TWI635066B - Non-calcined cementitious compositions, non-calcined concrete compositions, non-calcined concrete and preparation methods thereof - Google Patents

Abstract

The present invention provides a non-calcined cement composition comprising micron inorganic particles, the non-calcined cement composition provided can be used as a cementitious material, and a non-calcined concrete composition is provided; and a non-calcined concrete is provided, the physics thereof It is similar to or better than the engineering properties of traditional cement. The invention also provides a process for producing a non-calcined cement composition, a non-calcined concrete composition and a non-calcined concrete.

Description

Non-calcined cement composition, non-calcined concrete composition, non-calcined concrete and preparation method thereof

The present invention provides a non-calcined cement composition comprising micron inorganic particles, the non-calcined cement composition provided can be used as a cementitious material, and a non-calcined concrete composition is provided; and a non-calcined concrete is provided, the physics thereof It is similar to or better than the engineering properties of traditional cement. The invention also provides a process for producing a non-calcined cement composition, a non-calcined concrete composition and a non-calcined concrete.

Cement is a general term for cementitious materials commonly found in building materials and is one of the most important building materials available today. According to statistics from the Portland Cement Association, the global cement consumption in 2015 was about 4.1 billion tons, which is evident in its importance. The most common cement should be Portland cement, the main components of which are limestone, clay, antimony and iron slag. However, most of these materials are required to be mined in natural minerals, which has a significant impact on the environment. In addition, due to the use of raw materials such as limestone, high-temperature calcination is required in the process of preparing cement, which consumes a lot of energy and generates considerable carbon emissions; and limestone minerals in China and Taiwan are estimated to be only about 50 years old during mining or Shorter. These issues are all concerns about environmental protection and shortage of building materials.

To this end, the industry is trying to develop alternative raw materials to reduce the loss of natural resources and reduce carbon emissions in the process of manufacturing cement. A gelling material that does not use limestone is an alkali-excited cement in which a bismuth aluminum compound (fly ash) is polymerized with sodium citrate (water glass) by a strong alkali. However, it may cause problems such as large shrinkage, high heat release during the mixing process, easy cracking of the finished product, easy formation of salt crystals on the surface, and easy use of a large amount of strong alkali to corrode and rust the steel structure. Late strength may have adverse effects. The use of large amounts of strong bases is also detrimental to the scale of application. In addition, some alkali-activated cements need to be catalyzed at high temperatures for several hours before they can be hardened. Accordingly, there are still many limitations in the application of alkali-activated cement.

TW I491579 B discloses a low calcium cementitious material composition which is particularly low calcium fly ash, an alkali agent and a setting accelerator which are mixed and allowed to stand at room temperature to form a low calcium cementitious material. The focus of this technology is to solve the problem of the additional addition of calcium containing components when using low calcium fly ash by adding a setting accelerator.

WO 2011/008463 A1 discloses the use of cement comprising (1) at least one inorganic filler, (2) colloidal ceria, colloidal alumina or mixtures thereof, which form a binder phase to be sintered, and (3) a carrier fluid combination. However, the cement composition needs to be subjected to high temperature calcination (at least 1000 ° C) in the presence of a fluorine source to form a binder phase.

Therefore, there is still a great demand for cementitious materials that minimize the environmental impact during the manufacturing process and are easy to use on a large scale.

To achieve the foregoing objects, the present invention provides a non-calcined cement composition comprising: (a) from about 31% to 87% by weight of the total composition of the micron-inorganic having a particle size of from 1.0 to 100 μm Particles; (b) aluminum oxide compounds; (c) nano colloidal silica; and (d) a coagulation controlling agent.

This composition can play the same cementitious material role as cement in building materials without the need for calcination after mixing the components.

The present invention also provides a non-calcined concrete composition comprising: (a) from about 66% to 92% by weight of the total weight of the inorganic particles; (b) an aluminoxy compound; (c) a nano colloidal a colloidal silica; and (d) a coagulation controlling agent, wherein the inorganic particles comprise micron inorganic particles having a particle size of from 1.0 to 100 μm, the micron inorganic particles occupying 25% by weight of the inorganic particles 45%. The composition can be obtained without the calcination after the components are mixed, and the mechanical properties similar to those of the concrete made of general cement can be obtained, and the volume stability is good.

The present invention also provides a non-calcined concrete comprising a non-calcined cement composition or a non-calcined concrete composition.

The present invention also provides a method of preparing a non-calcined cement composition comprising the steps of combining micron inorganic particles, an aluminoxy compound, a nano colloidal ceria, and a coagulation controlling agent.

The present invention also provides a method of preparing a non-calcined concrete composition comprising the steps of combining inorganic particles, an aluminoxy compound, a nano colloidal ceria, and a coagulation controlling agent.

All numbers expressing levels, ratios, physical characteristics, and the like, used in the specification and claims are to be understood as being modified by the term "about" in all instances. Therefore, unless stated to the contrary, the values set forth in the following description and claims are intended to be The law changes and/or the characteristics required. At the very least, and not as an attempt to limit the application of the equivalents to the scope of the claims, the numerical parameters are at least construed in accordance with the number of significant digits disclosed.

All ranges disclosed herein are to be understood as encompassing any and all sub-ranges For example, the range of "1 to 10" shall be taken to include any and all sub-ranges between the minimum value 1 and the maximum value 10 and include a maximum value of 1 and a maximum value of 10; that is, 1 or greater than 1 All sub-ranges starting at the minimum and ending with a maximum of 10 or less, for example: 1 to 6.7, 3.2 to 8.1 or 5.5 to 10, and numerical values, for example: 1, 3.1, 5.2 or 8.

