CH713947B1 - Uncalcined cementitious compositions, uncalcined concrete compositions, uncalcined concrete and methods of making them. - Google Patents

Abstract

The invention provides uncalcined cementitious compositions comprising micrometer scale inorganic particles that can be used as binder material; and provides uncalcined concrete compositions; also uncalcined concretes are provided which have similar or better physical and mechanical properties than concretes made with conventional cements. The present invention also provides methods of making the uncalcined cementitious compositions, the uncalcined concrete compositions, and the uncalcined concretes.

Description

BACKGROUND OF THE INVENTION

1. Field of the invention

The invention provides an uncalcined cementitious composition comprising micrometer scale inorganic particles useful as a binder material; an uncalcined concrete composition; and an uncalcined concrete that has physical and mechanical properties similar or better than concretes made with conventional cements. The present invention also provides methods of making the uncalcined cementitious composition, the uncalcined concrete composition, and the uncalcined concrete.

2. Description of the state of the art

Cement is a general name for binder materials that are commonly used in building materials and is now one of the most important building materials at all. Statistical data from the Portland Cement Association shows that the global consumption of cement in 2015 was around 4.1 billion tons, which underscores the importance of cement. The most commonly used cement is Portland cement, the main components of which come from limestone, clay, silicate ore, iron slag and other materials. However, the majority of these materials are obtained by breaking down natural minerals, which has a major impact on the environment. In addition, due to the use of limestone and other raw materials, the manufacture of cements requires calcination at high temperatures, which consumes large amounts of energy and causes considerable carbon emissions. In addition, the estimated remaining recoverability of limestone minerals in China and Taiwan is only 50 years or less. This state of affairs, including a lack of building materials, poses potential problems in terms of environmental protection.

Accordingly, attempts have been made to use alternative raw materials in the sector in order to reduce the consumption of natural resources as well as the carbon emissions in the process of making cement. A lime-free, cementitious material is alkaline-activated cement, which is produced by polymerizing a silicoaluminate (fly ash) with sodium silicate (water glass) in the presence of a strong base. However, this is associated with possible dangers in terms of excessive shrinkage, heat dissipation during the mixing process, cracking in the end products, formation of salt crystals on the surface and other difficulties. Also, the use of a large amount of a strong base can easily lead to corrosion and rusting of the steel material, which affects the ultimate strength of the structure. The use of a large amount of a strong base limits the possibilities of large-scale use. In addition, some alkaline-activated cements have to be catalyzed at high temperatures for several hours before hardening. Accordingly, the practicability of alkaline activated cement is still characterized by numerous restrictions.

TW I491579 B (corresponds to US 8,562,734 B2) discloses a low-calcium cementitious material composition in which in particular low-calcium fly ash, a base and a solidifying agent were used, mixed at room temperature and left to stand to form a low-calcium cementitious material. The invention is primarily characterized by the use of a primary agent in order to solve the problem that when using fly ash that is low in calcium according to the prior art, a further calcium-containing component has to be added.

WO 2011/008463 A1 discloses the use of a cementitious composition comprising (1) at least one inorganic filler, (2) a colloidal silicon dioxide, a colloidal aluminum oxide or a mixture thereof, which forms a binding phase on firing, and (3 ) a carrier fluid. However, the cementitious composition must be calcined at high temperatures (at least 1000 ° C.) in the presence of a fluorine source in order to form a binder phase.

Therefore, there is still a great need for a cementitious binder material in which the environmental impact of the manufacturing process is minimized and which can easily be used for large scale applications.

BRIEF DESCRIPTION OF THE INVENTION

To achieve the above objects, the present invention provides an uncalcined cementitious composition comprising: (a) micrometer-scale inorganic particles having a grain size in the range of 1.0 to 100 µm at about 31% to 87% by weight the total weight of the composition; (b) an aluminum-oxygen compound; (c) nanocolloidal silica; and (d) a coagulant.

After the components of the composition have been mixed, the composition can be used as a binder material in building materials in the same way as cement, without calcination.

The present invention also provides an uncalcined concrete composition comprising: (a) inorganic particles at about 66% to 92% based on the total weight of the composition; (b) an aluminum-oxygen compound; (c) nanocolloidal silica; and (d) a coagulation regulating agent, wherein the inorganic particles comprise micrometer scale inorganic particles having a grain size in the range of 1.0 to 100 µm and the micrometer scale inorganic particles comprise about 25% to 45% of the total weight of the inorganic particles. After the components of the composition have been mixed, the composition, without calcination, has mechanical properties similar to those of a concrete produced with conventional cement, as well as a volume stability which is superior to the latter.

The present invention also provides an uncalcined concrete comprising an uncalcined cementitious composition or an uncalcined concrete composition.

The present invention also provides a method of making a non-calcined cementitious composition comprising a step of combining micrometer-sized inorganic particles, an aluminum-oxygen compound, nanocolloidal silica and a coagulant.

The present invention also provides a method of making an uncalcined concrete composition comprising a step of combining inorganic particles, an aluminum-oxygen compound, nanocolloidal silica and a coagulant.

BRIEF DESCRIPTION OF THE INVENTION

[0013] All numbers expressing contents, proportions, physical properties and others and which are set out in this description and in the claims are to be understood as modified by the term “about” at each occurrence. Accordingly, unless explicitly stated otherwise, the values set forth in the following description and in the appended claims may vary depending on the intended and / or desired properties of the present invention. Without restricting the application of the doctrine of equivalency to the scope of protection of the invention, the numerical parameters are to be interpreted at least on the basis of the disclosed number of significant digits and by applying general rounding.

All areas disclosed herein are to be understood as including each and all sub-areas contained therein. For example, the range 1 to 10 is understood to include any and all subranges between and including the minimum value 1 and including the maximum value 10; that means all subranges that start with a minimum value of 1 or more and end with a maximum value of 10 of the fewer, for example 1 to 6.7, 3.2 to 8.1 or 5.5 to 10; and includes any and all numeric values in the ranges, for example: 1, 3.1, 5.2, or 8.

The term "about" disclosed herein refers to a range of proximity as known to those skilled in the art, and the range of proximity is related to various features or physical properties. For example, “about” includes a range of ± 10%, ± 5%, ± 2% or ± 1% of the given value.

