JPS6319457B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crystallized glass molded product and a method for manufacturing the same. BACKGROUND ART A crystallized glass molded product in which fine crystals are formed inside the glass molded product is useful as a molded product with a beautiful appearance that can be compared with natural marble, granite, etc. due to the incident and reflection effects of light rays. The important issues in manufacturing crystallized glass molded products are the composition of the raw material mixture that can produce crystals with the desired appearance, the appropriate viscosity of the melt to enable molding, and the crystallization for crystal formation. This is temperature control during heat treatment. Currently, there are two methods for manufacturing crystallized glass molded products: a melting method and a sintering method. In the sintering method, glass powder with a composition capable of forming a specified crystal is heated at an intermediate temperature range higher than the softening point and lower than the melting point, and the glass powder is unified by sintering in a fused form. This is a method of obtaining a product by performing a crystallization heat treatment in which crystals are precipitated inside the molded product by operating at a temperature and time of This is a method in which a crystallization process is completed by molding and then reheating. Melting methods can be further divided into processing and molding methods and casting methods. Among these, processing and molding methods are suitable for continuous mass production of products, and include roll processing, such as sheet glass, and stamping, such as containers. By manufacturing crystallized glass molded products using this processing and molding method, we can expect quality stability and economical effects from mass production.
In particular, it would be extremely desirable if the production of plate-like bodies for building materials, etc., which are used in large quantities, could be made under the current manufacturing conditions for ordinary plate glass. However, in order to manufacture crystallized glass molded products using the usual method of manufacturing plate glass, there are essential conditions regarding viscosity and temperature. For example, as a reference condition, the raw material formulation is melted (1300-1500
After exiting the furnace, the viscosity decreases to 10 ^1.5 to 10 ^2.0 poise (1200℃ to 1300℃), and the viscosity gradually and continuously decreases at the feeder position, and when the molding machine starts molding, it drops to 10 ³ to ^{10 5} poise (1200℃ to 1300℃). 950℃~1200℃),
The viscosity-temperature conditions are such that it is ^10.7 poise (around 750℃) at the end of molding, and the time varies depending on the amount and size of the product, but from the time it comes out of the oven until the end of molding, it is 25.
It takes about 50 minutes. Next, it is charged into a lehr, but the temperature and time of the lehr can be varied slightly, and the upper limit temperature is the viscosity that does not cause deformation of the molded product, that is, the softening temperature (700℃ to 800℃), which is constant. It is possible to control the temperature, maintain the temperature for a certain period of time, etc. The essential difference between crystallized glass molded products and ordinary glass molded products is that the former undergoes crystallization treatment under strictly controlled conditions of temperature and time. In addition, when the melt is slowly cooled at a constant temperature at which crystals begin to precipitate, the viscosity increases rapidly (over 10 ⁷ poise) and becomes semi-solid. When applied to a product, the composition must be such that this phenomenon does not occur by the end of the molding process. Therefore, it is necessary to obtain a molded product by matching the temperature conditions for normal glass manufacturing methods with the temperature conditions that prevent crystals from precipitating due to supercooling. Therefore, the crystallization treatment of the molded product is performed by reheating. I have no choice but to. In this case, the common operation of the conventional method is the primary crystallization heat treatment step, which can be called the crystal nucleation step or ultrafine crystal precipitation step, in which the molded product is heated from a low temperature and carried out at a constant temperature. The production is carried out by adding a second crystallization heat treatment step, which can be called a crystal growth step, which is further heated and carried out at a constant temperature. In the crystallization heat treatment process, if the temperature conditions of the first crystallization heat treatment and the second crystallization heat treatment are performed at a temperature higher than the softening temperature at which the molded product deforms, or if they require a long time, , a special heating furnace process must be added to the post-molding process of the normal glass manufacturing method. The types of crystals produced in crystallized glass molded products using conventional processing and molding methods are β-wollastonite and β-wollastonite.
- spodiumen, β-eucryptite, etc. However, the problem with this conventional method is that, as mentioned above, a crystallization heat treatment step by reheating after molding is essential. This addition process varies slightly depending on the type of crystal, but approximately 700
Increase the temperature from above ℃ while controlling the temperature to a final temperature of 1000℃.
