RU2574513C2 - Method for manufacturing cement compositions, mortars, concrete, which contain calcium carbonate-based filling agent, (preliminarily) processed with superplasticiser, obtained compositions and cement products and application thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to method for manufacturing cement compositions, mortar, and concrete. Method for preparation of cement composition includes in the process of cement composition production introduction in it of filling agent, which contains calcium carbonate, surface of which is processed by processing means, which contains at least one superplasticiser and at least one plasticiser, with ratio between superplasticiser and plasticiser constituting from 95/5 to 85/15 counted per dry weight of materials.

EFFECT: method is intended for manufacturing improved high-quality flowing cement systems or compositions, mortars or concrete, which have higher compactness, improved flowability, as well as definitely improved processability and reproducibility of properties of final systems.

20 cl, 6 dwg, 6 tbl

Description

FIELD OF THE INVENTION

The present invention relates to the field of cement compositions, cementitious compositions, compositions of hydraulic binders, compositions of mortars, concrete compositions "(hereinafter also referred to as" systems "), and in particular to the type of compositions (or" systems ") of cement / hydraulic binders, mortars, concrete, which contain at least one crushed mineral of the type (s) of calcium carbonate as a filler, to their applications, as well as to the corresponding cement materials llamas, mortars, concrete products or elements, wherein said filler is "improved" according to the present invention to a "high-tech" or "high-quality" (HP) level of performance due to the method, which is an essential part of the present invention.

The present invention relates to a specific method for the manufacture of these compositions or "systems" (these terms are intended to be used as equivalent in this application and the claims) of cement, hydraulic binder material, mortar, concrete, to compositions obtained by this method, cement materials, construction mortars and concrete products, as well as their applications.

State of the art

It should be noted that the cement system (or equivalently “composition”) is a system containing particles of cement, water for mixing (or equivalently an aqueous composition for mixing that does not interfere with the specified system, which is known to a person skilled in the art), filler ( fillers), a variety of optional and conventional additives, such as air entraining additives, hardening inhibitors, hardening accelerators and the like, as well as any such conventional additives that are well known in the art. leaf in the art.

The mortar system further comprises an inert granular material, typically sand.

In addition, the concrete system additionally contains gravel.

The above information is well known and disseminated.

For simplicity purposes, and also, since the present invention relates to the use of additives designed to improve or “improve” the properties of any of these three systems, the terms “cement systems” (or “compositions”) will be further used to describe any of the above three main types compositions or "systems", that is, compositions or systems of cement, cementitious material, hydraulic binder, mortar or concrete. One skilled in the art will be able to determine that the system is cement, mortar, or concrete, given the presence or absence of sand and / or gravel. This simplification becomes possible because sand and gravel are inert materials and thus do not significantly affect the present invention.

In addition, it should be noted that even if in the subsequent text the information given describes, for example, “cement systems”, it also applies with corresponding changes to the systems of any of the other four types. The only difference between the systems is the presence or absence of sand and / or gravel.

In such compositions, a plasticizing agent (s) is often used.

In this area, European patent EP 0663892, issued to CHRYSO, is definitely the most relevant document that describes plasticizing polymers for mineral suspensions without hydraulic hardening or a suspension of hydraulic binders.

The applications described are compositions of coatings for paper, paints, synthetic polymers or rubbers.

According to the aforementioned prior art, it was known to introduce plasticizing additives in suspensions of mineral granular materials to reduce their viscosity and, in particular, to make paper, where this leads to an increase in the concentration of mineral substances, to improve processability and to reduce energy consumption for drying. For example, this is used in connection with suspensions of calcium carbonate.

In addition, it is known the introduction of such plasticizing additives in the “cement” (in the broad sense explained above) suspension, this time in order to reduce their water content and obtain a “cement” composition with a “denser structure” after hardening.

The problems that arise are the influence of electrolytes, which reduces the plasticizing effect and forces to increase the amount of plasticizing additives (which increases the cost), and also in the case of “cement”, the need not to change the hardening characteristics of the cement composition or its final properties in a negative direction.

Some well-known plasticizing agents are superplasticizers or plasticizers.

European patent EP 0663892, issued to CHRYSO, as well as French patents FR 2815627 and FR 2815629 and international patent application WO 2008/107790, which also describe superplasticizers of interest, also belong to this field.

Some known plasticizing agents have a lesser effect on hardening time, but are still unsatisfactory, such as the condensation products of sulfonated naphthalene and formaldehyde or melamine formaldehyde with a sulfonated compound. Some of these products are also superplasticizers, but are much less preferred.

In addition, European patent EP 0099954 relates to plasticizing agents obtained by condensation of an amino sulfonic acid having at least an aromatic ring with nitrogen-containing compounds having several amino groups and formaldehyde.

These additives do not significantly hinder the hardening of cement compositions, but are highly sensitive to electrolytes when their “activity” appears. They can also be obtained in low concentrations, usually not more than approximately 40% of the dry weight, since any increase in concentration, in turn, increases their viscosity to unacceptable levels.

A brief description of the desired properties is presented in the aforementioned European patent on page 3, starting on line 15.

It is also known to add filler (s) to the composition or “system” of cement, hydraulic binders, cementitious materials, concrete or mortar.

The purpose of adding such a filler (s) is to fill the voids between the particles, reduce the total cost and to a high degree improve the property called “consistency” (consistency is the ability or inability of the systems in question to flow easily or “self-level”), and a property called compactness (that is, the percentage of dry material in the final composition (the higher the percentage, the better compactness)).

In the present invention, said filler (s) used are defined as “calcium carbonate-based filler (s)”, that is, only carbonate-based materials (possibly of different origin, such as various, are provided in the present application and claims) natural rocks or various types of PCC), and this means the absence of any other filler of a different type, such as kaolin, bentonite, etc., known to a person skilled in the art, and pre are preferably provided (when the filler (s) are or contain GCC) carbonate rocks or, more generally, mineral materials containing at least 50 to 65%, preferably more than 80%, more preferably more than 90% CaCO ₃ in dry weight; as this filler (s) choose:

- material (s) based on natural calcium carbonate or finely divided calcium carbonate (GCC), such as, without limitation, GCC made from marble, chalk, calcite or from other naturally occurring well-known forms of natural calcium carbonate, which preferably meet the above criteria percentage

- PCC-based material (s), which is precipitated calcium carbonate, and exists in a variety of well-known forms depending on the well-known precipitation / fabrication method;

- or a mixture of said CaCO ₃ containing rocks or mineral materials with each other, as well as a mixture or composition of material (s) based on GCC and PCC.

The GCC / PCC ratio can be selected from 0/100 to 100/0% of the dry weight, preferably from 30/70 to 70/30% of the dry weight.

Typically, “filler” has the following properties:

The content of impurities (analysis with methylene blue) is less than 10 g / kg, preferably less than 3-5 g / kg, preferably less than 1-1.5 g / kg, with the most preferred value being 1.2 g / kg.

The median particle diameter or d ₅₀ is from about 1-3 to 30-50 microns when measured using equipment / techniques for determining the particle size distribution (PSD) of model 2000 from Malvern.

The specific surface according to Blaine, which, as is well known, is a characteristic feature of fillers, is from 180 to 2000 m ² / kg, preferably from 300 to 800 m ² / kg, when measured in accordance with European Union standards (European standard EN 196-6).

As you know, a "cement" (in the aforementioned broad sense) composition or "system" is composed mainly of:

cement (or a cementitious composition or hydraulic binder) + mixing water or an aqueous mixing composition that hardens but does not interfere with the system) + optional (usually inert) granular and / or fibrous filler (s) + inert agglomerate (agglomerates) ), such as optionally sand + optionally inert gravel (plus optionally well-known additives not described in detail or in full in this application, such as hardening accelerators, hardening inhibitors, air ekayuschie additives, etc.) + other "ordinary" additives intended to accurately perform end-user requirements.

