KR100315296B1 - Ultra-fine ceramic oxide powder, method for producing the ultra-fine ceramic oxide powder, ceramic paste produced using the ultra-fine ceramic oxide powder, and method for producing the ceramic paste - Google Patents

Abstract

The present invention comprises the steps of preparing a solution or dispersion mixture containing a ceramic component by dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium; Preparing a mixed solution by adding to the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, an amount or more citric acid necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component; And evaporating the solvent or dispersion medium by heat-treating the mixed solution at 100-500 ° C., and the added citric acid acts as a reducing combustion aid to remove the anion and non-explosive oxidation-reduction combustion reaction of the ceramic component. A method of preparing an ultrafine ceramic oxide powder in which an ultrafine ceramic oxide powder having a particle size of 1 μm or less and a uniform particle size distribution is finally obtained through a step of forming a ceramic oxide without scattering by heat of reaction, and an ultrafine ceramic oxide powder prepared by such a method. The present invention relates to a method for producing a ceramic paste using a fine ceramic oxide powder and an ultrafine ceramic oxide powder, and to a ceramic paste capable of forming a film at a low temperature prepared by such a method. Ceramic oxide powder with fine size and excellent reactivity To be prepared, and it is capable to use the produced ceramic oxide powder to prepare a ceramic paste which can be formed a film with only a heat treatment at a low temperature effect.

Description

Ultra-fine ceramic oxide powder, method for producing the ultra-fine ceramic oxide powder, ceramic paste produced using the ultra-fine ceramic oxide powder, and method for producing the ceramic paste}

The present invention relates to an ultra-fine ceramic oxide powder, a method for manufacturing the same, and a ceramic paste using the ceramic oxide powder and a method for producing the same. More specifically, the reactivity is reduced by a single process at low temperature using citric acid as a combustion aid. The present invention relates to a method for producing an excellent ultrafine ceramic oxide powder, to a ceramic oxide powder prepared by the method having excellent fine reactivity, and to a ceramic paste using the prepared ultrafine ceramic oxide powder.

Ceramic oxide powder, which is a raw material in the manufacture of various devices using ceramics such as inkjet heads, memory chips, and piezoelectric elements, has an emphasis on miniaturization of unit particles and uniform particle size distribution. This is because the fine particles can improve the reactivity and applicability by reducing the activation energy or charging the particles through surface treatment.

Conventional methods used to prepare ceramic oxide powders can be broadly divided into solid phase methods and combustion methods.

The solid phase method, also called an oxide method, is a method for producing ceramic oxide powder using an oxide or a molten salt. In the solid phase method, a raw material in a powder form is mixed, heat treated at 1000-1200 ° C., pulverized and sintered to prepare a ceramic oxide powder, and a manufacturing process of the ceramic oxide powder by the solid phase method is illustrated in FIG. 1A.

The particle size of the ceramic oxide powder produced by the solid phase method varies depending on the size of the raw material powder, and the particle size of the powder produced is relatively large, such as 0.2-2 μm, which is not suitable for obtaining particles of 0.1 μm or less. There is a disadvantage that the heat treatment at a high temperature of 1000 ℃ or more.

In the combustion method, a homogeneous solution is prepared by adding a combustion aid to the raw materials and the solvent constituting the ceramic, and the resulting solution is heat-treated at a temperature of 500 ° C. or lower to cause a combustion reaction of the combustion aid. The primary product is a method of producing a ceramic oxide powder by further heat treatment at a temperature of 500 DEG C or more to crystallize. The manufacturing process of the ceramic oxide powder by the combustion method is shown in Fig. 1B.

In general, as a combustion aid, an acid such as nitric acid or polyacrylic acid, a nitrogen-containing compound such as glycine, or urea is used. Using a high heat of 1000 ℃ or more generated by the combustion of such a combustion aid to proceed with the instant ceramic production reaction.

In order to obtain a fine ceramic powder with a particle size distribution, metal alkoxides, nitrates, acetates, etc. are mainly used as raw materials, and an appropriate organic solvent or water is used as a solvent to dissolve these raw materials.

This conventional combustion method has the advantage of obtaining a fine powder of 0.1 ㎛ or less at a low temperature of about 500 ℃.

However, there is a disadvantage in that the combustion reaction is violently causing the flame and the gas to be generated rapidly, resulting in the scattering of the powder, and the volume of the combustion product is expanded and the volume / weight ratio is too large.

In addition, combustion reaction products are generally amorphous in the form of ash containing a large amount of unburned carbon, and the particles have not yet crystallized. Therefore, in order to crystallize, the product must be further heat treated at a temperature above 500 ° C. There are disadvantages.

In addition, depending on the raw materials used, the intermediate product self-aggregates and has a disadvantage in that it is difficult to deal with the adhesive force. In particular, when citric acid is added, an intermediate with high adhesion is formed.

