KR940003463B1 - Method of glass ceramic having a crystalline phase - Google Patents

Abstract

The abrasion resistant crystallized glass is manufactured by (a) mixing 50-75 wt.% andesite, 15-30 wt.% dolomite, 5-10 wt.% silica sand refined byproduct, 1-4 wt.% borax and adding 1-6 wt.% the nucleant, (b) heating and melting the mixture at 1300-1450 deg.C for 1 hr., (c) molding and releasing the molten glass, and crystallizing at 600-1000 deg.C. The nucleant materials are mixture with two or four components of titania, chromium oxide, calcium fluoride, zirconium silicate etc. The composition of crystallized glass comprises 35-55 wt.% silica, 10-16 wt.% alumina, 5.0-8.5 wt.% ferric oxide, 0.5-2.5 wt.% boron oxide, 10-18 wt.% calcium oxide, 5-15 wt.% magnesium oxide, 0.5-3.0 wt.% sodium oxide, 0.5-3.0 wt.% potassium oxide and 0.1-1.0 wt.% manganese oxide.

Description

Manufacturing method of wear resistant crystallized glass and wear resistant crystallized glass produced by the method

Figure 1a is an X-ray diffraction analysis of conventional wear-resistant crystallized glass.

b is an X-ray diffractogram of sample ZR 32-3 of the present invention.

c is an X-ray diffractogram of sample ZR 71-1 of the present invention.

d is an X-ray diffractogram of sample ZR 72-2 of the present invention.

e is an X-ray diffractogram of sample ZR 73-3 of the present invention.

The present invention relates to a method for manufacturing abrasion resistant crystallized glass and to abrasion resistant crystallized glass, and in particular, a method for producing abrasion resistant crystallized glass having excellent abrasion resistance and acid resistance to alkali sand refining by-products, which are andesite, dolomite and quartzite mine waste. It relates to abrasion resistant crystallized glass produced by.

Conventional wear-resistant crystallized glass is manufactured using basalt as a main raw material, and there are US Pat. The reason for the use is that the basalt is widely distributed in the United States and Europe, so it can be easily obtained at low cost, and in the basalt, it is composed of minerals such as plagioclase, olivine, fluorite, magnetite, etc.SiO ₂ , MgO, Al ₂ O _{Since 3} , FeO, Fe ₃ O ₄ and the like are uniformly composed of components, it is easy to obtain crystals of clinopyroxene series having good mechanical properties.

U.S. Patent No. 1,893,382 describes two methods of basalt casting technology. First, under reducing conditions, the melt is injected into a mold and molded, and the glass is placed in a furnace controlled at 725 ° C. for about 1 hour, then reheated to 900 ° C., and the reheated glass is maintained at 900 ° C. for about 1 hour. Abrasion resistant glass was prepared, and secondly, the molten glass was melted under an oxidizing condition, and the melt was injected into a mold to be molded and immediately put into a furnace controlled at 900 ° C. and maintained for about 1 hour to prepare a wear resistant glass. In US Pat. No. 3,557,575, Like US Patent No. 1,893,382 as a main raw material, magnetite in basalt without special nucleating agent or additive is melted for a long time at 1,350-1600 ° C, and then molded and crystallized by two-step heat treatment at 645-670 ° C and 850-1000 ° C for 2 hours. One wear resistant crystallized glass was prepared. However, both of the above patents have a high melting temperature, which leads to a significant decrease in productivity due to high fuel costs and high viscosity during melting, making it difficult to remove bubbles that have a great influence on wear resistance and mechanical strength, and crystallinity by using magnetite as a nucleating agent without using a special nucleating agent. Has a disadvantage of significantly lower mechanical properties.

In addition, due to the large amount of iron contained in the basalt, refractory erosion in the furnace is severe during melting, and when melted with an electric resistance furnace, metal deposits in the lower part, preventing the cone nozzle, reducing productivity, and corroding electrodes, which shortens the life of the furnace. There is a problem.

