High-wear-resistance black microcrystalline glass, composition and preparation method

Abstract

The invention provides high-wear-resistance black microcrystalline glass, a composition and a preparation method. The composition of the high-wear-resistance black microcrystalline glass comprises a basic component and an additive, the basic component is prepared from the following components in parts by mass: 65 to 75 parts of silicon dioxide, 5 to 10 parts of aluminum oxide, 8 to 12 parts of lithium oxide, 3 to 5 parts of zirconium oxide, 1 to 2 parts of ferric oxide, 0.1 to 0.5 part of cobalt oxide and 0.2 to 0.6 part of nickel oxide; the additive comprises boric acid and sodium carbonate. The preparation method of the high-wear-resistance black microcrystalline glass comprises the following steps: mixing the components in the composition, and melting to obtain molten glass; s3, cooling the molten glass to an intermediate temperature to obtain a glass precursor; s4, the glass precursor is sequentially subjected to first heat preservation treatment, second heat preservation treatment, third heat preservation treatment and fourth heat preservation treatment, and a glass ceramic primary product is obtained. The wear resistance and optical performance of the black microcrystalline glass are improved, and meanwhile good mechanical performance is kept.

Description

Technical Field

[0001] The present invention belongs to the field of microcrystalline glass, and in particular relates to a highly wear-resistant black microcrystalline glass, a composition and a preparation method. Background Art

[0002] Glass-ceramics is a new material with high strength, hardness, good wear resistance, and excellent chemical stability. It is widely used in building materials, electronics, machinery, and other industries. Currently, market demand for black glass-ceramics is gradually increasing, but the wear resistance and optical properties of existing black glass-ceramics still need to be improved.

[0003] Chinese invention patent application publication number CN114213022A discloses a black glass-ceramic sheet using molten manganese alloy slag as the primary raw material and a method for its preparation. The raw materials for the black glass-ceramic sheet are 72-87% molten manganese alloy slag and 13-28% tempering material; the tempering material includes bauxite, feldspar, and chromium ore. The resulting glass melt has the following main chemical compositions: SiO₂ 38-45%, Al₂O₃ 9-17%, CaO₂ 8-37%, MgO 3.5-7%, R₂O 1-5%, MnO 3.5-6%, Fe₂O₃ 0.4-1.5%, and Cr₂O₃ 0.1-0.5%. Although the above patent application produces a black glass-ceramic sheet, the flexural strength of the glass-ceramic is only 76 MPa, which requires further improvement.

[0004] Chinese invention patent application publication number CN102491641A discloses a wear-resistant glass-ceramic sheet and its preparation method. The glass-ceramic is composed of the following components, by weight: 65-85 parts steel slag, 20-30 parts quartz sand, 6-10 parts magnesium oxide, 5-10 parts titanium dioxide, and 1-3 parts calcium fluoride. The steel slag composition and weight percentages are: SiO₂ 13-20%, FeO 10-15%, CaO 40-50%, MgO 5-10%, Al₂O₃ 2-5%, TFe 10-20%, MnO 2-5%, P₂O₃ 0.1-0.5%, and MFe 0.5-1.5%. Although the aforementioned patent application produces a wear-resistant glass-ceramic sheet, it primarily utilizes a secondary sintering process to produce the desired product. However, glass-ceramics produced using the secondary sintering method not only consumes high energy but also produces pores, limiting its application.

[0005] In view of this, it is necessary to provide a highly wear-resistant black microcrystalline glass, a composition and a preparation method to solve or at least alleviate the technical problem of how to obtain black microcrystalline glass while improving its comprehensive performance. Summary of the Invention

[0006] The main purpose of the present invention is to provide a highly wear-resistant black microcrystalline glass, a composition and a preparation method, aiming to solve the above-mentioned technical problem of how to obtain black microcrystalline glass while improving its comprehensive performance.

