KR101832144B1

KR101832144B1 - A method for manufacturing electromagnetism controllable ceramic compound particles

Info

Publication number: KR101832144B1
Application number: KR1020150097082A
Authority: KR
Inventors: 위성복; 최성철
Original assignee: (주)윈스; 전석원; 위성복
Priority date: 2015-07-08
Filing date: 2015-07-08
Publication date: 2018-02-26
Also published as: KR20170006454A

Abstract

In an embodiment of the present invention, there is provided a method for manufacturing a ceramic composite particle, comprising: preparing a solvent for dispersing ceramic compound particles, the volume ratio of an aprotic solvent constituting the solvent; Dispersing the ceramic compound particles in the solvent; Introducing and mixing a silicone compound into the dispersion to form a surface layer on the surface of the ceramic compound particle having a thickness in inverse proportion to the volume ratio of the aprotic solvent; Adding an acid or a base to the dispersion and heating the mixture; And drying the material obtained after the heating is completed to obtain a granular phase.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing ceramic compound particles capable of controlling electromagnetic characteristics,

The present invention relates to a method for producing ceramic compound particles capable of controlling electromagnetic characteristics, and more particularly, to a method for manufacturing ceramic compound particles capable of controlling electromagnetic characteristics by controlling the thickness of a surface layer of ceramic compound particles to change electron mobility and electric conductivity characteristics of ceramic compound particles. To a process for producing particles.

In modern quantum mechanics, it has been found that when the particle size of a material is reduced to the micrometer or nanometer level, qualitatively unique properties can be realized even in the same material, and thus the control of the particle size of the material affects the qualitative properties It has been proved that it can be a variable.

Particularly, in recent years, nanometer-sized ceramic particle materials have been widely used in various fields and their application possibility is also increasing. Particularly, interest in biotechnology, medicine, and BT has increased, and researches related to the synthesis, functionalization and application of ceramic particles have been actively carried out.

Attempts have been made to apply ceramic particles to pharmaceutical or biomedical fields, for example, taking into consideration such factors as the physicochemical properties of the ceramic particles, the stability of the colloid, and the possibility of bioavailability. In addition, the high-magnetic-field-sensitive ceramic particles made by surface modification can be used as a biocompatible material because the magnetic force is strengthened and extinction degree is controlled and the specific binding to the target site is induced according to the presence of the magnetic field.

In addition, the use of ceramic particles in various fields such as drug delivery, fever therapy, repair of damaged tissue, biological analysis and sensing, environmental restoration and water quality testing has become possible as well as contrast agents for magnetic resonance imaging (MRI).

In addition to these biological, medical, and pharmaceutical fields, the application range of ceramic particles from display fields to energy fields, aerospace materials, and battery materials fields is gradually expanding, There is an increasing demand for techniques for improving the dispersion stability and the structural stability of the particles themselves.

On the other hand, many researches have been conducted on the surface treatment of ceramic particles using hydrophobic silicates such as TEOS (Tetraethylorthosilicate) and TMOS (Tetramethoxysilane).

On the other hand, several techniques have been introduced to impart conductivity to ceramic particles for use as reflective displays, electronic shielding agents or absorbents for specific purposes, and techniques for imparting color to ceramic particles through structural color changes Is introduced.

For example, the photocrystallinity of ceramic particles may be changed to reflect color, thereby imparting electrical characteristics to the ceramic particles and controlling the arrangement of the ceramic particles to adjust the absorption and scattering properties of light. .

However, these methods have a problem that, in the production of the ceramic particles, an additional process such as a process of changing the photonic crystal or a process of giving the electrical characteristic must be involved.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to make it possible to control the electromagnetic characteristics of ceramic compound particles with an easy method.

According to an aspect of the present invention, there is provided a method of preparing a ceramic compound particle, comprising: preparing a solvent for dispersing ceramic compound particles, the volume ratio of an aprotic solvent constituting the solvent; Dispersing the ceramic compound particles in the solvent; Introducing and mixing a silicone compound into the dispersion to form a surface layer on the surface of the ceramic compound particle having a thickness in inverse proportion to the volume ratio of the aprotic solvent; Adding an acid or a base to the dispersion and heating the mixture; And drying the material obtained after the heating is completed to obtain a granular phase.

The solvent preparation step comprises adjusting the volume ratio of the aprotic solvent to the volume of the protic solvent constituting the solvent within a range of 1 or more or preparing the entire solvent with the aprotic solvent .

The silicon-based compound may have a polyfunctional group composed of at least one of a hydroxyl group, an amine group and a carboxyl group.

The method of manufacturing a ceramic compound capable of controlling the electromagnetic characteristics is characterized in that after the step of forming the surface layer, metal or carbide (carbide) particles are injected so that at least a part of the metal or carbide (carbide) particles and the multi- Induced, or coupled to each other.

The method for producing a ceramic compound capable of controlling the electromagnetic characteristics may further include, after the surface layer forming step, administering a dispersant together with the metal or carbide (carbide) particles.

The step of introducing and heating the acid or base may include adjusting the acid or base to be administered so that at least a part of the surface layer is etched in a range of 0.001 mol to 10 mol.

The method for producing a ceramic compound capable of controlling the electromagnetic characteristics comprises the steps of: after the step of obtaining the particulate phase, mixing the obtained particles with a suspension fluid to prepare a surface-treated ceramic compound solution; And adding a processing aid to the surface-treated ceramic compound solution, wherein the weight ratio of the processing aid to the fluid volume is adjusted so as to produce the surface-treated ceramic compound solution in any one of slurry, paste and gel Step < / RTI >

According to the embodiment of the present invention, it is possible to control the thickness of the surface layer, the dispersion degree according to the amount of the surface charge, and the amount of the metal or the metal compound by controlling the ratio of the content of the aprotic solvent in the solvent used in the step of preparing the dispersion of the ceramic compound particles. It becomes possible to control the bonding force with the carbide.