The word "about" as used herein is intended to mean an approximate range that can be understood by those of ordinary skill in the art to which the present invention pertains. The approximate range is related to different features or physical quantities. For example, the word "about" may include a range of ±10%, ±5%, ±2%, or ±1% of the stated value.

The compositions provided by the present invention comprise (micron) inorganic particles, an aluminoxy compound, a nano colloidal ceria, and a coagulation controlling agent. The components are described in detail below.

A. Inorganic particles

The inorganic particles contained in the composition of the present invention include inorganic particles containing at least one of cerium and aluminum, for example, at least one of cerium and aluminum and various metal elements or non-metal elements, and the metal may be, for example, Alkali gold, alkaline earth, metalloid and transition metal, non-metal elements may be, for example, carbon, hydrogen, oxygen, nitrogen, boron, phosphorus, sulfur, halogen, etc. Examples include, but are not limited to, cerium oxides (eg cerium) Acid salt, cerium oxide), carbide (for example, cerium carbide); various compounds formed by cerium, aluminum, oxygen; or a combination of such compounds; and further optional other inorganic components, such as the aforementioned metals And/or various substances formed by non-metallic elements, such as various compounds containing calcium, magnesium, boron, carbon, nitrogen, oxygen or any combination of such compounds. For example, inorganic particles can be derived from a variety of natural ores or rocks, quartz sand, terrestrial sand, Sand, river sand, sea sand, reservoir sludge or any combination of the foregoing, and the inevitable impurities contained therein. In one embodiment, the inorganic particles comprise quartz sand, crushed stone, or both, and may be mixed in any ratio when both are included.

In the non-calcined cement composition provided by the present invention, the inorganic particles having a particle size of 1.0 to 100 μm are referred to herein as micron inorganic particles; the micro inorganic particles are a main group of the non-calcined cement composition. The portion accounts for 31% to 87%, preferably 42% to 81%, more preferably 52% to 76%, based on the total weight of the non-calcined cement composition.

In the non-calcined concrete composition provided by the present invention, the inorganic particles are the most abundant, and the content thereof is about 66% to 92%, preferably 72% to 90%, based on the total weight of the non-calcined concrete composition. Good is 74% to 86%.

In the non-calcined concrete composition provided by the present invention, the particle size of the inorganic particles is not particularly limited and may be in the order of nanometer to millimeter; however, at least a part of the inorganic particles need to be micron inorganic particles: micron inorganic particles occupy inorganic particles. The total weight is from 25% to 45%, preferably from 27% to 43%, more preferably from 30% to 40%.

In one embodiment of the present invention, the particle size of the micron inorganic particles may be between 1.0 and 1.3 μm, between 1.3 and 1.6 μm, between 1.6 and 2.6 μm, between 2.6 and 6.5 μm, and between 6.5 and 8.0 μm. Between 8.0 μm and 10.0 μm, between 10.0 and 13.0 μm, between 13.0 and 28.0 μm, between 28.0 and 38.0 μm, between 38.0 and 45.0 μm, between 45.0 and 50.0 μm, between 50.0 and 53.0 μm Between 53.0 and 58.0 μm, between 58.0 and 75.0 μm, between 75.0 and 86.0 μm, between 86.0 and 100.0 μm, or the like, or in the range of any of the foregoing endpoints; or, the micron inorganic particles have the aforementioned The particle size of any of the endpoints is, 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, about 100 μm, and the like. .

In one embodiment of the present invention, the particle size distribution of the micron inorganic particles is a monomodal distribution; in another specific example, the particle size distribution is bimodal or multimodal; the distribution may be one or more groups of single particles. A diameter or any combination of one or more sets of particle sizes. For example, in a specific example, the particle size distribution of the micron inorganic particles may be, for example, a unimodal distribution between 1 and 2.6 μm; a unimodal distribution of about 1.3 μm; a unimodal distribution of about 1.6 μm; and a 8.0 μm to 13.0 μm Single peak distribution; single peak distribution of about 8.0 μm; single peak distribution of about 10.0 μm; bimodal distribution between 1 and 2.6 μm and between 6.5 and 13.0 μm; double peak of about 1.0 μm and about 8.0 μm Distribution; bimodal distribution of about 1.6 μm and about 13.0 μm; bimodal distribution between 6.5 to 13.0 μm and 45.0 to 58.0 μm; bimodal distribution between 6.5 to 10.0 μm and between 50.0 and 58.0 μm; a bimodal distribution between 8.0 and 10.0 μm and between 50.0 and 53.0 μm; a bimodal distribution of about 10.0 μm and about 45.0 μm; a bimodal distribution of about 6.5 μm and about 50.0 μm; about 10.0 μm and about 50.0 μm Bimodal distribution; bimodal distribution of about 10.0 μm and 45.0 to 50.0 μm; bimodal distribution of about 8.0 μm to 10.0 μm and 50.0 μm; between 1.0 and 2.6 μm, between 6.5 and 13.0 μm, and between 45.0 and 58.0 μm a three-peak distribution; a three-peak distribution between 1.6 and 2.6 μm, between 6.5 and 10.0 μm and between 45.0 and 50.0 μm; between 1.6 and 2.6 μm, between 6.5 and 10.0 μm and between 45.0 and 7 a three-peak distribution between 5.0 μm; a three-peak distribution of about 1.6 μm, about 8.0 μm and about 50.0 μm; a three-peak distribution of about 1.0 μm, about 10.0 μm and about 50.0 μm; about 1.6 μm, about 10.0 μm and about 45.0 μm Trimodal distribution; a three-peak distribution of about 1.6 μm, about 10.0 μm and about 50.0 μm; a three-peak distribution of about 1.3 μm, about 8.0 μm and about 58.0 μm; a three-peak distribution of about 1.6 μm, about 13.0 μm and about 75.0 μm; Four-peak distribution, five-peak distribution, and six-peak distribution of any combination. Micron inorganic particles having a bimodal or multimodal distribution of particle size distribution may also be referred to as grading particles. The distribution of particle sizes can be combined by sieving the pellets to form the distribution pattern. For example, inorganic particles having a large particle size can be obtained by dry or wet grinding into inorganic particles having a small particle size, and are obtained by gas flow classification. The micron-sized inorganic particles are distributed in a narrow particle size and further mixed to obtain a desired particle size distribution pattern. When the particle size of the particles is bimodal, the particles having the peak particle diameter may independently of each other at least about 30% to about 70%, for example, about 30%, about 35%, about 40%, respectively, of the total weight of the micron inorganic particles. , about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, etc.; when the particle size is trimodal, the weight of the particles having the peak particle diameter can be at least micrometer independently of each other. From about 20% to about 50% of the total weight of the inorganic particles, for example, independently of each other, about 20%, about 25%, about 27%, about 29%, about 30%, about 31%, about 33%, about 35%, about 37%, about 40%, about 45%, about 50%, and the like. Without wishing to be bound by theory, the use of grading particles in non-calcined cement compositions or non-calcined concrete compositions enhances the physical and engineering properties (e.g., compressive strength, etc.) of the resulting concrete.