The composition provided in the present invention comprises (micrometer-scale) inorganic particles, an aluminum-oxygen compound, nanocolloidal silicon dioxide and a coagulant. The components are detailed below.

A. Inorganic Particles

Inorganic particles contained in the composition of the present invention are as defined in claims 1 and 7. They are, for example, made of a material that is formed from at least silicon with various metal or non-metallic elements. The metal elements can include, for example, alkali, alkaline earth, semimetal, and transition metal elements, and the non-metallic elements can include, for example, carbon, hydrogen, oxygen, nitrogen, boron, phosphorus, sulfur, halogen, and the like. Examples include, but are not limited to, an oxide (e.g., silicate and silicon dioxide) and a carbide (e.g., silicon carbide) of silicon; various compounds formed from silicon, aluminum and oxygen; or a combination of these compounds. Other inorganic ingredients can optionally be present, for example various substances formed from the above-mentioned metal and / or non-metallic elements, for example various compounds containing calcium, magnesium, boron, carbon, nitrogen and oxygen, or any combination of these compounds. The inorganic particles can originate, for example, from various natural ores or rocks, quartz sand, land sandstone, silicon dioxide sand, river sand, sea sand, reservoir silt or any combination of the aforementioned, and inevitable impurities contained therein. In a specific embodiment, the inorganic particles comprise quartz sand, gravel, or both, and the quartz sand and gravel, when both are present, can be mixed in any proportion.

The uncalcined cementitious composition provided in the present invention comprises inorganic particles having a grain size in the range of 1.0 to 100 µm, which are referred to herein as micrometer-scale inorganic particles. The micrometer-sized inorganic particles are a major component of the uncalcined cementitious composition and constitute about 31% to 87%, preferably 42% to 81%, and more preferably 52% to 76% of the total weight of the uncalcined cementitious composition.

In the uncalcined concrete composition provided in the present invention, the inorganic particles are contained as a major proportion, which is about 66% to 92%, preferably 72% to 90%, and more preferably 74% to 86% of the total weight of the uncalcined cementitious composition matters.

In the uncalcined concrete composition provided in the present invention, the grain size of the inorganic particles is not particularly limited and may be nanometer to millimeter scale provided that at least a part of the inorganic particles are micrometer inorganic particles and the micrometer inorganic particles are 25%. to 45%, preferably 27% to 43% and more preferably 30% to 40% of the total weight of the inorganic particles.

In one embodiment of the present invention, the micrometer-scale inorganic particles can have a grain size in the range from 1.0 to 1.3 microns, 1.3 to 1.6 microns, 1.6 to 2.6 microns, 2.6 to 6.5 µm, 6.5 to 8.0 µm, 8.0 µm to 10.0 µm, 10.0 to 13.0 µm, 13.0 to 28.0 µm, 28.0 to 38.0 µm , 38.0 to 45.0 µm, 45.0 to 50.0 µm, 50.0 to 53.0 µm, 53.0 to 58.0 µm, 58.0 to 75.0 µm, 75.0 to 86.0 µm and 86.0 to 100.0 µm or in any range formed by any of the above-mentioned end points as the upper and lower limits. Alternatively, the micrometer scale inorganic particles can have a grain size corresponding to any of the above endpoints, for example about 1 µm, about 1.3 µm, about 1.6 µm ... about 8.0 µm, about 10.0 µm, about 13.0 µm ... about 50.0 µm, about 58.0 µm, about 75.0 µm, about 86.0 µm, and about 100 µm.

In one embodiment of the present invention, the micrometer-scale inorganic particles have a unimodal grain size distribution. In a further embodiment, the grain size distribution is bimodal or multimodal, and the distribution pattern can be any combination of one or more sets of individual grain sizes or one or more sets of grain size ranges. For example, in one embodiment, the micrometer-scale inorganic particles can have, for example, a unimodal grain size distribution of 1 μm to 2.6 μm; a unimodal grain size distribution at about 1.3 µm; a unimodal grain size distribution at about 1.6 µm; a unimodal grain size distribution at 8.0 to 13.0 µm; a unimodal grain size distribution at about 8.0 µm; a unimodal grain size distribution at about 10.0 µm; a bimodal grain size distribution at 1 to 2.6 µm and 6.5 to 13.0 µm; a bimodal grain size distribution at about 1.0 µm and about 8.0 µm; a bimodal grain size distribution at about 1.6 µm and about 13.0 µm; a bimodal grain size distribution at 6.5 to 13.0 µm and 45.0 to 58.0 µm; a bimodal grain size distribution at 6.5 to 10.0 µm and 50.0 to 58.0 µm; a bimodal grain size distribution at 8.0 to 10.0 µm and 50.0 to 53.0 µm; a bimodal grain size distribution at about 10.0 µm and about 45.0 µm; a bimodal grain size distribution at about 6.5 µm and about 50.0 µm; a bimodal grain size distribution at about 10.0 µm and about 50.0 µm; a bimodal grain size distribution at about 10.0 µm and 45.0 to 50.0 µm; a bimodal grain size distribution at about 8.0 µm to 10.0 µm and 50.0 µm; a trimodal grain size distribution at 1.0 to 2.6 µm, 6.5 to 13.0 µm and 45.0 to 58.0 µm; a trimodal grain size distribution of 1.6 to 2.6 µm, 6.5 to 10.0 µm and 45.0 to 50.0 µm; a trimodal grain size distribution of 1.6 to 2.6 µm, 6.5 to 10.0 µm and 45.0 to 75.0 µm; a trimodal grain size distribution of about 1.6 µm, about 8.0 µm and about 50.0 µm; a trimodal grain size distribution of about 1.0 µm, about 10.0 µm and about 50.0 µm; a trimodal grain size distribution of about 1.6 µm, about 10.0 µm and about 45.0 µm; a trimodal grain size distribution of about 1.6 µm, about 10.0 µm and about 50.0 µm; a trimodal grain size distribution of about 1.3 µm, about 8.0 µm, and about 58.0 µm; a trimodal grain size distribution of about 1.6 µm, about 13.0 µm and about 75.0 µm; and have a tetramodal, a pentamodal and a hexamodal grain size distribution in any combination and so on. The micrometer-scale inorganic particles with a bimodal or multimodal grain size distribution can also be referred to as graded particles. A grain size distribution having a specific distribution pattern can be obtained by sifting the particles based on the grain size and then mixing the particles having the appropriate sizes. For example, inorganic particles of large size can be wet or dry ground to inorganic particles of small size and then acroclassing to obtain micrometer-scale inorganic particles with narrow particle size distribution, which are then further mixed to achieve the intended particle size distribution. If the grain size distribution is bimodal, the particles with a grain size or a grain size range at the maximum can independently of one another at least about 30% to about 70%, for example about 30%, about 35%, about 40%, about 45%, about 50%, about 55% %, about 60%, about 65%, about 70%, etc. of the total weight of the micrometer scale inorganic particles. If the grain size distribution is trimodal, the particles with a grain size or a grain size range at the maximum value can independently of one another at least about 20% to about 50%, for example about 20%, about 25%, about 27%, about 29%, about 30%, about 31 %, about 33%, about 35%, about 37%, about 40%, about 45%, about 50%, etc. of the total weight of the micrometer scale inorganic particles. While not wishing to be bound by theory, the use of graded particles in the uncalcined cementitious composition or the uncalcined concrete composition can improve the physical and mechanical performances of the concrete produced (e.g., compressive strength, etc.).