In addition, when the ceramic oxide powder is prepared by the conventional method, since an excessive amount of acid is added, it is necessary to separately adjust the pH by adding a base, and at this time, an excessive amount of heat is generated by the neutralization reaction of the acid and the base, causing an explosion. There is a risk.

In manufacturing various film type devices using ceramics, a method of manufacturing ceramic paste using ceramic oxide powder and printing or molding the same on a diaphragm has been mainly used.

In particular, considering the recent situation in which miniaturization and elaboration of devices are important, it is urgent to develop a paste capable of printing or molding fine patterns and having a uniform quality.

In order to manufacture ceramic paste, conventionally, a binder that secures inherent properties as a paste, a vehicle that uniformly disperses ceramic particles to uniformize the paste and imparts proper fluidity for application to printing or molding, A method of mixing and stirring a ceramic particle having an average particle diameter of 1 μm prepared by a solid phase method to a solution in which a plasticizer that enables fine molding and a dispersant that gives homogeneity to a paste is dissolved in a solvent. Has been used.

The conventional method for producing a ceramic paste as shown in FIG. 3 is illustrated.

In this case, cellulose fiber such as ethyl cellulose is used as a binder, phthalate is used as a plasticizer, and terpineol is mainly used as a solvent.

In the case of using the ceramic oxide powder prepared by the conventional solid-state method, the above organic materials must be added. If the organic materials are not added, the viscosity of the ceramic paste is not controlled. When the ceramic paste is coated on the vibrating plate, the coating is made. There is a problem.

In addition, the ceramic paste prepared by this method is impossible to form at low temperatures because of the large size of the ceramic particles, the dispersant has a disadvantage that one-sided must be dependent on the supplier without any information on the composition or the manufacturing method.

In order to manufacture a ceramic film using the ceramic paste prepared by the above method, the ceramic paste is printed on a diaphragm, dried at 130 ° C. and heat-treated at 1000 ° C. or higher, and completely removed the added organic matter component before heat treatment after drying. There is a problem that a separate additional heat treatment should be performed at 500 ° C. or higher for the binder removal operation.

In addition, there is a problem in that the range of the selectable diaphragm is limited because the heat treatment should be performed at 1000 ° C. or higher.

In order to solve the above problems, the present invention provides a single process at low temperature by producing ceramic oxide powder by the combustion method using citric acid, which generates a high temperature of 1000 ° C. or more, and does not have a rapid combustion reaction as a combustion aid. It is an object of the present invention to provide a ceramic oxide powder having a very fine particle size and excellent reactivity, and a method of preparing the same.

In addition, the present invention can be formed at a lower temperature than the conventional ceramic paste by using the ultra-fine ceramic oxide powder, and the manufacturing process is simple, but the ceramic paste that can reproduce the inherent characteristics of the ceramic better in practical application and its It is an object to provide a manufacturing method.

1A is a process chart showing a manufacturing process of a ceramic oxide powder by a solid phase method;

1B is a process chart showing a manufacturing process of a ceramic oxide powder by a combustion method;

2 is a process chart showing a manufacturing process of the ceramic oxide powder according to the present invention;

3 is a process chart showing a manufacturing process of a conventional ceramic paste;

Figure 4 is a process chart showing a manufacturing process of the ceramic paste according to the present invention.

The present invention for achieving the above object comprises the steps of preparing a solution or dispersion mixture containing a ceramic component by dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium; Preparing a mixed solution by adding to the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, an amount or more citric acid necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component; And evaporating the solvent or dispersion medium by heat-treating the mixed solution at 100-500 ° C., and the added citric acid acts as a reducing combustion aid to remove the anion and non-explosive oxidation-reduction combustion reaction of the ceramic component. A method of preparing an ultrafine ceramic oxide powder in which an ultrafine ceramic oxide powder having a particle size of 1 μm or less and a uniform particle size distribution is finally obtained through a step of forming a ceramic oxide without scattering by heat of reaction, and an ultrafine ceramic oxide powder prepared by such a method. The fine ceramic oxide powder has its characteristics.

In another aspect, the present invention comprises the steps of preparing a solution or dispersion mixture containing a ceramic component by dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium; Preparing a mixed solution by adding to the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, an amount or more of citric acid required to cause an oxidation-reduction combustion reaction with the anion of the ceramic component; When the mixed solution is heat-treated at 100-500 ° C. to evaporate the solvent or the dispersion medium, the added citric acid acts as a reducing combustion aid to remove the anion and non-explosive oxidation-reduction combustion reaction of the ceramic component, and the reaction heat generated at this time The step of forming a ceramic oxide without scattering by the final step to obtain an ultra-fine ceramic oxide powder having a particle size of 1㎛ or less and uniform particle size distribution; Preparing a ceramic sol solution by dissolving ceramic components having the same or similar components as the ultrafine ceramic oxide powder based on water or an organic solvent; And preparing a ceramic paste by mixing the ultra fine ceramic oxide powder and the ceramic sol solution, wherein the ceramic sol solution acts as a reaction medium on the surface of the ultra fine ceramic oxide powder to react the powder surface. This improvement is characterized by the method of manufacturing a ceramic paste and the ceramic paste produced by such a method, which can be fired only by heat treatment at a low temperature.

