KR101155928B1 - Ultra fine lightweighting foamed glass porous ceramics and manufacturing method of the same - Google Patents

Abstract

The present invention relates to a foamed glass porous body in which a plurality of pores are distributed in a glass body, comprising a foamed precursor which forms pores upon glass holding and firing, wherein the foamed precursor is 0.5 to 15 weight parts based on 100 parts by weight of glass body. The present invention relates to an ultrafine foamed glass lightweight porous body comprising a first precursor synthesized by neutralization of an acetic acid-based organic acid monovalent anion and an inorganic alkali monovalent cation. According to the present invention, a plurality of uniform pores are distributed in the glass substrate, have a uniform pore size, and have a light weight, thereby obtaining an ultrafine foamed glass lightweight porous body which can be used as a heat insulating material, a sound absorbing material, and a sound insulating material.

Description

Ultra fine lightweighting foamed glass porous ceramics and manufacturing method of the same}

The present invention relates to a foamed glass porous body and a method for manufacturing the same, and more particularly to a foamed precursor synthesized by the neutralization reaction of an acetic acid-based organic acid monovalent anion and an inorganic alkali monovalent cation. The present invention relates to an ultrafine foamed glass lightweight porous body that is uniformly distributed, has a uniform pore size, and is light in weight, which can be used as a heat insulating material, a sound absorbing material, or a sound insulating material.

In general, styrofoam used for building insulation or soundproofing material is light and has good insulation and soundproofing effect, but it is weak in durability and fires and ignites well, thus causing toxic gas in case of fire. His use is limited.

Glass fiber or rock wool, which is widely used as a building insulation or soundproofing material, has a weak mechanical strength, and its use is gradually decreasing as it is found that dust generated by aging of the material is harmful to the human body.

There are wood sound absorbing materials that use wood as a sound absorbing material, but there are difficulties in the supply and demand of waste wood.

Although there is a metal sound absorbing material such as aluminum (Al), such metal sound absorbing material is expensive and there is a waste of cost and resources.

As the sound absorbing material, there are polymer-based organic sound absorbing materials such as polyurethane, polyester, and melamine, but there are many problems in the landfilling or the combustion disposal process.

Accordingly, in recent years, a building foam that can replace it has been newly developed, and among them, foam glass may be exemplified.

Foamed glass has many properties such as heat insulating material, sound insulation and sound-absorbing material because it has properties of inorganic glass and exhibits properties such as light weight, heat insulation, sound insulation and non-combustibility due to the formation of bubbles.

Republic of Korea Patent Publication No. 10-0194107 is prepared by adding a hydroxyapatite or calcium hydroxide phosphate compound together with soda lime glass crushed, waste glass crushed or glass polishing sludge to form a composition and then heat-treated by sintering and foaming The method is presented.

In addition, Korean Patent Laid-Open Publication No. 1999-008535 discloses compression by adding carbon, calcium carbonate, dolomite, calcium phosphate, silicon carbide, etc. as a blowing agent to waste glass powders such as crushed products of conventional glass products, abrasive sludge of CRT glass, etc. A foamed glass having a laminated structure foamed by pressing or molding using a die is proposed.

However, the problem of conventional foamed glass porous ceramics has a narrow plastic range, non-uniform pore size, and non-uniform pore distribution by relying on the addition of general blowing agents in the solid and slurry state, thus limiting the use of the product and limiting production.

The problem to be solved by the present invention includes a foamed precursor synthesized by the neutralization reaction of acetic acid monovalent monovalent acid and inorganic alkali monovalent cation, a number of pores uniformly distributed in the glass substrate, has a uniform pore size The present invention provides an ultra-fine foam glass lightweight porous body which can be used as a heat insulating material, a sound absorbing material, or a sound insulating material due to its light weight.

The present invention relates to a foamed glass porous body in which a plurality of pores are distributed in a glass body, comprising a foamed precursor which forms pores upon glass holding and firing, wherein the foamed precursor is 0.5 to 15 weight parts based on 100 parts by weight of glass body. And a foamed precursor comprises a first precursor synthesized by neutralization of an acetic acid monovalent anion and an inorganic alkali monovalent cation, wherein the anion is CH ₃ COO ⁻ ion and the cation is K ⁺ , Na ^It provides an ultrafine foamed glass porous body which is ⁺ , Ba ²⁺ , Mg ²⁺ , Ca ²⁺ or B ³⁺ .

The foamed precursor may be composed of a phosphoric acid alkali inorganic material synthesized by neutralization of a phosphoric acid inorganic acid and an alkali hydroxide and a second precursor synthesized by a heating stirring reaction.

The phosphoric acid inorganic acid is an inorganic acid containing HPO ₄ ^- ions or H ₂ PO ₄ ^{2 -} ions, and the alkali hydroxide is KOH, NaOH, Ba (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ and It may be composed of one or more hydroxides selected from B (OH) ₃ .

In addition, the foamed precursor may be composed of a third precursor synthesized by heating and stirring reaction by adding an inorganic divalent carbide surface-treated with an alkali hydroxide to the second precursor.

In addition, the foamed precursor is an inorganic type surface-treated with an alkali hydroxide on a second precursor obtained by synthesizing the phosphoric acid-based inorganic inorganic material and the alkali hydroxide by the neutralization of the alkali-based hydroxide and the first precursor by heating and stirring reaction. The divalent carbide may be added to consist of a fourth precursor synthesized by a heating and stirring reaction.

