Concrete-expanding additive and method of its obtaining

FIELD: chemistry.

SUBSTANCE: claimed invention relates to a concrete-expanding additive and to a method of obtaining thereof. Concrete with the said additive possesses higher stability in storage. The concrete-expanding additive is obtained by thermal treatment of a clinker or a powder-like clinker, which contains in wt.p. per 100 parts of the clinker free lime in an amount of 10-70, a hydraulic substance 10-50 and water-free calcium sulphate 1-50, in an atmosphere of gaseous carbon dioxide to form in it calcium carbonate. In the method of obtaining an expanding additive clinker, containing free lime, the hydraulic substance and water-free calcium sulphate are subjected to thermal processing to form in it calcium carbonate. The invention is developed in dependent items of the invention formula.

EFFECT: provision of considerable concrete expansion in the period from 2 to 7 days after laying, which makes it possible to develop high early compression strength.

9 cl, 7 tbl

 

The technical field to which the invention relates

The present invention relates to an expanding material for concrete used in civil construction, and method of its production.

The level of technology

Some variants of the expanding materials for concrete, able to significantly expand, when added in small quantities (Patent publication 1), and expanding the material for cement, in which the surface is covered with quicklime calcium carbonate (Patent publication 2). Also invited to tarboneserifut surface soft burned, high slaked or hydrated lime intended for use as a powder material for bonding cement concrete (Patent publication 3).

In the field of steel production method carbonation of lime for the inhibition of hygroscopicity of lime used as obeserver agent.

List of publications prior art

Patent publication

Patent publication 1: patent No. 4244261

Patent publication 2: JP(A) 54-93020

Patent publication 3: JP(A) 58-154779

Non-patent publication

Non-patent publication 1: “Regarding the inhibition of the hygroscopicity of quicklime by partial carbonation of the inhibition of hygroscopicity quicklime by cha is part of carbonization), Iron and Steel, 1978, Vol. 64, No. 2, pp 56-65.

The invention

A characteristic feature of normal expanding material is rapid expansion within one or two days after concrete placement and then slow expansion until the material age 7 days. However, at the age of one or two days, the hydration reaction of cement in concrete is not fast enough, so the matrix becomes grupocontinental, with significant dislodging that often likely leads to the absence of preliminary voltage generated by the expanding material in the steel reinforcement. Thus, there is still a growing need for expanding the material, which is added in small quantities, less expanded, when the material has aged one or two days, and expands more when the material has aged from 2 to 7 days, especially from 5 to 7 days. The problem inherent in the expanding material of the prior art, is that when stored for a long time in the atmosphere with high temperature and humidity, its ability to expand is reduced, and if it is pre-mixed with cement, the ability to expand is even worse. Storage ready expanding cement, in which there is an admixture of the expanding material is, convenient not only because it avoids the difficult casting concrete mixing plant, but also prevents the formation of bubbles due to coagulation of the expanding material, which is the result of poor mixing. However, the above-described problems are particularly severely hampered the use of this valuable property.

Therefore, the present invention is the provision of an expanding material, allowing significant expansion of the concrete during the period from 2 to 7 days after laying, allowing the concrete to develop high early compressive strength and has high storage stability; and a method of its production.

Means of achieving the specified objectives

In accordance with the present invention, it is provided by the expanding material, which differs in that it can be obtained by heat treatment of clinker or powdered clinker containing free lime, hydraulic substance and anhydrous calcium sulfate, in an atmosphere of carbon dioxide gas to form it of calcium carbonate.

In one of the embodiments of the invention, the expanding material contains a particle, in which the free lime, hydraulic substance, anhydrous calcium sulfate and calcium carbonate are present simultaneously. In another embodiment, about what westline of the invention, the expanding material contains calcium carbonate in an amount of from 0.5 to 10% of the mass.

In another one of the embodiments of the invention, the expanding material has a specific surface area according to blaine in the range from 1500 to 9000 cm2/year

In yet another embodiment of the invention, the expanding material additionally contains anhydrous calcium sulfate is added to the clinker or powdered clinker subjected to heat treatment in an atmosphere of carbon dioxide gas to form it of calcium carbonate.

In yet another embodiment of the invention, the expanding material further comprises a debilitating shrinkage agent is added to the clinker or powdered clinker subjected to heat treatment in an atmosphere of carbon dioxide gas to form it of calcium carbonate.

In yet another embodiment, the present invention provides a cement composition in which any of the above-expanding materials mixed with cement.

In yet another embodiment, the present invention provides a method of obtaining any of these expanding material by heat treatment or powdered clinker clinker containing free lime, hydraulic substance and todny calcium sulfate, in the atmosphere of carbon dioxide gas to form it of calcium carbonate.

