1/5 Al ₂ O _{3 is} dissolved in the supersaturated lime analogue of the proposed clinker hyperalite;
2) part of Fe ₂ O _{3 is} dissolved in free calcium oxide;
3) Al ₂ O ₃ and Fe ₂ O _3, after deductions specified in clauses 1 and 2, form analogues of calcium aluminates and aluminoferrites, the compositions of the latter are taken as the corresponding 2 (3СаО x х Al ₂ O ₃ ) · Fe ₂ O ₃ · 1,5SiO ₂ and 4-5 CaO · Al ₂ O ₃ x x Fe ₂ O ₃ · SO ₂ ; 4) to calculate the coefficient of lime saturation of the silicate components of clinker, the fractions of CaO and SiO ₂ are taken into account, which are not included in the above analogs of calcium aluminates and aluminoferrites;
5) the composition of hyperalite is taken corresponding to 3.5 CaO · SiO ₂ · Al ₂ O ₃ , and the coefficient at Al ₂ O ₃ (x) is taken as a variable depending on the content of hyperalite and Al ₂ O ₃ in the clinker, and is determined by the initial position adopted above 1;
6) KH is calculated by subtracting from the total amounts of CaO and SiO ₂ contained in the clinker, these oxides remaining free.

 From table 4 it follows that the derivation of the formulas for calculating the mineralogical composition of the proposed clinker in table 6 is carried out correctly, since there is obvious close similarity between the results of the calculation using these formulas and the data of quantitative microscopic analysis of the studied clinker samples. This also indirectly confirms the results of rational chemical analysis and the correctness of the chosen version of the methodology for its implementation.

 The absence of a calculated amount of an analogue of calcium aluminate in sample 2 of the proposed clinker according to formulas (9-24) in the presence of this phase in sample 2 of clinker according to rational chemical analysis (Table 5) in an amount of about 3% with a proximity of p to 0.64 is due to the existence of kinetic effect not taken into account by calculation formulas (9-24). In particular, in the composition of the raw material mixture, before sampling 2 of the proposed clinker, a particularly coarse glandular component pyrite cinders (III) was fed, which later came into contact with the rest of the raw material mixture. As a result, the actual content of the calcium aluminate analogue, according to the rational chemical analysis of clinker sample 2, turned out to be higher than zero, whereas this phase should have been absent by the calculation formulas. Kinematic effects are not taken into account by both the proposed and known calculation methods.

Figure 1 presents the structure of the well-known Portland cement clinker. Polished thin section. X 440. Etching HNO ₃ , alcohol solution. A alit, B whites, B intermediate: dark C ₃ A and alkaline aluminate, light C ₄ AF.

 In Fig.2 the structure of the proposed Portland cement clinker. Sample and etching conditions in figure 1. And the analogue alita, B whites, B is an intermediate substance (light). The zoning of A. is visible. Free calcium oxide is not visible under the microscope, although its amount in this sample is 7.3% (sample 1 in Table 4). You can also see the idiomorphism of the analogue alita in figure 2 and alita in figure 1 (idiomorphism is the identity of the form).

Figure 2 presents microphotographs from polished sections of the proposed clinker, demonstrating the idiomorphism of a lime-supersaturated analogue of the alite phase and analogue of calcium aluminoferrites with normal silica and calcium aluminoferrites dissolved in it in the well-known Portland cement clinker, which is easy to verify by comparing the micrographs shown in Fig. 2 with microphotographs of the NPC (figure 1), or similar photographs published, in particular, in the manual [34] The results of x-ray analysis of the proposed class nkera shown in Figure 3 in comparison with the known data for the clinker obtained in the same furnace of the same material. On these roentgenograms of the known (a) and proposed (b) clinkers, the interplanar distances d are multiplied by 10 ^-10 m. As follows from the above data, the alite reflections in the known clinker (d 3.024; 2.959; 2.771; 2.742; 2.179; 1.975; 1.540; triplet 1.926-1.929, doublet 1.822-1.824; doublet 1.624-1.626; doublet 1.482-1.484) are replaced in the alite analogue in the clinker according to the invention with reflexes with extended d (2.924; triplet 2.050-2.053; quartet 1.624-1.629; triplet 1.485-1.487) or with constant d (3.023; 2.771; 2.738; quartet 1.815-1.823, as well as quartet 1.760-1.764 used for quantitative analysis). The alite analogue in the clinker according to the invention is characterized by many reflexes in the form of triplets and quartets, which were not previously found in such forms, for example, the analytical quartet 1,760-1,764 previously occurred only in forms before triplets [3] Polyplets are known to be characteristic of solid solutions. The constancy of some d alite analogs in comparison with d alite indicates the layered nature of substitution / incorporation in these solid solutions. Reflections of the calcium aluminoferrite analogue in clinker according to the invention are characterized by expanded d (3.644 and 7.254) compared to calcium aluminoferrite in the well-known clinker produced under the same conditions (3.633 and 7.249). Belita d in the proposed and known clinkers are almost the same 2,880 and 2,876. We used an X-ray diffractometer DRON-1, monochromatic radiation CuK _α , voltage 2000 V, Al filter, goniometer speed 0.5 deg / min.

The results obtained indicate that the main reflexes of the analogue supersaturated with lime and the known alite phases coincide in interplanar distances, with the exception of some shift of the distances upward in the first, the same is characteristic of the aluminoferrite phases of the proposed and known clinkers. The free calcium oxide in the proposed clinker (test 1, table 4) has a loose structure, since the main analytical CaO reflections at 2.405 · 10 ^-10 m and 1.451 · 10 ^-10 m are very small in area, although the content of free calcium oxide in the clinker is very great, judging by the data of chemical and microchemical analysis. There is clinker glass (halo at 2 θ <19 ^about ).

 The results of determining the refractive index of light by the main components of the proposed and known clinkers are compared in table 7. They testify to the difference in their chemical compositions. In addition, as in the well-known clinker [28], inhomogeneity of the distribution of non-stoichiometry over the mass of the alite analog is observed.

The following varieties are found:
Isotropic phase with a refractive index close to normal alite;
Gray-blue phase with slightly higher values of the refractive index.

The blue and blue colors are due to the lack of conduction electrons in the crystal lattice of the clinker phases with a very small amount of SO ₃ in the clinker up to 0.1 wt. (see table 4). The only reason for this color may be superstoichiometric calcium in the interstices of the lattice, and the thicker the blue tint, the more such calcium.

Gray-black phase with high values of refractive index. This shade, in addition to CaO impurities, is caused by an admixture of MgO. A bright yellow-blue phase, in which there is simultaneously an excess of CaO and an admixture of an intermediate substance, in particular Fe ₂ O ₃ .

It is of interest that the rational chemical analysis (see Table 5) revealed only minor impurities of Fe ₂ O ₃ in the alite analogue. Thus, in this case, the Fe ₂ O ₃ impurity is combined with the CaO impurity in the form of a solid solution according to R. Bogg [2] during the decomposition of which during the analysis it precipitates in the form of C ₂ F CF ferrites, which underestimates the content of free CaO in its determination by the ethyl glycerate method (Table 4).

 Another important structural feature of the proposed clinker is the absence of free lime in it, visible in the form under an optical microscope, despite the large quantities determined by microchemical and chemical-analytical, for example, ethyl glycerate methods.

 An admixture of either iron hydroxides or siderite, in the form of yellowish non-continuous films, was found on the surface of the microvolumes of the intermediate substance of some particles. This is a sign of the presence of an impurity of iron oxide and then siderite in free calcium oxide in the proposed clinker. In this case, free calcium oxide is concentrated in the clinker intermediate. The content of iron impurities in calcium oxide is determined by the composition of an aliquot in the ethyl glycerate method for determining the content of free calcium oxide.

 The sample obtained by averaging samples 1-4 of the proposed clinker is ground in an agate mortar until it passes through an N006 sieve (60 μm) and hydrated with distilled water under an optical microscope in preparations with B / T of about 10 according to the known method [34] observing the hydration rate clinker initial components and composition of hydrated phases. In addition, the rate of hydration of the cement dough is studied under a microscope at W / T of about 1. The observation results shown in Table 8 indicate that in the clinker according to the invention, after grinding it with supersaturated lime, the alite analog (“hyperalite”) interacts with water faster, than analogs of calcium aluminate and calcium aluminopherite, i.e. intermediate substance. This creates a completely unexpected picture of hydration: portlandite and calcium hydroaluminates, as well as calcium hydroaluminoferrites, are visible in very small quantities with an generally high degree of clinker hydration, they are immersed in a mass of birefringent, i.e. highly basic calcium hydrosilicates, creating a monolithic structure.

 Thus, the fact of obtaining clinker is confirmed, the composition of which and the features of the hydration process indicate a fundamental difference from the existing level of technology.

PRI me R 2. The conditions of the invention according to example 1. Analysis of free calcium oxide shows that in the samples of clinker according to the invention, the content of Fe ₂ About ₃ is 5-28.5 wt. with a total CaO content in clinker of 3-18%, there is a relationship with a linear correlation coefficient of about 0.78 between an increase in the content of iron oxide in free calcium oxide and a decrease in the value of the alumina modulus of clinker. A significant relationship between the amount of free calcium oxide in clinker and the content of Fe ₂ O _{3 in it has} not been established. Similarly, no relationship was found between the content of Fe ₂ O ₃ in free calcium oxide and the clinker hydration rate in preparations with distilled water. After 1.5 years of storage of the sample with a minimum content of iron oxide (1-5 wt.) In free calcium oxide with the amount of the latter more than 5 wt. clinkers completely crumbled to a grain size of 1-2 mm, although the rate of hydration in micropreparations after 1.5 years of storage practically did not change compared to the initial one. Clinker samples containing more than 15% Fe ₂ O ₃ in free calcium oxide when the amount of the latter is less than 12 wt. clinkers did not crumble, and the rate of hydration under the same conditions also remained virtually unchanged. All this is explained by the inhibition of carbonation by an admixture of Fe ₂ O ₃ in free lime, which is established by direct observations of the amount of calcite in the samples of stale clinker.

 Thus, you can not be afraid of the decomposition of unhydrated clinker residues in hardening cement stone, mortar and concrete after prolonged storage, especially since the remains of the original clinker in these materials are mainly represented by calcium belite and aluminoferrites.

PRI me R 3. To obtain clinker use 3 rotary kilns with a diameter of 5 m and a length of 135 m, heated with natural gas according to example 1. The raw material mixture from the components of example 1 is prepared by the wet method in accordance with example 1. The furnaces operate on artificial draft with smoke exhausters with a vacuum in the furnace head of 0.5-2 mm water column (0.5-2 kg / m ² ), with dust precipitation devices and dust return from the hot end. The oxygen content in the exhaust gases by adjusting the sharp blast of the grate cooler is maintained within 0.5-1.5%. The proposed clinker is fired at the same output (50 t / h) as the well-known Portland cement clinker, at the same gas flow rate of 10800 nm ³ / h, despite the increased values of KH of the raw material mixture, the explanation of which is given in the description of example 1.

The chemical composition of the raw mix is varied to obtain the proposed clinker with different contents of analogues of alite, aluminate, calcium aluminoferrite and belite. According to rational chemical analysis, its phase composition, as well as the results of physical and mechanical tests of pure clinker cement obtained from it with the addition of gypsum stone (96% CaSO ₄ · 2H ₂ O) are presented in Table 8. The data obtained indicate that with an increase in the hyperalite content (3.3–3.7) of CaO · SiO _{2, the} hydraulic activity of clinker both with normal hardening and with steaming increases. Its dependence on the content of free calcium oxide is practically absent. Phases analogs of aluminate and calcium aluminoferrite have a slight effect on the hydraulic activity of the clinker.

The absolute level of hydraulic activity of the proposed clinker in pure clinker cement is not higher than that of NPK, and lower than that indicated in the proposal closest to the invention [28]
The objective of the invention is the creation of clinker, the most effective in the composition of composite and mixed cements containing more than 20 wt. active mineral additives.

Closest to the invention in terms of the composition of the cement obtained from clinker is cement comprising a powdered Portland cement clinker containing tricalcium silicate, dicalcium silicate, calcium aluminate and calcium aluminoferrite and a calcium sulfate ingredient, for example gypsum, having a specific surface area above 3000 cm ² / g and standard strength above 60 N / mm ² in a purely clinker version [36]
The disadvantages of this cement are its high energy intensity, due to the limited input of active mineral additives, with a content of which above 20%, the standard strength does not exceed 45 N / mm ² , and above 40% 30 N / mm ² , as well as its shrinkage during hardening increasing with increasing content of additives.

The cement obtained according to the invention is a cement comprising a powdered Portland cement clinker containing tricalcium silicate, dicalcium silicate, calcium aluminate, and calcium aluminoferrite and a calcium sulfate ingredient characterized in that use is made of a Portland cement clinker containing tri-silicate component of the composition (3.3-3.7) CaO x x SiO ₂ as a phase idiomorphic to alite as calcium aluminate component of the composition 2 (3CaO · Al ₂ O ₃ ) · Fe ₂ O ₃ · (1.5-3 ) SiO _2, alyumoferrita calcium composition as component (4,5-6) CaO · Al ₂ O ₃ · (1-3) x x Fe ₂ O ₃ · SiO ₂ and additionally free calcium oxide with the following ratio of ingredients, wt.

