JPS6213292B2 - - 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. Crystallized glass molded products, in which fine crystals are generated inside the glass molded product, are useful as molded products with a beautiful appearance that can be compared with natural marble, granite, etc. due to the incident and reflection effects of light rays. . Important issues in the manufacturing method of 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 temperature of the crystallization heat treatment to produce crystals. It is management. 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 predetermined crystal is heated at an intermediate temperature range higher than the softening point and lower than the melting temperature, the glass powder is unified by fused sintering, and then heated to a temperature higher than the softening point. This is a method of obtaining a product by performing a crystallization heat treatment that precipitates crystals inside the molded product using operations at a predetermined temperature and time. After obtaining a molded product through various processes such as complete melting in a melting furnace, melting, feeding into a molding machine, roller or press molding, strain removal, slow cooling, etc., using almost the same method as the product manufacturing method, This is a method of obtaining a product by heating it again and holding it at a temperature near the softening point for a certain period of time to perform a crystallization heat treatment to precipitate crystals inside the molded product. The present invention relates to the melting method of these two methods. The types of crystals produced in crystallized glass molded products using the conventional melting method are β-wollastonite and β-wollastonite.
- spodium, β-koukryptite, etc. The problem with this conventional method is that a crystallization heat treatment step by reheating after molding is essential. This process varies slightly depending on the composition, but in general, the temperature is raised from 700°C or higher while controlling the temperature, and the crystallization heat treatment is performed in a temperature range of 1000 to 1200°C. If such a crystallization heat treatment step in the conventional method could be carried out at a temperature within the range of the normal glass molded product manufacturing process without being added after the molding process, it would be economically and technologically possible. It is clear that this is a significant advantage. The present invention enables the crystals to be produced inside a crystallized glass molded product to be a specific fluorine mica or a derivative obtained by isomorphic substitution of the fluorine mica, thereby achieving the temperature conditions of the normal glass molded product manufacturing process. Without significantly changing the rapid cooling conditions or low-temperature slow cooling process within the range of It is characterized by producing a crystallized glass molded product by producing most of the crystals at a temperature lower than 0.3 °C. To explain a specific example of the normal glass product manufacturing process using the plate glass manufacturing process, the melting temperature is 1350 to 1500℃.
The melt is heated to 1300-1200℃ after being taken out of the furnace.
It is sent to a roller molding machine by a feeder at a nearby temperature, and is rolled and formed into a plate shape at a temperature range of 750 to 600℃.Then, it is sent to a slow cooling furnace (roller hearth furnace) with stainless steel rolls, where it is heated to a low temperature of around 100℃. cooled to temperature. It takes about 25 to 50 minutes to go from around 1300℃ to around 600℃ to 750℃ at the entrance of the lehr, and the time from the entrance to the exit of the lehr is 20 to 50 minutes.
It takes about 40 minutes. Therefore, in order to obtain a crystallized glass molded product using the normal plate glass manufacturing process,
It is necessary that crystal formation occurs within the glass melt-solidified product within the range of the above-mentioned temperature conditions. In the present invention, a fluorine muscovite crystal or a composition for producing fluorine muscovite crystals (hereinafter referred to as a fluorine muscovite substance) is blended into glass or a glass component (hereinafter referred to as a glass substance). Alternatively, the above-mentioned fluorine muscovite substance is blended with other fluorine mica derivative crystals or a composition for forming the fluorine mica derivative crystal (hereinafter referred to as other types of fluorine mica substances). This makes it possible to manufacture crystallized glass molded products under the temperature conditions used to manufacture ordinary glass. The basic raw material composition in the present invention is a combination of a glassy material as a base material and a fluorine muscovite material. The base glass material may be a glass composition, ie, a raw material batch, which is to be melted to make glass, or a frit-like glass obtained by vitrifying this raw material batch in advance and then pulverizing it. As a glass component,