The grain size of the inorganic particles can also be on the millimeter scale and be from 0.1 mm to 50.0 mm.

Alternatively, without being tied to a theory, the grain size of the inorganic particles can also be on the nanometer scale.

The inorganic particles contained in the composition of the present invention do not have to be calcined, but still allow the composition to have the properties of a binder material after mixing with other components of the composition. After mixing the components, a binder material is produced with properties similar to those of conventional cement, which greatly reduces carbon emissions and saves energy.

B. Aluminum-oxygen compound

The aluminum-oxygen compound contained in the composition of the present invention is an oxo acid of aluminum and derivatives thereof (for example, a salt such as an alkali or alkaline earth metal salt), an oxide of aluminum and a hydroxide of aluminum; and can also be a mixture consisting primarily of these compounds. Examples include, but are not limited to, sodium aluminate, calcium aluminate, alumina, aluminum hydroxide, and high alumina cement, or any combination thereof. Without wishing to be bound by theory, the aluminum-oxygen compound serves to stabilize the coagulation between the components to provide stable physical properties similar to those of cement.

In the uncalcined cementitious composition of the present invention, the aluminum-oxygen compound content can be at least 1.9%, at least 4.2%, at least 5.0%, at least 8.0% and at least 9.5% of the Be, but not limited to, the total weight of the composition; and can also be a maximum of 21.0%, a maximum of 18.0%, a maximum of 14.5%, a maximum of 8.5%, a maximum of 7.5%; at most 6.0% and at most 5.0% of the total weight of the composition, but is not limited thereto; or can be in any of the above-mentioned values as the upper and lower limits.

In the uncalcined concrete composition of the present invention, the aluminum-oxygen compound content can be at least 1.1%, at least 2.2%, at least 2.8%, at least 4.8% and at least 5.5% of the total weight of composition, but is not limited to; and can also be a maximum of 12.0%, a maximum of 10.0%, a maximum of 8.0%, a maximum of 5.5%, a maximum of 5.0%; at most 3.0% and at most 2.0% of the total weight of the composition, but is not limited thereto; or in any of the above-mentioned values as the upper and lower limits.

In a preferred aspect, the aluminum-oxygen compound comprises aluminum hydroxide or a mixture containing aluminum hydroxide, which can improve the strength of concrete after high-temperature hardening.

C. Nanocolloidal silica

The nanocolloidal silica contained in the composition of the present invention is a commonly known particulate silica suspended in a liquid phase and having a grain size on the nanoscale. The nanocolloidal silicon dioxide can also be aggregated to form a larger particle or to form a network structure. The nanocolloidal silicon dioxide can be commercially available or made with a silicon-containing material.

The solids content of the nanocolloidal silica can be 20 to 50 wt .-%, preferably 30 to 48 wt .-% and more preferably 35 to 45 wt .-%, for example about 20, about 25, about 30, about 35, about 36, about 37, about 38, about 39, about 40, about 42, about 44, about 45, about 46, about 48, and about 50 weight percent; or in any of the above-mentioned values as the upper and lower limits. The particle size of the particulate silicon dioxide contained in the nanocolloidal silicon dioxide can be from 8 to 90 nm, preferably from 10 to 85 nm and even more preferably from 15 to 80 nm; or about 8, about 10, about 15, about 18, about 30, about 50, about 60, about 80, and about 90 nm; or in any of the above-mentioned values as the upper and lower limits.

The nanocolloidal silicon dioxide can also have a bimodal grain size distribution at, for example, about 10 nm and about 90 nm, about 18 nm and about 90 nm, about 18 nm and about 80 nm, about 10 nm and about 80 nm, about 10 nm and about 30 nm, about 30 nm and about 80 nm, about 10 nm and about 50 nm, and various combinations. If the particle size distribution is bimodal, the particles with a particle size or a particle size range at the maximum can independently of one another at least 30% to about 70%, for example about 30%, about 35%, about 40%, about 45%, about 50%, about 55% , make up about 60%, about 65% and about 70% of the total weight of the nanocolloidal silica. A grain size distribution with a specific distribution pattern can be obtained by mixing nanocolloidal silica of different grain sizes.

In the uncalcined cementitious composition of the present invention, the content of nanocolloidal silica can be from 17.0% to 36.0%, preferably from 19.0% to 33.0%, and more preferably from 21.0% to 32.0% of the Be but not limited to the total weight of the composition.

In the uncalcined concrete composition of the present invention, the content of nanocolloidal silica can be 8.5% to 17.0%, preferably 9.5% to 15.0%, and more preferably 10.5% to 13.0% of the total weight of the composition, but is not limited thereto.