Japanese Patent Laid-Open Publication No. 55-45502 also prepared a crystallized glass by mechanically mixing crystallized powders of the same composition prepared in advance while melting basalt as a raw material at a temperature of 1,500 ° C for a long time and lowering the temperature to 1300 ° C. It has the same disadvantage as the patent, and also has a disadvantage in that a large amount of bubbles are generated because the mechanical mixing in the process of mixing the mother glass.

The present invention is to solve the problems of the patent, such as bubble generation, low crystallinity, melting temperature and melting time and high iron content to improve the wear resistance and mechanical properties.

In our view, basalt is distributed in some areas such as Jeju Island, Ulleungdo, and Pohang districts, so it is not easy to purchase basalt, and it is difficult to purchase or construct, so it is difficult to stabilize supply and demand. Extremely low and low iron content affecting the electrode and economically advantageous andesite was used as the main raw material.

Andesite is widely distributed in Korea, and semicrystals, which consist of plagioclase, hornblende, fluorite, and biotite, are contained in glass, taste, and microcrystalline stone. Andesite is basically SiO ₂ , CaO, MgO, Al ₂ O ₃ , Fe Volcanic rock composed of ₂ O _3, etc., with strong chemical resistance, especially alkali.

As can be seen in Table 1 below, andesite shows little variation in components.

TABLE 1

(unit: wt%)

A: 2203 Andesite (Lemaitre 1976)

B: 1775 Cenozoic Andesite (Cyayes 1976)

C: Eonyang Andesite Cancer Analysis (1989)

D: 〃 (1989)

E: Wong (1989)

F: 〃 (1989)

G: 〃 (1990)

H: 〃 (1991)

I: 〃 (1991)

And the present invention was added dolomite to increase the composition ratio of MgO, a component insufficient in andesite to precipitate a large amount of diopside crystals, which is an essential condition for improving the wear resistance, and also added a B ₂ O ₃ compound to increase the melting temperature of the wear-resistant crystallized glass It was found to be low, easy to remove bubbles, strengthened matrix glass, and increased thermal shock resistance during glass molding, and added water bath nucleating agent alone or in combination to improve crystallinity. To provide glass.

Hereinafter, the present invention will be described in detail.

Mixes uniformly with 55-75% of andesite, 15-30% of dolomite, 5-10% of siliceous refinery by-products, and borax 1-3% and nucleating agent 1-5% as B ₂ O ₃ raw materials. Then melted by heating at 1350 ℃ -1600 ℃ for 1-3 hours and poured the molten glass into a mold of 70 × 70 × 20 (mm), demolded the glass and maintained at 600-650 ℃ 30 minutes and 5 ℃ per minute After cooling slowly to room temperature at a speed of 2 ° C, heat treatment was carried out in two stages to precipitate the diopside crystal and the anodide crystal phase, which are essential conditions for improving abrasion resistance, and were kept at 650-800 ° C. for 30 minutes to 1 hour for nucleation. 5-10 ° C. to 850 ° C. for 30-1 hours at 850-1000 ° C. for crystal growth, and then cooled at a rate of 10 ° C. per minute at SiO ₂ 35-55 wt%, Al ₂ O ₃ 10-16 wt%, Fe ₂ O ₃ 5.0-8.5wt%, B ₂ O ₃ 0.5-2.5wt%, CaO 10-18wt%, MgO 5-15wt%, Na ₂ O 0.5-3.0wt%, K ₂ O 0.5-3wt%, MnO Abrasion resistant texture containing 0.1-1wt% Glass gets temper.

In the nucleation step, TiO ₂ , Cr ₂ O ₃ , CaF ₂ , ZnS, ZrSiO ₄ , Na ₂ SO ₄ were added as nucleating agents to promote nucleation, especially TiO ₂ and Cr ₂ O ₃ / TiO ₂ and Cr. Nucleating agents such as ₂ O ₃ and Na ₂ SO ₄ / TiO ₂ + Cr ₂ O ₃ + Na ₂ SO ₄ + ZrSiO ₄ / TiO ₂ + Cr ₂ O ₃ + ZrSiO ₄ / TiO ₂ + ZnS / TiO ₂ + Na ₂ SO ₄ + Cr ₂ O ₃ + ZnS The crystallization effect was much better when using.