Fillers, such as sand, inert gravel, or natural filler mixtures, are known materials that are so often used that their description is not required in this document.

As discussed above, the present invention also relates equally (using the general term “cement” for simplicity) to compositions or “systems” of mortars (which contain, as indicated above, an inert material such as sand but no gravel) and to cement compositions (similar to the above, but containing neither gravel nor sand).

“Mainly” means in this document that the system may contain, in the form of impurities or traces, some additives or auxiliary materials not mentioned in this application, such as air-entraining additives, accelerators, moderators, etc.

“Mixing water” means, in the present patent application, pure mixing water or aqueous mixing compositions, which are mainly water plus conventional additives providing normal hardening of the “cement” compositions without affecting other properties of the whole composition, or only through additives that enhance some common properties.

"Fillers" in the present invention are precisely defined above as fillers containing in any known form (namely GCC and / or PCC) only CaCO ₃ solid material, and optionally particles of some other inert fillers or fibrous material such as hemp and etc., but not containing any other type of filler, such as kaolin, bentonite, etc. and their various mixtures.

Throughout the text of this application and claims, the term "inert" means a material that does not produce a noticeable (or perceptible) effect or influence on the method according to the present invention and the resulting compositions, products and applications. Knowing the ingredients used, any person skilled in the art can easily appreciate this property.

Thus, according to the prior art, “cement” (in the broad sense, as defined above) systems to date have consisted mainly of:

cement (or hydraulic binders or cementitious compositions) + mixing water (or aqueous mixing compositions that do not interfere with the system) + optionally inert material (materials) such as sand + optionally gravel + aggregate (s) + “ordinary” additives.

In addition, it is known that cement / hydraulic binders / cementitious compositions, cements, mortars, and concrete compositions can mainly be classified into:

dry systems of unsatisfactory or "low" quality (high vibration and energy consumption during casting).

Plastic systems of medium quality (medium vibration and energy intensity).

High quality fluid systems or HP (low vibration and power consumption).

For the classification of systems, a very simple test is used, using a “miniconus alignment” known as a “self-alignment test” or “leakage cone alignment test”.

This test is well known and is carried out as follows in accordance with the recognized standard EN 196-1; the specified standard accurately defines the used mixing (also kneading) device, rotation speed, as well as any and all parameters used to reproduce the test. Therefore, this document does not require further clarification or definition for purposes of clarity or reproducibility.

For simplicity, in the entire text of this application, the term "cement" means not only a cement material, but also cementitious compositions, compositions of hydraulic binders (other than cement), and mixtures thereof. As indicated above, it also means appropriate mortar and concrete.

Self Leveling Test

Typically, “systems” of cement, mortar or concrete are made by mixing the above ingredients according to the usual practice, which is described in more detail below, although the technological conditions are well known, then the mixture is poured in accordance with the conditions of the above standard into an inverted cone, at the lower point which hole is located (the specified standard determines the dimensions, as well as all and any parameters used in this test).

Thus, a system of cement, mortar, or concrete flows into the cone and flows out of it through the lower hole, falling onto a horizontal slab, forming a figure with an upward pointing point (“beacon”).

Here a “plate” or “cone” is formed, also known as a “dry to plastic form”; they measure the diameter and visually determine a property, such as stickiness and "density", the latter property characterizing a "slow" or "viscous" mixture, that is, if it is "dense", it is difficult to work with it.

The larger the diameter, the more fluid the system. This is the main test for a given high consistency, which is the purpose of the present invention.

Taking into account the quality of the initial filler intended for use in the concrete system, namely, the place of its production, morphology, etc., the resulting cone will have a different diameter, which indicates a change in fluidity.

As an example, GCC, which is known to be used with little or no added water for mixing, and which exhibits such valuable properties, forms a very fluid, non-sticky cement or concrete composition. Such a composition can be fully used for "high-tech" (that is, "high-quality" or HP) concrete compositions, referred to above as the term "fluid".

In turn, a filler, namely a filler containing GCC, absorbs or uses a significant amount of water or contains some impurities, etc. The resulting composition will be less fluid and somewhat sticky. The end user will be forced, among other things, to add corrective auxiliary material (and bear the additional costs associated with this and the corresponding risk of the secondary effect of the composition as a whole) and / or introduce additional water (thereby damaging the consistency and causing risks associated with it). Such compositions will be used as medium quality compositions, referred to above as “plastic”.

On the other hand, the use of a filler, namely low quality GCC, will result in a composition that exits the mixer in the form of sticky granules. They can only be used for dry concrete compositions that are not part of the present invention.

This test will be sufficient for a person skilled in the art to evaluate the source material (s) based on GCC and / or PCC.

The same is true with the corresponding changes when using PCC or a mixture of GCC / PCC.

In order to provide a person skilled in the art with useful guidance and information about the meaning of the terms “low quality”, “medium quality, or“ high quality ”(HP) with respect to a filler, Table A below describes ten fillers from A to K of different origin and morphology (as provided for characterization by a person skilled in the art) that have been tested with respect to a variety of properties and qualities or deficiencies, with each line giving a quality classification: “low »”, “medium” or “high”.

Table a Characteristics of fillers having "low", "medium" and "high" quality, and their appearance Symbol for processing Geological description (age) Type of Median particle diameter d ₅₀ Blaine specific surface The content of impurities (analysis with methylene blue) (3 g) (4 g) Quality control Visual assessment of the appearance of the composition A White chalk facies (90 Ma) a piece of chalk 1,0 > 1400 2.0 Plastic appearance 220 Low Slow very thick B White chalk facies (90 Ma) a piece of chalk 2.2 1120 2.7 280 340 Average Thick C Urgon facies (115 Ma) Calcite 3,1 1171 0.3 200 290 Low Slow thick D Bioclastic facies (160 Ma) Calcite 6.0 720 1,0 Plastic appearance 338 Average Plastic E Urgon facies (115 Ma) Calcite 6.5 395 0.3 460 475 HP Flowing G Upper Jurassic facies (130 Ma) Marble 17.0 363 0.3 Dry appearance 365 Average Slow heavy H Upper Jurassic facies (120 Ma) Marble 13,4 385 0.3 337 413 Low Slow viscous H + 5% B X X X X 190 390 Average Slow viscous I H + 15% B X X X X 427 436 High Flowing K H + 20% B X X X X 340 410 Average Flowing thick

3 g or 4 g of Premia 196 superplasticizer are used, which is sold by CHRYSO and which is a commercial product at a concentration of 25.3% of the dry weight of cement (when measuring the dry extract according to EN 480-8).

In Table A indicated, “+ 15% B” obviously means the addition of 15% of product B to make a mixture or composition, with percentages indicating the ratio of the dry weight of the additive to the dry weight of the mixture.

Similarly, the columns “3 g” and “4 g” mean that 3 or 4 g of said superplasticizer are respectively added with respect to the dry weight of one cement component.

“Millions of years” means “millions of years” (rock age).

“Impurity content” means the result of a purity test with methylene blue.

This introduction of the present application clearly shows the need for improved systems or compositions of cement, mortar or concrete having improved compactness (the highest possible percentage of dry material), improved fluidity (that is, a non-sticky “plate” or “cone” of large diameter is formed in the test described above moreover, the larger the diameter, the higher the fluidity), as well as, generally speaking, a definitely improved “manufacturability” (manufacturability is the suitability of cement or concrete compositions for the manufacture, processing, handling and use to obtain high-quality or "high-tech" concrete) and significantly improved "reproducibility" of the properties of the final product, in particular, at the end-user level.

Obviously, some of these desirable properties are counteracting and, for example, it is expected that a high percentage of dry material will lead to unsatisfactory results in a yield test.

