RU2577340C2 - Nanocement and method for production thereof - Google Patents

Abstract

FIELD: construction.

SUBSTANCE: invention relates to a composition and production of nanocement (NC) based on portland cement (PC) clinker and modifier (M) - naphthalenesulphonates (NS). PC includes mineral phases - alite and belite (block microcrystals), aluminates and calcium alumoferrites, and particles are enclosed in nanoshells (capsules) of NS with thickness of 30-100 nm with specific surface area of 400-600 m²/kg. In disclosed NC molecular mass (MM) of NS in capsules is 600-800 Da. On top of capsules is diffused a layer (d-layer) from throttled at grinding NS with MM 300-600 Da, and under capsules - etched layer of mineral phases (TMF-layer) is result of contact interaction with gluing capsules of acid on alkaline alite substrate. Thickness of TMF-layer is 2-50 nm. It includes nanoblocks of alite with size of 1-20 nm. Technical result is increased persistence NC not less than 1 year without loss of strength, reducing factor and protection of cement stone from carbonisation; faster growth strength NC and concrete based thereon and improving its level to 3-4 class against portland cement. NC includes calcium sulphate component and mineral supplements, both active and fillers. Method of producing NC - combined grinding of said components to achieve: a) complete coating capsules d-layer by a criterion of minimum degree of aggregation of particles, which is determined by air permeability; b) complete coating PC-component with TMF-layer based on criterion of double maximum heat release on graph prepared from grinding product cement dough during setting in calorimeter. Both parameters are integral and characterise finished product.

EFFECT: composition and method can be used in cement industry and construction industry.

5 cl, 5 dwg, 4 tbl, 5 ex

Description

The invention relates to the field of building materials and products, namely, to nanocement and a method for its manufacture. It can be used in the construction materials industry, mainly in the cement industry, as well as in the construction industry.

Nanocement is a hydraulic binder based on Portland cement clinker and / or Portland cement and an organic modifier such as powdered superplasticizer, which generates nanostructured elements during mechanical chemoactivation of the mixture, which have a decisive influence on the macroscopic construction and technical properties of the product and its derivatives. The nanocement according to the invention relates to new generation cements compared to Portland cement, which is an internationally recognized fact under its former name - “binder of low water demand”. Its attribution to a new generation, that is, recognition as significantly superior to modern Portland cement, was confirmed by the decision of the International Editorial Board of the 10th International Congress on Cement Chemistry (Gothenburg, Sweden, 1997), which approved the title and text of the report on this subject [Ioudovitch, V.E. , Dmitriev, A.M., Zoubekhine, SA et al. Low-water requirement binders as new-generation cements. / 10-th International Congress on the Chemistry of Cement. Gothenburg. 1997. Proceedings. Vol. 3. P. 3iii 021; see also rus. translation: Yudovich B.E., Dmitriev A.M., Zubehin S.A. and others. Cements of low water demand - binders of a new generation. // Cement and its application, 1997, No. 1, p. 13-16]. These new generation cements (including low-clinker ones) are characterized in concrete, reinforced concrete products and structures by a number of advantages over Portland cement, allowing [Ioudovitch, V.E. et al., 1997, op. cit. and etc.; Yudovich B.E. et al., 1997, cit. Op.]:

1) in the field of technical properties of CNV:

- increase the strength of cement by 2-4 classes and more (2-4 grades and above);

- radically increase the rate of hardening (28-day strength of ordinary Portland cement - for 1 day at the central nervous system);

- increase the water resistance of cement stone by 1-3 steps;

- increase its frost resistance by 1-3 classes;

- increase the shelf life of the CNV with a guarantee from 1-2 months to 1 year (in practice, it was tested up to 12 years without reducing not only the strength class, but even the strength at 1-3 days of age); characteristic data are presented in table. 1 from the work [Yudovich B.E. et al. Cement of low water demand: new results and prospects. // Cement and its application. 2006. July-August (No. 3). S. 80-84];

2) in the field of effective technical solutions in the technology of the production of CNV:

- reduce specific fuel costs by 40-60 kg for the production of 1 ton of cement, or an average of 25 and 35 wt. % due to clinker savings [Bikbau M.Ya. Nanotechnology in cement production. M .: IMET. 2008.768 p.];

- increase (if necessary) the volume of production at any cement plant by 1.5-1.7 times without the construction of clinker roasting redistribution - only due to the development of grinding departments;

- create compact production lines for the modification of Portland cement to low-clinker CNVs by adding mineral additives without reducing strength (grade / grade), including those located at concrete and reinforced concrete enterprises;

- reduce emissions of CO _{2 by} cement plants, as well as heat loss by 30-40% also due to the introduction of mineral additives;

- increase the period of possible storage of cements from 2 months according to international and Russian standards to 1 year or more and ensure the rejection of the annual delivery of cement to the northern and equivalent climatic regions of Russia;

- reduce the cost of production of low-clinker cements due to the intensification of their production and expand the field of their effective application by accelerating their hydration and hardening;

- to effectively use substandard sands, slag, ash and rock waste in mines and mines as mineral additives in the production technology of CNF and concrete based on it;

3) in the field of effective technical solutions in concrete technology:

- on average, to halve the specific consumption of cement upon receipt of high-quality products and structures from precast and monolithic reinforced concrete due to the increased filling capacity of the CNV, based on the increased binding properties of the clinker part with grafted organics;

- reduce the cost of transporting non-metallic materials through a more efficient use of local raw materials in concrete production due to the possibility of using less high-quality small and large aggregates due to powerful binding properties;

- reduce energy costs for the heat treatment of reinforced concrete, and if possible, to exclude its use due to the high rates of hydration of the CVT and the increase in the strength of concrete based on them;

- use for the production of high-quality reinforced concrete products and structures a clinker for milling of CNF or Portland cement as a basis for dominating CNV from any suppliers - cement plants in combination with non-metallic materials of local origin;

techologie cementu. Praha. Nakl.

1961. 1107 s., s. 292-293] содержится обзор 15 работ, подтверждающих это положение.- to reduce the shrinkage and creep of concrete, despite the high specific surface of the CNV, due to the cessation or significant reduction of carbonization; this is due to three factors: increased resistance of calcium hydrosilicates with an admixture of grafted organics in relation to the effects of environmental agents; a decrease in the content of calcium hydroxide in the cement stone (by about 30%), a decrease in the cement content in concrete. It has been known since the 50s that the shrinkage and creep of cement materials by 50% is due precisely to carbonization. In the famous monograph [Barta R. Chemie

techologie cementu. Praha. Nakl.

1961.1107 s., S. 292-293] provides an overview of 15 works confirming this position.

This summary of the positive results of nanocement tests was obtained after stabilization of its quality when the first industrial batches of CNV were produced at the Zdolbunovsky Cement and Slate Plant (ZTsShK) under the leadership of NIIcement with the participation of NIIIZhB, TsNII-26, VNIIZhelezo-concrete (Moscow), NIISMI and NIISK (Kiev) , Yuzhgiprocement (Kharkov) in 1989. These batches were then tested at all the above institutes and at enterprises for the production of concrete and reinforced concrete with scientific support by the employees of these institutes, and the positive character ISTIC these parties were everywhere confirmed. Prior to this, when testing lots of VNV obtained at the NIIITsement Experimental Plant in 1988, the fluctuations in their activity at an early (1-3 days) and at 28 days of age, as well as the storage activity of the samples during storage, were significant. They were eliminated in production batches in 1989 thanks to an understanding of the prerequisites necessary for this (see below). The indicated positive results of testing new-generation cements are supplemented by the results of joint work by the Moscow Institute of Materials Science and Effective Technologies IMET (M.Ya. Bikbau) and NIIMosstroy (V.F. Korovyakov, V.F. Afanasyev, A.A. Boyko, S. V. Moshkovtseva) in 2010-2012. [Afanasyeva V.F. Test results of concrete using nanocement. // Concrete technology. 2012. No. 9-10. S. 16-17. Bikbau M.Ya. New concrete, structures and technologies for the construction of airfield coatings, roads and engineering structures. // Concrete technology. 2012. No. 7-8. S. 32-35. Bikbau M.Ya. Nanocement is the basis for the effective modernization of precast plants. 2012. www.concreteunion.ru/articles/cement.php?ELEMENT_ID=8213].

Evaluation of the economic efficiency of the use of new-generation low-clinker cements (nano-cements) showed (according to the data of IMET and NIIMosstroy, 2012) the possibility of saving from 500 to 1,500 rub / m ^{3 of} reinforced concrete (in 2012 prices), i.e. reduce its cost by 12-38%, depending on the range of products and designs. At the same time, the positive effect grows with increasing grades (classes) of concrete strength from 500 (B40) based on nanocement with mineral additives to 1000 (B90 and B100) according to [GOST 26633-2012 Heavy and fine-grained concrete. Technical conditions Ed. Institute of Standards. M. 2012. 15 pp.]) Based on nanocement without mineral additives.

It should be noted that, without exception, all the indicated properties of cement and concrete are not achieved if we try to produce new-generation cements (CNV, nanoc cement, and their analogues - see below) without using: a) a number of preconditions in domestic cement industry is not always carried out, and b) new methods of quality control compared to Portland cement, necessary for the manufacture of nanocements.

Prerequisites are divided into mechanical and technological. The first include:

A. Application for grinding or milling of CNV ball mills. Not a single experience of obtaining (not even producing!) A CVF, characterized by all of the above properties, using vibration, spring, single, double, and multi-tube, impact, jet, disk and other similar mills with short-term grinding effects is still not known , and the messages that appeared were either related to the preliminary grinding or did not pass the quality control of the obtained material according to the technical conditions qualifying the product as VNV or TsNV [TU 21-26-20-92 Astringent of low water demand . Technical conditions; TU 5744-992-00369171-97 An astringent of low water demand. Technical conditions; TU 5730-005-23454867-2005 Low water demand cement for corrosion-resistant concrete, disaggregated (D-TsNV). Specifications].

This is logical - for the vaccination of known powdery modifiers - naphthalene - and melaminesulfonates [Shishkina L.D., Bukreeva T.V., Yudovich B.E. and others. Spectroscopic studies of the interaction of dry modifiers with minerals of Portland cement clinker during co-grinding and subsequent hydration. / Proceedings of the Research Institute of Cement "Binders of low water demand (chemistry, technology, production and use)." Vol. 104. M.: Publishing. NIIcement. 1992. 294 pp., Pp. 114-133] it takes time for clinker minerals (alite and calcium aluminoferrites). The vaccination process includes the stages of physical and chemical adsorption of modifier particles by clinker, and then the stage of overcoming the activation barrier. Overcoming is initiated by grinding media, namely the energy released by the material being ground when contacted and sufficient, according to [Bowden F.P., Tabor D. The Friction and Lubrication of Solids. Oxford Univ. Press 1964. 442 p.], For the premelting of contacting substances. Prefusion is local in nature and occurs in contact zones of the surface of clinker particles (its minerals) and modifier. As a result of premelting, organomineral membranes (capsules) are formed, predicted by M.Ya. Bikbau in 2008 [Bikbau M.Ya., 2008, cit. Op., p. 605 and below], and then discovered by it under a scanning probe microscope (SPM) on particles of CNV, which he was the first to call nanocement (2011). These shells with a thickness of 30-100 nm surround small fractions of cement, giving them rounded and smooth outer surfaces [M. Bikbau. Discovery of the phenomenon of nanocapsulation of dispersed substances // Bulletin of the Russian Academy of Natural Sciences. 2012. Ser. physics. Number 3. S. 27-35].

The mechanism of nanocapsule formation is as follows (for the first time in this description). The bulk of the specific pressure on the fine fraction is transferred from grinding media to particles of medium cement fraction (5-30 μm), the duration of contact of which with grinding media, according to G. Hertz's contact theorem from the theory of elasticity, is two orders of magnitude longer than the contact time of grinding media to fine particles fractions (less than 5 microns). It follows that the middle fraction acts as a microstamp, squeezing out a small fraction of cement from a bed of material crushed in a mill [Yudovich V.E., Vlasova MT, Kalyanova V.N. Genesis of cement small fraction in ball mills. / XII Conference on silicate industry and silicate science (Siliconf-XII). Budapest. Akademiai Kiado. 1981. Sect. C-III. P. 11-15]. Due to the larger size, the voltage in the contacts for the particles of the middle fraction does not exceed the limit of the intergranular shift, and in the fine fraction it occurs with the destruction of the surface layer of the crystal lattice. This requires a lot of energy, which is manifested in a large endothermic effect [Yudovich B.E., Vovk A.I., Zubehin S.A. and others. On the mechanism and degree of interaction between the modifier and clinker in the process of grinding a binder of low water demand. / Proceedings of NIIcement. 1992, cit. Op. S. 69-113], lowering in the production mill the temperature of the crushed material by 3 ° C or more. At the same time, when plastically deformed, the most densely packed planes and directions in the crystal lattices remain connected, while during ordinary grinding they are the first to break due to increased fragility. Subsequently, with our participation, it was shown (and it is reported for the first time in this description) that this circumstance of preserving the connectedness of the most densely packed planes in the crystal lattices of phases in the particles of nanocement during grinding leads to the release of monomineral particles during its manufacture and, therefore, phase separation is in progress. For this reason, many monophasic particles are found in nanocement, which is practically not observed in Portland cement both during normal grinding and in the presence of surfactants.

The preservation of connectivity is ensured by the presence on the surface of the fine fraction of clinker particles of the film, first physically and then chemically adsorbed modifier. Given a number of defects of the contact surface [Akimov V.G. The influence of the defective structure of solid solutions of tricalcium silicate on their hydration activity and the strength of hardened stone. Abstract. diss. for a job. student step. Cand. tech. sciences. M .: MKHTI, 1980. 16 pp.] And their disclosure during grinding, we can conclude that the modifier film by spasmodic diffusion over homogeneous defects is distributed over the surfaces of this mineral in small (0.1-5 microns) and medium (5 -30 μm) fractions of nanocement. On this film, the deposition of new portions of the modifier continues. This creates a continuous film, which could reach about 60 molecular layers on each cement particle, if a significant part (up to 30% of the mass) of the modifier did not go under the surface of a small fraction of clinker particles by revealing defects, being impregnated with contact pressure initiated by grinding bodies and the middle fraction of nanocement. Impregnation is enhanced by the mutual activation of the modifier (solid acid) and the clinker component (solid alkali) as a result of a temperature surge during particle collisions combined with etching. Clinker particle surfaces are deformed to a considerable depth (Auger spectroscopy shows up to 1 μm [Shishkina LD et al., 1992, cit. Cit.]. It is this deformation of the clinker surface with a glued modifier that is a true prefusion, which determines such a significant value of the endothermic effect that it is found in a production mill [Yudovich B.E., Vovk A.I., Zubehin S.A. et al., 1992, cit. cit.]. As the modifier melts, which follows from the rounded surface of nanocapsules [Bickbau, 2012, cit. cit.], then, as from known [Vilnav J.-J. Glue compounds. M: Technosphere. 2007. 381 pp.], the mutual surface melting of contacting substances and the endothermic effect that accompanies it is the main symptom of the adhesive connection.

The sticking of oligomeric naphthalenesulfonate on the surface of clinker particles during grinding of nanocement (CNV) in the form of continuous nanoshells (nanocapsulation) and the “roots” of the oligomer under the shells in the dislocation cores of alite and in the interlayer spaces of the aluminoferrite calcium-cores should prevent mineral gratings in clinker particles during their plastic compression deformation under nanocapsules caused by the integrated specific pressure of grinding media in bed of crushed material in the working area of the mill. When the contact pressure in the finished cement is removed and the crystal lattices in the clinker minerals expand elastically, then calcium from the interlayer cation fund fills the vacancies, is drawn into the surface of the fine cement fraction, and the external particle is previously defective (with a fixed calcium deficiency compared to the stoichiometric ratio) the surface is no longer deficient in calcium (noted by Auger spectroscopy in [Shishkina et al., 1992, cit. cit.]). Under nanocapsules, the adsorbed modifier, which has acquired fluidity, is partially impregnated by grinding media into clinker particles and quickly drawn into dislocation cores in the crystal lattices of clinker minerals (implosion is a phenomenon first discovered by observing solid lubricants [Wyslocki M. Systemy smarownicze w przemysle cesium. Katowice: Katowice. . 1971. 174 s.], The opposite of explosions - ejection, explosion). These dislocations are formed in the contact zones of particles of a fine cement fraction after the specific pressure of the grinding media exceeds the shear limit in bed of the material crushed in the mill, namely, in the crystal lattices of clinker minerals - alite and calcium aluminoferrites. Belite with a rarer arrangement of traces of dislocations (Fig. 1) is less loaded, its shift does not occur, therefore, the adsorption and gluing of the modifier on the belite do not occur. The inclusions of grains of calcium aluminates in clinker do not contain dislocations at all, being glassy and brittle, which, despite their high basicity, also does not lead to the sticking of naphthalene sulfonate modifier on them. Gluing on alite and calcium aluminoferrites in the crushed material is achieved with a specific bed surface of at least 360-370 m ² / kg. Without this, the density of contacts of medium and fine cement fractions is insufficient to start gluing (grafting) a modifier - oligonaphthaleisulfonate. This is the reason for the required minimum specific surface area of nanocement (CNV), which is considered to be approximately equal to 400 m ² / kg.

B. The use of separators for cutting off and returning large fractions of cement to the mantle. For nanocement (CNV) and its derivatives, this is certainly advisable, since large fractions (more than 30 μm) and part of the middle ones (5-30 μm) are passive for bonding due to shear and crushing strength during collisions with grinding media. Moreover, the more accurate the separation boundary in the separator, the better; the modifier increases the accuracy of separation, as it reduces the aggregation of clinker particles. Separator tube mills are convenient with a two-chamber design, and in the second chamber, the small ball loading has an advantage over the cylindrical one in strict accordance with the Godin – Maloy theorem from the grinding theory: “The probability of grinding with a ball is twice as high as a cylinder of the same diameter, with a length equal to the diameter, and more than twice as compared with a cylinder whose length is greater than the diameter ”[Gaudin AM, Meloy TR Model and a comminution distribution equation for repeated fracture // Transactions of the American Institute of mining, metallurgical and petroleum engineers. 1962. V. 223. P. 43-50] and even more so in comparison with the “cone” tsilpebs - grinding media in the form of a truncated cone — which is unsuitable, but still allowed for use in Russia (the only country in the world).

B. Separate weight dosing of all components of nanocement: clinker, gypsum stone, an organic modifier, including its inorganic ingredients, if present, and mineral additives, excluding additives based on natural minerals of sedimentary origin prohibited in nanocement (the prohibition is due to the physical absorption of the last modifiers before they adhere to alite and calcium aluminoferrites). When using several mineral additives, they can be pre-mixed if they will not be delaminated after joint feeding into the hopper above the weight batcher. A computer is required that automatically maintains the specified weight ratio of the components when changing the flow of at least one of them. So, when slowing down or accelerating the supply of the clinker component, associated with a decrease or increase in its bulk density in accordance with fluctuations in its mass at the outlet of the dispenser, the masses of the remaining components of nanocement (CNV) entering the mill should be automatically adjusted to maintain their mass ratios unchanged.

D. Regulation of the intensity of aspiration and preliminary assignment of live sections of inter-chamber partitions and the outlet grill of the mill. The levels of all these factors should be lowered compared to those adopted when grinding Portland cement.

D. The composition of the grinding charge in all chambers should be supported by the appropriate choice for conventional high dispersion cements. The fill factor of the working chambers of the tube mill with grinding media must not be lower than 0.3.

The main mechanical conditions are listed above. Other, less significant - see the document [Guidelines for technology for binders of low water demand. M .: NIIcement. NIIZHB. 1992.25 p.].

Technological conditions:

A. Mandatory (critical):

- the specific surface of the CNV using oligonaphthalenesulfonates is not lower than 400 m ² / kg according to [Guide, 1992, cit. doc.] by the method of breathability according to [GOST 310.2-76 Cements. Methods for determining the fineness of grinding. Ed. standards. M. 1977. with reprint.]; this, as shown above, is a necessary condition for gluing the modifier on the clinker;

- the lack of a free modifier in the finished product [Ioudovich et al., 1997, op. cit; see also Bickbau, 2008, cit. Op., p. 583 and others]; the reason for this is the dissolution of nanocapsules in the presence of acid (and oligonaphthalene sulfonate is a strong acid with a pH of less than 3) in the mixing water of cement mortar and concrete, and nanocapsules are the main technological difference between nanocement and conventional Portland cement;

- humidity of the charge of the grinding (mixture of starting components in the calculated ratio) - not more than 3 wt. %; the reason is the dissolution of nanocapsules and the release of naphthalenesulfonate in free form before mixing cement with water;

- clinker temperature not more than 140 ° C. This is necessary so that when the temperature in the contact zone increases, it does not exceed the temperature of the onset of thermal decomposition (oxidation) of high-quality oligonaphthalene sulfonate (200-220 ° C); in this case, the term "high quality" means the completeness of the synthesis and the absence in the product of impurities of the feedstock.

Verification of the first two prerequisites can be carried out both during the adjustment of plants for the production of nanocement (CNV), and periodically, during their operation (for example, experience shows that the specific surface of 400 m ² / kg is maintained with a spread of not more than ± 1% at constant the settings of the weight batchers of the components of the mixture of the grinding) [Duda V.G. Cement. Electrical equipment, automation, storage, transportation. Reference manual. Per. from English Edited by B.E. Yudovich and I.A. Prozorova. M .: Stroyizdat, 1987. S. 170-179, 181-183]. The first three prerequisites are provided as standards in the technical specifications [TU on D-CNV, cit. doc.]. The temperature of the crushed material at the entrance to the mill in non-factory grinding plants is maintained without any special measures, and at cement plants it is monitored steadily.

B. Appropriate - contributing to the implementation of the prerequisites specified above:

- the content of tricalcium silicate (C ₃ S) in the clinker is not less than 62 wt. % according to calculation according to V.A. Kindu [Butt Yu.M., Sychev M.M., Timashev B.V. Chemical technology of binders. Textbook for high schools. M .: Higher school, 1980. 472 p.]; the actual content of alite in the clinker according to the petrographic analysis performed according to [Astreeva OM, Lopatnikova L.Ya. Petrography of binders. - M.: Gosstroyizdat. 1959. - 181 p.] - not less than 60%; The Rietveld method according to x-ray phase analysis (XPA, see about it in [Pushcharovsky D.Yu. X-ray of minerals. M.: ZAO “Geoinformation”. 2000.288 s, see pp. 272-279]) is often not suitable for orientation in the production of nanocements, since on clinker from a finely ground raw mix, as shown by production experience, it gives underestimated data on the alite content in the finished product in comparison with the calculation according to V.A. Kindu (cit. Cit.) Not by a permissible 2–3% as a petrographic analysis, but by 10–30%, in contrast to the XRD method according to the methodology of the Research Institute of Cement [Ryazin V.P. X-ray study and determination of the mineralogical composition of Portland cement clinker. Abstract. diss. for a job. student step. Cand. tech. sciences. M .: NIIcement. 1973. 30 pp.], The data of which coincide with those obtained by the petrographic method on any clinkers. The reason for such a radical discrepancy between the Kind calculation and the Rietveld calculation, which significantly reduces its value for the chemistry of special cements, is apparently the immanent defectiveness of clinker mineral crystals in highly active clinkers, which without the use of fluffy sets that are not used according to Rietveld , make alignment of experimental data by Fourier series inapplicable (however, over the past 2 years, the Rietveld method has been substantially improved precisely in the calculation plan, in particular using the Pearson profile function taking into account the texture parameter according to the March-Dollars model). Ryazin, on the other hand, used simple measurements of the areas of reflexes in powder X-ray diffraction patterns, which he systematically corrected according to the actual measurements of the areas of clinker phases on polished sections under an optical microscope;

- the content of free calcium oxide in clinker is not more than 1 wt. % when determined by methods [GOST 5382-91 Cements and materials of cement production. Chemical analysis methods. M .: Publishing. Institute of Standards, 1991. 36 p.];

- the content of gypsum stone (in the material composition of cement) in terms of SO ₃ depending on the clinker content of the sum of alkali metal oxides (R ₂ O) - potassium and sodium in terms of Na ₂ O according to the formula R ₂ O = Na ₂ O + 0.658K ₂ O with a final SO ₃ / R ₂ O dependence of 3 to 6 [RF Patent No. 2406710, 2008], with the excess of the limit of SO ₃ = 4 wt. % for clinkers containing R ₂ O≥1 wt. % provided for in [GOST 10178-85 Portland cement and slag Portland cement. Specifications] with observance as a mandatory limit in nanocement (CNV) of not more than 5.5 wt. % SO ₃ ;

- the content in the cement of the modifier in terms of naphthalenesulfonate in the range ensuring the completeness of its binding by clinker particles with a specific surface of ≥400 m ² / kg, - not less than 1 wt. % under the following additional conditions: a) the absence in the modifier of impurities of the starting materials: naphthalene and others in accordance with the completeness of the synthesis of the target substance, determined by chemical-analytical and spectrophotometric (in the ultraviolet frequency range) methods according to [Vovk A.I. Concrete with naphthalene formaldehyde superplasticizers of various compositions. Abstract. diss. for a job. student step. Cand. tech. sciences. - M.: Publishing. Institute of reinforced concrete and concrete. 1987. 24 pp.], And b) the absence of burnout during spray drying of the modifier solution, determined under an optical microscope from the dark core of dry spheres obtained from droplets of the solution, which should not be: the characteristic color of the high-quality naphthalene sulfonate modifier is brown, it should consist of balls with a shiny surface, corresponding in texture and shade to high-quality instant coffee (published here for the first time).

