WO2006001225A1 - Corps formé de cristal de corindon - Google Patents

Corps formé de cristal de corindon Download PDF

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Publication number
WO2006001225A1
WO2006001225A1 PCT/JP2005/011115 JP2005011115W WO2006001225A1 WO 2006001225 A1 WO2006001225 A1 WO 2006001225A1 JP 2005011115 W JP2005011115 W JP 2005011115W WO 2006001225 A1 WO2006001225 A1 WO 2006001225A1
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Prior art keywords
corundum crystal
corundum
flux
alumina
compound
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PCT/JP2005/011115
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English (en)
Japanese (ja)
Inventor
Katsuya Teshima
Shuji Oishi
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Dai Nippon Printing Co., Ltd.
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Priority to JP2006528492A priority Critical patent/JPWO2006001225A1/ja
Publication of WO2006001225A1 publication Critical patent/WO2006001225A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5072—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with oxides or hydroxides not covered by C04B41/5025
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00241—Physical properties of the materials not provided for elsewhere in C04B2111/00
    • C04B2111/0025—Compositions or ingredients of the compositions characterised by the crystal structure

Definitions

  • the present invention relates to a corundum crystal composition that can be used for, for example, a material for high hardness, a cutting material, a laser oscillation material, a standard material for measuring physical properties, jewelry, and high value-added daily necessities.
  • Corundum crystals are excellent in chemical resistance, wear resistance, and weather resistance, and show high electrical insulation even in high-temperature environments. Therefore, corundum crystals, instrument bearings, micro scalpels, optical switch elements, or laser oscillations are used. It is used for materials.
  • a flame melting method (Bernoulli method) in which crystal grains are grown while dropping a raw material powder of a corundum crystal in an oxygen and hydrogen flame, (2) corundum The raw material powder of the crystal is mixed with an appropriate flux and melted in a crucible, and the crystal is precipitated and grown while the solution is slowly cooled, or the solution is precipitated with a temperature gradient in the crucible and grown.
  • Non-Patent Document 1 and Non-Patent Document 2 a flux method in which crystals are precipitated and grown while the flux is evaporated.
  • the raw powder of corundum crystal is melted in a crucible, (4) A method of forming a raw powder of corundum crystals and then sintering it by heating at a high temperature for a long time in a hydrogen gas atmosphere (Patent Documents) (See 3) I can get lost.
  • the corundum crystal obtained by the above-described method can be stuck on the substrate, but the corundum crystal is poor in adhesion between the corundum crystal and the substrate, and the corundum crystal is easily peeled off. There is.
  • corundum crystals dark red corundum crystals to which chromium is added are generally called rubies. Since natural ruby is produced in a relatively small amount, corundum crystals that are close to natural rubies. There is a need for a method that allows the substrate to grow directly on the substrate.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 7-277893
  • Patent Document 2 JP-A-6-199597
  • Patent Document 3 Japanese Patent Laid-Open No. 7-187760
  • Non-Special Reference 1 Elwell D., Man-made gemstones, Ellis Horwood Ltd., Chichester (197 9)
  • the present invention has been made in view of the above problems, and a corundum crystal formed body in which a corundum crystal is directly grown on a substrate, and the corundum crystal formed body can be easily and inexpensively manufactured.
  • the main purpose is to provide a simple manufacturing method.
  • the present invention provides a corundum crystal formed body comprising an alumina base material and a corundum crystal formed on the alumina base material.
  • corundum crystals are formed directly on the alumina base material, and the corundum crystals are grown directly on the alumina base material.
  • the adhesive strength between the alumina base material and the corundum crystal is strong, and it can be used for various applications.
  • the corundum crystal may be colorless.
  • a coloring component at least one element selected from the group force consisting of chromium, iron, titanium, nickel, vanadium and cobalt may be added.
  • the present invention is characterized in that the flux and the alumina base material are heated to form a corundum crystal on the alumina base material by a flattening evaporation method in which the crystal is precipitated and grown using the evaporation of the flux as a driving force.
  • a method for producing a corundum crystal formed body is provided.
  • the alumina base material becomes a solute, it is possible to grow a corundum crystal directly on the alumina base material, and the corundum has an extremely strong adhesive force between the alumina base material and the corundum crystal.
  • a crystal former can be produced.
  • corundum crystals may contain elements contained in the flux as impurities, and since they are close to natural corundum crystals, corundum crystals that are highly valuable as jewelry are formed.
  • the body can be manufactured. Furthermore, since the apparatus used in the flux evaporation method is simple and the manufacturing process is simple, a high value-added corundum crystal formed body can be provided at low cost.
  • the flux preferably contains a molybdenum compound.