Hereinafter will be described according to an embodiment of the present invention.

Experiments were carried out with different nucleating agents added when homogeneously mixed with andesite 55-75%, dolomite 15-30%, silica sand byproducts 5-10%, and borax 1-3%.

Example 1

1.9% of TiO _{2 and} 1.2% of Cr ₂ O ₃ were added and mixed based on the raw material batch, and then heated and melted at 1350-1400 ° C. for 1 hour. The molten glass was poured into a mold, demolded slowly, and cooled to 10 / min at room temperature. After the temperature was raised to 700 ° C. and maintained at 700 ° C. for 30 minutes, the temperature was increased to 10 ° C. per minute to 975 ° C., and then cooled to room temperature at 10 ° C. per minute after maintaining at 975 ° C. for 30 minutes.

Example 2

TiO ₂ 1.9%, Cr ₂ O ₃ 1.7%, Na ₂ SO ₄ 0.4% was added and mixed based on the raw material batch, and then heated and melted at 1350-1400 ° C. for 1 hour. The molten glass was poured into a mold and demolded. After slow cooling, the temperature was raised to 10 ° C. per minute at 750 ° C., held at 750 ° C. for 30 minutes, and then heated to 10 ° C. per minute to 985 ° C., and then cooled to 10 ° C. per minute after holding at 985 ° C. for 30 minutes.

Example 3

TiO ₂ 1.9%, Cr ₂ O ₃ 1.4%, ZrSiO ₄ 0.3%, Na ₂ SO ₄ 0.9% was added and mixed, and then heated at 1350-1400 ° C. for 1 hour and then melted. After pouring into a mold and demolding slowly cooling to room temperature at 10 ℃ per minute to 780 ℃, after 30 minutes at 780 ℃ to 975 ℃ to 10 ℃ per minute and then held at 975 ℃ 30 minutes and cooled to room temperature 10 ℃ per minute .

Example 4

TiO ₂ 1.9%, Cr ₂ O ₃ 1.4%, ZrSiO ₄ 1.2% were added and mixed on the basis of the raw material batch, and then heated at 1350-1400 ° C. for 1 hour and melted. After the temperature was raised to 750 ℃ at 10 ℃ per minute at room temperature and maintained for 30 minutes at 780 ℃, and then heated to 10 ℃ per minute to 980 ℃ and cooled to room temperature at 10 ℃ per minute after holding for 30 minutes at 980 ℃.

Example 5

After mixing and mixing 1.9% of TiO ₂ and 1.2% of ZnS based on the raw material batch, the molten glass was heated at 1350-1400 ° C. for 1 hour and then melted. The molten glass was poured into a mold, demolded slowly, and cooled to 10 ° C. at 10 ° C. per minute at room temperature. After the temperature was raised to 30 ° C. and maintained at 750 ° C. for 30 minutes, the temperature was increased to 10 ° C. per minute up to 975 ° C., and then cooled to 10 ° C. after maintaining for 30 minutes at 975 ° C.

Example 6

TiO ₂ 1.9%, Na ₂ SO ₄ 0.4%, Cr ₂ O ₃ 2.0%, ZnS1.2% were added and mixed, and then heated at 1350-1400 ° C. for 1 hour and melted. After pouring into a mold and slowly demolding, the temperature was raised to 700 ° C. at 5 ° C. per minute at room temperature, and then held at 700 ° C. for 30 minutes, then heated to 5 ° C. per minute to 975 ° C., and then cooled to 5 ° C. per minute after holding at 975 ° C. for 30 minutes. .

The composition of the wear resistant crystallized glass according to the embodiments is shown in Table 2 below.

TABLE 2

Such characteristics of the wear-resistant crystallized glass according to the present invention are shown in Table 3.

TABLE 3

In addition, as a result of comparing the wear resistance of the wear-resistant crystallized glass and magnetic tiles, copper, cast iron, high manganese steel according to the present invention was as shown in Table 4.