For example, SiO ₂ −Al ₂ O ₃ −B ₂ O ₃ −CaO−K ₂ O−Na ₂ O
Or add P ₂ O ₅ , BaO, MgO, ZnO, PbO,
It contains TiO ₂ , ZrO ₂ , etc., and glass materials such as sheet glass, bottle glass, pressed glass, lighting glass, sealing glass, and crystal glass can be used in the usual glass product categories.
The blending ratio of these materials is determined by their melting temperature, viscosity,
It is determined as appropriate, taking into consideration manufacturing conditions such as the molding method, adhesion with other materials, and crystallization treatment to be described later. The fluorine muscovite substance can be used as a composition for producing fluorine muscovite crystals in a molten and solidified glass substance, that is, in an unheated raw material batch, or in advance from this raw material batch. It may be a glassy powder made by heating and melting or a fluorine muscovite crystal powder. The blending ratio of the glassy material and the fluorine muscovite material of the base material is determined by taking into consideration the maintenance of viscosity necessary for molding and the amount of crystal formation.
A range of approximately 30:70 to 70:30 is preferable. The fluorine muscovite used in the present invention is a type of fluorine mica, and the fluorine mica has the general formula
_{0.5 ~ 1.0 Y2.0 ~ 3.0 ( Z4O10} ) _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, and Z is a cation with a coordination number of 4.
The cation is usually based on the SiO ₄ tetrahedral Si, and Y is a cation with a coordination number of 6 and forms an octahedral layer. The crystal structure of fluorine mica is a hexagonal mesh plate of SiO ₄ tetrahedrons, with two sheets above and below, between which ions with octahedral coordination are bonded, and this structure is called a tablet. They are stacked in layers, with alkali or alkaline earth metal ions bonded between the tablets and called interlayer ions. The basic forms in which fluorine mica crystals are originally produced are the melting method, in which mixed raw materials are melted according to the crystal composition, and the crystals are precipitated by processing the melt under certain temperature conditions, and the mixed raw materials are mixed into powder. 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, thermal vibrations of solid particles cause
There is a solid phase reaction method in which atoms at crystal lattice points on the surface of a particle enter the radius of action of atoms on the surface of other particles, bonds are broken, and crystals are formed. There are crystals that are generated in Whether or not crystals can be formed using the melting method or the solid phase reaction method is determined by experimenting with various compositions. Furthermore, when a melt having a composition that causes mica crystals to precipitate is cooled rapidly below the crystal precipitation temperature, the amount of mica crystals crystallized is small, and the remainder becomes glass having the same composition as mica. Conventionally, this phenomenon has been utilized to produce fluorine phologopite [KMg ₃
(AlSi ₃ O ₁₀ ) F _{2 ]} or _tetrasilicon fluorine mica _{[ KMg 2} . There are mica glass ceramics manufactured by a method that increases the amount of mica crystals produced. This product has a crystal content of 50 to 90% by weight,
After obtaining each molded product, nucleation heat treatment is performed at 750-850°C for 1-6 hours, and nucleation heat treatment is performed at 1000-1150°C for 1-6 hours.
A two-step crystallization heat treatment including heat treatment for crystal growth, which is held for 6 hours, is an essential process. The present invention is applicable to conventional crystallized glass molded products such as β-wollastonite and β-spodiumene and mica.
This method makes it possible to perform crystallization within the scope of the normal glass product manufacturing process without requiring a two-step high-temperature, long-term crystallization heat treatment by reheating the molded product in glass-ceramics. be. In other words, we discovered that by combining and melting a fluorine muscovite substance and a glass substance, it is not only possible to form glass, but also that fluorine muscovite crystals are easily formed during the cooling process after processing. It is something that A composite melt of a fluorine muscovite substance and a glass substance undergoes precipitation and growth of crystals from around the softening point temperature (600 to 850℃) during the process of being molded and slowly cooled. The crystallization heat treatment can be carried out within the elapsed time of the step up to the initial stage of slow cooling (550 to 600°C) in the glass manufacturing process or with a slight extension of the time. However, in the case of a melt made only of fluorine muscovite materials, the temperature at which the viscosity range suitable for molding ( ^{10 3} to 10 ⁷ poise) can be maintained is around 850°C, which poses problems with the material used in the molding machine, and also prevents solidification. Due to the high speed, it was impossible to manufacture it using normal glass product manufacturing processes. In this regard, in the present invention, by blending the fluorine muscovite substance and the glass substance, the viscosity range suitable for molding is 700°C.
