KR20150134592A - An inorganic ceramic foam composition which can be cured at normal temperature and method of preparing the same. - Google Patents

Abstract

The present invention relates to an inorganic room-temperature-curing foam ceramic composition, and a production method thereof. The production method of the present invention includes the following steps: (1) weighing an inorganic bonding material composition comprising: 5-20 wt% of an inorganic filler, 5-20 wt% of a lightweight aggregate, 10-20 wt% of activated carbon, 40-80 wt% of an inorganic magnesium phosphate bonding material, and 0.5-10 wt% of a carbonate; (2) inserting, into a mixer, the lightweight aggregate, the activated carbon, the inorganic filler, and inorganic magnesium phosphate bonding material in sequence; (3) mixing the powder inserted in the mixer; (4) processing into slurry after adding 30-50 parts by weight of water with respect to 100 parts by weight of a uniformly mixed composition and then mixing the same thereafter; (5) inserting 0.5-11 parts by weight of the carbonate with respect to 100 parts by weight of the produced slurry; (6) injecting and generating bubbles in water while stirring the slurry mixed with the carbonate; (7) filling the material into a molding frame; (8) applying vibration onto the filled raw material for one to two seconds; (9) hardening the molded article filled in the molding frame; (10) removing the hardened and molded foam ceramic article from the molding frame; and (11) finishing the inorganic room-temperature-curing foam ceramic by curing the removed molded article.

Description

TECHNICAL FIELD [0001] The present invention relates to a foamed ceramic composition and a method for producing the foamed ceramic composition, and more particularly to an inorganic ceramic foam composition which can be cured at normal temperature and method of preparing the same.

The present invention relates to an inorganic room-temperature curing type foamed ceramic composition using magnesium phosphate cement as a basic composition and a method for producing the same. More specifically, the present invention relates to a cemented, The present invention relates to an environmentally friendly inorganic room temperature curing type foamed ceramic composition which does not use a cement and does not use mixed cement. And the pores are formed by the carbon dioxide generated as a byproduct of the ion reaction and the binder is cured during the process of forming the pores so that the molded product is completed in an early stage. At room temperature Type foam ceramic composition and to a method of manufacturing the same.

 Foam ceramics are used in various fields such as lightweight materials, carriers, filters, and vegetation materials, and manufacturing methods are also being implemented through various methods. Generally, a known method of producing a foamed molded product is a method of producing a lightweight foamed concrete, wherein a composition containing a metal component is subjected to an alkaline atmosphere under high temperature and high pressure in an autoclave to generate hydrogen gas by reacting with an alkaline substance, And forming a cured body by a hydration reaction of the cement, thereby producing a rigid foamed ceramic.

 Another method is to form carbon dioxide gas or other gas by forcing the product in a curing and drying step after molding, and another method is to add a surfactant as a foaming agent. This method promotes the slimming of the particles at the time of mixing, forms bubbles in the molding by forming bubbles, and forms a hard molded body by a curing process or drying.

The present invention relates to a green loess composition for environmentally friendly building materials and a loess block using the green loess composition, which comprises 15-40 parts by weight of magnesia powder, 8-25 parts by weight of ammonium phosphate, 20-20 parts by weight of loess 20 -50 parts by weight of an alkali silicate compound, 3 to 10 parts by weight of an alkali silicate compound and 15 to 30 parts by weight of a solvent, wherein the lightweight foamed material is prepared by a method of producing a lightweight foamed concrete, cm < ^{3 &} gt ;.

 Since this patent can be manufactured by the method of manufacturing the lightweight foamed concrete as described above, there is a problem that a large capacity device is required, and the lightweight foamed material has a specific weight of 0.051. That is, in the case of magnesia phosphate cement, the density is at least 1.5 to 3.3, and the lightweight bubble is about 0.051, so that the difference in density is as high as about 30 to 65 times. Therefore, it is very difficult to uniformly mix these materials. Even if it is mixed evenly, since it is very likely that material separation of raw materials will occur due to difference in density of powder by water when water is added, a thickener is required. However, such description is not described in the specification, The concentration gradient of the material may cause a problem of lowering the value as a product.

 Patent Document 10-2013-0027869 relates to a method for manufacturing an inorganic porous insulation material composition, and a method of manufacturing a high temperature fire-resistant insulation material having excellent heat insulation performance and a flame-resistant high temperature fireproofing material composition by simultaneously forming pores by foaming and hardening of a porous inorganic filler . 5-35 parts by weight of a high alkaline silicate (pH > 12), 10-78 parts by weight of a porous inorganic filler and 15-55 parts by weight of a magnesium phosphate based inorganic binder are cured by gelation through neutralization and drying How to make it. This method is a porous composition dependent on a porous material as in the prior patent document, which is prepared by preparing a porous silica powder at a drying temperature of 80 ° C and curing using a porous inorganic filler and a magnesium phosphate based inorganic binder. Uniformity is the most important in curing, etc., and there is a problem that it is difficult to realize the performance of the product unless the various factors that may arise from the difference in density presented are overcome.