Hereinafter, the present invention will be described in detail.

First, a method of manufacturing the ultrafine ceramic oxide powder as shown in FIG. 2 will be described.

In the method for preparing an ultrafine ceramic oxide powder of the present invention, a method of preparing a solution or dispersion mixture containing ceramic components by dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium, wherein the ceramic component is dissolved or Adding an amount of the citric acid or more necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component to the dispersed solution or the dispersion mixture, and preparing a mixed solution, and heat treating the mixed solution at 100-500 ° C. It may further comprise the step of increasing the crystallinity by further heat treatment at 700-900 ℃.

The raw material containing the ceramic component is selected from a ceramic component such as an oxide, carbonate or nitrate of the ceramic component, a salt of an organic or inorganic substance, or a complex of ceramic components.

As the ceramic component, it is preferable to use a piezoelectric / electrically distorted ceramic element having lead (Pb) and titanium (Ti) as a basic component.

In particular, the ceramic element is lead (Pb), zirconium (Zr), titanium (Ti) or lead (Pb), zirconium (Zr), titanium (Ti) / lead (Pb), magnesium (Mg), niobium (Nb) It is preferable to use what consists of components containing these.

As a solvent or dispersion medium for dissolving or dispersing the ceramic component raw material, one or more selected from among those capable of dissolving or dispersing the raw material containing the ceramic component in water or an organic solvent is used. Among the organic solvents, dimethyl formamide, methoxyethanol, acetic acid, glycols and alcohols are mainly used.

As a combustion aid, citric acid, an organic compound that can cause a combustion reaction, is used. In the conventional method, citric acid has been used to impart homogeneity of the reaction as a complexing agent, not as a combustion aid, and has been applied in processes such as the Pechini process. By using can cause a controlled combustion reaction rate.

The mixed solution is prepared by adding citric acid to a solvent or dispersed solution or dispersion mixture of ceramic components. The amount of citric acid to be added is added to the amount or more necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic element. The rate of progress of the reaction can be controlled depending on the amount of citric acid added.

The mixed solution mixed with citric acid is heat-treated at 100-500 ° C. As the temperature of the heat treatment increases, the crystallinity of the ceramic phase increases, but when the heat treatment temperature is 100 ° C. or higher, the combustion reaction of citric acid can be sufficiently initiated. The reaction may occur even when the heat treatment is performed above 500 ° C., but the heat treatment is performed at a higher temperature. Is meaningless compared to conventional methods.

More preferably, the heat treatment is carried out at 150-300 ° C., and the temperature range can sufficiently secure the crystallinity of the ceramic phase even at a considerably low temperature heat treatment.

Citric acid is removed during the combustion reaction, and ceramic oxide is formed without scattering by the heat of reaction of citric acid generated at this time.

In this reaction, components other than the ceramic component are removed by a combustion reaction for a sufficient time, thereby forming a ceramic oxide powder in a pure form in which impurities do not remain.

The ceramic oxide powder prepared by the above method is an extremely fine and uniform particle size distribution having a particle size of 1 μm or less, especially 0.01-0.1 μm, and having independent or weak aggregates of primary particles. It is present in the form of a fully burned ceramic phase and does not lose weight by further heat treatment.

In addition, since the surface is excellent in reactivity and can be formed only by heat treatment at low temperature, the degree of freedom of the vibration plate is high and various methods of printing on the vibration plate can be applied.

In order to increase the crystallinity of the prepared ultrafine ceramic oxide powder, the prepared ceramic oxide powder may further include heat treatment at 700-900 ° C.

A method of preparing a ceramic paste using the ultrafine ceramic oxide powder prepared as described above is shown in FIG. 4.

As a raw material of the ceramic paste, a ceramic sol solution prepared by dissolving a ceramic oxide powder and a ceramic component of the same or similar component having affinity with the ceramic oxide powder is used.

Since ceramic oxide powder is effective to use fine powder in consideration of its reactivity and to secure a system capable of low temperature molding, ceramic oxide powder prepared by the above method is used.

At room temperature, the surface of ceramic oxide powder is combined with more than one layer (monolayer) of water. The water bound to the surface affects the acidity and basicity of the surface of ceramic oxide powder. It is catalyzed when the sol solution is mixed.

Ceramic sol solutions are prepared by dissolving ceramic components based on water or organic solvents. Various organic solvents can be used as the base, but it is preferable to use mainly selected from acetic acid, dimethylformamide, methoxyethanol, glycols and alcohols.

The ceramic component used in the manufacture of the ceramic sol solution is preferably a component containing lead (Pb), zirconium (Zr), titanium (Ti), the concentration of the ceramic sol solution to be used is 0.1-5M It is preferable.