Also, according to the embodiment of the present invention, the surface electron mobility and conductivity of the finally obtained particles can be controlled only by controlling the content ratio of the aprotic solvent in the solvent used in the preparation of the dispersion of the ceramic compound particles.

Meanwhile, according to the embodiment of the present invention, a ceramic compound having controlled electromagnetic characteristics can be produced in a slurry, paste, or gel state by utilizing a processing aid.

1 is a flowchart illustrating a method of manufacturing a ceramic compound capable of controlling electromagnetic characteristics according to an embodiment of the present invention.
Figure 2 illustrates the role of the aprotic solvent in accordance with one embodiment of the present invention.
3 is a graphical representation of the results of measuring the zeta potential of the ceramic compound particles prepared according to an embodiment of the present invention.
FIG. 4 is a TEM (Transmission Electron Microscopy) image showing the characteristics of the ceramic compound particles prepared according to an embodiment of the present invention.
5 is a TEM image showing the thickness of a surface layer according to an embodiment of the present invention.
6 is a graphical representation of FT-IR (Fourier transform infrared spectroscopy) analysis results for a surface layer according to an embodiment of the present invention.
FIG. 7 is a graphical representation of a measurement result of the zeta potential with respect to the thickness of the surface layer according to an embodiment of the present invention.
Figure 8 is a graphical representation of the relationship between the ratio of aprotic solvent and magnetization density versus magnetic field in accordance with one embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" to another part, it includes not only "directly connected" but also "indirectly connected" . Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

As used herein, "dispersion" should be understood to mean a material in which solid particles are dispersed and suspended in a liquid.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view for explaining a method for producing ceramic compound particles capable of controlling conductivity according to an embodiment of the present invention; FIG.

Referring to FIG. 1, first, a step of dispersing the ceramic compound particles in a solvent to prepare a dispersion liquid is performed (S110).

Specifically, step S110 includes a step (S111) of preparing ceramic compound particles, a step (S112) of preparing an organic solvent, and a step (S113) of dispersing ceramic compound particles in a solvent to finally prepare a dispersion liquid.

The ceramic compound constituting the ceramic compound particles prepared in step S111 may be a metal or a non-metal compound represented by the following formula (1).

[Chemical Formula 1]

AxBy

Wherein A is selected from the group consisting of iron, manganese, chromium, cobalt, nickel, copper, zinc, samarium, gadolinium, neodymium, europium, barium, platinum, boron, aluminum, zirconium, silicon, titanium, tungsten, iridium, hafnium, Y is an integer of 1 to 5, and X and y are each independently an integer of 1 to 5, which is an element selected from the group consisting of indium, gold, silver, tin, magnesium or yttrium, B is boron, carbon, nitrogen, have.

Examples of the ceramic compound of Formula 1 include zirconium diboride (ZrB ₂ ), silicon carbide (SiC), magnetite (Fe ₃ O ₄ ), iron oxide (III) (Fe ₂ O ₃ ), boron carbide (B ₄ C), titanium diboride (TiB ₂ ), titanium nitride (TiN), titanium carbide (TiC), zirconium oxide (ZrO ₂ ) iridium oxide (IV) (IrO ₂ ) no.

When the ceramic compound contains a magnetic component such as nickel, copper or iron, it can be electromagnetically driven. On the other hand, when the ceramic compound does not include such a magnetic component, only electric driving is possible. And more preferably, it may be magnetite (Fe ₃ O ₄ ), or silicon carbide (SiC).

Further, the ceramic compound may be a metal or a non-metal compound represented by the following formula (2).

(2)

AxCzBy

Wherein A and C are selected from the group consisting of iron, manganese, chromium, cobalt, nickel, copper, zinc, samarium, gadolinium, neodymium, europium, barium, platinum, boron, aluminum, zirconium, silicon, titanium, tungsten, iridium, hafnium, Wherein x, y and z are each independently selected from the group consisting of lithium, gallium, indium, gold, silver, tin, magnesium and yttrium, B is boron, carbon, nitrogen, oxygen, May be one of integers from 1 to 5,

The ceramic compound represented by Formula 2 may be SiSiC, SiOC, SiO ₂ C, MnFeO ₃ , MnFeO ₄ , MnFe ₂ O ₃ , or MnFe ₂ O _{4 in} order to impart electromagnetic drive performance to the ceramic compound , But is not limited thereto.

In step S112, the organic solvent is prepared by mixing the proton magnetic solvent and the aprotic solvent to prepare an organic solvent. The volume of the proton magnetic solvent V _P and the volume V _A of the aprotic solvent And adjusting the mixing ratio (S112a).

The protic solvent may be a substance such as water, methanol, ethanol, t-butanol, acetic acid and the like.

The aprotic solvent may be at least one selected from the group consisting of halides, esters, ethers, ketones, amides, amines, lactones, carbonates, sulfones, nitriles, nitrates, phosphates, And mixtures thereof.