[0007] To achieve the above-mentioned objectives, the present invention provides a composition of highly wear-resistant black microcrystalline glass, which comprises basic components and additives; the basic components comprise, by mass, 65-75 parts of silicon dioxide, 5-10 parts of aluminum oxide, 8-12 parts of lithium oxide, 3-5 parts of zirconium oxide, 1-2 parts of iron oxide, 0.1-0.5 parts of cobalt oxide, and 0.2-0.6 parts of nickel oxide; the additives comprise boric acid and sodium carbonate.

[0008] Furthermore, the mass percentage of the boric acid and the basic component is 0.5-2%, and the mass percentage of the sodium carbonate and the basic component is 2-4%.

[0009] The present invention also provides a method for preparing highly wear-resistant black glass-ceramics, comprising the steps of:

[0010] S1, providing any composition described above;

[0011] S2, mixing the components of the composition and then melting them to obtain molten glass; the melting temperature is not less than 1580° C.;

[0012] S3, cooling the glass liquid to an intermediate temperature to obtain a glass precursor; the intermediate temperature is not less than 700° C.;

[0013] S4, sequentially subjecting the glass precursor to a first heat preservation treatment, a second heat preservation treatment, a third heat preservation treatment, and a fourth heat preservation treatment to obtain a primary glass-ceramic product;

[0014] The temperature of the first heat preservation treatment is 535-570°C, the temperature of the second heat preservation treatment is 650-690°C, the temperature of the third heat preservation treatment is 800-850°C, and the temperature of the fourth heat preservation treatment is 460-490°C.

[0015] Furthermore, the melting temperature is 1580-1600° C.; and the melting time is not less than 3 hours.

[0016] Furthermore, the intermediate temperature is 710-760°C.

[0017] Furthermore, the insulation time of the first insulation treatment is 3-4 hours, the insulation time of the second insulation treatment is 3-4 hours, the insulation time of the third insulation treatment is 1-2 hours, and the insulation time of the fourth insulation treatment is 2-3 hours.

[0018] Furthermore, the step S3 further includes: before cooling the molten glass to the intermediate temperature, casting the molten glass into a mold.

[0019] Furthermore, the step S4 also includes: mechanically processing the primary glass-ceramics to obtain highly wear-resistant black glass-ceramics.

[0020] Furthermore, the mechanical processing includes: cutting, CNC machining and polishing the primary microcrystalline glass product.

[0021] The present invention also provides a highly wear-resistant black microcrystalline glass, which is prepared using any of the above-mentioned methods for preparing highly wear-resistant black microcrystalline glass.

[0022] Compared with the prior art, the present invention has at least the following advantages:

[0023] The present invention obtains a highly wear-resistant black microcrystalline glass, which significantly improves its comprehensive performance while preparing the black microcrystalline glass; for example, the present invention has excellent effects in terms of volume density, compressive strength, bending strength, impact toughness, hardness, optics, etc., and no pores are generated; in the present invention, high wear resistance is mainly reflected in comprehensive indicators such as hardness, density, and compressive strength. Specifically, in the present invention, the composition for preparing microcrystalline glass is composed of basic components and additives, the basic components are silicon dioxide, aluminum oxide, lithium oxide, zirconium oxide, ferric oxide, cobalt oxide, and nickel oxide, and the additives are boric acid and sodium carbonate; and, on the basis of the above components, the present invention optimizes the raw material formula and crystallization process by setting different insulation methods, and the obtained product is in the shape of black ceramic, has excellent performance, and is suitable for a variety of application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0025] Figure 1 This is a physical picture of the microcrystalline glass product in Example 1 of the present invention.

[0026] The realization of the objectives, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0027] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0028] Moreover, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that ordinary technicians in this field can implement them. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0029] When numerical ranges are given in the examples, it should be understood that unless otherwise specified herein, both endpoints of each numerical range and any value between the two endpoints may be used. Unless otherwise defined, all technical and scientific terms used herein are consistent with the prior art as understood by those skilled in the art and the description of the present invention. Any prior art methods, devices, and materials similar or equivalent to those described in the examples of the present invention may also be used to implement the present invention.