  • the molybdenum compound is preferably molybdenum oxide or a compound that generates acid molybdenum by heating. Molybdenum compounds can be evaporated relatively easily and are therefore preferred as fluxes used in the flux evaporation method.
  • the flux may contain an evaporation inhibitor! /. This is because the flux evaporation rate is suppressed, and the generation of multinuclei and the crystal growth rate can be suppressed, so that high-quality corundum crystals can be obtained.
  • the evaporation inhibitor is an alkali metal compound.
  • the alkali metal compound is preferably an alkali metal oxide or a compound that generates an alkali metal oxide by heating.
  • the corundum crystal can be grown directly on the alumina base material using the alumina base material as a solute by the flux evaporation method, the adhesive strength between the alumina base material and the corundum crystal is strong. There is an effect.
  • a corundum crystal close to natural corundum crystals can be obtained, it has the effect of high value as a jewelry.
  • FIG. 1 is a schematic cross-sectional view showing an example of a corundum crystal formed body of the present invention.
  • FIG. 2 is a photograph showing an example of a cross section of the corundum crystal formed body of the present invention.
  • FIG. 3 is a photograph showing another example of a cross section of the corundum crystal formed body of the present invention.
  • FIG. 4 is a diffraction diagram showing an example of an X-ray diffraction pattern of a corundum crystal in the corundum crystal formed body of the present invention.
  • FIG. 5 is a process chart showing an example of a method for producing a corundum crystal formed body of the present invention.
  • the corundum crystal formed body of the present invention is formed on an alumina substrate and the alumina substrate.
  • FIG. 1 is a schematic cross-sectional view showing an example of a corundum crystal formed body of the present invention.
  • the corundum crystal formed body 1 of the present invention has an alumina base 2 and a corundum crystal 3 formed on the alumina base 2.
  • Fig. 2 and Fig. 3 show examples of photographs taken with a scanning electron microscope (manufactured by Hitachi, Ltd., S-5000) of a cross section of the corundum crystal formed body of the present invention.
  • the corundum crystal formed body of the present invention has nothing between the alumina substrate 2 and the corundum crystal 3, and is directly on the alumina substrate 2. Crystal 3 has grown. Therefore, the corundum crystal formed body of the present invention has an advantage that the adhesive strength between the alumina base material and the corundum crystal is different from that obtained by pasting the corundum crystal on the alumina base material, and is used for various applications. It is possible.
  • FIG. 3 is a photograph showing an example of a cross section of a corundum crystal formed body having a corundum crystal to which chromium is added as a coloring component.
  • the collandum crystal in the present invention is formed on an alumina substrate described later.
  • the corundum crystal has a random structure belonging to the trigonal system.
  • the cation (A1) regularly occupies 2Z3 in the hexacoordinate (octahedron) position of the lattice packed almost hexagonally close, and the AIO octahedron centered on the cation (A1).
  • the surface is shared in part and connected in the c-axis direction.
  • Corundum (Al 2 O 3) is the most stable of the alumina polymorphs.
  • Corundum crystals with a structure have a melting point of about 2050 ° C, high hardness (Mohs hardness 9), and excellent chemical resistance, wear resistance, and weather resistance. It also exhibits high electrical insulation even in high temperature environments. Because of these properties, corundum crystals are used in instrument bearings, micro knives, optical switch elements, laser oscillation materials, and the like. In addition, a part of A1 of corundum (Al 2 O 3) is replaced with Cr, Ti, Fe, etc. These crystals are generally called rubies and sapphires and are used as jewelry.
  • the corundum crystal used in the present invention may be colorless, or may be selected as a coloring component from a group force consisting of chromium, iron, titanium, nickel, vanadium and cobalt. At least one element is added. It may be.
  • the combination of elements of the coloring component is not particularly limited, for example, chromium only; nickel only; vanadium only; cobalt only; iron and titanium; nickel , Titanium and iron; chromium and nickel; chromium, nickel and iron; combinations of chromium, titanium and iron, and the like.
  • corundum crystals have different hues depending on the type of coloring component such as chromium, iron or titanium.
  • coloring component such as chromium, iron or titanium.
  • the color is colorless, the color added with nickel is yellow, the vanadium added is alexandrite color, the cobalt is green, iron and titanium. Blue added, nickel added, titanium and iron added yellow-green, chromium added dark red, red or pink, chromium and nickel, or chromium, nickel and iron added The one with orange is added, and the one with chrome, titanium and iron added becomes purple.
  • a corundum crystal having the above hue can be obtained by combining elements as described above.
  • a dark red corundum crystal to which chromium is added is called ruby
  • corundum crystals other than the red corundum crystal of the chrome-added basket are called sapphire.