When the ceramic oxide powder and the ceramic sol solution are mixed, the content of the ceramic sol solution is preferably 10 to 200 parts by weight based on the ceramic oxide powder. This is because when the content of the ceramic sol solution is 200 parts by weight or more, the ceramic oxide powder is diluted too much and the viscosity of the mixture is low. When the content of the ceramic sol solution is less than 10 parts by weight, the amount of the ceramic oxide powder is too high and the viscosity becomes too high.

When the ceramic oxide powder and the ceramic sol solution are mixed, the liquid ceramic sol solution uniformly coats the surface of the solid ceramic oxide powder and connects the ceramic oxide powder particles to effectively fill the pores between the powders.

In the powder-sol mixture thus formed, the ceramic oxide powder having the characteristics of ceramics is surrounded by the ceramic sol solution of the same or similar component and has a proper fluidity. The ceramic sol acts as a reaction medium on the surface of the ceramic oxide powder and thus the powder surface. The reactivity of is improved.

In addition, the organic component contained in the sol, in the future when the mixture is in contact with a separate organic material, it is possible to secure the stability of the contact interface to impart dispersibility and homogeneity.

In such a system, since the sol is thermally decomposed at a low temperature and converted into the same or similar composition as the ceramic oxide powder, a ceramic system with improved inter-particle connectivity can be obtained even at low temperatures.

In order to ensure the stability of the mixture of the ceramic oxide powder and the ceramic sol solution and the fluidity required for molding, an organic solvent for controlling properties may be added. Various physical solvents may be used as the organic solvent for controlling physical properties, but it is preferable to use glycols or alcohols having a certain viscosity and low vapor pressure at room temperature.

When adding an organic solvent for controlling physical properties to the mixture of ceramic oxide powder and ceramic sol solution, the amount of the organic solvent for controlling physical properties is preferably 1-100 parts by weight based on the ceramic oxide powder. This is because if the amount of the organic solvent for controlling physical properties is less than 1 part by weight, the effect of adding the organic solvent for controlling physical properties is not effective, and if the amount is more than 100 parts by weight, the mixture does not maintain viscosity and is too diluted to deteriorate moldability during molding.

The addition amount of the organic solvent for controlling physical properties is particularly preferably 10 to 40 parts by weight with respect to the ceramic oxide powder. In this range, the addition of organic solvent can be achieved while maintaining the viscosity of the mixture as appropriate.

In addition, a small amount of organic matter may be added to the mixture of the ceramic oxide powder and the ceramic sol solution in order to improve the homogeneity and homogeneity of the mixture in which the solvent for controlling physical properties is added. At this time, it is preferable to use long-chain alcohols or polar organic solvents to add.

Among the long chain alcohols, it is preferable to use pentanol or hexanol, and it is preferable to use acetylacetone or methoxyethanol as the polar organic solvent.

It is preferable that the addition amount of an organic substance shall be 1-50 weight part with respect to a ceramic oxide powder. This is because if the added amount of the organic material is less than 1 part by weight, there is no effect of adding the organic material. If the added amount is more than 50 parts by weight, the mixture does not maintain the viscosity and is too diluted, resulting in poor moldability.

The addition amount of the organic material is particularly preferably 10 to 40 parts by weight based on the ceramic oxide powder. In this range, the addition of the organic material can be effected while maintaining the viscosity of the mixture as appropriate.

The ceramic paste prepared by the above method may form a ceramic film by heat treatment at 100-500 ° C. Heat treatment at a low temperature of 100-500 ° C is sufficient for the reaction that water on the surface of the ceramic oxide powder hydrolyzes the ceramic sol solution and that the ceramic constituents of the ceramic sol solution liberated by hydrolysis are combined with the ceramic oxide powder. This is because the same reaction as firing can be achieved by the reaction of the liver. In addition, organic matter added during the heat treatment is removed.

As mentioned above, since the film can be formed only by heat treatment at low temperature, the degree of freedom of the diaphragm is high, so that not only metal, ceramics such as nickel and stainless steel, but also organic compounds such as plastic or resin can be used as the diaphragm. Can be molded or printed using a screen.

The present invention will be described in detail through the following examples. However, the following examples are illustrative of the invention and do not limit the scope of the invention.

(Example 1)

105.3 g of lead nitrate [Pb (NO ₃ ) ₂ ] was dissolved in 300 ml of dimethylformamide to prepare a lead nitrate-DMF solution, and 43.1 g of zirconium nitrate hydrate [ZrO (NO ₃ ) ₂ .2H ₂ O] was 30 ml. A solution of zirconium peroxide was prepared by dissolving in water.

59.3 g of citric acid was added to the lead nitrate-dimethylformamide solution to completely dissolve it, and then 44.5 ml of titanium isopropoxide [Ti ( i -C ₃ H ₇ O) ₄ ] was added thereto, stirred, and completely homogenized, followed by aqueous zirconium peroxide solution. Slowly added to prepare a mixed solution.