Specifically, the aprotic solvent may be a halogen-based solvent such as 1-chlorobutane, chlorobenzene, 1,1-dichloroethane, 1,2-dichloroethane, chloroform or 1,1,2,2-tetrachloroethane; Ester solvents such as methyl acetate, ethyl acetate, n-butyl acetate, cellosolve acetate, propylene glycol monomethyl acetate, 3-methoxybutyl acetate, methyl butyrate, ethyl butyrate and propyl propionate; Diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, octyl ether, hexyl ether, 1,4-dioxane, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethyl ether, dipropyl ether, dibutyl ether, ; Ketone solvents such as acetone, cyclohexanone, methyl amyl ketone, diisobutyl ketone, methyl ethyl ketone and methyl isobutyl ketone; Amide solvents such as N-methyl-2-pyrrolidone, 2-pyrrolidone, N-methylformamide, dimethylformamide, dimethylacetamide and tetramethylurea; Amine-based solvents such as triethylamine and pyridine; lactone type solvents such as? -butyrolactone; Carbonate-based solvents such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, ethylene carbonate, and dibutyl carbonate; Sulfone solvents such as dimethyl sulfoxide, diethyl sulfoxide, diethyl sulfone, and tetramethylene sulfone; Nitrile solvents such as acetonitrile and succinonitrile; Nitro-based solvents such as nitromethane and nitrobenzene; And phosphate-based systems such as hexamethylphosphoramide and tri-n-butylphosphate.

Considering the influence on the environment, the aprotic solvent may not contain a halogen atom, and the dipole moment of the aprotic solvent may be 3 to 5 from the viewpoint of solubility. Examples of the aprotic solvent having a dipole moment of 3 to 5 include amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and tetramethylurea, and lactone solvents. Dimethyl formamide, dimethylacetamide, N-methyl-2-pyrrolidone, but are not limited thereto.

The non-protonic solvent imparts (-) electric charge of -10 mV or more to the surface of the ceramic compound particles, whereby the repulsion force due to the electrostatic force is formed between the ceramic compound particles, The initial dispersion of the ceramic compound particles can be facilitated even without the dispersant. The initial dispersion of the ceramic compound particles is advantageous for subsequent surface modification or functionalizing.

The ratio (V _A / V _P ) of the volume (V _A ) of the aprotic solvent to the volume (V _P ) of the protonic solvent in step S112a is preferably selected to be 1 or more. If the value of V _A / V _P is less than 1, the ceramic compound particles can not be charged to a level necessary for dispersing the particles in the solvent, so that intergranular aggregation may occur. Further, there is a problem that a surface layer made of a silicon compound can be formed in an excessively thick film in a subsequent step.

On the other hand, according to the embodiment of the present invention, in the preparation of an organic solvent, the volume of the protic solvent (V _P) the ratio (V _A / V _P) of the volume (V _A) in an aprotic solvent for 1 By selecting appropriate values from the above values, the electron mobility and electrical conductivity of the finally obtained particles can be made to reach a desired value. That is, by adjusting the ratio (V _A / V _P ) of the volume (V _A ) of the aprotic solvent to the volume (V _P ) of the protonic solvent, the electromagnetic characteristics of the finally obtained particles can be appropriately adjusted have.

Specifically, depending on the ratio (V _A / V _P ) of the volume (V _A ) of the aprotic solvent to the volume (V _P ) of the protonic solvent, the thickness of the surface layer of the silicon compound to be formed in the subsequent step is varied. The amount of surface charge varies depending on the thickness of the surface layer of the silicon compound. Further, in a situation where a polyfunctional group is present in the silicon compound forming the surface layer, the degree of bonding between the polyfunctional group and the metal or carbide to be added subsequently may vary. That is, depending on the ratio (V _A / V _P ) of the volume (V _A ) of the aprotic solvent to the volume (V _P ) of the proton magnetic solvent, the electromagnetic characteristics of the finally obtained particles are changed, Physical properties such as attraction and repulsive force interacting with each other also vary.

If the intergranular distance is changed according to the physical properties of the particles, the wavelength of the light absorbed or scattered is changed. Accordingly, the color seen by the naked eye can be changed to realize the characteristic of color development in a desired color.

When the ratio (V _A / V _P ) of the volume (V _A ) of the aprotic solvent to the volume (V _P ) of the protonic solvent is increased, the thickness of the surface layer of the silicon compound to be formed in the subsequent step becomes thin. That is, the thickness of the surface layer is approximately inversely proportional to the ratio (V _A / V _P ) of the volume (V _A ) of the aprotic solvent to the volume (V _P ) of the protonic solvent.

When the thickness of the surface layer is reduced, the bond between the metal or the carbide to be added subsequently is also lowered when the silicon compound forming the surface layer has a polyfunctional group. As described later, the addition of a metal or a carbide is a process carried out for improving the inter-particle dispersion, and the distance between the particles becomes closer to each other as the degree of metal bonding with the polyfunctional group of the silicon compound becomes lower.

As the surface layer of the particles becomes thinner and the inter-particle dispersion becomes lower, the inter-particle distance becomes shorter, so that the wavelength of light absorbed or scattered moves to shorter wavelengths. Therefore, as the ratio of the volume (V _A ) of the aprotic solvent to the volume (V _P ) of the protonic solvent increases (V _A / V _P ), the color of the finally obtained particles corresponds to the shorter wavelength Color.

For example, the volume (V _P ) of the protonic solvent versus the volume (V _A ) of the aprotic solvent, V _P : When V _A is 1: 1, 1: 3 and 0: 1, the finally obtained particles are red, green and blue, respectively.

When preparation for the ceramic compound particles and the organic solvent is completed, the ceramic compound particles are dispersed in an organic solvent to prepare a dispersion (S113).

When step S110 is completed, a silicon compound is added to the dispersion and mixed to form a surface layer on the surface of the ceramic compound particles (S120).

Specifically, a silicone compound and a catalyst may be added to the dispersion prepared in step S110 and then mixed to form a surface layer of the silicone compound on the surface of the ceramic compound particles.