It was confirmed that the solidification rate was improved and became slower, and that fluorine muscovite crystals could be formed even in these mixed melts. The fluorinated muscovite used in the present invention can form crystals in a molten and solidified glass material through a solid phase reaction, and its chemical formula is XAl ₂
It is represented by (AlSi ₃ O ₁₀ )F ₂ . In the formula, X is K,
Collectively refers to Na ⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ , Rb ⁺ , etc. This fluorine muscovite has a structure called 2-octahedron, which has the general formula of fluorine mica, X ₀ .
_5-1 . ₀ Y ₂ . 0 _{- 3} . ₀ (Z ₄ O ₁₀ ) In F ₂ , there are usually three octahedral-coordinated Ys, but in the case of fluorine muscovite, Al ³⁺ has two octahedral coordinations. They are coordinated to form one cavity. The crystal formation mechanism in the present invention is that a mixed melt of a fluorine muscovite substance and a glassy substance undergoes a slowing process near the softening temperature (850 to 600°C) during the cooling process after melting, especially after the completion of molding (below 650°C). Cold early stage (650~
It is the formation of crystals by reactions of constituent atoms within a melt in a short period of 20 to 40 minutes at a temperature range of 500°C. The temperature treatment for crystallizing fluorine muscovite can be carried out at a temperature between 600 and 700°C, which means that the softening point of ordinary glass products is 700 to 750°C, but the Cooling period for 20-30 minutes
It has the advantage of being able to crystallize by keeping it at 600-700°C. The present invention is mainly based on producing fluorine muscovite crystals in a molten solidified glass material, but other types of fluorine mica crystals can be co-formed therewith. The fluorine mica to be co-synthesized has the general formula of fluorine mica [ _{X1.5 ~ 1.0 Y2.0 ~3} .
₀ (Z ₄ O ₁₀ )F ₂ ], where X is Na ⁺ , K ⁺ , Ca ²⁺ , Ba ²⁺ ,
Sr ²⁺ , Rb ⁺ , Y is Mg ²⁺ , Fe ²⁺ , Cu ²⁺ , Ni ²⁺ ,
Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Li ⁺ , Z (Al ³⁺ , Si ⁴⁺ ),
These are obtained by isomorphic substitution of Si ⁴⁺ , Ge ⁴⁺ , Al ³⁺ , Fe ³⁺ , and B ³⁺ . The above-mentioned fluorine mica crystal co-formed with the fluorine muscovite crystal in the molten solidified glass substance,
As described below, each type has its own crystallization conditions depending on temperature and time, so it is classified as follows to determine the combination according to the purpose of the product. (1) The temperature at which crystal precipitation begins during the cooling process of the melt is 1100°C or higher. Crystals in this temperature range are mainly produced by the above-mentioned melting method, and have a relatively fast cooling rate, for example, 30°C.
The rate is ~120°C/min, and when the temperature is maintained between the crystal precipitation temperature and 100°C lower than the crystallization temperature for 10 to 20 minutes, crystals with a size of 0.5 to 2.0 mm are produced. A typical example of this type is [KMg ₃
(AlSi ₃ O ₁₀ ) F ₂ , crystallization temperature (abbreviated as ct, same below) 1340°C] _, [KMg _2.5 (Si ₃ O ₁₀ ) F ₂ , c.
t1145℃], [KMg ₂ Li (Si ₄ O ₁₀ ) F ₂ , c.t1185],
[KMg ₃ (BSi ₃ O ₁₀ ) F ₂ , c.t1090] etc. (2) Crystal formation temperature ranges between 1100℃ and 600℃. Glass in this temperature range is mainly crystals produced by the above-mentioned solid phase reaction, and when held for 20 minutes or more between the crystal precipitation temperature and 100°C lower than the crystal precipitation temperature, the crystal size is often 0.5 mm or less. generate. The characteristics of this type of crystal are that Fe ²⁺ , Fe ^{3+ , Co 2+ ,} Co ³⁺ , Cr ³⁺ ,
Ni ²⁺ , Ni ³⁺ , Cu ²⁺ , Mn ²⁺ , Ti ³⁺ , Ti ⁴⁺ , Be ⁴⁺
Many of them are coordinated with ions such as, and each of these 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 , c.t 1100°C, blue or _pink ], [KMg _2.8 Ni _0.2 ( _{AlSi 3 O Ten} )
_F2 , c.t1000℃, green yellow〕,
_[ KMg _{2.65 ~ 2.80} Co _{0.35 ~ 0.2} ( _AlSi3O10 ) _F2 , c.
t1000℃ brownish], [KFe ₃ (FeSi ₃ O ₁₀ ) F ₂ , c.
t650℃, black gray], [ _{KMg 1.0 M2.0} (AlSi _{3 O 10 )}
F ₂ , c.t1000℃, brown], [KAlTi ³⁺ (AlSi ₃ O ₁₀ )
_F2 , c.t800℃, beige color], etc. The combination of the above-mentioned (1) and (2) fluorine mica co-formed with fluorine muscovite improves the appearance of the crystallized glass molded product, such as crystal size, pattern, and color.