Composition Component (3.3-3.7) x
x CaO · SiO ₂ as a phase,
idiomorphic alite 60-85
Dicalcium silicate 0.05-6
Component composition 2 (3CaO x
x Al ₂ O ₃ ) · (1.5-3) SiO ₂ 0.05-6
The composition component (4.5-6) CaO x
x Al ₂ O ₃ · (1-3) Fe ₂ O ₃ · SiO ₂ 10-25
Calcium Free Oxide
tion CaO 3-18
Calcium Sulphate
ingredient (in terms of
on SO ₃ with respect to
clinker) 0.04-5.6
In an embodiment of the invention, as a calcium sulfate ingredient, the cement comprises two-water gypsum or semi-water gypsum, or anhydrite, or gypsum stone, or phosphogypsum, or borogypsum, or titanogypsum, or mixtures thereof.

 In another embodiment of the invention, the cement further comprises an active mineral additive in an amount of 5-50 wt. in relation to the clinker.

 In a further embodiment of the invention, as an active mineral additive, cement contains a natural sedimentary pozzolana: flask or tripoli, or diatomite.

 In another embodiment of the invention, as an active mineral additive, this cement contains a natural pozzolana of volcanic origin: ash or tuff, or pumice, or slopes.

 In a further embodiment of the invention, as an active mineral additive, the proposed cement contains heat-treated materials: dehydrated kaolin or dehydrated kaolinite clay, or dehydrated clay, or shale, or burnt rock, or clay.

 In another embodiment of the invention, cement as an active mineral additive contains artificial material: blast furnace granulated slag or fly ash, or ash slag of thermal power plants.

 In an embodiment of the invention, the cement further comprises an expanding ingredient in the form of a mixture of calcium oxide and hydroxide in a ratio by weight (5: 1) to (0.2: 1) in an amount of 3% wt. in relation to the clinker.

 In a further embodiment of the invention, the cement further comprises a dry modifier comprising an organic water-reducing component in an amount of 0.5-10 wt. in relation to the clinker ingredient.

 In an embodiment of the invention, as an organic water-reducing component, cement contains the sodium salt of the condensate of naphthalene sulfonic acid with formaldehyde (I) or the sodium salt of the condensation product of sulfonated melamine formaldehyde resin (II), or technical lignosulfonate (III), or a mixture of these components in weight ratios I: III ( 10: 1) - (1: 2); II: III (5: 1) - (1: 2).

 In one embodiment, the proposed cement further comprises an accelerator for hardening the clinker ingredient. In an embodiment of the invention, as a last cement, it contains potassium sulfate or sodium sulfate, or hydrophobized sodium sulfate, or potassium chloride, or sodium chloride, or calcium chloride, or potassium carbonate, or sodium carbonate, or an alkaline by-product from the dry kiln by-pass kiln kiln cement production, in the amount of 0.05-0.3% of the mass of the clinker ingredient in terms of chloride ion for chloride-containing additives or 0.5-1.5% of the mass of the clinker ingredient based on alkali metal oxide for total additives.

 In a further embodiment of the invention, the cement based on the proposed Portland cement clinker further comprises a carbonation inhibitor of cement hydration products. In an embodiment of the invention, as a last cement, it contains triethanolamine or its salts in an amount of 0.07-0.25 wt. in relation to the clinker ingredient.

The proposed cement is obtained by joint or separate grinding of these ingredients to a specific surface above 3000 cm ² / g, preferably above 4000 cm ² / g in any industrial or laboratory grinder, preferably in a tube mill operating in an open or closed cycle with a separator.

The essence of the invention in terms of the composition of the cement consists in accelerated hydration and hardening of the highly basic calcium-silicate component of clinker in this cement of the alite analog supersaturated with lime. After cement is mixed with water, the hydration rate of this phase is ahead of the hydration rate of the aluminate and aluminoferrite phases analogues, as well as belite. Free calcium oxide, being very active, reacts with air moisture during cement grinding, and after mixing with water, quickly moving into the liquid phase, it increases its ionic strength and ultimately the basicity of calcium hydrosilicates CaO SiO ₂ H ₂ O formed during cement hardening, among which highly basic hydrosilicates with a CaO: SiO ₂ ratio higher than 1.5 prevail.

The specificity of the composition of the remaining clinker constituents in the proposed cement causes a change in the ratio of hydrated phases in it during hardening. If during the hardening of the OPC, the content of calcium hydroxide, mainly in the form of crystals of portlandite in the cement stone, gradually increases, starting from 5-10% after 1 day to 15-18% after 28 days, when hardening the pure clinker cement according to the invention, the content of Ca (OH) _{2 is} relatively stable and is in the range of 3-14% both after 1 day and after 28 days of hardening, while crystalline calcium hydroxide-portlandite is 1 / 5-1 / 3 of this amount. Thus, in this case, amorphous calcium hydroxide predominates, while when hardening a well-known cement based on Portland cement clinker, the ratio of portlandite and amorphous Ca (OH) _{2 is the} opposite.

The amount of hydroaluminates, hydroaluminoferrites and their hydrosulfonate and hydrosulfoaluminoferrite derivatives, in the designations AFm and AFt phases during hardening of known cements of the type OPC is 15-25% of the mass of hydration products [3] When hardening the proposed cement, their total amount does not exceed 7-8% by weight although some cement samples according to the invention may contain up to 12% calcium sulfate based on its weight, or 5.6% based on SO ₃ . The reason for this anomaly, in addition to the slower hydration of analogs of aluminate and calcium aluminoferrite, is the increased solubility of SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ ion in calcium hydrosilicates arising from the hardening of cement according to the invention. In well-known cements, during the formation of calcium hydrosilicates in a cement stone, the latter dissolves on average about 0.05-0.1 mol SO ₃ for each mol of CaO [3], whereas when hardening the proposed cement, it follows from the balance, about 2-4 times more, i.e. 0.15-0.2 SO ₃ for each mole of CaO in hydrosilicates. The reason for this is apparently not only the increased basicity of calcium hydrosilicates, which, according to the Le Chatelier principle, increases the possibility of SO acid anions entering their layered crystal lattice $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ , but also in the presence of an increased amount of hydrogranates in the composition of clinker hydration products, even at room temperature, an average of about 3-10% of the total mass of hydrates. Their interlinking with hydrosilicates obviously creates the possibility of an additional increase in the proportion of SO ₃ in the total matrix of calcium silicates in the cement stone, otherwise it is not possible to explain such a small amount of AFm and AFt phases, although the relationship between the content of SO impurities $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ in hydrosilicates and the content of hydrogranates was not previously seen.

It is the impurity of SO ₃ and the entry of hydrogranates in the matrix of calcium hydrosilicates in the cement stone according to the invention that creates the most unexpected effects of its low shrinkage or non-shrinkage during hardening and at the same time sulfate resistance, approximately 5 times higher than sulfate resistance of the best sulfate resistant cements produced in Russia, as follows from a given example.

In addition, unexpected effects associated with the composition of the proposed cement are manifested in its behavior in the form of composite and mixed cements, including active mineral additives. Due to the rapid and in large absolute quantities, the release of calcium hydroxide as a result of the hydrolysis of hyperalite clinker into the liquid phase of the cement paste during hardening, the pozzolanic reaction of calcium hydroxide with silica of an active mineral additive proceeds much faster than in known cements containing active mineral additives. So, the degree of pozzolanic reaction for a mineral additive from natural pozzolan sedimentary origin, such as flask, in ordinary pozzolanic cement containing 30% flask, in micropreparations with B / T about 10 is only 20-30% after 28 days of hydration and hardening cement [34] whereas in a similar cement obtained from the proposed clinker, the degree of pozzolanic reaction was achieved for the first time by the same period, amounting to 90-100%
On the other hand, in such cement, the hydration rate of the alite analogue supersaturated with lime from the proposed clinker is also significantly increased. So, to the degree of hydration of 80% in a hardening test of normal density, this phase reacts in the presence of pozzolana, for example, 40% of the flask is already in 25-28 hours, and up to 100% in 48 hours, which was first achieved for the phase, consisting mainly of silicate calcium.

In addition, for the first time during the hydration of this cement in the product of the pozzolanic reaction, at the boundary of the flask particle with the surrounding mass of the hydrated material, Fe ₂ O _{3 is} detected, which can be judged by the color change and the refractive index of the rim from the product of the said reaction.

It is known that iron ions in the hydrating cement paste do not migrate, in particular, when hydrating calcium aluminoferrites, iron does not leave, unlike aluminum and calcium, the zone in which the initial particle of calcium aluminoferrite was located, even after its complete hydration. In this case, the calcium aluminoferrite analog phase is hydrated even less, therefore, the presence of iron in the product of the pozzolanic reaction can be explained either by its penetration from the hydrating analog of calcium aluminate, or, more likely, from free iron oxide, in which iron is present as an impurity, and perhaps calcium hydroxide in this case is like a carrier of iron hydroxide, after the initial semi-amorphous mass of CaO with this impurity hydrates and begins to diffuse in the liquid phase cementing dough. The presence of iron in this case significantly stabilizes the shells of calcium hydrosilicates on the particles of active mineral additives. In addition, the product volume of the pozzolanic reaction is much higher, therefore, with an increase in the content of these additives in composite and mixed cements prepared on the basis of the proposed clinker, the degree of reduction in strength compared to pure clinker cement is much lower than that of similar cements based on ordinary clinker as with normal hardening and after heat and humidity treatment on a standard mode (GOST 3104-85) pre 2 h + 2 h exposure heating to 85 ^{° C} + 6 hours isothermal heating at this temperature + 2 hours cooling (FIGS. 4 and 5).

 Figure 4 shows the dependence of strength under normal hardening of cements based on the well-known clinker with slag (empty circles) and flask (squares) and based on the proposed clinker with flask (triangles) on the content of additives.

 Figure 5 presents a similar dependence of the strength of cements on the content of mineral additives after heat and moisture treatment, with the notation introduced above. Moreover, the maximum strength achieved in these cements with a reduced content of active mineral additives in the range of 5-20 wt. clinker-based cements are much higher than known ones. Based on this, the proposed cement is advisable to use in the form of mixed and composite cements with active mineral additives, and the least effective ones with respect to OPC, such as natural pozzolans, are much more effective in the composition of the proposed cement than the best of the known mineral additives of blast furnace granulated slags used in combination with the famous clinker. This is evidenced by the data shown in figures 4 and 5, where the advantage of the proposed cement in the form of mixed and composite cements in comparison with the known is obvious.

The presence of large amounts of water-soluble alumina in the composition of the active mineral additive in the proposed cement additionally accelerates the pozzolanic reaction and leads to the formation of ettringite 3СаО · Al ₂ O ₃ · 3CаSO ₄ · 32Н ₂ О along the periphery of the particles of the mineral additive in the cement stone. This can increase the strength of cement with a reduced total content of AFm, t-phases in the cement stone.

 It should be noted that despite the presence of active mineral additives in a number of compositions of the proposed cement, most of which usually lead to an increase in shrinkage deformations, the cement obtained in many versions of compositions with up to 40% mineral additives is expanding or non-shrink. The relevant data are presented below in one example.

When manufacturing grinding proposed cement of the free calcium oxide constituting the clinker is quenched, and the resulting cement comprises a mixture of free calcium oxide and calcium hydroxide, the ratio of which depends on the humidity: 5: 1 at ²⁰ ° C and relative humidity of 50% 2: 1 at 20 ^о С and humidity 85-90% If the free lime content in the proposed clinker is about 3% and in combination with an active mineral additive, it is necessary to achieve the effect of non-shrinkage or expansion, use an additional amount of when grinding the expanding component in the form of a mixture of calcium oxide and hydroxide in the above ratios.

 The proposed cement can also be obtained in the form of cement of low water demand by additionally introducing a dry modifier, including an organic water-reducing component, in particular a sodium salt of a condensate of naphthalene sulfonic acid with formaldehyde, or a sodium salt of a condensation product of sulfonated melamine formaldehyde resin, when co-grinding clinker and calcium sulfate, technical lignosulfonates, or mixtures of these materials with the following weight ratios: sodium salt a condensate of naphthalenesulfonic acid with formaldehyde to technical lignosulfonates (10: 1) - (1: 2), or a sodium salt of a condensation product of a sulphonated melamine-formaldehyde resin to the technical lignosulfonates (5: 1) - (1: 2).

 Due to the formation of poorly soluble complexes of these organic water-reducing components with ferric iron, which is present in almost all phases of the proposed clinker, the modifier can be introduced into the binder of low water demand based on the proposed clinker without fear of having a free modifier in the finished binder, the latter being absent when entering the modifier in much larger quantities up to 10% of clinker mass, in comparison with similar cement of low water demand, were made used on the well-known Portland cement clinker, the composition of which cannot be connected when grinding more than 2.5% by weight of any of the mentioned organic water-reducing components of the modifier.