The carbide may be made of at least one material selected from BaCO ₃ , MgCO ₃ and CaCO ₃ .

The present invention also comprises the steps of preparing a precursor by synthesizing the first precursor by neutralizing the anion of the acetic acid-based organic acid monovalent and the inorganic alkali monovalent cation, and preparing a glass powder, while grinding the glass powder Adding the liquid foam precursor to wet grinding, filtering and pressing the glass slurry obtained by wet grinding, adding and binder to form and drying, charging the dried molded body to the furnace, and adjusting the temperature of the furnace. Burning to remove the binder by raising the temperature above the temperature at which the binder is decomposed and lower than the glass transition temperature, and raising the furnace to a firing temperature higher than the glass transition temperature and lower than the melting temperature of the glass to cause foaming; and Lowering the temperature of the furnace to obtain a foamed glass porous body, wherein the foamed precursor Addition be contained by 0.5 to 15 parts by weight based on 100 parts by weight of powder, and the anions are CH ₃ COO ^- ions, and the cations ^{K +, Na +, Ba 2+} , Mg 2+, Ca 2+ or ³⁺ B Provided is a method for producing an ultrafine foamed glass lightweight porous body.

The preparing of the foam precursor may include synthesizing a phosphoric acid alkali inorganic material by neutralizing a phosphoric acid inorganic acid and an alkali hydroxide, and synthesizing a second precursor by heating and stirring the phosphoric acid alkali inorganic material and the first precursor. It may further include.

The preparing of the foam precursor may further include, after the synthesizing of the first precursor, treating the inorganic divalent carbide with an alkali hydroxide and heating and stirring the first precursor to synthesize a third precursor. have.

The preparing of the foam precursor may include synthesizing the phosphoric acid alkali inorganic material by neutralizing the phosphoric acid inorganic acid and the alkali hydroxide, and heating and stirring the phosphoric acid alkali inorganic material and the first precursor to form a second precursor. The method may further include synthesizing the inorganic precursor divalent carbide with alkali hydroxide, and heating and stirring the second precursor to synthesize a fourth precursor.

The carbide may be made of at least one material selected from BaCO ₃ , MgCO ₃ and CaCO ₃ .

According to the present invention, a plurality of pores are uniformly distributed in the glass substrate, have a homogeneous pore size, and have a light weight, thereby obtaining a foamed glass porous body which can be used as a heat insulating material, a sound absorbing material or a sound insulating material.

1 is a view showing for explaining a firing process for producing an ultra-fine foam glass lightweight porous body.
2 is a view showing the linear expansion rate of the ultra-fine foam glass lightweight porous body prepared according to Example 1.
3 is a view showing the volume expansion rate of the ultra-fine foam glass lightweight porous body prepared according to Example 1.
Figure 3 is a view showing the density and porosity of the ultra-fine foam glass lightweight porous body prepared according to Example 1.
Figure 5 is a photograph of the surface of the ultra-foam foam glass lightweight porous body prepared by firing at 690 ℃ according to Example 1 by a scanning electron microscope (Scanning Electron Microscope; SEM).
Figure 6 is a photograph of the surface of the ultra-foam foam glass lightweight porous body prepared by firing at 750 ℃ according to Example 1 by a scanning microscope (SEM).
Figure 7 is a photograph of the surface of the ultra-foam foam glass lightweight porous body prepared by firing at 690 ℃ according to Example 2 by a scanning microscope (SEM).
8 is a photograph of the surface of the ultra-foam foam glass lightweight porous body prepared by firing at 750 ° C. according to Example 2 with a scanning microscope (SEM).
Figure 9 is a photograph of the surface of the ultra-foam foam glass lightweight porous body prepared by firing at 690 ℃ according to Example 3 by a scanning microscope (SEM).
10 is a photograph observing the surface of the ultra-fine foam glass lightweight porous body prepared by firing at 750 ° C. according to Example 3 with a scanning microscope (SEM).
FIG. 11 is a photograph of the surface of the ultrafine foamed glass lightweight porous body prepared by firing at 690 ° C. according to Example 4, using a scanning microscope (SEM). FIG.
12 is a photograph observing the surface of the ultrafine foamed glass lightweight porous body prepared by firing at 750 ° C. according to Example 4 with a scanning microscope (SEM).

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the following embodiments are provided to those skilled in the art to fully understand the present invention, and may be modified in various forms, and the scope of the present invention is limited to the embodiments described below. It doesn't happen.

The present invention provides an ultra-fine foamed glass lightweight porous body in which pores are continuously dispersed in a glass matrix, and is an organic-inorganic composite precursor which is a composite prepared by neutralization of an acetic acid organic acid monovalent anion and an inorganic alkali monovalent cation. (First precursor), a mixed precursor (second precursor), which is a mixture of an alkali phosphoric acid-based precursor and a first precursor, a third precursor synthesized by adding an appropriate amount of an inorganic divalent carbide to the first precursor, and an inorganic divalent carbide. The present invention provides a method of preparing an ultrafine foamed glass lightweight porous body by adding at least one liquid foamed precursor selected from the fourth precursor synthesized by adding an appropriate amount to a second precursor.