The particle size of the inorganic particles may also be in the order of millimeters, and the particle size may range from greater than 0.1 mm to 50.0 mm.

Alternatively, without wishing to be bound by theory, the particle size of the inorganic particles may also be in the nanometer scale.

The inorganic particles contained in the composition of the present invention do not need to be calcined, but are mixed with other components to exhibit the properties of the cementitious material, and the components are mixed to obtain a cementitious material having properties similar to those of the conventional cement. Reduce considerable carbon emissions and save energy.

B. Aluminoxy compound

The aluminoxy compound contained in the composition of the present invention is a substance mainly composed of aluminum and oxygen, and in the case of a compound, may be an oxo acid of aluminum and a derivative thereof (for example, a salt, an example is an alkali gold group and an alkaline earth group). Salts, aluminum oxides, and aluminum hydroxides; also containing a mixture of such compounds as the principal component. Examples include, but are not limited to, sodium aluminate, calcium aluminate, alumina, aluminum hydroxide, high alumina cement, and the like, or any combination thereof. Without wishing to be bound by theory, the utility of the aluminoxy compound is to stabilize the coagulation between components to provide a solid cement-like stability.

In the non-calcined cement composition of the present invention, the content of the aluminum oxide compound may be, but not limited to, at least 1.9%, at least 4.2%, at least 5.0%, at least 8.0%, at least 9.5% of the total weight of the composition; May be, but is not limited to, up to 21.0%, up to 18.0%, up to 14.5%, up to 8.5%, up to 7.5%; up to 6.0%, up to 5.0%; or the content range of any of the foregoing values may form The scope.

In the non-calcined concrete composition of the present invention, the content of the aluminum oxide compound may be, but not limited to, at least 1.1%, at least 2.2%, at least 2.8%, at least 4.8%, at least 5.5% of the total weight of the composition; May be, but is not limited to, up to 12.0%, up to 10.0%, up to 8.0%, up to 5.5%, up to 5.0%, up to 3.0%, up to 2.0% by weight of the total composition; The scope.

In a preferred embodiment, the aluminoxy compound comprises aluminum hydroxide or a mixture thereof, which enhances the strength of the concrete after curing at a high temperature.

C. Nano colloidal silica (colloidal silica)

The nano colloidal cerium oxide contained in the composition of the present invention is a material known in the art which is a particulate cerium oxide suspended in a liquid phase having a particle size of nanometer. Nano colloidal cerium oxide may also aggregate into larger particles or form a network structure. Nano colloidal cerium oxide is commercially available or can be prepared from cerium-containing materials.

The nano colloidal cerium oxide may have a solid content of 20% by weight to 50% by weight, preferably 30% to 48% by weight, more preferably 35% by weight to 45% by weight, for example, about 20, about 25, or about 30, about 35, about 36, about 37, about 38, about 39, about 40, about 42, about 44, about 45, about 46, about 48, about 50% by weight, or comprised of any of the foregoing endpoints The scope. The granular colloidal cerium oxide contained in the nano colloidal cerium oxide may have a particle size of 8 to 90 nm, preferably 10 to 85 nm, more preferably 15 to 80 nm; or the particle size may be about 8, about 10 , about 15, about 18, about 30, About 50, about 60, about 80, about 90 nm; or the particle size may be in the range of any of the foregoing endpoints.

The particle size of the nano colloidal ceria particles may also have a bimodal distribution, such as 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, Various combinations of about 30 nm and about 80 nm, about 10 nm and about 50 nm are used. When the particle size of the particles is bimodal, the particles having the peak particle diameter may independently of each other at least 30% to 70%, for example, about 30%, about 35%, or about 30% of the total weight of the nano-sized colloidal cerium oxide. 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, and the like. The distribution of the particle diameters can be made into a distribution pattern by using a mixture of nano colloidal ceria having different particle diameters.

In the non-calcined cement composition of the present invention, the content of the nano colloidal cerium oxide may be, but not limited to, 17.0% to 36.0%, preferably 19.0% to 33.0%, more preferably, the total weight of the composition. It is 21.0 to 32.0%.

In the non-calcined concrete composition of the present invention, the content of the nano colloidal cerium oxide may be, but not limited to, 8.5% to 17.0%, preferably 9.5% to 15.0%, more preferably, the total weight of the composition. It is 10.5 to 13.0%.

