RU2518584C2 - Colmating composition (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to preparations used for increasing water resistance of concrete, namely to elaboration of novel concrete-colmating (imperforating concrete pores) composition. In basic version composition represents mixture of salts, formed by metals from the group: sodium, potassium, calcium, aluminium, and acids from the group: nitric, formic, sulfuric, carbonic, with the following ion ratio (ion weight in composition, g)/(100 g of composition): sodium 5.6-32, calcium 0.4-17.2, potassium 1.5-27.2, aluminium 0.5-7.6, nitrate 4.1-62.1, formiate 0.6-29.7, sulfate 10.3-54.7, carbonate 1.1-29.7, as well as complex-forming additives (such as, for instance, carbamide, nitryltriacetic acid, imino-N,N-diacetic-N-methylene phosphonic acid; glycin-N,N-di(methylene phosphonic) acid, iminodi(methylene phosphonic) acid; diaminopropanol- N,N,N',N'-tetraacetic acid; 2-hydroxypropylene diamine- N,N,N',N'-tetra(methylene phosphonic) acid; 2,3-dihydrobutylene-1,4-diamine- N,N,N',N'-tetra(methylene phosphonic) acid; 2,3-dihydroxybutylene-1,4-diamine- N,N,N',N'-tetraacetic acid; nitryl-tri(methylene phosphonic) acid; 1-hydroxyethylene diphosphonic acid; ethylenediamin- N,N,N',N'- tetra(methylene phosphonic) acid; ethylenediamine-N,N,N',N'- tetraacetic acid; in amount not more than 20% of colmating composition weight.

EFFECT: extension of arsenal of preparations, used to increase concrete water resistance.

5 cl, 3 tbl

Description

The invention relates to means used to increase the water resistance of concrete, and in particular to the development of a new composition, cobbing concrete (heal pores of concrete).

There are many colmatizing agents for waterproofing concrete used in construction. The main objective of such tools is to increase the water resistance of porous building materials (concrete) by overgrowing existing or newly emerging pores. Mudging agents used for waterproofing concrete, as a rule, are multicomponent compositions based on salts that form insoluble products in concrete pores when interacting with calcium ions. For example, compositions based on:

- sodium carbonate and potassium chloride (A.S. USSR 540847);

- sodium chloride, sodium carbonate and sodium sulfate (A.S. USSR 629184);

- hypochloride, calcium hydroxide and carbonate, oxides of magnesium, silicon, iron and aluminum (A.S. USSR 823360);

- carbonate, sulfate, nitrate, sodium chloride and calcium nitrate (RF patent 2052413);

- carbonate, sulfate, sodium nitrate, oxide, nitrate and calcium metasilicate (RF patent 2052413);

- carbonate, nitrate, sodium sulfate, chloride, carbide, calcium hydroxide (RF patent 2072335);

- carbonate, hydrogen carbonate, sulfate, sodium nitrate, hydroxide, calcium nitrate, carbonate, hydrogen carbonate, potassium nitrate and lithium nitrate (RF patent 2165911);

- mixtures of salts formed by metals from the list: lithium, sodium, potassium, calcium, magnesium, iron, aluminum, titanium and acids from the list: sulfuric, hydrochloric, nitric, nitrous, silicon, coal, boric, phosphoric (patent RF 2303586).

Each of these colmatizing agents has its advantages and disadvantages.

As a prototype of the present invention, the solution given in the application for the invention of the Russian Federation 2009100578 "Composition for waterproofing porous materials and a method for its preparation", namely the waterproofing composition of the sealing action for porous materials, representing a mixture of salts, characterized in that they use as a mixture of salts, is selected salts formed by metals from the list: sodium, calcium, magnesium, iron, aluminum, and acids from the list: nitric, formic, nitrous, sulfuric, coal, with the following ratio of ions (mass of ion on the composition, g) / (100 g of the composition):

 sodium 0.6-25.3  calcium 1.7-30.1  magnesium, no more 5  iron, no more 6.5  aluminum, no more 6.5  nitrate 3,5-75,8  formate 0.1-65.7  nitrite, no more 18.8  sulfate, no more 33.3  carbonate, no more 26.2

The key advantages that predetermined the choice as a prototype of the solution given in the application for the invention of the Russian Federation 2009100578 are

- lack of chlorides in his formulation. After all, chlorides are well-known activators of corrosion of metal reinforcement in reinforced concrete;

- the possibility of making a completely water-soluble composition (without an insoluble phase).

However, the prototype is not without drawbacks, in particular, the prototype does not allow to obtain selective compositions for the mudding of deep concrete layers, because clogging additives "work" already in the outer layers of concrete, providing a waterproof layer with a depth of 50-100 mm.