Ultra-fine foam glass lightweight porous body prepared according to a preferred embodiment of the present invention can be used for lightweight porous material, that is, beads, aggregates, plates, flooring, etc., having micropores of 10 ~ 20㎛ size, high porosity of 90% or more It has a compressive strength of 20 to 60 kgf / cm 2, and has a specific gravity of about 0.1 to 0.2, indicating ultralight weight. Since the ultra-foam foam glass lightweight porous body has high thermal insulation, non-combustibility, deformation stability, light weight, and cutting processability, it is expected to be utilized as a lightweight porous body for construction such as insulation, sound absorbing material, or sound insulating material.

The glass powder is not particularly limited, and for example, a pulverized product of a conventional glass product such as soda lime glass for plate glass, soda lime glass for bottle glass, borosilicate glass for chemistry, glass chamfering sludge, waste glass powder, and the like. Glass powders such as powders, pulverized products such as glass melts, and the like.

Oxide glass has a SiO ₄ tetrahedron structure, which is a mesh-like structure that shares only vertices and does not share faces and edges.The Na-O bond of limestone glass is weaker than the covalent Si-O bond. It has a basic structure with only one side connected to oxygen ions. Therefore, it can be said that most oxides in which monovalent and _divalent elements coexist in the glass structure in such a way that Na ₂ O enters.

There are four foam precursors used in the present invention. The organic precursors (first precursor), the mixed precursor (second precursor) synthesized by mixing the phosphate alkali inorganic material and the first precursor, and the alkali hydroxide surface The third precursor synthesized by mixing the reacted inorganic divalent carbide with the first precursor, and the fourth precursor synthesized by mixing the inorganic divalent carbide surface-treated with the alkali hydroxide with the second precursor.

The above-mentioned first precursors are acetic acid monovalent anions (CH ₃ COO ⁻ ions) and inorganic alkali monovalent cations (K ⁺ , Na ⁺ , Ba ²⁺ , Mg ²⁺ , Ca ²⁺ , B ^3+, etc.). And a second precursor is a synthetic mixture of a neutralized compound of a phosphoric acid inorganic acid and an alkali hydroxide and a first precursor. The third precursor is a precursor-carbide mixed composition in which an appropriate amount of inorganic divalent carbide is added to the first precursor. The fourth precursor is a precursor-carbide mixture composition in which an appropriate amount of inorganic divalent carbide is added to the second precursor. Foam precursor serves to form bubbles basically during the firing process.

The organic-inorganic composite precursor (first precursor) is an ionic polar material to form pores on the Na-O bond surface, and the mixed precursor (second precursor) is located on the Si-O bond side to form a stable pore bonded glass. It can be seen that. Synthesis of the organic-inorganic complex precursor (first precursor) utilizes a property of maintaining a pH of the mixed solution of weak acid (or weak alkali) and its salt in a small amount of acid and alkali by a buffer reaction between an acid and an alkali. Under a buffer solution in which carboxyl salt is present, the addition of a small amount of H, Ba, B (OH) ₃ , NaOH, etc. does not affect the pH change. Synthesis of the organic-inorganic complex precursor is prepared by acid-alkali neutralization titration reaction, for example, with acetic acid-based organic acid (for example, organic acid containing CH ₃ COO ⁻ ion such as C ₆ H ₄ (COOH) ₂ , CH ₃ OOH) Neutralization titration reaction of alkali hydroxides (KOH, NaOH, Ba (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ , B (OH) _3, etc.) is used. It can be prepared by making a dilute solution at a concentration between 1M and dropping the alkali hydroxide or acetic acid while stirring with acetic acid or alkali hydroxide in a beaker. At this time, the acid-alkali neutralization reaction is preferably terminated in the pH range of 6.5 ~ 7.5 which is hydrogen ion concentration. The organic-inorganic composite precursor thus prepared serves as a buffer when mixed with the glass powder and also serves to maintain the pH of the base to neutral.

The second precursor is a synthetic mixture of the phosphoric acid alkali inorganic material and the first precursor synthesized by neutralizing the phosphoric acid inorganic acid and the alkali hydroxide. Synthesis of the phosphoric acid-based alkali minerals include phosphoric acid-based inorganic acids (eg, inorganic acids containing HPO ₄ ^- ions or H ₂ PO ₄ ^2- ions such as H ₃ PO ₄ ) and alkali hydroxides (KOH, NaOH, Ba (OH)). ₂ , Mg (OH) ₂ , Ca (OH) ₂ , B (OH) _3, etc.) Inorganic Phosphate (Na ₃ PO _4- (Ca, Mg) ₁₀ (PO ₄ ) ₆ OH) ₂ ) is synthesized. At this time, the phosphoric acid-based inorganic acid and the alkali hydroxide is prepared as a suspension in the pH range of 9.5 ~ 9.0 by heating reaction or hydrothermal synthesis at 1 molar concentration or less. The phosphoric acid-based alkali inorganic material thus prepared is mixed with the organic-inorganic complex precursor (first precursor) by a heat stirring reaction within a range of 10% quantitatively (second precursor) (CH ₃ COONa-Ca ₁₀ (PO ₄ ) ₆ ( OH) ₂ ) can be synthesized.