 The proposed cement reacts to the presence of hardening accelerators in a similar fashion to the initial cement strength, although to a lesser extent than that of the known cement, and strength at 28 days of age is less dependent on the type and content of the accelerator compared to known cement.

 A different picture is observed when a carbonation inhibitor is introduced into the cement composition of hydration products containing amino groups, which are known to adsorb carbon dioxide. In view of the greater saturation with lime of the cement paste based on the proposed clinker, the positive effect of carbonation inhibitors introduced into the cement during grinding significantly increases compared to the known one.

PRI me R 4. The clinker obtained according to example 1, the compositions corresponding to samples 1, 2 and 4 of table 4, are crushed together with the calcium sulfate ingredient with two-water gypsum (98% pure calcium sulfate two-water) in a tube mill with a diameter 2.2 m and a length of 12 m, two-chamber, with a fill factor of grinding balls with an average diameter of 68 mm of the first chamber of the mill 0.28 and tsilpebs of the second chamber of the mill 0.31. Milling is carried out both with pure clinker cement (with two-water gypsum) and cement and with an active mineral additive, in this case, natural pozzolanic sedimentary origin flask, the chemical composition of which is as follows, wt. p.p.p. 17.36; SiO ₂ 52.03; Al ₂ O ₃ 6.25; Fe ₂ O ₃ 3.54; CaO 17.31; MgO 1.67; SO ₃ 0.05; Na ₂ O 0.25; K ₂ O 1.54; the amount of 100.00, the content of water-soluble Al ₂ O ₃ 3,5 wt. The activity of this flask in the pozzolanic reaction on the absorption of lime from a saturated lime-gypsum solution by the known method [36] 320 mg CaO / g flask for 30 days. The fineness of grinding of finished cement, both purely clinker and flask, is maintained at a level of 2-4 wt. the residue on a N 008 sieve (with 80 μm cells), the specific surface is not standardized, since this characteristic is sensitive to the content of active mineral additives and does not give an idea of the actual degree of grinding of cement in general.

 The results of physical and mechanical tests of the proposed cement in the pure-clinker version and with flask are presented in table.9. They indicate that the proposed cement, both without an active mineral additive and containing it, withstands the tests of uniformity of volume change, despite a significant amount of free calcium oxide in the clinker, the hydraulic activity of the cement in the pure-clinker version is not inferior to the well-known Portland cement, while in the presence of active mineral cement additives, it is significantly higher than that of well-known cement, here are all the test periods (Figs. 4 and 5).

In this case, known cement means Portland cement and cements with 20 and 40% flasks produced at the same production, i.e. based on the same raw materials, calcined to produce a well-known clinker in the same furnaces and ground in the same mill. It is impossible to obtain cement under these conditions according to the proposal [28], since for this it is necessary to substantially change the technological scheme, which would require significant costs for production conditions. As for the strength indicators of the known pure clinker cement [28], at a specific surface of 3000 cm ² / g, the data on standard strength of cement about 70 N / mm ² given in [28] seem to be overestimated by about 20 N / mm ² .

The data given in Table 9 allow us to conclude that cements made from clinker sample 1 are characterized by higher strength indicators, and from sample 4 the lowest, regardless of the content of active mineral additives and despite the high content of alite analog in sample 4. From The structural characteristics of these clinkers (Table 7) indicate that the indicated difference in strength, as in the well-known cement [28], is related to the CaO / SiO ₂ ratio in alite to a greater extent than to its amount. Since in sample 1, alite analog varieties with a high CaO / SiO ₂ ratio prevail, and in sample 4 they are in a minimal amount, this in this example has the main effect on the cement strength according to the invention.

The results of a petrographic analysis of the hydration rate of the obtained cement without an active mineral additive and in its presence, performed using an optical microscope in micropreparations with B / T of about 10 according to the procedure [34] are presented in Table 10. They fully confirm the above provisions on the invention in terms of the composition of cement. Especially characteristic is an increase in the volume of calcium hydrosilicates with an increase in the input of gypsum into the composition of the proposed cement. This directly confirms the mass dissolution of SO $\genfrac{}{}{0ex}{}{\text{2-}}{\text{4}}$ in hydrosilicates.

PRI me R 5. To obtain the cement according to the invention use the clinkers shown in table 8, example 3. The grinding of cement according to the invention based on these clinkers is carried out in a ball laboratory drum mill, two-chamber, with a chamber with a diameter of 0.5 m and 0.28 m long, 48 min ^-1 rotational speed, 1.1 kW electric motor power, 438 kg weight (without electric motor and gearbox), with the same loading of both chambers with grinding bodies: in each 6 pcs. balls with a diameter of 60 mm (6 kg), 17 pcs. balls with a diameter of 50 mm (8 kg), 36 pcs. balls with a diameter of 40 mm (8 kg), 91 pcs. balls with a diameter of 30 mm (8 kg) and tsilpebs (cylinders) with dimensions 18x32 mm (25 kg). In one chamber load 10 kg of clinker sample from 400 g of gypsum stone in example 3, and in another 6 kg of clinker sample, 4 kg of flask in example 1 and 400 g of gypsum stone. The grinding is carried out until the cement obtained in 1 chamber reaches a residual value of N 008 (80 μm) of 4% on the sieve. Both chambers are simultaneously freed from the cements crushed in them. The level of fineness of grinding cement with a mineral additive from the second chamber is characterized by the term 3-4% residue on sieve No. 008 for clinker ingredient, meaning the fineness of grinding cement without mineral additives, which it achieves with the same mechanical mode and grinding time as cement with mineral supplement.

 The results of physical and mechanical tests of the obtained cement with flask are given in table 11. They allow us to conclude that the cements from the proposed clinker in compositions with a mineral additive significantly exceed the known cements (Figs. 4 and 5) in terms of strength and are characterized by significantly lower shrinkage in the presence of an active mineral additive, which correlates mainly with the content of free calcium oxide in the initial clinker : with an increase in its content, shrinkage decreases.

 PRI me R 6. The conditions for the implementation of the invention according to example 5. As a calcium sulfate ingredient using two-water gypsum. Its composition is as follows, wt. calcium bicarbonate 95; admixture of quartz 3; feldspars 2. Cements of clinker and two-water gypsum are crushed to a residue on a sieve N 004 4 wt. The results of physical and mechanical tests of the obtained cements with different contents of calcium sulfate ingredient are presented in table 12.

The data presented in table 12 indicate that the limits of the content of calcium sulfate ingredient in the proposed cement compared with the known Portland cement can be significantly expanded: 0.04-5.6 wt.h. per 100 wt. including clinker, and cement of the last composition, including 5.6 · 2.15: 0.95 12.7 wt.h. gypsum per 100 parts by weight clinker, characterized by increased strength after heat treatment. Portland cement, including at the suggestion of [28], is characterized by a narrower interval of the permissible amount of calcium sulfate ingredient 1.5-3.5 parts by weight in terms of SO ₃ .

 The increased content of calcium sulfate ingredient in the proposed cement, which does not reduce its strength under normal conditions, indicates an increase in the ability of hydrated neoplasms arising from its hydration to bind sulfate ion. The low sensitivity of the strength indicators of the proposed cement to the content of calcium sulfate ingredient indicates its tolerance to changes in material composition, which is also manifested in relation to other ingredients, in particular mineral additives, and is a technical advantage of the invention.

 PRI me R 7. The conditions for carrying out the invention according to example 5.

As starting materials use clinker and two-water gypsum (example 6), as well as
semi-aquatic gypsum natural, including wt. CaSO ₄ · 0.5H ₂ O 92; CaSO ₄ · 2H ₂ O 2; quartzite 3; feldspars rest;
natural anhydrite, including, by weight. CaSO ₄ 85; CaSO ₄ · 0.5 H ₂ O 10; quartzite 3; feldspars rest;
gypsum stone, including, by weight. CaSO ₄ · 2H ₂ O 75; CaSO ₄ · 0.5H ₂ O 10; quartzite 5, feldspars 3, mudstones 6, hydromica and illite the rest;
phosphogypsum, including, by weight. p.p.p. (H ₂ O crystallization) 19.45; SiO ₂ 0.48; Al ₂ O ₃ 0.59; Fe ₂ O ₃ 0.18; CaO 31.08; MgO traces; SO ₃ 44.19; P ₂ O ₅ 1.80; F 0.16; impurities of rare earth oxides the rest;
borogypsum, including, by weight. CaSO ₄ xx 0.5H ₂ O 95; CaSO ₄ · 2H ₂ O 3; aluminosilicates 0.6; borates and boric acid the rest;
titanogypsum, including, by weight. CaSO ₄ xx 0.5 H ₂ O 92; FeOHSO ₄ 3.5; FeTiO ₃ 1.2; aluminosilicates 1,1; free sulfuric acid in terms of monohydrate rest.

All calcium sulfate ingredients are introduced into the composition of laboratory grinding cements, including in the form of mixtures based on SO _{3 of} 1.86 wt.h. per 100 parts by weight clinker.

 Grinding of all cements is carried out to a residue on a sieve N 008 4 ± 0.2%. The results of physical and mechanical tests of cement dough and cement-sand mortar according to GOST 310.1-4.81-85 are presented in Table 13. They indicate the possibility of using practically any kind of calcium sulfate ingredient in the cement composition according to the invention.

 Example 8. The conditions for the implementation of the invention according to example 5. The composition of the proposed cement from clinker (example 6) is additionally introduced an active mineral additive flask (example 4), while varying the content of calcium sulfate ingredient of gypsum stone (example 6). The grinding is carried out according to the time corresponding to obtaining the residue of 4 ± 0.2% on a sieve N 008 (80 μm) with the clinker ingredient.

 The results of physical and mechanical tests of the obtained cements are presented in table.14. They indicate that the standard strength of cement with an increase in the content of flask in cement with an optimal content of gypsum stone decreases in the range of 5-40 wt. flask for 100 parts by weight clinker is much slower than in the range of 40-50 wt.h. flasks, despite the decrease in the residue on sieve N 008. It follows that the maximum flask content in the proposed cement is 40%. This significantly exceeds the value of 15% flask in Portland cement made from the well-known clinker.

PRI me R 9. The conditions of the invention according to example 5. The composition of the proposed cement (example 6) and gypsum stone (example 6) is introduced as an active mineral additive natural pozzolan sedimentary origin flask (example 4), as well as tripoli composition wt. pp 8.81; SiO ₂ 73.95; Al ₂ O ₃ 7.66; Fe ₂ O ₃ 3,50; CaO 4.17; MgO 1.74; SO ₃ 0.17; diatomite composition, wt. p.p. p. 2.48; SiO ₂ 92.14; Al ₂ O ₃ 1.01; Fe ₂ O ₃ 1.22; CaO 0.96; MgO 0.21; SO ₃ 0.89; Na ₂ O, 0.89; K ₂ O 0.21; flask analog opoka clay (flask + bentonite).

 The results of physical and mechanical tests of the obtained cements are presented in table 15. From the above data it follows that the proposed mixed cement with natural pozzolans of sedimentary origin has a grade of 400 and according to technical requirements corresponds to class 32.5 according to the European norm pEN 197-92, whereas on the basis of the well-known Portland cement clinker such cement with mineral additives does not even meet the class 22.5, which is discontinued in the countries of the European Economic Community due to low strength. Thus, in terms of pozzolanic cements, the advantage of the invention over the current level of technology is obvious.

PRI me R 10. The conditions of the invention according to example 5. The composition of the proposed cement from clinker (example 6) and gypsum stone (example 6) is introduced as an active mineral additive the following natural pozzolans of volcanic origin:
ash composition, wt. p.p.p. 7.42; SiO ₂ 63.38; Al ₂ O ₃ 4.52; Fe ₂ O ₃ 14.40; CaO 2.43; MgO 1.04; SO ₃ 0.67; Na ₂ O 4.19; K ₂ O 1.95;
tuff composition, wt. p.p.p. 9.31; SiO ₂ 64.22; Al ₂ O ₃ 11.77; Fe ₂ O ₃ 1.95; CaO 6.68; MgO 0.92; SO ₃ 1.51; impurities Na ₂ O + K ₂ O the rest;
pumice composition, wt. p.p.p. 4.62; SiO ₂ 69.43; Al ₂ O ₃ 12.69; Fe ₂ O ₃ 2,52; CaO 6.70; MgO 0.98; SO ₃ 0.63; impurities Na ₂ O + K ₂ O the rest;
tracks of the composition, wt. p.p.p. 11.43; SiO ₂ 70.07; Al ₂ O ₃ 1.12; Fe ₂ O ₃ 10.88; CaO 2.71; MgO 0.35; SO ₃ 0.25; Na ₂ O 2.01; K ₂ O 1.18;
analogues of these components.

