CN1172778U - Glass-ceramic for building materials with natural marble pattern and manufacturing method thereof - Google Patents

Abstract

A glass-ceramic, using Glauber's salt as a clarifying agent, the composition is: SiO245-77%, Al2O31-25%, CaO2-25%, ZnO0-18%, BaO0-20%, Na2O1-15%, K2O0 in weight percentage -7%, Li2O0-5%, B2O30-1.5%, CeO20.01-0.5%, SO30.01-0.5%, melt the blended glass raw material, shape it, and make it crystallized. This glass-ceramic not only does not contain As2O3 and Sb2O3, but also has excellent solubility, high production efficiency, and whiteness equal to or higher than that of the old type.

Description

Glass-ceramic for building materials with natural marble pattern and method for producing the same

The present invention relates to the glass-ceramic for building interior decoration material and exterior decoration material and its manufacture method.

[002] This glass-ceramic is widely used as an interior and exterior decoration material for buildings as a natural stone substitute due to its excellent properties such as chemical durability and mechanical strength, as well as its beautiful appearance.

As such glass-ceramics, there have been various proposals in the past. In Japanese Patent Application Laid-Open No. 16446 (JP-A-3-16446, JP-A-3-16446) and Japanese Patent Laid-Open No. 6-247744 (JP-A-6-247744), a It is a kind of microcrystalline glass that precipitates β-wollastonite crystals (Wallastonite, CaO·SiO2) to form natural marble patterns.

[004] When manufacturing glass-ceramics on an industrial scale, the production efficiency of the glass is regarded as important. Although the production efficiency is affected by the grade of bubbles (seed) in the glass, it is the solubility of the glass that affects this grade.

Therefore, in order to improve solubility, generally in glass raw material, add clarifying agent (refiningagent) As O and Sb O. At the same time, melting is performed in a melting furnace provided with a molybdenum (Mo) electrode as required.

However, As O and Sb O Not only has greatly improved solubility, but also has the effect of improving the whiteness of glass transmittance micro-crystallized glass, so it is widely used as a clarifying agent, but the use of these components brings inconvenience to the environment. It has a good effect, so in recent years, it is hoped to reduce the usage. When melting in a melting furnace provided with a molybdenum electrode, if As2O3 and Sb2O3 are present in the glass, the electrode has to be replaced frequently, which is not satisfactory, since the electrode is eroded significantly.

One object of the present invention is to provide a kind of glass-ceramic, although it does not contain As2O3 and Sb2O3, but the solubility is good and the production efficiency is high, and has the whiteness more than equal to the old product.

Yet another object of the present invention is to provide a method for producing glass-ceramics having the above-mentioned advantages.

According to the present invention, it can be characterized in that having the composition as: in weight percent SiO 45-77%, Al O 1-25%, CaO 2-25%, ZnO 0-18%, BaO 0-20%, Na2O 1-15% K2O 0-7%, Li2O 0-5%, B2O3 0-1.5% CeO2 0.01-0.5%, SO3 0.01-0.5%, and the crystallized glass-ceramic whose main crystal is β-wollastonite is obtained .

According to the present invention, obtain a kind of manufacture method of glass-ceramic, it is characterized in that making clarifier with Glauber's salt, and its composition is: in weight percent SiO 45-77%, Al O 1-25%, CaO 2-25 %, ZnO 0-18%, BaO 0-20%, Na2O 1-15%, K2O 0-7%, Li2O 0-5%, B2O30-1.5%, CeO2 0.01-0.5%, SO3 0.01-0.5%, the The blended glass raw material is melted, shaped, and then crystallized.

The glass-ceramic of the present invention has its composition: by weight percent SiO 45-77%, Al O 1-25%, CaO 2-25%, ZnO 0-18%, BaO 0-20%, Na O 1-15%, K2O 0-7%, Li2O 0-5%, B2O3 0-1.5%, CeO2 0.01-0.5%, SO3 0.01-0.5%, a structure formed by precipitating β-wollastonite as the main crystal.

[012] In the glass-ceramic of the present invention and the method for producing the same, the reasons for limiting the content of each component are as follows.