The third precursor is a foamed precursor synthesized by subjecting the inorganic divalent carbide to a surface reaction treatment with an alkali hydroxide, followed by heating and stirring with an organic-inorganic composite precursor (first precursor). The carbide may be an inorganic divalent carbide such as BaCO ₃ , MgCO ₃ , CaCO ₃ , (Ca? Mg) CO ₃ . The surface reaction treatment means that the divalent carbide heat-treated at a temperature in the range of 450 to 600 ° C. is immersed in an alkali hydroxide such as NaOH and surface treated.

The fourth precursor is a foamed precursor synthesized by subjecting the inorganic divalent carbide to surface reaction treatment with an alkali hydroxide, followed by heating and stirring with a mixed precursor (second precursor). The carbide may be an inorganic divalent carbide such as BaCO ₃ , MgCO ₃ , CaCO ₃ , (Ca? Mg) CO ₃ .

Hereinafter, a method of manufacturing an ultrafine foamed glass lightweight porous body using the above-described liquid foam precursor is described.

In order to prepare the glass powder, a piece of waste glass, which is waste glass, is ground to a predetermined size (for example, 30 mesh) or less using a coarse grinding device such as a hammer mill to prepare the glass powder.

The foamed precursor is introduced while wet grinding the glass powder to perform a wet grinding process. It is preferable to add the said foaming precursor so that 0.5-15 weight part may be contained with respect to 100 weight part of glass powders. The wet grinding process may use various methods such as a ball milling method, a milling media, and the like. The grinding process by the ball milling method will be described in detail. First, the glass powder is charged into a ball milling machine and a foamed precursor is introduced while wet mixing with a solvent. The solvent may be water, alcohol, or the like. The glass powder is mechanically pulverized and uniformly mixed by rotating at a constant speed using a ball mill. Balls used for ball milling may use balls made of ceramics such as alumina and zirconia, and the balls may be all the same size or may be used with balls having two or more sizes. Grind to the size of the target particles by adjusting the size of the ball, milling time, rotation speed per minute of the ball mill. For example, in consideration of the particle size, the size of the ball is preferably set in the range of about 1 mm to 50 mm, and the rotation speed of the ball mill is set in the range of about 100 to 500 rpm. Ball milling is performed for 1 to 48 hours in consideration of the target particle size. By ball milling, the glass powder is pulverized into fine-sized particles, has a uniform particle size distribution, and is uniformly mixed with the foamed precursor to form a liquid foamed precursor coated on the surface of the glass powder particles.

The glass slurry obtained by the wet grinding is filtered and pressed using a filter press to obtain an ultrafine glass filter. A binder such as polyvinyl alcohol (PVA), methyl cellulose, sodium aluminate is added to the glass filter body thus obtained. It is preferable to add 0.1-1.0 weight part of said binders with respect to 100 weight part of glass filter bodies.

The glass filter body is formed into a desired shape, and then a drying process is performed. The molding step may be any known method such as press molding, die molding, slip casting, etc. Among them, in the case of press molding, the surface state of the molded body is good, the pore state is uniform, and the pore size is also good. Do. When the molding pressure is 10 kgf / cm 2 or less, the molding strength drops and foaming occurs too much. If the pressure is 100 kgf / cm 2 or more, the foaming occurs less. When slip casting is used, it is preferable to add materials such as Na ₃ PO ₄ and AlPO ₄ for demoulding.

The drying process may be performed by drying in air for 1 to 48 hours, followed by drying in an oven at 60 to 120 ° C. Drying is influenced by temperature and humidity of the outside air, and moisture is diffused from the inside of the molding to the outside, so it is controlled by temperature, pore size, shape, temperature difference between the surface and the inside, and the amount of moisture.

A firing process is performed on the dried molded body. 1 is a view showing for explaining a firing process for producing an ultra-fine foam glass lightweight porous body.

Referring to FIG. 1, the dried molded body is charged to a furnace (for example, an electric furnace), and the temperature of the furnace is higher than the temperature at which the organic binder is decomposed using a heating means and a glass transition temperature is obtained. It raises to lower temperature (for example, 350-450 degreeC) (t1 section of FIG. 1). When the temperature of the furnace is higher than the temperature at which organic matter decomposes and reaches a temperature lower than the glass transition temperature (about 650 ℃ in case of soda lime glass) (eg 350 ~ 450 ℃), the decomposition of organic matter occurs, but the inorganic matter has a high melting point. Therefore, decomposition does not occur. When the temperature of the furnace reaches a temperature higher than the temperature at which the organic matter is decomposed and lower than the glass transition temperature (eg 350 to 450 ° C.), it is maintained for a time (eg 30 minutes to 2 hours) at which the organic matter can be sufficiently decomposed ( Section t2 of FIG. 3).

Once the organics have been sufficiently removed, the furnace is raised to a target firing temperature (eg, 600-750 ° C.) above the glass transition temperature and below the melting temperature of the glass (t3 section in FIG. 3). When the temperature of the furnace is raised to a firing temperature above the glass transition temperature, foaming begins to occur. It is preferable to raise a temperature at the rate of 1-10 degree-C / min to the said baking temperature.