Crystallization heat treatment is performed at a temperature range of ~1200℃. In addition, this temperature range is above the softening deformation temperature of the molded product (800 to 850℃), so in order to prevent deformation, the molded product must be placed on a specific baking table and subjected to crystallization heat treatment. . The casting method, which is another method of the melting method, uses a composition that has a small difference between the melting temperature and the crystal precipitation temperature in the state of crystal formation, and also allows crystal formation to start easily even if the cooling rate is fast. This is a method for manufacturing crystallized glass molded products. An example of this is a method for producing mica glass ceramics that produces crystals of phlogopite or tetrasilicon mica, which are crystals belonging to the fluorine mica family. The composition for producing mica glass ceramics is such that at least 90 phlogopite or tetrasilicon mica crystals are present in the weight of the molded product, respectively.
% or more. Also, phlogopite [KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ , melting point (mp) 1375
℃, crystal precipitation temperature (cp) 1375℃] or tetrasilicon mica [KMg _2.5 (Si ₄ O ₁₀ ) F ₂ m.p 1176℃, c.
To explain the crystallization state of only [p1173℃], these melts (1300 to 1450℃) start crystal precipitation even at a cooling rate of 60 to 120℃ per minute, and at a cooling rate slower than this, crystal formation does not occur. The viscosity increases significantly, and the temperature decreases by 100℃ from the respective crystal precipitation temperature.
The viscosity of the normal glass products mentioned above is 10 ^{to 7.0} poise, so
It is impossible to apply manufacturing methods depending on temperature conditions.
That is, the viscosity is too high, leading to problems such as fractures and cracks occurring during molding, and insufficient heat resistance of processing equipment. Therefore, current mica glass ceramics are produced by pouring a molten material into a mold under supercooled conditions to obtain a molded product, and then performing a crystallization heat treatment by reheating at 750 to 850°C.
Crystal nucleation stage held for ~6 hours and 1000~1150
An essential step is a two-stage operation including a crystal growth stage held at a temperature of 1 to 6 hours at a temperature of 1 to 6 hours. The present invention is particularly applicable to conventional β-wollastonite and β-spodiumene-based crystallized glass molded products or mica glass ceramics that are cast in a high-temperature, high-viscosity state or crystallized over a long period of time at high temperatures. Molding and crystallization can be carried out within the normal manufacturing process of glass products, and the amount of crystallization can be further increased or the crystal diameter can be changed as necessary to express the pattern of the molded product. Even when crystallization treatment is performed by reheating to increase the temperature, a low-cost molded product can be obtained that can be performed at a temperature below which the molded product does not soften and deform. In the present invention, by blending glass or glass components (hereinafter referred to as glass substances) with specific fluorine mica or its derivatives or their raw material components, crystal precipitation is caused by a melting method. This makes it possible to manufacture crystallized glass molded products using the glass product molding method and temperature treatment conditions. Fluorine mica has the chemical formula X _0.5~1.0 Y _2.0~3.0 (Z ₄ O ₁₀
)
Denoted by _F2 . In this formula, X is a cation with a coordination number of 12, which is an interlayer ion of mica crystal, which is a layered crystal, Z is a cation with a coordination number of 4, which is usually based on Si, which is a SiO ₄ tetrahedron, and Y is a cation with a coordination number of 4. An octahedral layer is composed of cations of order 6. The crystal structure of fluorine mica is a plate-like structure in which SiO ₄ tetrahedrons are arranged in hexagonal grids.