This is a set of technical requirements, known, with few exceptions, from the prior art, which are required to guarantee the quality of nanocement (CNV). However, in the majority of publications on numerous works carried out since 1991 and up to now without the participation of the CNV authors who took part in the 1997 publications, the free modifier in the finished cement, as a rule, is not checked, although the control methods are microscopic [ Sklyarenko I.E., Yudovich B.E. Determination of the content of free organic component of the modifier in a binder of low water demand. / Proceedings of NIIcement, 1992, cit. Op. from. 245-254] and chemical [Kovaleva I.E., Neznamova S.G., Vdovichenko G.A. et al. Control in the VNV mass fraction of water-lowering organic components of modifiers., ibid., p. 228-244] are not only well known [Yudovich B.E., Dmitriev A.M., Zubehin S.A. et al. cit. cit., 1997], but also provided as mandatory and described in detail in the regulatory document [TU on D-CNV, 2001, cit. doc.]. That is why in the above-mentioned essentially artisanal works not only a whole complex of the indicated technical properties was not achieved, but also in all, without exception, its individual positions. So, the shelf life of these cements was sometimes announced no more than two weeks, although the authors of these binders and cements did indeed preserve them, as was established in the factory, without losing not only the brand strength (class), but also 1-day strength - from 9 up to 12 years (Table 1 from [Yudovich B.E. et al. Cement of low water demand: new results and prospects. // Cement and its application. 2006. No. 3. P. 80-84]). The same is true for the rest of the properties. Unfortunately, for a long time (from 1992 to 2001), the requests of centralized consumers for new generation cements (VNV, TsNV) were small up to the point that at times these cements with the participation of the authors in the process setup were produced only on one grinding plant with a capacity of up to 5 thousand tons / year under the direction of V.V. Fedunov, who worked under the auspices of the Central Research Institute-26 (Center. Construction Institute) of the Ministry of Defense of the Russian Federation; from the latter, N.F. is among the authors of new generation cements. Bashlykov - co-author of documents and publications [Guide, 1992, cit. doc .; TU 21-26-20-92 on VNV, cit. doc .; Ioudovich V.E. et al., 1997, op. cit; Yudovich B.E. et al., 1997, cit. Op .; Yudovich B.E. et al., 2006, cit. Op. and many others etc.], copyright certificates, patents, etc. In other organizations, until recently, the production of these cements was carried out practically without observing technical documentation at privatized grinding plants, previously owned by the Ministry of Defense, or newly built, including using vibration, planetary mills or their modifications, on which it is obviously difficult to obtain a high-quality product using naphthalenesulfonate as a modifier. It came to the point that the brand “binders, or cements of low water demand (VNV or TsNV)” was so discredited that it was sometimes asserted: the set of technical properties described above was not at all achievable [Khokhryakov OV, Khozin VG, Yakupov M.I., Baishev D.I., Sibgatullin I.R., Makhdeev U.X. The experience of assessing the persistence of properties of powdered cements of low water demand // Bulletin of the Kazan State. arch-build. University (KGASU). 2012. No2 (20). P. 214-220], and the corresponding experiments were described in which they were not given, and, probably, many of the technological conditions described above were not maintained. So, from this work, the quality indicators of the starting materials required for the production of nanocement are not known: for clinkers - the coincidence of the calculated and actual phase compositions, the presence of marginal phases; by modifiers - color, presence of formaldehyde residues, etc .; grinding - vibration mills, practically not allowing in the general case to produce nanocements (CNV); finally, the main thing: the question of the availability of a free modifier in the finished product is missed, and the obvious explanation for all the deviations of the product quality from that described in our works is precisely in the presence of a free modifier (see more on this below in the description section regarding the method of manufacturing nanocement (CNV).

As a result, participants in the building materials market in Russia are used to the poor quality of the so-called. "VNV and TsNV". Therefore, with the actual resumption of their production according to normal technological parameters, it was necessary to change the name so that the products were in demand.

The first of the new names was “cement of low water demand disaggregated ...” [TU from 2001, cit. doc.]. But demand remained small. I had to use a fundamentally new term “Portland cement with a dense contact zone” (PC PKZ) [Yudovich B.E., Zubehin S.A. Low water cement and Portland cement with a dense contact area. // International Analytical Review Alitinform (Alitinform). 2010. No3. S. 20-23. Number 4. S. 22-26]. It is based on observations of contact zones in the cement stone of new-generation cements: hydration products with the remains of the initial cement particles, with such particles fully hydrated, as well as the latter with fillers under a scanning electron microscope (SEM). There are no transition zones between the internal and external hydrated products in the cement stone of the PKZ PKZ. (Note that in the terminology accepted in cement chemistry [Taylor X. Cement chemistry. M .: Mir. 1996. 560 p., See p. 245] hydrates are called internal product inside the boundaries of the initial cement particles, and external - outside these boundaries). In contrast, in the cement stone of ordinary Portland cement (subject to observation difficulties), the mentioned boundaries are nevertheless visible at any age of the samples (see Taylor, 1996, op. Cit., Pp. 257-259). Demand for this cement, after taking a new name, increased, and not for the high-grade PCZ PKZ mineral grade additives (classes 82.5-92.5) obtained by milling Portland cement of class 42.5 with a modifier of proven quality naphthalenesulfonate type, with a choice for milling Portland cement is from reliable manufacturers, and at the PKZ PC of class 42.5 with 40-50% fly ash, the cost of which is about 15% lower compared to ordinary Portland cement of class 42.5 due to the difference in prices of clinker and fly ash. All the above requirements, both mechanical and technological, are maintained. The production of the PKZ PC is currently ongoing.

The next version of the new name of cement-analogues of CNV and PCZ PKZ - nanocement - was proposed by M.Ya. Bickbau [2012, cit. cit.] after the discovery of nanoshells on the particles of these cements. The name “nanocement” was assigned to the material under consideration based on the results of observations made at the Metrological Center of OJSC RUSNANO using high-resolution scanning electron microscopy, which allowed high-resolution scanning electron microscopy, which made it possible to visualize modifier nanoshells on clinker particles in nanocement [Certificate of Conformity for “nanocement general construction ”issued by IMET CJSC on December 10, 2012 by the certification body for products of ANO NANOSERTIFICA]. Currently, preparations are underway for the release of the pre-standard (PNST) of the Russian Federation [Project 112 PNST “Nanocement all-construction” 2013. 30 p.], Which is planned to be submitted for approval as a standard of the Russian Federation in 2014. Thus, all previous names of new generation cements received by nanocapsulation of particles (including the concepts of grafting and gluing modifier nanoshells onto clinker particles when mechanochemical activation is combined with a modifier during co-grinding of clinker with modifier) - VNV, TsNV, PTs PKZ, etc. - can be combined by one name - nanocement. Currently, the definition of nanocement compiled by M.Ya. Bickbau with the participation of the inventors, presented in [Project 112, 2013, cit. cit.], the following: “Nanocement is cement obtained on the basis of Portland cement clinker, gypsum or its derivatives, mineral additives and an organic modifier based on naphthalene sulfonates, by co-grinding these components until the modifier forms nanoshells on particles of Portland cement clinker in an altered state” . By an altered state is meant a change in the modifier during the grinding process. In the work [Shishkina L.D. et al., 1992, cit. Op., p. 131] it was shown that naphthalenesulfonate when grinding nanocement is enriched with calcium from the surface layer of alite.

Since this definition is certified, then in the description and claims, the name "nanocement" is used as officially recognized. But some colleagues still consider it not quite right to extend it to the WWI and CNV, understanding nanocement more narrowly, as a material containing nanoparticles. In contrast, RUSNANO OJSC made a decision (2008 [Site of the Russian National Nanotechnology Network http://www.rusnanonet.ru/tesaurus/ru/?PAGEN]) that for this name it is sufficient to have nanostructured dimensions in the cement ( from 0.1 to 100 nm, in this case, nanoshells). This approach is adopted below in the present description.

In addition, it is necessary to make an important remark related to the change in the quality of modern clinkers compared to those used for nanocement (VNV, TsNV) in the 80s and 90s of the XX century. In Russia, a significant part of modern clinkers in clinker kilns is not burned up due to excessive fuel economy, which was the first to be felt by the heads of laboratories of precast factories for dark glassy areas on the surface of products and structures that could not be attributed to defective mold greases and which do not hold well plaster layer in the preparation of facade products. It turned out that this is the result of clinker underburning - the presence of an impurity in it, which is first C ₁₂ A ₇ (mayenite, instead of part C ₃ A) and calcium ferrite (instead of part of the aluminoferrite phase, including Fe (II)), and then a mixture of these prehydrates phases formed during storage of cement from unburnt clinker in silos and during transportation in wagons as a result of their hydration with air moisture. Currently, this impurity, not previously observed and not described in textbooks, is the basis for the abnormal aggregation of particles of ordinary Portland cement during storage and transportation, traffic jams in silos and pipelines (it also includes free lime, sulfates and carbonates of alkali metals present as known impurities in any clinker and cement, but in case of underburning in a larger amount), as well as, often, semi-aquatic gypsum (Bassanite CaSO ₄ · 0,5Н ₂ О), formed from gypsum stone introduced into the cement when co-grinding with hot clinker (above 140 ° C). The above-mentioned mixture of prehydrates, together with clinker phases caused by underburning, after mixing ordinary Portland cement with water forms a mixed crystalloid product, the basis of which is the alumina hydrogel AlO (OH) - the product of hydration of the so-called first marginal phase - C ₁₂ A ₇ [En-tine ZB, et al. The liquid phase alite generation model in sintering portland cement clinker. 10th International Congress on the Chemistry of Cement. Gothenburg, Sweden, June 2-6, 1997. Proceedings, ed. by H. Justnes, Publ. Amarkai, Gothenburg 1997, v. 1, 1i046. 4 pp .; see also rus. perev. Entin Z.B. et al., Liquid-phase model of alite formation in sintered Portland cement clinker. // Cement and its application. 2007. No2. S. 40-42]. The dark product on concrete includes, in addition to the above-mentioned mixture, also C ₄ AH _14-19 calcium-aluminates, which are carbonized by steaming, and calcium hydroferrites, are black, and on the whole, the underburning product includes light carbonate “streaks” against the background of dark hydration products of non-stoichiometric C ₂ F (second marginal phase), including Fe monoxide (the estimated composition of this phase is 2СаО · 0.9Fe ₂ O ₃ · 0.1FeO · 8H ₂ O) combined with amorphous Ca (OH) ₂ and its carbonates - vaterite and calcite. The glass transition of this impurity mass at a steaming temperature is associated with a particularly high dispersion of the complex aluminum hydroxide AlO (OH) entering it, which is formed when the concrete mixture is mixed and partially remains as a sol in its liquid phase for up to 8 hours. This hydrosol during the sol-gel transition after mixing ordinary Portland cement with water absorbs any plasticizers and sharply reduces the effectiveness of their action. In the production of nanocement, it was experimentally established that this harmful mixture of prehydrates is able to block the formation of adsorption layers of naphthalene or melamine sulfonate around cement particles during grinding and actually does not allow the release of nanocement. If there is no other way out (replacing the supplier of clinker, or cement going to the domol with a modifier), then it is necessary to use a special additional chemical additive “from unburning” for the nanocement of cement from unbaked clinkers for nanocement with a mineral additive, composition which and application features are described in [RF Patent No. 2441853, 2010]. It decomposes the aforementioned harmful mixture of prehydrates and their products, without at the same time preventing the adsorption of naphthalene or melaminesulfonate to clinker during the milling process. This additive specifically such a cement subspecies as PCZ PKZ may differ in material composition from previous VNV and TsNV, the production of which, given the above technical effects, is currently extremely difficult for the classic version of clinker + gypsum stone + modifier based on unburnt clinkers or impossible. Note that the characteristics of incomplete clinkers, which in the form of cements can pass the standard test for uniformity of volume change according to [GOST 310.3-76 Cements. Methods for determining the normal density, setting time and uniformity of volume change], but, nevertheless, contain the mentioned marginal phases, whose prehydration and hydration products cause difficulties in the production of cements, are described in the report [B. Yudovich, S. A. Zubekhin. , Fedunov V.V. Environmental and technical and economic discipline in the production of cement and its use in concrete. / Concrete and reinforced concrete - development paths. Scientific works of the 2nd All-Russian (International) conference on concrete and reinforced concrete. September 5-9, 2005 Moscow, in 5 volumes. Volume 5. Reinforced concrete in transport construction. Environmental aspects of the use of concrete and reinforced concrete. Armature and welding. Part: Environmental aspects of the use of concrete and reinforced concrete. M .: Deepak, 2005, p. 337-346] and must be taken into account when organizing and controlling the production of both Portland cement, and especially nanocement. The above restrictions regarding unburnt clinkers, therefore, are added to the above technological conditions (parameters) for the production of nanocement. Since unfinished clinker and cements based on them are becoming more widespread, modern nanocements, independent of the indicated manufacturing difficulties, are becoming increasingly important, for which almost any initial components are suitable. The entire review given above is necessary in order to understand how these difficulties should be overcome so that the quality of nanocement can provide the whole complex of the above-mentioned construction and technical properties without exception due to the deterioration of the properties of the feedstock.

Nanocement is known from the prior art, containing (in wt.%): Portland cement clinker, a calcium sulfate component (in terms of SO ₃ ) and a powdery modifier that includes an organic water-reducing agent and a hardening accelerator (86.1-95.9) :( 2.5-4) :( 0.6-2.5) :( 1-7), respectively, obtained by joint grinding, or, which is the same, by co-grinding the components to a specific surface of 400-700 m ² / kg. In this case, both co-grinding and the indicated values of the specific surface are designed to guarantee the completeness of the binding in the finished product of the mentioned organic water-lowering agent with the clinker ingredient into an adhesive (chemisorption) compound [RF Patent No. 2029749, 1995]. Indeed, with a normal specific surface of 400 m ² / kg and reduced (in particular, at 370-395 m ² / kg), as shown by control experiments at a number of cement plants and a grinding plant in the city of Sergiev-Posad at the Sergiev-Posad plant of concrete goods and K, the probability of the appearance of a free modifier in samples in a product of normal dispersion is approximately 10%, but increases to 20-25% with the indicated decrease in dispersion. The growth of the specific surface to 600-700 m ² / kg reduces the probability of the appearance of a free modifier to 2-3%, but does not completely exclude it. The advantages of this technical solution are the set of positive effects of nanocement (CNV) mentioned above. The disadvantage is that the completeness of binding of the water-lowering component to the clinker ingredient is not controlled, and in the presence of a free organic component in the finished product, the technical properties of the latter sharply deteriorate [Ioudovich et al., 1997, op. cit .; Yudovich B.E. et al., 1997, cit. Op.].

Nanocement containing components (wt.%) Is also known from the prior art: Portland cement clinker, calcium sulfate component (in terms of SO ₃ ) and a powdery modifier, including an organic water-reducing agent and a hardening accelerator (84.1-95.9): (2.5-4) :( 0.6-2.5) :( 1-9) when components are co-milled to a specific surface of 400-700 m ² / kg, moreover, Portland cement clinker includes alkali metal compounds contained in the finished product in the composition of the aforementioned hardening accelerator in the form of a mixture (melt) of sulfates and carbonates of alkali metals with a degree of aggregation of particles of 5-15 vol. % [RF Patent No. 2207995, 2002]. The completeness of binding in the finished product of the mentioned organic water-lowering agent with a clinker component into an adhesive (chemisorption) compound, according to the authors, is characterized by the indicated minimum degree of particle aggregation. Indeed, control of the degree of aggregation according to [Vatutina L.S. et al. Auth. testimonial. USSR No. 1250917, G01N 15/08, 1985] indicates that with a specific surface area of 400 m ² / kg or more, the degree of aggregation of ordinary Portland cement particles is much higher and ranges from 35 to 70 vol. % [Vatutina L.S. et al. Determination of the degree of aggregation of cement particles by the method of breathability. / Proceedings of the Research Institute of Cement: "The use of physical instruments and methods in the study of clinkers and cements." 1987. No. 91. S. 221-238]. Note that this technical solution provides for the additional introduction of mineral additives into the material composition of nanocement, including hydraulically active from the groups: I - active silica: crushed or granular or ground silicate block; silica fume in powder or granular forms; II - granulated blast furnace slag, fuel slag, fly ash, volcanic ash, pumice, tuff, quartz sand, feldspar sand, granite screenings, ore dressing tailings, cullet, brick fight, expanded clay or glass ceramite dust. In the presence of mineral additives of group I, the degree of aggregation of particles of nanocement increases by about 1 / 5-1 / 3 of the above value, and of group II by about 1 / 8-1 / 5, since the water-lowering agent does not adsorb on the surface and does not plasticize cement -water systems. The advantage of this technical solution is to increase the reliability of achieving the complex of positive effects of nanocement (CNV) mentioned above. However, the degree of aggregation is an indirect indicator of the completeness of binding of an organic water-lowering agent, which even for nanocement without mineral additives, being explicitly associated with humidity and ambient temperature, is relatively reliable only at a temperature and relative humidity of the medium in the range of 5-30 ° C and 20, respectively -40%. Therefore, the disadvantage of this technical solution lies in the lack of a guarantee of the complete chemisorption of the entire mass of the modifier by the clinker component of the specified cement and, therefore, cannot guarantee the full range of construction and technical properties described above.

Closest to the invention (prototype), the purpose of which is to guarantee the complete chemisorption of the entire mass of the modifier by the clinker component, is nanocement based on Portland cement clinker, or Portland cement and an organic modifier, which includes the mineral phases alite, whitewash, aluminates and calcium aluminoferrites as a clinker component, the quality of the specified modifier is naphthalenesulfonates in the form of continuous organomineral nanoshells with a thickness of 30-100 nm on particles of the clinker component, with a specific surface of 40 0-600 m ² / kg [Bikbau M.Ya. Nanocement. The discovery of the phenomenon of nanocapsulation. // StroyPROFI (All-Russian information and analytical magazine for specialists in the construction industry). 2012. No7. Date of receipt: 10/05/2012. Online: www.stroyprofi.info/]. In nano-shells, this modifier is in an altered state with inclusions from clinker particles. The altered state, as mentioned, is characterized by the absorption of calcium from the outer layer of particles of the clinker component, and specifically, from alite [Shishkina L.D. et al., 1992, cit. Op.].

Indirect signs (calculation with a conventional landing area of naphthalenesulfonate in nm ² on the alite surface) indicated the polymolecular nature of the nanoshells with an average thickness of 1010 monomolecular layers, which, taking into account the absorption of organic matter by alite to a depth of 1-1.5 μm (Auger layer, detected at Auger spectroscopy [Shishkina et al., ibid.], below abbreviated O-layer) in an amount up to 30 wt. %, left the modifier material sufficient for the formation of an average calculated thickness of the nanoshells of about 50 nm. In other words, the presence of nanoshells on particles was supposed earlier. At the same time, the safety of the construction and technical properties of nanocement (CNV) for a long time is up to 9-12 years [Yudovich B.E. et al., 2006, cit. op.] testified to the continuity of the nanoshells. However, based on the work [Akimov V.G., 1980, cit. op.] it could be assumed that these shells have a mesh structure. Their elements could coincide with the most active from the set of active surface centers discovered by V.G. Akimov, and to ensure the preservation of the properties of cement over time, such a mesh coating at the most active centers would be sufficient. That is why in order to understand the mechanism of cement preservation, the dynamics of its hydration and strength growth, it was necessary to visualize the shells as continuous capsules without preliminary drying or coating the cement surface, for example, as is done to view the surface of cement particles under a transmission electron microscope.

The undoubted merit of M.Ya. Bickbau is the discovery of the presence of exactly continuous shells in nanoc cement around particles of a clinker component using scanning probe microscopy, which has never been used in cement chemistry, and their visualization using high-resolution scanning electron microscopy. The process of formation of shells is called capsulation (or rather, encapsulation) of particles in nanocement. The fact of encapsulation was established by M.Ya. Bikbau using the domestic scanning probe microscope (SPM) "Ntegra Prima" (St. Petersburg). Then they were able to visualize using a scanning electron microscope of high resolution f. GEOL. The results are shown in FIG. 2, a and b (with the kind permission of the author).

In FIG. 2a, the monomineral alite particle that arose during co-grinding of the components of nanocement is visible. Such particles in encapsulated cement are not uncommon. Separation of clinker minerals by co-grinding with a surfactant, predicted by Acad. P.A. As early as 1955, as a rebinder at lectures at Moscow State University, but not published in the open press, it was observed in practice for the first time in these experiments. Obviously, chemisorbable solid surfactants (powders) for the purpose of clinker phase separation during grinding are more efficient than liquid ones. The border visible on the surface of an alite particle is a shell made of a modifier. Her light tone, according to M.Ya. Bikbau is caused by a three-fold lower density of organics compared to clinker minerals.

With a large increase (Fig. 2, b), the continuity of the nano-shell of naphthalenesulfonates is visible and its thickness is measurable. Measurements of a number of particles recorded the thickness of the shells in the range of 30-100 nm. Since since 2008 each object with a size of less than 100 nm has been classified as nano-objects according to RUSNANO terminology [www.thesaurus.rusnano.corn / wiki / article1325], these shells were called nano-shells [M. Bikbau, 2012, StroyPROFI. cit. Op.]. Catalyzed for subsequent hydration by a grafted modifier, alite partially enters their internal volume. Therefore, the shell can be called organomineral. It can be seen that both surfaces of the shell (external and internal) are relatively smooth. This confirms the fact of micro-preassumptions, which was supposed due to the endothermic effect in the co-grinding of the ingredients of nanocement in the works [Ioudovitch V.E. et al, op. cit., 1997; Yudovich B.E. et al., 1997].

The above indicates that the nano-shell is located on the particle of nanocement on top of the O-layer. Fine grains without a rim in the field of view of the microscope in FIG. 2b presents quartz not adsorbing the modifier contained (10 wt.%) In this sample of nanocement with a strength class of 82.5.

The advantage of the technical solution according to the prototype is that the encapsulation of all particles of the clinker component would guarantee the completeness of binding of the water-reducing component (modifier) with the clinker. But control with any microscope cannot guarantee that all particles of nanocement are surrounded by similar shells. Thus, the indicated technical solution does not fully guarantee the positive effect of nanocement described above, which also relates to the persistence of construction and technical properties for a long, and even possibly unlimited storage time under protection against drip moisture. Thus, the drawback of this technical solution is approximately similar to the previous ones, but the discovery of the continuity of nanoshells in itself is such a fundamental fact that it creates the opportunity for rapid technological progress in the technology and properties of nanoc cement.

The present invention is devoid of the indicated drawbacks of the previous technical solutions and can guaranteedly provide the entire technical effect of nanocement (CNV) described above precisely because it relies on the discovery of M.Ya. Bickbau. The present invention in terms of the composition of cement consists in the fact that nanocement based on Portland cement clinker and an organic modifier, including mineral phases alite, belite, aluminates and calcium aluminoferrites as clinker, as the specified modifier - naphthalene sulfonates in the form of continuous organomineral nanoshells with a thickness of 30-100 nm on clinker particles, as well as a sulfate-calcium component and mineral additive, with a specific surface of 400-600 m ² / kg, contains (wt.%) the specified clinker 12-88 as a solid urine, including these mineral phases in wt. ratios (50-75) :( 10-20) :( 0.5-15) :( 10-15), respectively, moreover, alite and belite are represented by microcrystals with dislocation block sizes of 0.1-3 μm, aluminates are glassy and aluminoferrites calcium - lamellar submicrostructures, the specified modifier is 0.15-2.2 as a solid powdery acid, which is represented by naphthalenesulfonates with a molecular weight (MM) of 1800-2200 Yes, the calcium sulfate component is 0.2-4.9 (in terms of SO ₃ ) as a promoter of hydration mineral formation, represented by calcium sulfate in natural and / or artificial forms, a mineral additive from active groups 5-85 and / or fillers 5-50, and the finished nanocement includes, on top of these nano-shells, consisting of fused triboactivation with a co-milled clinker component of naphthalenesulfonates with a molecular weight (MM) of 600 -800 Yes, a diffuse layer of throttled during triboactivation of naphthalenesulfonates with MM 300-600 Yes and, in addition, nanocement on the particles of the clinker component contains a layer of etched last mineral phases under the indicated nanoshells a 2-50 nm comprising alite nanoblocks size 1-20 nm, and their aggregates.

In an embodiment of the invention, said nano-shells further comprise fragments of said etched mineral phase layer with said aggregates of alite nanoblocks.

In another embodiment of the invention, said nano-shells contain naphthalene sulfonates including calcium complexes, the calcium sulfate component contains calcium sulfate in natural forms from the gypsum stone group: two-water gypsum, semi-water gypsum, anhydrite, conglomerates thereof or in artificial forms from the chemical gypsum group: phosphogypsum, product purification of calcium carbonate waste sulfur dioxide industrial furnaces or reactors, or their binary mixtures, the mineral additive includes one or two components from the group of active home ny granulated slag, fuel slag, fly ash, and from the group of fillers, silica sand, feldspathic sand, screenings from granite crushing.