 Japanese Patent Laid-Open Publication No. 10-2013-0040083 relates to a method for producing an inorganic foam molded article at room temperature using magnesium oxide and a curing agent thereof. Magnesium oxide is slurried by using water and magnesium sulfate, magnesium chloride and ammonium monophosphate are diluted with water as a hardening agent, and an organic surfactant such as an amino acid type or an alkylsulfonic acid salt type is dispersed in water as a foaming agent, And then the three materials are mixed, molded and dried, and the product is completed. However, in order to generate bubbles in a product, it is difficult to put a large amount of the product on the spot because it depends on the shape and stirring speed of the stirrer, and there is also a problem that a drying process is required to remove moisture.

 The present invention has similar characteristics in terms of using a magnesium phosphate system as a binder. On the other hand, the mechanism for forming bubbles is completely different because the bubbles, the lightweight foam material and the surfactant described above are not used at all. Also, while the present invention does not involve a drying step, all of the three inventions have a difference in that a drying step is required to remove moisture.

 Porous products such as epoxy, urethane and melanin, which are organic binders, have a fatal danger such as generating volatile organic compounds in case of fire. However, the present invention does not use such organic materials at all, There is no concern.

The magnesium phosphate inorganic binder composition according to the present invention is similar to many magnesium phosphate cement compositions such as US 5,830,815, US 7,312,171 B2, and US 6,136,088, but the shape of the phosphate and the retarder are distinctive. It can be said that the foaming mechanism differs greatly from the use of boric acid and K ₂ CO ₃ as MgO-NH ₄ H ₂ PO ₄ composition as an acting substance of the foaming mechanism, apart from that used as a retarder.

 In this patent, magnesium phosphate cement was prepared as a remaining material by sufficiently reacting carbonates with phosphate to remove carbon dioxide. However, in the present invention, the composition and manufacturing method , The most significant difference is that the inorganic binder itself is used as a substrate and pores are formed, and the remaining components are designed to participate in the formation of struvite acting as a binder.

Patent Publication No. KR2012 -0123743 relates to cellular phosphate ceramic and manufacturing method thereof, and first mixing the binder, filler, and boric acid delays agent comprising a phosphate compound and a metal oxide, and second mixing by adding water, A foam for capturing an air bubble of the product is added, mixed, and cured at room temperature. Japanese Patent JP2, 516,530 discloses a porous body, and relates to a method of manufacturing the same phosphoric acid, a multivalent metal oxide, a resin emulsion, a process for producing a porous article comprising the step of curing the foam by mixing water with light blowing agent or foaming agent, and Thus on the produced porous material It can be manufactured by molding and curing at room temperature, and it can be used as a heat insulating material, a fireproof building material, a soundproofing material, JP2001 -0278677 discloses a thermal insulation properties, mechanical properties and water resistance that relates to a process for the preparation of inorganic foamed molded article having a good and uniform pores, an aqueous solution of phosphoric acid or aqueous dispersion, Periodic Table of the second group, the same group 13, the copper 14 and transition metals, and a metal carbonate at about -15 to + 10 占 폚, followed by heating and drying at about 90 占 폚. Also US 5,256,222 discloses the step, the core 12 comprises a mixture for producing a mixture comprising inorganic particles, inorganic binder, water (10-60%), a binder setting the two facing board (14, 16) And heating at a temperature of about 65 to 200 DEG C, and it can be said that the difference between the four patent technologies and the present invention is largely different. The feature of the present invention is that it is possible to cure at room temperature and that the curing of the product proceeds in a very short time and the difference in functionality is clear.

 It is an object of the present invention to solve the environmental problems such as the problem of air pollution caused by the use of cement and to provide a structure of a foamed ceramic which is environmentally friendly and which has no adverse effect on the human body which can minimize contamination of water quality and river water Environmentally-friendly room temperature curing type foamed ceramic composition which can purify water and air from the environmentally friendly inorganic ceramics, and a process for producing the same.

 Another object of the present invention is to provide an improved application of magnesium phosphate composition which has been used in the past, and to provide a new concept of foamed ceramic, and to provide a novel ceramic foam which has a low adhesive strength and durability And the like, and a method for producing the same.