Many techniques for coating the surfaces of ceramic compound particles with conventional silicone compounds have been proposed, but protic solvents such as water and alcohols are mainly used as reaction media. In this case, the silicon compound is reacted with the hydroxyl group (-OH) of the protic solvent before being coated on the ceramic compound particles to hydrolysis or condensation, The reaction is difficult to control and the silica itself reacts or agglomerates. Therefore, an excess amount of the silicon compound is required for uniform coating, which results in a problem that the process efficiency is lowered.

[Reaction Scheme 1]

Si-OR + HOH? Si-OH + ROH

[Reaction Scheme 2]

Si - OH + HO - Si - Si - O - Si + H ₂ O

Si-OR + HO-Si-> Si-O-Si + ROH

Figure 2 illustrates the role of an aprotic solvent, for example, N-methyl-2-pyrrolidone, in accordance with one embodiment of the present invention. 2, in the dispersion prepared in step S110, the alkyl group of the N-methyl-2-pyrrolidone (110) molecule surrounding the ceramic compound particles 100 captures the hydroxyl group (-OH) (Δ-) of the N-methyl-2-pyrrolidone (110) molecule forms a hydrogen bond and an electrical bond with the hydrogen group (δ +) of the water molecule to deactivate the water molecule, And the reaction rate can be controlled. Side reaction can be suppressed and the reaction rate can be controlled. Therefore, not only the reactivity and the efficiency at the time of forming the silicon compound, but also the deterioration of cohesion and dispersibility can be prevented, and the electrical performance of the particles can be improved.

The silicone compound may be one selected from the group consisting of an alkylsilane compound, an alkoxysilane compound, a chain siloxane compound, a cyclic siloxane compound, and a mixture thereof.

The alkylsilane-based compound is preferably a compound having at least one alkyl group, preferably a C ₁ to C ₂₀ chain, cyclic, or cyclic alkyl group at a silicon atom such as dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, phenyldimethylsilane, phenylsilane, Or an aromatic alkyl group, and the type of the functional group that can be introduced into other compounds is not particularly limited.

The alkoxysilane compound may be selected from the group consisting of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetramethyldimethyldimethoxydisilane, dimethyldimethoxysilane Methacryloxypropyltrimethoxysilane, 3-mercapto-propyltrimethoxysilane, and the like, such as dimethylmethoxysilane (DMDMOS), diethoxymethylsilane (DEMS), methyltriethoxysilane (MTES) Is one or more alkoxy groups, preferably C ₁ to C ₅ alkoxy groups, and the kind of the functional group that can be introduced into other compounds is not particularly limited.

The chain siloxane-based compound may be a compound having a chain of repeating units of Si-O bonds such as polysiloxane and octamethyltrisiloxane (OMTS), and the kind of the functional group that can be introduced into other compounds is not particularly limited.

The cyclic siloxane-based compound may be a compound in which the repeating unit of Si-O bond forms a ring such as octamethylcyclotetrasiloxane (OMCTS), tetramethylcyclotetrasiloxane (TOMCATS), etc., and the functional groups that can be introduced into other compounds But is not limited thereto.

Meanwhile, according to a preferred embodiment of the present invention, the silicon-based compound may be selected from a silicon-based compound having a polyfunctional group.

The polyfunctional group may be composed of at least one of a hydroxyl group (OH), an amine group (NH ₂ ) and a carboxyl group (COOH), and in addition, a thiol group, an ester group, an epoxy group, a sulfone group, an alkoxy group, an aldehyde group, a ketone group, or the like.

The silicon-containing compound having such a polyfunctional group may be used in combination with other compounds such as tetraethyl orthosilicate (TEOS), aminopropyl trimethoxy-silane (APS), silane PEG carboxylic acid .

Tetraethyl orthosilicate (TEOS) is a hydroxyl group (OH), aminopropyl trimethoxy silane (APS) is an amine group (NH ₂ ), silane polyethylene glycol carboxylate (Silane PEG Carboxylic acid acid includes a carboxyl group (COOH).

Here, the amine group (NH ₂ ) is selected from the group consisting of monoamine, diamine, triamine, ethylene diamine, and diethylenetriamine. Or more.

On the other hand, the catalyst may be a known acid or base catalyst, for example, hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, ammonium hydroxide, and the kind thereof is not particularly limited.

When formation of a surface layer composed of a silicon compound or a silicon compound having a multifunctional group is completed in the ceramic compound particles, a metal material is added to the dispersion (S130).

The metallic material may be selected from the group consisting of iron, manganese, chromium, cobalt, nickel, copper, zinc, samarium, gadolinium, neodymium, europium, barium, platinum, boron, aluminum, zirconium, silicon, titanium, tungsten, iridium, hafnium, , At least one material selected from metals such as gold, silver, tin, and magnesium and yttrium carbide-based compounds, carbides (carbides) such as silicon carbide and titanium carbide, and mixtures of two or more thereof.

The metal or carbide (carbide) is ionized in the dispersion. When the surface layer of the ceramic compound particles is composed of a silicon compound having a polyfunctional group, the polarities of the polyfunctional group and the ionized metal or carbide material are different, (For example, covalent bond).

Therefore, the van der Waals force between the ceramic compound particles is weakened by the administration of the metal material, and the inter-particle dispersibility can be improved.

On the other hand, with the administration of the metal or carbide material, a dispersant may be further administered.

The amount of the dispersant may be selected to be not more than 5% by weight based on the total weight of the dispersion.

The dispersing agent may be a water-soluble dispersing agent comprising a water-soluble polymer or a water-soluble dispersing agent comprising an organic polymer.