This structure is called a tablet, and these tablets are stacked in layers, and between the tablets there is an alkali or alkaline earth metal. Metal ions are bound together and are called interlayer ions. The basic forms in which this fluorine mica crystal is produced are two methods: a melting method in which mixed raw materials are melted according to the composition of the crystal, and the melt is treated under certain temperature conditions to precipitate crystals; When heated in the state of solid particles or in the state of a molded product, reactions such as dehydration and decomposition of adsorbed water occur one after another, and even before the melting temperature is reached, atoms at crystal lattice points on the surface of the particles are separated by thermal vibrations of the solid particles. There is a solid phase reaction method in which crystals are formed by entering the radius of action of the atoms on the surface of the particle and breaking bonds, and there are crystals that can be formed by this solid phase reaction even if the melting method cannot be applied. Whether or not crystals can be formed using the melting method or the solid phase reaction method is determined by experimenting with various compositions. The present applicant previously proposed a crystallized glass molded product made of a fused and solidified product of taeniolite crystals and glassy substances as meeting the above conditions (Japanese Patent Application No. 57-155630). This molded product can be manufactured under viscosity-temperature conditions from melting to completion of molding in a processing molding method using a normal glass manufacturing method. Taeniolite is a fluorine mica chemical formula X _0.5~1.0
In _Y2.0-3.0 ( _Z4O10 ) _F2 , Y is MgLi, X is K, Ba, etc., _and Z is Si. This also includes derivatives of taeniolite in which Z is AlSi ₃ or BSi ₃ . However, as mentioned above, taeniolite contains Li and is expensive, so there is a desire for an inexpensive raw material that has similar effects. As a result of further research, the present inventors discovered that barium fluorine mica, like taeniolite, can be used to produce crystallized glass by processing and molding, which is a normal glass manufacturing method, and the present invention has been achieved. It is. Barium fluorine mica is characterized by a mica composition that does not contain Li, and its composition is based on the chemical formula of the fluorine mica: X _0.5-1.0 Y _2.0-3.0
(Z ₄ O ₁₀ ) In F ₂ , X is Ba ²⁺ and Y is
Mg ₃ , where Z is disilicon type (Al ₂ Si ₂ ), preferably (B ₂ Si ₂ ), or Z is trisilicon type (AlSi ₃ ), preferably (BSi ₃ ). Specific examples of these are as follows. (1) Representative example belonging to disilicon mica BaMg ₃ (Al ₂ Si ₂ O ₁₀ ) F ₂ , melting point (mp) 1460
℃ BaMg ₃ (B ₂ Si ₂ O ₁₀ )F ₂ , m.p1385℃ (2) Typical example belonging to trisilicon mica Ba _0.5 Mg ₃ (Al Si ₃ O ₁₀ )F ₂ , m.p1264℃ Ba _0.2 Mg ₃ (B Si ₃ O ₁₀ ) F ₂ , m.p 1150°C The barium fluorine mica of (1) and (2) is a part of X (Ba ²⁺ ) (Ba ^{2 +} within 30%) for K ⁺ , Ca ²⁺ , Zn ²⁺ ,
Pb ²⁺ or Sr ²⁺ , part of Y (Mg ²⁺ ) (for Mg
(within 50%) with Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ , Al ³⁺ or Fe ³⁺ , and part of Z (within 30% based on the coordination number of Si ⁴⁺ ) may be substituted with Fe ³⁺ , Ge ⁴⁺ , Al ³⁺ , or B ³⁺ . In order to precipitate crystals of barium fluorine mica or partially substituted products thereof (these are referred to as barium fluorine mica type) in (1) and (2) above, barium fluorine mica type crystals may be used as the raw material. , its raw material composition (hereinafter referred to as barium fluorine mica composition). The present invention attempts to produce crystallized glass by a conventional glass processing and molding method by combining the above barium fluorine mica composition and a glassy substance. The glassy substance used in the present invention may be a raw material pad capable of forming glass, or a frit-like glass obtained by vitrifying this raw material pad in advance and then pulverizing it. Examples of glass components include SiO ₂ -
Al ₂ O ₃ ―B ₂ O ₃ ―CaO―K ₂ O―Na ₂ O or this
_P2O5 , BaO, MgO, ZnO, _PbO , _TiO2 , _ZrO2
In terms of the usual classification of glass products, they include plate glass, bottle glass, pressed glass, etc.
Glass materials such as lighting glass, sealing glass, crystal glass, etc. can be used. When selecting the composition of the glass material, care must be taken not to inhibit the formation of barium-fluorine mica-based crystals, and to maintain viscosity-temperature conditions that allow the forming process to be completed without any problems. That is, in the barium fluorine mica composition, for example, barium trisilicon mica [Ba _0.5
When the purpose is to generate Mg ₃ (Al Si ₃ O ₁₀ ) F ₂ ] crystals, other ions K ⁺ , Ca ²⁺ , Zn that can compete and coordinate to the position of X in the chemical formula of the fluorine mica are added. ^2+, etc., it is desirable to limit the crystal formation rate by these ions to within a certain value, preferably to about ₂₀ % in _the entire composition _. The same applies to the case where the purpose is to generate crystals of O ₁₀ )F ₂ ]. Furthermore, in the case of barium fluorine mica derivatives, the amount of barium fluorine mica crystals produced by substitution of other cations at the Y and Z positions can also be limited to within about 20% of the total composition. desirable. The blending ratio of the barium fluorine mica composition and the glassy substance is preferably 30 to 70 parts by weight when the total composition is 100 parts by weight. In the combination of the barium fluorine mica composition and the glassy substance according to the present invention, the elapsed time from the time the mixed melt is discharged from the furnace to the completion of molding is 30 to 50 minutes.