  • Natural ruby has a high rare value, and in the present invention, by adding chrome to the corundum crystal, a corundum crystal formed body having a red corundum crystal close to the natural corundum crystal can be obtained. Therefore, a corundum crystal formed body with high added value can be obtained.
  • EPMA electron beam microanalyzer
  • XPS X-ray photoelectron spectroscopy
  • EDX energy dispersive X-ray analysis
  • the content of the element in the corundum crystal varies depending on the type of element. As long as the amount of corundum crystals to be colored is contained, it may be a very small amount.
  • the composition of the corundum crystal is not limited to the stoichiometric one, but may be deviated from the stoichiometric composition.
  • the corundum crystal formed body of the present invention is produced by a flux evaporation method, which is preferably produced by a flux evaporation method as described later, the element contained in the flux is contained as an impurity in the corundum crystal.
  • the content of impurities in the corundum crystal is usually a very small amount of lmol% or less.
  • the corundum crystal can be identified using an X-ray diffractometer.
  • c 12.993A
  • JCPDS No. 46-1212 An example of an X-ray diffraction pattern of a corundum crystal obtained by adding chromium as a coloring component in the present invention is shown in FIG. 4 (a).
  • Figure 4 (a) shows the X-ray diffraction pattern measured by grinding to identify corundum crystals.
  • Fig. 4 (b) is the X-ray diffraction pattern of CPDS No. 46-1212.
  • the X-ray diffraction patterns of Figs. 4 (a) and 4 (b) were measured using CuKo; lines.
  • the corundum crystal formed body is preferably produced by a flux evaporation method! /.
  • a corundum crystal can be formed using an alumina base material described later as a solute, and a corundum crystal can be formed directly on the alumina base material.
  • corundum crystals obtained by the flux evaporation method may contain elements contained in the flux as impurities, they can be made into crystals containing impurities in the same way as natural corundum crystals. This is because it has the advantage of high value.
  • the equipment used in the flux evaporation method is simple as long as it has a high-temperature furnace, and corundum crystals can be obtained easily.
  • corundum crystal forming method such as a flux evaporation method is described in the section “B. Method for manufacturing corundum crystal formed body”, which will be described later.
  • the corundum crystal may intentionally contain impurities. As described above, by containing impurities, it can be made close to nature, and it has a great value as a jewelery product.
  • the corundum crystal may be formed on the entire surface of an alumina base material to be described later, or may be formed on a part thereof. The formation position of such a corundum crystal is appropriately selected according to the use of the corundum crystal formed body of the present invention.
  • an alumina substrate may be used alone, or an alumina substrate and a substrate may be laminated and used.
  • Such an alumina base material is not particularly limited as long as it is mainly composed of alumina, but the content of impurities with respect to alumina in the alumina base material is 5% or less. Is preferable, and it is preferably 1% or less. If the content of impurities relative to alumina is too high, there is a high possibility that impurities will be eluted when corundum crystals are formed, and this may lead to the possibility that crystallization of corundum crystals may be hindered. .
  • Examples of such impurities include general ones such as SiO,
  • the base material to be used is not particularly limited as long as it can form an alumina base material and does not adversely affect the formation of corundum crystals. Although not limited, it is preferable that it can withstand the maximum holding temperature described in the heating / evaporation process section of “B. Corundum crystal forming body” described later.
  • Examples of such a substrate include platinum, sapphire, alumina silica, silicon carbide, and alumina. Since the alumina substrate is not required to have a low impurity content and high purity, unlike the alumina substrate, it may be of low purity.
  • the alumina substrate may be partially formed or may be formed on the entire surface of the substrate, but may be partially formed.
  • platinum is used as the substrate. It is preferable to use it.
  • a substrate made of alumina is partially formed on a substrate other than platinum, when forming a corundum crystal, part of the substrate may elute and adversely affect the formation of the corundum crystal. Because. In addition, platinum is considered to have no effect on the formation of corundum crystals with low reactivity with alumina.
  • an alumina substrate is partially formed on a platinum substrate, corundum crystals are formed on the alumina substrate, and on the platinum substrate on which no alumina substrate is formed.
  • corundum crystal formed body in which a corundum crystal is formed only in a desired portion can be obtained. Furthermore, this is because a corundum crystal formed body having a corundum crystal formed in a pattern can be obtained by forming an alumina substrate in a pattern on a platinum substrate.
  • Examples of the method for forming the alumina substrate on the substrate include a physical vapor phase method such as a sputtering method and an electron beam (EB) method, an electrolysis method, and a compression molding method.
  • a physical vapor phase method such as a sputtering method and an electron beam (EB) method
  • EB electron beam
  • Examples of the method for forming the platinum layer include general physical vapor phase methods such as sputtering, ion plating, and vacuum deposition.