The essence of the invention in terms of the composition of nanocement is that for the first time according to scanning electron microscopy (see Fig. 2, b), it was found that the nano-shells are multilayer.

Their outer diffuse layer (“c” in Fig. 2b) is the felt-like products of the throttling of the molecules of the initial oligonaphthalene sulfonate with MM 1800-2200 Da (this is the optimum according to the data repeatedly verified by the production experience of the inventors, the check was carried out by A.I. Vovk the technique described in the work [Vovk AI 1987, cit. cit.]) that arose in the mentioned process of co-grinding of the components. Throttling (expressed in the termination of the final and lateral functional groups) occurs upon implosion (retraction) of the molecules of the starting naphthalenesulfonate with their hydrocarbon chains into the cracks in the clinker particles formed under the influence of grinding bodies. The mentioned chains come into contact with the solid phase of the clinker with their terminal functional groups, are fixed on the calcium centers of new surfaces and break during friction, while they are likely to linearize and divide. As a result, hydrocarbon chains turn into filaments with one or two functional groups, fixed on nanocapsules glued to Ca centers, and form a continuous “felt layer” visible along their surface. The thickness of this layer of “threads” interwoven into the felt — single hydrocarbon chains — is 5-15 nm, which determines the calculated value of their MM as 300-600 Da. This is precisely the minimum value of the MM of naphthalenesulfonates contained in the finished nanocement found by gel chromatography. It is the continuity of the hydrophobic "felt" of these hydrocarbon "threads", fixed by the ends (functional ionic groups) on the premelted nanoshells, that ensures the minimum degree of aggregation of nanocement and its maximum flowability. The “dry” nanocement according to the invention flows like water, penetrating through any cracks - this is how technical personnel dealing with this material express themselves, in particular at a pilot industrial grinding plant built, put into operation and functioning under the guidance of the authors of the present invention ( Fig. 3) with an estimated capacity of up to 100 thousand tons of nanocement per year (the production of pilot batches has now been mastered).

Under the indicated diffuse outer layer there follows a premelted nano-shell “a” (Fig. 2, b), open M.Ya. Bickbau in [Bickbau, 2012, cit. cit.] and containing the bulk of naphthalenesulfonate with MM 600-800 Yes according to the obtained by the authors of the present invention with the methodological manual A.I. Vovka data gel chromatography. This shell, if continuous, as seen in FIG. 2b, it ensures the preservation of the construction and technical properties of nanocement with very long - up to a dozen years, as mentioned above - shelf life in silos and / or in containers. She is also responsible for the water-reducing effect, which gave the first name to nanocement - VNV.

A layer of blocks “b” is visible under the nano-shell (Fig. 2, b) in the surface layer of alite crystals, the sizes of which are in the range from units to tens of nm, more precisely from 2 to 50 nm. They can rightfully be called alite nanoblocks. If we compare these sizes with the sizes observed for blocks on chips of mechanically destroyed alite and belite microcrystals, fixed under a transmission electron microscope on carbon replicas, reinforced with gelatin, with the participation of the authors (Fig. 1) and published in a number of works [I. Kravchenko, V.V. and others. High-strength and especially quick-hardening Portland cement. M .: Stroyizdat. 1971.208 p .; Yudovich B.E. et al. Electron microfractography of Portland cement clinker. / VI International Congress on the chemistry of cement. M., Stroyizdat. 1976.Vol. 1. S. 269-276. See also Papiashvili U.I. Electron microscopic study of the structural features of Portland cement clinker and the products of its interaction with water. Abstract. diss. for a job. student step. Cand. tech. sciences. M .: NIIcement, 1978.- 35 p. Malinin Yu.S. et al. Electron microfractography of Portland cement clinker. // Proceedings of NIIcement. 1977. No. 32. S. 221-243] in the range from 0.1 to 3 μm, it becomes clear: the difference in the sizes of alite blocks obtained by etching, combined with grinding mainly by abrasion, with the sizes of alite blocks obtained and / or exposed as a result of one grinding, reaches two to three orders of magnitude. In the process of etching with the acid part of the modifier at the final stage of mechanical activation, the initial alite blocks (0.3-1 μm) of particles with a specific surface of 400 m ² / kg are dispersed by grinding media using etching to nanoblocks. As regards the material composition of nanocement, this is achieved with dislocation-free blocks of alite and belite in the initial clinker of 0.1-3 microns (blocks in belite crystals are larger than in alite). And such a submicrostructure exists in rationally calcined clinkers based on optimally prepared cement raw mix, and not in any Portland cement clinker [Yudovich B.E. Study of the features of grinding, particle size distribution and construction and technical properties of high-strength Portland cement. Abstract. diss. for a job. student Art. Cand. tech. sciences. M .: NIIcement, 1972. 31 p.]. It should be added that the specific surface of nanocement, determined by the method of low-temperature nitrogen adsorption with the calculation according to the Brunauer – Emmett – Teller equation [Brunauer, Art. Adsorption of gases and vapors. M.: Publishing. 638 pp.], Two to three orders of magnitude higher than the specific surface determined by the method of breathability (in ordinary Portland cement, two orders of magnitude), which indicates the availability of the interunit alite surface for external agents, in particular, liquid nitrogen molecules.

Therefore, for the first time, a fundamentally new phenomenon of the formation of nanoblocks on the surface of the alite phase in nanoc cement made from optimally prepared Portland cement clinker or from Portland cement based on this clinker is observed. The main process of their formation takes place directly below the indicated nanoshells, in the O-layers of the blocks, and also inside the shells after the separation of the mentioned nanoblocks from the O-layer. In FIG. 2b, we conclude that the initial blocks of an alite crystal (alkali), actively reacting with a shell of a modifier impregnated by grinding media in the contact zone of a modifier comprising oligonaphthalene sulfonate (acid), divide (disperse) with the formation of zones of an alite nanoproduct mainly under this shell. These zones are the adduct: alite + oligomer, consisting of modified alite nanoblocks with interblock nanowires of solidified melt (visible under the nanoshell in the dark part of the crystal in Fig. 2b), which, judging by the Auger spectra [Shishkina L.D. et al., 1992, cit. cit.], a nano-impregnated oligomer + Ca complex (the term “nano-impregnation” was first introduced on the website [www.mediasphera.ru/journals/stomo/607/9372/]). The diameters of these alite nanoblocks are from 2 to 50 nm, and the melt nanosheets between them from 2 to 10 nm. In places, the nanolayers are dark-colored, which indicates local dissolution of an admixture of dark-colored calcium aluminoferrite calcium (C ₄ AF), or a composition in the series C ₄ AF↔C ₆ A ₂ F, as suggested in the prototype.

The foregoing allows us to conclude that, in fact, nano-shells on particles of nanocement are three-layered, of which only the middle - fused layer - is indicated as a nano-shell in [M.Ya. Bickbau, 2012, StroyPROFI, cit. cit.] - prototype, but it is it that is the basis of two others - the outer one, described above as a diffuse layer (D layer), and the inner one, described above as an etched layer of mineral phases (TMP layer), which is mainly represented by alite of nanoblock structure on the outside of the clinker component of nanocement, directly below the nano-shell. Moreover, the above-mentioned O-layer, to the depth of which penetrates into the Portland cement clinker, the melt of naphthalenesulfonates through cracks, is not identical to the TMF-layer. The TMF layer is continuous, being a kind of “lining” of nanoshells, and the O layer is discrete, with “streams” of melt and possibly layers of the TMF layer around the said “streams” inside the layer of unchanged alite and belite of the indicated microblock structure (0 1-3 microns). As for the D-layer, it facilitates the transportation of nano-cement through pipelines, its unloading from containers for transportation and storage, as well as the prevention of clumping of nano-cement in silos. When nanocement is mixed with water, the D-layer, like other hydrophobizing agents, for example, fatty acids having only one functional group - carboxyl - for bonds with the substrate surface, is removed from it and sorbed by newly formed hydrates, since no mixing is detected in the water, even rainbow stains on its surface, observed in the case of the presence of a free modifier in nanocement or some well-known water-repellents such as soap-naphtha.

The prevailing value of the TMF layer, i.e., the presence of the mentioned alite nanoblocks in cements mechanically activated with a modifier, as compared to the control cement without them, can be demonstrated by comparative measurements of the magnitude and dynamics of the heat release (Q) of their hydration (Table 2, FIG. 4) after mixing them with a predetermined amount of water corresponding to the normal density of the dough (paste). Samples of conventional Portland cement and nanocements with three-layer shells were of equal dispersion (S _y 400 m ² / kg) and were prepared from one alite clinker with a block submicrostructure of alite. It should be added that the heat of hydration is understood to mean the sum of the heat of wetting cement with water and the heat released during hydrolysis and hydration of cement [Bogue R.N. The chemistry of Portland cement .: 2-nd ed. N.-Y.: “Reinhold Publ. Corp. ”1955. 793 p., See p. 591-606, 669-670].

The first difference between the heat release process (manifestation of the heat of hydration Q) of nanocement with a variable modifier content in the above ranges compared to Portland cement is that due to the modifier and with an increase in its dosage, the value of Q increases dramatically. These data were previously inexplicable, since during hydration of synthetic alite, a modifier co-crushed with it, on the contrary, reduces Q.

The significance of these data is due to the fact that the magnitude and dynamics of heat release are traditionally considered the most objective integral quantitative characteristics of the hydration process of any cement during their interaction with water [Bogue R.N., 1955, op. cit., p. 592,669; Usherov-Marshak A.V. Calorimetry of cement and concrete. Kharkiv. "Fact". 2002.180 p.].

The second difference is the double exothermic effect after the mixing of nanocement with water against the single effect in the control Portland cement (Fig. 4) and in synthetic alite samples, control and mechanically activated in the presence of the modifier - naphthalenesulfonates. In the well-known data on the heat release of cements [Mchedlov-Petrosyan O.P. and others. Heat release during hardening of binders and concrete. M .: Stroyizdat. 1984. 225 p. Usherov-Marshak A.V., 2002, cit. op.] there is no evidence of double exothermic effects during the setting period. We also note that the MM of naphthalenesulfonate co-crushed with synthetic alite does not change compared to the initial one and, therefore, does not stick to the surface of this mineral.

Thus, the main features of nanocement in terms of heat release are a sharp increase in the initial and total heat release and a double exothermic effect in the setting process. In it, the first maximum is explained by the wetting of the middle layer of nanoshells and their rapid but limited hydrolysis (“disassembly”) to organo-calcium complexes (presumably C ₁₀ H ₇ SO ₃ Ca according to [Bikbau M.Ya., 2012, StroyPROFI, cit. Cit.] ) with their transition to the surface of primary hydrate particles on alite nanoblocks located inside the middle layer of nanoshells, and the second maximum is the wetting of the released (from the said middle layer) nanoshells of the surfaces of alite nanoblocks from the underlying parts of the TMF layer on the O- surface layers with the beginning of the addition of water molecules to them by the topochemical mechanism (TCM) and with the beginning of hydrolysis of the next layer of nanoblocks, accompanied by the transition of the mentioned complexes to the surface of the following primary hydrates. Therefore, with an increase in the dosage of the modifier, the first maximum increases to a greater extent than the second (Fig. 4). The total increase in the initial and final heat release of nanocements up to 2-2.5 times (Table 2) versus control cement (subject to the conditionality of the “final” indicator, since hydration continues even after setting, although more slowly) due to the presence of nanoblocks it exceeds Q growth by compared with the increase in Q observed when adding any hardening accelerators to the mixing water of ordinary Portland cement. Synthetic C ₃ S, co-milled with a modifier, does not undergo microfusion (there is no corresponding endothermic effect [Yudovich B.E., Vovk A.I., Zubehin S.A. et al., 1992, cit. Cit.)), Retains porous the external surface and simply sorb on it a modifier, which, after mixing with water, enters the liquid phase [Kurbatova II Astringent low water requirements. Chemistry and technology of application. NIIZHB-Polimod. Scientific and technical report "Stroyprogress". Section: Chemistry of hydration. M .: NIIZHB. 1991 (on the rights of the manuscript)] in an amount exceeding the optimum required for plasticization of cement-water systems. Therefore, the modifier co-grinded with C ₃ S reduces Q. Thus, the double exothermic effect on the heat-release curve of nano-cement acquires the characteristic of an express indicator of the presence of the indicated three-layer nano-shells on its particles and, accordingly, a sign that the tested cement is precisely nano-cement, which can be verified within 1 h (for nanocement without mineral additives) or up to 3 h (for nanocement with mineral additives and / or fillers) after the start of the test without significant material Cost x (see. for ease of observation technique express heat nanotsementa below in describing the present invention in terms of a method for producing nanotsementa).

The above allows us to consider alite nanoblocks from the TMF layer as a promoter of hydration of nanocement, significantly accelerating its hardening, just as in some old works a small fraction of cement was considered as a hydration promoter (less than 5 microns, or within 0.1-5 microns) [Veke V Theorie und Technologie der Zementvermahlung. // Silikattechnik (Berlin). 1962. V. 13. No. 4. S. 115-123; Kravchenko I.V. et al. 1991, cit. Op .; Yudovich B.E. Designing the particle size distribution of high-strength cements. // Proceedings of the Research Institute of Cement. 1992, cit. Op., p. 266-279]. Only the promoter effect of alite nanoblocks, accelerating the hydration of nanocement by 2–2.5 times compared to Portland cement, almost doubles the similar effect of the fine fraction of high-quality cements, accelerating their hydration compared to ordinary Portland cement by only 30%, i.e. 1.3 times.

The transition of organomineral nanoshells to calcium hydrosilicates in the process of phase formation after mixing the nanoscement with water is not at all obvious and has not been proven to date, since no one has observed these nanoshells directly on the said hydrosilicates in cement stone. There is only one work described in two articles [Zubehin S.A. et al. The role of double foam in the formation of structured elements of the submicrostructure of foam concrete. // Reports of the Academy of Sciences. 2009.V. 429. No. 5. S. 636-639; Yudovich B.E. et al. Submicrocrystalline foam concrete: new in the fundamentals of technology, part I // Cement and its application. 2009. No1. S. 81-85], in which the stone of nanocement, hydrated for 3 years, is visible in the foam concrete with a porosity of more than 90% (Fig. 5). On the surface of the cleavage, according to morphological features represented by calcium hydrosilicates, no carbonate sites are visible. There is a clear trace of a fully hydrated particle of nanocement. This picture shows, at least, that the boundary between the external and internal hydrates is absent, as already mentioned, and from the former clinker particle, in which, in places of traces of dislocation nuclei, the modifier melt passed into the O-layer, columns of high-water hydrates grew. Their genesis is explained by the aluminate-aluminoferrite phase dissolved in the melt, which generates ettringite columns stabilized by Si substitution of the Al cation, morphologically exactly the same as those observed in the stone of high-strength Portland cement at a high concentration of Ca (OH) ₂ in the liquid phase of the stone [B. Yudovich B.E. ., 1971, cit. Op.]. This corresponds to a high level of initial heat release during the hydration of nanocement. It can be seen that neither the hydrosilicate mass surrounding the ettringite columns, nor the columns themselves underwent carbonization, despite the high porosity of the foam concrete. There is no other option for protection against carbonization in a solid body so accessible to CO ₂ as highly porous and especially lightweight (with a density of less than 300 kg / m ³ ) foam concrete than nano-shells containing TMF layers on hydrosilicates and on columns of high-water hydrates. It also follows that, being glued to the alite surface, the nano-shells were not completely removed from the alite by water either during mixing or during the subsequent hardening of foam concrete based on nano-cement, but switched to alite hydrates as a result of the topochemical hydration mechanism.

The O-layer in this case (Fig. 5) occupies the entire volume of a small alite particle. It really contained layers of melt that passed deep into the particles. The fact that foam concrete on nanocement, despite its very high total porosity, was not carbonated in the least after 3 years of dry storage (it was in an air-moist environment for up to 28 days after mixing), was completely unexpected. The absence of carbonization was also found for samples of heavy concrete and mortars prepared on the basis of nanocement, although this is less unexpected compared to foam concrete, because their porosity was 3-5 times lower, although they were approximately similar to both foam concrete and heavy concrete and mortars prepared on ordinary Portland cement turned out to be carbonized by about 30 and 10-20%, respectively (the proportion of calcium carbonates in the total mass of hydrated neoplasms was determined) [B. Yudovich et al. 2009, cit. Op.]. Since it is known that naphthalenesulfonates protect hydrates from carbonization, as they are able to absorb CO ₂ [Batutina L.S. Intensification of cement hardening by preliminary surface hydration. Abstract. diss. for a job. student Art. Ph.D. M .: NIIcement, 1984. 24 pp.], These data support the assumption of the transition of the TMF layer to hydrates after mixing the nanocement with water, which ensures a clearly identified absence of carbonization of stone, mortars, and concrete on nanocement. The absence of naphthalenesulfonates in the liquid phase of cement paste and stone of rationally made nanoc cement, established by I.I. Kurbatova [cited. 1991 report], confirm the absence of the TMF layer into the water when mixing a rationally made nanocement (here and earlier, by this we mean fully consistent technology limitations described in detail above). Thus, there is indirect evidence that even in the absence of direct evidence allows us to assume that the transition of at least the TMP layer from nanoshells on particles of nanocement to its hydrated phases, mainly to calcium hydrosilicates, is actually carried out. And it is he who explains all the main positive effects of nanocement and materials based on it. So, it is known [Yudovich B.E. et al. Prospects for the use of composite materials based on cement matrices // ALITinform (International Review). Cement. Concrete. Dry mixes. 2013. No1 (28). P. 20-29] that concretes and mortars on nanocements aged 7 days or more exhibit a clear induction period of crack formation before failure under mechanical stress, and the higher the strength, the longer the accumulation period of intergranular shear cracks is longer in accordance with t. called tear-off theory of strength [Kholmyansky MM Concrete and reinforced concrete. Deformability and strength. M .: Stroyizdat. 1997. 569 pp.], According to which cement stone and concrete are a discrete conglomerate of commuting grains, and not a “cement matrix”, therefore cement materials are better described by the finite element method than by the theory of elasticity, which still underlies the design of reinforced concrete and concrete products and designs. There is no other factor that could explain the anomalous duration of the indicated induction period, which is an order of magnitude greater than that observed under mechanical loading of ordinary concrete, except for the TMF layers on calcium hydrosilicates and the stabilized columns or fibers of high-water hydrates, which slow down the development of fracture cracks by their damping effect, characteristic of adhesive joints [Pocius A. Glues, adhesion, bonding technology. SPb .: Profession. 2007. 376 p.], As well as the reinforcing action exhibited by the fibers. In the work [Zubehin S.A. et al., 2009, cit. cit.] found that a significant part of calcium hydrosilicates in the material based on nanocement forms hydrosilicate columnar layers around pores, which also protect the material from atmospheric carbon dioxide. Thus, the TMF layer generates columnar textures not only from high-water, but also from other hydrates. And this may indicate a sign of the location of chemisorption sites of naphthalenesulfonate functional groups from the TMF layer on the less dense planes of lattices of hydrosilicates and calcium hydrosulfoaluminates, which ensures an increase in the uterine supply from the liquid phase along the most dense planes of their crystal lattices, which is a factor causing columnar crystal growth or, as in this case, crystalloids. Thus, not only the nanoshells encapsulating cement in themselves, but, first of all, the TMF layer of alite nanoblocks included in their composition, which arises during the mechanical activation process, is responsible for the enhanced construction and technical properties of nanoc cement described at the beginning of the description of the invention. Of course, the remaining mass of calcium enriched naphthalenesulfonates in the composition of the nanoshells, exceeding their amount in the TMF layer, affects the strength. It is just it, apparently, with the initiating effect of the TMF layer, that is responsible in general for the induction effect of intergranular shear delay, which increases the strength of nanocement under mechanical load, which is mentioned above. It cannot be denied that the difficulty in intergranular shear restrains shrinkage and creep, and this makes it possible to use substandard aggregates and smoothes the dependence of the quality of nanocements on the difference in activity between active mineral additives and fillers, some of which can significantly reduce the resistance of a cement stone to intergranular shear in an ordinary cement stone, and in a stone based on nanocement it cannot manifest these drawbacks of its own - they are damped precisely by the material of the nanoshells, hydrates. In the development of these developments, undoubtedly, specific hydrated carriers of relics of nanoshells exhibiting such useful technical properties will be installed. For TMF layers, it is logical that their second "owner" after the transition from nanoalite to hydrated products as a result of mixing of the nanocement with water becomes calcium hydrosilicates obtained by hydration of cement in an adioxidic medium (ie, a medium free of atmospheric carbon dioxide - carbon dioxide compounds and water). This is precisely the internal environment in the nanocement-water system, and for this reason, probably, these hydrosilicates are similar in composition to Pellenk – Ulm nanoclusters [Pellenq RJ –M et al. A realistic molecular model of cement hydrates. // Nat. Academy of Science. Proceedings. Wash. 2009. V. 106. Iss. 38. P. 16102-16107], also formed in an adioxide medium, although a specific carrier phase from a large set of mineral phases related to calcium hydrosilicates has not yet been established in a nanocement stone.

It should be noted the importance of this fact. The fact is that Yu.S. Malinin et al. Demonstrated [Malinine Ju. S. et al. Prehydratation super-ficielle des ciments et son influence sur le processus de durcissement. / 7th Congress Internacional de la Chemie des Ciments. Proceedings. Septima. Paris 1980. V. 5. PP. V-125 - V-130] inheritance of the properties of prehydrates formed on the surface of cement particles during transportation and storage, the main hydrates after mixing cement with water. According to this paper, free of CO ₂ predgidraty Portland cement, for example, stored in a free of carbon dioxide (CO ₂₎ and air-moist, so-called adioksidnoy medium or predgidraty Portland cement, treated with adsorbents CO _2, generate within fixed hydrates fraction also free of CO ₂ . It was shown that this fraction has an increased density of interfacial contacts, it grows better together with the surface of the aggregates and, ultimately, has an increased strength [L. Vatutina, 1984, cit. Op.]. Obviously, nanoalite (alite blocks in the TMF layer having nanosizes) due to the adsorbing effect of the modifier on CO ₂ should also generate a fraction of hydrates free of CO ₂ , and more importantly, it will contribute, as a seed, carbonization resistance at least as much of the rest of the cement stone. This implies the second possible role of the TMF layer as a promoter not only of alite hydration, but also as a promoter of resistance to carbonization of cement stone and materials based on it, up to the most impressive example - foam concrete of especially high porosity - long-term resistant to carbonization.