D. Condensation control agent

The coagulation controlling agent included in the composition of the present invention functions to control the setting time of the component mixture so as to provide a desired application period. Examples may be hydroxycarboxylic acid or a salt thereof, a starch ether or a functionalized starch ether, etc., such as citric acid, tartaric acid, gluconic acid, salicylic acid and the like, alkali metal salts of the acid, methylol starch ether, Hydroxyethyl starch ether, hydroxypropyl starch ether or any combination thereof.

In the non-calcined cement composition of the present invention, the content of the coagulation controlling agent may be (but is not limited to The total weight of the composition is from 0.2 to 6.5%, preferably from 1.0 to 5.5%, more preferably from 2.2% to 5.0%.

In the non-calcined concrete composition of the present invention, the content of the coagulation controlling agent may be, but not limited to, 0.15 to 3.5%, preferably 0.6 to 3.0%, more preferably 1.1 to 2.5%, based on the total weight of the composition.

E. Selective additives

One or more optional additives may also be included in the compositions of the present invention, such as, but not limited to, coagulants, active cerium oxide, water reducing agents, and the like to control the composition to achieve different needs. The detailed description is as follows.

(i) coagulant

A coagulant may additionally be included in the compositions of the present invention to further promote coagulation reactions between the components of the invention. The coagulant comprises an alkali metal or alkaline earth oxide, hydroxide, sulfate or carbonate. 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 the like.

Accordingly, a preferred aspect of the invention is a non-calcined cement composition comprising a coagulant comprising: (a) from about 30% to 86% by weight based on the total weight of the composition, having from 1.0 to 100 μm a micron-sized inorganic particle having a particle size; preferably 40% to 80%, more preferably 50% to 74%; (b) an aluminoxy compound; the content may be, but not limited to, at least 1.8% by weight based on the total weight of the composition. , at least 4.0%, at least 4.8%, at least 8.0%, at least 9.2%; may also be, but not limited to, up to 20.0%, up to 17.5%, by weight of the total composition. 12.5%; or a content range thereof is a range in which any of the foregoing values can be formed; (c) a colloidal silica; the content may be, but is not limited to, 15.0% to 35.0% of the total weight of the composition, It is preferably from 18.0% to 32.0%, more preferably from 20.0 to 30.0%; (d) a coagulation controlling agent; the content may be, but not limited to, from 0.18 to 6.0%, preferably from 0.9 to 5.0%, based on the total weight of the composition. More preferably from 2.0% to 4.5%; and (i) a coagulant; the amount may be, but is not limited to, at least 2.2%, at least 2.6%, or at least 3.0%; or at most 6.5%, at most 5.8% of the total weight of the composition. , at most 5.0% or at most 3.0%; or the content range thereof is a range in which any of the foregoing values can be formed.

The composition can play the same cementitious material as the cement in the building material without the need for calcination after the components are mixed. Further, a preferred aspect of the present invention is a non-calcined concrete composition containing a coagulant. It comprises: (a) from about 65% to 90% by weight based on the total weight of the composition of inorganic particles; the content is preferably from 68% to 88%, more preferably from 70% to 85%; (b) aluminum oxide compound The content may be, but is not limited to, at least 1.0%, at least 2.0%, at least 2.5%, at least 4.6%, at least 5.2% of the total weight of the composition; and may be, but is not limited to, at most 10.0% of the total weight of the composition. , up to 8.5%, up to 6.0%, up to 5.2%, up to 4.6%, up to 2.5%, up to 2.0%; or its content range is any range of the foregoing values; (c) nano colloidal cerium oxide (colloidal) Silica); the content may be, but not limited to, 7.5% to 15.0%, preferably 9.0% to 13.0%, more preferably 10.0 to 12.5%, based on the total weight of the composition; (d) a coagulation controlling agent; the content may be, but not limited to, 0.1 to 3.0%, preferably 0.5 to 2.5%, more preferably 1.0 to 2.2%, based on the total weight of the composition; and (i) a coagulant, An oxide, hydroxide, sulfate or carbonate comprising an alkali gold or alkaline earth; the amount may be, but is not limited to, at least 1.0%, at least 1.5%, or at least 2.0%, or at most 3.0% of the total weight of the composition. , at most 2.8%, at most 2.4% or at most 2.0%; or a content range thereof, wherein the inorganic particles comprise micron inorganic particles having a particle size ranging from 1.0 to 100 μm, the micron inorganic particles The total weight of the inorganic particles is from 25% to 45%.

(ii) active cerium oxide

The active cerium oxide suitable for use in the composition of the present invention is a material known in the art which is a cerium oxide having a low overall density and a high specific surface area. Without wishing to be bound by theory, the addition of active cerium oxide to the composition allows the gelling material formed by the compositions of the present invention to be more water repellent, making the compositions of the present invention more versatile. The common active cerium oxide may be amorphous cerium oxide, such as fumed silica and precipitated silica, or the primary particles of the nanometer. It can also be cohesed into micron-sized micro-polymers. The primary particle diameter of the vapor phase cerium oxide can be, for example, but not limited to, 5 to 50 nm, and the particle diameter of the formed micro-polymer can be, but not limited to, 1 to 20 μm, and the specific surface area can be (but is not limited to) 50 to 600 m ² /g, for example 140 to 220 m ² /g. The primary particle diameter of the precipitated cerium oxide may be, for example, but not limited to, 5 to 100 nm, and the particle diameter of the formed micro-polymer may be, but not limited to, 1 to 40 μm, and the specific surface area may be (but not limited to) 5 Up to 100m ² /g.