  • the alumina base material becomes a raw material for the corundum crystal, and the corundum crystal is formed by elution of the alumina from the alumina base material. Therefore, the thickness and size of the alumina base material can maintain the shape of the alumina base material even after the alumina is eluted from the alumina base material when the corundum crystal is formed using the flux evaporation method.
  • the thickness and size are not particularly limited, and may be appropriately selected according to the use of the corundum crystal formed body of the present invention.
  • the shape of the alumina substrate used in the present invention is not particularly limited, and is appropriately selected depending on the use of the corundum crystal formed body.
  • containers such as crucibles, plate shapes, rod shapes, wire shapes, ring shapes, cube shapes, uneven shapes, spherical shapes, three-dimensional shapes, cone shapes (cones, pyramids, etc.), column shapes (columns, prisms, etc.), and the like can be mentioned.
  • the inside of the mesh nail may be hollow.
  • the method for producing a corundum crystal formed body of the present invention forms a corundum crystal on an alumina base material by heating the flux and the alumina base material by a flux evaporation method in which the crystal is precipitated and grown using the evaporation of the flux as a driving force. It is characterized by this.
  • the flux method is a kind of solution method and is also called a flux method.
  • an appropriate salt or oxide that becomes a flux and a raw material that becomes a solute are mixed, heated and melted, and then the solution is gradually cooled or the flux is evaporated. Create a supersaturated state and grow crystals. Depending on the difference in formation method of this supersaturated state, it is roughly divided into a flux evaporation method, a flux slow cooling method and a flux temperature gradient method.
  • the present invention uses the flux evaporation method among the above.
  • the flux evaporation method is a method that promotes nucleation and crystal growth using evaporation of flux as a driving force.
  • Fig. 5 (a) an alumina substrate filled with a sample 4 containing flux is used.
  • the crucible 2 is placed in the high-temperature furnace 12, heated to evaporate the flux in the sample 4, and the corundum crystal 3 is deposited and grown on the inner wall of the crucible, which is the alumina substrate 2.
  • 5 (b)) corundum crystal formed body 1 is obtained (Fig. 5 (c)).
  • the mechanism by which corundum crystals are formed on the alumina substrate is considered as follows.
  • the alumina base material becomes a solute, and the surface force of the alumina base material gradually elutes due to the heating of the flux and the alumina base material, and supersaturation occurs at the interface between the portion of the alumina base material where the alumina is dissolved and the flux that evaporates. Since a state is created, it is assumed that corundum crystals precipitate on the surface of the alumina substrate and grow.
  • corundum crystals are considered to precipitate and grow on the portion of the alumina base material where the alumina elutes and the flux that evaporates.
  • the portion of the alumina base material 2 where the alumina is eluted during the formation of the corundum crystal and the sample 4 evaporates. Since the corundum crystal 3 is formed at the portion that becomes the interface A with the flux, it is considered that a corundum crystal formed body 1 as shown in FIG. 5 (c) is obtained.
  • the present invention it is possible to grow corundum crystals directly on an alumina substrate by using the alumina substrate as a solute. Also, conventional flux Compared with the melting of the alumina powder used in the process, the rate at which the alumina substrate strength alumina elutes is slow, so the generation of polynuclears and the crystal growth rate can be suppressed, and high-quality corundum crystals can be produced. Obtainable. Furthermore, since the corundum crystals are precipitated and grown as described above using the alumina base material as a solute as described above, there is an advantage that a corundum crystal formed body having a very strong adhesive force between the alumina base material and the corundum crystals is obtained.
  • a crucible made of alumina that can be used as an alumina base material is alumina. It is a compression-molded powder of V and has a certain degree of heat resistance, so that a large amount of alumina does not elute easily. Therefore, in the present invention, the amount of elution of alumina from the alumina base material is maintained on the alumina base material while maintaining the shape of the alumina base material so as not to change the shape of the alumina base material. Collandum crystals can be formed.
  • the corundum crystals are formed even if the amount of alumina eluted from the alumina base material is small, the amount of alumina eluted may be small.
  • the corundum crystal may contain an element contained in the flux as an impurity, and a product close to natural corundum crystal is obtained. It is possible to produce a corundum crystal formed body having a high value.
  • the apparatus used for the flux evaporation method is simple if it has a high-temperature furnace 12, and as described above, the flux is evaporated to precipitate and grow crystals. Since a corundum crystal can be obtained, the production process is simple, and a high-value-added corundum crystal can be produced at low cost.
  • the method for producing a corundum crystal formed body of the present invention comprises a sample preparation step for preparing a sample containing a flux, heating the sample and the alumina substrate, and further maintaining the temperature at a high temperature to evaporate the flux.