The water-soluble dispersant may be a hydrophilic vinyl-based polymer such as polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl alcohol-polyvinylacetate copolymer and poly (N-vinylpyrrolidone); Polyalkylene glycols such as polyethylene glycol; Polyalkylene oxides such as polyethylene oxide and polyoxyethylene; Hydrophilic acrylic polymers such as polyhydroxyacrylate, polyacrylamide, polyhydroxyethyl acrylate, and polyacrylic acid; Polysaccharides such as polyaspartic acid, alginic acid, chitosan, hyaluronic acid, and dextran; Polyetherimide; Carboxymethylcellulose; Carbomer; gelatin; A carboxyl group-containing monomer unit; A sulfonic acid group-containing monomer unit; A phosphoric acid group-containing monomer unit; And a mixture thereof.

The oil-soluble dispersant may be a oil-soluble vinyl-based polymer such as polyvinylidene fluoride, polyvinylidene chloride, polyvinyl fluoride, polyvinyl chloride, polyvinyl bromide and polystyrene; But are not limited to, oleylamine, octylamine, hexylamine, butylamine, propylamine, hexadecylamine, octadecylamine, dioctylamine, dibenzylamine, dibutylamine, dihexylamine, trioctylamine, trihexylamine, tributyl Amines; Alkyl phosphates such as sodium alkyl phosphate, trioctyl phosphate and the like; Alkylphosphines such as trioctylphosphine, tributylphosphine and triphenylphosphine; Alkylphosphine oxides such as trioctylphosphine oxide; Olefins; Linoleic acid; Ricinoleic acid; Palmitic acid; Oleic acid; Stearic acid; Myristoylic acid; Palmitoleic acid; Sapietic acid; Arachidonic acid; Eicosapentaenoic acid; Erucic acid; Docosahexaenoic acid; Lauric acid; Dodecylic acid; Alkyldiols; Sodium alkyl sulphate; Monostearin; Polymethyl methacrylate; Sorbitan monooleate; Sorbitan trioleate; fatty acid; And a mixture thereof.

The dispersion force between the ceramic compound particles can be further increased by effectively applying the charge imparting and steric hindrance effect of the ceramic particles according to the addition of the dispersant.

When the metal or carbide (carbide) dosing step is completed, an acid or base is administered and heated (step S140).

When the acid or base is added, the acidic (pH) concentration of the dispersion is changed. If the ceramic compound particle has a negative zeta potential, the particles will become more strongly negative when the base is further added to the solution. On the contrary, when the acid is added, the particles reach a neutral point, and when the acid is further added, the particles are positively charged. That is, when the acidic (pH) concentration is lowered, the particles move in the direction of increasing the zeta potential. On the contrary, when the acidic (pH) concentration is higher, the particles move in the direction of lowering the zeta potential to 0V or lower. The surface charge of the ceramic compound particles can be induced by the above-mentioned principle by the administration of an acid or a base, so that the electrostatic bonding with the metal or carbide which has been administered in step S130 can be induced more effectively.

When acid or base administration and heating are performed, a part of the surface layer made of the silicon compound can be partially etched.

Part of the surface layer is etched so that some of the metal or carbide particles that have been applied in step S130 penetrate into the etched area, so that bonding between the surface layer-deposited particles and the metal or carbide particles can be more actively performed.

It is preferable to administer a base for surface layer etching, and it is preferable to appropriately control the amount of acid to be administered when an acid is administered. According to one embodiment, the acid to be administered is preferably adjusted within the range of 0.001 mol to 10 mol.

The base to be administered is selected from the group consisting of ammonia, ammonium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide, aluminum hydroxide, iron hydroxide, sodium bicarbonate, sodium carbonate, calcium carbonate, potassium carbonate, methylamine, , Preferably ammonium hydroxide, potassium hydroxide, or sodium hydroxide, but is not limited thereto.

On the other hand, the heating temperature after the acid or base administration is adjusted to 50 to 100 캜, preferably 50 to 80 캜.

After the acid or base administration and heating step, the product is dried to obtain a particulate phase (S150).

Meanwhile, according to the embodiment of the present invention, a slurry, paste or gel containing ceramic chemical particles can be obtained.

Specifically, the particles obtained according to step S150 are mixed with a water / oil suspension fluid (S160).

The particles are preferably administered in a weight ratio of 1 to 50% wt / vol to the volume of the suspended fluid.

The water-based fluid is composed of water and a water-soluble component, preferably 90-100 mass% water, and more preferably 95-100 mass% water and a water-soluble component.

The aqueous fluid may be water; Acetone; A hydrophilic alcohol solvent such as methanol or ethanol; Aldehyde solvent; A terpene derivative solvent such as an ester solvent and a ketone solvent; Ethyl acetate solvent; Chloroform solvent; Pyrrolidones such as N-methyl-2-pyrrolidone, 2-pyrrolidone and N-vinyl-pyrrolidone pyrrolidone solvents such as ethylene carbonate, propylene carbonate, 1,2-butylenes carbonate, 1,3-butylene carbonate, A carbonate solvent such as fluoro ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate or diethyl carbonate; As shown in FIG.

On the other hand, the oil-based fluid is composed of a water-insoluble component, preferably 90 to 100 mass% water-insoluble component, and more preferably 95 to 100 mass% water-insoluble component.