The temperature-viscosity conditions are such that the viscosity decreases continuously from the time of exit from the furnace and fluid movement (1200 to 1300°C, viscosity 10 ^1.5 to 10 ^2.0 poise) to the time of loading into the molding machine using a feeder, etc., and then at the start of molding (950 ~1100℃, 10 ^3.0 ~10 ^5.0
poise), at the end of molding (500 to 850℃, 10 ^6.5 to ^{10 7.0}
This corresponds to the range of ordinary plate glass (up to 100% polyester), and during this period, the phenomenon of viscosity increase due to crystal formation does not occur, making it possible to produce molded products without damage. In addition, the crystallization heat treatment process to generate crystals inside the molded product is performed at 700 to 850℃ for 40 to 40 minutes after the molding is completed.
This can be achieved by holding for 60 minutes, and it can be carried out continuously within the temperature operation range of the slow cooling process after molding is completed.
A crystallized glass molded product can be completed within the framework of a substantially normal glass product manufacturing process. Since the Ba-mica composition of the present invention has the effect of lowering the viscosity of the melt during glass melting, it not only does not cause a sudden change in viscosity from the melt to the end of molding, but also reduces the viscosity of the melt until the end of molding. It has the effect of extending time. In the present invention, the fluorine mica to be mixed with the glassy substance has a Ba-mica composition as its main component.
Other fluorine mica can be added to this. For example, as mentioned above, Ba-mica compositions have a viscosity-lowering effect, so K-phlogopite [KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ] and K-tetrasilicon mica [KMg _2.5 (Si ₄ O ₁₀ )F ₂ ], the crystal formation of these fluorine mica in the high temperature range (1400 to 1200°C) is suppressed. The amount of fluorine mica to be added is 80 parts by weight or less per 100 parts by weight of the barium fluorine mica composition. When this crystal suppression phenomenon is observed using electron micrographs when cooling at a rate of at least about 100°C or more per minute, it is found that extremely fine crystals (crystal diameter 10
~30 μm) is observed, but the weight is small. By mixing the barium fluorine mica composition with K-phlogopite etc. in this way, the increase in viscosity of the mixed melt with the glassy substance is suppressed, and the conditions that allow molding (Standard Example 10 ^4.0 poise - 1000°C) are suppressed.
~10 ^7.0 poise - 750℃). Furthermore, when a combination of K-phlogopite, K-tetrasilicon mica, and barium fluorine mica-based composition is crystallized, the temperature at the end of molding is 700 to 850°C.
When kept for about 1 hour, the barium fluorine mica crystals will precede the K-- formed in the molded product.
Generation and growth are promoted using microcrystals of phlogopite or K-tetrasilicon mica as crystal nuclei, and the amount of crystallization can be increased. In this combination, not only crystals of barium fluorine mica and K-phlogopite or K-tetrasilicon mica, but also solid solution crystals between the two are produced. For example, Ba ^0.5 - Mg ₃ (AlSi ₃ O ₁₀ ) F ₂ and K - Mg ₃
(AlSi ₃ O ₁₀ ) In addition to F ₂ K _0.5 Ba _0.25 Mg ₃ (AlSi ₃ O ₁₀ )
Solid solution crystals such as F ₄ also form in some cases. An additional 1,000 products have undergone crystallization heat treatment using this method.
When heated at ~1100℃ for 1 to 2 hours, the growth of K-phlogopite or K-tetrasilicon mica crystals is remarkable, and crystals with a diameter of 1 to 3 mm precipitate, creating a beautiful mottled pattern on the molded product. can be granted. Furthermore, in the present invention, in the combination of the above barium fluorine mica composition and other fluorine mica, in addition to introducing fluorine mica crystals by a melting method, a certain amount of fluorine mica is produced by a solid phase reaction mechanism. A mica composition can be added to co-form crystals. Those whose composition is based on solid phase reaction are
Fe ²⁺ at the Y and Z positions of the chemical formula of fluorine mica,
Fe ³⁺ , Co ³⁺ , Cr ³⁺ , Ni ²⁺ , Ni ³⁺ , Cu ²⁺ , Mn ²⁺ ,
Many of them are coordinated with ions such as Ti ³⁺ , Ti ⁴⁺ , and Be ⁴⁺ , each of which is a brilliantly colored fluorine mica crystal. Therefore, by selecting the composition of the colorable fluorine mica crystal, a wide variety of color tones can be imparted to the crystallized glass molded product. Examples of this type are [KMg _1.5 Co _1.5 (AlSi ₃ O ₁₀ ) F ₂ , ct 1100°C, blue or pink], [KMg _2.8 Ni _0.2 (AlSi ₃ O ₁₀ ) F ₂ , c.