The results of physical and mechanical tests of the obtained cements are presented in table.16. They indicate a slightly lower efficiency of the proposed cement with active mineral additives of volcanic origin in comparison with natural pozzolans of sedimentary origin (example 9). However, the well-known Portland cement clinker in combination with the same additives of volcanic origin allows to obtain mixed cements with a standard strength of another 5-8 N / mm ² lower than from the proposed clinker with the same content of these additives 40 wt.h. per 100 parts by weight clinker. The exception of the tracks, which when the content is 40 parts by weight per 100 parts by weight clinker allows you to get cement with a standard strength close to that achieved using highly active natural pozzolan sedimentary origin in example 9. Famous Portland cement clinker (100 parts by weight) in combination with 40 wt. including the track allows you to get the standard strength of the mixed cement with the same content of gypsum stone (option 4 of table 16) is lower by 5.1 N / mm ² with a strength in 1-day age of 2.1 N / mm ² . The advantage of the proposed cement (table 16) is obvious.

PRI me R 11. The conditions for carrying out the invention according to example 5. In the composition of the cement of the proposed clinker with free calcium oxide according to example 6 and gypsum stone according to example 6, artificial and natural heat-treated active mineral additives are introduced as an active mineral additive:
kaolin heat treated at 620 ^{° C} for 30 minutes, the composition by weight. p.p.p. 5.20; SiO ₂ 52.89; Al ₂ O ₃ 38.94; Fe ₂ O ₃ 0.99; CaO 0.96; MgO 0.23; SO ₃ 0.54; impurities Na ₂ O + K ₂ O the rest;
kaolin clay, heat-treated under the same conditions as kaolin, composition, wt. p.p.p. 3.06; SiO ₂ 57.85; Al ₂ O ₃ 31.94; Fe ₂ O ₃ 3.48; CaO 1.88; MgO 1.18; SO ₃ 0.22; impurities Na ₂ O + K ₂ O the rest;
shale, calcined at 970 ^{° C} for 45 min, the composition by weight. p.p. 1.12; SiO ₂ 40.19; Al ₂ O ₃ 0.75; Fe ₂ O ₃ 8.02; CaO 27.23; MgO 1.89; SO ₃ 8.46; TiO ₂ 0.50; impurities K ₂ O + Na ₂ O the rest;
burned rock, taken from a representative sample of a heap above a coal mine, composition, wt. p.p.p. 8.28; SiO ₂ 58.08; Al ₂ O ₃ 20.57; Fe ₂ O ₃ 9.01; CaO 1.02; MgO 0.31; SO ₃ 1,08; impurities Na ₂ O + K ₂ O the rest;
gliezh (clay, naturally burnt) composition, wt. p.p.p. 1.22; SiO ₂ 73.11; Al ₂ O ₃ 14.71; Fe ₂ O ₃ 4.62; CaO 0.85; MgO 0.39; SO ₃ 1,04; impurities Na ₂ O + K ₂ O the rest.

 The results of physical and mechanical tests of the obtained cement are presented in table 17. Based on the data obtained, it can be concluded that heat-treated active mineral additives of natural and artificial origin can be used as part of the proposed cement. The strength properties of cements, especially those made in combination with heat-treated kaolin and kaolin clay, are superior to those for cements with natural pozzolans of volcanic origin.

 In examples 6-11, manufactured cements are tested for uniformity in volume change. All samples made from these cements have passed the test.

 PRI me R 12. The conditions for carrying out the invention according to example 5. In the composition of the proposed cement from clinker (sample 2 of table 11 in example 5) and gypsum stone (example 7) use active mineral additives with different contents of total and water-soluble alumina , the content of which is determined by the method described in [36] flask according to example 4; tripoli according to example 9; heat-treated kaolin according to example 11.

The results of physical and mechanical tests of the obtained cements are given in table 18. They allow us to conclude that with an increase in the content of water-soluble alumina in an active mineral additive, despite the maximum content of free calcium oxide in the clinker (18%), the strength characteristics of mixed cement increase over almost all observation periods. At the same time, the effectiveness of the use of minerals in the series: trepoke flask kaolin heat-treated increases with increasing content of highly soluble alumina in them. The absolute values of the standard strength of cements in this example are very high (48-59.5 N / mm ² ) with a share of mineral additives of 40%. In this case, all these cements passed the tests for uniformity of volume change. Cement from the well-known Portland cement clinker, containing a share of these mineral additives, equal to 40%, is characterized by strength indicators lower by 20-25 N / mm ² at 28 days old and by 5-7 N / mm ² at 1 day olds. Therefore, the composition of the proposed cement is much more efficiently used active alumina pozzolana in comparison with the known cement.

PRI me R 13. The conditions for the implementation of the invention according to example 5. In the composition of the proposed cement from clinker (sample 3 from table 11 in example 5) and gypsum stone (example 7) as the active mineral additives use the following:
blast furnace granulated slag composition, wt. p.p.p. 0.36; SiO ₂ 31.75; Al ₂ O ₃ 10.63; Fe ₂ O ₃ 2.12; MnO 0.30; CaO 50.90; MgO 1.24; S (sulfide ion) 2.09; SO ₃ 0.30;
fly ash of thermal power plant composition, wt. p.p.p. 0.79; SiO ₂ 30.45; Al ₂ O ₃ 28.25; Fe ₂ O ₃ 13.01; CaO 3.23; MgO 1.59; SO ₃ 0.50; Na ₂ O 0.74; K ₂ O 0.15; TiO ₂ 1.29;
ash-slag thermal power plant composition, wt. p.p.p. 1.16; SiO ₂ 49.24; Al ₂ O ₃ 26.69; F ₂ O ₃ 17.53; CaO 2.51; MgO 0.55; SO ₃ 0.77; Na ₂ O traces; K ₂ O 0.43; TiO ₂ 1.13.

The results of physical and mechanical tests of the obtained cements are presented in table.19. indicate a lower effectiveness of these mineral additives in the composition of the proposed cement compared with natural pozzolans of sedimentary origin (example 9) and with heat-treated mineral additives (example 11). Nevertheless, the obtained cements are characterized by a significant advantage in strength indices of 10-15 N / mm ² at normal hardening and 5-7 N / mm ² after steaming in comparison with similar in material composition cements made under the same conditions based on the well-known Portland cement clinker.

PRI me R 14. The conditions for carrying out the invention according to example 5, and in addition to the proposed clinker (sample 1 in table 11 of example 5), gypsum stone (example 6) and the active mineral additive flask (example 4) in the composition of the proposed cement to achieve non-shrinkage, the expanding ingredient is introduced in the form of a mixture of calcium oxide and hydroxide in a ratio by weight (5: 1) to (0.2: 1). Calcium oxide and calcium hydroxide obtained by firing in a furnace at 1000 ^{° C} for 1.5 hours chalk (Example 1) and then quenching the firing product with water in a porcelain dish with stirring.

The test results of the obtained cements presented in Table 20 show that with a larger content of expanding ingredient (5 wt.), The expansion of the proposed cement (32 · 10 ^-5 ) significantly exceeds that observed on cement from the well-known Portland cement clinker (about 5 · 10 ^-5 ). Thus, even mildly acting expanding agents in the composition of the proposed cement can provide a more significant expansion than in known cements, or using the same effect to save about 40% (2/5) of the expanding agent. Moreover, the proposed cement (examples 13 and 14) passed the test for uniformity of volume change.

PRI me R 15. The conditions for carrying out the invention according to example 5, and the grinding of the proposed cement on the basis of clinker (sample 3 of table 11 of example 5) together with gypsum stone (example 3) and flask (example 1) is produced in a three-chamber mill 2 , 6x13 m with the following characteristics of the grinding load: I chamber: weighted average diameter of balls 78 mm, filling factor by grinding bodies 0.24; II chamber: the weighted average diameter of the balls is 42 mm, the filling coefficient of grinding media 0.28; III chamber: tsilpebs (cylinders) with a diameter of 18 mm, a length of 32 mm, a fill factor of 0.29. When the ambient humidity is 75%, the temperature is 20 ± 5 ^о С and the clinker is stored before grinding for 7 days, part of the free calcium oxide (6 wt.) In the clinker was extinguished (2 wt.), Which provides 80% of clinker in the charge an expanding ingredient in an amount of about 5% by weight of mixed cement.

 The results of physical and mechanical tests of the last obtained by grinding in the specified production mill and presented in table.21, allow us to conclude that the resulting cement is expanding. It should be noted that, as in other examples, this cement withstands tests for uniformity in volume changes. The well-known Portland cement clinker, made with free calcium oxide, under any grinding conditions in the composition of mixed cement, does not allow both the above and other ratios of these ingredients to obtain the expansion effect.

 PRI me R 16. The conditions for carrying out the invention according to example 5. In the composition of the proposed cement from clinker (sample 3 from table 11 of example 5) and gypsum stone (example 6) use a dry modifier that includes an organic water-reducing component introduced into the cement with joint grinding of the ingredients in an amount of 0.5-10 wt.h. per 100 parts by weight clinker component, mainly in the amount of 4 parts by weight per 100 parts by weight clinker component. As a modifier use a plasticizer C-3, including, by weight. sodium salt of polycondensate of naphthalenesulfonic acid with formaldehyde 94; heptahydrate sodium sulfate 5; amorphous silica (impurity) 1. In Table 22, this modifier is abbreviated as “substance A”. The grinding time in comparison with example 5 is reduced by 1.8 times.

 The results of physical and mechanical tests of the obtained three samples of pure clinker cement containing 0.5; 4 and 10 wt. including dry C-3 and 2.5 wt. including gypsum stone per 100 parts by weight clinker are presented in options 1-3 tables. 23. From the above data it follows that the composition on the basis of the proposed cement, obtained by introducing a dry modifier, is a binder of low water demand (VNV), characterized in samples 2 and 3 by the lowest value of V / C standard solution (0.23 and 0, 22) of all the previously produced lots of airborne forces. The strength characteristics of these two batches of binder, however, are not outstanding for binders such as VNV. However, the ultimate extensibility of these solutions, i.e. the ultimate relative tensile strain in determining the transverse strains of centrally compressed prisms under a load of up to 0.95 from the destructive one is 3-5 times or more higher than all previously achieved values, including for the VNV (Table 22, notes). Thus, at 10 parts by weight modifier per 100 parts by weight clinker component obtained material corresponding to the ultimate tensile properties and some other properties of polymer cement and polymer concrete.

Example 17. The conditions of the invention according to examples 5 and 16. In the composition of the proposed cement, in addition to gypsum stone (example 6) in one sample of the active mineral additive flask (example 4), contains three groups of dry modifiers, divided by type the following organic water-reducing components included therein:
sodium salt of a condensate of naphthalenesulfonic acid with formaldehyde;
the sodium salt of the condensation product of melamine sulfonic acid with formaldehyde;
technical lignosulfonate.

As representatives of these groups use:
plasticizer C-3, including the sodium salt of a condensate of naphthalene sulfonic acid with formaldehyde, characterized by an average molecular weight of 3200 Daltons, containing the following components, wt. sodium salt 93. sodium sulfate 6; amorphous silica 1 (denoted below as substance A);
the additive "10-43", which is a sodium salt of a condensate of melamine sulfonic acid with formaldehyde, characterized by an average molecular weight of 850 Daltons, containing the following components, wt. sodium salt 99; sodium sulfate 1 (hereinafter referred to as substance B);
technical sodium lignosulfonate containing the following components, wt. active substance 92; reducing substances 3; sodium sulfate 3; the remainder of the cooking base (impurities) 1, with an average molecular weight of the active substance of 22,000 Daltons (denoted below as substance B), as well as a mixture of substances A and B, B and C. The grinding time of cements in comparison with example 5 was reduced by about half.

The test results of 9 samples of the proposed cement of eight pure clinker and one with an active mineral additive flask are presented in options 4-13 of table 22. They allow us to conclude that the proposed cement with dry modifiers meets the requirements of the current technical conditions for VNV. Moreover, the ultimate tensile properties of the proposed cement with dry modifiers exceeds the ultimate tensile properties of the known VNV and, to a greater extent, the known Portland cement. For the offer they are in the range of (600-900) · 10 ^-5 for cements with substance A, (450-600) · 10 ^-5 for cements with substance B and (350-800) · 10 ^-5 for cements with substance B whereas for VNV from well-known clinker and Portland cement, this indicator, respectively, lies in the range of (180-220) · 10 ^-5 and (130-170) · 10 ^-5 , i.e., much lower. This characterizes the increased resistance of cement stone, mortars and concrete based on cement from the proposed clinker to crack propagation, and, therefore, the increased reliability of protection of steel reinforcement in reinforced concrete from the action of environmental agents. These cements also stand the test of volume uniformity.

 PRI me R 18. The conditions for carrying out the invention according to example 5. In the composition of the proposed cement from clinker (sample 3 from table. 11 of example 5), gypsum stone (example 6), dry modifier of substance A (example 17), an accelerator is additionally introduced hardening, which is used as sodium sulfate anhydrous chemical reagent qualification chemically pure Variants of the compositions of the proposed cement are presented in table.23 (options 1-4), which also shows the results of physical and mechanical tests of these cements.

The data obtained, analyzed in conjunction with the results of the experiments given in option 2 of table 22 and in figures 4 and 5, allow us to conclude that
the hardening accelerator both in the presence of a dry modifier in the proposed cement and without it increases the strength of the cement after 1 day of normal hardening by 10% or more, but reduces the standard strength of the proposed cement by 5-10%;
the hardening accelerator, acting under conditions of steaming, practically or slightly increases or does not change the strength of the proposed cement after steaming according to the standard mode;
in the presence of an active mineral additive flask, the hardening accelerator due to a sharp increase in the water demand of cement is relatively ineffective with normal hardening, but significantly increases the strength of the proposed cement after steaming.