It is determined in consideration of the suitability of manufacturing conditions such as slow cooling from a molten material during molding such as roll molding. The amount of fluorine mica to be produced is 0.5 parts by weight or less per 1.0 parts by weight of fluorine muscovite. To specifically explain the structure of the crystallized glass molded product of the present invention, the component composition of the base glass is
_SiO2 50%, _{Al2O3 8} %, _{B2O3 15} %, CaO10%,
Glass powder which is _K2O3 %, _Na2O15 % by weight 60
%, _SiO2 43%, _K2CO3 14 _% , _{K2SiF6 27} %,
Fluorinated muscovite (KAl ₂ (AlSi ₃ O ₁₀ ) F ₂ composition) consisting of a raw material batch with a composition of 16% Al ₂ O ₃ is blended with 40%, melted in a melting furnace at 1400°C, and then discharged from the furnace. The melt was heated between 1300 and 1100℃ at 30°C per minute.
Cool at a rate of ~40 °C. The viscosity at 1100℃ is approximately 10 ^4-
The material is then sent to a roller forming machine via a feeder, where it is formed into a plate shape approximately ^{50 mm thick at a viscosity of 106.5 poise} at a temperature between 800 and 650°C, and then sent to a roller hearth furnace. Crystallization heat treatment is performed at a temperature of 700°C to 600°C for 20 minutes, and then slowly cooled to 100°C for about 15 minutes. The physical properties of this molded body are 0% porosity, specific gravity 2.81, hardness (shoer) 92, and transverse rupture strength 968 Kg/cm ^2. When polished to a mirror-like finish, it is beautiful and comparable to natural marble. It has a pattern of spots. According to X-ray diffraction and quantitative analysis, the crystals precipitated inside the crystallized glass molded product are fluorine muscovite [KAl ₂ (AlSiO ₃ )F ₂ composition]
It is a layered crystal with a diameter of 0.05 to 0.5 mm, and the amount of crystal formation ranges from about 25 to 35% of the weight of the molded product. What should be noted in the present invention is that, as is clear from the above, the heat treatment step for crystallization is
It can be carried out in a temperature range of 750 to 550°C and in 25 to 35 minutes. In contrast to the process currently carried out as standard in the manufacture of glass, at the temperature of 750°C to 550°C, the molding process in the present invention has already been completed, and this is the temperature at which it is fed into the lehr. If the temperature control is adjusted to the crystal formation conditions of fluorine muscovite, crystallization of the glass molded product can be achieved without adding a special process for crystallization or reheating. Next, examples of the present invention will be shown. Example 1 Mixture (1) Suitable for light bulb glass as base material glass
_SiO2 67.4%, _{Al2O3 1.0} %, _{B2O3 4.5} %, CaO4.6
%, K ₂ O 12.0%, Na ₂ O 2.5%, ZnO 4.0%,
60 by weight raw material batches adjusted to BaO4%
(2) Fluorine muscovite [KAl ₂ (AlSi ₃ O ₁₀ )F ₂
Composition] SiO ₂ 43% for the purpose of crystal formation,
35 parts by weight of a raw material batch adjusted to 14% K ₂ CO ₃ , 27% K ₂ SiF _{6 ,} and 16% Al ₂ O ₃ , (3) Co _- synthesized fluorinated mica [KMg _1.5 Co _1.5
(AlSi ₃ O ₁₀ ) F ₂ composition] A blend of 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 placed in a SiC crucible, melted in a Matsufuru Elema furnace at 1350℃ for 30 minutes, taken out of the furnace, and the molten material is heated in the atmosphere from 1350℃ to 1100℃ along with the crucible.
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 800 to 750℃ 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 700°C, it was placed in an electric furnace that had been previously maintained at 700°C, held at 700°C to 600°C for 25 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
2.73, transverse strength 950 Kg/cm ² , Shore hardness 90, Shalpy impact strength 2.4 Kg-m/cm ² , and coefficient of thermal expansion (30 to 500°C) 72×10 ⁻⁷ . Example 2 Mixture (1) Glass composition (wt%)

【table】 (2) Fluorine mica composition

【table】 Manufacture of crystallized glass molded products

【table】

[Table] Appearance The product that underwent the polishing process became beautiful due to the formation of crystals. Product performance

【table】

Claims (1)

[Claims] 1. A crystallized glass molded product comprising a molten solidified glass substance and fluorine muscovite crystals. 2. A crystallized glass molded product consisting of a molten solidified glass substance, fluorine muscovite crystals, and other fluorine mica crystals. 3. A method for producing crystallized glass, which comprises mixing a glassy substance and a fluorine muscovite substance, melting and shaping the mixture, and then cooling it. 4. A method for producing crystallized glass, which comprises mixing a glass substance, a fluorine muscovite substance, and another fluorine mica substance, melting the mixture, molding it, and then cooling it.