When the temperature of the furnace reaches the target firing temperature, it is maintained for a time (eg, 10 minutes to 6 hours) in which sufficient foaming can occur (t4 section in FIG. 3). The main purpose of the firing is to produce a stable structure and mineral phase at high temperatures, foaming to form an appropriate independent and connecting pores, and to give sufficient strength. The firing step is preferably performed in the above temperature range for 10 minutes to 6 hours, preferably 30 minutes to 2 hours, in view of melting and foaming performance of the glass. That is, when the firing conditions are satisfied, the effect of foaming completely to the inside can be obtained. If the firing temperature is too high, it may be uneconomical because the glass may melt or irregular foaming and consume a lot of energy, and if the firing temperature is too low, sufficient foaming may not occur, so the firing temperature is 600 It is preferable that it is the range of -750 degreeC. In the firing process, the foamed precursor generates bubbles during firing to form continuous pores and independent pores in the glass substrate.

After the firing process, it may be quenched up to the glass transition temperature, but below the glass transition temperature should be naturally cooled to prevent cracking due to quenching.

≪ Example 1 >

To synthesize organic-inorganic precursors, acetic acid (CH ₃ OOH) and sodium hydroxide (NaOH) are prepared, and dilute acetic acid (CH ₃ OOH) and sodium hydroxide to a concentration between 0.1M and 1M and acetic acid in a beaker ( CH ₃ OOH) was added and sodium hydroxide (NaOH) was added dropwise while stirring to prepare a liquid organic-inorganic composite precursor. At this time, the acid-alkali neutralization reaction was terminated at a pH of 7.5 or less of neutral pH between 6.5 and 7.5.

In order to prepare the glass powder, the glass plate, which is waste glass, was put in a hammer mill and pulverized to 30 mesh or less to prepare a glass powder.

The glass powder was put into a ball mill and pulverized for 20 hours using alumina balls at a speed of 21 rpm. During the ball mill, a liquid organic-inorganic composite precursor was added together to obtain a glass slurry. The organic-inorganic composite precursor was added to 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, and 10 parts by weight based on 100 parts by weight of the glass powder, and the experiment was performed according to the content of the organic-inorganic composite precursor. At this time, the solid-to-liquid (precursor) ratio was 110 to 150% depending on the composition, and the glass particles obtained by the ball mill were ultrafine particles having a particle diameter of about 20 μm. Hereinafter, when 1 part by weight of the organic-inorganic composite precursor is prepared by foamed glass porous ceramics (FC: foamed glass porous ceramics) is represented by FC1, 3 parts by weight of the organic-inorganic composite precursor is added to the foamed glass porous body is prepared Is represented by FC3, 5 parts by weight of the organic-inorganic composite precursor is represented by FC5 when the foamed glass porous body is prepared, and 7 parts by weight of the organic-inorganic composite precursor is prepared by the foamed glass porous body is represented by FC7, When 10 parts by weight of the composite composite precursor is added to produce a foamed glass porous body, it is referred to as FC10.

The glass slurry was filtered and compressed using a filter press to obtain an ultrafine glass filter. The glass filter medium filtered by the filter press contains about 40 to 42% of water.

Polyvinyl alcohol (PVA) was added as a binder to the glass filter body thus obtained, and dried at a temperature of 80 ° C for 1 hour. 0.3-0.5 weight part of said polyvinyl alcohols (PVA) were added with respect to 100 weight part of glass filters.

Put the dried powder in a die and biaxial pressure molding at a pressure of 30kgf / ㎠, and then put in an electric furnace to gradually increase the temperature to 5 ℃ / min to increase the temperature to 450 ℃ and maintained for 1 hour at a temperature of 450 ℃ binder The components were removed, and the temperature was again raised to a calcination temperature of 660 ° C. to 750 ° C., and then maintained at the calcination temperature for 30 minutes to uniformly sinter, thereby preparing an ultrafine foam glass lightweight porous body.

By evaluating the expansion, density, porosity, thermal conductivity, and microstructure as physical properties of ultra-fine foamed glass porous body, it was confirmed that it has a high differentiation from existing foamed glass.

Physical properties of the ultrafine foamed glass lightweight porous body obtained by calcining at 660 ° C., 690 ° C. and 750 ° C., respectively, are shown in Table 1 and Table 2 and FIGS. 2 to 4. The linear expansion rate was 1.21 ~ 1.99 times, the volume expansion rate was 8.5 ~ 12 times, and the density was 0.18 ~ 0.62 and porosity 75.1 ~ 96.1%. The compressive strength ranged from 9.2 to 67.7 kgf / cm 2 with large and small pore sizes, thermal conductivity of 0.03 to 0.07 kcal / hr · m ℃, and micropore size of 10 to 20㎛.