PRI me R 19. The conditions for carrying out the invention according to examples 5 and 18. As the hardening accelerator use the following
hydrophobized sodium sulphate (in Table 23 SNOG): a secondary product of the production of higher fatty acids, including, by weight. Na ₂ SO ₄ · H ₂ O 95; higher fatty acids with 12-25 molecules in the carbon chain 5;
technical calcium chloride (in table 23 KCl): a product of the processing of natural salts, including, by weight. KCl 90; NaCl 9; K ₂ SO _{4 the} rest;
technical sodium chloride (in Table 23 NaCl): rock salt, including, by weight. NaCl (halite) 97, feldspars (albite, etc.) 3;
technical calcium chloride (in table 23 CaCl ₂ ), including: CaCl ₂ 98; CaCl ₂ · H ₂ O 2;
sodium sulfate anhydrous hydrophobized (the same as SNOG, in table 23 SNBG), including, by weight. Na ₂ SO ₄ 96; higher fatty acids 3;
calcium carbonate technical potash (in table. 23 K ₂ CO ₃ ), including, wt. K ₂ CO ₃ 98; Na ₂ CO ₃ 2;
sodium carbonate technical soda, including, by weight. Na ₂ CO ₃ 98; NaHCO ₃ 2;
alkaline product for the purification of bypass exhaust gas from clinker kilns of a dry production method (in Table 23, alkaline polypropylene), including, by weight SiO ₂ 15; KCl 22; K ₂ SO ₄ 5; K ₂ CO ₃ 21; CaO 21, impurities rest.

 The test results of the proposed cement, including these hardening accelerators, are presented in table.23 (options 5-14). When comparing with the strength indicators of the composition without additives accelerators (figure 4 and 5), these results indicate that the conclusions of example 18 on the behavior of sodium sulfate in combination with cements based on the proposed clinker are also valid for other additives accelerators hardening, and the dosage of the latter does not play a significant role. In terms of effectiveness, for strength after 1 day of normal hardening, calcium chloride and potash are released, and when steaming, calcium chloride, while carbonates are ineffective. The addition of alkali metal behaves as a hardening accelerator, but is relatively ineffective, however, this opens up the possibility of utilizing alkali metal as a part of cement without the construction of expensive plants for its preliminary separation into components.

 All these cements with hardening accelerators have passed the tests for uniformity of volume change.

 PRI me R 20. The conditions for carrying out the invention according to examples 5 and 17.

The composition of the proposed cement, including clinker, gypsum stone and a dry modifier substance A (example 17), is introduced as a carbonatization inhibitor triethanolamine (TEA) in the form of the sodium salt N (C ₂ H ₄ ONa) ₃ as a representative of amines and their derivatives, sorbing carbon dioxide at the bonds of the nitrogen atom. From a comparison of the results obtained in this case (Table 24, option 1) with the test results of similar cement without a carbonation inhibitor (Table 22, option 2), it follows that the introduction of a carbonization inhibitor increases the strength characteristics of cement at all hardening periods, both during normal hardening and and after steaming. The role of triethanolamine as an inhibitor of carbonation is seen in a decrease in the release of CO ₂ from hydrated neoplasms during differential thermal analysis of samples in parallel with samples that do not contain an inhibitor. In contrast to the Fe ₂ O ₃ impurity in free clinker calcium oxide (Example 1), triethanolamine mainly protects calcium hydroxide from carbonation formed in hardening cement as a result of hydrolysis of the alite analog supersaturated with lime in the proposed cement, which, as can be seen from the data of rational chemical analysis almost does not contain impurities Fe ₂ O ₃ .

 PRI me R 21. The conditions of the invention according to examples 5, 17, 20. As an inhibitor of carbonation, liquid triethanolamine is introduced in the form of a 10% aqueous solution (Table 24, option 2); calcium salt of triethanolamine in the form of a powder with a proportion of active substance of 85-86 wt. impurities the rest (table 24, options 3-5).

 Comparison of these data with those shown in FIG. 4 and 5 indicates an increase in the strength characteristics of cements with the addition of a carbonation inhibitor during all hardening periods both under normal conditions and after steaming, especially with the introduction of triethanolamine in the form of a dry salt. As for cement with granulated blast furnace slag, this conclusion is confirmed by comparing its characteristics with cement data without a carbonation inhibitor (Table 19 of Example 13). A contribution to this effect is made by the well-known improvement in the characteristics of the particle size distribution of cement, associated with the introduction of triethanolamine and its derivatives during its grinding.

 All cements with carbonation inhibitors passed the tests for uniformity of volume change.

 The above examples indicate that, in comparison with the prior art, the cement according to the invention is characterized by significantly better technical properties in the presence of increased amounts (20-40 wt.) Of active mineral additives in its composition. In their presence, the shrinkage deformations of this cement do not increase, and the strength indicators significantly exceed the data for known cements with the same content of active mineral additives. Other well-known additives introduced into the composition of cement, hardening accelerators, expanding additives, modifiers to obtain an astringent low water demand, etc. the proposed cement reacts in approximately the same way as well-known cements, including those without active mineral additives. This indicates the possibility and feasibility of using the proposed cement as a cement for general construction with a significant economic effect in the field of energy conservation. At the same time, clinker for its manufacture is fired in a smaller amount by 20-40%, and in options and with fuel economy in view of the large amount of calcium oxide that can be allowed in it. Cement is ground with significant energy savings, since the clinker itself, with a large amount of free calcium oxide, is easy to grind and effective in combination with easily milled sedimentary pozzolans such as tripoli and flasks.

 Mass production of the proposed cement at the wet production plants in the European part of Russia, which has large reserves of sedimentary pozzolan, is the easiest way out of the energy crisis, in which the wet production method turned out to be in competition with the dry method.

 For dry process plants, the production of this cement will reduce energy consumption to about 25% lower than the best specific energy consumption achieved per ton of cement in the world without loss of construction quality, and in some cases in terms of sulfate resistance of cement and concrete with its increase.

 Thus, the aim of the invention is the creation of cement for the effective use of pozzolan achieved.

 This allows you to see the part of the invention related to the method of manufacturing corrosion-resistant concrete based on the proposed cement.

 Closest to the invention in terms of manufacturing concrete from the proposed cement is a method of manufacturing corrosion-resistant concrete, comprising mixing cement, aggregates and water, laying, molding, compacting the resulting mixture and keeping the products and structures made from it under natural conditions or during heat and moisture treatment until the concrete has hardened and their formwork, characterized by the presence in concrete and the presence in cement of a reduced amount of tricalcium aluminate [40] Reactive cr mnezem in concrete binds alkaline reagents penetrating outside and prevents their impact on its technical properties, whereas nizkoalyuminatny cement prevents influence of sulfate ions medium on the technical properties of the concrete.

 A disadvantage of the known technical solution is the presence of shrinkage deformations of the manufactured concrete, which lead to the penetration of destructive agents of the environment along the contact zones with steel reinforcement, shrinkage joints in products, structures and structures made of reinforced concrete.

 The essence of the invention in terms of manufacturing concrete is that in a method of manufacturing corrosion-resistant concrete, comprising mixing cement, aggregates and water, laying and molding the resulting mixture, compacting concrete and keeping the manufactured products and structures under natural conditions or during heat and moisture treatment until the concrete has hardened and their stripping, carry out the mixing of aggregates, water and cement obtained by co-grinding Portland cement clinker, including, by weight.

Composition Component (3.3-3.7) x
x CaO · SiO ₂ as a phase,
idiomorphic alite 60-85
Dicalcium silicate 0.05-6
Component composition 2 (3CaO x
x Al ₂ O ₃ ) · Fe ₂ O ₃ · (1.5-3) SiO ₂ 0.05-6
Composition Component (4.5-6) x
xСаО · Al ₂ O ₃ · (1-3) · Fe ₂ O ₃ · SiO ₂ 10-25
Calcium Free Oxide
tion CaO 3-18 and calcium sulfate ingredient, mainly gypsum, in the amount of 0.04-5.6 wt. (in terms of SO ₃ in relation to the clinker).

 In an embodiment of the invention, when grinding clinker, an active mineral additive is introduced in an amount of 5-50 wt. in relation to the clinker.

 In another embodiment of the invention, flask or tripoli, or diatomite, or volcanic ash, or volcanic tuff, or pumice, or traces, or dehydrated kaolin, or dehydrated kaolinite clay, or heat-treated slate, or rock, or glizh, or blast furnace granulated slag, or fly ash, or ash and slag of thermal power plants.

 In a further embodiment of the invention, when mixing cement with aggregates and water, an active mineral additive in an amount of 7-40 wt. in relation to the clinker ingredient of cement, moreover, fly ash or silica fume, or pre-ground volcanic ash or volcanic tuff, or pumice, or slag, or blast furnace slag, or ash slag of thermal power plants are used as an active mineral additive.

 In an embodiment of the invention, a cement obtained by co-grinding Portland cement clinker, gypsum stone or the indicated ingredients and an active mineral additive further introduces a dry modifier, including an organic water-reducing component, in an amount of 0.5-10 wt. in relation to the cement clinker ingredient, moreover, the sodium salt of the β-naphthalene sulfonic acid condensate with formaldehyde (I) or the sodium salt of the condensation product of sulfonated melamine formaldehyde resin (II), or technical lignosulfonates (III), or a mixture of materials from these components are used as the organic water-reducing component in ratios by weight of I: III from 10: 1 to 1: 2, II: III from 5: 1 to 1: 2.

 In another embodiment of the invention, when cement is mixed with aggregates and water, a modifier is additionally introduced into concrete, including an organic water-lowering component in dry or liquid forms, for example, in the form of an aqueous solution, wherein the sodium salt of β-naphthalene sulfonic acid condensate with formaldehyde is used as an organic water-reducing component ( I) either the sodium salt of the condensation product of sulfonated melamine formaldehyde resin (II), or technical lignosulfonates (III), or mixtures of materials from these components s in the weight ratio I: III of from 10: 1 to 1: 2, II: III of from 5: 1 to 1: 2.

 In a further embodiment of the invention, cement is obtained by co-grinding the compositions: A Portland cement clinker and gypsum stone; B of composition A and an active mineral supplement; In compositions A and B with a dry modifier, a hardening accelerator is additionally introduced during grinding, moreover, potassium chloride or sodium chloride, or calcium chloride (I), or potassium sulfate, or sodium sulfate, or hydrophobized sodium sulfate (II) are used as the latter. or potassium carbonate or sodium carbonate (III), or technical products and / or wastes, including materials from these components (IV), or an alkaline product for treating bypass flue gas from clinker kilns of the dry cement production method (V) in quantities stvost (wt. in relation to the clinker component of cement): I 0.05-0.3 in terms of chloride ion; II-IV 0.1-0.6 in terms of alkali metal oxide; V 0.3-1.5 in terms of alkali metal oxide.

 In a variant of the invention, when cement is mixed with aggregates and water, a hardening accelerator is additionally introduced into concrete, moreover, potassium chloride or sodium chloride, or calcium chloride (I), or potassium sulfate, or sodium sulfate, or hydrophobized sodium sulfate (II) are used as the latter or potassium carbonate or sodium carbonate (III), or technical products and / or wastes, including materials from the specified components (IV), or an alkaline by-product of purification of bypass flue gas from kiln kilns of the dry process for the production of cement enta (V), introduced in an amount (wt. with respect to the clinker ingredient of cement, taking into account the accelerator contained in the cement): I to 0.3 in terms of chloride ion; II-III to 0.6 in terms of alkali metal oxide; V up to 1.5 in terms of alkali metal oxide.

 In another embodiment of the invention, a cement obtained by co-grinding Portland cement clinker and gypsum stone or the specified ingredients and an active mineral additive further introduces a carbonation inhibitor of cement hydration products, for example, triethanolamine or its salt.

 In a further embodiment of the invention, a mixture of a coarse aggregate of a fraction of more than 5 mm, mainly 5-40 mm, in the form of crushed stone or gravel, and a fine aggregate of a fraction of less than 5 mm, mainly 0.3-5 mm, in the form of sand with a mass fraction are used as aggregates fine in a mixture of aggregates of 0.2-0.8.

 In an embodiment of the invention, fine aggregate of a fraction of less than 5 mm, preferably 0.1-5 mm, in the form of sand is used as aggregates.

 In another embodiment of the invention, the materials used are fine aggregate: building sand or river sand, including up to 7 wt. clay and silt fractions, or sand dune, or sea sand with losses on ignition up to 10 wt. or quartz sand containing more than 90 wt. quartz.