D. Coagulation regulating agent

The coagulation regulating agent contained in the composition of the present invention serves to regulate the coagulation time of the components in the additive so that a desired application time can be provided. Examples include a hydroxycarboxylic acid or a salt thereof, a starch ether or a functionalized starch ether and the like, for example citric acid, tartaric acid, gluconic acid, salicylic acid and an alkali metal salt of these acids, hydroxymethyl starch ether, hydroxyethyl starch ether, hydroxypropyl starch ether or any combination thereof.

In the non-caicinated cementitious composition of the present invention, the content of the coagulant may be 0.2% to 6.5%, preferably 1.0% to 5.5%, and more preferably 2.2% to 5.0% of the Be but not limited to the total weight of the composition.

In the uncalcined concrete composition of the present invention, the content of the coagulant can be 0.15% to 3.5%, preferably 0.6% to 3.0%, and more preferably 1.1% to 2.5% of the total weight of the composition, but is not limited thereto.

E. Optional additives

The composition of the present invention also includes one or more optional additives, such as, but not limited to, active silica, a water reducing agent, and so on, for the purpose of adjusting the composition to meet different needs. A detailed description is given below.

Coagulant

The composition of the present invention may additionally comprise a coagulation aid to further facilitate the coagulation reaction between the components of the present invention. The coagulant comprises an oxide, hydroxide, sulfate or carbonate of an alkali metal or alkaline earth metal. Examples include, but are not limited to, lithium oxide, magnesium oxide, calcium oxide, barium oxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium sulfate, magnesium sulfate, calcium sulfate, lithium carbonate and so on.

Therefore, in a preferred aspect of the present invention there is provided an uncalcined cementitious composition containing a coagulant comprising: (a) micrometer-scale inorganic particles having a grain size in the range of 1.0 to 100 microns to about 30% 86%, preferably 40% to 80%, and even more preferably 50% to 74%, based on the total weight of the composition; (b) an aluminum-oxygen compound having a content that can be at least 1.8%, at least 4.0%, at least 4.8%, at least 8.0% or at least 9.2% of the total weight of the composition, but is not limited to; or can be at most 20.0%, at most 17.5% or at most 12.5% of the total weight of the composition, but is not limited thereto; or can be in any of the above-mentioned values as upper and lower limits; (c) nanocolloidal silica at a level which can be 15.0% to 35.0%, preferably 18.0% to 32.0%, and more preferably 20.0% to 30.0% of the total weight of the composition, however is not limited to this; (d) a coagulation regulating agent at a level which can be 0.18% to 6.0%, preferably 0.9% to 5.0% and more preferably 2.0% to 4.5% of the total weight of the composition, but is not limited to; and (i) a coagulant at a level that is at least 2.2%, at least 2.6%, or at least 3.0%; or may be at most 6.5%, at most 5.8%, at most 5.0% or at most 3.0% of the total weight of the composition, but is not limited thereto; or can be in any of the above-mentioned values as the upper and lower limits.

After the components of the composition have been mixed, the composition can be used as a binder material in building materials in the same way as cement, without calcination.

Further in a preferred aspect of the present invention there is provided an uncalcined concrete composition containing a coagulant comprising: (a) inorganic particles at about 65% to 90%, preferably 68% to 88%, and more preferably 70% up to 85% based on the total weight of the composition; (b) an aluminum-oxygen compound having a content that can be at least 1.0%, at least 2.0%, at least 2.5%, at least 4.6% or at least 5.2% of the total weight of the composition, but is not limited to; or a maximum of 10.0%, a maximum of 8.5%, a maximum of 6.0%, a maximum of 5.2%, a maximum of 4.6%, a maximum of 2.5% or a maximum of 2.0% of the total weight of the composition, but is not limited to this; or can be in any of the above-mentioned values as upper and lower limits; (c) nanocolloidal silica at a level which can be 7.5% to 15.0%, preferably 9.0% to 13.0%, and more preferably 10.0% to 12.5% of the total weight of the composition, however is not limited to this; (d) a coagulation regulating agent at a level which can be 0.1% to 3.0%, preferably 0.5% to 2.5% and more preferably 1.0% to 2.2% of the total weight of the composition, but is not limited to; and (i) a coagulant comprising an oxide, hydroxide, sulfate or carbonate of an alkali metal or alkaline earth metal at a content that is at least 1.0%, at least 1.5% or at least 2.0%; or can be at most 3.0%, at most 2.8%, at most 2.4% or at most 2.0% of the total weight of the composition, but is not limited thereto; or in any of the above-mentioned values as upper and lower limits, the inorganic particles comprising micrometer-scale inorganic particles with a grain size in the range from 1.0 to 100 µm and the micrometer-scale inorganic particles about 25% to 45% the total weight of the inorganic particles.

Active silica

The active silica useful in the composition of the present invention is a commonly known silica having a low overall density and a large specific surface area. While not wishing to be bound by theory, the addition of active silica to the composition imparts better waterproofing properties to the cementitious material formed with the composition of the present invention, so that the composition of the present invention has a wider range of uses. Ordinary active silicon dioxide can be amorphous silicon dioxide, such as fumed silicon dioxide or precipitated silicon dioxide, the primary particles of which are on the nanometer scale and can also be aggregated on the micrometer level to form microaggregates. The grain size of the primary particles of the fumed silicon dioxide can be, for example, 5 to 50 nm, but is not limited thereto; the grain size of the microaggregates formed can be 1 to 20 μm, but is not limited thereto; and the specific surface area may be 50 to 600 m 2 / g, for example 140 to 220 m 2 / g, but is not limited thereto. The grain size of the primary particles of the precipitated silicon dioxide can be, for example, 5 to 100 nm, but is not limited thereto; the grain size of the microaggregates formed can be 1 to 40 μm, but is not limited thereto; and the specific surface area can be 5 to 100 m 2 / g, but is not limited thereto.

In the uncalcined cementitious composition of the present invention, the active silica content may be at least 0.3%, at least 0.5%, at least 0.8%, at most 5.0%, at most 4.5% or at most 4, 2% of the total weight of the composition or any range formed by the above values as the upper and lower limits, but is not limited thereto.