  • a heating 'evaporation step for depositing and growing corundum crystals on an alumina substrate, a cooling step for cooling the sample heated in the heating'evaporation step, and a sample remaining after the caloric heat-evaporation step and the cooling step.
  • a separation step of separating the collandum crystal-former by dissolving them in a suitable medium will be described.
  • a sample preparation step for preparing a sample containing a flux is first performed.
  • the sample used in the present invention is not particularly limited as long as it contains a flux, and may contain a force coloring additive.
  • sample strength S flux is contained, colorless corundum crystals can be formed, and when flux and coloring additives are contained, colored corundum crystals can be formed.
  • a chromium compound is used as an additive for coloring and the sample contains a flux and a chromium compound, a red corundum crystal can be formed.
  • the flux used in the present invention is not particularly limited as long as it evaporates in a heating / evaporation process described later, and dissolves in an appropriate medium in a separation process described later. It is preferable to do. Molybdenum compounds can be evaporated relatively easily, and therefore are suitable as a flux used in the flux evaporation method.
  • molybdenum oxide or a compound that generates acid molybdenum by heating in a heating and evaporation step described later can be used.
  • the compound that generates molybdenum oxide by heating include molybdenum carbonate, molybdenum sulfate, molybdenum nitrate, molybdenum hydroxide, and hydrates thereof.
  • the flux may contain an evaporation inhibitor! /. This is because the evaporation rate of the flux can be suppressed and the generation of multinuclei and the crystal growth rate can be suppressed, so that a high-quality corundum crystal can be obtained. Further, as described above, the corundum crystal is precipitated and grows by forming a supersaturated state at the interface between the portion where the alumina base strength alumina is eluted and the flux that evaporates.
  • the evaporation rate of the flux is too high, even if a corundum crystal is deposited in a certain part of the alumina base material, it will not be in contact with the flux before it grows, and the corundum crystal may not grow any more.
  • by suppressing the evaporation rate of the flux it is possible to lengthen the time during which the alumina-eluting portion of the alumina base material is in contact with the flux. Crystals can be formed.
  • the evaporation rate of the flux is faster and the nucleation rate is faster than when the flux contains the evaporation inhibitor.
  • a relatively thin corundum crystal can be formed on the substrate.
  • the evaporation inhibitor is not particularly limited as long as it can suppress the evaporation of the flux and can be dissolved in an appropriate medium in the separation step described later. Is preferably used. This is because by using an alkali metal compound, evaporation of the flux can be effectively suppressed, so that a high-quality and thick corundum crystal can be formed on the alumina substrate.
  • an alkali metal compound an alkali metal oxide, or a compound that generates an alkali metal oxide by heating in a heating and evaporation step described later can be used.
  • the compound that generates an alkali metal oxide by heating include alkali metal carbonate, alkali metal sulfate, alkali metal nitrate, alkali metal hydroxide, and hydrates thereof.
  • the content of the alkali metal compound is 40 mol% or less, particularly 30 mol% or less, particularly 20 mol% or less with respect to the total number of moles of alkali metal atoms of the alkali metal compound. It is preferable to contain so that it may become. In the present invention, since nucleation and crystal growth are promoted by the evaporation of flux as driving force, crystallization may be hindered if the content of alkali metal compound is too large. [0071] (2) Additive for coloring
  • the coloring additive used in the present invention is different depending on the coloring component added to the corundum crystal as described in the above-mentioned section “A. Corundum crystal forming body”, and is appropriately selected and used.
  • a coloring additive is not necessary.
  • iron and titanium are added as coloring components!
  • iron compounds and titanium compounds are used as coloring additives.
  • chromium compounds and nickel compounds are used as coloring additives.
  • corundum crystals of iron and titanium-added calenders and corundum crystals of chromium-added calenders.
  • iron and titanium are added as coloring components to form corundum crystals
  • iron compounds and titanium compounds are used as coloring additives.
  • the iron compound is not particularly limited as long as it is melted in the heating and evaporation step described later, but is preferably a compound that generates iron ions by heating.
  • the compound that generates iron ions by heating are iron oxide, iron hydroxide, iron sulfate, iron carbonate, iron nitrate, iron chloride, iron citrate, iron phosphate, iron fluoride, iron iodide, and sulfur. Examples thereof include iron acids and hydrates thereof. Among them, it is preferable to use acid pig iron in the present invention.
  • the iron valence in the iron oxide may be bivalent or trivalent, and bivalent and trivalent iron may be mixed.
  • the titanium compound is not particularly limited as long as it can be melted in the heating and evaporation process described later, but is preferably a compound that generates titanium ions by heating.