The invention in terms of a method for the manufacture of corrosion-resistant concrete from the proposed cement, consists in the fact that due to the accelerated hydration of the supersaturated lime component of hyperalite (3.3-3.7) xx CaO · SiO ₂ after mixing the concrete mixture with water, it accounts for more water than on alit in the composition of the known concrete mix, since in the latter, after the mixing with water, the high-water hydrates of the aluminate-ferrite-sulfate composition (AFt and AFm phases) are formed. Due to the increased value of the amount of water acting on hyperalite and a much greater rate of hydration compared to stoichiometric (normal) alite, even the most active, as in Appendix [28], hydrolysis of hyperalite proceeds to the end and forms within 30 minutes of hydration, along with amorphous and crystalline Ca (OH) ₂ and calcium hydrosilicates, 3-4% by weight of the initial phase of the silica hydrogel. The composition of this gel can be expressed by Danilov’s formula SiO (OH) ₂ [39] and it can be seen as a border on hyperalite particles in micropreparations with B / T of about 10 and can be detected by the Malinin method [40] in the differential thermal analysis of hydrated cement using exothermic effect at 335 ± 10 ^о С, which is the result of crystallization of this gel. During hydration of stoichiometric alite, this gel is a marginal phase, which sometimes forms, then disappears, and finally completely disappears 1-1.5 days after mixing of the OPC with water. In cements, it is observed very rarely only occasionally during the hydration of high-grade cements from clinker, including rhombohedral alite.

 For concrete obtained by the proposed method, conditions are created under which amorphous and crystalline calcium hydroxides that occur together with silica hydrogel do not return to the rim on the particles of the initial cement, thereby converting silica hydrogel into low-basic calcium hydrosilicates, but are found in solution nuclei of medium-basic hydrosilicates, and, when combined with them, form highly basic calcium hydrosilicates. Practically only such C-S-H (II) hydrosilicates according to the Taylor classification [3] are observed in the hardening concrete according to the invention. Silica hydrogel remains free, and after 3-10 hours of normal hardening it is veiled from the external environment by the hydration products of analogues of the aluminate and aluminoferrite phases, which grow together and form close to its rim significant amounts of hydrogranates at normal ambient temperature, reminiscent of hydrogarnate pseudomorphs in residues slag grains in slag Portland cement, especially steamed in concrete. Thus, the silica hydrogel in concrete according to the invention is not a marginal phase, but is constantly present in it.

This gel guarantees protection against alkalis that escape into the liquid phase both from clinker and from mineral additives such as certain ashes in the presence of fillers that are reactive with respect to alkalis. In principle, the same protection is provided by active mineral additives that are part of the cement or directly introduced into the concrete in a crushed state. However, the advantage of this hydrogel over mineral additives is that the particles of the latter are surrounded by contour pores that separate them from the cement stone and are filled with hydration products only after a long time, while this hydrogel enters the main structural framework of the cement stone and the first portions of alkali reacting with it, and leading to the swelling of the hydrogel, clog the future path and autocatalytically heal the weak points of the frame. In principle, free amorphous calcium hydroxide also acts in exactly the same way, which, after 1-3 months of hardening, binding to this hydrogel, increases the strength of the main frame of the cement stone structure. An indispensable condition for this is the protection of the reacting pair of silica hydrogel amorphous calcium hydroxide from carbonation by air carbon dioxide, including dissolved in the liquid phase. In this case, the reaction product is afvillite C ₃ S ₂ H ₃ stable crystalline calcium hydrosilicate.

 Thus, dissolved carbon dioxide in water can completely change the direction of the hydration process. The concrete obtained according to the invention is most protected from this primarily by the rapid hydrolysis of hyperalite, which releases record amounts of amorphous calcium hydroxide, quickly releasing the liquid phase of the hardening concrete from active carbon dioxide, converting the latter into calcite. This allows the silica hydrogel to remain free until 2-3 years of hardening, and in some cases its amount reaches 10% of the mass of the initial hyperalite. This is facilitated by high-quality concrete compaction, which does not allow the presence of a large number of laying pores and other technological pores.

 The presence of an increased content of sulfate ion in the composition of hydrosilicates is an additional stabilizing factor, which, on the one hand, prevents the alignment of peak lime concentrations in the microvolumes of concrete and fixes them in the composition of calcium hydrosilicates, stabilizing the composition of the latter over time and preventing the migration of excess lime in the liquid phase, which is typical for Portland cement of unfavorable granulometry [9 and 19] on the other hand, the sulfate ion in the framework of hydrosilicates is the basis for the deposition of excess full-time calcium, aluminum or iron (near the initial grains) from the liquid phase, which leads to non-shrinkage or expansion of concrete, without the structural frame vibration characteristic of known expanding cements, first expanding and then reducing geometric dimensions [1] Concrete obtained by the proposed method, prone to shrinkage or slow expansion without such fluctuations, which is its fundamental difference from the known expanding concrete. Therefore, the corrosion resistance, in particular the sulfate resistance of the proposed concrete, is significantly higher than concrete based on standard sulfate-resistant Portland cement, ceteris paribus.

PRI me R 22. On the basis of the proposed cement concrete is made, including, in addition to cement, the following:
fine aggregate sand quartz fraction 1-5 mm, including, wt. quartz 97; feldspars 2; dark-colored minerals Epidote and other impurities 1 (voidness 38 vol.);
coarse aggregate crushed stone granite fractions 5-20 mm, including, wt. granite 95; quartzite 3; muscovite and other impurities 2 (void 42 vol.);
drinking water tap.

 All materials meet the requirements of relevant standards and specifications.

 For the preparation of samples, a horizontal laboratory mixer, forced action, with a capacity of 100 l, a vibration platform with an oscillation frequency of 50 Hz and mechanical fastening of the molds to the table surface, ferrous metal molds with a purity of processing according to the standard for cubic samples with an edge of 10 cm are used.

Testing of the samples is carried out after storage in humid air conditions (100% relative humidity at 20 ± 3 ° ^C). During the first days of storage, to prevent evaporation of moisture from the surface of the sample, the mold is covered with a cloth of coarse canvas moistened with water. Steaming is carried out in a laboratory chamber with automatic control according to the mode, the characteristics of which are given in the note to table 8. For testing the samples, a standard hydraulic press with a self-aligning top plate is used.

 The study of the process of hydration of cement from the proposed clinker in concrete is carried out according to the following method.

Before or after testing the strength of the samples, pieces that do not contain external faces of the sample are taken, coarse aggregate grains are beaten with a geological hammer, the remaining mass is crushed on a laboratory jaw crusher, and sifting through a sieve with 1 mm mesh is taken. These operations are carried out for no more than 1 hour after testing. The resulting nibble is quartered, placed in a desiccator above water to prevent drying, triturated in a mechanical mortar and subjected to differential thermal analysis on a Paulik / Erdey instrument at a heating rate of 8 deg / min (air atmosphere, corundum standard, Pt / PtRh thermocouple); X-ray diffraction analysis using a DRON-2 diffractometer (CuK _α radiation, Al filter, goniometer speed 0.5 deg / min).

 The initial powder is completely sieved before analysis through a No. 006 sieve (60 μm). No methods of preserving samples are used to stop the hydration process, all analyzes are completed no later than 5 hours after testing the samples for strength.

The test results of the physical and mechanical properties of concrete obtained according to the invention are presented in table 25. The following are used as cements in these concrete compositions:
for composition 1 cement with flask (example 4, table 9, option 3);
for composition 2 cement with dehydrated kaolin (example 11, table 17, option 1);
for composition 3 cement with blast furnace granulated slag (example 13, table. 19, option 1);
for composition 4 cement without an active mineral additive (example 4, table 9, option 1);
for composition 5, a mixture with dehydrated kaolin, introduced in parallel with non-admixture cement in a concrete mixer (a complete analogue of the composition of cement in example 11, table 17, option 1);
for composition 6, a mixture with fly ash introduced in parallel with non-additive cement in a concrete mixer (a complete analogue of the composition of cement in Example 13, Table 19, option 2);
for composition 7, a mixture with silica fume introduced in parallel with non-admixture cement (example 4, table 9, option 1) in a concrete mixer in an amount of 7% by weight of cement, silica fume was introduced as a slurry with a content of 40% solids in the mixing water;
for compositions 8 and 9, volcanic ash introduced respectively in the cement composition (example 10, table 16, option 1) and together with additive-free cement in a concrete mixer while maintaining complete analogy with the cement composition in the previous batch;
for compositions 10-13 cement with a modifier that includes an organic water-reducing component, respectively, substances A, B, C and a mixture of A and C (in a ratio of 1: 2 by weight) (example 17, table 22, options 2, 3, 4, 5 and 8);
for compositions 14-17, additive-free cement and mixing water, including substances A, B, C and a mixture of A and B in a ratio of 1: 2 by weight in quantities to the weight of cement, respectively, based on the dry matter, 0.3; 0.36; 0.25 and 0.25 by weight of the modifier introduced into the cement during grinding;
for compositions 18-21 cement with 20% flask and hardening accelerators (example 19, table 23), respectively, calcium chloride (option 10), sodium sulfate (option 2), potassium carbonate (option 12), alkaline by-product of clinker kiln bypass dry cement kilns (option 14);
for compositions 22-25 cement with 20% flask in combination with the same hardening accelerators, respectively, introduced directly into the concrete mixing device either with mixing water, or by preliminary mixing with cement for the bypass gas treatment product, in the same quantities as in the previous ones four batches;
for composition 26, cement is ground with triethanolamine sodium salt carbonation inhibitors (Example 20, Table 24, Option 1).

 The results obtained indicate that the effect of changes in the material composition of cement on concrete obtained according to the invention is relatively small. This property can be called the tolerance of concrete with respect to changes in the type and content of mineral additives in cement, while in well-known cements, including Portland cement, this property is usually absent. Similarly, the method of introducing a mineral additive into concrete made according to the invention has little effect on the quality of the concrete. The effect of hardening accelerators, modifiers in the composition of cement and in the composition of the concrete, as well as a carbonation inhibitor on concrete according to the invention corresponds to that usually observed for concrete on pure clinker Portland cement.

 It follows that the concrete made on the proposed cement, including an active mineral additive such as natural pozzolana of sedimentary origin, even in the latter embodiment, can be used as a general construction material, characterized, especially in the field of compositions with mineral additives, a clear advantage over concrete on mixed cements based on the well-known Portland cement clinker.

+

-гель; после пропаривания и 28 суток твердения: +

-фаза;
II 310-340^оС:

гель;
III 360-420^оС с максимумом при 395^оС: аморфный

;
IV 470-520^оС кристаллический

портландит;
V 571^оС: кварц (из заполнителей);
VI 615-630^оС афвиллит

VII 740-795^оС с максимумом при 760-775^оС:

На фиг. 7 приведена рентгенограмма цементного камня после пропаривания бетона согласно изобретению. Показанные на ней межплоскостные расстояния

умножены на 10^-10 м. Основные фазы установлены по рефлексам со следующими значениями

:

9,8; 3,072; 2,60; 1,844;

-гель гало при 3,34; афвиллит 6,61; 5,736; 2,844; 2,672; 3,19; тоберморит дуплеты 11,6-11,8; 5,693-5,736; 2,96-2,969; 3,079 и т.д. эттрингит и его производные: 9,73; 5,61; 3,89; 2,209; моносульфат МГСАК: 4,46; 2,454; 3,99; 2,87; 1,82; гидроалюмоферриты кальция:

дуплет 8,11-8,23;

дуплет 7,772-7,779;

дуплет 10,5-10,8;

8,845;

портландит 4,908; 3,098; 2,624; CH аморфный гало

в области 2,60-2,67;

ксонотлит 7,067; остатки исходных фаз 7,254; 5,965; 3,02; 2,743; 2,772; 1,91-1,93; Степень гидратации аналога алита по площади аналитического рефлекса при 1,76; отнесенной к площади аналогичного рефлекса на рентгенограмме исходного клинкера (см. на рис.3), равна 82% Степень гидратации алита в известном цементе после пропаривания равна 64% Карбонатизации гидратов не наблюдается: отсутствуют рефлексы гидрокарбоалюмоферритов кальция и кальцита. Основное

тоберморита (11,86) больше обычно наблюдаемых (11,3-11,7) в известных цементах.Figure 6 shows the results of DTA cement stone made of concrete according to the invention, namely, curves of temperature (T ° ^C), temperature differential (DTA), the weight loss (TG) and differential mass loss (DTG). Legend: 1 for the sample after steaming (solid lines); 2 for the sample 30 minutes after mixing the concrete with water; 3 -for sample after 28 days of hardening under natural conditions (20 ± 3 ° ^C and 100% relative humidity); 4 for testing after 1 year of hardening in vivo (dotted line, only TA). Interpretation of effects on DTA curves:
I 60 180 ^about C:

+

-gel; after steaming and 28 days hardening: +

-phase;
II 310-340 ^C:

gel;
III 360-420 ^о С with a maximum at 395 ^о С: amorphous

;
IV 470-520 ^about With crystalline

portlandite;
V 571 ^о С: quartz (from aggregates);
VI 615-630 ^about With affillit

VII 740-795 ^{° C} with a maximum at 760-775 ^{° C:}

In FIG. 7 shows an X-ray of a cement stone after steaming concrete according to the invention. The interplanar distances shown on it

multiplied by 10 ^-10 m. The main phases are established by reflexes with the following values

:

9.8; 3,072; 2.60; 1.844;

halo gel at 3.34; affillitis 6.61; 5,736; 2,844; 2,672; 3.19; tobermorite doublets 11.6-11.8; 5,693-5,736; 2.96-2.969; 3,079 etc. ettringite and its derivatives: 9.73; 5.61; 3.89; 2.209; MGSAK monosulfate: 4.46; 2,454; 3.99; 2.87; 1.82; calcium hydroaluminoferrites:

doublet 8.11-8.23;

doublet 7,772-7,779;

doublet 10.5-10.8;

8,845;

portlandite 4.908; 3,098; 2.624; CH amorphous halo

in the region of 2.60-2.67;

xonotlite 7.067; the remains of the initial phases of 7.254; 5,965; 3.02; 2.743; 2,772; 1.91-1.93; The degree of hydration of the alite analog over the area of the analytical reflex at 1.76; referred to the area of a similar reflex in the X-ray diffraction pattern of the initial clinker (see Fig. 3), it is 82%. The degree of hydration of alite in a known cement after steaming is 64%. No carbonation of hydrates is observed: there are no reflections of calcium and calcium calcite. Main

tobermorite (11.86) is more commonly observed (11.3-11.7) in known cements.