In the uncalcined concrete composition of the present invention, the active silica content may be at least 0.2%, at least 0.3%, at least 0.5%; at most 2.5%, at most 2% or at most 1.8% of the total weight of the composition or in any range formed by the above-mentioned values as upper and lower limits, but is not limited thereto.

Water reducing agent

The water reducing agents useful in the present invention are those that facilitate the absorption of water after the components of the composition have been mixed. Examples include lignin-based water-reducing agents, naphthalenesulfonic acid-based water-reducing agents, water-soluble resin-based water-reducing agents, and polycarboxylic acids such as calcium lignosulfonate, sodium lignosulfonate, magnesium lignosulfonate, lignosulfonate, naphthalenesulfonates, coumarone resin and so on.

The uncalcined cementitious composition of the present invention can exhibit cement-like behavior and meet building specification property requirements after the components are mixed at ambient temperature. Since the raw materials used include the main component of conventional cements, limestone, not as an essential component, with the uncalcined concrete composition of the present invention, a non-calcined concrete which (even if it optionally contains limestone) has properties that are comparable to those of existing concretes or surpass these without being produced without calcination. The energy required for the high-temperature calcination is therefore greatly reduced and the problem of environmental pollution resulting from the high-temperature calcination is avoided. While not wishing to be bound by theory, use of the uncalcined cementitious composition of the present invention can reduce carbon emissions by at least about 40% to about 70% compared to conventional portland cement. In addition, the raw materials used are more environmentally friendly, more accessible and have a lower impact on the environment, so that environmental and economic costs are reduced.

Method of making an uncalcined cementitious composition

The uncalcined cementitious composition of the present invention is formed by combining the selected components. In a preferred aspect of the present invention, the uncalcined cementitious composition is packaged in two portions, one comprising the micrometer-sized inorganic particles and the aluminum-oxygen compound and the other comprising the nanocolloidal silica and the coagulant. The two components are preferably not in contact with one another during the course of transport or before the composition is used. In a further preferred aspect of the present invention, the uncalcined cementitious composition of the present invention is packaged in two portions, one of which comprises the micrometer-scale inorganic particles, the aluminum-oxygen compound and the coagulant and the other the nanocolloidal silicon dioxide and the coagulation regulating agent. The coagulant is preferably not in contact with the nanocolloidal silicon dioxide during transport or before the composition is used. In one aspect, the uncalcined cementitious composition is packaged in two portions, one of which includes all of the components in the form of a solid and the other of which includes the components in the form of a liquid (e.g., a solution, suspension, or sol). The two components are preferably not in contact with one another during the course of transport or before the composition is used.

Process for making an uncalcined concrete composition

The uncalcined concrete composition of the present invention is formed by combining the selected components. In a preferred aspect of the present invention, the uncalcined concrete composition is packaged in two parts, one of which comprises the inorganic particles (comprising the micrometer-sized inorganic particles) and the aluminum-oxygen compound and the other the nanocolloidal silica and the coagulation regulating agent. The two components are preferably not in contact with one another during the course of transport or before the composition is used. In a further preferred aspect of the present invention, the uncalcined concrete composition of the present invention is packaged in two parts, one of which is the inorganic particles (comprising the micrometer-sized inorganic particles), the aluminum-oxygen compound and the coagulant and the other is the nanocolloidal silicon dioxide and the coagulation regulating agent comprises. The coagulant is preferably not in contact with the nanocolloidal silicon dioxide during transport or before the composition is used. In one aspect, the uncalcined concrete composition is packaged in two parts, one of which comprises all of the components in the form of a solid and the other of which comprises the components in the form of a liquid (e.g., a solution, a suspension or a sol). The two components are preferably not in contact with one another during the course of transport or before the composition is used.

Process for the production of uncalcined concrete

Most of the components included in the uncalcined cementitious composition and uncalcined concrete composition of the present invention do not require calcination, and only a few components need to be treated by low temperature calcination (e.g., the optional coagulant such as magnesium oxide).

The concrete generally comprises a binder material (cement), water, an aggregate and other components. The aggregate can be any material used in construction, for example from various natural ores or rocks, quartz sand, land sandstone, silica sand, river sand, sea sand, reservoir silt, or any combination of the aforementioned and inevitable impurities contained therein. In one embodiment, the inorganic particles comprise quartz sand, gravel, or both, and the quartz sand and gravel, if both are present, can be mixed in any proportion.

Therefore, the uncalcined cementitious composition of the present invention can be used as a binder material for making an uncalcined concrete. For example, the uncalcined cementitious composition of the present invention can be mixed with the aggregate and other components to make a concrete. For example, the aggregate can be mixed uniformly first with the micrometer-scale inorganic particles and then with the aluminum-oxygen compound; and then the nanocolloidal silica and the coagulant can be added and the components mixed to obtain an uncalcined concrete. Alternatively, the components except for the nanocolloidal silica and the coagulation regulating agent can be mixed until uniform and then the nanocolloidal silica and the coagulation regulating agent can be added sequentially or simultaneously and the components can be mixed to produce an uncalcined concrete.

In one aspect, in which a non-calcined concrete with a non-calcined cementitious composition comprising a further added optional component (for example, one or more of a coagulant, active silica and a water reducing agent) is prepared, the aggregate is first with the micrometer-scale inorganic Particles and then uniformly mixed with the coagulant and the aluminum-oxygen compound; and then the nanocolloidal silica and the coagulant are added and the components are mixed to obtain an uncalcined concrete. In a further aspect, the aggregate and the micrometer-scale inorganic particles are first mixed and then mixed uniformly with the aluminum-oxygen compound; and thereafter the nanocolloidal silica, the coagulant and the active silica are added and the components are mixed to obtain an uncalcined concrete. In a further aspect, the aggregate is mixed with the micrometer-scale inorganic particles and then mixed uniformly with the aluminum-oxygen compound and the coagulation aid; and thereafter the nanocolloidal silica, the coagulant and the active silica are added and the components are mixed to obtain an uncalcined concrete. In a further aspect, the aggregate is mixed with the micrometer-scale inorganic particles and then mixed uniformly with the water-reducing agent and the aluminum-oxygen compound; and then the nanocolloidal silica and the coagulant are added and the components are mixed to obtain an uncalcined concrete. Alternatively, in the above aspects, the components except for the nanocolloidal silicon dioxide, the coagulation regulating agent and the active silicon dioxide (if present) are first mixed uniformly and then the nanocolloidal silicon dioxide, the coagulation regulating agent and the active silicon dioxide (if present) are added and the components mixed to make an uncalcined concrete. Alternatively, in the above aspects, the components in the form of a solid are first mixed, and then the components are added in the form of a liquid (e.g., a solution, a suspension or a sol) and the components are mixed to prepare an uncalcined concrete.