In yet another embodiment, the invention is a method of obtaining an expanding material includes filling the carbonizing tank or powdered clinker clinker with the purpose of the education of calcium carbonate at a flow rate of carbon dioxide gas from 0.01 to 0.1 l/min per liter of the tank and at the prevailing reservoir temperatures from 200 to 800°C.

Advantages of the invention

In accordance with the present invention, can be obtained by expanding the material, allowing significant expansion of the concrete during the period when the material has aged from 2 to 7 days after laying, allowing the concrete to develop high early compressive strength, when the material has an age of 7 days, and stable from the viewpoint of a decrease in the ability to expand, even when stored for a long time.

Embodiments of the invention

Unless otherwise specified, "parts" and "%" in this document are given by weight.

In the context of this document, the term "concrete" is a General term referring to the cement paste, cement mortar and cement concrete.

The expanding material of the present invention is obtained by treatment with gaseous carbon dioxide clinker in nephros obraznoi or powdered form, where clinker is produced by heat treatment of the mixture given initial Cao initial Al2O3original Fe2O3original SiO2original CaSO4.

"Free lime" is what is usually called f-Cao.

Referred to in this document as "hydraulic substance" is, for example, haüyne, represented by the formula 3CaO·3Al2O3·CaSO4, calcium silicate represented by the formula 3CaO·SiO2(denoted for brevity, C3S) or 2CaO·SiO2(denoted for brevity, C2S), almaterra calcium, represented by the formula 4CaO·Al2O3·Fe2O3(denoted for brevity, C4AF), 6CaO·2Al2O3·Fe2O3(denoted for brevity, C6A2F) or 6CaO·Al2O3·Fe2O3(denoted for brevity, C6AF) and calcium ferrite represented by the formula 2CaO·Fe2O3(denoted for brevity, C2F). Preferably, these compounds are used individually or in combination of two or more of them. The morphology of the calcium carbonate contained in the expanding material of the present invention, has certain limitations.

The CaO source includes limestone and hydrated or gidratirovannuyu lime; the original Al2O3includes bauxite, aluminum bottom ash is so; the source of Fe2O3includes copper slag or commercially available iron oxide; a source of SiO2includes fluorite, etc.; source CaSO4includes dowolny calcium sulfate, semi-aquatic calcium sulfate and anhydrous calcium sulfate.

These source materials often contain impurities, however, in terms of harm to the achievement of the advantages of the present invention, they are, in fact, pose no problems. Examples of impurities include MgO, TiO2, ZrO2, MnO, P2O5, Na2O, K2O LiO2, sulfur, fluorine and chlorine.

Although thermal testing of clinker used in the expanding material of the present invention, no specific limitation is preferred to burn the clinker at a temperature of from 1100 to 1600°C, especially from 1200 to 1500°C in an electric furnace, kiln, etc. At a temperature of less than 1100°C is not reached satisfactory ability to extend, at a temperature of over 1600°C is likely the decomposition of anhydrous calcium sulphate.

The content of the relevant minerals present in the clinker used in the expanding material of the present invention, preferably lies in the following ranges. The free lime content is preferably from 10 to 70 parts, more preferably from 40 to 60 parts per 100 parts of clinker. With the holding of the hydraulic substance is preferably from 10 to 50 parts, more preferably from 20 to 30 parts per 100 parts of clinker. The content of anhydrous calcium sulfate is preferably from 1 to 50 parts, more preferably from 20 to 30 parts per 100 parts of clinker. When the content of anhydrous calcium sulphate in less clinker in the manufacture of the expanding material of the present invention, it is preferable to use fresh anhydrous calcium sulfate. Any deviation from these ranges often can cause either too strong expansion, resulting in lower compressive strength or weakening of expansion in the period when the age of the material is from 2 to 7 days, especially from 5 to 7 days.

Mineral content can be confirmed using conventional, conventional methods of analysis. For example, a powder sample is placed in the powder x-ray diffraction device, identify the minerals present and analyze these data by the Rietveld method (Rietveld), thereby determining the amount of these minerals. The number of minerals can also be obtained numerically on the basis of chemical composition and identification results using powder x-ray diffraction.

Handling of gaseous carbon dioxide with the aim of obtaining the expanding material of the present invention preferably correspond to the trace of the relevant ranges.