 Another object of the present invention is to provide a foamed ceramic which can be used in various fields such as architecture, civil engineering, construction site, vegetation mat, water purification material, and air purification filter by means of the inorganic room temperature curing type foamed ceramic composition.

 It is still another object of the present invention to provide an application technique in the field of the production of concrete secondary products which requires light weight through weight reduction using the above-mentioned composition.

 It is a further object of the present invention to provide an environmentally friendly and environmentally friendly water treatment system capable of transferring clean water to an underground ecosystem by adsorbing water such as P as a reaction product magnesium phosphate phosphoric acid and a green algae causing substance in a river and heavy metals such as Pb And to provide a finished product made therefrom.

It is a further object of the present invention to provide a method for the production of an insoluble compound having a low pH value by additionally used metal sulfates and an insoluble compound having a solubility several times to several tens of times that of Ca (OH) ₂ or CaSO ₄ It is an object of the present invention to minimize the adverse effects of inorganic ions in the surrounding environment by suppressing elution.

 The room temperature inorganic curing type foam ceramic composition of the present invention comprises 5 to 20% by weight of an inorganic filler, 5 to 20% by weight of a lightweight aggregate, 10 to 20% by weight of an activated carbon, an inorganic magnesium phosphate binder composition (100% 20 to 60% by weight of magnesium oxide composed of 70:30 to 85:15% by weight of reactive magnesia, 30 to 70% by weight of aluminum phosphate and 30 to 70% by weight of monopotassium phosphate and 27 to 67% by weight of ammonium monophosphate 35 to 75% by weight of a metal sulfate, 0.1 to 1.5% by weight of a metal sulfate, 0.5 to 10% by weight of a metal sulfate, 20 to 60% by weight of a phosphate constituted by 2-10% by weight of a boric acid- % By weight.

 Hereinafter, the present invention will be described in detail.

 Mineral fillers refer to earth, natural minerals, industrial byproducts, and any of these may be used. The role of the inorganic filler acts as a filler and a reactant necessary for the composition of the porous ceramic. Inorganic fillers are generally available in red clay (red mud), yellow clay (mud), and kaolin (kaolin), white clay, and marathon. Natural rocks such as wollastonite, diatomaceous earth, hempite, basalt, stones, and quartz can be pulverized and pulverized to obtain a particle size of 325 mesh or more. It is also possible to use activated clay which is activated by calcination of kaolin or clay at 800 ° C. This is to solve the problem of low reactivity of natural minerals, and the ion elution is fast in an acidic or alkaline atmosphere, and since the plasticity of the raw material is removed, slurries can be prepared very easily compared with natural clay.

 Fly ash, blast furnace slag, silica fume, and other incinerators generated from a thermal power plant as an industrial by-product. Fly ash or silica fume currently used as a cement admixture is suitable because it contains no heavy metals, Is not limited in size, but it is preferable to use purified and commercialized raw materials.

 The inorganic filler physically adsorbs water or harmful substances in the air in contact with the particles and particles in the binder composition, and exerts the same effect as far-infrared radiation in the air. The particle size range of the inorganic filler is suitably from 0.1 to 30 mu m. When the particle size is large, the expected effect as a filler can not be obtained. The amount of the inorganic filler used is preferably in the range of 5 to 20% by weight. When the amount of the inorganic filler is below the range, the filler effect is lowered, and the far-infrared radiation effect, organic matter adsorption, If the amount is over the range, the physical properties such as the compressive strength are decreased due to the decrease of the binding agents relatively, resulting in a problem that the durability is lowered. In addition, there is a problem that it acts as an excessive impurity in the process of foaming and becomes a cause of vesiculation which destroys pores.

 The lightweight aggregate used in the present invention is not particularly limited, but includes pearlite, vermiculite, foamed glass, slate, fly ash residue, lightweight ash, bottom ash, and volcanic ash. It is good to do. The particle size of the lightweight aggregate may be in the range of 0.5 to 10 mm or less, preferably in the range of 1 to 5 mm. The lightweight aggregate is preferably used in a range of 5 to 20% by weight. When the amount is less than 5% by weight, the strength is excellent, but the amount is insufficient for crosslinking to increase the volume at the time of foaming. If the amount is more than 20% by weight, There is a problem that the product can not be commercialized due to deterioration of the physical properties required for the production. Exceeding or not exceeding the range can not achieve the desired properties of the binder. In the use of the lightweight aggregate, it is preferable to use a material having porosity in the lightweight aggregate itself. Porous products themselves are capable of controlling adsorption and physically adsorbing and lightening hazardous volatiles.