t 1000℃, horizontal green], [KMg _2.66 ~ _2.80 , Co _0.35 ~ _0.2
(AlSi ₃ O ₁₀ )F ₂ , ct 1000℃ brown], [KFe ₃
(FeSi ₃ O ₁₀ ) Fe ₂ , ct 650℃, black gray], [KMg _1.0
Mn _2.0 (AlSi ₃ O ₁₀ ) F ₂ , ct 1000℃, brown],
[KAlTi ³⁺ (AlSi ₃ O ₁₀ ) F ₂ , ct 800°C, beige color], etc. The combination with barium fluorine mica, which is the main subject of the present invention, and the fluorine mica produced by the above-mentioned solid phase reaction mechanism will affect the appearance of the crystallized glass molded product, such as crystal size, pattern and color tone, and roll forming. It is determined by considering the suitability of manufacturing conditions such as slow cooling of the melt during molding. The amount of the fluorine mica to be co-formed is 30 parts by weight or less when the total of the barium fluorine mica composition and K-phlogopite or the barium fluorine mica composition and K-tetrasilicon mica is 100 parts by weight. be. The fluorine mica to be co-formed may be not only its crystals but also raw material compositions for crystal formation (these are referred to as other fluorine mica compositions). Therefore, other fluorine mica compositions that can be added to the barium fluorine mica composition in the present invention include the above-mentioned K-phlogopite and the colored fluorine mica. EXAMPLES The crystallized glass molded product of the present invention will be specifically explained below using Examples. Example 1 The composition of the glassy substance is 72% SiO ₂ and Na ₂ O
13.0%, CaO 11.5%, MgO 1.9%, _{Al2O3 +} ,
60 parts by weight of 1.6% Fe ₂ O ₃ and barium disilicon mica [BaMg ₃ (Al ₂ Si ₂ O ₁₀ ) F ₂ ] have a composition of 23.1% SiO ₂ , 28.0% BaO, 19.6% Al ₂ O ₃ ,
A raw material batch containing 40 parts by weight of 15.5% MgO and 13.8% MgF ₂ was melted at 1480°C, and a crystallized glass molded product was produced in accordance with the manufacturing process of plate glass. The viscosity of the melt at a cooling rate of 30 minutes from 1350℃ to 900℃ from the furnace to the feeder and just before charging into the molding machine is 1300℃−10 ^1.5 poise, 1200℃−
10 ^2.6 poise, 1100℃−10 ^3.7 poise, 1000℃−10 ^4.7
The temperature was 900℃−10 ^5.4 poise. 900℃～
After forming into a plate-shaped body approximately 20 mm thick by roll forming at 800°C, a crystallization treatment was performed at a temperature of 800°C for 60 minutes to obtain a milky white crystallized glass molded product.
The physical properties of this molded product are porosity 0, specific gravity 2.91,
Hardness (shoer) 87, transverse rupture strength 975Kg/ ^cm2 ,
According to X-ray diffraction, electron micrographs, and other measurements, mica crystals mainly composed of BaMg ₃ (Al ₂ Si ₂ O ₁₀ ) F ₂ crystals (more than 85%) were formed during molding in an amount of 28 to 32% by weight. It was observed that the crystal grain size was distributed between 300 and 600 μm. Example 2 Barium disilicon mica with the above molded product formulation
Of the 40 parts by weight, 7 parts by weight were converted into K-phlogopite [KMg ₃ (AlSi ₃ O ₁₀ ) F ₂ ] with a composition of 41.8% SiO ₂ ,
_K2O 10.9%, _{Al2O3 11.8} %, MgO 18.7%,
Plates were produced by replacing it with one consisting of 16.8% MgF ₂ . The blend is melted in a melting furnace at 1450°C, and the melt discharged from the furnace is then cooled to 1200°C. 1200
The viscosity at °C is 10 ^3.5 poise and the viscosity at 1100 °C is
10 It was ^4.0 poise. A portion of it was poured onto a heat-resistant stainless steel plate and rapidly cooled to obtain a sample piece. When this sample piece was observed, it was observed that a small amount of fine crystals around 10 μm were homogeneously distributed. The molten material at approximately 1100℃ is sent to a feeder, then charged into a roller molding machine through the feeder, and the viscosity is adjusted between 900 and 800℃.