The consumption of carbon dioxide gas supplied into the carbonizing tank, is preferably from 0.01 to 0.1 l/min per liter of the volume of the carbonizing tank. At the rate the extent of 0.01 l/min carbonation clinker often takes a long time, and increase the flow of higher than 0.1 l/min does not lead to further increase in the rate of carbonation is economically disadvantageous. Note that these conditions for consumption are true only in relation to the case when the carbonizing tank using a crucible, placed in an electric furnace, through which is passed an excess of carbon dioxide gas that reacts with clinker; that is, these conditions do not apply to other cases, when gaseous carbon dioxide reacts with clinker otherwise. Use of exhaust gases leaving the kiln lime kiln, instead of carbon dioxide gas is preferable from the viewpoint of improving its ability to expand.

The carbonizing temperature in the tank is preferably set from 200 to 800°C. At a temperature less than 200°C. the carbonization reaction of clinker often stops at temperatures above 800°C is often impossible the formation of calcium carbonate, because even though the coal is converted into calcium carbonate reaction takes place decarbonise the AI.

It should be noted that the clinker in poroshkoobraznoj form may be subjected to carbonization as such or, alternatively, before carbonization clinker can be turned into powder. Specified in this document carbonizing tank is not imposed certain restrictions; in other words, there may be used any type of tank, provided that the contact and reaction of the clinker with gaseous carbon dioxide. For example, there may be used an electric furnace, heating furnace with a fluidized bed and a small mill grinding clinker.

The proportion of calcium carbonate is preferably from 0.5 to 10 parts, more preferably from 1 to 5 parts per 100 parts of clinker. If the proportion of each mineral does not match the specified ranges may not be achieved nor sufficient ability to expand or high early compressive strength and stability during storage.

The content of calcium carbonate can be quantified on the basis of weight change during decarbonation of calcium carbonate using differential thermal analysis (TG-DTA) or differential scanning calorimetry (DSC).

In the expanding material of the present invention preferably free lime, hydraulic substance, anhydrous sulfate Kal the Oia and calcium carbonate are simultaneously present in the same particle.

Are there any free lime, hydraulic substance, anhydrous calcium sulfate and calcium carbonate at the same time in the same particle can be determined using an electron microscope, etc.

More specifically, the expanding material is covered with resin and are buried in it, the surface is treated by a laser beam on argon ion laser with the aim of examining the structure of the cross section of the particles and perform elemental analysis, thereby determining whether the calcium carbonate in the same particle.

The fineness of the powder for the expanding material of the present invention is in a range preferably from 1500 to 9000 cm2/g, more preferably from 2000 to 4000 cm2/g in units of specific surface area according to blaine. If this value is less than 1500 cm2/g-expanding material will not expand over a long period of time, which often leads to the destruction of concrete structures, if more than 9000 cm2/g, often reduces the ability to expand.

Number, in which the use of the expanding material of the present invention, no specific restrictions as to its value varies depending on the amount of mixing of concrete; however, it is generally preferred to use from 3 to 12 parts, especially from 5 to 9 parts per 100 parts to the position of the cement, containing cement and expanding material. If this number is less than 3 parts, it is often impossible to obtain a sufficient ability to expand if more than 12 parts, often redundant expansion, causing the formation of concrete cracking due to expansion.

The cement used in the cement composition of the present invention, for example, is a Portland cement, such as Portland General purpose, rapid hardening Portland cement, particularly rapid hardening Portland cement, maternity Portland cement and moderate thermic Portland cement, cement mixtures containing these cements mixed with blast furnace slag, fly ash and dust and silicon oxide, and putty, mixed with powdered limestone.

The expanding material of the present invention can be used in combination with sand, gravel, plasticizing additives, high-performance plasticizing additives, plasticizing additives AE, high-performance plasticizing additives AE-thinning additives, defoaming additives, thickeners, anti-corrosion additives, additives which lower the freezing point, agents that weaken shrinkage, polymer emulsions and regulators setting, as well as additives for quick setting, clay minerals such as bentonite, ion exchange materials, such as zeolite, fine powders of silicon oxide, calcium carbonate, calcium hydroxide, calcium sulphate, calcium silicate, and fibrous materials such as vinyl fiber, acrylic fiber and carbon fiber. Especially in the case when the expanding material of the present invention used in combination with agents that weaken shrinkage, achieved a greater expansion of the concrete. The type of agent that weakens shrinkage, does not have certain restrictions; however, particular preference is given to low molecular weight copolymers of accelerated derived glycol ether aminoalcohols and adducts of accelerated and lower alcohols. There are commercially available products such as SK Guard production DENKA, HUBIGUARD production FBK, HIBIDAN production TAKEMOTO OIL &FAT CO., LTD., TETRAGUARD production TAIHEIYO CEMENT CORPORATION.

Further, the present invention is described in more detail with reference to examples.