[013] The content of SiO2 is 45-77%, preferably 52-72%. When SiO2 is more than 77%, the melting temperature of the glass is increased, and at the same time, the viscosity is increased, and the fluidity during heat treatment is deteriorated. On the other hand, when it is less than 45%, devitrification at the time of molding is severe.

[014] The content of Al2O3 is 1-25%, preferably 3-15%. When Al2O3 is more than 25%, the solubility of the glass is deteriorated, and at the same time, the stability of the color tone is deteriorated. On the other hand, when Al2O3 is less than 1%, the devitrification phenomenon is strong, and at the same time, the chemical durability is lowered.

[015] The content of CaO is 2-25%, preferably 8-18%. When the amount of CaO is more than 25%, the devitrification property is strong and forming is difficult, and when the precipitation amount of β-wollastonite is too large, it is difficult to obtain the desired surface smoothness. On the other hand, when it is less than 2%, when the amount of precipitation of β-wollastonite is too small, the mechanical strength is lowered, and it does not have practicality resistance as a building material.

[016] ZnO is a component added to promote the fluidity of glass during crystallization heat treatment. The ZnO content is 0-18%, preferably 2-15%. When ZnO is more than 18%, β-wollastonite is difficult to precipitate.

[017] The BaO content is 0-20%, preferably 0-10%, more preferably 1-10%. When BaO exceeds 20%, the precipitation amount of β-wollastonite is very small.

[018] The content of Na2O is 1-15%, preferably 3-10%. When Na2O is more than 15%, chemical durability deteriorates. On the other hand, when it is less than 1%, the viscosity increases, and the solubility and fluidity deteriorate.

[019] The content of K2O is 0-7%, preferably 0-5%, more preferably 0.1-5%. When K2O is more than 7%, chemical durability deteriorates.

[020] Li2O has the effect of accelerating the crystallization speed, and its content is 0-5%, preferably 0.1-3%. When Li2O is more than 5%, chemical durability decreases.

[021] The content of B2O3 is 0-1.5%, preferably 0-1%. When B2O3 exceeds 1.5%, different crystals are precipitated, and desired properties cannot be obtained.

[022] CeO2 is a component that can improve the transmittance of glass without reducing the solubility of glass. The content of CeO2 is 0.01-0.5%, preferably 0.05-0.3%. With the change of valence, CeO2 is mixed as impurities to inhibit the coloring of Fe2O3, especially by coexisting with SO3 (glauber's salt), the effect is more significant. Therefore, when CeO2 is more than 0.5%, the coloring due to Ce4+ is too strong, and the transmittance of the glass is lowered, and when it is less than 0.01%, the above-mentioned effects cannot be obtained.

[023] The content of SO3 is 0.01-0.5%, preferably 0.02-0.4%. The reason for this is that when SO3 is more than 0.5%, dissimilar crystals are precipitated, and when it is less than 0.01%, the solubility is lowered and the quality of the glass is deteriorated.

[024] In addition, in the present invention, when the total amount of CaO, Li2O, and B2O3 is adjusted to 10-17.5%, the stability of the color tone of the glass-ceramic can be improved. In addition to the above-mentioned components, for example, colored oxides and the like may be contained.

[025] The method for producing the glass-ceramic of the present invention is described below.

At first, blend glass raw material, make clarifier with Glauber's salt, make it consist of: in percentage by weight: SiO 45-77%, Al O 1-25%, CaO 2-25%, ZnO 0-18%, BaO 0-20%, Na2O 1-15%, K2O0-7%, Li2O 0-5%, B2O3 0-1.5%, CeO20.01-0.5%, SO3 0.01-0.5%. By using Glauber's salt, the molybdenum electrode is hardly corroded, and the solubility can be improved.

[027] Next, the prepared glass raw material is melted and vitrified. In melting, it is preferable to use a melting furnace provided with molybdenum electrodes. The melting temperature and melting time are preferably 1450-1550°C, respectively, for 8-16 hours.

[028] Next, after forming the molten glass, it is crystallized. In this series of glass, after the glass is processed into small spherical, flake and other glass bodies, it is stacked in the mold, and it is heat-treated to make it crystallized. Because the obtained glass-ceramic has high mechanical strength, and It presents a beautiful natural marbling pattern, which is satisfying. In addition, the heat treatment is carried out at a rate of 1-6°C/min, to 1020-1100°C, and maintained for 2-4 hours.