The reason for this allows us to understand the results of differential thermal and radiographic analysis, shown in Fig.6 and 7, which indicate:
after 30 minutes and up to 1 year (test period), silica hydrogel is present in the cement hydration products in concrete, which is fixed by the exothermic effect at 310-340 ^о С, after processing the samples with milk of lime this effect disappears, which confirms its above interpretation;
afvillite is fixed in hydration products by its main analytical reflexes, while it is known [42] that afvillit occurs only in an environment free of active carbon dioxide;
the main interplanar distance in the tobermorite-like hydrosilicate phase is greater than 11.7 · 10 ^-10 m, which confirms the expansion accompanying the entry of the sulfate ion into the interlayer space of calcium hydrosilicates;
the degree of hydration of the (3.3-3.7) phase of CaO x x SiO ₂ in concrete is 50-60% after 1 day of normal hardening and 85-90% after 28 days according to x-ray analysis.

 All this confirms the above essence of the invention in part related to the method of manufacturing corrosion-resistant concrete.

It should be noted the possibility veiling exoeffects SiO (OH) ₂ at 310-340 ^{° C} endothermic effects cubic calcium gidroalyumoferritov C ₃ (A, F) H ₆ produced in the process of the DTA primary products of hydration of calcium aluminate and analogues alyumoferritov comprising the clinker component cement. Then, microscopy remains an important means of confirming the presence of this hydrogel in the form of an isotropic border with a refractive index of about 1.52 (the SH gel also has a halo in the X-ray diffraction patterns with center d ≈ 3.34 · 10 ^-10 m).

 PRI me R 23. The conditions for the implementation of the method of obtaining corrosion-resistant concrete according to example 22. In parallel, use the well-known Portland cement (example 4, table 9, option 11) and the proposed cement (example 4, table 9, option 3).

 The test results of various properties, including deformation and corrosion resistance of concrete, presented in table 26, allow us to conclude the following.

2,2 раза больше.1. For concrete, obtained according to the invention on the basis of cement, containing 40% flask, it was found that its use can significantly save the consumption of clinker cement ingredient in concrete while maintaining high quality concrete in comparison with manufactured on the basis of the well-known Portland cement. So, when the cement consumption in the proposed concrete is 300 kg / m ³ (about 180 kg of clinker / m ³ concrete), the concrete is characterized by a compressive strength class of B 40. The consumption of well-known Portland cement for producing concrete of this class is 400 kg / m in average strength ³ , or 400 180

2.2 times more.

 2. All the main characteristics of concrete according to the invention based on cement, comprising 40% flask (prismatic strength, modulus of elasticity, prismatic strength coefficient, Poisson's ratio, etc.), correspond to the characteristics of concrete on Portland cement, including 0-10% of mineral additives and can be taken as for cement for general construction purposes according to SNiP 2.03.01-84.

3. With a relatively high modulus of the surface of the samples M _about 0.4, the concrete according to the invention showed the ability to expand over time instead of shrinkage. Therefore, in real structures, in which, as a rule, the surface modulus is higher than 0.4, expansion strains partially or fully compensate for concrete shrinkage strains. The absolute expansion strain of the samples is also higher than the creep strain of the concrete according to the invention under continuous loading. It follows that for the first time on the basis of cement containing an active mineral additive in large quantities (40%), it was possible to produce non-shrink and creep-resistant concrete. Moreover, this applies to the composition with a mineral additive pozzolana sedimentary origin, especially susceptible to shrinkage and creep in the composition of cement and concrete.

 4. Concretes according to the invention are characterized by increased resistance in aggressive sulfate environments, despite the increased basicity of calcium hydrosilicates, which form the basis of its structure. According to GOST 22266-76, the cement on the basis of which the concrete according to the invention is made can be classified as sulfate-resistant cements, and it is superior in sulfate resistance to the normal sulfate-resistant pure clinker Portland cement produced from the same raw material, which corresponds to GOST 22266-76 in composition and is one of the best in Russia.

5. Frost resistance of concrete made from the proposed cement, without additional additives that increase the frost resistance of plasticizing, air-entraining, etc. 50 corresponds to the mark F, which allows to use such concrete in civil works in saturation conditions episodic and air-wet with estimated winter temperature to ^-20 ° C according to Table. 9 Building Norms and Rules 2.03.01-84. Thus, for the first time, concrete is characterized by a sufficiently high frost resistance in the presence of 40% pozzolana of sedimentary origin in the cement composition.

PRI me R 24. The conditions of the method for producing corrosion-resistant concrete according to example 22. In parallel, used the following:
fine aggregate:
N 1 sand building fraction of 0.3-5 mm, including, wt. quartz 72; feldspars 15; dark-colored minerals 8; clay minerals 5; voidness 42 vol.

N 2 sand of the river fraction of 0.1-5 mm, including, wt. quartz 87; feldspars 2; dark-colored minerals 4; clay and silty impurities 7;
N 3 sand dune fraction 0.1-5 mm, including, wt. quartz 55; feldspars 12; dark-colored minerals 8; loess fractions 25;
N 4 sand marine fraction 0.3-5 mm, including, by weight. quartz 55; calcite 15; feldspars 8; dark-colored minerals 22; p.p.p. 10;
N 5 sand quartz fine aggregate according to example 22;
coarse aggregate:
N 1 crushed stone granite fractions 5-40 mm, including, wt. granite 97; impurities 3; voidness 44 vol.

 N 2 gravel fraction 5-25 mm, comprising about 85% of the rounded particles by weight, mainly from dense sandstone; voidness 44 vol.

 N 3 crushed stone according to example 22.

 The test results of the physical and mechanical properties of the concrete obtained according to the invention are presented in table 27, which allows us to conclude that using the proposed cement for the first time it was possible to obtain fine-grained concrete without coarse aggregate or with a reduced consumption (at r to 0.8), characterized by shrinkage and creep within the standard values for concrete on coarse aggregate.

 This also applies to river, sand and sea sand contaminated with impurities, the use of which in concrete was previously not allowed by technical standards.

 The explanation of the effect obtained is the absence of shrinkage and creep of the cement stone itself and the binding of calcium hydroxide from hyperalite impurities in various sands.

 The data presented indicate the fundamental differences in the technical properties of concrete according to the invention based on mixed cement with 40% flask from concrete based on Portland cement with 10% flask with obvious advantages on the side of the former.

 Thus, the high corrosion resistance and non-shrinkage of the concrete obtained according to the invention are fully confirmed.

 The foregoing allows us to conclude that the clinker according to the invention is characterized by the presence of a supersaturated lime phase of an alite analog and the presence of silica in the phases of analogs of aluminate and calcium aluminoferrite, which radically changes its properties and the properties of cements and concrete obtained on its basis.

Thus, the proposed cement containing 40% pozzolans of sedimentary origin, which usually enhances the phenomena of shrinkage and creep and sharply reduces frost resistance, is characterized by grade 500, the strength after steaming is higher than that of Portland cement grade 550, is non-shrink, practically has no creep in concrete, and made concrete from it is characterized by frost resistance, ensuring its operation in general construction works under conditions of occasional water saturation and in the air-wet state with an average design winter her temperature to -20 ^about C.

The proposed cement may contain any materials having pozzolanic activity. At the same time, its production is economical, since in addition to saving the clinker component, this cement allows
use sandy cement raw materials due to the increased dissolving ability with respect to silica of the highly basic clinker melt;
reduce the cost of the silicate component of the raw mix by almost 1/3, which is especially important for cement plants that lack clay;
reduce energy costs for grinding cement, if pozzolans (sedimentary origin) are used as a mineral additive, at least the invention equates these rocks with blast furnace granulated slags by their value as a component of mixed cements, which are significantly cheaper than slags;
to achieve 2-5 times higher sulfate resistance and water tightness of concrete compared to standard sulfate-resistant Portland cement, which allows it to be used with high efficiency for collectors, water conduits, transport tunnels, etc.

to reduce the consumption of coarse aggregate (crushed stone, gravel) in the composition of concrete up to obtaining fine-grained (sand) concrete with strength and deformation properties corresponding to ordinary heavy concrete on a mixture of coarse and fine aggregates, the possibility of saving crushed stone or gravel for some geographical regions is even more significant, than cement;
to get cheap polymer cements with high tensile strength at a minimum (2-4%) consumption of an organic modifier, costing an order of magnitude less than a conventional polymer.

References:
1. Kuhl H. Zement Chemie. VTB Berlin 1958. Bd. II, s. 270, 305, etc.

 2. Bogue R. H. The chemistry of Portland cement. New York Reinhold 1955, pp. 180 etc.

 3. Taylor H.F.W. Cement Chemistry. London et al. Acad Press 1990, pp. 217 etc.

 4. German patent N 143604, cl. C 04 V, 1903.

 5. German patent N 394005, cl. C 04 V, 1919.

 6. Ferrari F. Ciments siderurgiques de haute valeur. Revue de Materiaux de Construc-tion et de Travaux Publics. Chaux Ciment Platre. Paris 1956, N 493, p. 251.

 7. Ferrari F. Cementos silico-basicos de endurecimiento rapidissimo. Cemento-Hormigon. Madrid. 1965, v.31, N 380, p.709.

 8. Ferrari F. Per generalizzare limpiego del cemento ferrico tipo Ferrari. II Cemento. Milano, 1966, v. 63, No. 6, p. 233.

 9. Kravchenko I.V. and others. High-strength and especially quick-hardening Portland cement. M. Stroyizdat, 1971, p. 208.

 10. German patent. N 729840, CL From 04 to 7/06, 1942.

 11. Kind V.A. Chemical characteristics of Portland cement. L.-M. Gosstroyizdat, 1932, p.22 and below. See also Duda V. Cement. M. Stroyizdat. 1981, p. 17 and below.

 12. Cirilli Vet al Composizione de la phase ferrico en del clinker portland. Industria ital. cemento. Milano 1953, v.23, N 8, p. 289.

 13. Barbanyagre V.D. and others. Clinker formation when changing the sequence of interaction of reagents. Cement. L. 1990, N 12, s13-15.

 14. Royak S.M. and others. On the determination of the mineralogical composition of clinker by chemical analysis methods. Informational messages of the Research Institute of Cement. M. 1951, N 8, p. 23-41.

 15. Tacashima S. Semento Gijutsu Nenpo (in Japan). 1958. v.12, p. 49.

 16. Boykova A. I. et al. Composition and hydration activity of the aluminate phase of clinker. Cement. L. 1976, N 8, p.20-23.

 17. Japanese application N 51-93673, CL C 01 C 49/008, 1978.

 18. Application of Japan N 1-51533, cl. C 04 B 7/36, 1990.

 19. Kravchenko IV. Et al. Chemistry and technology of special cements. M. Stroyizdat, 1979, p.168.

 20. Jung V.N. and other technology of binders. M. High School. 1952, p. 401.

 21. Shestoperov S. Century. Durability of concrete. 2nd ed. M. Motor Transport, 1960, p. 278.

 22. Moskvin V.M. Corrosion of concrete. M. Promstroiizdat, 1952, p. 175.

 23. Sheikin A.E. and other non-shrinking Portland cement. M. Stroyizdat, 1966, p. 93-98.

 24. Grandma V.I. Physico-chemical processes of corrosion of concrete and reinforced concrete. M. Stroyizdat, 1968, p. 101.

 25. Bogue R.H. Spesial Publication: Portland Cement Assoc. Fellowship at the National Bureau of Standards. Washington. 1949, Technical Paper N 55.

 26. Cembureau guide for Standards of Cements. Bruxelles, pp. 3-198.

 27. Royak S.M. and others. Special cements. M. Stroyizdat. 1983, p. 135.

 28. Copyright certificate of the USSR N 1398731, cl. C 04 B 7/00, 1987 (prototype).

 29. US patent N 3437329, CL. C 04 V, 1969.

 30. Baigalina L.G. Composition and properties of the belite phase of Portland cement clinker. Abstract. Cand. diss. L. 1969, p. 11.