  • the compound that generates titanium ions by the above heating include titanium oxide, nitrogen Titanium chloride, titanium tetraisopropoxide, titanium oxalate, titanium sulfate, titanium bromide, titanium chloride, and hydrates thereof. Among them, it is preferable to use acid titanium in the present invention.
  • examples of the valence of titanium in the above-mentioned titanium oxide include divalent, trivalent and tetravalent.
  • the valences of titanium may be single or mixed.
  • the addition amount of the iron compound and the titanium compound is not particularly limited as long as the addition amount is sufficient to color the corundum crystals! /.
  • a chromium compound is used as the coloring additive.
  • the chromium compound is not particularly limited as long as it can be melted in the heating and evaporation step described later, but is preferably a compound that generates chromium ions by heating.
  • the compound that generates chromium ions by the above heating include acid chrome, chromium hydroxide, chromium sulfate, chromium carbonate, chromium nitrate, and hydrates thereof. Among them, it is preferable to use acid-chromium for the present invention.
  • the amount of the chromium compound to be added is not particularly limited as long as the amount of corundum crystals that can be colored is added. /.
  • a nickel compound, vanadium compound or cobalt compound when forming a corundum crystal to which nickel, vanadium or cobalt is added as a coloring component, a nickel compound, vanadium compound or cobalt compound may be used as a coloring additive.
  • the nickel-rich compound is not particularly limited as long as it can be melted in the heating and evaporation step described later, but is preferably a compound that generates nickel ions by heating.
  • the compound that generates nickel ions by the heating include nickel acetate, nickel carbonate, nickel chloride, nickel hydroxide, nickel iodide, nickel nitrate, nickel oxide, nickel sulfamate, nickel sulfate, and hydrates thereof. Etc.
  • the nickel valence in the above-mentioned nickel oxide may be bivalent or trivalent, or it may be a mixture of bivalent and trivalent nickel.
  • the vanadium compound is not particularly limited as long as it melts in the heating and evaporation step described later, but is preferably a compound that generates vanadium ions by heating.
  • the compound that generates vanadium ions by the above heating include vanadium carbide, vanadium chloride, vanadium oxide, vanadium oxide sulfate, vanadium oxide oxide, and hydrates thereof.
  • vanadium oxide it is preferable to use vanadium oxide.
  • the valence of vanadium in the above acid vanadium includes trivalent, tetravalent and pentavalent.
  • the valences of vanadium may be single or mixed.
  • the cobalt compound is not particularly limited as long as it is melted in a heating and evaporation step described later, but a compound that generates a corona ion by heating is preferable.
  • the compound that generates cobalt ions by the heating include cobalt bromide, cobalt chloride, cobalt citrate, cobalt fluoride, cobalt dalconate, cobalt hydroxide, cobalt iodide, cobalt nitrate, cobalt oxalate, Examples include cobalt oxide, cobalt phosphate, cobalt stearate, cobalt sulfate, cobalt sulfate, and hydrates thereof.
  • cobalt citrate it is preferable to use cobalt citrate, cobalt fluoride, cobalt dalconate, cobalt hydroxide, cobalt iodide, cobalt oxalate, cobalt oxide, cobalt phosphate, and cobalt stearate.
  • cobalt oxide, cobalt hydroxide, cobalt stearate, or cobalt phosphate it is preferable to use cobalt oxide, cobalt hydroxide, cobalt stearate, or cobalt phosphate.
  • the cobalt valence in the above cobalt toy compound may be bivalent or trivalent, and both divalent and trivalent cobalt may be mixed! / /.
  • the amount of the nickel compound, vanadium compound, or cobalt compound added is not particularly limited as long as it is added in an amount sufficient to color the corundum crystals.
  • a corundum crystal is formed in which chromium as a coloring component and at least one element selected from the group force consisting of iron, titanium, nickel, vanadium and cobalt are added.
  • an iron compound, a titanium compound, a nickel compound, a vanadium compound, or a cobalt compound may be used.
  • the addition amount of the iron compound, titanium compound, nickel compound, vanadium compound, or cobalt compound described above is not particularly limited as long as an amount sufficient to color the corundum crystal is added. Not something! /.
  • the above-mentioned iron compound, titanium compound, chromium compound, nickel compound, vanadium compound or cobalt compound can be used in various combinations, and the mixing ratio of these compounds is as follows. It is appropriately selected according to the use of the corundum crystal formed body.
  • the flux and coloring additives are usually stirred.
  • the stirring method is not particularly limited as long as it is a method capable of stirring uniformly.
  • a method of sufficiently stirring the flux and coloring additive in a mortar can be mentioned.
  • the sample may contain impurities. This makes it possible to obtain crystals that are close to natural V, have high value as jewelry, and can form corundum crystals.
  • the sample may contain an aluminum compound!