Further, the concrete can also be made with the uncalcined concrete composition provided in the present invention. First, the inorganic particles are mixed uniformly, and then other components are added to make an uncalcined concrete. For example, the inorganic particles are mixed with the micrometer-sized inorganic particles in a ratio as described above and then mixed with the aluminum-oxygen compound uniformly; and then the nanocolloidal silica and the coagulant are added and the components are mixed to obtain an uncalcined concrete. In one embodiment, in which a concrete with a non-calcined concrete composition comprising a further added optional component (for example, one or more of a coagulant, active silica and a water reducing agent) is prepared, the inorganic particles with the micrometer-scale inorganic particles in a described above Ratio mixed and then mixed evenly with the aluminum-oxygen compound and the coagulant; and then the nanocolloidal silica and the coagulant are added and the components are mixed to obtain an uncalcined concrete. In a further embodiment, the inorganic particles and the micrometer-scale inorganic particles are mixed in a ratio as described above and then mixed uniformly with the aluminum-oxygen compound; and thereafter the nanocolloidal silica, the coagulant and the active silica are added and the components are mixed to obtain an uncalcined concrete. In a further embodiment, the inorganic particles are mixed with the micrometer-scale inorganic particles in a ratio described above and then evenly mixed with the aluminum-oxygen compound and the coagulation aid; and thereafter the nanocolloidal silica, the coagulant and the active silica are added and the components are mixed to obtain an uncalcined concrete. In a further specific embodiment, the inorganic particles are mixed with the micrometer-scale inorganic particles in a ratio described above and then uniformly mixed with the water-reducing agent and the aluminum-oxygen compound; and then the nanocolloidal silica and the coagulant are added and the components are mixed to obtain an uncalcined concrete. Alternatively, in the above embodiments, the components except for the nanocolloidal silicon dioxide, the coagulation regulating agent and the active silicon dioxide (if present) are first mixed uniformly and then the nanocolloidal silicon dioxide, the coagulation regulating agent and the active silicon dioxide (if present) are added and the components mixed to make an uncalcined concrete. Alternatively, in the above aspects, the components in the form of a solid are first mixed, and then the components are added in the form of a liquid (e.g., a solution, a suspension or a sol) and the components are mixed to prepare an uncalcined concrete.

The aggregate for the production of the concrete can include land sandstone, quartz sand, river sand, sea sand, reservoir silt and the like. In one embodiment, the inorganic particles of the present invention are also considered an aggregate. In a preferred embodiment, the aggregate is subjected to a salt removal treatment (comprising the removal of cations and / or anions) before use.

The uncalcined cement made with the uncalcined cementitious composition or the uncalcined concrete composition of the present invention exhibits physical and mechanical properties comparable to or even better than conventional concrete made from conventional Portland cement. For example, in one embodiment of the uncalcined cementitious composition or the uncalcined concrete composition of the present invention produced uncalcined concrete in a stress-strain test carried out in accordance with CNS 1010 (ASTM C109) or CNS 1232 (ASTM C39), a mechanically acceptable stress-strain test Compressive Strength, for example, a 28 day compressive strength of at least 1,800 psi, at least 2,000 psi, preferably at least 3,000 psi, preferably at least 4,500 psi, and more preferably at least 6,000 psi. In a more preferred embodiment, the uncalcined cementitious composition or the uncalcined concrete composition of the present invention has a 28 day compressive strength of at least 8,000 psi, at least 10,000 psi, at least 12,000 psi, or at least 14,000 psi. In one embodiment, with the uncalcined cementitious composition or the uncalcined concrete composition of the present invention, the uncalcined concrete produced in a flexural tensile strength test carried out in accordance with CNS 1238 (ASTM C348) has a mechanically acceptable flexural tensile strength, for example a 28-day flexural tensile strength of at least 200 psi , preferably at least 300 psi, preferably at least 450 psi, and more preferably at least 600 psi. In one embodiment, the with the uncalcined cementitious composition or the uncalcined. Concrete composition of the present invention produced uncalcined concrete in a splitting tensile strength test carried out according to the standard CNS 3801 (ASTM C496) a mechanically acceptable splitting tensile strength, for example a 28-day splitting tensile strength of at least 200 psi, preferably at least 300 psi, preferably at least 450 psi and more preferably at least 600 psi. In a specific embodiment, the uncalcined cement made with the uncalcined cementitious composition or the uncalcined concrete composition of the present invention has a mechanically acceptable linear shrinkage, for example a linear 28-day, in a linear shrinkage test carried out in accordance with CNS 14603 (ASTM C157) Shrinkage of at most 1,500 μ, preferably at most 1,200 μ, more preferably at most 600 μ, even more preferably at most 400 μ and even more preferably at most 200 μ.

In one embodiment, with the uncalcined cementitious composition or the uncalcined concrete composition of the present invention produced uncalcined concrete in a compressive strength test carried out on a cylindrical concrete sample in accordance with standard CNS 1232 (ASTM C39) has a mechanically acceptable compressive strength, for example a compressive strength of at least 4,500 psi, preferably at least 5,000 psi, and more preferably at least 6,000 psi.

The following examples are provided to make the present invention better understood by those skilled in the art to which the invention pertains, but are not intended to limit the scope of the invention.

Examples

example 1

An uncalcined cementitious composition having the components listed in Table 1 below was prepared.

Unless otherwise stated, the nanocolloidal silicon dioxide was prepared by mixing nanocolloidal silicon dioxide of 18 nm and nanocolloidal silicon dioxide of 80 nm in a ratio of about 8: 2 (solids content: 40% by weight).

An uncalcined cementitious composition was prepared with the components listed in Table 1A below.