In the non-calcined cement composition of the present invention, the active cerium oxide content may be, but not limited to, at least 0.3%, at least 0.5%, at least 0.8%, at most 5.0%, at most 4.5%, of the total weight of the composition. Up to 4.2%, and any combination thereof can form a range.

In the non-calcined concrete composition of the present invention, the active cerium oxide may be, but is not limited to, at least 0.2%, at least 0.3%, at least 0.5%, and at most 2.5%, up to 2%, of the total weight of the composition. Up to 1.8%, and any combination thereof can be formed.

(iii) Water reducing agent

The water reducing agent of the invention is beneficial for absorbing water after mixing the components of the composition, and examples include lignin-based water reducing agent, naphthalenesulfonic acid-based water reducing agent, water-soluble resin water reducing agent, polycarboxylic acid, etc., such as calcium lignosulfonate, Sodium lignosulfonate, magnesium lignosulfonate, sulfonated lignin, naphthalenesulfonate, and xanthonone resin.

The non-calcined cement composition of the present invention, when mixed at room temperature, exhibits behavior similar to cement and exhibits properties meeting the requirements of engineering specifications. Since the raw materials used are not made of limestone, which is the main component of conventional cement, the non-calcined concrete composition of the present invention can be made into non-calcined products which exhibit comparable or better properties to existing concrete without calcination. Concrete (even if it may contain limestone), can greatly save the energy required for high temperature calcination, and avoid the pollution caused by high temperature calcination. Without wishing to be bound by theory, the use of the non-calcined cement compositions 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 and easy to obtain, and have less environmental impact, reducing environmental costs and economic costs.

Method for preparing non-calcined cement composition

The non-calcined cement compositions of the present invention are combined by the choice of components. In a preferred embodiment of the present invention, the non-calcined cement composition is packaged in two parts, one part comprising micron inorganic particles and an aluminum oxide compound, and the other part comprising nano colloidal ceria and a coagulation controlling agent; Preferably, the two portions do not contact each other during or prior to delivery of the composition. In another preferred embodiment of the present invention, the non-calcined cement composition of the present invention is packaged in two parts. a part, wherein a part comprises micron inorganic particles, an aluminum oxide compound and a coagulant, and the other part comprises a nano colloidal ceria and a coagulation controlling agent; preferably, the coagulant is not in the process of transporting the composition or before use. Contact with nano colloidal cerium oxide. In one embodiment, the non-calcined cement composition is packaged in two parts, one portion comprising all components in solid form and the other portion comprising components in liquid form (eg, solution, suspension, sol); Preferably, the two parts are not in contact with each other during or prior to the delivery of the composition.

Method for preparing non-calcined concrete composition

The non-calcined concrete compositions of the present invention are combined by the choice of components. In a preferred embodiment of the present invention, the non-calcined concrete composition is packaged in two parts, one of which contains inorganic particles (including micron inorganic particles) and an aluminum oxide compound, and the other part contains nano colloidal ceria. And a coagulation controlling agent; preferably, the two portions are not in contact with each other during or prior to the delivery of the composition. In another preferred embodiment of the present invention, the non-calcined concrete composition of the present invention is packaged in two parts, a part of which comprises inorganic particles (including micron inorganic particles), an aluminum oxide compound and a coagulant, and another part comprises Nano colloidal cerium oxide and a coagulation controlling agent; preferably, the coagulant is not in contact with the nano colloidal cerium oxide during or before use of the composition. In one embodiment, the non-calcined concrete composition is packaged in two parts, one portion comprising all components in solid form and the other portion comprising components in liquid form (eg, solution, suspension, sol); Preferably, the two parts are not in contact with each other during or prior to the delivery of the composition.

Method for preparing non-calcined concrete

The non-calcined cement composition and the non-calcined concrete composition of the present invention do not need to be calcined in multiple arrays, and only a few components are subjected to low temperature calcination (for example, selective addition of a coagulant, an example is magnesium oxide). ).

Concrete generally contains components such as cementitious materials (cement), water, and aggregates. The aggregate may be any engineeringly applicable material, examples being materials derived from various natural ores or rocks, quartz sand, terrestrial sand, sand, river sand, sea sand, reservoir sludge, or any combination of the foregoing, and It contains unavoidable impurities and the like. In one embodiment, the inorganic particles comprise quartz sand, crushed stone, or both, and may be mixed in any ratio when both are included.

Therefore, the non-calcined cement composition of the present invention can be made into a non-calcined concrete as a cementitious material. For example, the non-calcined cement composition of the present invention may be mixed with a component such as an aggregate to prepare a concrete; for example, the aggregate is mixed with the micron inorganic particles, and then mixed with the aluminum oxide compound, and then added to the nanometer. The non-calcined concrete can be obtained by mixing the colloidal cerium oxide and the coagulation controlling agent; or, the components other than the colloidal cerium oxide and the coagulation controlling agent can be mixed firstly, and then added simultaneously or simultaneously. Nano colloidal cerium oxide and a coagulation controlling agent are mixed to prepare a non-calcined concrete.