Example 1

Initial Cao initial Al2O3original Fe2O3original SiO2original CaSO4mixed with each other in such a way as to obtain the ratio of these minerals are listed in table 1, the mixture was stirred, were crushed to powder and subjected to heat treatment at 1350°C in order to synthesize clinker, which, is turn, crushed in a ball mill to obtain a specific surface area according to blaine 3000 cm2/, Twenty-five (25) grams of powdered clinker was placed in a crucible made of alumina, which is then set in an electric furnace. When the flow of carbon dioxide gas in the interior of the electric furnace 0.05 l/min and the firing temperature of 600°C for one hour was carried out by the reaction of conversion of clinker in the expanding material, which was determined by the content of the formed calcium carbonate.

Expanding the material used in the amount of 4 parts or 7 parts per 100 parts of the cement composition containing the cement and the expanding material, with the aim of obtaining building solutions, characterized by the ratio of water/cement composition of 50% and a composition ratio of cement/sand 1/3 at a temperature of 20°C in the room. Then researched each mortar to measure relative changes in length and compressive strength.

For comparison carried out a similar experiment using powdered clinker, not containing hydraulic substance and anhydrous calcium sulphate, expanding materials obtained only by thermal treatment of this clinker gaseous carbon dioxide (experiments No. 1-8, 1-9, 1-10, 1-11), the expanding material is from the clinker without heat treatment with gaseous carbon dioxide (experiments No. 1-12, 1-13, 1-14) and the expanding material containing powdered calcium carbonate, mixed with the expanding material, subjected only to grinding, without heat treatment with gaseous carbon dioxide (experiment No. 1-15). With appropriate expanding materials and compositions of expanding cement conducted accelerated test for persistence.

Raw materials

The original Cao: lime

The original Al2O3: bauxite

The source of Fe2O3: iron oxide

The original SiO2: quartzite

Source CaSO4: dowolny calcium sulfate

Gaseous carbon dioxide: the product

Sand: standard sand by JIS (Japanese Industrial Standards Japanese industrial standards)

Cement: commercial product: Portland General purpose

Powdered calcium carbonate: the product, the 200-mesh

Test methods

Mineral content was determined by calculation on the basis of chemical composition and identification results using powder x-ray diffraction.

The amount of the formed calcium carbonate was determined on the basis of weight change associated with decarbonisation, on the differential thermoanalytical (TG-DTA) at a temperature of from 500 to 750°C.

To determine the distribution of minerals in the expanding particle Mat is Rial expanding material was placed in a silicon container, which ran utverjdali epoxy resin. Then the epoxy resin was subjected to processing in the cross-section of the ion-beam treatment (SM-09010 production JEOL Ltd.) to determine the distribution of minerals by SEM-EDS (scanning electron microscope with energy dissipating x-ray spectroscopy).

The relative change in length until the material age 7 days (d) was measured in accordance with test method for expansion JIS And 6202, Annex 1.

The compressive strength was determined by making test sample 4×4×16 cm and measuring its compressive strength at the age of material 7 days in accordance with JIS R 5201.

For accelerated tests for persistence (expanding material) 100 grams of each of the expanding materials are widely scattered on a square tray stainless steel 10×10 cm, was left at the room temperature of 20°C/humidity 60% for 10 days, nothing placing on top of it. After 10 days the samples were collected and conducted measuring the relative length change of mortar.

For accelerated tests for persistence (expanding cement) each of the compositions of expanding cement was placed in a paper bag, which was sealed by heat sealing for storage for one month at a temperature in the premises of the Institute 35°C/humidity 90%, and the relative length change of mortar.

Table 1
No. exp.The mineral composition of clinker %Treatment with gaseous dioxide
carbon
The amount of the formed calcium carbonate, %
f-CaohaüyneC4AFC2SCaSO4
1-1103051045held2,0
1-220302345held3,0
1-340205530the rst is and 4,5
1-450105530held5,0
1-550502520held5,0
1-66050530held6,0
1-770105510held7,0
1-81000000not held0,0
1-9100 0000not held0,0
1-101000000held8,0
1-111000000held8,0
1-12103051045not held0,0
1-1350105530not held0,0
1-1470105510 not held0,0
1-1550105530not held5,0

No. exp.The presence of particles
containing all
essential minerals
The share of added
expanding
material parts
1-1detected7
1-2detected7
1-3detected7
1-4detected7
1-5detected7
1-6detected7
1-7detected7
1-8not found4
1-9not found7
1-10not found4
1-11not found7
1-12not found7
1-13not found7
1-14not found7
1-15not found7