Solved technical problem (s)

The main objective of the present invention is to develop a method intended for the manufacture of improved "high-quality" fluid systems or compositions of cement, mortar or concrete having improved compactness (the highest possible percentage of dry material), improved fluidity (that is, non-sticky " plate "or" cone "of large diameter in the test described above, and the larger the diameter, the higher the yield), and, generally speaking, definitely improved" nologological ”(manufacturability is the suitability of a cement or concrete composition for the manufacture, processing, handling and use to produce high-quality or“ high-tech ”systems or compositions of cement, mortar or concrete).

Another property that is absent in the prior art, despite its high need for industry, is the "reproducibility" of the properties of the final systems.

It was unexpectedly found that according to the present invention, this set of problems can be solved by processing the filler (s) in a specific way, as described below, using only small amounts of processing agents and obtaining a very expressive technical effect.

SUMMARY OF THE INVENTION

The present invention is, first of all, a method of manufacturing the compositions or systems of cement / mortar / concrete defined above (for simplicity, hereinafter referred to as “cement” compositions or systems) of a well-known type, as defined above, containing filler (s) in which (fillers) is (constitutes) or contains (contains) “calcium carbonate-based filler (s)” as defined above, characterized in that it comprises at least one step, g de specified filler based on calcium carbonate (fillers) is treated with an effective amount of at least one treatment agent containing or constituting a superplasticizer (superplasticizers).

This treatment is provided only for the part of the filler (s), which is a material (materials) based on calcium carbonate, and, for example, not for other granular or fibrous fillers, if they exist, which are considered inert in this process.

This preferred option or best mode is called the term “pretreatment” or equivalent to “pretreatment” (in Tables 1-6, which correspond to laboratory experiments where the fillers are pretreated in a small laboratory mixer).

It should be noted that the Lödige tests mentioned in these tables also represent the pretreatment tests according to the present invention, but performed using a well-known industrial mixing device, the so-called Lödige equipment.

The term "representing or containing" means that the fillers can contain calcium carbonate-based material (s), optionally mixed (mixed) with non-interfering fillers, and that the treatment agent (s) can (can) be exclusively a superplasticizer ( superplasticizers) or mixtures of superplasticizer (s) and non-interfering plasticizer (s) (as defined below) and / or conventional inert additives.

The terms "degree of effective processing" or "effective surface coating of particles or grains of fillers" "or" effectively processed "used by the authors in this application mean that at least 50, preferably at least 60 or better, according to at least 80 or 90% or even better closer to 100% of the surface of the filler particles (fillers) was subjected to physico-chemical interaction with superplasticizer (superplasticizers). At the time of filing this application, this physicochemical interaction is not fully understood and only its effects and results are properly identified and correlated with the superplasticizer (s) for processing, but, not limited to any theory, the applicant believes that this interaction or “Treatment” is a surface treatment or a “surface coating” treatment, which includes ionic, physical, mechanical and / or chemical treatments and the use of a decree all interactions (interactions). Thus, this effective processing or degree of processing should be significant enough to cover the indicated percentage of the surface of the particles, as will be further explained and described in more detail.

The term “surface coating” means that superplasticizers, according to the applicant, are not limited by theory, participate in the interaction of electric charge potentials with ionic charges of the filler surface, which contributes to the fixation of the superplasticizer on the surface and / or near the surface, and thus reduces the “available” the surface of the particles and said treatment does not saturate the surface of the grains.

This corresponds to the "unblocking" of particles or grains, which first "initiates" and then develops the freedom of mobility of the particles relative to each other.

This is not a fluidization process, but an “initiating action”, leading to the process of unblocking or sudden elimination of interaction / friction between particles, without which it is impossible to achieve other properties and, in particular, the required fluidity.

It is believed that this “unblocking” function “initiated” in this way is one of the most important parameters that allow one to evaluate the corresponding “treatment” or “surface coating”.

The term “comprising” in this application means that the treatment agent may contain exclusively superplasticizer (superplasticizers) (one or more mixed with each other, preferably one) or mixtures of superplasticizer (superplasticizers) that do not exhibit interaction with each other (i.e. are unable to significantly influence the aforementioned “processing”), including the amount or ratio of known plasticizer (s) for the purpose of cost reduction, as explained below It is Busy in more detail.

1. According to the best embodiment of the present invention, as currently defined, said filler (s) are efficiently processed before being introduced into the mixing device (“pre-treatment”, also called “initial” in tables 1-6), for example, using an external mixing laboratory equipment; on an industrial scale, such pre-treatment can be carried out using an industrial device, such as a Lödige mixer, or any other industrial mixing equipment known in the art.

2. According to a less preferred embodiment, said filler (s) are treated after being introduced into the mixing device (“internal processing”). In such a case, said filler (s) are efficiently treated after the filler (s) are introduced into the mixing device (“internal processing”), and an effective amount of processing agent (s) for processing is introduced into the mixing device simultaneously or so that the filler (s) ) and an effective amount of funds (funds) for processing come separately, but very close in place and time.

3. According to yet another embodiment, said filler (s) are efficiently treated partially before being introduced into the mixing device (“partial pre-treatment”), for example using well-known Lödige equipment, and partially after being introduced into the specified mixing device in a pre-processed state, moreover only two partial treatments are “effective” with respect to the degree of treatment, surface treatment, etc., as defined above, moreover, in “mixed “processing”, the second part or amount of the processing agent (s) is introduced into the mixing device simultaneously with the pre-processed fillers or in such a way that the pre-processed filler (s) and the second part of the processing agent (s) arrive separately, but very close in place and time.

When filler (s) are intended to be processed at least partially within a mixing device (“mixed processing”), one skilled in the art will recognize that the appropriate amount or ratio of superplasticizer (s) for processing needs to be added directly to the specified mixing device or mixed with the filler in question immediately before introduction into the mixing device, using in the latter case, e.g. measures weighing device ( "scales"), which is arranged directly before entering powdered products in Mixture device. The term “immediately before” is easy to understand as such a place and time when the filler (s) and processing means do not have the ability or time for mutual mixing, which could cause the start of processing. A good example is a balance on which two powders are placed together and then introduced almost immediately into a mixing device without first preparing the mixture.

It is much more preferable to choose the place and time of introduction of the specified ratio of the means for processing as close as possible to the place and time of introduction of partially processed filler (s) so that there is no dilution with previously introduced products that are already present in the mixing device (such like sand, gravel, water for mixing, optionally ordinary additives) so that the treatment agent is fully accessible to the filler (s) .

This is also true of the “internal processing” option.

Essentially, in both cases, if the place and time of introduction of the filler is excessively removed from the place and time of introduction of the treatment agent, regardless of the order of administration, it is possible to switch to a processing mode that is excessively late; in fact, this leads to a possible “expenditure” of the treatment agent for other ingredients before the introduction of the filler, or if the filler is introduced primarily, this leads to subsequent processing, that is, to the mode of “subsequent administration” in tables 1-6 (when “Subsequent administration” of the agent (s) for processing after a certain time after the introduction of the filler, as will be seen from tables 1-6 and FIGS. treatment according to the present invention).

Any subsequent administration should be excluded.

The present invention also includes an industrial embodiment, characterized in that at least a part of the effective amount of superplasticizer (s) for processing or all of the indicated effective amount is mixed with filler (s) using a weighing device ("scale") leading to the mixture preparation device. This can be considered as simultaneous administration or “almost simultaneous” administration.

In addition, according to the present invention, it is possible to provide a method in which part of the filler (s) are subjected to effective "pre-treatment", and the second part of the fillers is effectively treated "inside" the mixing device.

Some of the above embodiments are obviously complicated and / or require additional equipment or modifications to existing equipment. Thus, they are much less preferred, with a pre-treatment or initial treatment being most preferred.

Currently, the “best option”, which eliminates these disadvantages, is obviously the preparation of a pre-treated filler, which is then delivered to the end user and introduced unchanged into the mixing device, most preferably after the introduction of water for mixing, sand and gravel, if are present to enable subsequent preparation of the mixture in the usual manner accepted in the industry (the difference is that in the present invention and the filler is processed, which is absent in the prior art).