[0030] The present invention provides a highly wear-resistant black microcrystalline glass composition, which comprises basic components. Calculated by mass, the basic components include: 65-75 parts of silicon dioxide, 5-10 parts of aluminum oxide, 8-12 parts of lithium oxide, 3-5 parts of zirconium oxide, 1-2 parts of ferric oxide, 0.1-0.5 parts of cobalt oxide, and 0.2-0.6 parts of nickel oxide.

[0031] In the present invention, the composition further comprises an admixture, which comprises boric acid and sodium carbonate; the mass percentage of the boric acid and the basic component is 0.5-2%, further 0.5-1%; the mass percentage of the sodium carbonate and the basic component is 2-4%, further 2-3%.

[0032] The present invention also provides a method for preparing highly wear-resistant black glass-ceramics, comprising the steps of:

[0033] S1, raw material combination: provide any composition as described above.

[0034] S2, raw material melting: mixing the components of the composition and then melting them to obtain molten glass.

[0035] In the present invention, the melting temperature is not less than 1580°C; further, the melting temperature is 1580-1600°C; the melting time is not less than 3 hours, further, the melting time is 3-5 hours.

[0036] Specifically, the present invention mixes the components in the composition and then melts them in a high-temperature furnace to obtain uniform glass liquid.

[0037] S3, forming: cooling the glass liquid to an intermediate temperature to obtain a glass precursor; the intermediate temperature is not less than 700°C.

[0038] The step S3 of the present invention further includes: before cooling the molten glass to the intermediate temperature, casting the molten glass into a mold.

[0039] Furthermore, the intermediate temperature is 710-760°C. In the present invention, the molten glass is cast into a mold and cooled to 710-760°C to form a glass precursor. The present invention cools the glass to 710-760°C before subsequent heat preservation, mainly because glass is less likely to generate stress in this temperature range.

[0040] S4, sequentially subjecting the glass precursor to a first heat preservation treatment, a second heat preservation treatment, a third heat preservation treatment, and a fourth heat preservation treatment to obtain a primary glass-ceramic product.

[0041] In the present invention, the intermediate temperature, the temperatures of the first heat preservation treatment, the second heat preservation treatment, the third heat preservation treatment, and the fourth heat preservation treatment are connected in sequence.

[0042] In the present invention, the temperature of the first insulation treatment is 535-570°C, the temperature of the second insulation treatment is 650-690°C, the temperature of the third insulation treatment is 800-850°C, and the temperature of the fourth insulation treatment is 460-490°C.

[0043] Specifically, in operation, the present invention cools the glass liquid to the intermediate temperature after casting; then continues to cool it to the temperature of the first insulation treatment for insulation; then increases it to the temperature of the second insulation treatment for insulation, then increases it to the temperature of the third insulation treatment for insulation, then decreases it to the temperature of the fourth insulation treatment for insulation; and finally cools it down and takes it out of the furnace.

[0044] In the present invention, the insulation time of the first insulation treatment is 3-4 hours, the insulation time of the second insulation treatment is 3-4 hours, the insulation time of the third insulation treatment is 1-2 hours, and the insulation time of the fourth insulation treatment is 2-3 hours.

[0045] In the present invention, the first heat preservation treatment belongs to the pre-nucleation process, the second heat preservation treatment belongs to the nucleation process, the third heat preservation treatment belongs to the crystallization process, and the fourth heat preservation treatment belongs to the annealing process.

[0046] Step S4 of the present invention further includes mechanically processing the primary glass-ceramics to obtain highly wear-resistant black glass-ceramics; the mechanical processing includes cutting, CNC machining, and polishing the primary glass-ceramics. Specifically, the present invention cuts, CNC machines, and polishes the primary glass-ceramics to obtain a product with the desired size and surface finish.

[0047] As an example of a preferred embodiment of step S4, step S4 includes:

[0048] Pre-nucleation: Heat the glass precursor to 535-570℃ and keep it warm for 3-4h.

[0049] Nucleation: Heat to 650-690℃ and keep warm for 3-4h.

[0050] Crystallization: Further increase the temperature to 800-850℃ and keep warm for 1-2h.

