JP3443639B2 - Gradient functional material and manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to quantitatively and gradiently adhering the additive concentration to a prepared porous raw material fired body without mixing the additive substance into the raw material fired body which is a mother material from the beginning. And perform zone melting using the raw material fired body,
The present invention relates to a mixture and a method for producing the mixture in which the crystal or glass as a base material has a graded change in properties.

[0002]

2. Description of the Related Art Generally, in the zone melting (floating zone) method, when an additive is mixed, it is prepared by mixing it with a raw material powder in advance. Additives are uniformly mixed in this raw material fired body, and a single crystal is produced using this raw material fired body.
However, it is difficult to obtain a so-called tilted single crystal in which the amount is increased or decreased at a constant ratio along the crystal growth direction, that is, the length direction. This is because it is difficult to intentionally increase the concentration of the additive when the raw material is processed into a fired body.

[0003]

DISCLOSURE OF THE INVENTION The present invention makes it easy to produce a mixture of crystals or glass in which the concentration of the additive is intentionally inclined in the lengthwise direction in the raw material fired body which is the base material. The task is to do.

[0004]

A principle view of the present invention is shown in FIG. A raw material fired body 2 having a gradient in the longitudinal direction was prepared by changing the number of spots 3 having a constant area of a constant concentration of an additive substance on the porous surface and changing the number of the spots 3 per unit area of the porous surface, Then, the melting zone 4 is held between the seed crystals 1 or the firing rods of the same substance 1, and the melting zone 4 is moved toward the raw material firing body. At this time, the material into which the additive is mixed in a gradient is gradually cooled from the melting zone to produce crystals, and rapidly cooled to produce an amorphous (glass) substance. By gradually changing the amount of the additive, it is possible to manufacture a single crystal and glass in which the electric resistance, the color, the refractive index, etc., which are the functions of the material, change in a tilted manner. The present inventors came to the present invention as a result of earnestly researching in order to solve the said subject. In particular, this method calculates the amount of the desired additive per unit length of the raw fired body by knowing in advance the diameter of the raw fired body and the weight per unit length of the mother substance, and attaches this. This makes it possible to easily control the additive amount.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material fired body of the present invention is preferably porous in order to facilitate the attachment of additives. The additive may be a compound in any form, but an oxide is particularly convenient. An additive dissolved in water or alcohol was applied or attached with a brush, a toothpick, etc., but in the case of a mother material that is weak against water, it is necessary to find another suitable solvent. The diameter of the raw material fired body is determined by the melting temperature of the raw material and the viscosity of the melting zone, and is 1 mm to several tens of cm capable of holding the melting zone. In carrying out these, since the melting point varies depending on the kind and amount of the additive, in order to cope with the melting point which changes momentarily during scanning of the melting zone, it is possible to observe the melting zone and adjust the lamp power. is important. Patent publication Sho 60-112
In order to increase the luminous efficiency in Japanese Patent Publication No. 45, silica glass to which rare earth is added has a molar ratio of Al ₂ O ₃ or P ₂ O ₅ which is 10 times that of rare earth.
However, in the present invention,
In such a glass for laser, it is possible to incline the rare earth, or incline Al ₂ O ₃ or P ₂ O ₅ . The embodiment of the present invention is as follows. (1) A porous raw material calcined body adhered so that the concentration of an additive inclines in the moving direction of the melting zone is prepared, and the raw material calcined body is melted at a high temperature, and then a seed crystal or a raw material calcined body is prepared. By contacting with the same substance, forming a melting zone that holds the melting point temperature, and by moving the melting zone in one direction,
A mixture obtained by sequentially melting and solidifying the mixture, in which the concentrations of the additives are mixed obliquely in the longitudinal direction . (2) The mixture according to the above item 1, wherein the raw material fired body using alumina seed crystals is alumina. (3) Additives are Cr, Ni, Ti, Co, V, S
The mixture according to the above 2, which is one or more compounds of r, La, Er, and Yb. (4) The mixture as described in 1 above, wherein the substance to be brought into contact is glass, and the raw material fired body is glass. (5) A porous raw material calcined body adhered so that the concentration of the additive inclines in the moving direction of the melting zone is prepared, and the raw material calcined body is melted at a high temperature, and then the seed crystal or the raw material calcined material is obtained. By contacting with the same substance, forming a melting zone that holds the melting point temperature, and by moving the melting zone in one direction,
A method for producing a mixture in which the concentrations of additives are mixed in a gradient in the length direction, which are obtained by sequentially performing melting and solidification. (6) The concentration of the additive is adjusted by applying the additive as a solution having a constant concentration, applying the solution with a spot having a constant area on the surface of the porous raw material fired body, and changing the number of the spot per unit area. 6. The method for producing the mixture as described in 5 above, wherein the mixture is attached so as to be inclined in the length direction .