 The activated carbon used in the present invention is not particularly limited. In general, as activated carbon produced for purification of water and purification for air purification, products of 1 mm or less, 1 to 3 mm, or 3 to 8 mm can be used, and particles of 3 to 8 mm are preferably used. This is because the coarse particles are more likely to float than the remaining particles, and the bubbles due to the weight difference during foaming are reduced, and when the surface is processed due to the large particle size, a definite pattern can be given. In the fields used for water purification and atmospheric purification, it is possible to exhibit a more excellent purification effect by using smaller particles. The use range of the activated carbon is from 10 to 20% by weight, and when it is outside this range, desired physical properties and purifying function can not be obtained.

 The inorganic magnesium phosphate binder composition used in the present invention is not particularly limited. In general, it is a magnesium phosphate cement composition. Preferably, the inorganic magnesium phosphate binder material invented by the present inventors is used. 20 to 60% by weight of magnesium oxide consisting of 70:30 to 85:15% by weight of light magne- sis oxide and reactive magnesia in 100% by weight of the total binder component, 3% by weight of aluminum phosphate and 30-70% by weight of potassium monophosphate 20 to 60% by weight of phosphate consisting of 27 to 67% by weight of ammonium phosphate monobasic, 2 to 10% by weight of a reaction retarding agent mixed with boric acid and magnesium sulfate, and 0.5 to 2% by weight of pigment, 35-75% by weight.

 The magnesia oxide is produced by calcining a rock mined from a magnesium mine in a temperature range of 800-1,000 ° C., a light magnesia having a purity in the range of 88 to 90%, a medium and small magnesia crystallized in a temperature range of 1,450-2,300 ° C., (97% or more) magnesium oxide reactive magnesium oxide obtained by heat treatment of magnesium hydroxide extracted from seawater, magnesium hydroxide, magnesium oxide generated after completion of the lifetime of the refractory, and the like, One or more of these may be used in combination.

 Foam ceramics should be prevented from fraying after foaming begins. That is, when the molding frame is narrowed when it is foamed by the foam mechanism, the foam (a phenomenon in which the foam is blown off at the time of foaming) is suppressed by the molded article which maintains a constant pressure. In this case, if only the light magnesia is used, an excellent product at low cost can be produced. On the other hand, when the product to be manufactured is in the form of a tile, a board, or a panel, since the exposed surface area is wide, the portion near the forming mold at the time of foaming is likely to form bubbles based on the wall surface, There is a problem that a high viscosity should be maintained or a support base must be installed at the center in order that the bubbles generated due to the bubbles are formed as they are.

 When the viscosity is high, the fluidity remarkably lowers. Therefore, it is also difficult to form the bubbles generated at the time of foaming in a uniform and well-formed state, because it requires much more energy than when the viscosity is low. When a plate material or the like having a large area is produced, a defoaming phenomenon is generally generated. When bubbles are formed by foaming and the curing time is controlled, the defoaming phenomenon can be suppressed. The time of foaming by the carbonate is in the range of about 1 to 5 minutes, and if the curing reaction proceeds after 5 minutes, the defoaming phenomenon can be suppressed.

 However, the hardening magnesia and retarding composition require a curing time of 25 minutes or more, and measures for suppressing the fraying phenomenon are required when a large-sized plate is manufactured. The reactive magnesia is a substance having a very rapid curing reaction, and has the same components as the light magnesia, has a high degree of powderiness and excellent reactivity, and exhibits physical properties higher than that of light magnesia. It is preferable to mix 15 to 30% by weight of reactive magnesia (purity: 97% or more) in light magnesite oxide magnesia in a process in which a large amount of foaming is required such as a plate material. The light magnesia oxide is economically inexpensive, has low purity and low reactivity, and the reactive magnesia extracted from seawater is very fine in particle size (> 10 μm). Its purity is high and its reactivity is excellent. have. It is preferable that the purity of light magnesia magnesia has a purity of about 90% in terms of workability and economy. If less than 15% is used, desired early strength can not be secured. If it is used in excess of 30%, price competitiveness becomes worse, resulting in poor business efficiency. In addition, have. However, the use of such light magnesia and reactive magnesia oxide is not particularly limited. It should be used according to the purpose of production of the product.

Magnesium oxide reacts with added phosphate to form a complex of magnesium + alkaline earth metal + phosphoric acid. The principle of the bonding reaction depends on the ionic reaction, and more specifically, the principle of solidification of the magnesium-based cement. When potassium monophosphate is used, the added materials react with water to form MgKPO ₄ · 6H ₂ O, and the surface of silica is stimulated by the OH- ions generated by the reaction with water to form irregularities on the surface , The open Si ions generate MSH (magnesium silicate hydrate) in combination with Mg ions and cure.