In Examples 2 to 9 below, the compressive strength is tested in accordance with the CNS 1010 standard (ASTM C109), except for the duration of the strength test, for which the information given herein is relevant.

Example 2

An uncalcined concrete composition was prepared with the components listed in the table below. The inorganic particles (the aggregate) and the micrometer-sized inorganic particles (SiO2) were mixed according to the weight ratio shown in Table 2 and then mixed uniformly with the aluminum-oxygen compound. Thereafter, the nanocolloidal silica and the coagulant were added and the components mixed, and after curing for 28 days, the compressive strength was measured.

The nanocolloidal silicon dioxide was prepared by mixing nanocolloidal silicon dioxide of 18 nm and nanocolloidal silicon dioxide of 80 nm in a ratio of about 8: 2 (solids content: 40% by weight).

Example 3

An uncalcined concrete composition was prepared with the components listed in the table below. The inorganic particles (the aggregate) and the micrometer-scale inorganic particles (SiO2) were mixed according to the weight ratio shown in Table 3 and then mixed uniformly with the coagulant and the aluminum-oxygen compound. The nanocolloidal silica and coagulant were then added, the components mixed, and after curing for 14 or 28 days, the compressive strength was measured.

The nanocolloidal silicon dioxide was prepared by mixing nanocolloidal silicon dioxide of 18 nm and nanocolloidal silicon dioxide of 80 nm in a ratio of about 8: 2 (solids content: 40% by weight).

* The strength of No. 9 is 14 day strength.

Example 4

An uncalcined concrete composition was prepared with the components listed in the table below. The micrometer-scale inorganic particles (SiO2) were formed as graded powders by mixing according to the grain sizes and weight percentages shown in Table 4. The inorganic particles (the aggregate) were evenly mixed with the graded powder and then with the coagulant and the aluminum-oxygen compound. Thereafter, the nanocolloidal silica and the coagulant were added and the components mixed, and after curing for 28 days, the compressive strength was measured.

Except for Nos. 28 to 30, the nanocolloidal silicon dioxide was prepared by mixing nanocolloidal silicon dioxide of 18 nm and nanocolloidal silicon dioxide of 80 nm in a ratio of about 8: 2 (solids content: 40% by weight).

Example 5

An uncalcined concrete composition was prepared with the components listed in the table below. The micrometer-scale inorganic particles (SiO2) were formed as graded powders by mixing according to the grain sizes and weight percentages shown in Table 5. The inorganic particles (the aggregate) were evenly mixed with the graded powder and then with the coagulant and the aluminum-oxygen compound. The nanocolloidal silica and coagulant were then added, the components mixed, and after 7 or 28 days of curing, the compressive strength was measured.

The nanocolloidal silicon dioxide was prepared by mixing nanocolloidal silicon dioxide of 18 nm and nanocolloidal silicon dioxide of 80 nm in a ratio of about 8: 2 (solids content: 40% by weight). * The strength of No. 20 and 23 to 25 is a 2-day strength at 180 ° C. ** The strength of # 26 is a 7 day strength.

Example 6

An uncalcined concrete composition was prepared with the components listed in the table below. The micrometer-scale inorganic particles (SiO2) were formed as graded powders by mixing according to the grain sizes and weight percentages shown in Table 6. The inorganic particles (the aggregate) were evenly mixed with the graded powder and then with the coagulant and the aluminum-oxygen compound. The nanocolloidal silicon dioxide and the coagulant (citric acid) were then added and the components mixed, and after 10 or 28 days of curing, the compressive strength was measured.

The nanocolloidal silicon dioxide was prepared by mixing nanocolloidal silicon dioxide of 18 nm and nanocolloidal silicon dioxide of 80 nm in a ratio of about 8: 2 (solids content: 40% by weight). * The strength of Nos. 414 and 415 is a 10-day strength.

Example 7

An uncalcined concrete composition was prepared with the components listed in the table below. River sand was first ground, graded and used as micrometer-scale inorganic particles with which graded powders were formed by mixing according to the grain sizes and weight percentages shown in Table 7. The inorganic particles (the aggregate) were evenly mixed with the graded powder and then with the coagulant and the aluminum-oxygen compound (alumina-rich cement). The nanocolloidal silicon dioxide and the coagulant (citric acid) were then added and the components mixed, and after curing for 28 days, the compressive strength was measured.

The nanocolloidal silicon dioxide was prepared by mixing nanocolloidal silicon dioxide of 18 nm and nanocolloidal silicon dioxide of 80 nm in a ratio of about 8: 2 (solids content: 40% by weight).

The test result allows the conclusion that the easily accessible sand is also useful in the present invention.

Example 8

A calcium-free concrete composition was made with 52.8% by weight quartz sand, 8.0% by weight 1.6 μm SiO2, 11.8% by weight 10 μm SiO2, 6.2% by weight. -% 45-μm SiO2, 5.9% by weight of cement rich in aluminum oxide, 1.8% by weight of magnesium oxide, 1.3% by weight of citric acid and the nanocolloidal silicon dioxide with different particle sizes in the combination shown in Table 8 . The micrometer-scale inorganic particles (SiO2) were formed as graded powders by mixing. Then the inorganic particles (the aggregate) were evenly mixed with the graded powders and then with the coagulant (magnesium oxide) and the aluminum-oxygen compound (aluminum oxide-rich cement). Thereafter, the nanocolloidal silica (a single component or a combination of more than one component) and the coagulant (citric acid) were added and the components mixed and, after curing for 28 days, the compressive strength was measured.

Example 9

A concrete composition with the components listed in the table below was prepared. The aggregate and the micrometer-scale inorganic particles (SiO2) were mixed according to the percentages by weight shown in Table 9 and then mixed with the coagulation aid. The nanocolloidal silicon dioxide and the coagulant (citric acid) were then added and the components mixed, and after curing for 28 days, the compressive strength was measured.

Example 10

A concrete composition having the components listed in Table 10 below was prepared.

The composition sets to form a block in an extremely short time, which is disadvantageous for the application.

Example 11

A concrete was made with an uncalcined cementitious composition and raw aggregate as shown in Table 11 below.