The prepared mixed solution was heat treated at 200 ° C. using a heater. By heat treatment, water and dimethylformamide, which were solvents, were first evaporated, followed by the combustion reaction of citric acid.

The first combustion product was yellowish green, but as the combustion reaction progressed, it became pale orange and became yellowish white fine powder. After the container was cooled, the powder was collected and lightly ground in agate.

Samples obtained by further heat treatment of the original powder and the original powder at 300 ° C., 500 ° C. and 700 ° C. for 2 hours were subjected to X-ray diffraction (XRD), SEM (Scanning Electron Microscopy), and EDS (Energy Dispersive). The crystallographic structure, microstructure, particle size and composition were identified by spectroscopy, energy dispersive spectroscopy) and TGA (Thermogravimetric analysis).

As a result of TGA, the powder obtained after the combustion reaction was found to be a completely burned ceramic phase because no further weight loss was observed in the further heat treatment.

EDS results showed that all samples had a composition ratio of PZT (52/48).

As the heat treatment temperature increased, the crystallinity of the ceramic phase increased, but no phase transition or peak shift was found.

From the SEM results, it was found that the powder was present in the form of an independent particle or a soft aggregate with an average particle size of 50 nm.

(Example 2)

After dissolving 26.3 g of lead nitrate [Pb (NO ₃ ) ₂ ] in 200 ml of high-purity distilled water, 10.8 g of zirconium nitrate peroxide [ZrO (NO ₃ ) ₂ .2H ₂ O] was added to dissolve and titanium oxide. 2.9 g of (TiO ₂ ) was added and stirred to prepare a solution.

14.8 g of citric acid was added to this solution to completely dissolve it, and then heated to 200 ° C. using a heater.

By heating, the water first evaporated, the water evaporated and the combustion reaction of citric acid began, gradually expanding the whole vessel. After combustion, the container was cooled, the powder was collected and lightly ground in agate.

Crystallographic structure, microstructure, particle size and component were confirmed by XRD, SEM, EDS and TGA on the raw powder and the sample heat-treated at 300 ° C, 500 ° C and 700 ° C for 2 hours. It was the same as Example 1.

(Example 3)

207.8 g of lead nitrate [Pb (NO ₃ ) ₂ ] was dissolved in 350 ml of DMF, and 20.8 g of magnesium nitrate [Mg (NO ₃ ) ₂ ] was added to dissolve it, followed by titanium isopropoxide [Ti ( i -C ₃ H ₇ O). ₄ ] 50.9g was added to prepare a clear yellow solution.

A solution in which 50.8 g of zirconium peroxide hydrate [ZrO (NO ₃ ) ₂ .2H ₂ O] was dissolved in 100 ml of water was prepared separately and added to the above solution. 21.5 g of niobium oxide (Nb ₂ O ₁₁ ) and 108.3 g of citric acid were added to the solution, and the mixture was completely dissolved and heated to 150 ° C. After some evaporation of the solvent the temperature was raised to 250 ° C. and maintained.

Orange fine powder of the combustion reaction was collected and lightly ground in agate induction.

The crystallographic structure, microstructure, particle size and component were confirmed by XRD, SEM and EDS on the raw powder and the sample heat-treated at 700 ° C and 900 ° C for 3 hours, and the results are the same as those in Example 1. It was.

(Example 4)

20 g of PZT / PMN fine powder was mixed with 6 g of PZT (52/48) sol. 2 g of trimethylene glycol and 1 g of 1-pentyl alcohol were added, followed by stirring under autonomous induction.

The obtained paste was screen printed on a SUS 316L vibration plate and a nickel vibration plate using a fine pattern made of a 250 mesh steel screen.

After drying for 10 minutes at 70 ℃ was heat-treated for 2 hours at 300 ℃. The upper electrode was formed by vacuum deposition of aluminum, and the displacement of the diaphragm due to the piezoelectric phenomenon was measured by applying an electric potential.

As a result of measuring the displacement of the diaphragm, the piezoelectric properties represented by the displacement of the diaphragm were superior to the ceramic paste prepared by the conventional method.

(Example 5)

5 g of PZT / PMN fine powder was mixed with 3 g of PZT (52/48) sol, 2 g of 1-pentyl alcohol was added, and the mixture was stirred by autonomous induction.

The obtained paste was filled in a nickel vibrating plate to which a mold formed of a photosensitive film was attached. After drying at room temperature it was heat-treated for 1 hour at 200 ℃.

The silver paste was printed by screen printing to form an upper electrode, and the displacement was applied to the piezoelectric phenomenon by measuring the potential.

As a result of measuring the displacement of the diaphragm, the piezoelectric properties represented by the displacement of the diaphragm were superior to the ceramic paste prepared by the conventional method.

In the present invention as described above, by producing a ceramic oxide powder by the combustion method using citric acid as a combustion aid, the particle size of the particle is combusted extremely finely and completely by a single process at a temperature of 300 ° C. or less, and further heat treatment is performed. Since it is possible to manufacture an ceramic oxide powder that is not required, it is possible to secure process safety, low energy, and high yield, and the problems noted in the conventional combustion method do not occur.