The flowable fluid may be an epoxide solvent such as dacane epoxide and dodecane epoxide; Vinyl ether solvents such as cyclohexyl vinyl ether and Decave (International Flavors & Fragrances, Inc., New York, NY); Aromatic hydrocarbon solvents such as toluene and naphthalene; Examples of the solvent include tetrafluorodibromo ethylene, trichlorethylene, tetrachlorethylene, trifluorochloroethylene, 1,2,4-trichlorobenzene, carbon tetrachloride, halogenated organic solvents such as tetrachloride, dichloromethane, dichloroethane and dichlorobenzene; Dodecane, tetradecane, aliphatic hydrocarbons of the Isopar series (Exxon, Houston, TX); Hydrocarbon solvents such as Norpar, naphtha, and other petroleum; Silicone oil solvents such as octamethylcyclosiloxane and high molecular weight cyclic siloxane, poly (methylphenylsiloxane) poly (methylphenylsiloxane), hexamethyldisiloxane, and polydimethylsiloxane; Low molecular weight halogen-containing polymer solvents such as Galden (perfluorinated ether of Ausimont, Morristown, NJ) and Krytox of Dupont (Wilmington, DE); Poly (chlorotrifluoroethylene) poly (chlorotrifluoroethylene) polymer (Halogenated hydrocarbon Inc., River Edge, NJ) solvent; As shown in FIG.

When the mixing in step S160 is completed, the shape and viscosity are adjusted by administering the mixture processing aid (S170).

Through processing aids, the form and viscosity of the mixture can be adjusted to a slurry, paste or gel type.

The processing aid is preferably thickened by adding 0.5 to 60% wt / vol of the weight ratio to the volume of the fluid. The state of the final product may be prepared as a slurry, a paste or a gel by adjusting the weight ratio to the volume of the fluid. Depending on the type of processing aid, the weight ratios to be added to the fluid volume may be different.

As the processing aid when the aqueous fluid is used in the mixing in step S160, a crosslinked acrylic acid polymer (CTFA name: carbomer); Methyl cellulose, ethyl cellulose, hydroxy ethyl cellulose, hydroxypropyl methyl cellulose, nitrocellulose, sodium cellulose sulfate, Carboxymethyl cellulose, microcrystalline cellulose, powdered cellulose, polyvinyl pyrrolidone, polyvinyl alcohol, carboxyvinylpolymer, guar gum, Gum, guar gum, hydroxypropyl guar gum, xanthan gum, arabic gum, tragacanth, galactan, carob gum, Agar, Cydonia oblonga Mill, starch (rice, corn, potato, wheat) (starch), algae colloid (wheat germ), carrageenin, carrageenin, pectin, colloid Cellulose derivatives and modified cellulose polymers such as cellulose derivatives; Microbiological polymers such as dextran, succinoglucan, and puleran; Starch based polymers such as carboxymethyl starch, methylhydroxypropyl starch; Based polymer such as sodium alginate, sodium propylene glycol alginate; Acrylate polymers such as sodium polyacrylate, polyethylacrylate, polyacrylamide, and polyethylene amine; Inorganic water-soluble substances such as bentonite, aluminum, magnesium, silicate, rapportneat, hectorite and anhydrous silicic acid; And acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, croto acid, Or carboxylic acid monomers obtained by copolymerizing a carboxylic acid monomer such as? -Chloroacrylic acid and a carboxyl ester having an alkyl chain of 1 to 30 carbon atoms, anionic and nonionic polymers such as carboxylic acid / carboxylate copolymers; Is used.

Meanwhile, as the processing aid in the case of using the oil-based fluid in the mixing in step S160, a hydrogenated styrene-isoprene block copolymer, ethylene and propylene rubber (OCP), acrylates or Polymers prepared by ester polymerization of the methacrylate group, polyisobutylene, disteardimonium fectorite, ozokerite, carnauba wax, Bis PEG-12 Dimethicone bees wax, Bis PEG-12 Dimethicone Candelillate, Bisphage-18 Dimethicone Methyl Ether Dimethylsilane ( Bis PEG-18 Dimethicone Methyl ether Dimethyl silane, Stearyl dimethicone, C30-45 Alkyl dimethicone and C30-45 olefin (C30-45 Olefin), Behenoxy dimethicone (Behenoxy Dimethicone), Stearoxy Dimethicone and Cetyl Dimethicone; Is used.

On the other hand, if necessary, the additive may be further administered together with the processing aid.

The additive comprises at least one of a dispersing agent, a flow enhancer, an antifoaming agent, an antioxidant, a UV absorber, and an organic film forming agent.

Hereinafter, various embodiments for producing ceramic compound particles surface-treated with a silicon compound will be described.

Example One

10 g of magnetite (Fe ₃ O ₄ ) particles were washed with 200 mL of DIW three times using a magnetic bar and DIW: N-methyl-2-pyrrolidone (NMP) was added at a volume ratio of 1: 1 The mixed organic solvent is added and ultrasonic waves are applied for 10 minutes to disperse the magnetite particles to prepare a dispersion.

Thereafter, 1000 mL of ethanol and the above dispersion were added to a 3 neck RBF (round bottom flask) having a capacity of 3 L and stirred for 10 minutes, then 10 mL of NH ₄ OH was added and stirred for 30 minutes. Thereafter, 20 mL of tetraethyl orthosilicate (TEOS) was added dropwise to the RBF, and the mixture was stirred for 12 hours.

On the other hand, a metal material solution containing platinum (Pt) and silver (Ag) and NMP are dispersed in a solvent by applying ultrasonic waves for 10 minutes to prepare a metal material solution, 10% by weight.

Thereafter, the metal material solution prepared in the RBF was added dropwise while stirring for 30 minutes, and then 15 mL of NH ₄ OH was added and the temperature of the RBF was raised to 80 ° C while stirring. Stirred for 12 hours while maintaining the temperature, washed three times with ethanol and dried at 80 DEG C to obtain a particulate product.