Linear expansion Volume expansion rate Firing temperature 660 ℃ 690 ℃ 750 ℃ 660 ℃ 690 ℃ 750 ℃ FC1 1.21 1.51 1.61 1.95 3.78 7.76 FC3 1.59 1.79 1.8 5.18 8.66 10.12 FC5 1.59 1.77 1.84 5.25 9.67 12.34 FC7 1.61 1.78 1.93 5.19 9.88 13.16 FC10 1.74 1.91 1.99 6.48 11.56 13.01

Firing temperature Name of sample density
(g / cm3) Porosity (%) Compressive strength
(kgf / cm2) Thermal conductivity
(㎉ / hr? M ℃)

660 ℃

FC1 0.620 75.1 67.7 0.07 FC3 0.488 90.1 32.8 0.05 FC5 0.376 92.4 29.7 0.05 FC7 0.372 92.6 23.3 0.05 FC10 0.272 94.8 18.2 0.04

750 ℃

FC1 0.227 91.0 26.5 0.05 FC3 0.248 95.1 13.0 0.04 FC5 0.238 94.9 13.3 0.04 FC7 0.218 96.0 13.8 0.03 FC10 0.184 96.1 9.2 0.03

As shown in Table 1 and Table 2, the ultrafine foamed glass lightweight porous body of FC3 and FC5 having a composition of 3 parts by weight and 5 parts by weight of an organic-inorganic composite precursor added is 8 times the volume expansion at a firing temperature of 690 ° C. Above, the porosity is more than 90% and the compressive strength is 20kgf / ㎠ or more, the ultra-foam foam glass lightweight porous body exhibiting these properties is expected to be used as a variety of interior wall material and panel material.

Figure 5 is a photograph of the surface of the ultra-foam foam glass lightweight porous body prepared by firing at 690 ℃ according to Example 1 by a scanning microscope (Scanning Electron Microscope; SEM), Figure 6 at 750 ℃ according to Example 1 It is a photograph observing the surface of the ultrafine foamed glass lightweight porous body produced by firing with a scanning microscope (SEM).

As a result of the experiments, it was observed that the ultra-foam foam glass lightweight porous body had an initial foaming at a firing temperature of about 600 ° C. and uniform foaming up to a firing temperature of 750 ° C., and a nonuniform excess when the firing temperature exceeded 750 ° C. Foaming occurred and melting was observed at 1000 ° C.

The porous foamed glass of the present invention is expected to be able to adjust the porosity and strength in the firing temperature range of 600 ~ 750 ℃ without problems of uneven pore distribution and plastic stability of the foamed glass so far, bead and aggregate It is expected to be possible to manufacture and manufacture panels, tubes, and flooring materials. For example, since the porosity is 70%, the compressive strength 60kgf / ㎠ or more physical properties can be used as aggregate, tube tube and flooring material.

<Example 2>

Inorganic phosphate (Na ₃ PO _4- (Ca, Mg) ₁₀ ) as a colloidal solution from phosphoric acid (H ₃ PO ₄ ) solution and aqueous alkali hydroxide solution (NaOH, Ca (OH) ₂ , Mg (OH) ₂ ) (PO ₄ ) ₆ (OH) ₂ ) was synthesized directly. At this time, the phosphoric acid and the alkali hydroxide solution was prepared as a suspension of about 2% solids in the pH range of 9.5 ~ 9.0 by heating reaction or hydrothermal synthesis at 1 molar concentration or less.

This suspension inorganic phosphate synthesized the mixed precursor (CH ₃ COONa-Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ) with the organic-inorganic composite precursor prepared in Example 1 by heat stirring within a range of 10% quantitatively. . At this time, the heating and stirring reaction was performed by stirring at 50 rpm at a temperature of 80 ℃.

In order to prepare the glass powder, the glass plate, which is waste glass, was put in a hammer mill and pulverized to 30 mesh or less to prepare a glass powder.

The glass powder was put into a ball mill and pulverized for 20 hours at a speed of 21 rpm using an alumina ball. During the ball mill, the liquid mixed precursor was added together to obtain a glass slurry. The mixed precursor was added to 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, and 10 parts by weight of the glass powder, respectively, and the experiment was performed according to the content of the mixed precursor. At this time, the solid-to-liquid (precursor) ratio was 110 to 150% depending on the composition, and the glass particles obtained by the ball mill were ultrafine particles having a particle diameter of about 20 μm.

The glass slurry was filtered and compressed using a filter press to obtain an ultrafine glass filter.

Polyvinyl alcohol (PVA) was added as a binder to the glass filter body thus obtained, and dried at a temperature of 80 ° C for 1 hour. 0.3-0.5 weight part of said polyvinyl alcohols (PVA) were added with respect to 100 weight part of glass filters.

Put the dried powder in a die and biaxial pressure molding at a pressure of 30kgf / ㎠, and then put in an electric furnace to gradually increase the temperature to 5 ℃ / min to increase the temperature to 450 ℃ and maintained for 1 hour at a temperature of 450 ℃ binder The components were removed, and the temperature was again raised to a calcination temperature of 660 ° C. to 750 ° C., and then maintained at the calcination temperature for 30 minutes to uniformly sinter, thereby preparing an ultrafine foam glass lightweight porous body.

7 is a photograph of the surface of the ultrafine foamed glass lightweight porous body manufactured by firing at 690 ° C. according to Example 2, and FIG. 8 is a photograph obtained by firing at 750 ° C. according to Example 2 The surface of the ultra-fine foamed glass porous body was observed by scanning microscope (SEM).

<Example 3>

The inorganic bivalent carbide surface-treated with alkali hydroxide (NaOH) was heated and stirred with the organic-inorganic composite precursor prepared in Example 1 to obtain a third precursor. At this time, the heating and stirring was performed at 50 rpm at a temperature of 80 ℃. The carbides were tested for two types of CaCO ₃ and (Ca? Mg) CO ₃ , respectively.

In order to prepare the glass powder, the glass plate, which is waste glass, was put in a hammer mill and pulverized to 30 mesh or less to prepare a glass powder.