  • the alumina base material becomes a solute, and the surface force of the alumina elutes to form a collandum crystal.
  • the aluminum compound is further included as the solute. You can also.
  • the content of the aluminum compound is appropriately determined in consideration of the balance between the elution of alumina from the alumina base material and the melting of the aluminum compound so as not to prevent the precipitation and growth of corundum crystals on the alumina base material. Prepared. For example, if the content of the aluminum compound is too large, crystals may grow with the aluminum compound serving as a nucleus, and it may be difficult to form a corundum crystal on the alumina substrate.
  • alumina as such an aluminum compound, alumina (acid aluminum) or a compound that generates alumina by heating in a heating / evaporation process described later can be used.
  • the compound that forms alumina by the above heating include hydroxyaluminum aluminum, aluminum sulfate, aluminum carbonate, aluminum nitrate, and hydrates thereof. In the present invention, among these, it is preferable to use alumina.
  • the heating / evaporation step in the present invention is a step of heating the sample and the alumina base material, further evaporating the flux by maintaining the temperature at a high temperature, and depositing and growing corundum crystals on the alumina base material.
  • the alumina base material 2 is filled with the sample 4 containing the flux as shown in FIG. 5 (a). Cover the crucible with the lid 13 and place it in the high temperature furnace 12.
  • the flux in sample 4 evaporates, and the crucible force that is alumina substrate 2 also elutes alumina, driving the evaporation of this flux.
  • the precipitation and growth of collandum crystal 3 is promoted (Fig. 5 (b)).
  • a corundum crystal formed body 1 in which the collandum crystal 3 is formed on the alumina substrate 2 is produced (FIG. 5 (c)).
  • the maximum holding temperature in this step is not particularly limited as long as it is a temperature at which the flux evaporates, the coloring additive melts, and the alumina substrate strength alumina elutes. 950 o C ⁇ 1300 o C, Chudechi 975 o C ⁇ 1250 o C, it is preferred that within the limits of the special [this 1000 o C ⁇ 1200 o C.
  • the rate of temperature rise when setting the maximum holding temperature a sample containing a flux and an additive for coloring, etc., and a rate capable of uniformly heating the alumina substrate are particularly effective. It is not limited. Further, the holding time at the maximum holding temperature is not particularly limited as long as it is a time during which the corundum crystal can be sufficiently grown.
  • the alumina base material is the same as that described in the above-mentioned section "A. Corundum crystal formed body", description thereof is omitted here.
  • the alumina base material is a container such as a crucible in which the sample is filled, and the sample may be placed in a container that is the alumina base material. It may be placed inside.
  • the container used is not particularly limited as long as it can withstand the above-mentioned maximum holding temperature and has low reactivity with the sample. Use a container that also has strength.
  • the alumina base material and the sample are mutually compatible. It arrange
  • the alumina base material becomes a solute, and the alumina also gradually elutes the surface force of the alumina base material by heating. Since a supersaturated state is created at the interface, it is considered that corundum crystals precipitate on the surface of the alumina substrate. From this, for example, when the crucible, which is the alumina substrate 2 as shown in FIG. 5 (a), and the sample 4 containing the flux are heated, the flux evaporates, so FIG. 5 (b) As shown, the upper side force of the inner wall of the crucible which is the alumina base material 2 is assumed to gradually form the corundum crystal 3.
  • the cooling step in the present invention is a step of cooling the sample or the like heated in the heating and evaporation step.
  • the crucible which is the alumina base material 2 filled with the sample 4 containing the flux is taken out from the high temperature furnace 12 as shown in FIG. 5 (a) and cooled to room temperature.
  • the cooling method include a method of allowing the crucible to cool as long as it can be cooled to room temperature.
  • the separation step in the present invention is a step of separating the corundum crystal formed body by dissolving the sample remaining after the heating / evaporation step and the cooling step in an appropriate medium.
  • a sample such as a flux remains after the cooling step such that the flux is not completely evaporated in the heating / evaporating step, or the evaporation inhibitor remains undissolved.
  • the corundum crystal formed body can be easily separated by dissolving these remaining samples in an appropriate medium.
  • the medium used for dissolving the remaining sample is not particularly limited as long as it can dissolve the remaining sample other than the corundum crystal and the alumina base material without affecting the corundum crystal.
  • the medium used for dissolving the remaining sample is not particularly limited as long as it can dissolve the remaining sample other than the corundum crystal and the alumina base material without affecting the corundum crystal.
  • cold water, hot water, hot water and the like can be mentioned.
  • corundum crystal formed by the method for producing a corundum crystal formed body of the present invention is the same as that described in the above-mentioned section "A. Corundum crystal formed body”. Is omitted.