[0051] Annealing: Cool down to 460-490℃ and keep warm for 2-3h to eliminate internal stress.

[0052] Post-processing: The crystallized glass-ceramics are cut, CNC-machined and polished to obtain products with the required size and surface finish.

[0053] The present invention also provides a highly wear-resistant black microcrystalline glass, which is prepared using any of the above-mentioned methods for preparing highly wear-resistant black microcrystalline glass.

[0054] The following are specific examples of the present invention:

[0055] Example 1

[0056] A method for preparing glass-ceramics, comprising the following steps:

[0057] S1, providing a glass-ceramic composition; the glass-ceramic composition is composed of a basic component and an additive;

[0058] The composition of the basic components is as follows, by mass: 75 parts of silicon dioxide, 6 parts of aluminum oxide, 10 parts of lithium oxide, 5 parts of zirconium oxide, 1 part of ferric oxide, 0.2 parts of cobalt oxide, and 0.3 parts of nickel oxide.

[0059] The admixture consists of boric acid and sodium carbonate; the mass percentage of the boric acid to the basic component is 0.5%, and the mass percentage of the sodium carbonate to the basic component is 2%.

[0060] S2, mixing the components of the above composition and then melting them to obtain a uniform glass liquid; in this embodiment, the melting temperature is 1580° C. and the melting time is 4 hours.

[0061] S3, casting the molten glass into a mold, cooling it to 750°C, and forming it into a glass precursor.

[0062] S4, keep the glass precursor at 550℃ for 4h (first insulation treatment); then heat it to 660℃ and keep it for 3h (second insulation treatment); then heat it to 850℃ and keep it for 1h (third insulation treatment); finally, cool it to 480℃ and keep it for 3h (fourth insulation treatment); after the insulation is completed, cool it to 80℃ and take it out of the furnace to obtain the initial microcrystalline glass; cut, CNC process and polish the initial microcrystalline glass to obtain a microcrystalline glass product with the required size and surface finish.

[0063] In this embodiment, the actual picture of the glass-ceramic product is shown in Figure 1 The microcrystalline glass has no pores, is black, has a pure color, and is ceramic-like, without any reflection. The performance analysis of the microcrystalline glass product is shown in Table 1.

[0064] Table 1 Performance analysis of glass-ceramic products

[0065]

[0066] Comparative Example 1

[0067] Compared with Example 1, this comparative example only omitted the admixture, and other conditions remained unchanged from Example 1.

[0068] In this comparative example, the performance analysis of the glass-ceramic product is shown in Table 2.

[0069] Table 2 Performance analysis of glass-ceramic products

[0070]

[0071] Comparative Example 2

[0072] Compared with Example 1, this comparative example only omitted the boric acid in the admixture, and other conditions remained unchanged from Example 1.

[0073] In this comparative example, the performance analysis of the glass-ceramic product is shown in Table 3.

[0074] Table 3 Performance analysis of glass-ceramic products

[0075]

[0076]

[0077] Comparative Example 3

[0078] Compared with Example 1, this comparative example only omitted the sodium carbonate in the admixture, and other conditions remained unchanged with Example 1.

[0079] In this comparative example, the performance analysis of the microcrystalline glass product is shown in Table 4.

[0080] Table 4 Performance analysis of glass-ceramic products

[0081]

[0082] Comparative Example 4

[0083] Compared with Example 1, in this comparative example, only zirconium oxide in the base component is omitted, and other conditions remain unchanged from Example 1.

[0084] In this comparative example, the performance analysis of the microcrystalline glass product is shown in Table 5.

[0085] Table 5 Performance analysis of glass-ceramic products

[0086]

[0087]

[0088] Comparative Example 5

[0089] Compared with Example 1, in this comparative example, only aluminum oxide in the basic component is omitted, and other conditions remain unchanged from Example 1.

[0090] In this comparative example, the performance analysis of the microcrystalline glass product is shown in Table 6.