No. exp.The relative length change, %
01 d2 d3 d5 d7 d2-
7 d
5-
7 d
A* In*S*D*
1-102050130150185135351809718097
1-201510020023025015020250100250100
1-30101302803804302405042098440103
1-40 152002903904502506044098460102
1-50201602003804202604041599420100
1-60203003754905202203051098540104
1-70608301,2001,2501,270440 201,200941,13089
1-80400430440450450200501120044
1-901,0502,0602,0902,1002,1004007003390043
1-1001020450470480460104008339081
1-11 01201,8792,7202,8002,810940102,200782,30082
1-120508511016018095201206715083
1-1301903804154504557552204833073
1-140400440480490500 60102004034068
1-15018043046048049060102304735071
A*: stored 7 days of the expanding material
In*: speed residual expansion (stored material 7 d/7 d)
With*: stored 7 days of the expanding cement material
D*: speed residual expansion (stored material 7 d/7 d)

No. exp.Compressive strength,
N/mm27 days
Notes
1-137,5And the attainment
1-237,4According to the invention
1-336,0According to the invention
1-435,0According to the invention
1-532,6According to the invention
1-632,4According to the invention
1-728,1According to the invention
1-8to 25.3Comparative
1-920,5Comparative
1-1017,9Comparative
1-1110,3Comparative
1-1237,4Comparative
1-1333,0Comparative
1-14 26,7Comparative
1-1533,3Comparative

As can be seen from table 1, the expanding materials according to the invention (experiments No. 1-1 to 1-7), in which the powdered clinker containing free lime (f-Cao), hydraulic substance (haüyne, C4AF, C2S) and anhydrous calcium sulfate (CaSO4), was subjected to a heat treatment in an atmosphere of carbon dioxide gas to form it of calcium carbonate, was characterized by a greater relative change in length by 2-7 d and 5-7 d, allowing a much greater extension of the compositions of cement (concrete) in the age of the material from 2 to 7 days, allowing the concrete to develop a higher compressive strength at the age of material 7 days and providing a smaller reduction in the ability to expand, even when stored for a long period of time.

On the contrary, comparative expanding materials (experiments No. 1-8 and 1-9), in which the powdered clinker containing free lime (f-Cao) without hydraulic substance and anhydrous calcium sulphate, was not heat treated in the atmosphere of carbon dioxide gas was characterized by a smaller relative change of length and lower strength in compression on the 2-7D and 5-7 d, and when storing for a long period of time, their ability to expand significantly decreased. Comparative expanding materials (experiments No. 1-10 and 1-11), in which the clinker was subjected to a heat treatment in an atmosphere of carbon dioxide gas was characterized by a large relative change in length by 2-7 day, but a small relative change of length and low strength in compression 5-7 days, their ability to expand slightly decreased. With increased content of carbon dioxide gas the ability to expand enormously increased, causing an even bigger decrease in the compressive strength.

Comparative expanding materials (experiments No. 1-12, 1-13 and 1-14), in which the clinker was subjected to only grinding into powder without treatment with gaseous carbon dioxide, and comparative expanding material (experiment No. 1-15), in which the clinker, subject only to grinding into powder without treatment with gaseous carbon dioxide was mixed with powdered calcium carbonate, was characterized by a smaller relative change in length by 2-7 d and 5-7 d, and the storage for a long period of time, their ability to expand significantly decreased.

Example 2

Example 1 was repeated, except that the content of 100 hours is she clinker free lime, of haüyne, almateria calcium (4CaO·Al2O3·Fe2O3: C4AF), calcium silicate (2CaO·SiO2: C2S) and anhydrous calcium sulphate has always remained equal to 50 parts, 10 parts, 5 parts, 5 parts and 30 parts, respectively, and the flow of carbon dioxide gas, the temperature of heat treatment and reaction time were changed as shown in table 2.

Table 2
No. exp.Handling of gaseous carbon dioxideNumber
formed
carbonate
calcium, %
Flow rate l/minTemperature, °CTime, hour
2-10,0160010,5
1-40,0560015,0
2-20,16001 5,2
2-30,056000,11,0
2-40,056000,251,6
2-50,05600109,8
2-60,0560020to 12.0
2-70,0540011,5
2-80,0520010,5
2-90,058001a 3.9
2-100,05100010,0

No. exp. The presence of particles, containing all the essential mineralsPortion of the expanding material, parts
2-1detected7,0
1-4detected7,0
2-2detected7,0
2-3detected7,0
2-4detected7,0
2-5detected7,0
2-6detected7,0
2-7detected7,0
2-8detected7,0
2-9detected7,0
2-10not found7,0