The possibility of a higher content, in contrast to Portland cement, of the active mineral additives 5-85 and / or fillers 5-50, provided for in the embodiment of the composition of nanocement, provided for in the embodiment of the invention, is due to the fact that after the nanocement is mixed with water during the hydrolysis of alite, the nanoblocks react with water under a protective coating against CO ₂ , forming nanoclusters of calcium hydrosilicates [Pellenq RJ - M. et al. 2009, op. cit.], the gross composition and nanostructure of which approximately corresponds to the same characteristics of the most stable of the known calcium hydrosilicates, not subject to phase transitions - afvillite C ₃ S ₂ H ₃ [Yudovich B.E. The main laws of hydration and hardening of Portland cement. // Sat Academic Readings, ded. 100th birthday A.V. Volzhenskogo "Development of theory and technology in the field of silicate and gypsum materials." Part 1. M .: MGSU. 2000, p. 20-33]. Afvillit, in turn, arises at room temperature, as shown in the last source, only in an acidic medium, i.e. atmosphere isolated from carbon dioxide (CO ₂ ) atmosphere. Thus, it can be considered proven that the mentioned nano-shells protect the stone of nano-cement and, therefore, all materials based on it - mortar, concrete, etc. from carbonization, which is an important factor in ensuring their reduced shrinkage, increased frost resistance and durability. Intergrowth of nanoclusters composition, according to [Pellenq RJ - M. et al., 2009, op. cit.] described by the gross formula (CaO) _1.65 (SiO ₂ ) (H ₂ O) _1.75 (with an average effective nanocluster size of С-S-Н 5.5 nm), which is close to the gross composition of afvillite under nano-shells, as it was found goes between the outer layers in these nanoclusters enriched in siloxane chains [Ulm F.-J. What’s the matter with concrete? XX Convegno Nationale Int. Gruppa Frattura. Torino 24-26 guigno 2009. Proceedings. P. 3-10], with the formation of nano-, submicro- and microaggregates, growing together into a granular macro-conglomerate of cement stone, and on its basis - mortar and concrete [Constantinides G. et al. On the use of nanoindentation for cementitious materials. // Materials and Structures. 2003. V. 36. No. 3. P. 191-196]. The mentioned siloxane chains consist of three-membered groups (silicon-oxygen tetrahedra with silicon atoms in the centers) of the form

in which the part in bold is 60 ° deviated from the rest, and all tetrahedra with multidirectional vertices [Pellenq RJ - M. et al. Engineering the bonding scheme in C-SH. The ion-covalent framework. // Cement and Concrete Research. 2010. V. 40. No. 2. P. 159-174]. For the purposes of the present description, it is important that these chains in the surface layers of С-S-Н nanoclusters associated with calcium-oxygen groups in the cavities deviate in composition (compared to the total composition of С-S-Н nanoclusters in the test and stone) to the side silica enrichment [Pellenq RJ - M. et al., 2010, op. cit.]. This brings them closer to the gross composition of the outer atomic layers of particles of active mineral additives (mainly aluminosilicate composition), where the proportion of aluminum due to its variable coordination Al ^IV ↔Al ^VI in the surface layer of the particles being ground is reduced - this is the phenomenon of “escape” of aluminum ions from the surface of the particles being ground , weakening the crystal lattice and enriching the outer atomic layers with silica, Acad. N.V. In his lectures, to facilitate memorization, Belov figuratively called "betrayal of aluminum" [Belov N.V. Essays on structural mineralogy. M .: Subsoil. 1976. 344 p.]). As for silicate fillers, the submicrostructural similarity of their outer atomic layers with the aforementioned siloxane chains is generally almost 100%. This similarity of the calcium hydrosilicate nanostructures in the hydrates of nanocement and in the outer atomic layer of microparticles of active mineral additives and fillers increases the frequency of intergrowth contacts per surface unit and provides a greater share of covalence in them and, accordingly, increases the strength of their intergrowth with nanocement compared to Portland cement. The latter is fused with mineral additives and fillers through the polar bridges of the composition

whose strength is about 30% lower due to the weak link - the calcium-oxygen polar insert than the polar-covalent bridges (1), and the number of contacts of the fusion of the bridges (2) with the surface of the particles of fillers and filler grains is about half as low as that of the bridges (1) ) Hence, at least 60% increased capacity of the stone of nanocement in relation to mineral additives and fillers and increased filling capacity of mortars and concrete on nanocement compared to all of the specified materials on Portland cement and all its varieties in relation to all nanocements with similar material compositions for the main components [Ioudovitch , V.E. et al., 1997, op. cit. and etc.; Yudovich B.E. et al., 1997, cit. Op .; Bikbau M.Ya. 2008, cit. Op .; Afanasyeva V.F., 2012, cit. Op .; Babaev Sh.T. and others. The effectiveness of binders of low water demand and concrete based on them. // Concrete and reinforced concrete. 1998. No. 6. S. 3-6; Babaev Sh.T. and others. Features of technology and properties of concrete based on binders of low water demand. // Industry builds. fishing. Ser. 3 / Industrial precast concrete. Sat VNIIESM. M .: 1992. Issue. 2.108 p.]. As for the fillers of predominantly silicate nature, in particular, quartz sand, its outer nanolayer is completely identical to the described three-membered siloxane groups. Hence the increased chemical affinity of the cement stone of nanocement with respect to quartz fillers and aggregates, and their special gain in strength compared with other materials. All this creates an opportunity to reduce the consumption of nanocement by 50-100% compared to the control Portland cement in equal strength mortars and concrete, which is feasible and follows from the data given in table. 3.

From the analysis of the data table. 3 it follows that all the technical and economic effects described above are confirmed. New in these data is the fact that the type of mineral additives affects the strength of nanocement at 28 days of age to a much lesser extent than in the early stages of hardening (1 and 3 days). So, cements, differing only in that in one of them blast furnace granulated slag, one of the best known active mineral additives, and in the other much less active fly ash (moreover, both of these specific additives are one of the best in their types), at the age of 28 days they have almost the same strength (Table 3, lines 8 and 9). The same can be said about nanocement, containing, in addition to the last two active mineral additives, also a classic filler - quartz sand (Table 3, lines 11-13). This cannot be explained otherwise than by confirmation of the observation of crystallographers [Ulm, 2010, op. cit.], according to which, in the absence of atmospheric carbon dioxide (which Ulm forgets to mention in this report, conducting all his work only in a carbon-free environment) for intergrowths (aggregates) of С-S-Н cement stone nano-, submicro-, and microclusters shells are enriched with siloxane chains (1) nanolayer. It is through these layers that the Portland cement stone in the atmosphere free of carbon dioxide should grow together with particles of mineral additives similar in aluminosilicate composition of the outer atomic layer with chains (1), and with particles of quartz sand, identical in the outer atomic layer with chains (1) with approximately equal strength indicators, as in table. 3. But in the well-known works on the hydration of calcium silicates and Portland cement in a carbon-free atmosphere [Brunauer, St. Cement Hydration. / Science of engineering materials. Ed. by J.E. Goldman. John Wiley a. Sons, N.Y., 1957, Bull. No. 80, pp. 21-30; Malinin Yu.S. Study of the composition and properties of the main clinker mineral alite and its role in Portland cement. Abstract. diss. for a job. student step. Dr. tech. sciences. M .: Mosk. Chem. - technologist. Institute of them. DI. Mendeleev, 1969. - 28 pp.] Close or equal in strength composite compositions with mineral additives and fillers of different activity have never been observed.

What explains the novelty of the results given in table. 3, compared with the known from the prior art? It is the effect of the predominance of siloxane chains (1) in the outer hydrate layers in the stone of nanocement, as a result of which, as was experimentally established, all active mineral additives and fillers, especially at the age of 28 days, show so close results in the composition of nanocements that they almost coincide with typical data presented in table. 3. There is no need to separately provide data for the different types of mineral additives and fillers listed above - they are all about the same.

Inst. Eng., Stockholm. 1940. S. 298-314]. Это было доказано лишь в 1996 г. фактом обнаружения эттрингитного геля с последующей его кристаллизацией в волокна под растровым электронным микроскопом, ранее никогда не фиксированного в виду недостаточного разрешения прежних электронных микроскопов [Emanuelson A. et al. Ferrite Microstructure in clinker and hydration of synthetic phases in sulphate resisting cements. / 10-th International Congress on the Chemistry of Cement (ICCC). Gothenburg, Sweden, 2-6 June 1997. Proceedings, ed. by H. Justnes. Amarkai AB and Congrex Gutenborg AB, 1997, vol. 1 (Plenary lectures. Clinker and Cement Production). 1i060. 8 pp.]. Первая фаза - образования золя - в наноцементно-водных системах длиннее, чем в портландцементных системах в связи с пространственным разделением первых исходных фаз, а в результате первой гидратной фазой, образующейся в смеси наноцемента с водой является не эттрингит, как в портландцементе, а гидросиликаты кальция. Это обращение порядка фазообразования - весьма существенный момент [Юдович Б.Э. Цементы с избирательной гидратацией. (Второй эффект Ребиндера). Международная конференция по коллоидной химии и физико-химической механике, посвященная 100-летию со дня рождения акад. П.А. Ребиндера, Москва, МГУ, 4-8 октября 1998 г. Сб. тезисов докладов, М.: Наука, 1998]. Именно обращение порядка фазообразования определяет присутствие упомянутых силоксановых цепочек в наружных зонах наноцементного камня, а эттрингитная составляющая, или так называемые многоводные гидраты (в отличие от гидросиликатов, где на каждую CaO-группу приходится в среднем по две молекулы воды и/или гидроксилов, на CaO-группы в многоводных гидратах приходится от 5 до 12 молекул воды и/или гидроксилов) находятся внутри гидросиликатной структуры - точно так же, как камне портландцемента, гидратированного в адиоксидной среде (т.е. в среде, свободной от CO₂), что было впервые постулировано Ст. Брунауэром в 1957 г. [Brunauer S., 1957, op. cit.], а теперь экспериментально подтверждено группой под руководством Ф.-Й. Ульма [Constantinides G. et al., 2007, op. cit.; Ulm F.-J. 2009, op. cit.].Similarly, close results on strength data show the various types of calcium sulfate component listed above in the composition of a rationally manufactured nanocement. This component can be called the promoter of mineral formation, since upon separation of nanocement into sets of monomineral particles, the localization of hydrated phases in a nanocement stone increases compared to a stone from Portland cement, where polymineral particles predominate. The hydration phases generated by the calcium sulfate component require the participation of all mineral phases in cement synthesis during hydration, sometimes with the exception of calcium aluminoferrites. The unifying role of this component allows it to accelerate the hydration of nanocement by binding calcium, aluminum, and often iron from sols in the liquid phase of the cement paste to gel-like products, and then to ettringite crystalline high-water hydrates (3CaO · Al ₂ O ₃ · 3CaSO ₄ · (28-31) H ₂ O). Lennart Forsen first postulated the three-stage nature of this process in Portland cement-water systems, first the sol during the initial dissolution of the components, then the gel after the sol-gel transition, then the crystals as a result of crystallization of the gel with the binding of an additional amount of water [Forsen LR The chemistry of accelerators and retardants. / II International Symposium on the Chemistry of cements. Proceedings, Stockholm, 1938, Ed. Svenska

Inst. Eng., Stockholm. 1940. S. 298-314]. This was proved only in 1996 by the fact of the discovery of an ettringite gel with its subsequent crystallization into fibers under a scanning electron microscope, which had never before been fixed in view of the insufficient resolution of previous electron microscopes [Emanuelson A. et al. Ferrite Microstructure in clinker and hydration of synthetic phases in sulphate resisting cements. / 10-th International Congress on the Chemistry of Cement (ICCC). Gothenburg, Sweden, 2-6 June 1997. Proceedings, ed. by H. Justnes. Amarkai AB and Congrex Gutenborg AB, 1997, vol. 1 (Plenary lectures. Clinker and Cement Production). 1i060. 8 pp.]. The first phase - sol formation - in nano-cement-water systems is longer than in Portland cement systems due to the spatial separation of the first initial phases, and as a result, the first hydrated phase formed in the mixture of nano-cement and water is not ettringite, as in Portland cement, but calcium hydrosilicates . This reversal of the phase formation order is a very significant point [B. Yudovich Cement with selective hydration. (Second Rebinder effect). International Conference on Colloid Chemistry and Physico-Chemical Mechanics, dedicated to the 100th anniversary of the Acad. P.A. Rebinder, Moscow, Moscow State University, October 4–8, 1998 Sat. Abstracts, Moscow: Nauka, 1998]. It is the reversal of the phase formation order that determines the presence of the aforementioned siloxane chains in the outer zones of the nanocement stone, and the ettringite component, or the so-called high-water hydrates (in contrast to hydrosilicates, where, on average, two water molecules and / or hydroxyls per CaO group account for CaO -groups in high-water hydrates account for 5 to 12 water molecules and / or hydroxyls) located inside the hydrosilicate structure - just like stone Portland cement hydrated in an oxide medium (i.e., in a medium vobodnoy of CO _2), which was first postulated Cm. Brunauer in 1957 [Brunauer S., 1957, op. cit.], and now experimentally confirmed by a group led by F.-J. Ulm [Constantinides G. et al., 2007, op. cit .; Ulm F.-J. 2009, op. cit.].

The physical and chemical consequence of this is two factors: 1) the protection of the stone of nanocement from carbonization, since calcium hydroaluminates and ettringite, characterized by a fluctuating water content, are quite easily carbonized, especially in the presence of impurities of phosphorus, boron and others found in chemical gypsum or clay impurities in natural gypsum stone, but in this case they are located inside the hydrosilicate texture, therefore neither impurities nor fluctuations in the water content on the carbonizability of these phases and nano-cement stone in generally have no effect; this also determines the reduced sensitivity of the nanocement stone to the forms of the calcium sulfate component and the small effect of undesirable impurities in it, such as clay, on the quality of the nanocement; 2) Si impurity in place of Al in ettringite, arising from the hydrosilicate environment, further reduces the tendency of this hydrated phase to change under the influence of the medium, in particular, to the harmful effects of low humidity and high temperature; and in the nanocement stone with the ubiquitous presence of siloxane nanochains (1) and an increased content of mineral additives, which always ensure the presence of dissolved silica in the liquid phase of the stone, an increased degree of substitution in ettringite Al for Si is practically ensured. Therefore, any calcium sulfate component, if it provides the necessary sulfate ion content in terms of SO ₃ in nanocement, is in principle suitable and equally effective in the composition of nanocement.

Thus, it is precisely for the indicated physicochemical reasons that the nanocement according to the invention has a number of decisive advantages in comparison with the prior art, and above all, that the unique complex of construction and technical properties described above is fully guaranteed and 100% achievable within the framework of the present invention. This was not provided by technical solutions known from the prior art.

The foregoing indicates that the present invention includes several fundamental elements of novelty, as it relies on the discovery of M.Ya. Bikbau nano-shells on particles of nano-cement (prototype):

A. Alite nanoblocks as a part of a layer of clinker mineral phases etched by nano-shells, in which alite predominates as the most basic phase of all clinker minerals, the most intensively etched by acid modifier nano-shells. It is chemical and mechanical dispersion at the last stage of grinding nanocement that produce nanoblocks in alite, which are 2-3 orders of magnitude smaller in size in comparison with blocks exposed during grinding without a chemical component. This is the specific content of the so-called mechanical activation of cement when co-grinding with a modifier that has an acidic reaction.

B. These alite nanoblocks in the layer of etched mineral phases have two main functions: a promoter of hydration of nanocement and a promoter of carbonate resistance of its hydrates, generating a fraction of hydrated neoplasms, most likely calcium hydrosilicates, free of carbon dioxide and preventing its entry into the submicrostructure of cement stone. Both of these functions, summing up their contributions, lead to an increase in the strength of the cement stone of nanocement, as well as materials based on it - concrete, mortar, dry mixes.

B. The rest of the material of the nanoshells slows down the development of cracks under mechanical stress, reduces the shrinkage and creep strains, since it slows down the intergranular shift in cement stone and materials based on it. These results correspond to the view of a cement stone not as a continuous matrix in the representations of the theory of elasticity, which is a very crude simplification [Karpenko NI General models of reinforced concrete mechanics. M .: Stroyizdat. 1996. 416 pp.], But as a system of aggregates - grains, where the intergranular or interfiber shift plays the most important role [Morozov V.I. and others. Crack formation of dispersed reinforced concrete from the standpoint of fracture mechanics. // Bulletin of Kazan 2012. No1. S. 110-117], and quite successfully described by modern, the so-called detached theories of destruction [Kholmyansky MM, 1997, cit. cit.], in particular, using the finite element method [Kharitonov AM Prediction of concrete cracking based on the finite element method. www.pandia.ru/text/77/313/34719.php (Basic presentation); Klovanich S.F. and others. The finite element method in the mechanics of reinforced concrete. Odessa. 2007.110 p.]. Thus, damping elements can be represented as a model of distributed cohesive zones in a cement stone [Jing-hui Liu, et al. Numerical simulation of a crack in the cement stabilized stone using cohesion zone models. / Int. Conf. on Experim. Mechanics Nov. 2008. Nanjing (China). SPIE Proceedings 7375.24 Aug. 2009. doi10.1117 / 12.8390044]. It is hoped that these elements or zones will soon be able to be identified as mineral carriers of the mechanical properties of stone and concrete, i.e. to bind their abstract images to specific physical and chemical elements of the texture.

D. The diffuse layer of naphthalenesulfonates surrounding the particles of nanocement on top of the nanoshells is mainly responsible for the absence or small degree of aggregation of particles, facilitating transportation and unloading from wagons and silos, while the nanoshells themselves, which are retained on the particles during the mixing of the nanocement with water, packing and compaction mortar and concrete mixtures, are responsible for the low water demand of nanocement and excellent water-reducing effect, which gave the basis for their first name: astringent low water demand. In the present description, special emphasis is placed on novelty elements associated with the molecular weight of naphthalenesulfonates, with respect to which only general information is known in the world literature about its relationship with their water-reducing effect upon the introduction of mixing water [Ramachandran V.S. et al. (Eds). Handbook of Analytical Techniques in Concrete Science and Technologie. Principles, Techniques and Applications. Noyes Publ. and William Andrew Publ .: Park Ridge (N.J.) and Norwich (N.Y.). 2001.964 pp .; see also: Ferrari G. et al. The influence of the Molecular Weight of Beta-Naphtalene Sulfonate to Based Polymers on the Rheological Properties of Cement Mixes. // Cemento. 1986. V. 83. No. 4. PP 445-454], and questions about the relationship of MM of individual fractions of naphthalenesulfonates with their effect on cement and cement-water systems were not covered.

D. The specified water-reducing effect creates a significant, but not prevailing factor in the increase in the strength of nanocement compared to Portland cement, since the strength increases by 3-4 classes, or by 50-100%, and water demand decreases by no more than 25-30%. An excess increase in the strength of nanocement is determined by both the promoting effects of nanoblock alite described above and the inhibition of intergranular shear nanoshells with the rest of the material, with an increase in the induction period of the development of a fracture crack in a nanocement stone and materials based on it.

E. The main economic effect of nanocement with the modern branded composition of concrete and mortar in the Russian construction complex is created by compensating for the excessive increase in the strength of materials based on it by reducing the content of Portland cement clinker and the increase in the share of mineral additives - active and fillers - in the composition of nanocement to previously unthinkable values ( 80 wt.% And more). This allows us to reduce the burden from the cement industry on the environment by reducing fuel and electricity consumption for clinker firing and reducing greenhouse gas emissions, also in previously unattainable volumes. At the same time, nanocement significantly simplifies the technology of High Performance Concretes - highly processed concrete, in particular, high-strength and especially durable, which is one of the necessary conditions for the sustainable development of Russia. For this reason, nanocement is an important reserve for the future, which so far is not found in any of the developed countries of the world. This our national priority should be used as soon as possible to solve long-overdue problems:

- a sharp acceleration in the pace and expansion of housing construction by increasing cement production without creating new cement plants, only due to an increase in grinding capacities; this is the path to affordable housing, which in our country has not been around for more than about 40 years;

- improving backward urban and township environments, and finally

- the beginning of the construction of a modern road (both railway and road) network throughout the country, including the northern and equivalent territories, the absence of which today is the main brake on the country's economic development.

Nanocement is able to provide all these possibilities if it is widely implemented [M. Bikbau. New concrete, structures and technologies for the construction of airfield coatings, roads and engineering structures. // Concrete technology. 2012. No. 7-8. S. 32-35. He is. Nanocement is the basis for the effective modernization of precast plants. 2012. www.concrete-union.ru/articles/cement.php?ELEMENT_ID=8213 He is. New materials, products, structures and technologies in the construction of road surfaces and engineering structures. 2012. www.concrete-union.ru/documents/cudocs/Bikbau_dorogi.docx.]. The authors of the present invention also join many other specialists who adhere to the views of the possibilities offered by this new generation of cements similar to those presented.

The nanocement according to the invention is prepared for widespread industrial implementation.

The whole range of positive construction and technical properties of nanocement according to the invention is reliably achievable only if the method for producing nanocement described below is also used, which is also radically different from the prior art.

Indeed, from the prior art there is known a method of manufacturing nanocement by co-grinding a composition of the above components, in which the samples taken at the outlet of the mill determine the specific surface area of the product by the method of breathability and the presence of free naphthalenesulfonate in immersion preparations under an optical microscope, and the results of determinations are compared with the desired parameters for the specific surface area of at least 400 m ² / kg at zero free Content modifier - on talinsulfonata [TU. 2001, cit. doc.]. In the case of a reduced specific surface and the presence of a free modifier, the fineness of cement is increased until a specific surface of at least 400 m ² / kg is reached and the free modifier disappears in the samples due to new surfaces opening upon cement milling. In the finished product, as a rule, there is no free modifier. Other options should be excluded if the adjustment and start-up of production of nano-cement was carried out in accordance with the technical documentation [Guide, 1992, cit. Op.]. However, experiments have shown that this method does not guarantee the absence of a free modifier, because its regular determination is not provided.

There is also known a method of manufacturing nanocement, in which the samples taken at the outlet of the mill, determine the magnitude of the degree of aggregation of particles and compare with the required value of 5-15 vol. % [RF patent No. 2207995, 2003]. Moreover, the degree of aggregation is determined by the quantitative method [ed. testimonial. USSR No. 1250917, 1986], with the use of the PX breathability device (the device of the Khodakov system specified in [GOST 310.2-76 Cements. Methods for determining the fineness of grinding], or its modern analogues in accordance with [http://www.khodakov.ru/ index.php? option = com_content & task = category & sectionid = 4 & id = 15 & Itemid = 217].

This method is also used in the production of cement with a dense contact zone according to [TU 5730-001-86664502-09 Portland cement with a dense contact zone (PC PKZ)].

The team of authors of the works and documents cited above in the field of new generation cements (VNV, TsNV and nanocements), as well as a monograph devoted to a new direction of the same research and the most voluminous ever published in Russian in the field of cement chemistry [M. Bikbau I., 2008, cit. cit.] the opinion was created that these sources in total are sufficient for the efficient production and use of the mentioned cements, taking into account the quality criteria specified in them, which ensure the mentioned technical effects. However, this opinion was inaccurate. Still there are works in which the mentioned quality criteria are not taken into account, and it seems that the authors of these works do not know anything about these criteria, except for two - weight dosing of the components of nanocement and specific surface area of at least 400 m ² / kg. Moreover, heat dissipation of cements called “low water demand cements”, which determine their hydration in cement stone and concrete, is taken as an indisputable criterion, and they prove that its value when passing to such cements decreases compared to ordinary Portland cement of grade 500 [Khokhryakov O. V., Bakhtin M.A. On the role of changing the state of water in hardening cement of low water demand // Izvestiya Kazan GASU. 2011. No3 (17). S. 166-170], as is the case in cases of overdose of superplasticizers in the mixing water of cement paste or concrete. Thus, it is allegedly stated that the results indicated above in the listed sources, having international and academic approbation, as well as explaining their provisions, generally expressing the position of not only the authors of the works cited above, but also the common position of all the institutes of the cement industry of the Russian Federation and a number of others CIS countries, contained in the general scientific and technical report presented in the USSR Ministry of Construction Materials, 1992, are erroneous. It follows that the authors of new generation cements were not able to convey to the country's engineering and scientific community the basics of the technology for producing these cements, the above sources are incomplete, the data on heat generation during hydration of new generation cements are not mentioned clearly enough, and the criterial quality factors of these cements should include the heat release indicator as the most integral indicator characterizing the positive complex of construction and technical properties described above. The mentioned criticism should be considered, according to the authors of the present invention, essentially false (the facts about the particularly high quality of the new generation cements are undeniable), but fair in relation to the scattered form of their presentation in the mentioned sources. There is no generally accessible manual ([Manual, 1992, cit. Doc.] Had a print run) on the technology of new generation cements, which causes errors in the statement of work. So, the mentioned authors from Kazan State Autonomous University of Ukraine did not attach importance or did not find in the works [Ioudovich et al, 1997, op. cit.] and [Bickbau, 2008, cit. cit.], respectively, of mentioning that: a) vibration mills are not suitable for the production of nanocements, since they do not contribute to the grafting of naphthalenesulfonates on the clinker, and b) the need to check the presence of a free modifier (superplasticizer) in the finished cement, since this means that his grafting did not take place during the grinding process, and / or, in addition, in the presence of a free modifier when mixing the nanocement with water, the existing nano-shells are removed from the cement particles, which can be easily verified experimentally, adding to the mixing water of concrete or mortar based on nanocement a modifier already contained in nanocement. The result is exactly the one that was recorded in [Khokhryakov O.V. et al., 2011, cit. cit.] - retardation of hydration, decrease in strength, low persistence and, finally, explaining all this reduced heat generation, even in comparison with ordinary Portland cement. The absence of a free modifier, a necessary requirement, which we have to assume, was not fulfilled in the work [O. Khokhryakov, et al., 2011, cit. cit.], and this despite fixing it as mandatory in the works [Ioudovich V.E. et al, 1997, op. cit .; Yudovich B.E. et al., 1997, cit. cit.], as well as in the technical specifications for the WWII and CNV [1992 and 2001, cit. doc.]. The mentioned works of KSASU employees do not say anywhere that this most important criterion was met. That is why cement quality indicators, including storage and heat dissipation, were not consistent with the above mentioned positive effects.

A necessary conclusion from the foregoing is the joint mention in the present description of all the criteria for the quality of new generation cements (HVB, CNV, nanocement) known from the prior art and their addition with a criterion based on heat release during hydration, directly explaining their high hydration activity. For this, we consider in detail the methodological part of determining the heat release during cement hydration.

The method for determining the type of cement by heat during hydration was first proposed by T. Torvaldson et al., Who described their results in a classic four-part article [Thorvaldson T., Brown W.G., Peaker C.R. // Journal of American Chemical Society. 1929. V. 51. P. 2678; 1930. V. 52. PP. 80; 910; 3927].

There is also known a method for assessing cement belonging to a special type - for massive hydraulic structures (dams) by the amount of heat during hydration in the calorimeter, which should not exceed 60 cal / g after 7 days, or 60 · 4.18 J / cal = 250.8 J / g = 250.8 kJ / kg cement. This method proposed by [Woods N., Steinour N.N., Starke H.R. // Industrial and Engineering Chemistry. 1932. V. 24. P. 1207] and improved using a four-socket differential calorimeter in [Lerch W. // Proceedings of American Testing Materials. 1946. V. 46. P. 1252] was standardized as a criterion for cement with moderate exothermy in the USA (type IV cement) in the 1956 standard [ASTM C 150-56] with fixation as the norm of the above limiting heat release (60 kcal / kg). This norm was then standardized in Great Britain and the British Commonwealth of Nations [BS 1370: 1958]. To mix cement with water, the method uses a propeller stirrer installed in the calorimeter, which introduces an inaccuracy in the determination, since mixer switching parameters depend on the acceleration characteristics of the motor and the voltage in the network. Nevertheless, L. Copeland et al., Who included two authoritative groups of researchers led by prominent scientists from the USA and Great Britain, respectively S. Brunauer (member of the US Academy of Sciences and foreign member of the USSR Academy of Sciences) and F. Lee ( British Royal Society) [Copeland LE, Kantro DL, Verbeck G. The Chemistry of Hydration of Cement. // IV Internat. Symposium on the Chemistry of Cement. Wash. 1960 // Proceedings. 1962. V. 1. P. 429-442], we checked these results by another method - by the heats of dissolution of ordinary Portland cement in water and in a mixture of nitric and hydrofluoric acids on cements of various types, including type IV (with moderate exothermy) according to ASTM over different periods, and received data that almost coincided with the above. This testified to the reliability of the calorimetric method up to at least a 7-day hydration period with rational instrumentation. Now it has become possible to consider the maximum simplification of the latter to expedite practical use.