10 A molded product with no damage was obtained by molding into a plate with a thickness of about 20 mm on a ^5.8 poise table. Next, a primary crystallization heat treatment was performed by heating at 800°C for about 1 hour, and a secondary crystallization heat treatment was further performed at 1100°C for about 1 hour to obtain a crystallized glass molded product. When this was observed and measured, K-phlogopite crystals were found in the molded product with a diameter of 500 μm or more.
They grow to 2000 μm and are scattered, and the polished surface has a beautiful marble-like appearance. Example 3 [Blend] (1) SiO ₂ suitable for light bulb glass as base material glass
65.5%, _Al2O3 1.5 _% , _{B2O3 5.0} %, CaO 4.8
%, _K2O 11.50%, _Na2O 3.0%, ZnO 4.3%,
60 by weight raw material batch adjusted to 5.4% BaO
(2) Barium trisilicon mica [Ba _0.5 Mg ₃
(AlSi ₃ O ₁₀ ) F ₂ composition]
_SiO2 39.5%, BaO 16.8%, _MgF2 14.9%,
35 parts by weight of a raw material batch adjusted to 17.7% MgO and 11.1% Al ₂ O ₃ , (3) Co-synthesized fluorine mica [KMg _1.5 Co _1.5
(AlSi ₃ O ₁₀ )F ₂ composition] SiO ₂ 36%, K ₂ O 9.5%, Co ₂ O ₃ 25%,
5 parts by weight of a raw material batch adjusted to 19.3% MgF ₂ and 10.2% Al ₂ O ₃ were homogeneously mixed with these raw material batches (1), (2), and (3) to prepare a raw material batch. [Manufacturing] 1 kg of raw material batches are collected in a SiC crucible, melted in a Matsufuru-type Elema furnace at 1470℃ for 40 minutes, taken out of the furnace, and the molten material is heated together with the crucible in the air from 1470℃ to 1100℃.
Allow to cool at a cooling rate of 30-35℃/min, then cool to 1100℃
Adjust the temperature drop by heating the outer periphery of the crucible to 1000℃ for at least 20 minutes with a gas flame, take out the molten material from the crucible, and spread and shape it at 850 to 820℃ using an experimental mini roller made of Stellite heat-resistant steel. A pale blue molded body measuring 10 cm and approximately 35 cm in length was obtained. Molded body is 700℃
When the temperature reached 800°C, it was charged into an electric furnace that had been maintained at 800°C in advance, and held at 800 to 820°C for 60 minutes, and then the electricity was turned off and cooled in the furnace. After the molded body was taken out of the furnace, its upper and lower surfaces were polished to a mirror finish using a conventional polishing method to obtain a crystallized glass molded product. The product had a beautiful pattern of homogeneous clusters of pale blue sesame-like crystals. In addition, the physical properties of the product are a specific gravity of 2.84,
Transverse bending strength 762Kg/cm ² , Shoer hardness 91, Searby impact strength 2.8Kg-m/cm ² , Coefficient of thermal expansion (30-500
℃) 74×10 ^-7 . Example 4 [Blend] (1) Composition of glassy substance (wt%) SiO ₂ 73, Al ₂ O ₃ 1.8%, MgO 17, CaO 8,
B ₂ O ₃ 0.2 Blending ratio 45 parts by weight (2) Mica composition (% by weight) M-1: (a) BaMg ₃ (B ₂ Si ₂ O ₁₀ ) F ₂ (barium disilicon mica) BaO 27.5, MgO 14.5,
MgF ₂ 11.3, B ₂ O ₃ 25.1, SiO ₂ 21.6 Blending ratio 40 parts by weight M-2: (B) Ba _0.5 Mg ₃ (BSi ₃ O ₁₀ ) F ₂ (barium trisilicon mica) BaO 17.4, MgO 18.3,