[0006]

EXAMPLE In the example, as shown in FIG.
An infrared heating type crystal growth furnace equipped with a converging spheroidal mirror 7, a halogen lamp or xenon lamp 6 as a heat source, a monitoring window 8, a lens 9 and a screen 10,
The grown crystal 11 was manufactured by the floating zone method. Example 1 A ruby whose shade of color changed was prepared as follows. A round bar-shaped alumina raw material was fired at 1400 ° C for 12 hours, and a solution of Cr ₂ O ₃ powder dissolved in water was applied to the tip of the brush. First, 1 point, then 2 points. A raw material fired body was produced by increasing the number of the particles, and this raw material fired body was used. The front end of the raw material is melted in a crystal furnace to hold a melting zone between the seed crystal and the alumina firing rod. Next, the crystals were grown by the floating zone method in which the molten zone was scanned at 5 to 10 mm / h in the direction of the raw material fired body, and the grown crystals changed their color intensity from pale pink to red and dark red. Manufactured. At this time, depending on the diameter and length of the raw material fired body, the relationship between the amount of Cr ₂ O ₃ powder added and the color per unit volume and weight does not change, and the production can be performed with good reproducibility.

Example 2 Using a raw material fired body in which a plurality of different kinds of additive substances are provided in the raw material fired body with a concentration gradient, a plurality of types of single crystals are continuously produced in the crystal as follows. did. Cr ₂ O ₃ beaten in water alumina raw material sintered body, Co ₂ O _3, NiO powder is attached to brush provided three zones with a slope by providing a spot. Zone melting (floating zone) was performed by the apparatus of FIG. 2 to produce the same red, blue and yellow single crystals. That is, about 3% of the weight of the alumina raw material fired body was used as an additive, and 1/3 of the weight was used for each of Cr ₂ O ₃ , Co ₂ O ₃ , and NiO.
A powder was prepared and dissolved in water to prepare a solution. The material is applied in spots on a porous surface with a brush or a toothpick, and the spot per unit area is adjusted to prepare a raw material fired body having a gradient in the concentration of the added substance. This raw material fired body is melted in a crystal furnace, and the crystal is grown by the floating zone method in which the melting zone is scanned at 5 to 10 mm / h in the direction of the raw material fired body, and red, blue, and yellow single crystals are obtained. Was manufactured. In other words, it was possible to manufacture gems with the same existence of ruby, blue sapphire, and yellow sapphire.

Example 3 A spinel having different shades of color was prepared as follows.
MgAl ₂ O ₄ consisting of MgO and Al ₂ O ₃ is processed into a round bar shape and 1200 ℃
By firing for 12 hours, a raw material fired body is prepared. A solution of Co ₂ O ₃ powder dissolved in water was applied to a brush, and first, 1 point and then 2 points were added to create a raw material fired body with spots per unit area increased and attached. It is melted in a crystal furnace using this melting zone at 1.0 cm / h in the direction of the raw material firing body.
Crystal growth was carried out by the floating zone method in which the grown crystal was manufactured by changing the color density from light blue to blue and dark blue. Example 4 Raw materials of SrCO ₃ , La ₂ O ₃ and Fe ₂ O ₃ are mixed well in a molar ratio of 2: 1: 1 and calcined at 1000 ° C. for 12 hours. After that, the raw material powder was formed into a cylindrical rod shape having a diameter of 6 mm by a press die and fired at 1400 ° C. for 2 hours. A solution of Mn ₂ O ₃ powder in water was applied to this raw material rod with a brush, and the first point was 1 and the second point was 2
That is, a raw material fired body having spots per unit area increased and adhered to the raw material fired body is melted in a crystal furnace using the raw material fired body, and the melting zone is 5 mm in the direction of the raw material fired body.
/ H, the atmosphere was atmospheric air, the growth temperature was 1650 ° C., and crystal growth was carried out by a floating zone method of an infrared concentrated heating system using a halogen lamp. The grown crystal was glossy black, and the electric resistance was slightly different in the growth length direction, that is, the one having the slope of the electric resistance was manufactured. Example 5 As a typical example of RVO ₄ (R = rare earth), an example of grading Nd ₂ O ₃ in a laser host material obtained by adding Nd to YVO ₄ will be shown. Y ₂ O ₃ and V ₂ O ₅ raw materials are mixed well at a molar ratio of 1: 1 and
Calcination is performed at 1400 ° C for 12 hours. After that, the raw material powder was made into a cylindrical rod shape with a diameter of about 6 mm by a press die, and 1500
Calcination was carried out for 2 hours. A solution of Nd ₂ O ₃ powder dissolved in water was applied to this raw material rod with a brush, and a raw material fired body was prepared by increasing the number of spots per unit area by attaching 1 point first and then 2 points. The raw material fired body is melted in a crystal furnace, and this melting zone is 2 to 5 mm / in the direction of the raw material fired body.
h, the atmosphere was atmospheric air, the growth temperature was 1810 ° C., and crystal growth was performed by a floating zone method of an infrared concentrated heating system using a halogen lamp. Crystals that changed from yellow transparent to yellow green and blue could be produced.