This is exactly what was done in the method of accelerated cement quality assessment by the criterion of heat release in a thermostatically controlled conductive calorimeter in a massive metal case [ed. testimonial. USSR No. 1229606, 1985], measuring thermal power with an electric measuring device for up to 3 days, i.e. accelerated compared with the previous 7-day determination, moreover, to mix cement and water, it uses a more reliable measuring cell with a tilting partition, providing instant wetting of cement with water [ed. testimonial. USSR No. 893247, 1979]. This, according to the author of the indicated calorimeter and cell V.M. Gurevich (Institute of General and Inorganic Chemistry, USSR Academy of Sciences), increases the reproducibility of measurement results by 20-30% compared with the previous method. From the point of view of the accumulated experience of using installations with Dewar vessels and propeller mixers (according to T. Torvaldsen et al.) And the latter method (according to V. M. Gurevich and [GOST 310.5-94. Cements. Method for determining heat release. Ed. 2003. Ed. . Standartinform. 6 p.]), Available to the authors of the present invention, the advantage of the latter in reproducibility is not so great compared to the previous ones, but the simplification of the determination procedure is undoubtedly due to the rejection of the mixer and the simple design of the measuring cell. That is why, in our opinion, the latter method was reasonably used in the specified RF standard [GOST 310.5-94]. Judging by the heat transfer diagram of Portland cement given in this publication, called there “curve of deviation of the pen of the recorder”, the first peak (exothermic effect) of heat generation, which, according to [Bogue R.N. The Chemistry of Portland Cement. New York: Reinhold. 1955. 793 p., See pp. 591 a. else], associated with the wetting of the surface of the cement particles with water, lasts for about 5 to 40 minutes after mixing the cement with water, after which the so-called induction period begins (term of W. Hansen, 1929) - suspension of hydration with a temporary minimum level of heat release.

In the most comprehensive review of the heat release of cements and concrete [Mchedlov-Petrosyan O.P., Usherov-Marshak A.V., Urzhenko A.M. Heat release during hardening of binders and concrete. M .: Stroyizdat. 1984. 225 pp.] With a close to the modern standard method for estimating heat release, the specified peak for coarse-ground and belite cements shifts to 50-80 min after mixing with water, and for especially finely ground alite cements, it starts after 3 minutes and ends after 30 minutes . In all cases, this peak is single.

The fact that in the latest standards for cement with moderate heat release, or sulfate-resistant Portland cement, in contrast to the previous works cited above, is not limited to heat release, but only the content (in wt.%) Of the hydrationally most active phases in the clinker: alite (C ₃ S ) - not more than 50 and C ₃ A - not more than 5 for sulfate-resistant and not more than 8 - for cement with moderate heat generation (then the last norm in the USSR was transferred from the standard to SNiP), which means that scientists and practitioners are completely sure that what is the relationship of the calculated mineral ogicheskogo composition of clinker and cement heat is rigid (unambiguous) enough to limit the amount of active minerals in the clinker and the cement, then heat will limit itself. But in the last decade of the XX century. and in the first decade of the XXI century. fuel economy for clinker firing (the share of fuel costs exceeded 40% of the cost of clinker) increased so much that it began to cause a burn, which turned into a global problem due to the appearance of marginal phases in the clinker (term in [Entine et al, 1997, op. cit. ; Entin 3.B. et al., 2007, cit. Cit.]), Which increase the heat release without regard to the calculated mineralogical composition of clinker and cement based on it. Thus, the relationship of the mineralogical composition of clinker with the heat release of cement again ceased to be rigid, as was the case in the 30s and 80s of the 20th century. Currently, clinker mineralogical composition (wt.%) Is again normalized for cement with reduced heat release: C ₂ S 65-80, C ₃ A + C ₄ AF 9-16, C ₃ S 2-6, and heat release - not more than 310 kJ / kg [Japanese Patent No. 2011112094, 2011]. Due to the better control of the composition of the raw materials and the ultra-low content of alite in the clinker, this technical solution adopted a less stringent heat release rate (instead of 250 kJ / kg - 310 kJ / kg).

The tendency to erosion of the mineralogical composition of clinker with the technical properties of cement in the XXI century. reached its climax, which is characterized by the following technical solution [Japan patent No. 2007271448, 2006], describing a method for accelerated evaluation of cement quality and a quality control method using this assessment. According to this patent, a cement plant regulates the quality of its products using a regression model that takes into account the quantitative characteristics of the following groups of factors: the mineralogical composition of clinker, the material composition of cement, the microstructure of clinker minerals, the content of clinker in small components, the dispersion of cement according to two factors - specific surface area and residual size on a sieve with cells of 45 microns, and the plant evaluates the products according to these factors, parameterizable strength indicators. This multifactorial dependence is used for current cement quality control by comparing the strength predicted by the model and indicated in the certificates of shipped products with the actual strength values determined through the standard hardening periods (2 and 28 days). It should be noted that this is a large amount of work even for modern computer technology, requiring well-functioning technical control at all stages of the production process, with the exception of raw material redistribution, which can be considered a drawback of this technical solution.

To this we add that the Research Institute of Cement and the Sebryakovsky Cement Plant in 1979 [Scientific and Technical Report of the Research Institute of Cement. M: 1979, on contractual topic No. 9-78: "Improving the quality of cement at the Sebryakovsky cement plant with the release of a pilot batch of high-strength Portland cement grade 700". Performers: from the lab. special cement B.E. Yudovich, from the lab. firing I.A. Prozorov with the participation of the cement plant II. Senichkina, V.A. Churyumova, A.M. Dmitrienko and N.A. Bezrodny] used a technical solution similar to the last of the above ones with much lower computational capabilities of the then Cement-1 computer, composing a regression model of 23 parameters of cement production, including the chemical composition of the raw mix components for the main oxides - CaO, SiO ₂ , Al ₂ O _3, Fe ₂ O ₃ and SO ₃ and the impurity within 1 month using the regression relationship and 3-day branded (28-day) cement strength and other quality parameters - timing setting, normal density test, and t kzhe strength after heat and humidity treatment (TVO, steaming) for the standard mode 2 + 3 + 6 (85 ° C) +2 h (shutter speed, temperature rise, isothermal heating, cooling) of all 23 parameters. The hydration rate was also among the parameters, but was estimated not by heat release, but by the content of hydrolytic Ca (OH) ₂ in the cement stone after 3 days of hardening. Unfortunately, the work was left without implementation, despite the release of a production batch of cement of grade 700 (according to the old evaluation method, or 550 according to the modern evaluation method) due to a lack of sensors and difficulties in tracking the entire set of parameters. Original results were obtained, for example, the dependence of the cement strength after TBO on the content of Fe ₂ O ₃ in clay, which was explained only after 50 years. Thus, the noted work of Japanese specialists turned out to be a development of the domestic development unknown to them above. Such quality control is also useful in the production of nano-cement, although its implementation under production conditions at the current level of development of the domestic cement industry is difficult.

From the cited literature, an already existing and unremitting tendency to determine the quality of cement by assessing the amount of heat during hydration is already 80 years old. It follows that the quality of nanocement by the heat of hydration can also be determined quite accurately, but subject to a real determination of its value, without calculation by phase or mineralogical compositions. However, this requires an express method that is affordable and convenient for the factory laboratory. It is this approach that underlies the present invention.

Its analogue is a cement production method with a criterion quality assessment by the amount of heat generated during hydration during setting, determined in a calorimetric installation by recording the temperature rise of the cement paste [Yudovich B.E., Vlasova M.T., Vovchok G.I. and others. Ultrahigh-hardening cements for monolithic and precast concrete. Overview. M .: Publishing. TsINIS Gosstroy of the USSR. 1978. 60 S.], in which the value of heat Q (determined in the simplest measuring cell from a thermocouple, a Dewar vessel and a vessel (cup) placed in it with a cement-water mixture at W / C 0.4) during the period from the beginning of mixing until the end of setting (about 40 min, Q ₄₀ ) the level of strength was predicted - from 6- and 12-hour to 1- and 3-day - of the mentioned ultrahard-hardening cement, including, in addition to alite, belite, traces of C ₃ A and 2-3 wt . % C ₄ AF, as the most important phase, fluoromeinite C ₁₁ A ₇ · CaF ₂ from 12 to 20 wt. %, which gives this cement the property of particularly rapid hardening during quick setting - start from 5 to 15 minutes, end - after 20-40 minutes. It was found that when Q _{40 is} not lower than 90 kJ / kg, the strength of cement after 6 hours is not lower than 5 MPa. This method then found short-term practical application: after all, it is usually inconvenient to test the strength 6-12 hours after the cement has been mixed with water, since a highly qualified laboratory assistant has to work up to 16 hours / day for this. However, strength after 1 day is also considered to be a quickly determined characteristic of cement, in particular, for the main area of its application at that time - in concrete coatings of platforms for taxiing aircraft at airfields. There, knowledge of 1-day strength was sufficient. After 6 years, this cement was replaced during repairs with an expanding type of cementitious mixture, including alumina cement, Portland cement and asbestos fiber, developed by Y.N. Novikov et al. [Novikov Y.N., Mogilevsky V.D., Petrov Yu.N. and other instructions for waterproofing precast and cast-iron lining of undergrounds of the closed method of work. M .: Glavtonnelmetrostroy. 1984. 137 p., Pp. 2.11-2.13: Quick-setting sealing compound (BEAD)] used by Mosmetrostroy to date. The BUSH sets and hardens as fast as fluorinated cement, but is more crack resistant due to the presence of asbestos. There, due to round-the-clock work, strength tests at the age of 6 hours were not difficult, therefore Ya.N. Novikov told one of the authors of the present invention that although the determination of cement heat release in the composition of the SCC for the compositions used is useful in order to verify and stabilize the work of the SCC producing Ochakov Mosmetrostroy plant, it is not necessary, since the next change will recognize the strength of the SCC in the workshop laboratory in fact, and manufacturers of works in tunnels, after warning about incomplete compliance of the quality of busbars with the requirements of technical documentation, have time to increase the degree of compaction of not quite good quality C when minting seams between blocks or tubing of the tunnel lining to obtain a given level of water resistance. Mosmetrostroy is currently trying to replace asbestos in the busbar with a more environmentally friendly fiber.

Another analogue of the invention in terms of the method is a method of manufacturing cement by co-grinding the clinker and calcium sulfate components at least to a specific surface of 400 m ² / kg and continuing to grind until the calculated value of the normalized strength of the obtained cement (R) is reached by the heat release criterion (Q) when it hydration during setting in a calorimetric cell with recording the temperature of the cement-water mixture during setting, moreover, the water-cement ratio of the mixture (W / C) is taken to be 0.32, and Strength score is linearly calculated:

R = aQ-b,

where a and b are constant coefficients depending on the period of testing the rated strength [Romanian Patent No. 122320, 2009]. The setting time according to this technical solution is in the range from 0.45 to 3 hours only in the presence of calcium chloride, without which, at the indicated value of W / C, the setting time is delayed up to 4-7 hours, which prevents the expressness of the method. The choice of W / C equal to exactly 0.32, according to the authors of the prototype, allows to exclude the influence of random factors such as false setting (58 reasons for false setting were previously known according to the list of J. Kalousek [Kalousek GL Abnormal set of Portland Cement, causes and correctives. Ed . US Department of the Interior, Bureau of Reclamation. // General Report No. 45. Denver. 1968. 33 pp.], When clinker is not burned, ten more are added to them) or fluctuations in the material composition of cement.

For the aforementioned fluorine-containing cement and its normative strength R = 5 MPa in 6 hours with a specific surface of 400 m ² / kg in this dependence Q = 90 kJ / kg, a = 0.055; b = 0, with a range of estimates of R ± 0.3 MPa (12%). For nanocement, such a regression dependence does not allow reliable convergence of the experimental data due to the fact that the preliminary conditions (the absence of a free modifier in the sample and the constant degree of particle aggregation at a specific surface of 400 m ² / kg) may not be fulfilled. Therefore, this technical solution is not suitable for evaluating it, although if the above technological conditions are met and the tolerance is much larger than the ordinary Portland cement, the variance of estimates (more than 20%) is more suitable due to its simplicity than, in particular, it is much more complicated to methodically, accelerated assessment of cement quality by the conductivity of cement paste and other cement-water systems in combination with measurements of the heat of hydration [Berdov G.I., Aronov B.L. Express control and quality management of cement materials. Novosibirsk: Publishing House Novosibirsk, state un-that. 1992. 252 pp.] With approximately the same accuracy of strength assessment. In addition, the suspension of grinding, even in commissioning tests, required to select the time to reach the set value of R and, accordingly, determine the value of Q with the subsequent calculation of the values of a and b in production conditions, is difficult to achieve.

The closest analogue of the invention (prototype) in terms of the method of production of nanocement is a method of producing cement of low water demand (as mentioned above, it is almost a synonym for the term "nanocement") by co-grinding clinker containing alite, belite, calcium aluminate and calcium aluminoferrites with a naphtha modifier -linsulfonate type, filler and gypsum. As a result of joint grinding to a specific surface of 400-600 m ² / kg, a nanoscale shell is formed on clinker particles. In this case, the modifier is throttled and it interacts with the radicals and active centers of the mushroom-activated particles of clinker minerals with the formation of a continuous nano-shell from the adsorption complex on the surface of the clinker-mineral particles (by a nano-shell we mean a film up to 100 nm thick) [M. Bikbau. Nanotechnology in cement production M .: IMET. 2008. S. 538-560, 584-585]. For all the advantages of the method and the resulting product described above, it does not provide for an express evaluation of the finished product, which does not require a preliminary determination of its strength indicators. And without this, only the accumulated experience of constant cement production in accordance with the given technological parameters remains the only guarantee of the quality of the material, which is insufficient when the quality changes of cement components always occur in production conditions.

The present invention is free from these disadvantages. It consists in the fact that in the method of manufacturing nanocement according to claim 1 by co-grinding these components with quality control in successively selected samples of the finished product, grinding is carried out until two indicators are achieved - completeness of coverage of the said nanoshells with the specified diffuse layer, fixed by the quantitative criterion of the minimum degree aggregation of particles coated with the indicated nano-shells, determined in the grinding product by the method of breathability, and continue grinding until the second indicator is reached - p the completeness of the coating of the clinker component particles with the etched mineral phase layer, fixed by the criterion for the appearance of a double maximum on the temperature recording chart in the calorimetric cell during heat release, determined by the thermostatic conductive calorimetry method, during the setting of the cement test prepared from sequentially selected samples of the grinding product.

In an embodiment of the method of manufacturing nanocement, said grinding is carried out with fixing a minimum degree of aggregation of the product equal to 5-20 vol. %, and continue grinding until registration in the finished product named double maximum on the specified schedule for 1-3 hours

The essence of the invention in terms of the method of manufacturing nanocement is determined by the double thermal effect when mixing the cement in question with water and during the setting process of the suspension obtained with this with cement-water (synonymous with cement paste). The first of the mentioned effects (a synonym for extrema on the heat release graph) is caused by the removal of water of three-layer nanoshells (nanocapsules) from the surface of particles with the separation of functions of each layer specified above in the description during the removal process. The second is associated with accelerated hydrolysis of the surface of cement minerals free of nanoshells, etched by nanoshells and the seed role of the TMF layer mentioned above. Thus, the presence of a double thermal effect is a sign of the completeness of coverage of the surface of clinker particles of nanocement with three-layer nano-shells. This is the reason for the radical water-reducing effect of nanocement (which gave rise to the name “binders of low water demand”) in cement-water suspensions, which include both cement dough (paste) and mortar and concrete.

Note that to obtain nano-cement coated with three-layer nano-shells with the above described complex of construction and technical properties, not every grinding device is suitable. The suitability of tube mills with certain grinding conditions, in particular with limited suction, was studied. Jet mills and similar impact grinding devices are unsuitable for the manufacture of nano-cement of the reduced composition, since the short contact times of clinker particles with grinding surfaces, even if they are also represented by clinker, as in jet mills, does not allow gluing of the modifier based on naphthalene sulfonates to the clinker, because, as described above, this is a multi-stage process. However, this applies to a modifier based on naphthalenesulfonates. It is possible that modifiers on a different chemical basis, including liquid ones, will be able to adhere even with short-term contacts and high impact speeds and, accordingly, with short-term grinding effects. In other grinding devices with an intermediate grinding time between ball and jet mills, an experimental test of suitability is required based on test grindings of the mentioned composition of the Portland cement clinker, modifier, calcium sulfate component and mineral additives with observations of a practically absent (or presence) as non-aggregated particles (in particular, with quantitative measurements on a PSC-type instrument), as well as the double maximum on the heat plot dividing the cement-water mixtures during their curing. The presence of these two effects indicates the suitability of this grinding device with these operating parameters for obtaining nanocement according to the invention. For the indicated compositions without mineral additives and fillers, the aforementioned minimum degree of aggregation usually corresponds to less than 5% on a PSC instrument (G.S. instructions of the company LLC “Khodakov” [http://www.khodakov.ru]). The observation period of the double maximum on the heat release graph of compositions without mineral additives in the instrument of the V.M. system Gurevich, standardized in GOST 310.5-94, or in the new edition of GOST 30744 and used according to [RF patent, 1986, cit. cit.] and the standards mentioned, is usually less than 1 hour. For compositions with the aforementioned mineral additives, the specified minimum degree of aggregation corresponds to 5-20 vol. %, since the presence of unencapsulated particles of mineral additives increases the lower limit of the disaggregation of nanocement. The same unencapsulated particles reduce the fraction of alite nanoblocks on the surface of nano-cement, promoting the interaction of mixing water freed from the nano-shells with mixing water with the transition of these nano-shells, consisting of a modified modifier, to hydration products. This is the reason for the slowdown in heat release of nanocements with mineral additives and fillers and the extension of the setting time of the cement-water suspension and, accordingly, the observation period of the mentioned double maximum, which according to the invention is 1-3 hours

After both of the above effects have appeared on the finished product, the grinding process is fixed in the established stationary mode of the grinding device. To do this, using the process control system, which should be equipped with a grinding device for the production of nanocement, determine the set of operational indicators characterizing the stationary state of the grinding process in the grinding device used. These include the performance of the grinding device, the composition of the specified composition, such parameters of each of its inorganic components (type, chemical and particle size distribution, microstructure, submicrostructure, humidity). An even more rigorous approach should be to the choice of an organic component - a modifier based on naphthalenesulfonates. It is necessary to take into account the color of the powder, the gloss of the particles, the passport data, in particular, the value of the initial MM, the content of sodium sulfate, and also the impurities of the original formaldehyde (in the absence of relevant data in the passport, a rough estimate is possible by a characteristic odor). The color of the naphthalenesulfonate particles is indirectly related to the yield of the useful substance in the synthesis process. When it is not completely carried out and the product contains an admixture of the starting formaldehyde, such a modifier has a lighter color in the range from brown - the color of instant coffee - to straw yellow. Gloss of particles indicates the normal course of the drying process of the solution of the intermediate in the fluidized bed until the product. The presence of black cores in the particles of the modifier indicates its burning during drying, and from the surface the burned core is covered with a yellow layer relative to a suitable product that has managed to cool, and the core is charred due to slower cooling. This is the conclusion of chemists from the University of Limerick (Ireland), whose work, at the request of the inventors, was paid for by CRH. Such naphthalenesulfonate particles do not have a characteristic luster and are able to aggregate and stick in the hopper above the weighing batcher. In a usual situation, the weighted dosage of naphthalenesulfonate powder goes without problems.

On the indicator devices of the process control system (examples of such process control systems are presented in [Duda V.G., 1987, cit. Cit.]), The parameters of the aforementioned set are fixed by means of the settings on the processors in the computer, which regulate the material composition of the specified composition of the nanocement and the operation of the grinding device. So, the machine determines the feed rate of the material into the dispensers, observes their ratio, the stationarity of their parameters, monitors the operation of suction fans, filters, devices for transporting the finished product: unloading augers, conveyors, etc.). After this, the grinding is continued with computer control according to the selected mode with periodic visual observation by the operator of the grinding device of the parameters of a continuously conducted process record (usually it is sufficient to analyze the grinding mode twice a shift) until the material composition of the nanocement and / or the characteristics of its components change, after which the named process selection of the specified grinding mode is repeated.

durch Verschleiss von Panzerplatten // Zement - Kalk - Gips. 1958. V. 11. №3. S. 118-121 и многие другие], водопадный режим работы мельницы для эффективного режима помола не только не обязателен, но даже не вполне желателен [Rolf L., 1993, op. cit.], в частности, и для получения наноцемента. Currently, as a grinding device, a tube mill with freely moving grinding bodies operating in an open cycle (with a single passage of co-milling materials), or, more efficiently, in a closed cycle with a separator that returns a coarse fraction of the crushed material to the mantle ( Krupka) [Krykhtin G.S. Grinding cement. In the book. Handbook of cement production. Ed. I.I. Choline. M .: Gosstroyizdat. 1963. S. 333 and below]. Since it has now been established that the main working area of the mill is not the so-called “heel” of the waterfall part of the grinding media layer, but the contact zone of the bulk of them with the milled material at the rise of the indicated mass of grinding media to the lining at each revolution of the mill, where they are kept centrifugal forces and the downward vector of gravitational force [Rolf L. Motional and stressing phenomena in ball mills // Zement - Kalk - Gips. 1993. V. 46. No. 5. PP E127 - E132 (Engl, version). See also Germ. vers. ibidem, No. 3. S. 117-122]. Rolf's classic work, based on direct measurements of the pressure of grinding media on the milled material by means of radio dynamometers built into the hollowed-out cavities of the balls, closed by spherical spring caps [Rolf L. Instrumentation of balls for measuring of energy distribution in ball mills. // Chemische Technik. 1999. V. 51. No. 5. P. 238], testifies that, contrary to the well-known old, purely speculative views [Naske S. Zerkleinerungs - Verrichtungen and Mahlanlagen. Leipzig, 1918; Deshko Yu.I. etc. Grinding materials in the cement industry. Ed. 2nd. M .: Stroyizdat. 1966. 271 s .; Zeisel N.-G. Veringerung des

durch Verschleiss von Panzerplatten // Zement - Kalk - Gips. 1958. V. 11. No. 3. S. 118-121 and many others], the waterfall operation of the mill for an effective grinding mode is not only not necessary, but not even completely desirable [Rolf L., 1993, op. cit.], in particular, and to obtain nanocement.

From this new point of view, the application of the so-called high-energy tube mills for the manufacture of nanocement was tested:

- with planetary [http://www.leotec.ru/catalog/index.php?SECTION_ID=1174], the location of the grinding chambers around the axial, where the combination of gravitational and centrifugal forces acts on the mass of grinding bodies, and through it on the crushed material , or

- with the internal location of one or more grinding chambers in the axial chamber (example with a single camera [High energy ball milling. GIF. User (author): Luu Ly. 2008], due to its special importance it is included in Wikipedia - see [http: //www.google.com/imgres?imgurl=http://upload.wikimedia.org/wikipedia/commons/4/4f/Highenegy_ball_milling.gif&imgrefurl=http://en.wikipedia.org/wiki/Ball_mill&h=206&w= 206 & sz = 64 & tbnid = g3wDLtjQQL4ZPM: & tbnh = 77 & tbnw = 77 & zoom = 1 & usg = _vDj6WJlzpkKMSwqW_iWJDS_btWQ = & docid = rjGZQaZWqGY4QM & sa = X & ei = hm-aUaHOE8SM4ATT4oEw & ved = 0CFYQ9QEwAQ & dur = 6372]), it opens not only on the direct address, but also when typing the author's name in the search engines . In the last example, in addition to the mass of grinding media, which acts on the material being crushed by gravitational, inertial forces and the Coriolis force, which is caused by the rolling of the internal grinding chamber along the lining of the axial chamber, the atmosphere in the inner chamber also affects, because of the tightness, freed from CO ₂ impurities. And this is useful for both the strength and durability of the concrete obtained [Kantro DL et al. The ball mill hydration of tricalcium siliucate at room temperature // Journal of Colloid Science. 1959. V. 14. PP. 363-376. Malinin Yu.S. and others. On the morphological foundations of the structure of cement stone. // Reports of the Academy of Sciences of the USSR. 1977. T. 233. No. 4. S. 653-656]. In a centrifuge-type mill (centrifugal-impact grinding), the main grinding effect — centrifugal-impact with a crushing stage — is ensured by the fall of particles, including composite cements, into the grinding chamber and by centrifugal force, which throws the crushed material onto the crushed layer and presses the crushed material to the lining [Garkavi M. et al. Mischcemente auf Basis von Elektrostalwerkschlacken durch Tzentrobezhno-Stosszerkleinerung / 17 Internationale Baustofftagung. Weimar. 2009. P. 1-0609 - 1-0612].