The glass powder was put into a ball mill and pulverized for 20 hours using alumina balls at a speed of 21 rpm. During the ball mill, a liquid precursor was added to obtain a glass slurry. The third precursor was added to 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, and 10 parts by weight of the glass powder, respectively, and the experiment was performed according to the content of the foaming catalyst. At this time, the solid-to-liquid (precursor) ratio was 110 to 150% depending on the composition, and the glass particles obtained by the ball mill were ultrafine particles having a particle diameter of about 20 μm.

The glass slurry was filtered and compressed using a filter press to obtain an ultrafine glass filter.

Polyvinyl alcohol (PVA) was added as a binder to the glass filter body thus obtained, and dried at a temperature of 80 ° C for 1 hour. 0.3-0.5 weight part of said polyvinyl alcohols (PVA) were added with respect to 100 weight part of glass filters.

Put the dried powder in a die and biaxial pressure molding at a pressure of 30kgf / ㎠, and then put in an electric furnace to gradually increase the temperature to 5 ℃ / min to increase the temperature to 450 ℃ and maintained for 1 hour at a temperature of 450 ℃ binder The components were removed, and the temperature was again raised to a calcination temperature of 660 ° C. to 750 ° C., and then maintained at the calcination temperature for 30 minutes to uniformly sinter, thereby preparing an ultrafine foam glass lightweight porous body.

9 is a photograph of the surface of the ultrafine foamed glass lightweight porous body manufactured by firing at 690 ° C. according to Example 3, and is a photograph obtained by scanning microscope (SEM), and FIG. 10 is manufactured by firing at 750 ° C. according to Example 3 The surface of the ultra-fine foamed glass porous body was observed by scanning microscope (SEM).

<Example 4>

An inorganic bivalent carbide surface-treated with alkali hydroxide (NaOH) was heated and stirred with the mixed precursor prepared in Example 1 to obtain a fourth precursor. At this time, the heating and stirring was performed at 50 rpm at a temperature of 80 ℃. The carbides were tested for two types of CaCO ₃ and (Ca? Mg) CO ₃ , respectively.

In order to prepare the glass powder, the glass plate, which is waste glass, was put in a hammer mill and pulverized to 30 mesh or less to prepare a glass powder.

The glass powder was put into a ball mill and pulverized for 20 hours using an alumina ball at a speed of 21 rpm. During the ball mill, the fourth liquid precursor was added together to obtain a glass slurry. The fourth precursor was added to 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, and 10 parts by weight of the glass powder, respectively, and the experiment was performed according to the content of the foaming catalyst. At this time, the solid-to-liquid (precursor) ratio was 110 to 150% depending on the composition, and the glass particles obtained by the ball mill were ultrafine particles having a particle diameter of about 20 μm.

The glass slurry was filtered and compressed using a filter press to obtain an ultrafine glass filter.

Polyvinyl alcohol (PVA) was added as a binder to the glass filter body thus obtained, and dried at a temperature of 80 ° C for 1 hour. 0.3-0.5 weight part of said polyvinyl alcohols (PVA) were added with respect to 100 weight part of glass filters.

Put the dried powder in a die and biaxial pressure molding at a pressure of 30kgf / ㎠, and then put in an electric furnace to gradually increase the temperature to 5 ℃ / min to increase the temperature to 450 ℃ and maintained for 1 hour at a temperature of 450 ℃ binder The components were removed, and the temperature was again raised to a calcination temperature of 660 ° C. to 750 ° C., and then maintained at the calcination temperature for 30 minutes to uniformly sinter, thereby preparing an ultrafine foam glass lightweight porous body.

11 is a photograph of the surface of the ultrafine foamed glass lightweight porous body manufactured by firing at 690 ° C. according to Example 4, and is a photograph observed by scanning microscope (SEM), and FIG. 12 is manufactured by firing at 750 ° C. according to Example 4 The surface of the ultra-fine foamed glass porous body was observed by scanning microscope (SEM).

5 to 12, the pore size and pore distribution of the ultra-fine foam glass lightweight porous body is compared to the case where the ultra-fine foam glass lightweight porous body is prepared using the organic-inorganic composite precursor (first precursor) according to Example 1 , According to Example 2, it can be seen that uniform foaming occurs when the ultrafine foam glass lightweight porous body is prepared using a mixed precursor (second precursor) synthesized by mixing an phosphate alkali inorganic material with an organic-inorganic composite precursor.

In addition, the pore size and distribution of the ultra-fine foamed glass lightweight porous body manufactured using the fourth precursor were observed by 70 times and 140 times scanning microscope, and as a result of homogeneous circular pores and pores with 10-20 μm micropores. It can be seen that this is uniformly distributed. In other words, mixed precursor and carbide promote decomposition reaction ? It can be confirmed that the decomposition reaction can be controlled by the influence of suppression.

Organic CH ₃ COO ^- is ₃ ^{2 CO-thereof} by a role of suppressing the decomposition ^of-promoting decomposition of the CO ₃ ^{2 -} is OH ^-, and promote decomposition of the (phosphate), and the OH station ^- is CO ₃ ² The proper amount of composition will control and adjust the pore size and distribution. In addition, the larger the porosity and the higher the porosity, the higher the porosity and the higher the porosity in the compressive strength and compression history curve. The lower the yield point and the shorter the yield time. This is similar to the effect that occurs slowly with elasticity when the sponge is pressed.