Since the majority of descriptions of colmatizing compositions use the method of determining its composition "by dosage", i.e. for the initial salts used at the stage of preparation of the composition, and a more accurate ionic scheme (given above) is rarely used, then for the convenience of comparison we give some more close solutions in terms of the ionic scheme, each of which can also be considered to some extent as a prototype the proposed composition.

The mass of the ion in the composition, g / (100 g of the composition) And he RF patent 2165911 RF patent 2149849 RF patent 2052413 RF patent 2303586  lithium 0-5.6 0 0 0-6.9  sodium 2.0-32.5 23.0-23.9 23.6-42.7 0.7-48.2  potassium 0-46.9 0 0 0-41.5  calcium 0-17.3 10.6-12.6 0.1-4.7 5-25  magnesium 0 0 0 0-6  iron 0 0 0 0-4.9  aluminum 0 0 0 0.01-4.9  titanium 0 0 0 0-4,2  sulfate 3.4-8.4 19.1 11.5-22.5 0.8-28.6  chloride 0 0 0.2-0.3 0.01-5.8  nitrate 16.5-49.2 26.6-28.1 10.9-31.5 4.9-64  nitrite 0 0 0 0-24.5  silicate 0 2.7-4.3 0 0-10  carbonate 3.2-9.2 4.3-4.9 9.2-15.9 0,1-10  formate 0 0 0 0  borate 0 0 0 0-4,2  phosphate 0 0 0 0-6.7

The objective of the invention is the expansion of the arsenal of tools used to increase the water resistance of concrete.

The problem is solved by creating a new colmatizing composition, in which the opportunity is provided:

1. mudding of deep concrete layers (basic composition);

2. obtaining the composition in a water-soluble form (water-soluble version of the composition).

1. The basic version of the composition

As a result of the studies, the following composition of the proposed means for increasing the water tightness of concrete was revealed, namely, a clogging composition representing a mixture of salts and complexing additives, characterized in that salts formed by metals from the list are used as a mixture of salts: sodium, potassium, calcium, aluminum, and acids from the list: nitric, formic, sulfuric, carbonic, with the following ratio of ions, (mass of ion in the composition, g) / (100 g of composition):

 sodium 5,6-32  calcium 0.4-17.2  potassium 1.5-27.2  aluminum 0.5-6.7  nitrate 4.1-62.1  formate 0.6-29.7  sulfate 10.3-54.7  carbonate 1.1-29.7

And as complexing additives (to increase the coiling of concrete to a depth of over 100 mm), additives such as, for example, urea are used; nitrile triacetic acid; imino-N, N-diacetic-N-methylenephosphonic acid; glycine-N, N-di (methylenephosphonic) acid; iminodi (methylenephosphonic) acid; diaminopropanol-N, N, N ′, N′-tetraacetic acid; 2-hydroxypropylenediamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; 2,3-dihydroxybutylene-1,4-diamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; 2,3-dihydroxybutylene-1,4-diamine-N, N, N ′, N′-tetraacetic acid; nitrile tri (methylenephosphonic) acid; 1-hydroxyethylene diphosphonic acid; ethylene diamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; ethylenediamine-N, N, N ′, N′-tetraacetic acid. The effective concentration of complexing additives is not more than 20% by weight of the colmatizing composition.

The proposed composition differs from the prototype and close solutions in other ingredients and their concentration, in particular the use of complexing additives.

As a result, after processing the concrete with the proposed composition, when testing the water resistance of concrete in accordance with GOST 12730.5-84, cutting the processed sample cylinder into disks 50 mm thick was found to increase the water resistance of concrete at a depth of 100-150 mm.

For additional security:

- operability during storage;

- uniform distribution over the surface of the treated concrete;

- prolonged contact with the treated concrete;

- more uniform distribution in the volume of concrete with the addition of the composition to the concrete mixture;

the carrier usual for clogging compositions can be used - cement, sand. In addition to cement, sand, lime can be added to the carrier, which, like cement, helps protect against moisture and, like cement, can enhance the effectiveness of the composition. In the case of using a carrier, its weight should preferably be at least 50% by weight of the co-colt composition.

2. Water-soluble version of the composition

The second variant of the proposed composition is a colmatizing composition, which provides the possibility of making a completely water-soluble mixture (without an insoluble phase).

The same prototype was used for the fully water soluble colmatating composition as for the first (base) composition. Indeed, the solution provided in the application for the invention of the Russian Federation 2009100578 also provides for the possibility of making a completely water-soluble mixture.