The present invention also includes such a pre-treated “calcium carbonate-based filler (s)” as a new industrial product, which is thus delivered to the end user, optionally after any processing to facilitate transportation.

As is known, in laboratory tests, due to the small volumes or loads used, sometimes a small amount of “plasticizing additives” is first placed on the bottom of the laboratory mixing device, some of these plasticizing additives may be superplasticizers, but many are not. However, even when some small amounts of superplasticizers are present as “plasticizing additives”, they cannot “process” the fillers “efficiently” as in the present invention, that is, according to the above definition. Essentially, they act as plasticizing additives in such a way that they interact mainly with other downloadable components, such as sand, gravel, mixing water, etc., which are mixed together or separately for a predetermined period of time, as a result of which fluidization of particles or aggregates in suspension is appropriate; in this operation, the additives are “bound” or “absorbed” by said particles of inert materials, which definitely need fluidization. Otherwise there would be no fluidization. Thus, they then cease to be accessible to fillers; for the sake of completeness, even if for a moment we assume that some (necessarily very small) amount of such plasticizing additive would remain available only partially and only indirectly, it could only interact to a minimum extent with the filler, that is, in any case, it would not corresponded to the actions of "effective" processing or "surface coating" or "unlocking", which produce superplasticizers, intentionally added according to the present invention at a time at such times that to ensure the conditions of “efficient processing”. Simply put, it would be impossible to achieve the necessary state of “threshold” or “initiation” for unlocking, and without such “initiation” any “unlocking” would be completely absent.

No prior art document has ever reported any improvement or improvement that could be related to plasticizing materials (in this case, many plasticizing materials are simply plasticizers, not superplasticizers); there is no doubt that if, in particular, in the design and research laboratory such an improvement were discovered, it would be described in the reports. The absence of such a message is simply due to the fact that such an “initiating” effect of “unlocking” was never observed.

On an industrial scale, most plasticizing additives are not most often used or, in some exceptional cases, they are used in small quantities to fluidize the mixture: again plasticizing additives are “used” for the fluidization of sand, gravel, etc. and turn out to be inaccessible to fillers, and thus, they cannot in any way “initiate” “unlocking” the system, which is an essential part of the present invention.

As indicated above, said filler (s) are made from calcium carbonate-based material (s) or mixtures thereof, which are mainly GCC or PCC materials, or a mixture of GCC materials, or a mixture of PCC materials, or a mixture of GCC materials and PCC.

The present invention also provides for said “cement compositions” (in the broad sense defined above) and their use, as well as “cement elements or products” obtained in this way from said compositions, and their use in “cement” industries.

The term "cement elements or products" throughout the text of this application means any and every structure or structure (or any element or product for any other industrial purpose known to a person skilled in the art, including offshore cement work or cementing of oil wells where " cement "compositions), which are produced from these compositions.

This will be described in detail below.

DETAILED DESCRIPTION OF THE INVENTION

As provided for by the detailed and most preferred embodiment (the “best embodiment” as of now), the method for manufacturing said “cement” compositions or systems is characterized (in the so-called “pre-treatment” or, in particular, in tables 1-6) ) is equivalent to the “initial” embodiment):

a) the manufacture of a powder of material (materials) based on dry calcium carbonate as a filler or fillers, which is defined above as “filler (s) based on calcium carbonate”, hereinafter referred to as “filler” or “fillers”,

b) mixing said filler (s) with an effective treatment amount of at least one superplasticizer, resulting in “pretreated filler (s)”,

c) introducing said pretreated filler (s) into a mixing device that already contains mixing water or an aqueous mixing composition, possibly containing conventional or “non-interfering” additives (“aqueous mixing composition”) (hereinafter for simplicity) called “mixing water”)

d) optionally introducing before or after, preferably prior to step c), inert materials such as sand and / or gravel, and possibly other “non-interfering” conventional additives or auxiliary materials,

e) kneading or stirring said loaded material for an effective period of time,

f) recovering said “cement” composition.

The term "non-interfering" means the complete or practical absence of interference during the specified processing or method according to the present invention.

The term "effective time period" means the full period of time after which a homogeneous mixture or composition is formed and which is from about 2 to 15 minutes, preferably for "standard" mixtures or compositions from 30 to 60 seconds. The following is a detailed discussion.

An end-user application example is as follows: if the end-user requires medium or “standard” properties for his final cement composition, for example, with final mixing in his device of a fixed installation, etc., he will use compositions that are of corresponding simplicity, that is, they are not particularly complex or sensitive to conventional additives, superplasticizer, filler, etc .; thus, the end user will need mixing for a relatively short time, for example from 35 to 65 seconds.

If, on the contrary, the end user requires properties at a high or very high level, he will use correspondingly more complex compositions and more sensitive components, for example, a more sensitive filler or superplasticizer, or sensitive conventional additives designed to achieve a certain property, etc., and, as a rule, he will use less or significantly less water for mixing; thus, he will need mixing for a much longer time, for example from 1-3 to 10-15 minutes.

Obviously, a “high-tech” composition or system means a high level of quality (see the “Testing Self-Leveling” section above) or it is “fluid” (also see above), and, on the contrary, a “standard” final composition means a low level of quality, then it is “dry” or, more likely, “plastic” (see above).

In both cases, that is, for “high-tech” or “standard” compositions, as explained in this application, the general task is to prepare a homogeneous composition, and, which is also explained in more detail in this application (see below), “ the main essential criterion is that the final product must be homogeneous. ”

The above working principles are well known to those skilled in the art and are provided for completeness only. The above meanings and examples are given solely as a guide that a person skilled in the art can easily use to fulfill the essential “main criteria”.

It is clear that it is impossible to provide examples or data for any type of final composition or ingredient, since interactions, their kinetics, etc. are complex, but these parameters are known to a person skilled in the art.

According to a less preferred embodiment, said method of manufacturing said “cement” compositions or systems is characterized by a “mixed treatment” mode, which includes:

a) the manufacture of a powder of material (s) based on calcium carbonate as a filler, as defined above,

b) mixing said filler (s) with a portion or fraction of an effective processing amount of at least one superplasticizer, resulting in partially pretreated filler (s),

c) introducing said partially pretreated filler (s) into a mixing device that already contains water for mixing or an aqueous composition for mixing, possibly containing conventional additives (“water composition for mixing”) (hereinafter referred to as “water for mixing "),

d) introducing, before or during, preferably during step c), into said mixing device the remainder of said processing effective amount or ratio of superplasticizer (s),

e) optionally introducing before or after, preferably prior to steps c) and d), inert materials such as sand and / or gravel, and possibly other conventional additives that do not interfere with said treatment,

f) kneading and stirring said loaded material for an effective period of time,

g) recovering said “cement” composition.

According to yet another embodiment, said method of manufacturing said “cement” compositions or systems is characterized by an “internal processing” mode, which includes:

a) the manufacture of a powder of material (s) based on calcium carbonate as filler (s), as defined above,

b) introducing said untreated filler (s) into a mixing device in which there is already an effective treatment amount of at least one superplasticizer, or which takes it immediately after introducing said untreated filler (s), water for mixing, or an aqueous mixing composition possibly containing conventional additives (“water composition for mixing”, hereinafter referred to as “water for mixing” for simplicity),

c) kneading and stirring said loaded material for an effective period of time,

d) optionally introducing before or after, preferably prior to step c), inert materials such as sand and / or gravel, and possibly other conventional additives or auxiliary materials that do not interfere with said processing,

e) recovering said “cement” composition.

The term “immediately after” means that the treatment agent can be administered before or after the untreated filler (s), but in the second case it must be administered quickly after the filler (s), say, within a few to 10 seconds, etc. so that the filler remains completely accessible to the impact of the processing means without any obstacle due to the preparation of the mixture with sand, gravel, etc.

As a rule, it is most preferable to first introduce inert materials such as sand and gravel into the mixing device, and optionally mix them with a small amount of water and / or a plasticizing agent (see above) before performing other steps.