In addition, the prepared ceramic oxide powder has excellent surface reactivity so that the viscosity can be adjusted only by additional mixing with ceramic sol solutions of the same or similar composition, and the coating can be performed without adding an organic substance. Since the film can be formed only by heat treatment, the applicability is high.

In other words, the high degree of freedom of the diaphragm can be used as a diaphragm, as well as metals such as nickel and stainless steel, ceramics, as well as organic compounds such as plastics and resins, it is possible to produce a film in various ways.

The ceramic paste prepared by the method of the present invention is suitable for practical applications such as printability and stability, and can be directly heat-treated without a separate binder process after printing, and a desired ceramic pattern can be formed at a much lower temperature than a conventional paste. There is an effect that can be obtained.

In addition, in the case of forming a ceramic film using the ceramic paste prepared by the method of the present invention, the piezoelectric properties represented by the displacement of the diaphragm, despite the low temperature treatment, are superior to the conventional results, and the components of the paste and the manufacturing process are simplified The manufacturing process of the ceramic thick film using the same has the effect of lowering energy and greatly reducing the lead time of the process.

Claims (64)

Dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium to prepare a solution or dispersion mixture containing the ceramic component; Preparing a mixed solution by adding to the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, an amount or more citric acid necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component; And When the mixed solution is heat-treated at 100-500 ° C. to evaporate the solvent or the dispersion medium, the added citric acid acts as a reducing combustion aid to remove the anion and non-explosive oxidation-reduction combustion reaction of the ceramic component, and the reaction heat generated at this time A method for producing an ultrafine ceramic oxide powder, which obtains an ultrafine ceramic oxide powder having a particle size of 1 µm or less and a uniform particle size distribution through a step of forming a ceramic oxide without scattering. The method of claim 1, wherein the ceramic component material is selected from a complex of a ceramic component such as an oxide, a carbonate or a nitrate of the ceramic component and an organic or inorganic material, or a complex of ceramic components. Ultrafine ceramic oxide powder manufacturing method. The method of claim 2, wherein the ceramic component is a piezoelectric / electrically distorted ceramic element based on lead (Pb) and titanium (Ti). The method of claim 3, wherein the ceramic component is made of a component containing lead (Pb), zirconium (Zr), titanium (Ti) or lead (Pb), magnesium (Mg), niobium (Nb) Ultrafine ceramic oxide powder production method characterized in that. The ultrafine ceramic oxide powder according to claim 1, wherein the solvent or dispersion medium is selected from one or more of organic solvents such as water, dimethylformamide, methoxyethanol, acetic acid, glycols, and alcohols. Manufacturing method. The method of manufacturing an ultrafine ceramic oxide powder according to claim 1, wherein the heat treatment temperature is 150-300 ° C. The method of claim 1, further comprising the step of further heat treatment at 700-900 ℃ to increase the crystallinity. The method of claim 1, wherein the ultrafine ceramic oxide powder has a particle size of 0.01-0.1 µm. The method of manufacturing an ultrafine ceramic oxide powder according to claim 1, wherein the citric acid is used as a combustion aid so that non-explosiveness is maintained during the oxidation-reduction combustion reaction to enable mass production. Dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium to prepare a solution or dispersion mixture containing the ceramic component; Preparing a mixed solution by adding to the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, an amount or more citric acid necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component; And When the mixed solution is heat-treated at 100-500 ° C. to evaporate the solvent or the dispersion medium, the added citric acid acts as a reducing combustion aid to remove the anion and non-explosive oxidation-reduction combustion reaction of the ceramic component, and the reaction heat generated at this time The step of forming a ceramic oxide without scattering by the final step to obtain an ultra-fine ceramic oxide powder having a particle size of 1 ㎛ or less and uniform particle size distribution; including a particle size of 1 ㎛ or less and the particle size distribution is Ultra fine ceramic oxide powder with good uniformity and surface reactivity. 11. The method according to claim 10, wherein the ceramic component raw material is selected from among a ceramic component such as an oxide, a carbonate or a nitrate of a ceramic component, a salt of an organic or inorganic substance, or a complex of a ceramic component. Fine ceramic oxide powder. 