To obtain a water-soluble coagulating composition, studies have been carried out, as a result of which the required composition has been found, namely, a coagulating composition, soluble in water, which is a mixture of salts, characterized in that salts formed from metals from the list are used as a mixture of salts: sodium, potassium , calcium, aluminum, and acids from the list: nitric, formic, with the following ratio of ions (mass of ion in the composition, g) / (100 g of composition):

 sodium 0.3-20  calcium 3.6-28.1  potassium 0.6-33.7  aluminum 0.3-9.4  nitrate 16.4-80.8  formate 2,3-52,4

The proposed composition differs from the prototype in other ranges of concentrations of ingredients and, primarily, the presence of salts formed by potassium.

For additional security:

- stability of the composition (exclusion of clumping);

- a more uniform distribution in the volume of concrete when adding the composition to the concrete mixture

water can be used as a solvent and carrier of colmatizing additives. In the case of using water, its mass should preferably be at least 50% by weight of the colmatizing composition.

To increase the effect of the use of a water-soluble colmatizing composition, a plasticizing agent for concrete mixtures, for example, sulfonate, polyacrylate or polycarboxylate type, can be used.

The method for preparing the composition is conventional mechanical mixing of free-flowing salts.

The practical use of the proposed composition is illustrated by the following examples.

1. The basic version of the colmatizing composition

The composition is prepared by mixing the salts in dry form. Salts are selected so as to provide the desired ionic composition. In particular, the following compositions were tested:

1-1) 1.84 g of potassium formate, 19.94 g of sodium nitrate, 3.07 g of potassium carbonate, 46.01 g of sodium carbonate, 21.47 g of sodium sulfate, 6.13 g of aluminum sulfate, 1.53 g calcium nitrate;

1-2) 13.89 g of potassium formate, 5.56 g of potassium carbonate, 2.78 g of sodium carbonate, 13.89 g of sodium sulfate, 41.67 g of aluminum sulfate, 22.22 g of calcium nitrate;

1-3) 1.19 g of potassium formate, 10.43 g of sodium nitrate, 1.59 g of potassium carbonate, 0.8 g of sodium carbonate, 11.15 g of sodium sulfate, 3.18 g of aluminum sulfate, 71.66 g calcium nitrate;

1-4) 2.36 g of potassium formate, 20.47 g of sodium nitrate, 3.15 g of potassium carbonate, 1.57 g of sodium carbonate, 22.05 g of sodium sulfate, 47.24 g of aluminum sulfate, 3.15 g calcium nitrate;

1-5) 54.55 g of potassium formate, 1.82 g of sodium nitrate, 3.64 g of potassium carbonate, 1.82 g of sodium carbonate, 27.27 g of sodium sulfate, 7.27 g of aluminum sulfate, 3.64 g calcium nitrate.

The mass of the ion in the composition, g / (100 g of the composition) And he Composition designation 1-1 1-2 1-3 1-4 1-5  sodium 32 5,6 6.7 13.3 10  calcium 0.4 5.3 17,2 0.8 0.9  potassium 2.6 9.6 1,5 2.9 27,2  aluminum one 6.7 0.5 7.6 1,2  nitrate 15.7 16.9 62.1 17.3 4.1  formate one 7.5 0.6 1.3 29.5  sulfate 19.8 44,4 10.3 54.7 24.7  carbonate 27.5 four 1,1 2,3 2.6

Complexing additives such as urea were tested as complexing additives to increase the depth of concrete mastication; nitrile triacetic acid; imino-N, N-diacetic-N-methylenephosphonic acid; glycine-N, N-di (methylenephosphonic) acid; iminodi (methylenephosphonic) acid; diaminopropanol-N, N, N ′, N′-tetraacetic acid; 2-hydroxypropylenediamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; 2,3-dihydroxybutylene-1,4-diamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; 2,3-dihydroxybutylene-1,4-diamine-N, N, N ′, N′-tetraacetic acid; nitrile tri (methylenephosphonic) acid; 1-hydroxyethylene diphosphonic acid; ethylene diamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; ethylenediamine-N, N, N ′, N′-tetraacetic acid.

Complex-forming additives were introduced in an amount of not more than 20% by weight of the clogging composition, namely: 0.5%, 1%, 5%, 10% and 20% by weight of the clogging composition.

The performance of the resulting colmatizing composition was tested in comparison with the prototype in terms of water resistance by the "wet spot" method according to GOST 12730.5-84 "Concretes. Methods for determining water resistance. "

The colmatizing composition was used in two ways:

1) by introducing it into a concrete solution in an amount of 1% by weight of cement;

2) by introducing it into a cement-sand mixture (1: 1 ratio) in an amount of 1% of the cement-sand mixture. This mixture was closed with water to the consistency of thick sour cream and applied with a layer of 2 mm on one of the ends of the concrete sample cylinder. In this case, the sample cylinder was moistened before treatment with the mixture, and after processing it was stored in humid conditions.