A specific aspect of preparing a non-calcined concrete from a non-calcined cement composition comprising a further added optional component (for example, one or more of a coagulant, an active ceria, a water reducing agent, etc.) After the aggregate is mixed with the micron inorganic particles, it is uniformly mixed with the coagulant and the aluminum oxide compound, and then the nano colloidal ceria is added with the coagulation controlling agent to obtain a non-calcined concrete. Another specific aspect is that the aggregate is mixed with the micron inorganic particles, and then uniformly mixed with the aluminum oxide compound, and then the nano colloidal ceria, the coagulation controlling agent and the active ceria are added for mixing, thereby obtaining non-forging. Burning concrete. Another specific aspect is that the aggregate is mixed with the micron inorganic particles, and then uniformly mixed with the aluminum oxide compound and the coagulant, followed by adding the nano colloidal cerium oxide, the coagulation controlling agent and the active cerium oxide for mixing, that is, Non-calcined concrete is available. Another specific aspect is that the aggregate is mixed with the micron inorganic particles, and then mixed with the water reducing agent and the aluminum oxide compound, and then the nano colloidal cerium oxide and the coagulation controlling agent are added for mixing, thereby obtaining non-calcining. Concrete. Alternatively, in the above aspect, the components other than the nano colloidal cerium oxide, the coagulation controlling agent and the active cerium oxide (if included) may be first mixed uniformly, and then the nano colloidal cerium oxide is added. The coagulation controlling agent is mixed with the active ceria (if included) to prepare a non-calcined concrete. Alternatively, in the foregoing aspect, the components in a solid form may be first mixed, and then the components in the form of a liquid (for example, a solution, a suspension, a sol) may be added to prepare a non-calcined concrete.

In addition, the concrete can be prepared from the non-calcined concrete composition provided by the invention; the inorganic particles can be uniformly mixed, and then other components can be added to obtain non-calcined concrete. For example, the inorganic particles and the micro-inorganic particles are first mixed in the above ratio, and then uniformly mixed with the aluminum-oxygen compound, and then mixed with nano-colloidal ceria and a coagulation controlling agent to obtain a non-calcined concrete. A specific example of preparing a concrete from a non-calcined concrete composition comprising a further added optional component (for example, a coagulant, an active ceria, a water reducing agent, etc.), the inorganic particles and the micron After the inorganic particles are mixed in the above ratio, they are uniformly mixed with the aluminum oxide compound and the coagulant, and then added with nano colloidal ceria and a coagulation controlling agent to obtain a non-calcined concrete. In another specific example, the inorganic particles and the micro-inorganic particles are first mixed in the foregoing ratio, and then uniformly mixed with the aluminum-oxygen compound, followed by adding nano-gel colloidal cerium oxide, a coagulation controlling agent and active cerium oxide for mixing. Non-calcined concrete is available. In another specific example, the inorganic particles and the micro-inorganic particles are first mixed in the foregoing ratio, and then mixed with the aluminum oxide compound and the coagulant, followed by the addition of nano colloidal ceria, a coagulation controlling agent, and active dioxide. Non-calcined concrete can be obtained by mixing. In another specific aspect, the inorganic particles and the micro-inorganic particles are first mixed in the foregoing ratio, and then uniformly mixed with the water reducing agent and the aluminum-oxygen compound, and then the nano-colloidal ceria is added with the coagulation controlling agent for mixing, that is, Non-calcined concrete can be obtained. In the above specific aspect, the components other than the colloidal cerium oxide, the coagulation controlling agent and the active cerium oxide (if included) can be mixed first and then added. The rice colloidal cerium oxide, the coagulation controlling agent is mixed with the active cerium oxide (if included) to prepare a non-calcined concrete. Alternatively, in the foregoing aspect, the components in a solid form may be first mixed, and then the components in the form of a liquid (for example, a solution, a suspension, a sol) may be added to prepare a non-calcined concrete.

The aggregate used for preparing concrete may include land sand, sand, river sand, sea sand, reservoir sludge, and the like. In one embodiment, the inorganic particles of the present invention may also be considered as aggregates. In a preferred embodiment, the aggregate is used after desalting (including removal of cations and/or anions).

The non-calcined concrete made from the non-calcined cement composition or the non-calcined concrete composition of the present invention has physical or engineering properties comparable to or better than those of conventional concrete made of conventional Portland cement. For example, in one embodiment, the non-calcined concrete made from the non-calcined cement composition or the non-calcined concrete composition of the present invention is determined by the CNS 1010 (ASTM C109) standard or the CNS 1232 (ASTM C39) standard. The stress-strain test exhibits an engineeringly acceptable compressive strength, such as 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, 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 is exhibited. In one embodiment, the non-calcined concrete made from the non-calcined cement composition or the non-calcined concrete composition of the present invention exhibits engineering feasibility in the bending test test determined by the CNS 1238 (ASTM C348) standard. Acceptable flexural strength, such as a 28-day flexural 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 non-calcined concrete produced from the non-calcined cement composition or the non-calcined concrete composition of the present invention exhibits engineering acceptance in a split test as measured by the CNS 3801 (ASTM C496) standard. The splitting strength, for example 28 days at least 200 psi, preferably at least 300 psi, preferably at least 450 psi, more preferably at least 600 psi Splitting strength. In one embodiment, the non-calcined concrete made from the non-calcined cement composition or the non-calcined concrete composition of the present invention exhibits engineering feasibility in a linear shrinkage test according to the CNS 14603 (ASTM C157) standard. The linear shrinkage amount accepted is, for example, a linear shrinkage amount of at most 1,500 μ, preferably at most 1,200 μ, more preferably at most 600 μ, still more preferably at most 400 μ, and still more preferably at most 200 μ.

In a specific example, the non-calcined concrete made of the non-calcined cement composition or the non-calcined concrete composition of the present invention exhibits a concrete column compression test result according to the CNS 1232 (ASTM C39) standard. An acceptable compressive strength, such as a compressive strength of at least 4,500 psi, preferably at least 5,000 psi, more preferably at least 6000 psi.

The following examples are provided to enable those of ordinary skill in the art to understand the present invention, but are not intended to limit the scope of the invention.