12. The ultrafine ceramic oxide powder according to claim 11, wherein the ceramic element is a piezoelectric / electrically distorted ceramic element based on lead (Pb) and titanium (Ti). The method of claim 12, wherein the ceramic component is lead (Pb), zirconium (Zr), titanium (Ti) or lead (Pb), zirconium (Zr), titanium (Ti) / lead (Pb), magnesium (Mg) Ultrafine ceramic oxide powder, characterized in that used as a component containing niobium (Nb). The ultrafine ceramic oxide powder according to claim 10, wherein the solvent or dispersion medium is one or more selected from water or organic solvents of dimethylformamide, methoxyethanol, acetic acid, glycols and alcohols. The ultrafine ceramic oxide powder according to claim 10, wherein the heat treatment temperature is set at 150 to 300 ° C. 11. The ultrafine ceramic oxide powder according to claim 10, further comprising the step of increasing the crystallinity by further heat treatment at 700-900 ° C. The ultrafine ceramic oxide powder according to claim 10, wherein the ultrafine ceramic oxide powder has a particle size of 0.01-0.1 µm. The ultrafine ceramic oxide powder according to claim 10, wherein the citric acid is used as a combustion aid to maintain non-explosiveness during oxidation-reduction combustion. Manufactured by non-explosive oxidation-reduction combustion reaction using citric acid as a combustion aid at low temperature of 100-500 ℃, ultrafine ceramics with particle size of less than 1㎛ and basic elements of lead (Pb) and titanium (Ti) Oxide powder. The method of claim 19, wherein the ceramic component is lead (Pb), zirconium (Zr), titanium (Ti) or lead (Pb), zirconium (Zr), titanium (Ti) / lead (Pb), magnesium (Mg) Ultrafine ceramic oxide powder, characterized in that used as a component containing niobium (Nb). 20. The ultrafine ceramic oxide powder according to claim 19, wherein the ultrafine ceramic oxide powder has a particle size of 0.01-0.1 mu m. 20. The ultrafine ceramic oxide powder according to claim 19, wherein the heat treatment temperature is 150-300 占 폚. Dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium to prepare a solution or dispersion mixture containing the ceramic component; Preparing a mixed solution by adding to the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, an amount or more citric acid necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component; When the mixed solution is heat-treated at 100-500 ° C. to evaporate the solvent or the dispersion medium, the added citric acid acts as a reducing combustion aid to remove the anion and non-explosive oxidation-reduction combustion reaction of the ceramic component, and the reaction heat generated at this time The step of forming a ceramic oxide without scattering by the final step to obtain an ultra-fine ceramic oxide powder having a particle size of 1㎛ or less and uniform particle size distribution; Preparing a ceramic sol solution by dissolving ceramic components having the same or similar components as the ultrafine ceramic oxide powder based on water or an organic solvent; And And preparing a ceramic paste by mixing the ultrafine ceramic oxide powder and the ceramic sol solution, and the ceramic sol solution acts as a reaction medium on the surface of the ultrafine ceramic oxide powder to increase the reactivity of the powder surface. The improved method for producing a ceramic paste, characterized in that the firing is possible only by heat treatment at low temperatures. 25. The method of claim 24, wherein the ceramic component is a component containing lead (Pb), zirconium (Zr) and titanium (Ti) in the preparation of the ceramic sol solution. 25. The method of claim 24, wherein the organic solvent serving as a base in the preparation of the ceramic sol solution is selected from acetic acid, dimethylformamide, methoxyethanol, glycols or alcohols. 25. The method of claim 24, wherein the concentration of the ceramic sol solution is 0.1-5M. 25. The method of claim 24, wherein the content of the ceramic sol solution is 10 to 200 parts by weight based on the ceramic oxide powder. 25. The ceramic according to claim 24, further comprising adding a solvent for controlling physical properties to the mixture of the ultrafine ceramic oxide powder and the ceramic sol solution to ensure the stability of the ceramic oxide powder-ceramic sol solution mixture and the fluidity required for molding. Method of Making Paste. 30. The method of claim 29, wherein the solvent for controlling physical properties uses glycols or alcohols. 31. The method of claim 30, wherein the amount of the solvent for controlling physical properties is 1-100 parts by weight based on the ceramic oxide powder. 32. The method of claim 31, wherein the amount of the solvent for controlling physical properties is 10 to 40 parts by weight based on the ceramic oxide powder. 30. The method of claim 29, further comprising adding a small amount of organic material to improve the homogeneity and homogeneity of the ceramic oxide powder-ceramic sol solution mixture. 34. The method of claim 33, wherein the organic material is a long chain alcohol or a polar organic solvent. 35. The method of claim 34, wherein the long chain alcohol is pentanol or hexanol. 35. The method of claim 34, wherein acetylacetone or methoxy ethanol is used as the polar organic solvent. 