[0091] Table 6 Performance analysis of glass-ceramic products

[0092]

[0093] Comparative Example 6

[0094] Compared with Example 1, in this comparative example, only the silicon dioxide in the base component was adjusted to aluminum oxide, and other conditions remained unchanged from Example 1.

[0095] In this comparative example, the glass was not formed and could not be crystallized into a plate.

[0096] Comparative Example 7

[0097] Compared with Example 1, this comparative example only changes the boric acid in the admixture to sodium carbonate, and other conditions remain unchanged from Example 1.

[0098] In this comparative example, the performance analysis of the microcrystalline glass product is shown in Table 7.

[0099] Table 7 Performance analysis of glass-ceramic products

[0100]

[0101] Comparative Example 8

[0102] Compared with Example 1, this comparative example only omits the first heat preservation treatment in step S4, and other conditions remain unchanged from Example 1.

[0103] In this comparative example, the cross section of the microcrystalline glass is glass-like and exhibits obvious reflection. The performance analysis of the microcrystalline glass product is shown in Table 8.

[0104] Table 8 Performance analysis of glass-ceramic products

[0105]

[0106] The above technical solutions of the present invention are only preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made using the contents of the present invention specification under the technical concept of the present invention, or direct / indirect applications in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A highly wear-resistant black glass-ceramic composition, characterized in that: The composition includes a base component and an admixture; The basic components include, by mass, 65-75 parts of silicon dioxide, 5-10 parts of aluminum oxide, 8-12 parts of lithium oxide, 3-5 parts of zirconium oxide, 1-2 parts of ferric oxide, 0.1-0.5 parts of cobalt oxide, and 0.2-0.6 parts of nickel oxide; and the additives include boric acid and sodium carbonate.

2. The composition according to claim 1, characterized in that The mass percentage of the boric acid and the basic component is 0.5-2%, and the mass percentage of the sodium carbonate and the basic component is 2-4%.

3. A method for preparing highly wear-resistant black glass-ceramics, characterized in that: Including steps: S1, providing the composition according to claim 1 or 2; S2, mixing the components of the composition and then melting them to obtain molten glass; the melting temperature is not less than 1580° C.; S3, cooling the glass liquid to an intermediate temperature to obtain a glass precursor; the intermediate temperature is not less than 700° C.; S4, sequentially subjecting the glass precursor to a first heat preservation treatment, a second heat preservation treatment, a third heat preservation treatment, and a fourth heat preservation treatment to obtain a primary glass-ceramic product; The temperature of the first heat preservation treatment is 535-570°C, the temperature of the second heat preservation treatment is 650-690°C, the temperature of the third heat preservation treatment is 800-850°C, and the temperature of the fourth heat preservation treatment is 460-490°C.

4. The method for preparing highly wear-resistant black glass-ceramics according to claim 3, characterized in that: The melting temperature is 1580-1600° C.; and the melting time is not less than 3 hours.

5. The method for preparing highly wear-resistant black glass-ceramics according to claim 3, characterized in that: The intermediate temperature is 710-760°C.

6. The method for preparing highly wear-resistant black glass-ceramics according to claim 3, characterized in that: The insulation time of the first insulation treatment is 3-4 hours, the insulation time of the second insulation treatment is 3-4 hours, the insulation time of the third insulation treatment is 1-2 hours, and the insulation time of the fourth insulation treatment is 2-3 hours.

7. The method for preparing highly wear-resistant black glass-ceramics according to claim 3, characterized in that: The step S3 further includes: before cooling the molten glass to the intermediate temperature, casting the molten glass into a mold.

8. The method for preparing highly wear-resistant black glass-ceramics according to claim 3, characterized in that: The step S4 further includes: mechanically processing the primary glass-ceramics to obtain highly wear-resistant black glass-ceramics.

9. The method for preparing highly wear-resistant black glass-ceramics according to claim 8, characterized in that: The mechanical processing includes: cutting, CNC processing and polishing the primary microcrystalline glass product.

10. A highly wear-resistant black glass-ceramic, characterized in that: The high-wear-resistant black glass-ceramics is prepared using the preparation method according to any one of claims 3 to 9.

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