When the amount is less than the above range, the bonding force is lowered and the particles constituting the foamed ceramic can not be bonded strongly. If it exceeds this range, the phosphate is reduced to a relatively low level. There is a problem that the bonding force is lowered. In addition, when MgO is used excessively, the long-term strength is lowered by the dehydration reaction while continuing the reaction with water when exposed to water. In addition, there is a problem that the amount of Mg (OH) ₂ is increased by the hydration of magnesium ions and the pH value is increased.

Phosphates are phosphate compounds such as AlPO ₄ , LiH ₂ PO ₄ , Na ₂ H ₂ P ₂ O ₇ , (NaPO ₃ ) 5 ~ 9, NH ₄ H ₂ PO ₄ , KH ₂ PO ₄ , NaH ₂ PO ₄ And one or more materials may be mixed and used. It is more preferable to use 3 wt% of aluminum phosphate in powder form, 30 to 70 wt% of potassium hydrogen phosphate, and 27 to 67 wt% of ammonium hydrogen phosphate. Aluminum phosphates act to increase the solubility of MgO and phosphate itself by adjusting the pH of the phosphate to pH 1 ~ 2, and potassium hydrogen phosphate produces stburbite (MgKPO ₄ 6H ₂ O) And ammonium hydrogen phosphate forms a compound of NH ₄ MgPO ₄ nH ₂ O, which is another form of sturuobite, in addition to maintaining the pH value of the final product in the neutral region. In addition, inorganic phosphate such as magnesium oxide, hempite and silica is stimulated by the PO ₄ ^{3 -} ion of these phosphates, and they are ionized by Mg ^{2 +} , Al ^{3 +} , Si ^{4 +} etc., (Or potassium) phosphate complex, and magnesium ions and aluminum ions act to produce hydrotalcite (Mg ₄ Al ₂ (OH) ₁₂ CO _{3 3} H ₂ O). The resulting magnesium hydrogen phosphate, magnesium potassium phosphate, hydrotalcite, and the like are known to have a high adsorption efficiency of heavy metals, and the adsorption capacity of phosphorus is also excellent. According to the preliminary preliminary experiment, the ratio of potassium monophosphate to ammonium monophosphate was about 30 to 70 and 67 to 27, and when used, exhibited a higher compressive strength value as compared with when used singly. However, there is no problem with the use of ammonium monophosphate or potassium monophosphate and other usable phosphates alone, so it is not particularly limited to raw materials for use.

 An appropriate amount of phosphate is 20 to 60% by weight. When the amount is less than this range, the amount of reaction products such as magnesium hydrogen phosphate, magnesium potassium phosphate, and hydrotalcite decreases due to the reaction with magnesium oxide, If it exceeds this range, there is a problem that excessive use of phosphate may cause eutrophication, green tide, etc. due to inflow of unreacted phosphoric acid into the river or inflow of the lake. In recent years, the price of phosphate has been rising, and the prices of phosphate-based phosphate, which is currently acidic, are trading at over KRW 4,000 per kg. There is a problem that it becomes worse. More preferably, the phosphate is used in an excess amount over the magnesia. That is, 100 parts by weight of magnesium oxide is used in 100 parts by weight to 200 parts by weight of phosphate.

The reaction retarder to be used in the present invention is not particularly limited and may be selected from the group consisting of boric acid, borax, citric acid, sodium polyphosphate, Mg (OH) ₂ , carboxylic acid, polycarboxylic acid, Sodium hydroxide, potassium hydroxide, magnesium hydroxide, ammonium hydroxide, alkali metal carbonate, sodium chloride, potassium chloride, calcium chloride, sodium pyrophosphate, potassium nitrate, sodium nitrate, sodium sulfate, potassium sulfate, magnesium sulfate, magnesium nitrate, sodium carbonate and potassium carbonate It is possible. The amount of the retarder to be used is suitably from 2 to 10% by weight. If it is used in an amount of not more than 2% by weight, it is difficult to control the toughness caused by the use of the reactive magnesia oxide, so that the minimum time required for the production of the foam ceramic can not be secured for 5 minutes, Therefore, there is a problem that the desired density can not be obtained. On the other hand, when the amount exceeds 10% by weight, the initial workability can be secured, but the desired effect can not be obtained because the effect of suppressing the fogging phenomenon due to the early curing of the reactive magnesia is deteriorated. A preferred retarder is a combination of boric acid and magnesium sulfate (MgSO ₄ ). The ratio of boric acid and magnesium sulfate is characterized in that magnesium sulfate is fixed at 1% by weight and the remainder is charged with boric acid. If the amount of magnesium sulfate used is too high or the amount of boric acid used is too low, the retarding effect may interfere with the formation of bubbles in the product, so an appropriate amount is required.