At least one superplasticizer (and possibly at least one superplasticizer, possibly containing some inert amount of plasticizer) is used as a treatment agent.

According to the above definition, the processing agents, the so-called filler processing agents, are either contain superplasticizer (s) or at least one superplasticizer (and optionally at least one plasticizer to reduce the total cost) and preferably contain at least one superplasticizer and an optionally effective cost-reducing amount of at least one plasticizer and most preferably one superplasticizer and, optionally, an effective cost-reducing amount of one plasticizer.

Superplasticizers are well-known agents and, in their quality, the following products or families of compounds and mixtures thereof should be best selected:

polycarboxylates, polycarboxylate ethers, or much less preferred products derived from sulfonated naphthalene condensate or sulfonated melamine formaldehyde. Those products are known to those skilled in the art, which are described in detail in the documents of the prior art that are cited above.

According to a best embodiment of the present invention, the treatment agent (product A and product B) belongs to the family of superplasticizers and has the formula of a polycarboxylate ether.

It should be noted that the products indicated by the letters A to K in Table A are fillers that should be distinguished without creating confusion with the preferred processing agents A and B presented above, which are superplasticizers.

The term “effective time period” as used herein means a time period of from about 35 to 65 seconds for standard compositions and from 1-3 to 10-15 minutes for “high-tech”, that is, more complex and / or more sensitive compositions, such as known to specialists in this field of technology.

For a “standard” composition, the mixing time may be, for example, 10-15-20 s for gravel and sand (preparing a dry mix is preferred), then 10 s for mixing the hydraulic binder and untreated filler, then 10 to 15 s for mixing means (means) for processing and water for mixing (this happens in the so-called “internal processing” mode), then from 5 to 15 s for preparing the finished mixture containing the “usual additives” introduced last.

The main and essential criteria for the indicated “mixing period” are that the final product must be homogeneous and the (treatment) means for processing should be absorbed or adsorbed by sand or gravel to the minimum possible extent.

The term "effective amount" of plasticizer (when present with a superplasticizer) in this application means the amount or ratio of plasticizer that can reduce the cost of processing without interference to the system, namely, the behavior of the filler (s), in particular with respect to surface activity and reaction abilities); the same criteria apply to “inert additives”.

The term “present” means that said treatment agents consist essentially or completely of superplasticizer (s) as defined, and may also contain, as explained, a cost-effective amount of at least one plasticizer and may also contain inert additives, useful for the intended end use, such as defoamers, moderators, accelerators, etc., which are absolutely known to the person skilled in the art.

Conventional additives of an inert nature can be introduced at the points of introduction known to the person skilled in the art, as previously indicated.

The mixing device can be operated in batch mode, semi-continuous mode or continuous mode, and the changes are readily available to the average person skilled in the art.

Essentially, it was unexpectedly discovered that such a superplasticizer (s), which (which) were previously used simply as “plasticizing additives”, is able (able) to increase the quality of fillers from medium and sometimes from low to high.

The dosage of superplasticizer (superplasticizers) is used for pretreatment and processing of filler (s).

At the end-user location, the dosage of superplasticizer (s) is from 0.3 to 3 kg per 100 kg of cement, preferably from 0.8 to 1.2 kg per 100 kg of cement, based on dry materials.

In laboratory conditions, the same ratio is from 0.05 to 0.1% with respect to the dry weight of carbonate, that is, from 0.1 to 0.3 kg per 100 kg of cement, calculated on dry materials.

In laboratory conditions, 0.8 to 1.1 kg per 100 kg of cement, based on dry materials, is used to compile Table A.

At the location of the end user, the mass ratio of superplasticizer (s) and plasticizer (s) can be from 100/0 to 95 / 5-90 / 10, preferably not less than 85/15, based on dry materials.

The present invention also provides for the specified composition (or system) of cement (in the broad sense specified above, that is, including cement, cementitious composition, mortar, concrete):

- on their own, since they can be distinguished from similar compositions of the prior art by their physical structure and their properties,

- or prepared as described above according to the present invention,

and they are used in these cement systems or compositions for the manufacture of concrete elements

and, ultimately, in cement elements:

- on their own, as they can be distinguished for the same reasons as compositions,

- and prepared using these compositions,

- as well as in a filler (s) based on calcium carbonate, which (which) are pretreated with the pretreatment method according to the present invention.

Another objective, obviously, is to fulfill the requirements of the customer, according to which the diameter of the "plate" or "cone" must exceed 250 mm, preferably equal to 300 mm or more preferably exceeding 300 mm at an economical dosage.

Some excipient containing compositions satisfy this requirement depending on the origin of the excipient. This can be easily and quickly evaluated by a person skilled in the art by conducting a cone and plate test.

Thus, this test allows us to distinguish between fillers and to choose the best quality filler and even the best quality superplasticizer (superplasticizers), taking into account the final properties required by the end user.

Obviously, many materials definitely do not meet this requirement.

Typically, the test (prior art method) is carried out using untreated filler.

In this application, superplasticizers are used as agents for treating fillers in the particular inventive method.

Thus, another objective of the present invention is to increase the average or low quality of the filler-containing compositions or systems of cement, mortar and concrete (for simplicity, referred to as "cement") to a high level, obtaining high-quality compositions by introducing into the mixing the device specified superplasticizer (superplasticizers) and optionally (see above) at least one cost-effective amount of plasticizer (plasticizer ) To improve the behavior of the filler (fillers) and thus the total composition.

The plasticizer (s) are preferably selected from the above compounds.

Families of these compounds are very well known to those skilled in the art. The merit of the authors of the present invention was not to detect these families or to use them as superplasticizers in the general sense of the prior art, but to discover the possibility of a significant improvement in cement filler (and therefore cement compositions) by treating fillers based on calcium carbonate by such compounds.

It was noted that certain compositions have such a small cone diameter (“self-leveling test”), stickiness, etc., that there is no way to improve them; this demonstrates the difficulty of the task of the present invention.

Some compositions can be improved, but only by adding in large proportions the superplasticizers used according to the present invention, and even in such cases the diameter requirement can be fulfilled, but the “plate” or “cone” retains stickiness and a thick consistency, and despite the fact that “ plate ”has the correct diameter, this means that the resulting composition cannot be considered as an improved concrete composition to a high quality.

It must be remembered that for the acceptability of a composition or system as a high-quality composition or to improve low or medium quality to high quality, two conditions must be fulfilled simultaneously:

- the diameter of the "plate" or cone should exceed about 250 mm, or better than 300, or even better than 350 mm, and

- The “plate” or cone should have a sticky or thick consistency.

There is another measure of a very complex problem for which the present invention is intended, and the present invention has made a very significant technical and scientific contribution to the current state of the art.

As can be seen in the attached table A, “low-quality” fillers cannot be improved since they never fulfill both of these conditions.

This is also true for some “medium quality” fillers, such as D, B, G, I, and K, which may exhibit good fluidity, for example, at a dosage of 4 g, but have poor appearance or operating behavior.

Using table A and the notes above and below, one skilled in the art will be able to distinguish between excipients that can be improved according to the present invention and those (considered as “low quality” according to the test results in table A) that cannot be improved.

To achieve these goals, a specialist in the art should remember, first of all, that a certain ratio of water and cement is directly related to the manufacturability of the composition and, in addition, it is mandatory to give the final product high quality properties, such as hardening properties, drying properties, mechanical strength, namely compressive strength, and other properties at a high-tech level.

As indicated above, the present invention provides, first of all, surface treatment of CaCO ₃ filler (s) with one superplasticizer or several superplasticizers), optionally in the form of a mixture with one or more plasticizers. One skilled in the art will be able to easily calculate the amount of plasticizer as an effective cost-reducing amount that does not interfere with the overall processing, as described above.