When grinding nanocements under their former names - VNV and TsNV - it was not allowed to introduce grinding intensifiers as technological additives due to their prevention from sticking naphthalenesulfonate modifier to clinker and a sharp decrease in product quality. However, the authors of the present invention found that if the adhesive bond is achieved, then neither water vapor nor surfactant grinding intensifiers in powder or dissolved form, when sprayed with nozzles, do not harm the quality of nanocement, and can reduce the energy consumption for grinding at least on 10%. So, an additional grinding intensifier is introduced at the grinding stage with a specific surface of the material being crushed not lower than 370 m ² / kg by injection in powder or liquid state from the side of the outlet pin of the mill when working in an open cycle or onto a separator grain returned to the mantle when working in closed cycle (the latter option requires the design of sequential or parallel operation of several mills, as NIICement practiced in the 80s). The grinding intensifier is even more effective when it is injected onto the indicated active mineral additives, introduced in the ground state into the ground composition or onto the separator grain returned to the mantle. This allows, as shown for the modified lignosulfonates of the LSTM-2 type as a grinding intensifier (0.07-0.1 wt.% Of the clinker fraction in nanocement), to increase the productivity of the Doppel-rotator separator mill to a much greater extent, and by 15-25% both in a powdered state (there were difficulties in dosing and feeding due to stickiness), and in the form of a 30% aqueous solution for said grains with its specific surface area of at least 250 m ² / kg and the specific surface area of the finished product product 430-450 m ² / kg as compared with the process of grinding without intensifier.

Note that to control the process in the implementation of the present invention, the following are used and are recommended for its implementation:

- To determine the degree of aggregation of nanocement - G.S. Khodakova (PSX), in particular, devices from PSX-2 to PSX-11, see [http://www.khodakov.ru/index.php?option=com_content&task=view&id=39&Itemid=217]. Determining the degree of aggregation using this device - according to the method described in [L. Vatutina et al. Determination of the degree of aggregation of cement particles by the method of breathability. / Proceedings of the Research Institute of Cement: "The use of physical instruments and methods in the study of clinkers and cements." 1987. No. 91. S. 221-238. See also Auth. testimonial. USSR No. 1250917, 1985]. In addition, one can be guided by the flowability index defined in the same device, which is a quantity that has physical meaning in the systems of units MKS or CGS [Yudovich B.E. et al. Determination of flowability of cement using the method of breathability. / Proceedings of NIIcement, 1987, cit. ed. S. 238-245]; while the maximum flowability corresponds to the minimum degree of aggregation of nanocement;

- To determine the dynamics of heat release - using the method of thermostatically controlled conductive calorimetry in the device of the system V.M. Gurevich [Aut. testimonial. USSR No. 1229606, 1986]. Methodology in accordance with GOST 310.5-94 as amended. 2003 can be used in the absence of an observer after the start of the test due to the continuous recording of the thermal power of the process of heat release of nanocement.

It should be added that with the established regime of grinding nano-cement, the use of simplified options for determining both of the mentioned criteria is allowed. So, instead of the minimum degree of aggregation of particles of nanocement for a rough assessment of the finished grinding product according to this criterion, it is possible to measure the angle of repose of the cone of the finished product, a portion of which is poured into the top of a cube model made of papier-mâché, cut out like a protractor with a zero point at the top of the corner and compared slope angle of the original cement without a modifier with smaller slope angles of the finished product. To be sure of the results, it is necessary to purchase nanocement, produced at certified plants, in order to have an idea of the slope angle of nanocements of various material composition, including those containing no mineral additives and fillers and including them in the material composition, and to calibrate a similar model of the probe. In an established operating mode, to control the method of manufacturing nanoc cement for heat dissipation, the present invention can also use a simple installation consisting of a Dewar vessel and a thermometer fixed in a tripod, or a thermocouple lowered into a cement paste placed in a vessel in a thin polyethylene liner for a while, while the dough has not yet set. Two heat dissipation maxima are visible on thermometers or thermocouples of any systems, but require continuous monitoring for up to 3 hours from the moment the nanocement is mixed with water, which, of course, takes the operator’s time and requires attention, but is suitable for monitoring the operational mode of operation.

We emphasize that if there are two, described above, product quality criteria - nanocement, recorded during the implementation of the method according to the invention by means of these devices, all the above-described technical and economic effects of the use of nanocement are guaranteed. Then the need for continuous and even selective quality control of samples of nanocement under a scanning electron microscope disappears. It can be reduced to inspections 1-2 times a year.

The foregoing is confirmed by the examples of the invention presented in table. 2-4.

Example 1. Cement according to TU on CNV [cit. cit.] according to the prototype {thickness of nanoshells up to 100 nm using a GEOL scanning electron microscope} based on a pilot clinker 1 (wt.%) 87.7, two-water gypsum 4.9 in terms of SO ₃ , or 4 9 × 2.15 = 10.5 ¹ ; ( ¹ See note 4 to table. 2) and modifier 1.8; clinker included according to petrographic analysis (wt.%): Alit 50, Belit 20, C ₃ A 15, C ₄ AF 15, M - SP-1 of the Novomoskovsk plant; control - without mineral additives, 5 batches, average data, fluctuations in 28-day strength within 6 MPa, increasing after 6 months. storage up to 8 MPa (table. 2, lines 1 and 2), which does not guarantee the strength class (grade) of cement and leads to an increase in average cement consumption in concrete by an average of 12%, since this is a difference in standards [SNiP 82.02- 95 Federal (standard) elemental norms of cement consumption in the manufacture of concrete and reinforced concrete structures] is provided for when reducing the quality of cement on the brand. This is the disadvantage of cement according to the prototype and, at the same time, the method of its production, since quality control under a microscope does not guarantee the homogeneity of the material in individual samples, although other integrated control methods proposed in this technical solution are also, although, as shown below, to a much lesser extent, they do not completely protect against heterogeneity of cement quality. To eliminate the heterogeneity and guarantee the stationarity of the quality of Portland cement at a spread of 2 MPa (that is, the fluctuation range is ± 1 MPa), achieved, according to the information of Giprocement-Nauka LLC [L. Bernshtein Report on missions to cement plants in Germany and the USA. Scientific and Technical Report, 2009, as a manuscript; publication is expected], at one of the 12 visited cement plants, more than $ 90 million was spent. The level of swing of the 28-day cement strength ± 1 MPa is, according to the general opinion of the cement industry workers, a world achievement. Such stability of product quality allowed the use of 26 types of various additives in technological fuel at this cement plant to reduce its share of its cost in the cost of Portland cement clinker, which had previously reached 40%, as is the case at many other enterprises. In the case of nanocement according to the invention, a decisive effect is achieved, in addition to reducing the variation in product strength compared to the prototype, improving the quality of clinker, which, while reducing the clinker factor (this term has gained worldwide distribution over the past decade, although, according to available information, has not yet been standardized anywhere ; it means wt.% of the clinker component in the cement and was, for the first time, essentially introduced into the technical conditions of four development institutes at the VNV in 1986 at the proposal of NF Bashlykov, and now presented in draft at predstandarta nanomodified cement developed under the leadership of MJ Bikbayev [op. cit.], wherein the clinker factor is included in the designation of cement species), reduces the scatter of strength, especially after prolonged storage.

The second series of samples of nanocement according to the prototype was obtained by co-grinding the specified clinker with a filler - quartz sand (3 samples). Cement composition (wt.%): Clinker 50 (clinker factor 50), quartz sand 44.8, gypsum stone 2 (according to SO ₃ ), or 2 × 2.15 = 4.3; modifier 0.9. The remaining indicators are presented in table. 2 (lines 3 and 4). The activity of cement compared to cements in rows 1 and 2 of the same table decreased, but most importantly, the quality spread increased at 28 days of age, especially after long-term storage.

Example 1a In the next series of experiments, the nanocement according to the invention (Table 2, lines 1a - 1e) is made of Portland cement clinker of a similar mineralogical composition, obtained using a raw mixture of increased reactivity, achieved by replacing part of the pyrite cinder in its composition with blast furnace dust. It is known that in this case, the aluminoferrite phase often acquires a lamellar submicrostructure, alite and whiteite become finely crystalline, and the blocks in them acquire sizes that fall within the range of 1–3 μm, as was observed. Nanocement was made by measuring the degree of aggregation and heat release during setting. A total of 14 batches of cement of various compositions (wt.%) Were produced without mineral additives with a calcium sulfate component in natural and artificial forms and in their mixtures, as well as with mineral additives (MD); of each composition, six samples were taken, of which three samples were tested immediately after manufacture, the rest after 6 months. air storage storage:

No. 1a: clinker 96 (the example is included for reference, since cement does not contain the mineral additive required according to the invention, the data are given for comparison), two-water gypsum in the form of gypsum stone (93%, impurities - the rest) 1.5 (wt. % by SO ₃ ), i.e. 1.5 × 2.15 × 0.93 = 3 (wt.%), M 1, only 100%; double exoeffect on the heat release graph (DEGT), the last maximum after 0.65 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 800 Yes, MM diffuse layer approx. 600 Yes (Table 2, lines 1a, 1aa);

No. 1b: clinker 88, MD: blast furnace granulated slag (DGS) of the Orsk-Khalilovsky Metallurgical Plant 5, two-water and semi-water gypsum in a ratio of about 1: 1 by weight in the form of 93% (impurity - the rest) conglomerate 2.6 (by SO ₃ ), i.e. 2.6 × (2.15 + 1.6) × 0.5 × 0.93 = 4.5 (wt.%), M 2.5, total 100%; double exoeffect on the heat release graph (DEGT), the last maximum after 1.1 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 800 Yes, MM diffuse layer approx. 600 Yes (tab. 2, lines 1b, 1bb);

No. 1c: clinker 88, indicated by DGSh 5, two-water and anhydrous (anhydrite) gypsum in a ratio of about 1: 1 by weight in the form of 93% (impurity - the rest) conglomerate 4.5 (SO ₃ ), i.e. 4.5 × 2.15 × 0.5 × 0.93 = 4.5 (wt.%), M 2.5, total 100%; double exoeffect on the heat release graph (DEGT), the last maximum after 1 h; MM measurements using gel chromatography according to A.I. Vovka approx. 800 Yes, MM diffuse layer approx. 600 Yes (tab. 2, lines 1c, 1cv);

No. 1g: clinker 88, specified by ДГШ 5, a product for the purification of waste sulfur dioxide from industrial furnaces with calcium carbonate (including, wt.%: Anhydrous calcium sulfate 88, calcium carbonate 10, impurities - the rest) 5 (SO ₃ ), i.e. 5.0 × 0.88 × 1.12 = 5 (wt.%), M 2, only 100%; double exoeffect on the heat release graph (DEGT), the last maximum after 1.2 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 800 Yes, MM diffuse layer approx. 600 Yes (tab. 2, lines 1 g, 1yy);

No. 1d: clinker component 88, indicated by DGSh 5, a mixture of gypsum stone, that is, two-water gypsum (93%) and phosphogypsum (including, wt.%: Two-water calcium sulfate 98, phosphates in terms of P ₂ O ₅ 0.8 , impurities - the rest) in a ratio by mass of 3: 1 2.7 (by SO ₃ ), i.e. 2.7 × 2.15 × 0.93 × 0.75 + 2.7 × 2.15 × 0.98 × 0.25 = 5.47 ≈5.5 (wt.%), M 1.5, only 100%; double exoeffect on the heat release graph (DEGT), the last maximum after 1.35 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 800 Yes, MM diffuse layer approx. 600 Yes (tab. 2, lines 1e, 1dd);

No. 1e: clinker 88, indicated by DGSh 5, a mixture of gypsum stone, that is, two-water gypsum (93%) and phosphogypsum (including, wt.%, Semi-aqueous calcium sulfate 95, phosphates in terms of P ₂ O ₅ 0.6, impurities - the rest) in a weight ratio of 1: 1 2.95 (SO ₃ ), i.e. 2.95 × 2.15 × 0.93 × 0.5 + 2.95 × 1.6 × 0.95 × 0.5 = 5.19 ≈ 5.2 (wt.%), M 1.8, only 100%; double exoeffect on the heat release graph (DEGT), the last maximum after 1.25 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 800 Yes, MM diffuse layer approx. 600 Yes (tab. 2, lines 1e, 1ee);

No. 1zh: clinker 88, indicated by DGSh 5, a calcium sulfate component — a mixture of: a) a calcium carbonate purification product — crushed natural limestone — waste sulfur dioxide from industrial furnaces and / or reactors in non-ferrous metallurgy (production of non-ferrous metals from sulfide ores), production mineral fertilizers, petrochemicals, including less than 4 wt. % SO ₂ (more concentrated off-gases go to the production of sulfuric acid); purification product - a mixture of calcium sulfate, lime, residual calcite and impurities; there is experience of its use in the cement industry of Germany as an additive to Portland cement clinker as a regulator of setting time; b) phosphogypsum - according to example 1e; the technical effect is due, firstly, to the fact that an admixture of lime in component “a” neutralizes an admixture of phosphoric acid in component “b”, which prevents excessive retardation of cement hardening with soluble P ₂ O ₅ ; secondly, the fact that the mixture of lime and limestone from component “a” facilitates the granulation of phosphogypsum “b”, which does not contain the gel-forming component, necessary for the stable granulate required by the cement industry; ready calcium sulfate component (mixture "a" + "b" 1: 2) includes, by weight. %, calcium sulfate anhydrous 20, calcium sulfate semi-aqueous 60, residual calcite 10, lime 5, impurities 5, including insoluble calcium phosphate; its moisture content is 10%; the content of granules of the composite sulfate-calcium component in nanocement is 2.95 (by SO ₃ ), i.e. (2.95 × 1.42 × 0.2 + 2.95 × 1.6 × 0.6) × 12 × 1.1≈4.8 (wt.%), M 2.2, total 100%; double exoeffect on the heat release graph (DEGT), the last maximum after 1.15 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 800 Yes, MM diffuse layer approx. 600 Yes (tab. 2, lines 1zh, 1zhzh).

Example 2. Laboratory grinding cements were made from industrial Portland cement clinker with a calculated composition (wt.%): Alit 65, belite 14, C ₃ A 6, C ₄ AF 13, impurities 2, actual composition (by petrography, wt.%): Alit 65, whitewash 15, an intermediate substance (the sum of aluminates and aluminoferrites with impurities - small components (R ₂ O, that is, Na ₂ O and K ₂ O, MgO, SO ₃ , TiO ₂ , etc.) 20, with block sizes the first two phases of 0.3-2 microns, with the glassy third and lamellar submicrostructure of the fourth phase, M - SP-1 of the Pervouralsky plant; the composition of nanocement is presented below (tested 4 samples of each composition, two after manufacture and two after 6 months of storage in the container): No. 1: clinker 60, MD DGSh Orsk-Khalilovsky MK 35.9, sulfate-calcium component - 1.3 (for SO ₃ : conglomerates (natural mixtures) of two-water gypsum, hemihydrate and anhydrite with a conversion factor of SO ₃ ƒ 1.86, i.e. 1.3 × 1.86 = 2.5; M 1.6; total 100%; DEHT, the latter after a maximum of 1.9 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 700 Yes, MM diffuse layer approx. 400 Yes (tab. 2, lines 5, 6);

No. 2 (for reference): clinker 60, MD: same DGSh + tailings of ore processing of quartzite ores in wt. ratio 4: 1 35, the sulfate-calcium component is the same 3.5, M 1.5, the amount of 100%; DEGT, the last maximum after 2.5 hours; MM measurements using gel chromatography according to A.I. Vovka are the same (tab. 2, lines 7, 8);

No. 3: clinker 60, MD: DGSh the same + sowing from crushing granite 4: 1 35, the remaining components are the same, in the same quantities; the amount of 100%; DEGT, the last maximum after 2.25 hours; MM measurements using gel chromatography according to A.I. Vovka the same (tab. 2, lines 9, 10);

No. 4: clinker 60, MD: DGSh the same + a mixture of quartz and feldspar sand 4: 1, an admixture of feldspar sand in quartz about 20%; the remaining components are the same, in the same quantities; the amount of 100%; DEGT, the last maximum after 2.15 hours; MM measurements using gel chromatography according to A.I. Vovka are the same (Table 2, lines 11, 12).

The sizes of alite nanoblocks in the released nanocements: in No. 1, they turned out to be on average about 10-15, and in the rest - their aggregates.

Other cement test results are presented in table. 2.

An obvious decrease in the amplitude of fluctuations in the strength of nanocement according to example 2 compared with cements according to example 1 is a significant advantage of nanocement and the method of its manufacture according to the invention compared to the prototype. This is confirmed by data obtained on the basis of others, including industrial clinker (table. 2, see the following examples).

Example 3. Laboratory grinding cements were made from an experimental Portland cement clinker with a calculated composition (wt.%): Alit 75, white 8, C ₃ A 0.5, C ₄ AF 14.5, impurity 2, actual composition (by petrography, wt. %): alit 75, white 5, intermediate (the sum of aluminates and aluminoferrites with impurities - small components (R ₂ O, that is, Na ₂ O and K ₂ O, MgO, SO ₃ , TiO ₂ , etc.) 20, with block sizes in the first two phases of 0.3 - 3 μm, rare glassy grains of the third and lamellar submicrostructure of the fourth phase, M - SP-1 of the Pervouralsky plant; enes below (4 samples were tested for each composition, two and two after production after 6 months storage in a container.):

No. 1: clinker 55.3; MD DGSh Chelyabinsk MK + fly ash of the Revdinskaya TPP, containing 1.5% carbon 1: 1 - 32, calcium-sulfate component - two-water gypsum 4.9 (SO ₃ ); 4.9 × 2.15 = 10.5 (since the aluminoferrite phase turned out to be highly aluminate, and the DHS and ash were reactive). These components were jointly ground to a specific surface of 250 m ² / kg, then clinker and M SP-1 of the Pervouralsky plant 2.2, the sum of 100%, were added to them, and grinding continued; DEGT, the last maximum after 1.8 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 700 Yes, MM diffuse layer approx. 400 Yes (tab. 2, lines 13, 14);

No. 2: clinker 60, MD: DGSh the same + fuel slag, dry sample from the ash and slag dump of the Troitsk state district power station located in Kazakhstan, 2.3% coal (permissible maximum 3%), wt. 4: 1 35 ratio, the calcium sulfate component is the same 2.6 (according to SO ₃ ), or 2.6 × 2.15 = 3.5, mixed and clinker and M 1.5 were added, the amount is 100%, then continued grinding DEGT, the last maximum after 2.9 hours; MM measurements using gel chromatography according to A.I. Vovka are the same (tab. 2, lines 15, 16);

No. 3: clinker 12, MD: quartz sand (KP) + specified DGSh, dry samples in wt. 1: 1 ratio, the calcium sulfate component is the same 4.9 (according to SO ₃ ), or 4.9 × 2.15 = 10.5, mixed and clinker and M 2.2 were added, the amount is 100%, then grinding continued . DEGT, the last maximum after 3 hours; MM measurements using gel chromatography according to A.I. Vovka are the same (tab. 2, lines 17, 18).

The sizes of alite nanoblocks in laboratory grinding nanocements: in No. 1, they were on average about 15–20; in No. 2 and 3, aggregates of nanoblocks were present.

Other cement test results are presented in table. 2.

Example 4. Cement laboratory grinding was made from clinker according to example 2, and as MD used only quartz sand; cement composition (wt.%): Portland cement clinker 50, specified sand 44.8, gypsum stone 2 (according to SO ₃ ), or 2 × 2.15 = 4.3; modifier 0.9. DEGT, the last maximum after 2.5 hours; MM measurements using gel chromatography according to A.I. Vovka approx. 600 Yes, MM diffuse layer approx. 300 Yes (tab. 2, lines 19, 20).

The sizes of alite nanoblocks in laboratory grinding nanocements were on average about 10–15 nm.

Given in the table. 2 data allow us to conclude that the objective of the invention is solved: the compositions and method for the production of nanocement according to the invention can significantly reduce the quality spread of nanocement with various mineral additives at 28 days of age, bring it in their presence to levels acceptable for industrial production and guarantee the quality of nanocement without mineral additives and with mineral additives for at least 6 months. storage under protection against drip water. The use of clinker with improved submicrostructure in the composition of nanocement compared to nanocement according to the prototype, in which the clinker structure is not standardized, allowed us to improve the quality of nanocement by about class (grade), which was especially evident during long-term storage (table. 2, lines 3, 4 - nanocements according to the prototype, lines 17, 18 - nanocements according to the invention, both with 50% clinker, the rest is mainly sand). Therefore, for the production of nanocement it is advisable, as for any other types of cement, to improve the composition and microstructure of clinker.

It is also noted that, without loss of activity, it is possible to use not only natural, but also artificial types of calcium sulfate component in the composition of cements according to the invention. It should be noted that this applies not only to the product of the purification of calcium carbonate from the waste sulfur dioxide of industrial furnaces or reactors, which is very active in accelerating hydrated mineral formation (in the absence of poisonous impurities, agreed with specific suppliers), but also to other so-called chemical gypsum, in particular phosphogypsum, regardless of the form of calcium sulfates contained in them - aqueous, semi-aqueous or anhydrous, taking into account the hardening impurities of phosphoric and other similar acids, usually when combined ohm introducing them into the cement with natural forms of calcium sulfate.

Finally, a low-clinker nanocement with 12% clinker was found to have strength at the level of class 32.5 with an acceptable scope, albeit on the basis of a particularly alite clinker, the firing of which is a difficult but solvable technical problem.

The question arises: is it possible to use nanocement with mineral additives as cement with moderate exothermy, for example, with a heat of hydration not exceeding 250 kJ / kg in the above calorimeters (or 250 / 4.18 = 60 kcal / kg) for 7 days when using Portland cement clinker, the composition of which does not meet the requirements for sulfate-resistant Portland cement, or cement with low exotherm, contained, for example, in the relevant standards of the British standard [BS 1370: 1979 Specification for Low Heat Portland cement. Act. 2012] or in the domestic standard [GOST R 55224-2012 Cements for transport construction. TU] for sulfate-resistant Portland cement. In both standards, in addition to the requirements for fineness of grinding, the content of silicate minerals and the amount of smooth minerals in clinkers that do not completely coincide, the only general requirement for the mineralogical composition is of interest for this description: C ₃ A less than 3.5 wt. % This is important because the industry departments of the Russian Federation decided to introduce this standard into the developed standard for sulfate-resistant Portland cement to replace the canceled one [GOST 22266-94. Cement sulfate resistant. TU]. The answer to this question was obtained in the example embodiment of the invention described below.

Example 5. The heat dissipation of sulfate-resistant Portland cement of one of the cement plants of the Urals from clinker of the calculated composition (wt.%) Was studied: alit 50, belite 30, C ₃ A 3,5, C ₄ AF 14, impurities 2.5, as a benchmark for comparison , as well as freshly made nanocements according to the prototype and according to the invention according to examples 1-4. The test results are presented in table. 3.

As follows from the above data, the production of a sulfate-resistant nanocement with moderate exothermy, corresponding to even more stringent requirements for heat release for 7 days at a temperature of 21 ± 2 ° C compared with the standard ones, is possible on the basis of various clinkers without restrictions on C ₃ A≤3.5 % and C ₃ S≤55% due to the increased content of mineral additives without reducing strength indicators, remaining at the level of strength requirements contained in all the above standards. The requirements for heat dissipation and sulfate resistance are fulfilled for nanocements according to the invention, the characteristics of which are presented in lines 5-11 in comparison with the standard sulfate-resistant Portland cement presented in row 12 of the table. 3. Only at a maximum C ₃ A content of 15% do the nanocements according to the invention exhibit neither moderate exothermy nor sulfate resistance (data in rows 3, 4 of Table 3), which is to be expected due to the excessive aluminate nature of the clinker. It should be noted that fuel slag and fly ash (lines 8, 9 in Table 3), as mineral additives in nanocement, carry the ability to go beyond the established standards for product quality due to unwarranted homogeneity in chemical and mineral composition, therefore especially careful averaging in warehouses before use in cement production. Low clinker nanocement (12% clinker) was characterized by a particularly low heat release and sulfate resistance at the level of nanocement according to the prototype, which is a notable technical achievement.

The results of experiments in the field of nanocements according to the invention without mineral additives in comparison with cements without additives according to the prototype show a significantly smaller dispersion of strength, especially after prolonged storage, which is explained by more stringent quality control of the finished product.

The results of experiments in the field of nanocements according to the invention with mineral additives show perhaps the best strength indicators for cements in the entire history of observations, including (table 4, lines A, B, C, 3-6, 8-17), in which mineral additives practically did not reduce or reduced the strength of the product to a much lesser extent, namely, their disproportionate introduction into the composition of cement compared with cements without additives according to the prototype (table 4, lines 1, 2) and with nanocement for optional comparison without mineral additives, line 7 ) A surprise is the tolerance of the quality of nanocements according to the invention not only with respect to the content of mineral additives, but also with their type: cements with blast furnace granulated slag (fly ash), fly ash (ZU) and silica sand at 20% of these additives (table 4, lines 8-10) and even at 40% they remain high-strength and noticeably differ in strength only when the content of Portland cement clinker is 35%, while remaining high-strength by definition according to the old, graded scale of cement strengths, for example, according to [Kravchenko I.V. et al., 1971, cit. Op.]. The explanation of this phenomenon was attributed to the similarity in the structure of the outer atomic layers of Portland cement clinker in alite nanoblocks as a result of etching of naphthalenesulfonates and silicate chains in mineral additives of both active and fillers.