  • an alumina substrate is partially formed on a white metal substrate as described in the above-mentioned section “A. Corundum crystal formed body”
  • the alumina substrate is formed.
  • Corundum crystals may also be formed on an unplated platinum substrate.
  • an acid melting treatment is performed using an acid flux such as potassium hydrogen sulfate.
  • the corundum crystals formed on the platinum substrate can be peeled off.
  • Corundum crystals formed on the alumina base material are not peeled off by the acid melting treatment. Thereby, a corundum crystal formed body in which a corundum crystal is formed only in a desired portion can be obtained.
  • the acid fusion is performed. Corundum crystals formed on the platinum layer by the treatment can be peeled off.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an example, and has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same operational effects or equivalents thereof. Anything is included in the technical scope of the present invention.
  • Iron oxide (0.004 g), titanium oxide (0.004 g), molybdenum oxide (28.5 g) and lithium carbonate (0.5 g) were weighed and placed in a mortar.
  • This mixed sample was dry mixed in a mortar for about 20 minutes. Thereafter, the mixed sample was filled in an alumina crucible (purity 99.6%), covered, and placed in an electric furnace. The electric furnace was heated to 1100 ° C at a rate of 45 ° C per hour and held at that temperature for 5 hours. After the holding, the alumina crucible was taken out from the electric furnace and allowed to cool to room temperature.
  • a photograph of the cross section of the obtained corundum crystal formed body is shown in FIG. As shown in FIG. 2, a corundum crystal 3 having a thickness of about 150 / zm was formed on the inner wall of the alumina crucible 2.
  • Acid chrome (0.008 g), molybdenum oxide (28.5 g) and lithium carbonate (0.5 g) were weighed and placed in a mortar.
  • This mixed sample was dry mixed in a mortar for about 20 minutes. Thereafter, the mixed sample was filled in an alumina crucible (purity 99.6%), covered, and placed in an electric furnace. The electric furnace was heated to 1100 ° C at a rate of 45 ° C per hour and held at that temperature for 5 hours. After the holding, the alumina crucible was taken out from the electric furnace and allowed to cool to room temperature.
  • Fig. 2 shows a photograph of the cross section of the resulting corundum crystal formed body. As shown in FIG. 3, a red corundum crystal 3 having a thickness of about 150 m was formed on the inner wall of the alumina crucible 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

Est décrit un corps formé de corindon dans lequel on fait grandir un cristal de corindon directement sur une base. Est également décrit un procédé pour fabriquer facilement et à moindre coût un tel corps formé de cristal de corindon. Est particulièrement décrit un corps formé de cristal de corindon qui se caractérise du fait qu’il comprend une base d’alumine et un cristal de corindon formé sur la base d’alumine.
PCT/JP2005/011115 2004-06-28 2005-06-17 Corps formé de cristal de corindon WO2006001225A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016509246A (ja) * 2012-12-11 2016-03-24 ジーティーエイティー コーポレーションＧｔａｔ Ｃｏｒｐｏｒａｔｉｏｎ 改質サファイアを含有してなる携帯用電子機器
JP2020074443A (ja) * 2014-07-22 2020-05-14 株式会社Flosfia 結晶性半導体膜および半導体装置

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS4843000A (fr) * 1971-10-08 1973-06-21
JP2002053946A (ja) * 2000-08-04 2002-02-19 Kobe Steel Ltd 硬質皮膜および耐摩耗部材並びにその製造方法
JP2004083407A (ja) * 2002-08-24 2004-03-18 Carl Zeiss Stiftung コランダム単結晶を成長させる方法および装置

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS4843000A (fr) * 1971-10-08 1973-06-21
JP2002053946A (ja) * 2000-08-04 2002-02-19 Kobe Steel Ltd 硬質皮膜および耐摩耗部材並びにその製造方法
JP2004083407A (ja) * 2002-08-24 2004-03-18 Carl Zeiss Stiftung コランダム単結晶を成長させる方法および装置

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016509246A (ja) * 2012-12-11 2016-03-24 ジーティーエイティー コーポレーションＧｔａｔ Ｃｏｒｐｏｒａｔｉｏｎ 改質サファイアを含有してなる携帯用電子機器
JP2020074443A (ja) * 2014-07-22 2020-05-14 株式会社Flosfia 結晶性半導体膜および半導体装置
US11069781B2 (en) 2014-07-22 2021-07-20 Flosfia Inc. Crystalline semiconductor film, plate-like body and semiconductor device
US11682702B2 (en) 2014-07-22 2023-06-20 Flosfia Inc. Crystalline semiconductor film, plate-like body and semiconductor device
JP7352226B2 (ja) 2014-07-22 2023-09-28 株式会社Flosfia 結晶性半導体膜および半導体装置

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