Two products as superplasticizers provide the best results. As indicated above, at the filing date of this application, they represent the “best option” as they are (products A and B from the polycarboxylate ether family).

It should be noted, quite unexpectedly, that when using the present invention, the ratio of the processing agent (s) containing superplasticizer (s) and the CaCO ₃ filler (s) at a level as low as 0.03 or from 0.05 to 0 is sufficient ,one%. The complete surprise is that such insignificant amounts of processing agents are capable of improving even high-quality and low-quality fillers to a high level of quality.

Many such plasticizers, superplasticizers or plasticizing additives are known, which are described, for example, in European Patent EP 0663892 issued by CHRYSO.

Other products that have been successfully tested as superplasticizers suitable for use in the method according to the present invention to perform surface treatment of a carbonate filler, like the CHRYSO ™ products described in the European patent cited above, are, for example, PREMIA 196 ™ or NRG 100 from Mappei ™.

As a rule, some conventional additives, such as air-entraining additives, retarders or hardening accelerators, etc., can be administered at a place known to one skilled in the art, for example, with water or after the addition of superplasticizers.

As for the “powders”, that is, the cement and the filler, cement can first be added and then the filler, or alternatively, they can be added together as a pre-prepared mixture.

However, it is preferable to introduce cement and filler together in the form of a pre-prepared mixture, so as to ensure the formation of a homogeneous mixture of two powders and their wetting with water.

Periodic modes are described above.

You can also provide such continuous modes in which the introduction is carried out in the above sequences, for example, in a mixing device equipped with an endless screw (and the introduction is carried out at various points along the length of the equipment), possibly with the introduction of pre-prepared mixtures at some point (points) , or, as another example, in a series of sequential mixing devices, also with the possibility of introducing a pre-prepared mixture (s) in one of quiet devices. It will be obvious to a person skilled in the art that, in particular, the latter option (including several mixing devices) has numerous disadvantages, even if the necessary premises and investments are available.

Periodic modes, which will be described below, are preferred.

Conventional tests can help a person skilled in the art choose the most suitable options, taking into account the available equipment and end-user practices, as well as using the following tables and drawings that are attached to this application.

Tables 1-3 and FIGS. 1-3

In tables and figures 1-3, a “medium-quality” filler is used, which shows a “cone” in the test, a diameter of 170 mm without introducing the processing agent (left column), and a “plate” is formed, the appearance of which is determined by the dosage of the processing agent ( the dosage is expressed as a mass percentage of the dry detergent and the dry CaCO ₃ after the self-leveling process As discussed above, a diameter of 170 mm is completely insufficient.

Table 1 and figure 1 correspond to the surface treatment described above superplasticizer A at a dosage that is presented in the corresponding table.

Table 2 and figure 2 correspond to the surface treatment described above superplasticizer B at a dosage that is presented in the corresponding table.

Table 3 and figure 3 correspond to surface treatment with the product NRG 100 at the dosage that is presented in the corresponding table.

Table 1 "Medium-quality" filler Test Number 2312 / B 2312 / B1 2312 / B2 2312 / B3 2312 / B10 2312 / B11 2248/1 2312 / B12 2312 / B21 Processing mode Absent Subsequent introduction Subsequent introduction Subsequent introduction Initial introduction Initial introduction Initial introduction Initial introduction Processing at Lödige for 3 minutes Processing agent Absent A A A A A A A A Dosage of the treatment agent, expressed as the ratio of the weight of the dry treatment agent and dry calcium carbonate X 0.025% 0.05% 0.5% 0.025% 0.05% 0.1% 0.5% 0.1%

The diameter of the plate obtained in the cone self-alignment test 170 mm 238 mm 306 mm 477 mm 280 mm 308 mm 442 mm 451 mm 435 mm Result D1 C1 B1 A1 C1 B1 A1 A1 A1 Appearance Plastic appearance, but without spreading Uniform appearance Plastic appearance Fast flowing liquid Uniform appearance Plastic appearance Fluid appearance Fluid appearance Fluid appearance

table 2 "Medium-quality" filler Test Number 2312 / B 2312 / B4 2312 / B5 2312 / B6 2312 / B13 2312 / B14 2312 / B15 2312 / B16 2312 / B22 Processing mode Absent Subsequent introduction Subsequent introduction Subsequent introduction Initial introduction Initial introduction Initial introduction Initial introduction Processing at Lödige for 5 minutes Processing agent Absent B B B B B B B B Dosage of the treatment agent, expressed as the ratio of the weight of the dry treatment agent and dry calcium carbonate X 0.025% 0.05% 0.5% 0.025% 0.05% 0.1% 0.5% 0.1% The diameter of the plate obtained in the cone self-alignment test 170 mm 335 mm 395 mm 457 mm 382 mm 390 mm 425 mm 441 mm 437 mm Result D1 B1 A1 A1 A1 A1 A1 A1 A1 Appearance Plastic appearance, but without spreading Plastic appearance Fluid appearance Fast flowing liquid Fluid appearance Fluid appearance Fluid appearance Fluid appearance Fluid appearance

Table 3 "Medium-quality" filler Test Number 2312 / B 2312 / B7 2312 / B8 2312 / B9 2312 / B17 2312 / B18 2312 / B19 2312 / B20 2312 / B23 Processing mode Absent Subsequent introduction Subsequent introduction Subsequent introduction Initial introduction Initial introduction Initial introduction Initial introduction Processing at Lödige for 5 minutes Processing agent Absent NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 Dosage of the treatment agent, expressed as the ratio of the weight of the dry treatment agent and dry calcium carbonate X 0.025% 0.05% 0.5% 0.025% 0.05% 0.1% 0.5% 0.1% The diameter of the plate obtained in the cone self-alignment test 170 mm 220 mm 383 mm 465 mm 328 mm 413 mm 432 mm 451 mm 435 mm Result D1 C1 A1 A1 B1 A1 A1 A1 A1 Appearance Plastic appearance, but without spreading Uniform appearance Fluid appearance Fast flowing liquid Plastic appearance Fluid appearance Fluid appearance Fluid appearance Fluid appearance

Of the three curves in FIGS. 1-3, the curve corresponding to the addition of superplasticizer (superplasticizers) after all other ingredients (comparative and much less preferred embodiment) is marked with diamonds (the “subsequent administration” option in the tables), while the curve corresponding to the variant the implementation of the present invention, which uses "pre-treatment" or "initial processing" (laboratory version of the pre-treatment) is marked with squares (option "pre introduction ”in the tables).

The “triangle” in the tables is an isolated point corresponding to 100% pre-treatment of the filler in an external mixing device, such as Lödige, for 3 or 5 minutes before being introduced into the mixing device (right column in the tables, 435, 437 and 435 mm for “ plates ”in a cone test at a dosage of only 0.1%).

The indicated “triangle” is sometimes difficult to see in FIGS. 1-6 because it is overlapped by squares and / or rhombuses, with FIGS. 1-6 being divided into FIGS. 1a-6a (curves) and FIGS. 1b-6b (schematic diagrams in zoomed out showing approximate position of overlapping signs).

It was assumed that when processing a coarser filler, the amount of auxiliary material (s) should be noticeable or significantly higher. Quite unexpectedly, the opposite happens, that is, ratios such as from 0.03-0.05 to 0.1-0.5% are quite effective.

The authors unexpectedly noted that the curves in FIGS. 1 and 2 (and the percentages in the corresponding tables 1 and 2) show a “plateau” of about 0.12%, so it is useless to introduce more than about 0.1% of auxiliary material.

Thus, the best range is from 0.1% to 0.12%.

It should be noted that the study of the lower part of the curves, namely, related to the processing of material B, shows that the obvious technical effect is manifested in the range from 0.03 to 0.05%: a very sharp increase in diameter (consistency) can be detected and this represents a threshold dosage (lower limit of the interval) at which the requirement of self-alignment (“plate” or cone) is fulfilled, comprising from 250 to 300 mm.