However, this is not the only point. New in the data presented in table. 4, the fact that the type of mineral additives affects the strength of nanocement at 28 days of age is much less than in the early stages of hardening (1 and 3 days). So, cements, differing only in that in one of them blast furnace granulated slag, one of the best known active mineral additives, and in the other much less active fly ash (moreover, both of these specific additives are one of the best in their types), at the age of 28 days have almost the same strength (table. 4, lines 8 and 9). The same can be said about nanocement, containing, in addition to the last two active mineral additives, also a classic filler - quartz sand (Table 4, lines 10 and 13). This was explained above by confirmation of the observation of crystallographers [Ulm, 2010, op. cit.], according to which, in the absence of atmospheric carbon dioxide (which Ulm forgets to mention in this report, conducting all his work only in a carbon-free environment) for intergrowths (aggregates) of С-S-Н cement stone nano-, submicro-, and microclusters shells are enriched with siloxane chains (1) nanolayer. It is through these layers that the Portland cement stone in the atmosphere free of carbon dioxide should grow together with particles of mineral additives similar in aluminosilicate composition of the outer atomic layer with chains (1), and with particles of quartz sand, identical in the outer atomic layer with chains (1) with approximately equal strength indicators, as in table. 3. But in the well-known works on the hydration of calcium silicates and Portland cement in a carbon-free atmosphere [Brunauer, St. Cement Hydration. / Science of engineering materials. Ed. by J.E. Goldman. John Wiley a. Sons, N.Y., 1957, Bull. No. 80, pp. 21-30; Malinin Yu.S. Study of the composition and properties of the main clinker mineral alite and its role in Portland cement. Abstract. diss. for a job. student step. Dr. tech. sciences. M .: Mosk. chemical technologist Institute of them. DI. Mendeleev, 1969. - 28 pp.] Close or equal in strength composite compositions with mineral additives and fillers of different activity have never been observed.

. Inst. Eng., Stockholm. 1940. S. 298-314]. Это было доказано лишь в 1996 г. фактом обнаружения эттрингитного геля с последующей его кристаллизацией в волокна под растровым электронным микроскопом, ранее никогда не фиксированного в виду недостаточного разрешения прежних электронных микроскопов [Emanuelson A. et al. Ferrite Microstructure in clinker and hydration of synthetic phases in sulphate resisting cements. / 10-th International Congress on the Chemistry of Cement (ICCC). Gothenburg, Sweden, 2-6 June 1997. Proceedings, ed. by H. Justnes. Amarkai AB and Congrex Gatenborg AB, 1997, vol. 1 (Plenary lectures. Clinker and Cement Production). li060. 8 pp.]. Первая фаза - образования золя - в наноцементно-водных системах длиннее, чем в портландцементных системах в связи с пространственным разделением первых исходных фаз, а в результате первой гидратной фазой, образующейся в смеси наноцемента с водой является не эттрингит, как в портландцементе, а гидросиликаты кальция. Это обращение порядка фазообразования - весьма существенный момент [Юдович Б.Э. Цементы с избирательной гидратацией. (Второй эффект Ребиндера). Международная конференция по коллоидной химии и физико-химической механике, посвященная 100-летию со дня рождения акад. П.А. Ребиндера, Москва, МГУ, 4-8 октября 1998 г. Сб. тезисов докладов, М.: Наука, 1998]. Именно обращение порядка фазообразования определяет присутствие упомянутых силоксановых цепочек в наружных зонах наноцементного камня, а эттрингитная составляющая, или так называемые многоводные гидраты (в отличие от гидросиликатов, где на каждую СаО-группу приходится в среднем по две молекулы воды и/или гидроксилов, на СаО-группы в многоводных гидратах приходится от 5 до 12 молекул воды и/или гидроксилов) находятся внутри гидросиликатной структуры - точно так же, как камне портландцемента, гидратированного в адиоксидной среде (т.е. в среде, свободной от CO₂), что было впервые постулировано Ст. Брунауэром в 1957 г. [Brunauer S., 1957, op. cit.], а теперь экспериментально подтверждено группой под руководством Ф.-Й. Ульма [Constantinides G. et al., 2007, op. cit.; Ulm F.-J. 2009, op. cit.]. Об эффективности этого механизма фазообразования в камне наноцемента свидетельствует также высокий уровень прочности малоклинкерного цемента, о чем упоминалось при анализе данных табл. 3.Undoubtedly, there is an additional factor that explains the novelty of the results given in Table. 4, in comparison with known from the prior art. A certain contribution to its explanation is made by the behavior of the calcium sulfate component. Like different forks of mineral additives, different mineral forms of the calcium sulfate component show similar results in terms of strength data in the composition of rationally made nanoc cement. This component can be called a promoter of hydrated mineral formation, since when nanoc cement is divided into sets of monomineral particles, the localization of hydrated phases in the nanocement stone increases compared to a stone from Portland cement, where polymineral particles predominate. The hydration phases generated by the calcium sulfate component require the participation of all mineral phases in cement synthesis during hydration, sometimes with the exception of calcium aluminoferrites. The unifying role of this component allows it to accelerate the hydration of nanocement by binding calcium, aluminum, and often iron from sols in the liquid phase of the cement paste to gel-like products, and then to ettringite crystalline high-water hydrates (3CaO · Al ₂ O ₃ · 3CaSO ₄ · (28-31) H ₂ O). Lennart Forsen first postulated the three-stage nature of this process in Portland cement-water systems, first the sol during the initial dissolution of the components, then the gel after the sol-gel transition, then the crystals as a result of crystallization of the gel with the binding of an additional amount of water [Forsen LR The chemistry of accelerators and retardants. / II International Symposium on the Chemistry of cements. Proceedings, Stockholm, 1938, Ed. Svenska

. Inst. Eng., Stockholm. 1940. S. 298-314]. This was proved only in 1996 by the fact of the discovery of an ettringite gel with its subsequent crystallization into fibers under a scanning electron microscope, which had never before been fixed in view of the insufficient resolution of previous electron microscopes [Emanuelson A. et al. Ferrite Microstructure in clinker and hydration of synthetic phases in sulphate resisting cements. / 10-th International Congress on the Chemistry of Cement (ICCC). Gothenburg, Sweden, 2-6 June 1997. Proceedings, ed. by H. Justnes. Amarkai AB and Congrex Gatenborg AB, 1997, vol. 1 (Plenary lectures. Clinker and Cement Production). li060. 8 pp.]. The first phase - sol formation - in nano-cement-water systems is longer than in Portland cement systems due to the spatial separation of the first initial phases, and as a result, the first hydrated phase formed in the mixture of nano-cement and water is not ettringite, as in Portland cement, but calcium hydrosilicates . This reversal of the phase formation order is a very significant point [B. Yudovich Cement with selective hydration. (Second Rebinder effect). International Conference on Colloid Chemistry and Physico-Chemical Mechanics, dedicated to the 100th anniversary of the Acad. P.A. Rebinder, Moscow, Moscow State University, October 4–8, 1998 Sat. Abstracts, Moscow: Nauka, 1998]. It is the reversal of the phase formation order that determines the presence of the aforementioned siloxane chains in the outer zones of the nanocement stone, and the ettringite component, or the so-called high-water hydrates (in contrast to hydrosilicates, where each CaO group has, on average, two water and / or hydroxyl molecules, CaO -groups in high-water hydrates account for 5 to 12 water molecules and / or hydroxyls) located inside the hydrosilicate structure - just like stone Portland cement hydrated in an oxide medium (i.e., in a medium f, CO ₂ free), which it was first postulated Cm. Brunauer in 1957 [Brunauer S., 1957, op. cit.], and now experimentally confirmed by a group led by F.-J. Ulm [Constantinides G. et al., 2007, op. cit .; Ulm F.-J. 2009, op. cit.]. The effectiveness of this phase formation mechanism in the stone of nanocement is also evidenced by the high level of strength of low clinker cement, as mentioned in the analysis of the data in Table. 3.

The physical and chemical consequence of this is two factors: 1) the protection of the stone of nanocement from carbonization, since calcium hydroaluminates and ettringite, characterized by a fluctuating water content, are quite easily carbonized, especially in the presence of clay impurities in natural gypsum stone, but in this case they are located inside the hydrosilicate textures, therefore, neither impurities nor fluctuations in the water content on the carbonizability of these phases and nano-cement stone as a whole have an effect; this determines the reduced sensitivity of the nanocement stone to the forms of the calcium sulfate component and the small effect of undesirable impurities in it, such as phosphates and clay, on the quality of the nanocement; 2) Si impurity in place of Al in ettringite, arising from the hydrosilicate environment, further reduces the tendency of this hydrated phase to change under the influence of the medium, in particular, to the harmful effects of low humidity and high temperature; and in the nanocement stone with the ubiquitous presence of siloxane nanochains (1) and an increased content of mineral additives, which always ensure the presence of dissolved silica in the liquid phase of the stone, an increased degree of substitution in ettringite Al for Si is practically ensured. Therefore, any natural calcium sulfate component, if it guarantees the necessary sulfate ion content in terms of SO ₃ in nanocement, is in principle suitable and equally effective in the composition of nanocement. As for chemical gypsum, in low clinker compositions they have not been studied; accumulation of additional data is required.

Thus, it is precisely for the indicated physicochemical reasons that the nanocement according to the invention has a number of decisive advantages in comparison with the prior art, and above all, that the unique complex of construction and technical properties described above is fully guaranteed and 100% achievable within the framework of the present invention. This was not provided by technical solutions known from the prior art.

It should be added that the nanocement according to the invention corresponds to the technical specifications and the certificate for nanocement - the last documents issued for these new generation cements in 2012 [TU 5733-067-66331738-2012 "Nanocement is general construction. Technical conditions. " Certificate of Conformity No. РОСС RU. I750. НЖ02], as well as the draft preliminary national standard of the Russian Federation, subject to approval. Based on the foregoing, it can be argued that the mismatch between the two specified criteria - according to the degree of aggregation and the double effect of heat release during the setting of the cement test - means that the tested cement has nothing to do with nanocement. In this regard, the test results of the cements according to the invention are indicative in comparison with the cements of the prototype and ordinary Portland cements, are given in table. 2-4.

The present invention, in accordance with the foregoing, is fully prepared for widespread industrial implementation.

The future is undoubtedly for nanocements.

Notes: 1 - nanocement (VNV) in bags - Zdolbunovsky cement-slate plant, dry storage under a canopy in the open air, without access to drip moisture; a similar nanocement produced at the Belgorod cement plant was stored in a metal silo; when the state order in 1992 was canceled and the Ministry of Defense refused to use nanocement (VNV), the silo was drowned out until a large consumer was able to pay the same high price as the previous military customer; such appeared only in 2001; 2 - on a Blaine device, see approx. 5; 3 - according to EN 197-1.2000 and TU 5733-067-66331738-2012 “Nanocement is general building. Technical conditions. " Nanocement tests are carried out at variable values of V / Ts. This is not new to the cement industry around the world. Strength tests of cement in cement-sand mortars were carried out with a variable W / C with the selection of water content according to the consistency of the test of normal density according to Wilhelm Michaelis (Germany) in Russia from 1874 to 1968, i.e. for 94 years, in Germany - from 1866 to 1942 (76 years). Around the same years, with variable H / C, cement was tested in all countries of the world. Kurt Waltz (Germany) in 1942 proposed a constant, and approximately twice as high V / C = 0.5 for cement testing. He thereby solved two problems: a) to facilitate and accelerate the compaction of the mortar mixture using a vibrating table (with an amplitude of 0.35 mm ), now replaced by a shaking table with an amplitude of 1 mm; b) increase the fineness of cement grinding, since at that time all cement plants in the world crushed cement so roughly that by the 1st year of hardening the degree of hydration of the clinker part of pure clinker cements, according to a number of works, including Hans Kühl (Germany), did not exceed 40 wt. %; this meant that only 60% of the fuel used to burn clinker was used. The idea of Waltz was that the W / C increase required an increase in the degree of hydration in order to fill the increased porosity of the samples with the neoplasms, and those cement plants that began to increase the fineness of grinding of their cement won in product evaluation. After 1 year, German cement plants, firstly, began to intensively introduce new devices for determining the fineness of cement grinding not by sieve residues, but by specific surface area; secondly, they began to advertise vibratory platforms for concrete compaction instead of previously used manual rammers. This initiated the acceleration of German concrete work, since the world war did not allow the borrowing of vibratory platforms in the USA directly. Thus, in Germany cement is tested at a constant H / C from 1942 to the present. time (71 years), in Russia - since 1968 (45 years), but in our country the task of increasing the fineness of cement grinding remained unfulfilled, despite the increased value of the standard H / C, due to the lack of competition between manufacturers in most remote regions and significant off-market factors in the European part of the country; a return to the I / C variable for our country is the least sensitive compared to other countries; 4 - 6-layer bituminized; 5 - unloading from the silo was carried out without difficulty in view of the absence of lumps; in the initial cements and stale, the degree of aggregation was approximately the same (for ordinary Portland cement this is an absolutely unattainable result). Note that in the world only Russia can quantitatively determine the degree of aggregation of powders, in particular cement. To understand the reasons for this, we should briefly outline the history of the development and distribution of instruments for determining the specific surface by the method of breathability, since this issue is not covered in the world literature on cement (even the Wikipedia article is incomplete). In 1938, F.M. Having visited South Africa, Lee and R. Nurses (Great Britain) borrowed an instrument invented by Paul Karman in 1932 for determining the specific surface of powders by the time a given portion of water flows through a sample in a cuvette. In 1939, they transformed a device for measuring the flow of air portions, since water is not suitable for cement because of its activity in relation to cement. (F.M. Lee in 1940, despite the World War II, received for this achievement both a book on cement chemistry in 1939. A Bailby medal and a prize from the Royal Chemical Society of Great Britain; another example of the award of this medal to a cement worker happened only after 50 years). In 1940, Karl Dickerhoff (Germany) discovered and improved the Li-Ners device in occupied France, and in 1941 began the production of his device for the market. Therefore, German cement plants after the proposal of Waltz had the opportunity to gradually increase the fineness of cement grinding, precisely controlling this process. The Dickerhoff device in 1942 came to Spain (the authors of the present invention saw it there in working condition even in 1991), and from there to the United States. In 1943, Robert Blaine improved the Dickerhoff instrument, simplifying its design and calibration as much as possible. The calibration quartz sands they all took from Karman through Lee and Nars. In 1945, Vladimir V. Tovarov (USSR), while in Germany, tried to work on a Dickerhof device. According to his employee, Maria T. Vlasova, Tovarov in Germany improved it, like Blaine, but independently, improving the Dickerhof metal cuvette. At Blaine it was glass, which increased the accuracy of calibration and results, but made it difficult to use - Blaine's instruments often broke. Today, Blaine devices with metal ditches are also on the market, but they have become much more expensive. Tovarov took his device to the USSR in 1946 and received the author on it. testimonial. (1947), and in 1949 it was standardized in the USSR. I received the calibration sand of Goods from Karman through Dickerhoff. Note that the Blaine device was standardized in the United States later than in the USSR. In 1957, Heinrich S. Khodakov, having studied in detail the work of Karman et al., Was able to improve the calculation of S _y , calibrate the sands without using the Pocket standard, and improved the Tovarov device by adjusting the degree of powder compression in the cell. In the first model of his instrument, PSX-2 (1958), the degree of compression was measured using a nonius ruler attached to a powder seal plug in the cell, and the sample was compressed in the cell manually. Khodakova's device was standardized in the USSR in 1962 with the assistance of Acad. Peter A. Rebinder. In the modern model of the device, the compression of the powder sample is carried out automatically - by a constant load. It is believed that the porosity of the layer is 50 ± 2 vol. % does not preserve particle aggregates in powder, i.e. it is completely disaggregated. This thesis is supported in all calculation schemes, but is really controlled only in Khodakov’s devices. The specific surface is calculated by the mass of the material and the transit time of the measured portion of air, adjusted for the dependence of air viscosity on temperature. To determine the degree of aggregation of particles in a powder, first, its specific surface is determined in a separate sample, and the height of the layer h _{1 of the} disaggregated powder in the cuvette is determined by nonius. Then, the same sample of powder is freely poured into the same cuvette and the height of the freely poured layer of aggregated powder h _{2 is} calculated from the known specific surface. The degree of aggregation of particles is considered the value A = [1- (h ₁ / h ₂ )] × 100 (vol.%). A link to the authors of the method for determining the degree of aggregation is given in the description text. PSC devices are the only ones in the world that allow quantifying the degree of aggregation of powders. For a wide scientific audience, this method of determining the degree of aggregation was little known, therefore, in the publications on the excellent preservation of VNV (CNV), the degree of aggregation was omitted. In fact, they are just as important for the preservation of cements as strength, and only in their combination can they be completely convincing.

97

Notes: 1 - nanocement in bags - dry storage under a canopy in the open air, without access to drip moisture; 2 - note that in the world only in Russia can quantitatively determine the degree of aggregation of powders, in particular cement. To understand the reasons for this, we should briefly outline the history of the development and distribution of instruments for determining the specific surface by the method of breathability, since this issue is not covered in the world literature on cement (even the Wikipedia article is incomplete). In 1938, F.M. Lee and R. Nurses (Great Britain) borrowed a device invented by Paul Karman (South Africa) in 1932 for determining the specific surface of powders by the time a given portion of water flows through a sample in a cuvette. In 1939, they transformed a device for measuring the flow of air portions, because water is not suitable for cement because of its activity in relation to cement (F.M. Lee in 1940, despite the World War II, received an achievement for this and a book 1939 Cement Chemistry Bailby Medal and Prize from the Royal Chemical Society of Great Britain; another example of the award of this medal to a cement worker occurred only 50 years later). In 1940, Klaus Dickerhoff (Germany) discovered and improved the Lee-Nersa device in occupied France, and in 1941 he began producing his device for the market. Therefore, German cement plants, after the Waltz proposal (see Note 3), were able to gradually increase the fineness of cement grinding, strictly controlling this process. The Dickerhoff device in 1942 came to Spain (the authors of the present invention saw it there in working condition even in 1991), and from there to the United States. In 1943, Robert Blaine improved the Dickerhoff instrument, simplifying its design and calibration as much as possible. The calibration quartz sands they all took from Karman through Lee and Nars. In 1945, V.V. Tovarov (USSR), while in Germany, tried to work on a Dickerhoff device. According to his employee M.T. Vlasova, Tovarov in Germany improved it, like Blaine, but independently of it, retaining the Dikerhoff metal cuvette. At Blaine, it became glass, which increased the accuracy of calibration and results, but made it difficult to use - Blaine's instruments often broke. Today, Blaine devices with metal ditches are also on the market, but they have become much more expensive. Tovarov took his device to the USSR in 1946 and received the author on it. testimonial. (1947), and in 1949 it was standardized in the USSR.

The calibration sand of Goods was also received through Dickerhoff. Note that the Blaine device was standardized in the United States later. In 1957 G.S. Khodakov, having studied in detail the work of Karman et al. (Kotseni), was able to improve the calculation of S _y , calibrate the sands without using the Karman standard, and improved the Tovarov device by adjusting the degree of compression in the cell of high-fineness powder. In the first model of the device of the Khodakov system - PSX-2 (1958), the degree of compression was measured using a nonius ruler attached to a powder seal plug in the cell, and the sample was compressed in the cell manually. Khodakova's device was standardized in the USSR in 1962 with the assistance of Acad. P.A. Rebinder. In the modern model of the device, the compression of the powder sample is carried out automatically - by a constant load. It is believed that the porosity of the layer is 50 ± 2 vol. % does not preserve particle aggregates in powder, i.e. it is completely disaggregated. This thesis is supported in all calculation schemes, but is really controlled only in Khodakov’s devices. The specific surface is calculated by the mass of the material and the transit time of the measured portion of air, adjusted for the dependence of air viscosity on temperature. To determine the degree of aggregation of particles in a powder, first, its specific surface is determined in a separate sample, and the height of the layer h _{1 of the} disaggregated powder in the cuvette is determined by nonius. Then, the same sample of powder is freely poured into the same cuvette and the height of the freely poured layer of aggregated powder h _{2 is} calculated from the known specific surface. The degree of aggregation of particles is considered the value A = [1- (h ₁ / h ₂ )] × 100 (vol.%). PSC devices are the only ones in the world that allow quantifying the degree of aggregation of powders. For a wide scientific audience, this method of determining the degree of aggregation was little known, therefore, in the publications on the excellent preservation of VNV (CNV), the degree of aggregation was omitted. In fact, data on the degree of aggregation are just as important for the preservation of cements as strength, and only in their combination can be quite convincing; 3 - according to EN 197-1.2000, TU 5733-067-66331738-2012 "Nanocement is general building. Specifications "and the draft pre-standard of the Russian Federation PNST 19-20 .." Portland cement nano-modified. Technical conditions. " Nanocement tests are carried out at variable values of V / Ts. This is not new to the cement industry around the world. Strength tests of cement in cement-sand mortars were carried out with a variable W / C with the selection of water content according to the consistency of the normal density test according to Wilhelm Michaelis (Germany) in Russia from 1874 to 1968, i.e. for 94 years, in Germany - from 1866 to 1942 (76 years). Around the same years, with variable H / C, cement was tested in all countries of the world. Kurt Waltz (Germany) in 1942 proposed a constant, and approximately twice as high V / C = 0.5 for cement testing. He thereby solved two problems: a) to facilitate and accelerate the compaction of the mortar mixture using a vibrating table (with an amplitude of 0.35 mm ), now replaced by a shaking table with an amplitude of 1 mm; b) increase the fineness of cement grinding, since at that time all cement plants in the world crushed cement so roughly that by the 1st year of hardening the degree of hydration of the clinker part of pure clinker cements, according to a number of works, including Hans Kühl (Germany), did not exceed 40 wt. %; this meant that only 40% of the fuel used to burn clinker was useful. The idea of Waltz was that the W / C increase required an increase in the degree of hydration in order to fill the increased porosity of the samples with the neoplasms, and those cement plants that began to increase the fineness of grinding of their cement won in product evaluation. After 1 year, German cement plants, firstly, began to intensively introduce new instruments for determining the fineness of cement grinding not by sieve residues, but by specific surface area (S _y ); secondly, they began to advertise vibratory platforms for concrete compaction instead of previously used manual rammers; thirdly, they began to use polyfractional standard sands. This initiated the acceleration of German concrete work, since the world war did not allow the borrowing of vibratory platforms in the USA directly. Thus, in Germany cement is tested at a constant W / C from 1942 to the present, time (71 years), in Russia - since 1968 (45 years), but in our country the task of increasing the fineness of grinding of cement remained unfulfilled, despite the gradual an increase in the standard W / C value (first to 0.4 - from 1968, then to Waltzowski 0.5 after the introduction of three-fraction sand - from 1997), due to the lack of competition between manufacturers in most remote regions and significant non-market factors in the European parts of the country. Due to the shorter period of use of the permanent W / C standard solutions, the return to the variable W / C for our country is the least sensitive compared to other countries; 4 - test results at 2 days of age according to EN 196-2000, GOST 30515-2003 and PNST 19-2004; 5 - the degree of aggregation, as a rule, is antibatic (inverse) to the content of the calcium sulfate component in cement; to switch from the content of sulfur trioxide (SO ₃ ) determined by chemical analysis to the content of gypsum stone taken into account in the material composition of cement, the conversion factor ƒ = [MM CaSO ₄ · 2H ₂ O] / [MM SO ₃ ] = 136/64 = is used 2.125, in a rough approximation of 2.15; with a lower water content of the calcium sulfate component, the value of ƒ is reduced, for anhydrite, ƒ = 1; intermediate values of ƒ between 2.15 and 1 are calculated from the actual content of crystallization water in the calcium sulfate component; they mean the presence in it of all or part of these forms of calcium sulfate; 5 - determination method: spraying cement onto a single-sided adhesive tape, rolling it into a tube and blowing with a blower for 1 h, then gel chromatography of the separated (deflated) modifier.