No. exp.The relative length change, %
01 d2 d3 d5 d7 d2-
7 d
5-
7 d
A*In*S*D*
2-10180360420450490130403707646094
1-40152002903904502506044098460 102
2-20518026533038020050380100390103
2-3080300440500550250505309654098
2-4014039047043059020016059010058098
2-50080130 16022014060220100220100
2-60010601001501405015010014093
2-701503303804404801504046096490102
2-8017036040044047011003035074 85
2-90100290350420475185554208345095
2-10019039041045048090302004235073
A*: stored 7 days of the expanding material
In*: speed residual expansion (stored material 7 d/7 d)
In*: speed residual expansion (stored material 7 d/7 d)
With*: stored 7 days of the expanding cement material
D*: speed the residual expansion (stored material 7 d/7 d)

No. exp.Compressive strength,
N/mm27 days
Notes
2-134,9According to the invention
1-435,0According to the invention
2-235,7According to the invention
2-338,8According to the invention
2-439,0According to the invention
2-536,8According to the invention
2-628,0Comparative
2-736,0According to the invention
2-837,0According to the invention
2-936,3According to the invention
2-10/td> 36,0Comparative

As can be seen from table 2, the expanding material according to the invention (experiment No. 1-4 and experiments No. 2-1 to 2-9), obtained in accordance with the method of obtaining the present invention provides for the formation of calcium carbonate in the following conditions treatment with gaseous carbon dioxide: flow rates from 0.01 to 0.1 l/min and a temperature of from 200 to 800°C, was characterized by a greater relative change in length by 2-7 d and 5-7 d, allowing a much greater extension of the compositions of cement (concrete) in the age of the material from 2 to 7 days, allowing the concrete to develop a higher compressive strength in the age of the material 7 days and providing a smaller reduction in the ability to expand, even when stored for a long period of time.

On the contrary, comparative expanding material (experiment No. 2-10), obtained using the comparative method of obtaining, in which treatment with gaseous carbon dioxide was carried out at 1000°C without the formation of calcium carbonate, was characterized by a smaller relative change in length by 2-7 d and 5-7 d, and the storage for a long period of time its ability to expand significantly decreased.

Example 3

Example 1 was essentially repeated, except the fact the treatment was subjected to mass-produced expanding material. The results are presented in table 3.

Serial expanding material:

50 parts of free lime, 12 parts of haüyne, 5 parts of almateria calcium (4CaO·Al2O3·Fe2O3), 3 parts of calcium silicate (2CaO·SiO2) and 30 parts of anhydrous calcium sulphate.

Serial expanding material:

52 part of the free lime, 4 parts of almateria calcium (4CaO·Al2O3·Fe2O3), 10 parts of calcium silicate (2CaO·SiO2), 12 parts of calcium silicate (3CaO·SiO2) and 20 parts of anhydrous calcium sulphate.

Table 3
No. exp.The type of the expanding materialTreatment with gaseous carbon dioxide
3-1The expanding material And treated with CO2held
3-2The expanding material And treated with CO2held
3-3The expanding material Andheld
3-4The expanding material In, clicks the mapped CO 2held
3-5The expanding material In the treated CO2held
3-6The expanding materialnot held

No. exp.Handling of gaseous carbon dioxideThe amount of the formed calcium carbonate, %
Flow rate l/minTemperature, °CTime, h
3-10,056000,251,7
3-20,056001,05,0
3-3---0,0
3-40,056000,25 1,9
3-50,056001,05,8
3-6---0,0

No. exp.The presence of particles
containing all
essential minerals
The share of added
the expanding material
parts
3-1detected7,0
3-2detected7,0
3-3not found7,0
3-4detected7,0
3-5detected7,0
3-6not found7,0

0
No. e the JV. The relative length change, %
01 d2 d3 d5 d7 d2-
7 d
5-
7 d
A*In*S*D*
3-101203704605005201502051098520100
3-201019028039044025050440100450102
3-320038042045046080102305033072
3-401002503704204902407049010048098
3-50513023030039026090390100400103
3-6016037038039040030 101804528571
A*: stored 7 days of the expanding material
In*: speed residual expansion (stored material 7 d/7 d)
With*: stored 7 days of the expanding cement material
D*: speed residual expansion (stored material 7 d/7 d)

No. exp.Compressive strength, N/mm27 daysNotes
3-1a 38.5According to the invention
3-238,0According to the invention
3-334,0According to the invention
3-434,2According to the invention
3-533,5/td> According to the invention
3-630,0Comparative

As can be seen from table 3, the expanding materials according to the invention (experiments No. 3-1, 3-2, 3-4 and 3-5), in which serial expanding material formed of powdered clinker containing free lime, hydraulic substance and anhydrous calcium sulfate, subjected to heat treatment in the atmosphere of carbon dioxide gas with the purpose of formation of calcium carbonate, was characterized by a greater relative change in length by 2-7 d and 5-7 d, allowing a much greater extension of the compositions of cement (concrete) in the age of the material from 2 to 7 days, allowing the concrete to develop a higher compressive strength at the age of material 7 days and providing a smaller reduction in the ability to expand, even when stored for a long period of time compared with comparative expanding materials (experiments No. 3-3 and 3-6), which was not accompanied by the formation of calcium carbonate.