The pigment to be used in the present invention is not particularly limited, but may be TiO ₂ , Fe ₂ O ₃ , Fe ₃ O ₄ , MnO ₂ And the amount is 0.1 to 2.0% by weight. When the amount is out of this range, it is difficult to express a desired color or it is economically problematic. The preferred amount used is 1.5% by weight.

It is preferable to use the inorganic magnesium phosphate binder composition in an amount of 35 to 75% by weight. The use of less than 35% by weight, it is difficult to maintain the form and physical properties expressed by the cured foam, when it exceeds 75% by weight, the physical properties are excellent economic efficiency drops to a price increase, with a 0.5g / cm ³ or less There is a problem that it is not easy to obtain the density.

 The metal salt used in the present invention is not particularly limited, but metal sulfates such as Cu, Ni, Fe, Al, Co and Mg including a sulfate group can be used. These metal sulfates can be used alone or in combination. In the present invention, the metal salt acts to lower the alkalinity by its own liquidity, and at the same time, forms an insoluble compound on the surface of the metal salt, so that the metal salt does not dissolve ions in the material.

In addition, it plays a role of enhancing the reactivity by promoting the dissolution of the magnesium-based composite by utilizing the strong acidic property of the metal salt. In addition, the metal components included in the metal salt are the hydroxide which is opened on the surface, the hydroxide precipitated by Mg, Ca, K, OH ^- is selectively consumed to change the pH value to a neutral region.

The working principle is as follows. The added FeSO ₄ is ionized by contact with water and converted to Fe ^{2 +}

(OH) ₂ (solubility 0.129%) and CaSO ₄ (solubility 0.208%) were reacted with OH ^- ions generated in the binder composition and re-precipitated as insoluble compounds such as Fe (OH) ₂ and FeOOH Since the solubility is 1 / 10,000 ~ 1 / 100,000,000 or less, the water resistant property can be maintained even if water comes into contact with the surface. Insoluble compounds such as iron hydroxide, aluminum hydroxide, nickel hydroxide, cobalt hydroxide and the like are well known as adsorbents which absorb not only very low solubility but also harmful heavy metals, so that they can be given a function of purifying through adsorption of harmful heavy metals in the water There are characteristics. In addition, since the pH of the metal salt is in the range of 1.0 to 4.0, the pH value of the binder composition is lowered. The amount of the metal salt to be used is preferably 0.1 to 1.5% by weight.

The carbonate to be used in the present invention is not particularly limited but may be selected from the group consisting of sodium carbonate, sodium hydrogencarbonate, sodium percarbonate, potassium carbonate, potassium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate, ammonium carbamate, urea, magnesium carbonate, , Carbonated water containing sodium carbonate such as fanta, cider, sprite, beer, etc. can be used. One or more of the carbonates may be used in a solid or liquid form. The amount of the carbonate to be used is suitably in the range of 0.5 to 10% by weight in the case of powders or granules, and in the case of the liquid phase, 5 to 30% by weight may be diluted in water. In the present invention, the use of a carbonate is very advantageous in forming bubbles in the composition, and K ions, Na ions and NH ₄ ions react with Mg and PO ₄ ions to form struvite.

 Generally, the principle of generating air bubbles is to generate air bubbles by forming bubbles mainly by forcibly injecting carbon dioxide, or by generating hydrogen gas by forming strong acid or strongly alkaline pellets in metal powder, It is common to add a surfactant (such as a surfactant) to artificially generate bubbles in the composition to produce a porous form. There is also a method in which a composition is mixed with a carbonate or an organic material, molded, and then heat-treated at a temperature sufficient to cause carbon dioxide gas or at a temperature at which organic matter can be carbonized.

 Until now, the carbonate used in the magnesium phosphate cement system has no potassium carbonate, and the role of potassium carbonate is used as a retarder. Potassium carbonate has a buffering effect that effectively lowers the heat of reaction by increasing the pH of the composition, and potassium ions are designed to participate in the formation of sturubutite. It has been found that the composition produced by such action mechanisms is a ceramic product with a very tight and dense density.

 On the other hand, the foaming principle using the carbonate to be provided in the present invention is characterized in that no foam is generated in a composition mainly composed of cement produced by a combination of clinker minerals, a geopolymer composition, magnesium oxychloride cement, It acts to generate carbon dioxide at room temperature in a composition containing magnesium and phosphate.