It was found that for all concrete cylinder samples containing both the additive of the prototype and the additive of the proposed coagulating composition, the water resistance was 1-1.8 MPa, which is acceptable for most applications of such compositions.

For control samples without additives, the water resistance was 0.2-0.4 MPa.

For concrete samples-cylinders treated with a cement-sand mixture with the addition of a prototype, and with the addition of the proposed co-coating composition, the depth of concrete was checked. To do this, the processed concrete cylinder samples (height 150 mm) were cut into 50 mm thick disks and the water resistance of each disk was checked. It turned out that when processing the surface of concrete at a depth of more than 100 mm, the prototype is less effective and, moreover, less susceptible to the influence of complexing additives than the proposed composition. The water resistance of concrete at a depth of 100-150 mm with the introduction of complexing additives was:

- for the prototype - 0.4-1.0 MPa;

- for the proposed composition is 0.8-1.4 MPa.

With equimolar substitution of salts in the composition while maintaining the overall qualitative and quantitative composition of ions in the composition, the same results were obtained. In particular, with equimolar replacement:

- potassium formate and calcium nitrate to potassium nitrate and calcium formate (according to the equation:

2KHCO ₂ + Ca (NO ₃ ) ₂ = 2KNO ₃ + Ca (HCO ₂ ) ₂ );

- sodium nitrate and aluminum sulfate to sodium sulfate and aluminum nitrate (according to the equation:

6NaNO ₃ + Al ₂ (SO ₄ ) ₃ = 3Na ₂ SO ₄ + 2Al (NO ₃ ) ₃ ).

To provide:

- stability colmatizing composition (exclusion of clumping);

- uniform colmatizing composition distribution over the surface of the concrete being processed;

- prolonged contact of the matting composition with the treated concrete;

- a more uniform distribution of the cobbing composition in the concrete volume when the composition is added to the concrete mixture;

It was checked as the carrier of the composition - cement, sand, incl. with lime additives. The resulting mixture is easily loose, has a less tendency to clump, and provides more convenient work with a clumping composition. It has been established that it is possible to effectively combat clumping of a composition (especially when in contact with air) if a carrier is used in an amount of not less than 1: 2 by weight of the composition, i.e. the weight of the carrier should preferably be not less than 50% by weight of the colmatizing composition.

2. Collimating composition, soluble in water

The composition is prepared by mixing the salts in dry form. Salts are selected so as to provide the desired ionic composition. In particular, the following compositions were tested:

2-1) 2.47 g of calcium formate, 1.23 g of potassium formate, 74.09 g of sodium nitrate, 2.47 g of aluminum nitrate, 19.74 g of calcium nitrate;

2-2) 3.66 g of calcium formate, 73.19 g of potassium formate, 1.22 g of sodium nitrate, 2.44 g of aluminum nitrate, 19.5 g of calcium nitrate;

2-3) 75.02 g of calcium formate, 1.25 g of potassium formate, 1.25 g of sodium nitrate, 2.5 g of aluminum nitrate, 19.98 g of calcium nitrate;

2-4) 2.41 g of calcium formate, 1.2 g of potassium formate, 12.05 g of sodium nitrate, 72.29 g of aluminum nitrate, 12.05 g of calcium nitrate;

2-5) 11.24 g of calcium formate, 63.47 g of potassium formate, 1.12 g of sodium nitrate, 2.25 g of aluminum nitrate, 17.96 g of calcium nitrate.

The mass of the ion in the composition, g / (100 g of the composition) And he Composition designation 2-1 2-2 2-3 2-4 2-5  sodium twenty 0.3 0.3 3.3 0.3  calcium 5.5 5.8 28.1 3.6 7.8  potassium 0.6 33.7 0.6 0.6 31  aluminum 0.3 0.3 0.3 9,4 0.3  nitrate 71.2 17.8 18.3 80.8 16,4  formate 2,4 42 52,4 2,3 44,2 The solubility of the composition in water + + + + + Note: the "+" in the column "solubility in water" means that the composition in an amount of 10 g is completely dissolved in 1000 cm ^{3 of} water

With equimolar salt replacement while maintaining the overall qualitative and quantitative composition of ions in the composition, the same results were obtained. In particular, with equimolar replacement:

- potassium formate and calcium nitrate to potassium nitrate and calcium formate (according to the equation:

2KHCO ₂ + Ca (NO ₃ ) ₂ = 2KNO ₃ + Ca (HCO ₂ ) ₂ );

- aluminum nitrate and calcium formate to aluminum formate and calcium nitrate (according to the equation:

2Al (NO ₃ ) ₃ + 3Ca (HCO ₂ ) ₂ = 2Al (HCO ₂ ) ₃ + 3Ca (NO ₃ ) ₂ ).