As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to the said embodiment, A various deformation | transformation by a person of ordinary skill in the art within the scope of the technical idea of this invention is carried out. This is possible.

Claims (9)

In the foamed glass porous body in which a plurality of pores are distributed in the glass body,
It includes a glass precursor and a foamed precursor that forms pores during firing, the foamed precursor is contained 0.5 to 15 parts by weight based on 100 parts by weight of the glass substrate, the foamed precursor is a monovalent anionic and inorganic alkali monovalent of acetic acid-based organic acid A first precursor synthesized by neutralization of a cation, wherein the anion is CH ₃ COO ⁻ ion and the cation is K ⁺ , Na ⁺ , Ba ²⁺ , Mg ²⁺ , Ca ²⁺ or B ³⁺ Ultra-fine foam glass lightweight porous body characterized in that.
The method of claim 1, wherein the foam precursor,
An ultrafine foamed glass lightweight porous body comprising a phosphoric acid alkali inorganic material synthesized by neutralization of a phosphoric acid inorganic acid and an alkali hydroxide and a second precursor synthesized by heating and stirring reaction.
The method of claim 2, wherein the phosphoric acid inorganic acid is an inorganic acid containing HPO ₄ ^- ions or H ₂ PO ₄ ^2- ions, wherein the alkali hydroxide is KOH, NaOH, Ba (OH) ₂ , Mg (OH) ₂ , Ultra-fine foam glass lightweight porous body, characterized in that consisting of at least one hydroxide selected from Ca (OH) ₂ and B (OH) ₃ .
The method of claim 2, wherein the foam precursor,
An inorganic divalent carbide surface-treated with an alkali hydroxide is added to the second precursor, and is composed of a third precursor synthesized by a heating and stirring reaction, and the carbide is at least one material selected from BaCO ₃ , MgCO _3, and CaCO ₃ . Ultra-fine foam glass lightweight porous body, characterized in that consisting of.
The method of claim 1, wherein the foam precursor,
An inorganic divalent carbide surface-treated with alkali hydroxide is added to a second precursor obtained by neutralizing phosphoric acid inorganic acid and alkali hydroxide and the first precursor synthesized by heating and stirring reaction, and heated. A fourth precursor synthesized by a stirring reaction, wherein the carbide is ultra-light foam glass lightweight porous body, characterized in that made of at least one material selected from BaCO ₃ , MgCO ₃ and CaCO ₃ .
Preparing a precursor by synthesizing the first precursor by neutralizing the acetic acid monovalent anion and the inorganic alkali monovalent cation;
Preparing a glass powder;
Wet grinding by adding the foamed precursor in a liquid phase while grinding the glass powder;
Filtering the glass slurry obtained by wet grinding, and adding and forming a binder and drying the binder;
Charging the dried molded body to a furnace, and burning the binder by raising the temperature of the furnace to a temperature higher than a temperature at which the binder is decomposed and lower than a glass transition temperature;
Raising the furnace to a firing temperature above the glass transition temperature and below the melting temperature of the glass to cause foaming; And
Lowering the temperature of the furnace to obtain a foamed glass porous body,
The foamed precursor is added in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the glass powder, the anion is CH ₃ COO ⁻ ion, and the cation is K ⁺ , Na ⁺ , Ba ²⁺ , Mg ²⁺ , Ca ^{2 +} Or B ³⁺ ultrafine foam glass lightweight porous body characterized in that the method.
The method of claim 6, wherein preparing the foam precursor is
Neutralizing the phosphoric acid inorganic acid and the alkali hydroxide to synthesize a phosphoric acid alkali inorganic material; And
Comprising a step of synthesizing the second precursor by heating and stirring the phosphoric acid-based alkali minerals and the first precursor,
The phosphoric acid inorganic acid is an inorganic acid containing HPO ₄ ^- ions or H ₂ PO ₄ ^2- ions, and the alkali hydroxide is KOH, NaOH, Ba (OH) ₂ , Mg (OH) ₂ , Ca (OH) ₂ and Method for producing an ultra-fine foam glass lightweight porous body, characterized in that consisting of at least one hydroxide selected from B (OH) ₃ .
The method of claim 6, wherein preparing the foam precursor is
After the step of synthesizing the first precursor, further comprising the step of synthesizing a third precursor by an alkali hydroxide treatment of the inorganic bivalent carbide and heating and stirring with the first precursor,
The carbide is a manufacturing method of ultra-fine foam glass lightweight porous body, characterized in that consisting of at least one material selected from BaCO ₃ , MgCO ₃ and CaCO ₃ .
The method of claim 6, wherein preparing the foam precursor is
Neutralizing the phosphoric acid inorganic acid and the alkali hydroxide to synthesize a phosphoric acid alkali inorganic material;
Synthesizing a second precursor by heating and stirring the phosphate alkali inorganic material and the first precursor; And
Alkaline hydroxide treatment of the inorganic bivalent carbide and the step of heating and stirring with the second precursor to synthesize a fourth precursor,
The carbide is a manufacturing method of ultra-fine foam glass lightweight porous body, characterized in that consisting of at least one material selected from BaCO ₃ , MgCO ₃ and CaCO ₃ .

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