As for table 3 and figure 3, it can be seen that the curve in the "preliminary introduction" variant is very similar to the curves in figures 1 and 2, that is, the "plateau" is very clearly manifested after 0.1-0.12-0.20 % or approximately in this area, and a similar sharp increase in consistency with a decrease in dosage, while the curve in the “subsequent administration” mode shows similar behavior at low dosages, but (above 0.05% or approximately in this area) shows a regular increase but with less speed. For this superplasticizer A, it can be seen that the useful dosage range in the “preliminary administration” method is from 0.05% (corresponds to a consistency of 300 mm) to 0.1-0.12% -0.20% (the beginning of a clear “plateau” , as on curves 1 and 2); in contrast, the “follow-up” curve at the lower dosage threshold is approximately the same (the two curves overlap at approximately 300 mm), while approximately 0.3% of the NRG 100 product needs to be added to achieve approximately 425 mm compared to approximately 0.1% for curve in case of pre-treatment or Lödige device.

However, it can be seen that in the “pre-introduction” embodiment, the curve may reach a plateau at 450 mm, when approximately 0.1-0.12-12.15% of the treatment agent A is used in the method according to the present invention, while in in the case of means B and NRG 100, the same percentages were used (and for the curve in the “preliminary administration” variant) at approximately 425 mm.

Thus, we can say that the technical effect appears (depending on the curves and on the desired value of consistency in millimeters) when the mass ratio of dry superplasticizer (superplasticizers) and cement is higher than 0.02-0.03-0.05%, and with this ratio the system is unlocked due to auxiliary material (materials); that is, it is an unlock point. This "unlock point" is probably an explanation of the unexpected effect of the method according to the present invention. Thus, again, depending on the auxiliary material and the desired consistency value, as well as for a given filler, it can be deduced from the indicated unlocking point that the optimum ratio is approximately 0.08-0.1-0.12.12-0.15% (since “plateau” follows, there is no need to add expensive auxiliary material, for example, there is no need to add it up to 0.5%) and it is most preferable to use the method in the “preliminary” or “first” embodiment initial treatment, that is, a method in which superplasticizer (s) as an auxiliary material (s) are added together (or at the same point of addition) with a filler (that is, the filler is first pretreated with a superplasticizer as an auxiliary material in separate equipment, similar to the well-known Lödige mixing device (but without actually improving the result, see the points marked with a “triangle” above), or superplasticizer (superplasticity cathodes) (and optionally, a cost-reducing amount of plasticizer (s)) are added along with the filler, since, as can be seen in FIGS. 1-3, the curve in the embodiment with “pre-treatment” or “initial” processing is always better than the curve in “subsequent administration” mode (that is, when the treatment agent is added after all the main ingredients, including after the filler (s)).

It may even be risky to use a more than optimal ratio of auxiliary material of 0.1-0.12-0.15%, because as a result of the excessive content of auxiliary materials in the system, free polymer will remain, which is an auxiliary material. Present in excess of the specified auxiliary material (free polymer) can interact with cement, other additives, etc., which leads to a possible imbalance in the system.

Tables 4-6 and Figures 4-6

The principle and procedures are the same as in tables 1-3 and the corresponding figures 1-3.

The authors attach tables 4-6 (corresponding to FIGS. 4, 5 and 6), which are the same tests as described above, but with a different filler, as a result of which in this case there is very good behavior in testing the cone, where the diameter is already before processing it is 288 mm, and a non-sticky, sparse and very fluid self-leveling cone or “plate” is obtained.

Table 4 High quality filler Test Number 2312 / A 2312 / A1 2312 / A2 2312 / A3 2312 / A10 2312 / A11 2239 / 3b 2312 / A17 Processing mode Absent Subsequent introduction Subsequent introduction Subsequent introduction Preliminary introduction Preliminary introduction Preliminary introduction Processing at Lödige for 3 minutes Processing agent Absent A A A A A A A Dosage of the treatment agent, expressed as the ratio of the weight of the dry treatment agent and dry calcium carbonate X 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1%

The diameter of the plate obtained in the cone self-alignment test 288 mm 237 mm 335 mm 406 mm 383 mm 403 mm 401 mm 415 mm Result B1 C1 B1 A1 A1 A1 A1 A1 Appearance Compact sticky appearance Homogeneous compact appearance Plastic appearance Fluid appearance Fluid appearance Fluid appearance Plastic appearance with proper spreading and sediment Fluid appearance, but with sediment

Table 5 High quality filler Test Number 2312 / A 2312 / A4 2312 / A5 2312 / A6 2312 / A12 2312 / A13 2239/9 2312 / A18 Processing mode Absent Subsequent introduction Subsequent introduction Subsequent introduction Preliminary introduction Preliminary introduction Preliminary introduction Processing at Lödige for 3 minutes Processing agent Absent B B B B B B B Dosage of the treatment agent, expressed as the ratio of the weight of the dry treatment agent and dry calcium carbonate X 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1%

The diameter of the plate obtained in the cone self-alignment test 288 mm 190 mm 334 mm 417 mm 394 mm 413 mm 415 mm 425 mm Result B1 D1 B1 A1 A1 A1 A1 A1 Appearance Compact, sticky appearance Slow spreading Plastic appearance Fluid appearance Fluid appearance Fluid appearance, but with sediment Fluid appearance Fluid appearance, but with sediment

Table 6 High quality filler Test Number 2312 / A 2312 / A7 2312 / A8 2312 / A9 2312 / A14 2312 / A15 2312 / A16 2312 / A19 Processing mode Absent Subsequent introduction Subsequent introduction Subsequent introduction Preliminary introduction Preliminary introduction Preliminary introduction Processing at Lödige for 3 minutes Processing agent Absent NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 Dosage of the treatment agent, expressed as the ratio of the weight of the dry treatment agent and dry calcium carbonate X 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1% The diameter of the plate obtained in the cone self-alignment test 288 mm 235 mm 361 mm 426 mm 367 mm 400 mm 414 mm 418 mm Result B1 C1 A1 A1 A1 A1 A1 A1 Appearance Compact sticky appearance Uniform appearance Compact appearance with proper spreading Fluid compact appearance with sediment Compact appearance with proper spreading Compact appearance with proper spreading Compact appearance with proper spreading and sediment Fluid appearance, but with sediment

As you can see, there is a pronounced difference for this kind of “good” or “high-quality” filler between the curves corresponding to two different processes.

However, it can be seen that for both types of curves there is an upper optimal limit for the ratio of superplasticizer (s) as an auxiliary material and dry cement of approximately 0.1%, while here auxiliary material A again behaves in a slightly different way from materials B and NRG 100.

However, as indicated above, it must be remembered that two conditions must be met simultaneously in order to obtain a high-quality or high-tech system:

- high consistency, that is, roughly speaking, high fluidity / processability, which can be observed in a self-leveling test, in which a diameter is obtained that exceeds approximately 250-300 or better exceeds 320-350 mm (as well as compactness or density, which corresponds to low porosity) , and at the same time

- non-sticky “sparse” (that is, easy to handle) “non-plastic” (and, obviously, “dry”) product without precipitation.

This can be seen in the six tables above.

For example, in tables 1 and 2 (medium filler (170 mm) + superplasticizer A or B), you can see the following:

- Tests 2312 / B1 and B4, both in the “subsequent introduction” mode: when using 0.025% of auxiliary material, the resulting system has a good diameter (335 mm) only in test 2312 / B4, despite a decrease compared with the dosage of 0.05% ( 395 mm), but B4 forms an unsuitable product because it has a “plastic appearance”: the second condition is not fulfilled, while B5 forms a “fluid” and usable product. In contrast, B1 has a uniform appearance at 0.05%, but the diameter is only 238 mm, which is insufficient.

- Tests 2312 / B10 (in the "initial introduction" mode, that is, "pretreatment") and B13 (also in the pretreatment mode): at the same dosage of 0.025%, product B in table 2 leads to a better diameter, but, in addition to in all, forms a “fluid” product, while B10 forms only a homogeneous product. At the same dosage, B4 with product B forms a plastic product.