Example 4

Example 1 was essentially repeated, except that the serial expanding material And subjected to the processing of flue gases leaving the kiln lime kiln, and not gaseous carbon dioxide. Exhaust gases from the furnace on the jig lime contained 40% CO 2, 7% O2, 3% and 50% N2. The results are presented in table 4.

Table 4
No. exp.Gas typeThe amount of the formed calcium carbonate, %The presence of particles, containing all the essential mineralsPortion of the expanding material
parts
3-2Carbon dioxide5,0detected7,0
4-1Exhaust gases3,6detected7,0

No. exp.The relative length change, %
01 d2 d3 d5 d7 d2-
7 d
A*In*S*D*
3-20101902803904402505044010043599
4-1060240330450530290805209852098
A*: stored 7 days of the expanding material
In*: speed residual expansion (stored material 7 d/7 d)
With*: stored 7 days of the expanding cement material
D*: speed residual expansion (stored material 7 d/7 d)

No. exp.Compressive strength,
N/mm27 days
Notes
3-238,0According to the invention
4-1a 38.5According to the invention

As can be seen from table 4, the expanding material (experiment No. 4-1), carbonated flue gases of the lime kiln have the highest ability to extend than the expanding material (experiment No. 3-2), carbonated gaseous carbon dioxide.

Example 5

Clinker having the composition shown in table 5, were obtained using as starting materials limestone and Portland cement General purpose, and then subjected to carbonization. In addition, 80 parts of clinker, is not subjected to carbonization, and 20 parts of anhydrous calcium sulphate formed the expanding material. Example 1 was essentially repeated, except that the expanding material is present in an amount of 7 parts per 100 parts of the cement composition containing CE the UNT and the expanding material. The results are presented in table 5.

The materials used

The original Cao: lime

Cement: Portland General purpose commercial product

Source CaSO4: anhydrous calcium sulfate with a specific surface area according to blaine 3000 cm2/year

Table 5
No. exp.The mineral composition of clinker %Treatment with gaseous carbon dioxideThe amount of the formed calcium carbonate, %
f-CaohaüyneC4AFC2SC3SCaSO4
5-1604512181held5,2
5-2604 512181not held0,0

No. exp.The presence of particles
containing all
essential minerals
The share of added
the expanding material
parts
5-1detected7,0
5-2not found7,0

No. exp.The relative length change, %
01 d2 d3 d5 d7 d2-
7 d
5-
7 d
A*In*S*D*
5-1 010120130300420300120420100420100
5-2030037040042043060101002329067
A*: stored 7 days of the expanding material
In*: speed residual expansion (stored material 7 d/7 d)
With*: stored 7 days of the expanding cement material
D*: speed residual expansion (stored material 7 d/7 d)

No. exp. Compressive strength,
N/mm27 days
Notes
5-135,2According to the invention
5-230,0Comparative

As can be seen from table 4, the expanding material of the present invention (experiment No. 5-1), in which the powdered clinker containing free lime (f-Cao), hydraulic substance (haüyne, C4AF, C2S, C3S) and anhydrous calcium sulfate (CaSO4), was subjected to a heat treatment in an atmosphere of carbon dioxide gas with the mass of calcium carbonate, and by adding anhydrous calcium sulphate, was characterized by a greater relative change in length by 2-7 d and 5-7 d, allowing a much greater extension of the compositions of cement (concrete) in the age of the material from 2 to 7 days, allowing the concrete to develop a higher compressive strength at the age of material 7 days and providing a smaller reduction in the ability to expand, even when stored for a long period of time compared with comparative expanding material (experiment No. 5-2), which did not occur the formation of calcium carbonate.

Example 6

Tested the e on the formation of bubbles was done with expanding cement, in which he used the expanding material obtained in experiment No. 3-2. Mortar consisting of 7 parts of the expanding material to 100 parts of the expanding cement composition comprising cement and an expanding material with the ratio of water/cement composition of 50% and a ratio of the cement composition/1/3 sand, mixed at room temperature 20°C, mixing time after loading of materials was changed as shown in table 6. In another experiment cement and mass-produced an expanding material As used in experiment No. 3-3, individually downloaded in different stirrers, as for conventional concrete slab. The results are presented in table 6.