Example

Example 1

Non-calcined cement compositions were prepared according to the components listed in Table 1 below:

Nano colloidal cerium oxide is prepared from 18 nm and 80 nm (solids content 40% by weight) at a ratio of about 8:2, unless otherwise specified.

Non-calcined cement compositions were also prepared according to the components listed in Table 1A below:

The compressive strengths shown in Examples 2 to 9 below are measured by the standards specified by CNS 1010 (ASTM C109), except for the period in which the strength is determined.

Example 2

The preparation of the non-calcined concrete composition was carried out using the components listed in the table below. First, the inorganic particles (aggregate) and the micro-inorganic particles (SiO ₂ ) are mixed according to the weight percentages listed in Table 2, and then uniformly mixed with the aluminum-oxygen compound, followed by the addition of nano-gel colloidal cerium oxide and a coagulation controlling agent. After mixing, the compressive strength was measured after 28 days of curing.

The nano colloidal cerium oxide used was prepared at a ratio of about 8:2 (solid content of 40%) at 18 nm:80 nm.

Example 3

The preparation of the non-calcined concrete composition was carried out using the components listed in the table below. First, the inorganic particles (aggregate) and the micron inorganic particles (SiO ₂ ) are mixed according to the weight percentages listed in Table 3, and then uniformly mixed with the coagulant and the aluminum oxide compound, followed by adding the nano colloidal ceria and The coagulation controlling agent was mixed, and the compressive strength was measured after 14 or 28 days of curing.

The nano colloidal cerium oxide used was prepared at a ratio of about 8:2 (solid content of 40%) at 18 nm:80 nm.

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

Example 4

The preparation of the non-calcined concrete composition was carried out using the components listed in the table below. First, the micron inorganic particles (SiO ₂ ) are mixed according to the particle diameters listed in Table 4 to form a graded powder, and the inorganic particles (aggregate) are mixed with the graded powder, and then with the accelerator and aluminum. The oxygen compound was uniformly mixed, and then nano-gelled cerium oxide and a coagulation controlling agent were added for mixing, and the compressive strength was measured after 28 days of curing.

In addition to the numbers 28 to 30, the nano colloidal cerium oxide used was prepared at a ratio of about 8:2 (solid content of 40%) at 18 nm:80 nm.

Example 5

The preparation of the non-calcined concrete composition was carried out using the components listed in the table below. First, the micron inorganic particles (SiO ₂ ) are mixed according to the particle diameters listed in Table 5 to form a graded powder, and the inorganic particles (aggregate) are mixed with the graded powder, and then with the coagulant and aluminum. The oxygen compound was uniformly mixed, followed by the addition of nano colloidal cerium oxide and a coagulation controlling agent for mixing, and the compressive strength was measured after 7 or 28 days of curing.

The nano colloidal cerium oxide used was prepared at a ratio of about 8:2 (solid content of 40%) at 18 nm:80 nm.

*No. 20 and 23 to 25 are the strength of 2 days at 180 °C.

**The strength of No. 26 is 7 days strength.

Example 6

The preparation of the non-calcined concrete composition was carried out using the components listed in the table below. First, the micron inorganic particles (SiO ₂ ) are mixed according to the particle diameters listed in Table 6 to form a graded powder, and then the inorganic particles (aggregate) are mixed with the graded powder, and then with the accelerator and aluminum. The oxygen compound was uniformly mixed, followed by addition of nano colloidal cerium oxide and a coagulation controlling agent (citric acid), and the compressive strength was measured after 10 or 28 days of curing.

The nano colloidal cerium oxide is prepared from 18 nm and 80 nm (solid content 40% by weight) at a ratio of about 8:2.

* No. 414 and 415 are 10 day strength

Example 7

The preparation of the non-calcined concrete composition was carried out using the components listed in the table below. First, the river sand is ground and classified into micron inorganic particles. According to the particle size and weight percentage listed in Table 7, the inorganic powder (aggregate) is mixed with the graded powder, and then promoted. The coagulant and the aluminum oxide compound (high aluminum cement) were uniformly mixed, and then the nano colloidal ceria and the coagulation controlling agent (citric acid) were added for mixing, and the compressive strength was measured after 28 days of curing.

The nano colloidal cerium oxide used was prepared at a ratio of about 8:2 (solid content of 40%) at 18 nm:80 nm.

From the test results, it is understood that the use of sand which is easily available can also be applied to the present invention.

Example 8

52.8 wt% quartz sand, 8.0 wt% 1.6 μm SiO ₂ , 11.8 wt% 10 μm SiO ₂ , 6.2 wt% 45 μm SiO ₂ , 5.9 wt% high alumina cement, 1.8 wt% magnesium oxide, 1.3 wt. The preparation of a non-calcined concrete composition was carried out by using 5% citric acid and nanometer colloidal cerium oxide of different particle size combinations listed in Table 8. First, after mixing the micron inorganic particles (SiO ₂ ) to form a graded powder, the inorganic particles (aggregate) are mixed with the graded powder, and then with a coagulant (magnesia) and an aluminum oxide compound (aluminum cement). Mix well, then add nano-gelatinous cerium oxide (single component or combination), coagulation control agent (citric acid) for mixing, and measure compressive strength after 28 days of curing:

Example 9

The preparation of the concrete composition was carried out using the components listed in the table below. First, the aggregate and the micron inorganic particles (SiO ₂ ) are mixed according to the weight percentages listed in Table 9, and then uniformly mixed with the coagulant, followed by the addition of nano colloidal ceria and a coagulation controlling agent (citric acid). After mixing, the compressive strength was measured after 28 days of curing.

Example 10

The preparation of the concrete composition was carried out using the components listed in Table 10 below.