TABLE 4

In addition, an X-ray diffractometer was used to analyze the crystallization of the sample according to the present invention (Sample Names ZR32-3, ZR71-1, ZR72-2, ZR73-3) and the sample name GENMANY of Schmeltz-Bacht, Germany, a conventional wear-resistant crystallized glass. As a result, as shown in FIGS. 1a, b, c, d, and e, the crystallization of the wear-resistant crystallized glass of the present invention is excellent.

In addition, the wear resistance crystallized glass according to the present invention and the wear resistance of German and Japanese products were compared.

The abrasion resistance test was performed for 52 days after standardizing (70 × 70 × 20mm) the specimens at the silica sand refinery. In this case, the experiment was conducted under the same conditions with Schmelz basalt kelebon, a wear resistant material of West Germany, and a product manufactured by Japan Battung Co., Ltd.

1) Period: June 22, 1991-1991.8.10 (52 days)

2) Number of Tests: 6 Example Products

3 German products

3 Japanese products

3) Pipe Inner Diameter (Im / MФ): 790

4) Radius of curvature (Rm / mФ): 1200

5) Angle (θ): 90 ℃

6) Working temperature: 130 ℃

7) Transport Speed: 22m / s

8) Uptime: 24 hours / day

9) Wind Pressure: 650㎜Aq

The results were as follows.

As described above, the wear-resistant crystallized glass according to the present invention has improved the utilization efficiency of domestic resources by using andesite as a main raw material, and lowers the melting temperature of the wear-resistant crystallized glass and facilitates bubble removal, thereby making it easy to wear-resistant crystallized glass at low cost. It was prepared to, in particular, as can be seen in the above example was extremely excellent wear resistance.

Claims (5)

50-75wt% andesite, 15-30wt% dolomite, 5-10wt% silica sand byproduct, 1-4wt% borax, uniform composition of SiO ₂ 35-55wt%, Al ₂ O ₃ 10-16wt%, Fe ₂ O ₃ 5.0-8.5wt%, B ₂ O ₃ 0.5-2.5wt%, CaO 10-18wt%, MgO 5-15wt%, Na ₂ O 0.5-3.0wt%, K ₂ O 0.5-3wt%, MnO 0.1 Method of producing a wear-resistant crystallized glass, characterized in that the crystallization to be -1wt% and 1-6wt% of the nucleating agent added thereto. The wear-resistant crystallization according to claim 1, wherein 1 to 6 wt% of 2 to 4 selected from TiO ₂ , Cr ₂ O ₃ , CaF ₂ , ZnS, ZrSiO ₄ , and Na ₂ SO ₄ is used as a nucleating agent. Method of making glass. According to claim 1, Crystallization conditions are SiO ₂ 35-55wt%, Al ₂ O ₃ 10-16wt%, Fe ₂ O ₃ 5.0-8.5wt%, B ₂ O ₃ 0.5-2.5wt%, CaO 10-18wt %, MgO 5-15wt%, Na ₂ O 0.5-3.0wt%, K ₂ O 0.5-3wt%, MnO 0.1-1wt% and 1-6wt% of the nucleating agent added at about 1300-1450 ℃ Heated for 1 hour, melted, poured into mold, demolded slowly cooled to 5-10 ° C. per minute from room temperature to 650-800 ° C. and maintained at 650-800 ° C. for 30 minutes-1 hour, then 5-10 ° C. to 850-1000 ° C. The method for producing abrasion-resistant crystallized glass, characterized in that it is slowly cooled by 5-10 ° C per minute after the temperature is raised and maintained for 30 minutes-2 hours. SiO ₂ 35-55wt%, Al ₂ O ₃ 10-16wt%, Fe ₂ O ₃ 5.0-8.5wt%, B ₂ O ₃ 0.5-2.5wt%, CaO 10-18wt%, MgO 5-15wt%, Na ₂ Abrasion-resistant crystallized glass, characterized by containing O 0.5-3wt%, MnO 0.1-1wt% and nucleating agent 1-6wt%. The wear-resistant crystallization according to claim 4, wherein the nucleating agent contains 1-6 wt% of 2 to 4 selected from TiO ₂ , Cr ₂ O ₃ , CaF ₂ , ZnS, ZrSiO ₄ , and Na ₂ SO ₄ . Glass.