31. Zhmoidin G.I. and others. Slags for metal refining. Dynamics of the properties of the CaO system Al ₂ O ₃ CaF ₂ . M. Metallurgy, 1986, p. 175 and below.

 32. Liebau F. Physical chemistry of silicates. M. Mir, 1990, p. 158.

 33. Pascal P. Notice sur la vie et les travaux de Henry Le Chatelier (1850-1936). Bulletin de la Societe chimique de France. 1937, v. 4, N 10, p. 1557.

 34. Astreeva O. M. Petrography of binders. M. Gosstroyizdat, 1959, p. 125.

 35. St. Gyorgyi A. Introduction to submolecular biology. M. Science. 1984, p. 69.

 36. Butt Yu.M. and others. Workshop on the chemical technology of binders. M. Higher School, 1973, p. 303 (prototype).

 37. Belotelova N. Z. et al. Quantitative determination of free CaO in clinkers and binders. Cement, 1991, N 3-4, S. 50-51.

 38. Panina N.S. et al. Evaluation of the accuracy of determining the phase composition of Portland cement by a rational chemical method. Chemical and physico-chemical methods for the study of materials of cement production. Proceedings of the Research Institute of Cement, vol. 106, M. 1992, p. 34-39.

 39. Danilov V.V. On the hydration mechanism in cement paste. Sixth International Congress on Cement Chemistry. M. Stroyizdat, 1976, vol. II, p. 73-76.

 40. Malinin Yu. S. Study of the composition and properties of the main clinker mineral alite and its role in Portland cement. Abstract. Doct. dis. M. Mosk. chemical technologist Institute of them. D.I. Mendeleev, 1970, p. 22 (prototype).

 41. Mchedlov-Petrosyan O.P. and others. Expanding compositions based on Portland cement. M. Stroyizdat, 1965, p. 85.

 42. Batutina L.S. Intensification of cement hardening by preliminary surface hydration. Abstract. Cand. diss. M. NIIcement, 1984. p. 18.

Claims (25)

1. Portland cement clinker, comprising non-stoichiometric crystals of variable calcium tricalcium silicate, calcium dicalcium silicate, calcium aluminate and calcium aluminoferrite, characterized in that it contains a component of the composition (3.3 3.7) CaO • SiO ₂ in the form phase idiomorphic to alite, as calcium aluminate, a component of composition 2 (3CaO • Al ₂ O ₃ ) Fe ₂ O ₃ • (1.5 3) SiO ₂ , as a component of calcium aluminoferrite, a component of composition (4.5 6) CaO • Al ₂ O ₃ • (1 3) Fe ₂ O ₃ • SiO ₂ and additionally contains free calcium oxide CaO in the following ratio of components, wt. Composition component (3.3 3.7) CaO • SiO ₂ as a phase idiomorphic to alite 60 85
Dicalcium silicate 0.05 6.00
Composition component 2 (3CaO • Al ₂ O ₃ ) • Fe ₂ O ₃ • (1.5 3.0) SiO ₂ 0.05 6.00
Composition component (4.5 6.0) CaO • Al ₂ O ₃ • (1 - 3) Fe ₂ O ₃ • SiO ₂ 10 25
Free calcium oxide CaO 3 18
2. Clinker according to claim 1, characterized in that the free calcium oxide contains Fe ₂ O ₃ more than 1%, preferably 5.0 28.5%
3. Cement, including powdered Portland cement clinker, containing tricalcium silicate, dicalcium silicate, calcium aluminate and calcium aluminoferrite, and a calcium sulfate ingredient, characterized in that Portland cement clinker containing a component of composition 3 as tricalcium silicate is used (3 - 3.7) CaO • SiO ₂ as a phase idiomorphic to alite, as a component of calcium aluminate, component 2 (3CaO • Al ₂ O ₃ • Fe ₂ O ₃ • (1.5 3.0) • SiO ₂ , as calcium aluminoferrite component composition (4.5 6.0) CaO • Al ₂ O ₃ • (1 3) Fe ₂ O ₃ • SiO ₂ and additionally free calcium oxide in the following ratio of ingredients, wt. Composition component (3.3 3.7) CaO • SiO ₂ as a phase idiomorphic to alite 60 85
Dicalcium silicate 0.05 6.00
Composition component 2 (3CaO • Al ₂ O ₃ ) Fe ₂ O ₃ • (1.5 3.0) SiO ₂ 0.05 6.00
Composition component (4.5 6.0) CaO • Al ₂ O ₃ • (1 - 3) Fe ₂ O ₃ SiO ₂ 10 25
Free calcium oxide CaO 3 18
Sulphate-calcium ingredient (in terms of SO ₃ relative to clinker) 0.04 5.6
4. Cement according to claim 3, characterized in that, as a calcium sulfate ingredient, it contains two-water gypsum, or semi-water gypsum, or anhydrite, or gypsum stone, or phosphogypsum, or borogypsum, or titanogypsum, or mixtures thereof.  5. Cement according to claims 3 and 4, characterized in that it additionally contains an active mineral additive in an amount of 5 to 50% by weight of clinker.  6. Cement according to claim 5, characterized in that, as an active mineral supplement, it contains a natural pozzolana of sedimentary origin: flask, or tripoli, or diatomite.  7. Cement according to claim 5, characterized in that as an active mineral additive it contains a natural pozzolana of volcanic origin: ashes, or tuff, or pumice, or slopes.  8. Cement according to claim 5, characterized in that as an active mineral additive it contains heat-treated materials: dehydrated kaolin, or dehydrated kaolinite clay, or dehydrated clay, or shale, or burnt rock, or clay.  9. Cement according to claim 5, characterized in that as an active mineral additive it contains artificial material: blast furnace granulated slag, or fly ash or ash and slag of thermal power plants.  10. Cement under item 5, characterized in that it further comprises an expanding ingredient in the form of a mixture of calcium oxide and hydroxide in a ratio by weight of 5.0 to 0.2 1 in the amount of 3 to 5% by weight of clinker.  11. Cement according to claims 3 to 5, 7 to 10, characterized in that it further comprises a dry modifier comprising an organic water-reducing component in an amount of 0.5 to 10.0% by weight of clinker.  12. Cement according to claim 11, characterized in that as an organic water-lowering component it contains the sodium salt of a condensate of naphthalene sulfonic acid with formaldehyde (I), or the sodium salt of the condensation product of sulfonated melamine formaldehyde resin (II), or technical lignosulfonates (III), or a mixture these components in ratios by weight of I III 10 1 1 2, II III 5 1 1 2.  13. Cement according to claims 3 to 12, characterized in that it further comprises a hardening accelerator.  14. Cement according to item 13, characterized in that as the hardening accelerator it contains potassium sulfate, or sodium sulfate, or hydrophobized sodium sulfate, or potassium chloride, or sodium chloride, or calcium chloride, or potassium carbonate, or sodium carbonate, or alkaline by-product cleaning product of clinker kilns of the dry method for cement production in an amount of 0.05 0.3% by weight of clinker ingredient based on chloride ion for chloride-containing additives or in an amount of 0.5 - 1.5% by weight of clinker ingredient into account to alkali metal oxide for the other additives.  15. Cement according to claims 3 to 5, 7 to 14, characterized in that it further comprises an inhibitor of carbonation of cement hydration products.  16. Cement according to clause 15, characterized in that as an inhibitor of the carbonation of cement hydration products it contains triethanolamine or its salts in an amount of 0.07 0.29% by weight of clinker.  17. A method of manufacturing corrosion-resistant concrete, including mixing cement, aggregates and water, laying and molding the resulting mixture, compacting concrete and keeping the manufactured products and structures under natural conditions or during heat and moisture treatment until the concrete has hardened and stripping, characterized in that the aggregates are mixed , water and cement obtained by co-grinding Portland cement, including, by weight. Composition component (3.3 3.7) CaO • SiO ₂ as an idiomorphic alite phase 60 85
Dicalcium silicate 2CaO • SiO ₂ 0.05 6.00
Composition component 2 (3CaO • Al ₂ O ₃ ) • Fe ₂ O ₃ • (1.5 3.0) SiO ₂ 0.05 6.00
Composition component (4.5 6.0) CaO • Al ₂ O ₃ • (1 - 3) Fe ₂ O ₃ • SiO ₂ 10 25
Free calcium oxide CaO 3 18
and sulphate-calcium ingredient, mainly gypsum, in the amount of 0.04 to 5.6 wt. (in terms of SO ₃ ).  18. The method according to 17, characterized in that when grinding the clinker, an active mineral additive is introduced in an amount of 5 to 50% by weight of clinker.  19. The method according to p. 18, characterized in that as an active mineral additive use flask, or tripoli, or diatomite, or volcanic ash, or volcanic tuff, or pumice, or traces, or dehydrated kaolin, or dehydrated kaolinite clay, or heat-treated slate, or burnt rock, or slag, or blast furnace granulated slag, or fly ash, or ash slag of thermal power plants.  20. The method according to PP. 17 19, characterized in that when mixing cement with aggregates and water, an active mineral additive is added to concrete in an amount of 7 to 40% of the cement clinker ingredient, and fly ash, or silica fume, or pre-ground volcanic ash is used as an active mineral additive or volcanic tuff, or pumice, or slopes, or blast furnace slag, or ash and slag of thermal power plants.  21. The method according to PP. 17 20, characterized in that in the cement obtained by co-grinding Portland cement clinker, gypsum stone or these ingredients and an active mineral additive, in addition to the dry grinding process, a dry modifier is introduced, including an organic water-reducing component in an amount of 0.5 to 10.0% of clinker cement ingredient, moreover, the sodium salt of the β-naphthalene sulfonic acid condensate with formaldehyde (I) is used as the organic water-reducing component, or the sodium salt of the sulfonated condensation product melamine formaldehyde resin (II), or technical lignosulfonates (III), or mixtures of these components in weight ratios I III 10 1 1 2; II III 5 1 1 2.  22. The method according to PP. 17 22, characterized in that when mixing cement with aggregates and water, a modifier is additionally introduced into concrete, including an organic water-lowering component in dry or liquid forms, for example, in the form of an aqueous solution, and the sodium salt of β-naphthalene sulfonic acid condensate c is used as an organic water-lowering component formaldehyde (I), or the sodium salt of the condensation product of sulfonated melamine formaldehyde resin (II), or technical lignosulfonates (III), or mixtures of these components in ratios I III mass of January 10 January 2, II III 1 May 1 February.  23. The method according to PP.17 to 22, characterized in that the cement obtained by co-grinding the compositions: A Portland cement clinker and gypsum stone; B of composition A and an active mineral supplement; In compositions A and B with a dry modifier, a hardening accelerator is additionally introduced during grinding, moreover, potassium chloride, or sodium chloride, or calcium chloride (I), or potassium sulfate, or sodium sulfate, or hydrophobized sodium sulfate (II) are used as the latter ), or potassium carbonate, or sodium carbonate (III), or technical products and / or wastes, including materials from the specified components (IV), or an alkaline product for the purification of bypass flue gas from kiln kilns of the dry cement production method (V) Twe (wt. with respect to the clinker component of cement): I 0.05 - 0.3 in terms of chloride ion; II IV 0.1 0.6 in terms of alkali metal oxide; V 0.3 1.5 in terms of alkali metal oxide.  24. The method according to PP.17 to 23, characterized in that when mixing cement with aggregates and water, a hardening accelerator is additionally introduced into the concrete, moreover, potassium chloride, or sodium chloride, or calcium (I) chloride, or potassium sulfate is used, or sodium sulfate, or hydrophobized sodium sulfate (II), or potassium carbonate, or sodium carbonate (III), or technical products and / or wastes, including materials from these components (IV), or an alkaline by-product from the treatment of clinker kiln by-pass exhaust gas dry way cement (V), introduced in an amount (by weight of cement clinker in relation with the accelerator ingredient contained in the cement.) I to 0.3 in terms of chloride ion; II IV to 0.6 in terms of alkali metal oxide; V up to 1.5 in terms of alkali metal oxide.  25. The method according to PP.17 to 24, characterized in that the cement obtained by co-grinding Portland cement clinker and gypsum stone or the specified ingredients and an active mineral additive, additionally introduce a carbonation inhibitor of cement hydration products, for example triethanolamine or its salt. 26. The method according to PP.17 to 25, characterized in that as the fillers use a mixture of coarse aggregate fractions of more than 5 mm, mainly 5
40 mm, in the form of crushed stone or gravel and fine aggregate fractions of less than 5 mm, mainly 0.3 5.0 mm, in the form of sand with a mass fraction of fine in the aggregate mixture from 0.2 to 0.8.  27. The method according to PP.17 to 26, characterized in that as the aggregates use fine aggregate fractions of less than 5 mm, mainly 0.1 5.0 mm, in the form of sand.  28. The method according to PP.17 to 28, characterized in that as a fine aggregate use materials: building or river sand, including up to 7 wt. clay and silt fractions, or sand dune, or sea sand with losses on ignition up to 10 wt. or quartz sand containing more than 90 wt. quartz.

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