MgF ₂ 16.0, B ₂ O ₃ 8.0, SiO ₂ 40.3 Blending ratio 45 parts by weight [Production] The melting temperature was 1450°C for M-1 and 1400°C for M-2, and the other methods were the same as in Example 3. . [Product characteristics] [Table]

Claims (1)

[Claims] 1. A molten solidified product of a glassy substance and a chemical formula of
X _0.5-1.0 Y _2.0-3.0 (Z ₄ O ₁₀ ) F ₂ [X is Ba ²⁺ or
Ba ²⁺ is partially replaced with at least one ion selected from K ⁺ , Ca ²⁺ , Zn ²⁺ , Pb ²⁺ , and Sr ²⁺ , Y is Mg ³⁺ or Mg ^{3 +} part of Fe ²⁺ ,
Substituted with at least one ion selected from Ni ²⁺ , Mn ²⁺ , Co ²⁺ , Al ³⁺ , Fe ³⁺ , Z is (Al ₂ Si ₂ ), (B ₂ Si ₂ ), (AlSi ₃ ), (BSi ₃ ) or a part of these silicon compositions as Fe ³⁺ , Ge ⁴⁺ , Al ³⁺ ,
A crystallized glass molded product comprising a barium fluorine mica crystal substituted with at least one type of ion selected from B ³⁺ . 2 Melted and solidified glass substance and chemical formula is
X _0.5-1.0 Y _2.0-3.0 (Z ₄ O ₁₀ ) F ₂ [X is Ba ²⁺ or
Ba ²⁺ is partially replaced with at least one ion selected from K ⁺ , Ca ²⁺ , Zn ²⁺ , Pb ²⁺ , and Sr ²⁺ , Y is Mg ³⁺ or Mg ^{3 +} part of Fe ²⁺ ,
Substituted with at least one ion selected from Ni ²⁺ , Mn ²⁺ , Co ²⁺ , Al ³⁺ , Fe ³⁺ , Z is (Al ₂ Si ₂ ), (B ₂ Si ₂ ), (AlSi ₃ ), (BSi ₃ ) or a part of these silicon compositions as Fe ³⁺ , Ge ⁴⁺ , Al ³⁺ ,
^1. A crystallized glass molded product comprising barium fluorine mica-based mica crystals represented by the following formula and other fluorine-mica composition crystals. 3 Glassy substance and chemical formula is X _0.5~1.0 Y _2.0~3.0
(Z ₄ O ₁₀ )F ₂ [X is Ba ²⁺ or a part of Ba ²⁺ as K ⁺ ,
Substituted with at least one ion selected from Ca ²⁺ , Zn ²⁺ , Pb ²⁺ , Sr ²⁺ , Y is Mg ³⁺
Or a part of Mg ³⁺ can be converted into Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ ,
Substituted with at least one kind of ion selected from Al ³⁺ and Fe ³⁺ , Z is (Al ₂ Si ₂ ),
(B ₂ Si ₂ ), (AlSi ₃ ), (BSi ₃ ) or a part of these silicon compositions with at least one kind selected from Fe ³⁺ , Ge ⁴⁺ , Al ³⁺ , B ³⁺ 1. A method for producing a crystallized glass molded product, which comprises mixing a barium fluorine mica-based composition represented by [indicating one substituted with ions], melting it, processing and molding it, and then cooling it. 4 Glassy substance and chemical formula is X _0.5~1.0 Y _2.0~3.0
(Z ₄ O ₁₀ )F ₂ [X is Ba ²⁺ or a part of Ba ²⁺ as K ⁺ ,
Substituted with at least one ion selected from Ca ²⁺ , Zn ²⁺ , Pb ²⁺ , Sr ²⁺ , Y is Mg ³⁺
Or a part of Mg ³⁺ can be converted into Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Co ²⁺ ,
Substituted with at least one kind of ion selected from Al ³⁺ and Fe ³⁺ , Z is (Al ₂ Si ₂ ),
(B ₂ Si ₂ ), (AlSi ₃ ), (BSi ₃ ) or a part of these silicon compositions with at least one kind selected from Fe ³⁺ , Ge ⁴⁺ , Al ³⁺ , B ³⁺ Crystallization characterized by mixing a barium fluorine mica-based composition represented by [indicating one substituted with ions] and other fluorine-based mica-based compositions, melting, processing and molding the same, and then cooling. Manufacturing method for glass molded products.