Example 2

Magnetite particles were prepared in the same manner as in Example 1, except that DIW: N-methyl-2-pyrrolidone (NMP) was mixed in a volume ratio of 1: 3 in the preparation of the magnetite dispersion. &Lt; / RTI >

Example 3

The surface treated magnetite particles were obtained in the same manner as in Example 1, except that a solvent composed solely of N-methyl-2-pyrrolidone (NMP) was used in the preparation of the magnetite dispersion.

Comparative Example One

The surface-treated magnetite particles were obtained in the same manner as in Example 1 except that a solvent consisting only of DIW was used in the production of the magnetite dispersion.

Comparative Example 2

Treated magnetite particles were prepared in the same manner as in Example 1, except that DIW: N-methyl-2-pyrrolidone (NMP) was mixed in a volumetric ratio of 3: 1 during the preparation of the magnetite dispersion. &Lt; / RTI >

Experimental Example 1: Depending on the composition of the mixed solvent Zeta potential Measurement experiment

The electrical properties of the surface-treated magnetite particles can be confirmed by measuring the Zeta potential. The particles dispersed in the solution are electrically or negatively charged by dissociation of the surface polar group and adsorption of ions. Therefore, in the vicinity of the particles, ions having an opposite sign existing in excess to neutralize the interface charge and ions having a small amount of the same charge are diffusively distributed. When an electric field is applied to the solution from the outside, the particles migrate in a direction opposite to the sign of the surface potential. The intensity of the electric field and the hydrodynamic effect (viscosity of the solvent, permittivity, etc.) The calculated value is the zeta potential.

The zeta potential represents a potential on a slip plane near the interface between the pinned layer and the diffusion layer. However, since it is difficult to directly measure the surface potential of the colloidal particles, the information on the surface potential can be obtained mainly from the zeta potential value obtained by the electrophoresis experiment. In the case of fine particles or colloids, when the absolute value of the zeta potential obtained experimentally is high, the repulsive force between the particles is strengthened to increase the stability of the particles, while when it is small, the particles tend to aggregate.

Generally, if the absolute value of the zeta potential is less than 10 mV, the electric characteristic is weak because the electric charge is hardly applied. Therefore, the zeta potential can be used as a measure of the dispersion stability of the particles.

The results of measuring the zeta potential of the magnetite particles surface-treated in accordance with Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Fig. Referring to FIG. 3, the magnetization particles of Comparative Examples 1 and 2 were found to have weak electrification levels of 5.0 mV and -10.0 mV, respectively. In Examples 1 to 3, however, the magnetite particles exhibited an electric or electromagnetic It was verified that the motor was sufficiently charged for driving.

Experimental Example 2: Depending on the composition of the mixed solvent Intergranular Physical Characteristics Analysis

Comparative Example 1 and the sample for 2 and are shown in the first embodiment by sampling a result of the TEM measurement Figure 4 (a) to 4 in (c).

4 (a) and 4 (b) are TEM images of the samples of Comparative Example 1 and Comparative Example 2, respectively, and FIG. 4 (c) is a TEM image of the sample of Example 1.

4A and 4B, when the proton magnetic solvent is 100% (FIG. 4A), when the volume ratio of the proton magnetic solvent to the non-protic solvent NMP is 3: 1 4 (b)), it can be seen that the physical and electromagnetic characteristics including the degree of dispersion between particles are not uniform.

On the other hand, referring to FIG. 4 (c), it can be seen that when the ratio of the proton magnetic solvent to the NMP as the aprotic solvent is 1: 1, the inter-particle dispersion is uniform and stable electromagnetic characteristics are exhibited.

This is because when the volume ratio of NMP which is an aprotic solvent to the protonic solvent is 1 or more, the TEOS coating layer is formed to have an appropriate thickness and the bonding with the metal is made smoothly, .

In addition, as described with reference to Fig. 3, in Comparative Examples 1 and 2, since the zeta potential is close to 0 V, it is explained that the charging level of the particles is weak and the stability of the electrical characteristics is degraded.

Experimental Example 3: Depending on the composition of the mixed solvent Morphology ( morphology ) analysis

After dropwise addition of 20 mL of tetraethylorthosilicate (TEOS) and stirring were completed in Examples 1 to 3, the results of TEM and FT-IR analyzes of the respective samples were shown in Figs. 5 and 6, respectively .

5 (a) to 5 (c) are TEM images of the samples of Examples 1 to 3, respectively. 5, as the relative content of NMP as an aprotic solvent increases to 1: 1, 1: 3, and 100%, the thickness of the surface layer made of the silicon compound is about 30 nm, 15 nm to 18 nm, and 8 nm to 10 nm As shown in Fig.

Referring to FIG. 6, it can be seen that as the relative content of NMP as an aprotic solvent to protic solvents increases to 1: 1, 1: 3, and 100%, the transmittance gradually decreases in the entire wavelength range. This is because as the relative content of NMP as an aprotic solvent increases to 1: 1, 1: 3, and 100%, the thickness of the TEOS layer becomes thinner, so that the distance between particles becomes relatively close.

On the other hand, from Fig. 6, peaks corresponding to Si-O bonds were observed in all of Examples 1 to 3, and it was found that a surface layer made of TEOS was well formed on the surface of the magnetite particles.

Experimental Example 4: Depends on the thickness of the surface layer Zeta potential Measurement experiment

The relationship between the thickness of the TEOS layer formed on the surface of the magnetite particles and the measured zeta potential according to Examples 1 to 3 is shown in Fig. Referring to FIG. 7, in Examples 1 to 3 in which the TEOS layer has a thickness of 30 nm, 15 nm to 18 nm, and 8 nm to 10 nm, the zeta potential increases as the thickness of the TEOS layer increases. However, Indicating a zeta potential value of less than -10 mV.