Example 6 A calcined body of SiO ₂ raw material was calcined at 1400 ° C. for 12 hours, and a solution of Co ₂ O ₃ powder in water was applied to a brush, and the first unit was 1 point and the second unit was 2 units. A raw material fired body with increased spots per area and adhered to it was melted in a crystal furnace using this raw material fired body, and this melting zone was 2.0 cm / h in the direction of the raw material fired body.
By scanning with, it was possible to manufacture glass that changed its lightness from light blue to blue and dark blue. Example 7 ZrO ₂ in the silica _{glass, TiO 2, Al 2 O 3} , GeO 2, P 2 O 5, B
₂ O ₃ , F, etc. are added to change the refractive index, but ZrO ₂ with the largest change in refractive index was added in an inclined manner. The SiO ₂ raw material fired body was fired at 1400 ° C. for 12 hours, and a solution of ZrO ₂ powder dissolved in water was applied to a brush, and spots were first added per unit area, followed by 2 points, to attach them. A raw material fired body was produced, melted in a crystal furnace using this raw material fired body, and this melting zone was scanned in the direction of the raw material fired body at 2.0 cm / h, whereby transparent glass with a changed refractive index could be produced. . Example 8 In a glass laser in which rare earths were added to quartz glass, Nd was used as the rare earths and Nd ₂ O ₃ and Al ₂ O ₃ were added in an inclined manner. First, the SiO ₂ raw material fired body was fired at 1400 ° C. for 12 hours. Apply a solution of a mixed powder of Al ₂ O ₃ : Nd ₂ O ₃ = 10: 1 in water in a molar ratio to a brush, first add 1 point, then add 2 points, etc. The raw material fired body thus prepared was melted in a crystal furnace using the raw material fired body, and the melting zone was 2.0 cm / h in the direction of the raw material fired body.
By scanning with, the transparent glass with Al and Nd added obliquely could be manufactured.

[0010]

EFFECTS OF THE INVENTION Although crystal and glass in which the concentration of the additive is changed in a gradient manner, which has been a difficult technique to realize until now, the present invention has made it possible to easily and relatively inexpensively manufacture. The application of this makes it possible to produce artistic jewelry with totally irregular colors and different densities. If applied to glass,
It is possible to manufacture glass in which the optical characteristics change in an inclined manner, and it can be used for various applications such as optical connectors.

[0011]

[Brief description of drawings]

FIG. 1 is a principle diagram of the present invention.

[FIG. 2] Crystal growth apparatus by the floating zone method

[Explanation of symbols]

1 Seed crystal or same material as raw material fired body 2 Raw material fired body 3 Spots of added substances 4 melting zone 5Quartz tube 6 Halogen or xenon lamp 7 Spherical mirror 8 monitoring windows 9 lenses 10 screens 11 grown crystal

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-60-81090 (JP, A) JP-A-3-75292 (JP, A) JP-A-49-69268 (JP, A) JP-A-49- 115998 (JP, A) JP 58-199746 (JP, A) JP 59-137393 (JP, A) JP 60-11245 (JP, A) JP 63-195132 (JP, A) JP 63-206318 (JP, A) JP 63-225205 (JP, A) JP 8-62435 (JP, A) JP 39-9217 (JP, B1) JP 49-15986 (JP, B1) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C30B 1/00-35/00 C03B 37/014 JISST file (JOIS)

Claims (6)

(57) [Claims] 1. A porous raw material calcined body is produced in which the additive concentration is inclined in the direction of movement of the melting zone, and the raw material calcined body is melted at a high temperature and then seed crystals or raw material calcined. The additive obtained by contacting with the same substance as the body, forming a melting zone holding the melting point temperature, and moving the melting zone in one direction to sequentially perform melting and solidification, A mixture in which the concentration is mixed in the lengthwise direction . 2. A raw material fired body using an alumina seed crystal,
The mixture according to claim 1, which is alumina. 3. The additive is Cr, Ni, Ti, Co,
The mixture according to claim 2, which is one or more compounds of V, Sr, La, Er and Yb. 4. The substance to be brought into contact is silica glass,
The mixture according to claim 1, wherein the raw material fired body is an optical fiber preform. 5. A porous raw material calcined body, which is adhered so that the concentration of the additive inclines in the moving direction of the melting zone, is prepared, and the raw material calcined body is melted at a high temperature, and then seed crystals or raw material calcined. The additive obtained by contacting with the same substance as the body, forming a melting zone holding the melting point temperature, and moving the melting zone in one direction to sequentially perform melting and solidification, A method for producing a mixture in which the concentrations are mixed obliquely in the length direction . 6. A solution is prepared from an additive and a solvent, the solution is applied to the surface of a porous raw material calcined body in spots having a constant area, and the number of the spots per unit area is changed. The method for producing a mixture according to claim 5, wherein the additive is attached so that the concentration of the additive is inclined in the longitudinal direction .