In addition, the glass-ceramics of the present invention that obtains, because when the glass is melted, produces the SO as clear gas , the result makes the SO in the glass composition reduces, so for the raw material of glass, its composition, should do appropriate change.

[030] Here, the preferred embodiments of the present invention will be described.

Example 1

Table 1 shows the microglass of the present invention showing CeO and Glauber's salt (SO ) effect. Sample a is old glass-ceramic, sample b is glass-ceramic with Sb2O3 removed from sample a, sample c is glass-ceramic with mirabilite instead of Sb2O3 as a clarifying agent, sample d is added instead of Sb2O3 CeO2 glass-ceramic, sample e is a glass-ceramic that replaces Sb2O3 with Glauber's salt as a clarifying agent, and adds CeO2 at the same time.

[033] Each sample was prepared as follows.

Silica sand (Silica sand), alumina, calcium carbonate, hydrozincite (Hydrozincite), barium carbonate, soda ash (Soda ash), feldspar (feld spar), spodumene ( spodumene), sodium nitrate, antimony oxide, cerium oxide, and sodium sulfate, melted at 1500°C for 10 hours. Next, the molten glass was formed into a predetermined shape, and after processing, the foam powder and the average transmittance were measured. The molten glass is crushed with water, dried, and classified to obtain vitreous bodies of 1-5 mm. Next, these vitreous bodies were deposited in a refractory mold whose inner wall was coated with alumina powder, put into an electric furnace, heated at a rate of 2°C/min, and kept at 1050-1100°C for 2 hours, so that each After the vitreous body was melted into one body and simultaneously crystallized, the appearance, whiteness (L value) and main crystallization were evaluated. The results are shown in Table 1 below.

As can be seen from the following table 1, the surface smoothness of each sample is all very high, presents natural marble pattern, and is white glass-ceramic. The main crystal of any one is β-wollastonite. However, in the sample b glass-ceramic in which Sb2O3 was removed from the old type of the sample a, the number of bubbles was 100, which was 10 times the number of bubbles in the sample a, and it was found that the solubility was deteriorated. In addition, the transmittance was 11% lower than that of the sample a, so the whiteness was also lowered by "3".

On the other hand, replace Sb O Make the sample C of clarifier with Glauber's salt, the bubble powder is 2, has improved dissolubility largely, reduced transmittance.

Table 1 Sample A b C d E glass composition (weight) SiO2Al2O3caoznobaona2ok2oli2O3Cao3ceo2SO3 61.0 6.0 15.5 6.0 5.0 3.5 2.0 15.5 6.0 5.0 3.5 2.0 0.5 - - - 61.0 6.0 15.5 6.0 5.0 3.5 2.0 0.5 - - 0.3 61.0 6.0 15.5 6.0 5.0 3.5 2.0 0.5 - 0.2 - 61.0 6.0 15.5 6.0 5.0 3.5 2.0 0.5 - 0.2 0.3 Bubbles (1 / 100g) 10 100 2 100 2 Average transmittance (%) 86 75 78 80 89 appearance surface light Good nature, good, good, good tone, white series, white series, white series, white series, white series pattern, natural marble pattern, natural marble pattern, natural marble pattern, natural marble pattern, natural marble pattern, whiteness (L value) 93 90 91 92 94 main Crystalline Beta-Wollastonite Beta-Wollastonite Beta-Wollastonite Beta-Wollastonite Beta-Wollastonite

[038] As shown in Table 1 above, sample d to which CeO2 was added had a high transmittance of 80% and a whiteness of "92" higher than that of sample C, but the number of bubbles was 100, and the solubility was poor.

Again, replace Sb O Make clarifier with Glauber's salt, add CeO simultaneously again The embodiment of the present invention sample e, the number of bubbles is 2, and solubility is excellent, and, due to CeO And SO Addition effect, through The rate was 89%, and the whiteness was "94", which was further improved than that of sample d. Even compared with the old varieties, this is more than the same value.

[040] In addition, the number of bubbles was obtained as follows. First, molten glass is placed on a carbonaceous stage in a calm flow to form a plate-like body, which is annealed at 650-700°C. Next, a sample having an angle of 5 cm was cut out from the plate-like body, and the actual number of bubbles was counted under a microscope and converted into the number per 100 g.