The composition condenses into a block in a very short time, which is not conducive to application.

Example 11

The concrete was prepared using the non-calcined cement composition of Table 11 below and the coarse aggregate:

After mixing the components, a plurality of concrete samples were prepared by injecting into the mold body, and after 28 days of standing, the compressive strength was measured by a concrete cylindrical compression test CNS1232 (ASTM C39), and the obtained compressive strength was as shown in Table 12 below. :

Example 12

The flexural strength was measured using a concrete cylindrical bending test CNS1238 (ASTM C348) using the concrete specimen prepared as in Example 11, and the obtained compressive strength is shown in Table 13 below:

Example 13

The splitting strength was measured using a concrete cylindrical splitting test CNS3801 (ASTM C496) using the concrete specimen prepared as in Example 11, and the obtained splitting strength is shown in Table 14 below:

It can be seen from Examples 11 to 13 that the concrete prepared from the non-calcined cement composition or the non-calcined concrete composition of the present invention can exhibit good physical and engineering properties.

Example 14

The concrete specimen (S01) obtained in Example 11 and the concrete specimen (R01) obtained from the commercially available Portland cement and aggregate were used to measure the linear shrinkage amount by the CNS 14603 (ASTM C157) standard. The linear shrinkage (μ) is shown in Table 15 below:

From the test results, it is understood that the concrete prepared from the non-calcined cement composition or the non-calcined concrete composition of the present invention is far superior to the one exhibited by the conventional Portland cement.

Claims (14)

A composition comprising: (a) from 31% to 76% by weight of the total composition of micron inorganic particles having a particle size of from 1.0 to 100 μm, wherein the micron inorganic particles are inorganic particles containing cerium; (b) from 1.9% to 21% by weight based on the total weight of the composition; (c) from 17.0% to 36.0% by weight of the total composition of colloidal silica, and d) a coagulation controlling agent of from 0.2 to 6.5% by weight based on the total weight of the composition. The composition of claim 1, wherein the micron inorganic particles have a particle size distribution of at least a bimodal distribution. The composition of claim 1, wherein the particle size distribution of the micron inorganic particles is a trimodal distribution, wherein the particles having the peak particle diameter may independently of each other at least 20% to 50% of the total weight of the micron inorganic particles, respectively. The composition of claim 1, wherein the particle size distribution of the nano colloidal ceria is a bimodal distribution, wherein the particles having the peak particle diameter can independently occupy at least the total of the nano colloidal ceria, respectively. 30% to 70% by weight. The composition of claim 1, further comprising a coagulant, an active ceria, and a water reducer At least one of them. A composition comprising: (a) from 66% to 90% by weight of the total weight of the inorganic particles; (b) from 1.1% to 12% by weight based on the total weight of the composition; (c) The total weight of the composition is 8.5% to 17.0% of colloidal silica, and (d) is from 0.15 to 3.5% of the total weight of the composition of the coagulation controlling agent, wherein the inorganic particles comprise The micron inorganic particles having a particle size of 1.0 to 100 μm, wherein the micron inorganic particles contain inorganic particles of cerium and account for 25% to 45% of the total weight of the inorganic particles. The composition of claim 6, wherein the micron inorganic particles have a particle size distribution of at least a bimodal distribution. The composition of claim 6, wherein the particle size distribution of the micron inorganic particles is a trimodal distribution, wherein the particles having the peak particle diameter may independently of each other at least 20% to 50% of the total weight of the micron inorganic particles, respectively. The composition of claim 6, wherein the particle size distribution of the nano colloidal ceria is a bimodal distribution, wherein the particles having the peak particle diameter can independently occupy at least the total of the nano colloidal ceria, respectively. 30% to 70% by weight. The composition of claim 6, further comprising at least one of a coagulant, an active ceria, and a water reducing agent. A composition comprising: (a) from 30% to 80% by weight of the total composition of micron inorganic particles having a particle size of from 1.0 to 100 μm, wherein the micron inorganic particles are inorganic particles containing cerium; (b) from 1.8% to 20.0% by weight based on the total weight of the composition; (c) from 15.0% to 35.0% by weight of the total composition of colloidal silica; a coagulant controlling agent in an amount of from 0.18% to 6.0% by weight based on the total weight of the composition; and (i) from 2.2% to 6.5% by weight based on the total weight of the composition, comprising an alkali metal or alkaline earth oxide , hydroxide, sulfate or carbonate. A composition comprising: (a) from 65% to 90% by weight of the total weight of the inorganic particles; (b) from 1.0% to 10.0% by weight based on the total weight of the composition; (c) The total weight of the composition is from 7.5% to 15.0% of colloidal silica; (d) from 0.1% to 3.0% by weight of the total composition of the coagulation controlling agent; and (i) in combination a total amount of 1.0% to 3.0% of a coagulant comprising an alkali metal or alkaline earth oxide, hydroxide, sulfate or carbonate; wherein the inorganic particles comprise particles having a range of from 1.0 to 100 μm Diameter-sized micron inorganic particles The micron inorganic particles contain inorganic particles of cerium and account for 25% to 45% by weight of the total of the inorganic particles. A concrete comprising the composition of any one of claims 1 to 12. The concrete of claim 13 comprising at least one of the following properties: 28 days compressive strength of at least 1,800 psi under CNS 1010 (ASTM C109) standard or CNS 1232 (ASTM C39) standard test, at CNS 1238 (ASTM) C348) has a 28-day flexural strength of at least 200 psi under standard test, 28-day splitting strength of at least 200 psi under CNS 3801 (ASTM C496) standard test, and up to 1500 μ under CNS 14603 (ASTM C157) standard measurement 28 Daily linear shrinkage.