For additional security:

- storage stability (clumping exclusion) of the clogging composition;

- a more uniform distribution of the cobbing composition in the concrete volume when the composition is added to the concrete mixture

water can be used as a solvent and carrier of colmatizing additives.

The resulting mixture is an aqueous solution. As a result, the risk of clumping of the composition is completely eliminated. The composition is easier and faster to distribute in the concrete mixture in comparison with the powder version and provides the most convenient work with the clogging composition.

It has been found that it is possible to obtain a solution from a soluble colmatizing composition if water is used in an amount of not less than 1: 1 by weight of the composition, i.e. preferably, the mass of water should be not less than 100% by weight of the colmatizing composition.

The performance of the resulting colmatizing composition, soluble in water, was tested in comparison with the prototype in terms of water resistance by the method of "wet spot" according to GOST 12730.5-84 "Concrete. Methods for determining water resistance. "

Used a cobbing composition by introducing it into a concrete solution in an amount of 1% by weight of cement;

It was found that for all concrete cylinder samples containing both an additive of the prototype and the additive of the proposed co-coating composition, the water resistance was 1-1.8 MPa, which is acceptable for most applications of such compositions.

For control samples without additives, the water resistance was 0.2-0.4 MPa.

Additionally, it was found that to increase the effect of the use of a water-soluble colmatizing composition, a plasticizing agent for concrete mixtures, for example, sulfonate, polyacrylate or polycarboxylate type, in particular sodium lignosulfonate, sodium naphthalene methylene sulfonate, sodium polyacrylate, sodium polycarboxylate in an amount of up to 200% can be used by weight of the colmatizing composition.

Plasticizing additives were introduced in an amount of not more than 200% by weight of the clogging composition, namely: 1%, 5%, 10%, 50%, 100% and 200% by weight of the clogging composition. As a result, it was possible to further increase the water resistance of concrete (water resistance was 1.2-2.0 MPa). Moreover, plasticizing additives were introduced both into a powder co-mating composition and into its solution in water.

Claims (5)

1. Colmatizing composition, consisting of a mixture of salts and complexing additives, characterized in that as a mixture of salts using salts formed by metals from the list: sodium, potassium, calcium, aluminum, and acids from the list: nitric, formic, sulfuric, coal, with the following ratio of ions (mass of ion in the composition, g) / (100 g of composition):
sodium 5,6-32 calcium 0.4-17.2 potassium 1.5-27.2 aluminum 0.5-7.6 nitrate 4.1-62.1 formate 0.6-29.7 sulfate 10.3-54.7 carbonate 1.1-29.7
as complexing agents, additives such as urea, for example, are used; nitrile triacetic acid; imino-N, N-diacetic-N-methylenephosphonic acid; glycine-N, N-di (methylenephosphonic) acid; iminodi (methylenephosphonic) acid; diaminopropanol-N, N, N ′, N′-tetraacetic acid; 2-hydroxypropylenediamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; 2,3-dihydroxybutylene-1,4-diamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; 2,3-dihydroxybutylene-1,4-diamine-N, N, N ′, N′-tetraacetic acid; nitrile tri (methylenephosphonic) acid; 1-hydroxyethylene diphosphonic acid; ethylene diamine-N, N, N ′, N′-tetra (methylenephosphonic) acid; ethylenediamine-N, N, N ′, N′-tetraacetic acid, in an amount of not more than 20% by weight of the clogging composition. 2. The composition according to claim 1, characterized in that it additionally contains sand, cement, lime, and their mass should preferably be at least 50% by weight of the matting composition. 3. Collimating composition, soluble in water, consisting of a mixture of salts, characterized in that as a mixture of salts using salts formed by metals from the list: sodium, potassium, calcium, aluminum, and acids from the list: nitric, formic, with the following ratio ions (mass of ion in the composition, g) / (100 g of composition):
sodium 0.3-20 calcium 3.6-28.1 potassium 0.6-33.7 aluminum 0.3-9.4 nitrate 16.4-80.8 formate 2,3-52,4 4. The composition according to claim 3, characterized in that it additionally contains water, and the mass of water should preferably be not less than 100% by weight of the clogging composition. 5. The composition according to claim 3 or 4, characterized in that it additionally contains plasticizing additives for concrete mixtures in an amount of not more than 200% by weight of the cobbing composition.