[041] In addition, the average transmittance was measured as follows. First, the molten glass is processed and shaped to obtain a glass plate with a thickness of 10-12 mm, which is annealed at 650-700°C. Next, the glass plate was ground to have a mirror surface of 10 mm±0.1 mm, and it was determined with a spectrophotometer.

And then measure the whiteness with a colorimeter. The main crystal was measured with an X-ray diffraction apparatus.

Example 2

Table 2 below shows sample No. 1-5 of the present invention.

[045] Each sample was prepared as follows.

Blend by the glass composition of table 2, silica sand, aluminium oxide, calcium carbonate, hydrozinite, barium carbonate, soda ash, feldspar, spodumene, borax (borax), cerium oxide and mirabilite (salt cake) ), melted at 1500°C for 10 hours. Next, the molten glass was formed into a predetermined shape, and after processing and molding, the number of cells and the average transmittance were measured in the same manner as in Example 1.

The molten glass is crushed with water, dried and classified to obtain vitreous bodies with a particle size of 1-5 nm. After crystallization, the surface state, main crystal and whiteness are evaluated by the same method as in Example 1. The crystals are shown in Table 2.

[048] Table 2 Sample No. 1 2 3 4 5 Glass Composition (wt )SiO2Al2O3CaOZnOBaONa2OK2OLi2OB2O3CeO2SO3 59.0 6.5 17.0 6.0 4.0 4.0 2.0 0.6 0.7 0.1 0.1 62.0 6.5 15.0 6.0 3.5 4.0 2.0 0.2 0.5 0.1 0.2 64.0 6.0 13.0 7.0 3.0 5.0 1.5 0.4 - 0.3 0.1 64.0 5.5 14.0 7.0 3.0 0.2 62.0 5.5 16.0 5.0 5.0 2.5 3.0 0.2 0.3 0.2 0.3 Bubbles (1 / 100g) 2 2 1 2 3 Average transmittance (%) 89 89 87 88 88 appearance Surface finish Good Good Good Tone White Series White Series White Series White Series White Series Pattern Natural Marble Pattern Natural Marble Pattern Natural Marble Pattern Natural Marble Pattern 3 Natural Marble Pattern Whiteness (L Value) 94 94 93 9 93 Main Crystal β-Wollastonite Stone β-Wollastonite

As can be known from Table 2, each sample has a very high smooth and smooth surface, showing a natural marble pattern, and β-wollastonite is precipitated as the main crystal, which is a white glass-ceramic. The number of bubbles is 3 or less, the solubility is good, the average transmittance is 87% or more, and the whiteness is 93 or more.

[050] As explained above, according to the glass-ceramics of the present invention, since As2O3 and Sb2O3 are not contained, there is no influence on the environment.

[051] The glass-ceramic according to the present invention has high mechanical strength and chemical durability, and since it has a whiteness equal to or higher than that of the old type, it is very suitable for use as an interior and exterior decoration material.

According to the present invention manufactures the method for glass-ceramic, due to use Glauber's salt to make clarifying agent, so solubility is good, because containing CeO , so the transmittance of glass is also very high. Therefore, glass-ceramics having the same whiteness as the old type can be produced efficiently. When melting in a melting furnace without molybdenum electrodes, the cost of melting is also reduced because electrodes do not have to be replaced frequently.

Claims (2)

1. A glass-ceramic, characterized in that the composition comprises: by weight percentage, SiO2 45-77%, Al2O3 1-25%, CaO 2-25%, ZnO 0-18%, BaO 0-20%, Na2O 1-15%, K2O 0-7%, Li2O 0-5%, B2O3 0-1.5%, CeO2 0.01-0.5%, SO3 0.01-0.5%, the precipitation main crystal is β-wollastonite. 2. A method for manufacturing glass-ceramic, characterized in that: using Glauber's salt as a clarifying agent, and blending glass raw materials according to the following composition, SiO2 45-77%, Al2O3 1-25%, CaO 2-25% by weight percentage , ZnO 0-18%, BaO 0-20%, Na2O 1-15%, K2O 0-7%, Li2O 0-5%, B2O30-1.5%, CeO2 0.01-0.5%, SO3 0.01-0.5%, and The prepared raw materials are melted, processed and formed, and then crystallized.