However, in the present invention, carbonic acid ions are separated at room temperature, not the principle applied in this conventional method. The carbonic acid gas generated at this time functions as a foaming mechanism, and residual Na, K, and NH ₄ ions except carbon dioxide are converted into MgM = Na, K, NH ₄ ) PO ₄ to form struvite, which acts to compensate the strength of the foamed ceramic.

The present invention can reduce air pollution by suppressing the emission of CO ₂ gas generated in the production of cement due to the absence of cement, and it is possible to reduce the amount of Cr ^{6 +} Struvite, hydrotalcite, and the like, which are known to be capable of adsorbing harmful substances such as P, Pb and the like in the water quality without causing environmental pollution, It is possible to filter the pollution source, so that the effect of protecting the water environment can be obtained.

In addition, by solving the problem of ion leaching of metal salts that can occur from existing products, it is possible to prevent the pollution of the river in advance, and it is possible to suppress the problem of decrease in water resistance due to ion leaching, so that the quality of the product can be maintained for a long time It is possible to reduce the maintenance cost. Further, it is possible to provide an eco-friendly architectural finishing material in which natural marble texture is artificially added by fillers, pigments, and functional powders added such as black and white of pearlite and activated carbon, red of loess, and white of titanium dioxide.

1 is a photograph showing a manufacturing process and a product according to an embodiment of the present invention,
FIG. 2 is a perspective view of a foamed ceramic panel (width 500 mm × length 500 mm × height 10 mm) manufactured in various colors according to the embodiment,
FIG. 3 is a photograph of various types of foamed ceramics according to an embodiment,
4 is a photograph showing the water permeability of the foamed ceramic produced by the example.

(Examples 1 to 31) and (Comparative Examples 1 to 8)

An inorganic room temperature curing type foamed ceramic composition was prepared by the following method.

 1) weighing the composition as listed in Tables 1 to 5 in a respective container using a balance;

 2) Each of the weighed powdery raw materials is charged into a kitchen mixer in the order of lightweight aggregate → activated carbon → mineral filler → inorganic magnesium phosphate binder (the composition of the inorganic magnesium phosphate binder is 80 wt% of light oxidized magnesia and 20 wt% of reactive oxidized magnesia % By weight of magnesium phosphate consisting of 3% by weight of aluminum phosphate, 55% by weight of potassium monophosphate and 42% by weight of ammonium monophosphate, 4.5% by weight of a mixture of boric acid and magnesium sulfate mixed retardant, 1.5% by weight of titanium oxide pigment was used);

 3) mixing the powder phase slowly and uniformly for 5 minutes at the kitchen mixer level 1 (about 30 rpm), raising the level to 3 (about 60 rpm) and quickly mixing for 1 to 2 minutes;

 4) adding the water set in the homogeneously mixed powdery composition at a time and rapidly mixing at the same level of speed for 30 seconds to prepare a slurry;

 5) introducing carbonate into the prepared slurry;

6) Bubbles are injected into the water while raising the mixed slurry to the level 5 (120 rpm) and stirring rapidly. When the carbonate reacts with MgO and PO ₄ ions, the initial form is lost and M ⁺ or M ⁺⁺ (M = Na , K, NH _4, as the step of separation in the form of M ⁺⁺ = Ca, Mg, Ba, etc.), and CO ₂ generating a bubble by the CO ₂ gas;

 7) Stop stirring within 30 seconds so that the bubbles generated are not bubbled, and immediately fill the bubbles in the mold (bubbles may occur when physical impact is applied at the stage of bubbling);

8) Vibration is applied for 1 to 2 seconds so that the charged raw material can penetrate well in the molding die. (In this step, the unreacted carbonate introduced into the slurry exhibits a fouling phenomenon by applying vibration to the slurry. And bubbling is promoted by contact with MgO and PO ₄ ions);

 9) The step of curing the molding filled in the molding mold within 5 ~ 20 minutes (the curing time can be adjusted by changing the addition amount of retarding agent depending on the area and size of the product to be molded);

 10) Cured Foam Ceramic Molded Body is demolded after lapse of 30 to 60 minutes of natural curing time (demould time can be changed by controlling the curing time, the product is completed according to desorption time, productivity is largely influenced) ;

 11) Completing the final product by aging the demolded molded product for 28 days of natural curing;

11) -1 Completing the final product by maintaining the demolded molded article in a hot-air dryer at a temperature of 30-35 占 폚 for 24-72 hours

Example 9 was carried out in the same manner as in Example 1 except that 1.5 weight% of titanium oxide pigment was changed to Fe ₃ O ₄ black pigment.

Example 11 was carried out in the same manner as in Example 1 except that 1.5 weight% of titanium oxide pigment was changed to Fe ₂ O ₃ earthy color pigment.