In tests B13-B16 with the "pre-treatment" mode, as shown in Table 2, all systems are fluid and the difference is how the diameter (consistency) increases depending on the dosage.

Lödige: if you compare 2312 / B21 (using a pre-prepared mixture in a Lödige device at a dosage of 0.1% and a pre-treatment without a Lödige device at the same dosage of 0.1%, i.e. 2248/1 (table 1), you can see that in both cases fluidity is ensured and that the Lödige device leads to a slightly smaller diameter (435 compared to 442 mm), which, obviously, does not justify the use of additional Lödige equipment.

Thus, the “initial” or “pre-treatment” mode is best implemented by “simultaneously” introducing the filler (s) and the treatment tool (s) at a very close point of addition in terms of time and place.

Each table and curve can be analyzed in a similar way, and one skilled in the art will be able to use these numerous data using a variety of parameters, various superplasticizers, two different types of fillers (one untreated medium quality with a consistency of 170 mm, the other unprocessed high quality with a consistency of 280) and two options for implementation, to “build” your own system, taking into account the above parameters, as well as your specific requirements or conditions.

Mixed Processing Test

A laboratory test was performed by reproducing test 2248/1 of table 1 (the dosage of the treatment agent was 0.1%), except that the filler was treated by adding 50% (0.05%) of an effective amount of superplasticizer A to the total amount of filler ( GCC of “average” quality) and mixing both products in a laboratory mixer, after which the remaining amount (50%) of superplasticizer was quickly introduced into the mixing device, then after 5 seconds the filler was pretreated with the first a portion (50%) of superplasticizer A. The diameter in the self-leveling test was 392 mm and the appearance was “fluid”; thus, it can be considered that the mixed treatment gives a slightly smaller diameter, but, obviously, is part of the present invention.

Thus, the entire interval of the addition of superplasticizer (s), as well as, optionally, reducing the cost of the amount of plasticizer (s), taking into account all the above tests and curves and the general information given in this application, can be defined as the mass ratio of auxiliary material (materials ) and dry cement as: from 0.02-0.03-0.05% to 0.08-0.1-0.12-0.15%, which can easily be adjusted by a person skilled in the art.

You can see that all the tasks of the present invention, that is, the conditions and requirements of modern industry, are performed:

- at a low dosage (therefore, at a low cost) of surface treatment with at least one of the auxiliary materials described above,

- without the need for additional equipment,

- moreover, fillers from medium to low quality (rejected at the prior art or processed with unreasonable costs and investment) can be easily improved by obtaining high-quality fillers, capable of forming with other conventional ingredients compositions or systems of cement, mortar or concrete, which relate to " high-tech ”category, having a high or very high consistency in excess of 250, 300 or even 350 mm in the standard self-leveling test, high or about very high compactness (density), high or very high percentage of dry material in the final product, comprising from 87 to 95% wt. dry material in the final finished system, which provides a specialist in this field of technology the opportunity not only to meet the most stringent and relevant requirements of the industry, but also to obtain products whose properties characterize, first of all, “reproducibility”, that is, the ability to predict.

This "reproducibility" is a new distinctive feature that was not provided in the prior art, despite the needs of industry; it is believed, without being limited by theory, that technological stages and the used superplasticizers are responsible for this “reproducibility”.

Ensuring “reproducibility” is made possible by adjusting the dosage of the above surface treatment products A and B or by selecting other products as described above, and adjusting the dosage using the test method described above ensures constant properties, which is called the term “reproducibility”.

Application (s)

Applications are all areas in which the compositions or systems of cement, mortar, or concrete described above are typically used.

Cement products

They are products or elements that are known to be made from the above cement, mortar or concrete compositions in the construction industry or any other industry using a well-known method.

Claims (20)

1. A method of preparing a cement composition, including during the production of the cement composition, introducing into it a filler containing calcium carbonate, the surface of which is treated with a processing agent containing at least one superplasticizer and at least one plasticizer, wherein the ratio between the superplasticizer and plasticizer is from 95/5 to 85/15 based on the weight of dry materials. 2. The method according to claim 1, characterized in that said filler containing calcium carbonate is calcium carbonate, finely divided calcium carbonate, precipitated calcium carbonate or a mixture of finely divided calcium carbonate and precipitated calcium carbonate. 3. The method according to claim 1, characterized in that the superplasticizer is selected from the group consisting of polycarboxylate, polycarboxylate ether, sulfonated naphthalene condensate and sulfonated melamine formaldehyde. 4. The method according to claim 1, characterized in that the superplasticizer is a polycarboxylate or polycarboxylate ether. 5. The method according to claim 1, characterized in that at least 80% of the surface of the calcium carbonate particles is coated with at least one superplasticizer. 6. The method according to claim 1, characterized in that at least 90% of the surface of the particles of calcium carbonate is coated with at least one superplasticizer. 7. The method according to claim 1, characterized in that 100% of the surface of the particles of calcium carbonate is coated with at least one superplasticizer and plasticizer. 8. The method according to claim 1, characterized in that the cement composition contains from 0.3 to 3 kg of at least one superplasticizer per 100 kg of cement composition. 9. The method according to claim 1, characterized in that the cement composition contains from 0.8 to 1.2 kg of at least one superplasticizer per 100 kg of cement composition. 10. The method according to claim 1, characterized in that the calcium carbonate is treated from 0.05 to 0.1 wt.% Superplasticizer based on the dry weight of calcium carbonate. 11. The method according to claim 1, characterized in that the cement composition contains from 0.02 to 0.05 wt.% Superplasticizer based on the weight of the dry cement composition. 12. The method according to claim 1, characterized in that the cement composition contains from 0.08 to 0.15 wt.% Superplasticizer based on the weight of the dry cement composition. 13. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate, treated with at least one superplasticizer and at least one plasticizer, an inert material, a hydraulic binder, an air-entraining additive, a hardening inhibitor, a hardening accelerator, antifoam, auxiliary material and plasticizing agent. 14. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate treated with at least one superplasticizer and at least one plasticizer, an inert material, a hydraulic binder, an air-entraining additive, a hardening inhibitor, and a hardening accelerator, antifoam, auxiliary material, plasticizer and water. 15. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate treated with at least one superplasticizer and at least one plasticizer, an inert material, sand, a hydraulic binder, an air-entraining additive, a hardening inhibitor, an accelerator hardening, antifoam, auxiliary material and plasticizing additive. 16. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate treated with at least one superplasticizer and at least one plasticizer, an inert material, sand, a hydraulic binder, an air-entraining additive, a hardening inhibitor, an accelerator hardening, antifoam, auxiliary material, plasticizing additive and water. 17. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate, treated with at least one superplasticizer and at least one plasticizer, an inert material, sand, gravel, a hydraulic binder, an air-entraining additive, a hardening retardant , hardening accelerator, antifoam, auxiliary material and plasticizing additive. 18. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate, treated with at least one superplasticizer and at least one plasticizer, an inert material, sand, gravel, a hydraulic binder, an air-entraining additive, a hardening retardant , hardening accelerator, antifoam, auxiliary material, plasticizing agent and water. 19. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate treated with at least one superplasticizer and at least one plasticizer, an inert material, a hydraulic binder, an air-entraining additive, a hardening inhibitor, and a hardening accelerator, antifoam, auxiliary material, a plasticizing agent and optionally a superplasticizer and / or plasticizer. 20. The method according to claim 1, characterized in that the cement composition contains a filler containing calcium carbonate, treated with at least one superplasticizer and at least one plasticizer, an inert material, a hydraulic binder, an air-entraining additive, a hardening inhibitor, a hardening accelerator, antifoam, auxiliary material, a plasticizing agent and water, and optionally a superplasticizer and / or plasticizer.

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