As described above, if the absolute value of the zeta potential is less than 10 mV, the electric characteristics are insufficient because almost no electric charge is applied. In the case of Examples 1 to 3, the absolute values of zeta potential are all 10 mV or more, It can be said that the electric field is sufficiently charged for electric or electromagnetic driving.

Experimental Example 5: Measurement of magnetization density according to thickness of surface layer

Figs. 8 (a) to 8 (c) show graphs of magnetization densities measured when a magnetic field is applied to each of Examples 1 to 3 above.

8 (a) to 8 (c), as the relative content of NMP, which is an aprotic solvent for protic solvents in organic solvents, is increased to 1: 1, 1: 3, and 100% Lt; RTI ID = 0.0 > magnetization < / RTI >

As described above, since the thickness of the TEOS layer becomes thinner as the relative content of NMP as an aprotic solvent increases, the interval between the magnetite particles decreases. Therefore, as the relative content of NMP as an aprotic solvent increases, the value of magnetization density increases with magnetic field application.

Hereinafter, examples of a method for producing the magnetite particles obtained in the above Examples 1 to 3 in a slurry, paste or gel state will be described.

Example 4

After dissolving 0.4 g of polyvinylpyrrolidone in 34 mL of water, 8 g of magnetite particles were added and dispersed by ultrasonic wave for 30 minutes.

When the above dispersion is carried out, 1 g of xanthan gum and 1.5 g of gelatin are added to the mixture at a rate of about 10 times while slowly maintaining the temperature at 50 캜.

At this time, sufficiently wait until the dispersant completely melts, then divide the temperature by 5 steps, cool slowly, and maintain at 5 캜 for 20 minutes to prepare a magnetite particle paste that maintains paste state even at room temperature.

Example 5

After dissolving 0.6 g of OLOA in 30 mL of Isopar G solvent, 6 g of magnetite particles are added and dispersed for 30 minutes by ultrasonic waves.

10 g of polyisobutylene dissolved in a solvent of 5 wt% Isopar G was added to the mixture as a processing aid while the mixture was dispersed and maintained at 50 캜 while stirring with ultrasonic waves.

After sufficiently waiting until both of the two solutions are mixed, the temperature is cooled slowly to 5 steps and maintained at 5 캜 for 20 minutes to produce a magnetite particle paste that maintains the paste state even at room temperature.

Example 6

3 g of carboxyvinyl polymer was added to 36 mL of ethanol and stirred at about 50 DEG C for 20 minutes.

When the solvent becomes transparent, 0.2 g of polyvinylpyrrolidone is dissolved, 4 g of magnetite particles are added, and the mixture is subjected to ultrasonic treatment at 50 캜 for about 10 minutes to disperse the particles.

When the particles of the mixture are dispersed evenly, 3 g of carboxymethyl cellulose is added as a processing aid to the mixture, and the mixture is allowed to dissolve for a sufficient time.

Next, when the carboxymethyl cellulose is completely dissolved, the solution is slowly cooled to 5 steps, and the magnetite particle gel is maintained at 10 캜 for 30 minutes to maintain the gel state even at room temperature.

Example 7

3 g of stearoxydimethicone was added to 34 mL of tetrachlorethylene, and the mixture was stirred at about 50 DEG C for 20 minutes.

When the solvent becomes transparent, 0.4 g of OLOA is dissolved, 4 g of magnetite particles are added, and the mixture is subjected to ultrasonic treatment at 50 캜 for 10 minutes to disperse the particles.

When the particles of the mixture are uniformly dispersed, 4 g of the zinc stearate is mixed and sufficiently dissolved in the processing aid as the processing aid.

After confirming that all of the processing aid is dissolved, the temperature is cooled slowly to 5 steps, and the magnetite particle paste is maintained at 10 캜 for 30 minutes to maintain the gel state even at room temperature.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

100: Ceramic compound particles
200: Silicone compound
210: Surface layer

Claims

The DIW and N-methyl-2-pyrrolidone were mixed so that the volume ratio of N-methyl-2-pyrrolidone (NMP) to the volume of DIW was not less than 1, Preparing an organic solvent using the organic solvent;
Dispersing the magnetite particles in the solvent;
Introducing TEOS into the dispersion in which the magnetite particles are dispersed in the solvent and mixing them to form a surface layer having a thickness in inverse proportion to the volume ratio of the N-methyl-2-pyrrolidone on the surfaces of the magnetite particles;
Adding an acid or a base to the dispersion and heating the mixture; And
And drying the obtained material after heating is completed to obtain a granular phase.

delete

The method according to claim 1,
After the surface layer forming step,
Further comprising the step of administering metal or carbide particles to cause at least some of the metal or carbide particles and the functional groups of the TEOS to be mutually coupled or bonded.

5. The method of claim 4,
After the surface layer forming step,
Further comprising the step of administering a dispersant together with said metal or carbide particles.

The method according to claim 1,
The step of adding and heating the acid or base,
And adjusting the acid or base to be administered so that at least a part of the surface layer is etched, within a range of 0.001 mol to 10 mol.

The method according to claim 1,
After the particulate phase obtaining step,
Mixing the obtained particles with a suspension fluid to prepare a surface-treated magnetite solution; And
Further comprising the step of adding a processing aid to the surface-treated magnetite solution, and adjusting the weight ratio of the processing aid to the fluid volume so as to produce the surface-treated magnetite solution in any one of slurry, paste and gel Wherein the ceramic composition is capable of controlling electromagnetic characteristics.