Test method for the formation of bubbles

Mixed mortar poured into the reservoir 20×20×50 cm, the surface is leveled. After exposure to a temperature of 20°C and humidity 60% of the surface mortar examined on the subject of bubbles.

6-1
Table 6
Exp. No.MaterialMixing timeThe appearance of bubblesNotes
Expanding cement
using serial expanding material And processed Sao2
15 secnot foundAccording to the invention
6-2Expanding cement
using serial expanding material And processed Sao2
60 secnot foundAccording to the invention
6-3Simultaneously
download serial expanding material and cement
15 secdetectedComparative
6-4Simultaneously
download serial expanding material and cement
60 secnot foundComparative

As can be seen from table 6, the expanding cements (experiments No. 6-1 and 6-2), which used the expanding material of example 6, in which the powdered clinker was subjected to a heat treatment in an atmosphere of carbon dioxide gas for the formation of the AC is of Bonita calcium, not peculiar to the formation of bubbles even at low mixing time, however, in the samples (experiments No. 6-3 and 6-4)obtained simultaneous loading of cement, and in comparative expanding material, which was not formed calcium carbonate, appeared bubbles when mixing time was enough.

Example 7

Physical properties of mortar were studied using extensible material obtained in experiment 2-3, and debilitating shrinkage agent. To 100 parts of the expanding cement composition comprising cement and an expanding material, the expanding material is added in an amount of 7 parts, weakening shrinkage agent is added in amount of 2 parts and replaced in the form of water. Mortar with the ratio (water plus debilitating shrinkage agent)/(cement composition) of 50% and a composition ratio of cement/sand 1/3 was stirred at the room temperature is 20°C With the aim of the study the ability to expand. A similar test is also conducted for serial expanding material As used in experiment No. 3-3.

The materials used

Debilitating shrinkage agent: commercial product SK Guard production DENKA.

As can be seen from table 7, EXT the decomposing material (experiment No. 7-1) of example 7, in which powdered clinker was subjected to a heat treatment in an atmosphere of carbon dioxide gas to form in it calcium carbonate, with the addition of debilitating shrinkage agent had improved performance from the standpoint of relative changes in length by 2-7 d and 5-7 d in comparison with comparative expanding material (experiment No. 7-2), in which the powdered clinker did not contain calcium carbonate, but contained debilitating shrinkage agent.

Industrial applicability

The expanding material of the present invention and the method of obtaining this expanding material can be widely used in civil construction, as the expanding material of the present invention allows for greater expansion of the concrete in the age of the material from 2 to 7 days, allows him to develop high early compressive strength, provides improved stability during storage and sufficient liquid communication with expanding cement, in which bubbles do not appear even at low mixing time.

1. Expanding additive for concrete, characterized in that it is obtained by heat treatment of clinker or powdered clinker containing in parts by weight per 100 parts of clinker free lime in the amount of 10-70, hydraulic is emesto 10-50 and anhydrous calcium sulfate 1-50, in the atmosphere of carbon dioxide gas for the formation therein of calcium carbonate.

2. Expanding additive according to claim 1, which includes a particle, in which the free lime, hydraulic substance, anhydrous calcium sulfate and calcium carbonate are present at the same time.

3. Expanding additive according to claim 1, which contains calcium carbonate in an amount of from 0.5 to 10% of the mass.

4. Expanding additive according to claim 1, which has a specific surface area according to blaine from 1500 to 9000 cm2/year

5. Expanding additive according to claim 1, in which the anhydrous calcium sulfate added to clinker or powdered clinker subjected to heat treatment in the atmosphere of carbon dioxide gas for the formation therein of calcium carbonate.

6. Expanding additive according to claim 1, in which weakening shrinkage agent is additionally added to the clinker or powdered clinker subjected to heat treatment in the atmosphere of carbon dioxide gas for the formation therein of calcium carbonate.

7. The composition of the cement, in which the expanding additive according to claims 1-6 mixed with the cement.

8. The method of obtaining the expanding additive according to claims 1 to 6, characterized in that the or powdered clinker clinker containing free lime, hydraulic substance and anhydrous calcium sulfate, under the will eraut heat treatment for the formation therein of calcium carbonate.

9. The method of obtaining the expanding additive of claim 8, in which the clinker or powdered clinker placed in the carbonizing tank, the consumption of carbon dioxide gas is from 0.01 to 0.1 l/min per liter tank, prevailing in the reservoir temperature is from 200 to 800°C for the formation therein of calcium carbonate.



 

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2 tbl

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1 ex, 1 tbl

FIELD: construction.

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1 ex, 1 tbl

FIELD: chemistry.

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1 tbl

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1 tbl

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2 tbl

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FIELD: chemistry.

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1 tbl

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