The components were mixed and poured into a mold to produce several concrete samples, which were allowed to stand for 28 days and then tested for compressive strength of cylindrical concrete samples according to CNS1232 (ASTM C39). The compressive strength is shown in Table 12 below.

Table 12

C01 6927 6529 C02 6002 C03 6642

Example 12

The flexural tensile strength of the concrete samples produced in Example 11 was measured in a flexural tensile strength test for cylindrical concrete samples according to CNS1238 (ASTM C348). The flexural strength is shown in Table 13 below.

Table 13

B01 689.4 635.8 B02 574.6

Example 13

The splitting tensile strength of the concrete samples produced in Example 11 was measured in a splitting tensile strength test for cylindrical concrete samples according to CNS3801 (ASTM C496). The splitting tensile strength is shown in Table 14 below.

Table 14

T01 533.3 473.6 T02 486.4 T03 381.2

From Examples 11 to 13, it can be concluded that the concrete made with the uncalcined cementitious composition or the uncalcined concrete composition of the present invention has good physical and mechanical properties.

Example 14

The linear shrinkage of the concrete sample produced in Example 11 (SOI) and the concrete sample produced with the commercially available Portlang cement and an aggregate (R01) was measured according to the standard CNS14603 (ASTM C157). The linear shrinkage (µ) is shown in Table 15 below.

Table 15

R01 147 252 312 399 503 S01 52 120 132 176 176

From the test results, it can be concluded that the concrete made with the uncalcined cementitious composition or the uncalcined concrete composition of the present invention far outperforms the concrete made with the conventional Portland cement in terms of linear shrinkage.

The above-described embodiments of the present invention are to be considered as illustrative only. Numerous alternative embodiments can be devised by those skilled in the art without departing from the scope of the appended claims.

Claims (14)

1. An uncalcined cementitious composition comprising: a) Micrometer-scale inorganic particles, containing silicon and at least one non-metallic element, with a grain size in the range from 1.0 to 100 µm to about 31% to 87%, based on the total weight of the composition, with “about” a range of ± 10 includes% of the stated values; b) an aluminum-oxygen compound selected from an oxo acid of aluminum, a derivative thereof, an oxide of aluminum, a hydroxide of aluminum and a mixture of these compounds; c) nanocolloidal silicon dioxide and d) a coagulation regulating agent. 2. Uncalcined cementitious composition according to claim 1, wherein the grain size distribution of the micrometer-scale inorganic particles is at least bimodal. 3. Uncalcined cementitious composition according to claim 1, wherein the micrometer-scale inorganic particles have a trimodal grain size distribution, the weight of the particles having a grain size or a grain size range at a maximum of the trimodal grain size distribution regardless of the weight of the particles having a grain size or a grain size range to the other Maximum values of the trimodal grain size distribution makes up at least 20% to 50% of the total weight of the micrometer-scale inorganic particles. 4. Non-calcined cementitious composition according to claim 1, wherein the nanocolloidal silicon dioxide has a bimodal grain size distribution, the weight of the particles with a grain size or a grain size range at a maximum value of the bimodal grain size distribution regardless of the weight of the particles with a grain size or a grain size range at the other maximum value bimodal grain size distribution makes up at least 30% to 70% of the total weight of the nanocolloidal silicon dioxide. 5. The uncalcined cementitious composition of claim 1, further comprising at least one of a coagulant, active silica and a water reducing agent. 6. A non-calcined cementitious composition according to claim 1, comprising a coagulant which comprises an oxide, hydroxide, sulfate or carbonate of an alkali metal or alkaline earth metal, and wherein the micrometer-scale inorganic particles a) make up 31% to 86%, based on the total weight of the composition . 7. An uncalcined concrete composition comprising a) inorganic particles containing silicon and at least one non-metallic element, from about 66% to 92%, based on the total weight of the composition, with “about” including a range of ± 10% of the stated values; b) an aluminum-oxygen compound selected from an oxo acid of aluminum, a derivative thereof, an oxide of aluminum, a hydroxide of aluminum and a mixture of these compounds; c) nanocolloidal silicon dioxide and d) a coagulation-regulating agent, wherein the inorganic particles comprise micrometer-scale inorganic particles with a grain size in the range of 1.0 to 100 µm and the micrometer-scale inorganic particles make up 25% to 45% of the total weight of the inorganic particles. 8. Uncalcined concrete composition according to claim 7, wherein the grain size distribution of the micrometer-scale inorganic particles is at least bimodal. 9. Uncalcined concrete composition according to claim 7, wherein the micrometer-scale inorganic particles have a trimodal grain size distribution, the weight of the particles having a grain size or a grain size range at a maximum value of the trimodal grain size distribution regardless of the weight of the particles having a grain size or a grain size range at the other maximum values the trimodal grain size distribution makes up at least 20% to 50% of the total weight of the micrometer-scale inorganic particles. 10. Uncalcined concrete composition according to claim 7, wherein the nanocolloidal silicon dioxide has a bimodal grain size distribution, the weight of the particles with a grain size or a grain size range at a maximum value of the bimodal grain size distribution regardless of the weight of the particles with a grain size or a grain size range at the other maximum value of the bimodal Grain size distribution makes up at least 30% to 70% of the total weight of the nanocolloidal silicon dioxide. 11. The uncalcined concrete composition of claim 7, further comprising at least one of a coagulant, active silica and a water reducing agent. 12. An uncalcined concrete composition according to claim 7 comprising a coagulant comprising an oxide, hydroxide, sulfate or carbonate of an alkali metal or alkaline earth metal, and wherein the inorganic particles (a) constitute 66% to 90% based on the total weight of the composition. 13. Concrete comprising a non-calcined cementitious composition according to any one of claims 1 to 6 or a non-calcined concrete composition according to any one of claims 7 to 12. 14. The concrete of claim 13 having at least one of the following properties: a 28 day compressive strength of at least 1,800 psi measured according to ASTM C109 or ASTM C39, a 28 day flexural tensile strength of at least 200 psi measured according to the ASTM C348 standard, a 28-day split tensile strength of at least 200 psi, measured according to the ASTM C496 standard, and a 28-day linear shrinkage of at most 1500 μ, measured according to the ASTM C157 standard.