34. The method of claim 33, wherein the amount of the organic material added is 1-50 parts by weight based on the ceramic oxide powder. Dissolving or uniformly dispersing the ceramic component material in a solvent or a dispersion medium to prepare a solution or dispersion mixture containing the ceramic component; Preparing a mixed solution by adding to the solution or dispersion mixture in which the ceramic component is dissolved or dispersed, an amount or more citric acid necessary to cause an oxidation-reduction combustion reaction with the anion of the ceramic component; When the mixed solution is heat-treated at 100-500 ° C. to evaporate the solvent or the dispersion medium, the added citric acid acts as a reducing combustion aid to remove the anion and non-explosive oxidation-reduction combustion reaction of the ceramic component, and the reaction heat generated The step of forming a ceramic oxide without scattering by the final step to obtain an ultra-fine ceramic oxide powder having a particle size of 1㎛ or less and uniform particle size distribution; Preparing a ceramic sol solution by dissolving ceramic components having the same or similar components as the ultrafine ceramic oxide powder based on water or an organic solvent; And And preparing a ceramic paste by mixing the ultra fine ceramic oxide powder and the ceramic sol solution, and the ceramic sol solution acts as a reaction medium on the surface of the ultra fine ceramic oxide powder to increase the reactivity of the powder surface. Ceramic paste, characterized in that the firing is possible only by heat treatment at low temperatures. 39. The ceramic paste of claim 38, wherein the ceramic component comprises a component including lead (Pb), zirconium (Zr) and titanium (Ti) in the preparation of the ceramic sol solution. 39. The ceramic paste of claim 38, wherein the organic solvent serving as a base in the preparation of the ceramic sol solution is selected from acetic acid, dimethylformamide, methoxyethanol, glycols or alcohols. 39. The ceramic paste of claim 38, wherein the concentration of the ceramic sol solution is 0.1-5M. 39. The ceramic paste of claim 38, wherein the content of the ceramic sol solution is 10 to 200 parts by weight based on the ceramic oxide powder. 39. The ceramic according to claim 38, wherein the ultrafine ceramic oxide powder and the ceramic sol solution are further added with a solvent for controlling physical properties to ensure the stability of the ceramic oxide powder-ceramic sol solution mixture and the fluidity required for molding. Paste. 45. The ceramic paste of claim 43, wherein glycols or alcohols are used as the solvent for controlling physical properties. The ceramic paste according to claim 43, wherein the amount of the solvent for controlling physical properties is 1-100 parts by weight based on the ceramic oxide powder. 46. The ceramic paste according to claim 45, wherein the amount of the solvent for controlling physical properties is 10 to 40 parts by weight based on the ceramic oxide powder. The ceramic paste according to claim 43, wherein a small amount of organic matter is further added to improve dispersibility and homogeneity of the ceramic oxide powder-ceramic sol solution mixture. 48. The ceramic paste of claim 47, wherein the organic material is a long chain alcohol or a polar organic solvent. 49. The ceramic paste of claim 48, wherein the long chain alcohol is pentanol or hexanol. 49. The ceramic paste according to claim 48, wherein acetylacetone or methoxy ethanol is used as the polar organic solvent. 48. The ceramic paste according to claim 47, wherein the amount of the organic material added is 1-50 parts by weight based on the ceramic oxide powder. Manufactured by non-explosive oxidation-reduction combustion reaction using citric acid as a combustion aid at low temperature of 100-500 ℃, ultrafine ceramics with particle size of less than 1㎛ and basic elements of lead (Pb) and titanium (Ti) It is prepared by mixing an oxide powder with a ceramic sol solution of the same or similar component as the ultrafine ceramic oxide powder prepared on the basis of water or an organic solvent, and the ceramic sol solution is a reaction medium on the surface of the ultrafine ceramic oxide powder. The ceramic paste, characterized in that the reactivity of the powder surface is improved to be fired only by heat treatment at low temperatures. 53. The ceramic paste of claim 52, wherein the ceramic component is a component including lead (Pb), zirconium (Zr) and titanium (Ti) in the preparation of the ceramic sol solution. The ceramic paste according to claim 52, wherein the organic solvent serving as a base for the preparation of the ceramisol solution is selected from acetic acid, dimethylformamide, methoxyethanol, glycols or alcohols. The ceramic paste of claim 52, wherein the concentration of the ceramic sol solution is 0.1-5M. The ceramic paste of claim 52, wherein the content of the ceramic sol solution is 10 to 200 parts by weight based on the ceramic oxide powder. 53. The ceramic according to claim 52, wherein the ultrafine ceramic oxide powder and the ceramic sol solution are further added with a solvent for controlling physical properties to ensure the stability of the ceramic oxide powder-ceramic sol solution mixture and the fluidity required for molding. Paste. 59. The ceramic paste of claim 57, wherein glycols or alcohols are used as the solvent for controlling physical properties. 59. The ceramic paste according to claim 57, wherein the amount of the solvent for controlling physical properties is 1-100 parts by weight based on the ceramic oxide powder. 60. The ceramic paste according to claim 59, wherein the amount of the solvent for adjusting physical properties is 10-40 parts by weight based on the ceramic oxide powder. 60. The ceramic paste according to claim 57, wherein a small amount of organic matter is further added to improve the dispersibility and homogeneity of the ceramic oxide powder-ceramic sol solution mixture. 63. The ceramic paste of claim 61, wherein the organic material is a long chain alcohol or a polar organic solvent. 63. The ceramic paste according to claim 62, wherein the long chain alcohol is pentanol or hexanol. 63. The ceramic paste according to claim 62, wherein acetylacetone or methoxyethanol is used as the polar organic solvent. The ceramic paste according to claim 61, wherein the amount of the organic material added is 1-50 parts by weight based on the ceramic oxide powder.