Примечания. *справочно; 1 - по диаграммам тепловыделения; обозначения экзотермических эффектов римскими цифрами - по табл. 1; 2 - сокращенные наименования минеральных добавок: доменный гранулированный шлак ДГШ, топливный шлак ТШ, зола-унос ЗУ, кварцевый песок КП, полевошпатовый песок ПП, высевки от дробления гранита ВДГ, хвосты обонащения руд ХОР (данные приводятся справочно; хвосты состоят преимущественно из кварцитов с примесью железной руды гематитового остава); 3 - в приборе системы Гуревича по ГОСТ 310.5 (цит. док. см. в тексте описания), по пересчету согласно примечаниям к табл. 1, кДж/кг; ДЭГТ - время окончания, в часах, двойного экзоэффекта на графике тепловыделения (ДЭГТ) от начала затворения цемента водой в ячейке калориметра; 4 - в растворе Na₂SO₄ с концентрацией сульфат-иона 34 г/л по показателям: а) расширения D (dilatation) в мм/м образцов-призм 1×4×16 см из стандартного (по ТУ на наноцемент [цит. соч.] цементно-песчаного раствора в 28-суточном возрасте; б) по потере прочности ΔR, %, образцов-кубиков по Г. Кюлю [1931, цит. соч.] с ребром 1,41 см через 90 сут хранения; 5 - удельная теплота гидратации клинкерных минералов, кДж/кг, при водотвердом отношении (В/Т) 0,4 и 21 С за 1 год: C₃S 490, βC₂S 226, С₃А 1167, C₄AF 377 при значениях степени их гидратации (G, в долях единицы): C₃S 490/517=0,95; βC₂S 226/262=0,86; С₃А 1167/1672=0,7; C₄AF 377/418=0,9; все данные согласно [Тейлор X. Химия цемента. М. Мир. 1996. 560 с, см. с. 277 по данным М. Коллепарди и сотр., 1972]. Несмотря на парадоксы в этих данных (в частности, по 100%-ной гидратации C₄AF за 7 сут), они общепризнаны в настоящее время [Soo Geun Kim. Effect of heat generation on mass concrete placement / Iowa State Univ. Thesis. 2010], с оговоркой о необходимости их коррекции в связи с конкретными условиями укладки и твердения цементных систем и того факта, что приведенные данные относятся к индивидуальной гидратации минералов, а в цементе они образуют конгломерат, скорость гидратации в котором следует оценивать по данным рентгенофазового анализа для каждого минерала. Именно этого подхода придерживались Ю.С. Малинин и его школа, в том числе В.П. Рязин [цит. соч.]. Данные, использованные в настоящем описании, были установлены В.П. Рязиным для партий ВНВ в 1991 г. согласно источнику [Научно-технический отчет НИИЦемента, НИИЖБа, ВНИИжелезобетона и ЦНИИ 26 «Вяжущие низкой водопотребности. Технология и свойства». М.: 1992. Официально не регистрировался в связи с оборонной областью применения ВНВ]. Согласно этим данным, при естественном твердении в составе наноцемента (ВНВ) через 7 сут при В/Ц 0,33 в цементном тесте степень гидратации G C₃S 0,55 (против 0,43 по [Тейлор, 1996, цит. соч.]), C₂S 0,3 (против 0,16), С₃А 1 (как и по Тейлору), C₄AF 0,35 (против 1 по Тейлору). Как показано в этом отчете, активные минеральные добавки (данные относились к высокоактивным ДГШ Криворожского МК) при вводе в количестве 50%, снижая долю ПК в наноцементе, повышают степень гидратации за 7 сут C₃S до 0,65, C₂S до 0,4, C₄AF до 0,45. Большинство изученных авторами настоящего описания ДГШ в период с 1992 г. по наст. время, позволяют достигнуть примерно 50% от указанного прироста G (именно C₃S до 0,55, C₂S до 0,35, C₄AF до 0,4). а золы-унос - всего лишь около 20% прироста G (C₃S до 0,57, C₂S до 0,32, C₄AF до 0,41). Что касается наполнителей на основе кварца, то здесь парадокс: при 50% песка (без примесей) прирост G достигает 70% от получаемого вводом активного ДГШ (C₃S до 0,62, C₂S до 0,37, C₄AF до 0,43-0,44), а при 40% барханного песка (с 30% лесса от массы песка) прирост G составил 30%, то есть больше, чем от золы-унос (последняя содержала ок, 2 мас. % угля). В этих экспериментах не было отмечено какой-либо специфики влияния минеральных добавок на особые индивидуальные изменения скорости гидратации отдельных клинкерных минералов вне указанных соотношений, как выделенных выше полужирным шрифтом, так и производных от них. Именно посредством такого расчета были получены данные, представленные в последнем, 17 столбце табл. 3; 6 - одинарный эффект смачивания; 7 - пример расчета показателя в строке 1, столбце 17 табл. 3: для всех минералов общий множитель 0,87 (доля клинкера), C₃S 0,55 (степень гидратации наноцемента за 7 сут) × 490 (удельной тепловыделение за 7 сут) × 0,87=234 кДж/кг; C₂S 0,3×226×0,87=59 кДж/кг; С₃А 1×1167×0,87=1015 кДж/кг; C₄AF 1×377×0,87=328 кДж/кг; полученные результаты умножают на долю этих минералов в клинкере: C₃S 234×0,5=117 кДж/кг; C₂S 59×0,2=29,5 кДж/кг; С₃А 1015×0,15=152.3 кДж/кг; C₄AF 0,35×328×0,15=18,3 кДж/кг. Сумма 117+29,5+152,3+18,3≈317 кДж/кг; 8 - показатели не предусмотрены по прототипу, но определялись справочно, согласно изобретению; 9 - данный малоклинкерный наноцемент, принимая во внимание пластификацию как клинкерного, так и сульфатно-кальциевого компонентов с учетом особо высокой дисперсности и частичного активирующего обезвоживания последнего с его быстрой гидратацией после затворения водой, представляет собой новый аналог гипсо-цементно-пуццоланового вяжущего, сульфатостойкость и безусадочность которого в свете общеизвестных работ А.В. Волженского - А.В. Ферронской не вызывают сомнений; 10 - сульфатостойкий портландцемент по ГОСТ 22266-94 класса по прочности 42,5 одного из уральских цементных заводов, используемый также в качестве одного из видов тампонажного цемента согласно [ГОСТ 1581-91 Портландцемента тампонажные. Технические условия].

Notes. * for reference; 1 - according to heat dissipation diagrams; designations of exothermic effects in Roman numerals - according to the table. one; 2 - abbreviated names of mineral additives: blast furnace granulated slag ДГШ, fuel slag ТШ, fly ash ЗУ, silica sand KP, feldspar sand ПП, seedlings from crushing of granite VDG, tailings of ore refinement ores KHOR (data are given for reference; tails consist mainly of quartzite with admixture of iron ore hematite residue); 3 - in the device of the Gurevich system according to GOST 310.5 (cit. Doc. See in the text of the description), in terms of recalculation according to the notes to the table. 1, kJ / kg; DEGT - the end time, in hours, of the double exoeffect on the heat release graph (DEGT) from the beginning of cement mixing with water in the calorimeter cell; 4 - in a Na ₂ SO ₄ solution with a sulfate ion concentration of 34 g / l in terms of: a) expansion D (dilatation) in mm / m of prism samples 1 × 4 × 16 cm from standard (according to TU for nanocement [cit. cit.] cement-sand mortar at 28 days of age, b) the loss of strength ΔR,%, sample cubes according to G. Kul [1931, cit. op.] with an edge of 1.41 cm after 90 days of storage; 5 - specific heat of hydration of clinker minerals, kJ / kg, with a water-hard ratio (W / T) of 0.4 and 21 C for 1 year: C ₃ S 490, βC ₂ S 226, C ₃ A 1167, C ₄ AF 377 at the values of the degree of hydration (G, in fractions of a unit): C ₃ S 490/517 = 0.95; βC ₂ S 226/262 = 0.86; C ₃ A 1167/1672 = 0.7; C ₄ AF 377/418 = 0.9; all data according to [Taylor X. Chemistry of cement. M. World. 1996.560 s, see p. 277 according to M. Kollapardi et al., 1972]. Despite the paradoxes in these data (in particular, the 100% hydration of C ₄ AF in 7 days), they are generally recognized at present [Soo Geun Kim. Effect of heat generation on mass concrete placement / Iowa State Univ. Thesis. 2010], subject to the need for their correction in connection with the specific conditions of laying and hardening of cement systems and the fact that the data given refer to individual hydration of minerals, and in cement they form a conglomerate, the hydration rate in which should be estimated from the data of x-ray phase analysis for every mineral. It was this approach that Yu.S. Malinin and his school, including V.P. Ryazin [cit. Op.]. The data used in the present description were established by V.P. Ryazin for the VNV parties in 1991 according to the source [Scientific and Technical Report of the Research Institute of Cement, Research Institute of Reinforced Concrete, All-Russian Research Institute of Reinforced Concrete and Central Scientific Research Institute 26 “Binders of low water demand. Technology and properties. ” M .: 1992. It was not officially registered in connection with the defense field of application of the airborne forces]. According to these data, with natural hardening in the composition of nanocement (VNV) after 7 days at a W / C of 0.33 in a cement test, the degree of hydration of GC ₃ S is 0.55 (against 0.43 according to [Taylor, 1996, cit. Cit.] ), C ₂ S 0.3 (versus 0.16), C ₃ A 1 (as per Taylor), C ₄ AF 0.35 (versus 1 according to Taylor). As shown in this report, active mineral additives (data related to the highly active DHS of Krivorozhsky MK), when added in an amount of 50%, reducing the proportion of PC in nanocement, increase the degree of hydration in 7 days C ₃ S to 0.65, C ₂ S to 0 , 4, C ₄ AF up to 0.45. Most studied by the authors of the present description of secondary school in the period from 1992 to the present. time, allow to achieve approximately 50% of the indicated increase in G (namely, C ₃ S to 0.55, C ₂ S to 0.35, C ₄ AF to 0.4). and fly ash - only about 20% of the increase in G (C ₃ S to 0.57, C ₂ S to 0.32, C ₄ AF to 0.41). As for quartz-based fillers, there is a paradox: at 50% of sand (without impurities), an increase in G reaches 70% of that obtained by introducing active DHS (C ₃ S to 0.62, C ₂ S to 0.37, C ₄ AF to 0.43-0.44), and at 40% sand dune (with 30% loess of the mass of sand), the increase in G was 30%, that is, more than from fly ash (the latter contained approx. 2 wt.% Coal) . In these experiments, no specific features of the influence of mineral additives on particular individual changes in the hydration rate of individual clinker minerals were noted outside the indicated ratios, both highlighted in bold and derivatives thereof. It was through such a calculation that the data presented in the last, 17th column of the table were obtained. 3; 6 - single wetting effect; 7 is an example of calculating an indicator in row 1, column 17 of the table. 3: for all minerals, a common factor of 0.87 (clinker fraction), C ₃ S 0.55 (degree of hydration of nanocement for 7 days) × 490 (specific heat release for 7 days) × 0.87 = 234 kJ / kg; C ₂ S 0.3 × 226 × 0.87 = 59 kJ / kg; C ₃ A 1 × 1167 × 0.87 = 1015 kJ / kg; C ₄ AF 1 × 377 × 0.87 = 328 kJ / kg; the results are multiplied by the fraction of these minerals in the clinker: C ₃ S 234 × 0.5 = 117 kJ / kg; C ₂ S 59 × 0.2 = 29.5 kJ / kg; C ₃ A 1015 × 0.15 = 152.3 kJ / kg; C ₄ AF 0.35 × 328 × 0.15 = 18.3 kJ / kg. Sum 117 + 29.5 + 152.3 + 18.3≈317 kJ / kg; 8 - indicators are not provided for the prototype, but were determined for reference, according to the invention; 9 - this low-clinker nanocement, taking into account the plasticization of both clinker and calcium sulfate components, taking into account the particularly high dispersion and partial activating dehydration of the latter with its rapid hydration after mixing with water, is a new analogue of gypsum-cement-pozzolanic binder, sulfate resistance and whose shrinkage in the light of the well-known works of A.V. Volzhensky - A.V. Ferronskaya is not in doubt; 10 - sulfate-resistant Portland cement in accordance with GOST 22266-94 of class 42.5 strength of one of the Ural cement plants, also used as a type of grouting cement according to [GOST 1581-91 Portland cement grouting. Specifications].

Notes: * for reference; 1 - draft PNST 19-20 .. "Nanomodified Portland cement. Technical conditions. " Designations of cement varieties are as follows: NANOCEMENT-90 (below abbreviated as NTs-90) includes (wt.%) Portland cement clinker (PC) or Portland cement (PC) without mineral additives (MD) 90-98, MD 2-10; NTs-75: PK 75-88, MD 12-25; NTs-55: PK 55-74, MD 26-45; NTs-45: PK 45-54, MD 46-55; NTs-35 PK 35-44, MD 56-65; NTs-30: PK 30-34, MD 66-70; the text of the PNST project regarding regulatory requirements is identical to the text of TU 5730-001-86664502-09 “Portland cement with a dense contact zone (PC PKZ). Technical conditions. " The presence of DEGT is recorded according to the heat release diagrams with a double exothermic effect, taken in 1991 according to the scientific and technical report of 4 research institutes [cit. cit.] in note 5 to the table. 3; 2 - in g.k. all natural minerals of calcium sulfate were found as conglomerates, without exception, therefore the conversion factors from SO ₃ to gypsum stone are variable; 3 - TU 21-26-20-92 “Binders of low water demand (VNV). Technical conditions ”, according to which the industrial production of VNV was carried out at a number of cement plants; the differences in the method of strength testing from the modern methodology under the PNST project consist in the use of two-fraction sand (in the denominator) as opposed to three-fraction sand (in the numerator) at present; in both cases, with a lower V / C compared with that adopted in the current GOST 30744-2003 and equal to 0.5; 4 - heat and humidity treatment (TVO, h): preliminary exposure 2 hours + temperature rise 3 hours + isothermal heating 6 hours at 80-85 ° C + cooling to room temperature 3 hours; samples of 28 days of age, aged in standard air-wet conditions; 5 - Zdolbunovsky cement-slate plant, Rivne region, Ukraine; mills 2.4 × 10.6 and 3 × 14 m, closed cycle; initial clinker: composition (wt.%): C ₃ S 64, C ₂ S 14, C ₃ A 6, C ₄ AF 13, impurities 3; alite and whiteite of a block submicrostructure with block sizes less than 3 microns, vitreous calcium aluminates and lamellar microstructure aluminoferrites; from an available sample of VNV laboratory storage (in a waxed bottle, 21 years old), it turned out that the SP film was preserved: 10–30 nm thick, and the nanoblock etched alite blocks formed an aggregate layer with a thickness of approx. 20 nm; after opening after 1 day, both this layer and the shell from the SP merged; the available data on the MM of nanoshells (the maximum from the above results) and the diffuse layer of the MM (the minimum from the above results) are 600 and 300 Da, respectively; 6 - two-fraction sand was prepared according to the technical specifications at the VNV [1989, cit. cit.], and three-fraction sand - imported according to EN 196-1 from Czechoslovakia; 7 - Belgorod cement plant, Belgorod-region., Russian Federation; 3 × 14 m mill, closed loop; initial clinker: composition (wt.%): C ₃ S 62, C ₂ S 19 C ₃ A 4, C ₄ AF 13, impurities 2; included alit and belite block submicrostructures with block sizes less than 2 μm, calcium aluminates, vitreous and aluminoferrites, lamellar microstructures; a laboratory storage sample was unsuitable for studying the nanostructure; the available data on the MM of the nanoshells and the diffuse layer of M 700 and 400 Da, respectively; 8 - mill 1 × 1.2 m, tsilpebs; 9 - DGSh - granulated blast furnace slag according to GOST 3476-74 “Blast-furnace and electrothermophosphoric slags for cement production. Technical conditions "; in this case, Children's Art School of Kryvyi Rih Metallurgical Plant, Ukraine; KP - quartz sand of the Volsky deposit according to GOST 6139-91 “Normal sand for testing cements. Technical conditions "(monofractional); ZU fly ash of Ryazan TPP according to GOST 25818-91 “Fly ash of thermal power plants for concrete. Technical conditions "; TSH - from the old ash dump of the same TPP; indicators of this sample and other samples with TS were not included in the publication, since it turned out that the quality of nanocement with TS was lower than with KP; a possible reason is the carbon content in TS at the limit of about 2.5% of the TS weight; 10 - high-strength Portland cement based on clinker, also used for cements according to lines 1, 3-16; its grinding was carried out in a closed cycle. According to the specialists of the Center, this is the best option as a control for comparison with the SC; 11 - cement according to line 17, tested with the introduction of SP-1 into the mixing water, in terms of dry matter of 0.6% of the mass of clinker, in the form of a 30% aqueous solution; models modifier input into concrete; 12 - Portland cement of class 62.5, with silica fume (MK, ≈5 wt.% According to the passport); import delivery in a plastic bag; brand name - see table.

Captions

FIG. 1. The surface relief of the fracture of high-quality Portland cement clinker (Zdolbunovsky TSHK), used in the manufacture of Portland cement grade 600 (class 52.5), under an electron transmission microscope

Gelatin-fortified carbon replica. The scale on the right is 1 μm.

A - alit, "brook" pattern - a consequence of the block structure with blocks of size from 0.1 to 0.5 microns; B - whitens from 0.2 to 1 micron; B is an intermediate substance (ferrite phase of a lamellar submicrostructure); the aluminate phase does not have a characteristic relief at the fracture, since it is glassy [IV Kravchenko And others. High-strength and especially quick-hardening Portland cement. M .: Stroyizdat. 1971; fig. 22a, p. 113]. In other high-quality Portland cement clinkers, the characteristic limits of alite blocks are higher - from 0.3 to 1 μm, belita from 0.8 to 3 μm.

FIG. 2. Particles of nanocement (alite) in a scanning electron microscope (SEM)

a - scale to the right of 1 μm;

b - scale on the right 200 nm

About the term "nanocement" see in the text of the description.

but. One can see intracrystalline formations under the outer surface of an alite particle, probably intergrowths of nanoblocks shown in b.

b. Organomineral nanoshells are visible (a) on a monomineral alite microparticle; under the shells and inside them - nanoblocks (b) alite (1-20 nm), morphologically altered, and therefore chemically; on top of the nanoshells - a diffuse layer (c, felt) of single hydrocarbon chains of naphthalenesulfonates.

FIG. 3. The scheme of the grinding installation for the manufacture of nanocement (formerly called PCC PKZ) and its application at the Sergiev-Posad plant of reinforced concrete products, Moscow region.

Description of the technological scheme of production and use of nanocement

Cement in containers of MKP type weighing up to 1.5 tons, brought by rail in open gondola cars, is fed with a special beam using a crane beam to the unloader (1), from where the cement is transported through conveyors (2 and 3), an elevator (4) and a conveyor (5) enters the silo (6). It is possible to accept cement in bulk through a magnetic metal trap with a hopper for scrap (not shown). From the silos through the conveyor (7), cement is fed to continuous weighing batchers (8). Other weight batchers serve mineral additives or fillers. Next, the components enter the conveyor (9), where the modifier (M) is also dosed.

The modifier in the MKP enters a separate sealed distributor, from where it is fed through a disk conveyor to two silos with mechanical cultivators (one for storage, the other a worker). Through the weighing batcher, the conveyor modifier (9), together with the remaining components, enters the 2 × 10.5 m (10) tube mill, two-chamber, with tsilpebsny loading. Ready nanocement by conveyors (11 and 12) is fed to the elevator (13) and from it to the silo (14). At the entrance to the conveyor (11), automatic samplers are installed to control the quality of nanocement. From silos (14), the finished nanocement is fed to the elevator (15) and then used in three directions:

A) Through the conveyor (16) to the department for the production of cellular blocks, namely, into the feed hopper (17), then through the loading and unloading units (18) and weighing batchers (19) into a high-speed mixer for preparing a cement-water suspension (in mind small scale is not visible), which also serves water through a dispenser. From the specified mixer, the cement-water suspension is fed into a foam mixer, where it is mixed with technical foam from a foam generator (not shown) until a foam concrete mix is formed, which is fed through a pump into molds (20). After the initial hardening in molds, foam concrete masses are freed from formwork and fed to a cutting machine (21), from where the massif (22) cut into building blocks is folded onto a pallet through a tilter, then fed to a distribution conveyor (23), and then to conveyors of the climatic hardening zone (24). After climatic hardening (no higher than 45 ° C), the blocks are removed from the conveyors in pairs and transported to the finished goods warehouse.

B) Through the conveyor (26), dry mix compartments are fed into the supply silo (27), where dry sand brought to the MCR enters through the boring device (30) and the elevator (29) into the silo (28). Cement and sand are fed through weighing batchers to a mixer (32) and then to a bagging machine (31). The mixture packaged in bags is placed on pallets and taken to a warehouse.

B) From silos (14) through existing conveyors, nanocement with a low content of clinker component (less than 40%) is sent to the usual production of reinforced concrete structures and products (not shown in the diagram, it is not in the jurisdiction of the owners of the grinding plant).

The diagram shows the reserved space for the installation of the second mill (25) when the demand for nanocement is exceeded more than 100 thousand tons / year. Such installations can be located at any cement plant, or at any enterprise in the construction industry.

At the grinding plant for the manufacture of nanocement and its use, pneumatic transport is not used.

FIG. 4. The dynamics of heat during hydration of the control cement (without modifier, A) and nanocement (B-D), all without mineral additives (for reference)

Determination of heat release - according to GOST 310.5-94 (after its cancellation - according to GOST 30844 in a new edition)

a) general view of heat dissipation diagrams; abscissa - time, hours; ordinate - temperature of the cement-water mixture in conventional. units;

b) the initial effects of heat during the setting of cements.

The designations of the coordinate axes are the same.

Legend: A - without modifier (M); B - from 1% M; B - from 1.25% M; G - from 1.5% M; D - from 1.75% M.

The modifier is sodium naphthalenesulfonate.

The numbering of effects (Roman numerals) is conditionally assigned to the periods of heat release on the graphs “a”.

FIG. 5. A fully hydrated particle of nanocement (mainly alitic) on the surface of the pores of foam concrete after 3 years of hardening in a dry atmosphere

There is no boundary between the internal and external calcium hydrosilicates (hence the former name of nanocement “cement with a dense contact zone”). Columnar crystals of high-water hydrates (in this case, according to morphological characteristics - ettringite) are located along the melt flows of the modifier, which contained impurities of the aluminate and aluminoferrite phases in the nanoshell, and which penetrated deep into the particles, forming the O layer, which occupied its entire volume. Morphological signs of carbonization of calcium hydrosilicates and ettringite are absent. No carbonization and according to x-ray phase analysis (XRD). Other details - see the description text.

Claims (6)

1. Nanocement based on Portland cement clinker and an organic modifier, including mineral phases alite, belite, aluminates and calcium aluminoferrites as clinker, naphthalene sulfonates in the form of continuous organomineral nanoshells with a thickness of 30-100 nm on clinker particles, as well as sulfinker, as well as clinker a calcium component and a mineral additive, with surface areas of 400-600 m ² / kg, characterized in that nanotsement comprises (wt.%), said clinker 12-88 as a solid alkali, comprising said m phase-sectoral wt. ratios (50-75) :( 10-20) :( 0.5-15) :( 10-15), respectively, moreover, alite and belite are represented by microcrystals with dislocation block sizes of 0.1-3 μm, aluminates are glassy and aluminoferrites calcium - lamellar submicrostructures, the specified modifier is 0.15-2.2 as a solid powdery acid, which is represented by naphthalenesulfonates with a molecular weight (MM) of 1800-2200 Yes, the calcium sulfate component is 0.2-4.9 (in terms of SO ₃ ) as a promoter of hydration mineral formation, represented by calcium sulfate in natural forms, a mineral additive from active groups 5-85 and / or fillers 5-50, while the finished nanocement includes, on top of the indicated nanoshells, consisting of fused triboactivation with a co-milled clinker component of naphthalenesulfonates with a molecular weight (MM) of 600-800 Da, diffuse a layer of throttled during triboactivation of naphthalenesulfonates with MM 300-600 Yes and, in addition, nanocement on the particles of the clinker component contains a layer of etched last mineral phases 2-50 nm thick under these nano-shells, including nanoblocks alite size 1-20 nm, and their aggregates. 2. Nanocement according to claim 1, characterized in that said nano-shells additionally contain fragments of said etched mineral phase layer with said aggregates of alite nanoblocks. 3. Nanocement according to claim 1, characterized in that said nano-shells contain naphthalene sulfonates including calcium complexes, the calcium sulfate component contains calcium sulfate in natural forms from the gypsum stone group: two-water gypsum, semi-water gypsum, anhydrite, conglomerates thereof, or artificial forms from the group of chemical gypsum: phosphogypsum, the product of calcium carbonate purification of waste sulfur dioxide from industrial furnaces or reactors, or their binary mixtures, the mineral additive includes one or two components from the ac group ivnyh: granulated blast furnace slag, fuel slag, fly ash and fillers from the group: quartz sand, feldspathic sand, screenings from granite crushing. 4. A method of manufacturing nanocement according to claim 1 by co-grinding these components with quality control in sequentially selected samples of the finished product, characterized in that the grinding is carried out until two indicators are achieved - completeness of coverage of the said nanoshells with the specified diffuse layer, fixed by the quantitative criterion of the minimum degree of aggregation particles coated with the indicated nano-shells, determined in the grinding product by the method of breathability, and continue grinding until the second indicator is reached - completeness coating the etched mineral phases of the clinker component particles with the mentioned layer, fixed by the criterion for the appearance of a double maximum on the temperature recording chart in the calorimeter cell during heat release, determined by the thermostatically controlled conductive calorimetry method, during the setting of the cement test prepared from sequentially selected samples of the grinding product. 5. The method according to p. 4, characterized in that in the manufacture of nanocement, said grinding is carried out with fixing the minimum degree of aggregation of the product equal to 5-20 vol.%, And grinding continues until the named double maximum is registered in the finished product on the specified schedule for 1 -3 hours

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