*: MgCl ₂ (3.6M aqueous solution)

The physical properties of the specimens obtained by the Examples and Comparative Examples were as shown in Table 6 below.

 [Comparative Example 9]

 Comparative Example 9 is a reproduction of Example 2 of the inventive composition disclosed in Korean Patent Laid-Open Publication No. 1999-014664.

 22 g of potassium carbonate

 Ammonium phosphate 36g

 Fly ash 25g

 Magnesium oxide 38 g

Water 17ml

As a result, the compressive strength of 28 days was 27.8 MPa. The initial curing time was 4 minutes and 40 seconds, the termination time was 5 minutes and 10 seconds, the density was 1.98 g / cm ³ , and the absorption rate was 6.9%.

 [Comparative Example 10]

 Comparative Example 10 shows Example 1 of the inventive composition described in US 5,830,815.

15% of potassium carbonate was added to an aqueous phosphoric acid solution (50%) to prepare an aqueous solution. Then, 50 g of oxide was added to 100 g of the aqueous solution. The oxide is a mixture of calcined MgO 85% and boric acid 15%. Addition of potassium carbonate did not cause hydration.

As a result, compact specimens with open pores of 6.1%, density of 1.77 g / cc (g / cm ³ ), cloth pore of 10.2% and compressive strength of 3,700 psi (25 MPa) were obtained. This is because K ₂ CO ₃ and H ₃ PO ₄ are neutralized to produce KH ₂ PO ₄ and further reacted with MgO to form sturubite. Therefore, all of the generated carbon dioxide is removed It is impossible to obtain a foamed product by using a production method in which MgO is added after stabilization.

Claims (7)

A method for producing an inorganic ordinary temperature curing type foamed ceramic composition comprising the steps of:

1) An inorganic binder composition comprising 5 to 20% by weight of an inorganic filler, 5 to 20% by weight of a lightweight aggregate, 10 to 20% by weight of activated carbon, 40 to 80% by weight of an inorganic magnesium phosphate binder, and 0.5 to 10% Weighing the container using a balance;
2) charging each weighed powdery raw material into a mixer in the order of lightweight aggregate, activated carbon, inorganic filler, and inorganic magnesium phosphate binder;
3) mixing the powder phase charged in the mixer;
4) adding 30 to 50 parts by weight of water to 100 parts by weight of the uniformly mixed powdery composition, and mixing to prepare a slurry;
5) charging 0.5 to 11 parts by weight of carbonate with respect to 100 parts by weight of the prepared slurry;
6) Bubbles were injected into the water while stirring the slurry mixed with the carbonate, and the carbonate lost its initial shape due to reaction with MgO and PO ₄ ions, and M ⁺ or M ^{+ +} (M = Na, K, NH ₄ , comprising: M ⁺⁺ = Ca, as separated in the form of Mg, Ba, etc.), and CO ₂ generating a bubble by the CO ₂ gas;
7) stopping the agitation so that the generated bubbles are not bubbled, and filling the bubbles in a mold;
8) applying vibration to the filling material for 1 to 2 seconds so as to allow the filling material to penetrate well in the forming mold;
9) curing the molding filled in the mold within 5 to 20 minutes;
10) a step of demolding the cured foamed ceramic formed body after a natural curing time elapses from 30 to 60 minutes;
11) Curing the demolded molded article to complete the inorganic room temperature curing type foamed ceramic
The method of claim 1, wherein
The inorganic magnesium phosphate binder composition is prepared by mixing 40 wt% of magnesium oxide consisting of 80 wt% of light magnesia magnesia and 20 wt% of reactive magnesia, 3 wt% of aluminum phosphate and 55 wt% of monopotassium phosphate in 100 wt% 54 weight% of phosphate consisting of 42 weight% of ammonium monophosphate, 4.5 weight% of boric acid and magnesium sulfate mixture retarder, and 1.5 weight% of titanium oxide pigment.
The method according to claim 1,
Wherein the step of mixing the phase is performed for 5 minutes at a slow speed (30 rpm), and the mixture is rapidly mixed for 1 to 2 minutes (60 rpm)
The method according to claim 1,

Wherein the step of mixing the carbonate slurry with the slurry is carried out rapidly at a rate of 100 to 150 rpm.
A foamed ceramics composition prepared by any one of claims 1 to 4 and capable of room temperature curing and having a water absorption rate of 45% or more.
6. The method of claim 5,

And a density of 0.64 to 0.98 (g / cm < ³ >). 6. The method of claim 5,

And a surface hardening time of 7 to 19 minutes.

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