A glass-ceramic article and a method of making the same

Abstract

This invention relates to a glass-ceramic product and its preparation method, comprising component A and component B; wherein the raw materials include: silica-calcium silicate microcrystalline glass powder, solvent, dispersant, ethylene glycol diglycidyl ether, diethylenetriamine, defoamer, thickener, and hydantoin epoxy. The beneficial effects are that, through the two-component method, the raw materials are pre-mixed uniformly in components A and B, improving the uniformity of the resin and curing agent slurry. Through this preparation method, each component can undergo cross-linking and curing reactions under air conditions, and the curing process can be controlled by controlling changes in the external ambient temperature. Furthermore, the two-component method avoids curing during the mixing process, achieving control over the timing and process of curing. The resulting green body is uniformly cured, has high strength, and good integrity. The finished product has the advantages of high density, good mechanical properties, and excellent overall performance, making it suitable for structural parts, appearance parts, etc.

Description

Technical Field

[0001] This invention relates to the field of glass-ceramic preparation technology, and in particular to a glass-ceramic product and its preparation method. Background Technology

[0002] Because the crystals of the Canasite system grow in both the transverse and longitudinal directions and are interlocked, the fracture energy is increased to a certain extent due to the inconsistent crack paths during fracture, thus producing microcrack toughening. Therefore, high toughness and high impact resistance are the outstanding advantages of this system of microcrystalline glass.

[0003] The main preparation processes of silica-alkali-calcium silicate glass ceramics include glass powder preform processing and sintering (sintering), glass melt casting and heat treatment (casting), and glass softening state hot pressing and heat treatment (hot pressing).

[0004] Gel injection molding, a molding process, has the following advantages:

[0005] 1. It is a net-size forming technology that produces green bodies with uniform density and minimal deformation during drying, debinding, and sintering. The sintered samples can maintain the shape and size of the green body, so it can be used to prepare ceramic parts of various complex shapes.

[0006] 2. The gel curing time can be controlled by changing the reaction temperature and the amount of monomer, crosslinking agent, and initiator added;

[0007] 3. The molded body is a composite material of ceramic powder and polymer, which has high strength and can be directly machined.

[0008] 4. Gel injection molding has no special requirements for molds. Molding can be achieved in various molds such as metal, plastic or glass. The equipment is simple and readily available, the cost is low, and it is easy to industrialize.

[0009] Currently, there is no successful method for preparing silica-calcium silicate glass ceramics using gel casting molding because their softening point is similar to the carbon removal temperature of gel casting. Summary of the Invention

[0010] (a) Technical problems to be solved

[0011] In view of the above-mentioned shortcomings and deficiencies of the prior art, the present invention provides a glass-ceramic product and its preparation method, which solves the technical problem that the silica-calcium silicate glass-ceramics currently on the market have not been successfully prepared using the gel casting process because their softening point is similar to the carbon removal temperature of the gel casting process.

[0012] (II) Technical Solution

[0013] To achieve the above objectives, the main technical solutions adopted by the present invention include:

[0014] This invention provides a glass-ceramic product comprising component A and component B; wherein component A, by weight, comprises the following raw materials:

[0015]

[0016] Component B, by weight, includes the following raw materials:

[0017]

[0018] Preferably, the solvent is deionized water or an organic solvent.

[0019] Preferably, the organic solvent is one or more of ethanol, tert-butanol, or ethylene glycol.

[0020] Preferably, the dispersant is one or two of sodium polyacrylate, ammonium polyacrylate, and polydimethyldiallylammonium chloride.

[0021] Preferably, the defoamer is n-octanol, isooctanol, or a polyether defoamer.

[0022] Preferably, the particle size of the silica-calcium silicate microcrystalline glass powder is 1–20 μm.

[0023] On the other hand, the present invention also provides a method for preparing glass-ceramic articles, which includes the following steps:

[0024] S1: The silica-calcium silicate microcrystalline glass powder, solvent, dispersant, diethylenetriamine, ethylene glycol diglycidyl ether, defoamer, and thickener are mixed evenly to form a slurry, which is called component A;

[0025] S2: The silica-calcium silicate microcrystalline glass powder, solvent, dispersant, hydantoin epoxy resin, defoamer, and thickener are mixed evenly to form a slurry, which is called component B;

[0026] S3: Mix components A and B evenly in proportion to form a slurry, degas it under vacuum, pour it into a mold, demold it after curing, heat and dry it, then sinter it, and cool it to obtain a glass-ceramic product.

[0027] Preferably, in S1 and S2, the A and B components are mixed and then ball-milled using a drum ball milling method, with a ball-to-material ratio of 3:1 to 4:1 and a ball milling time of 1 to 5 hours.

[0028] Preferably, in S3, the solid content of the mixture of components A and B is preferably 50.0-60.0 vol%, the viscosity is <1 Pa·s, the curing temperature is 20-60℃, and the curing time is 2-24 h.

[0029] Preferably, in step S3, the heating rate during drying is 5-10℃ / h, the temperature is raised to the final drying temperature of 60-80℃ and held for 24-48h; during sintering, the temperature is raised to 400-600℃ at 0.5-1℃ / min and held for 1-3h, then raised to 850-1000℃ at 5-10℃ / min for sintering, and the sintering time is 30min-4h.

[0030] (III) Beneficial Effects

[0031] The beneficial effects of this invention are as follows: Compared with current methods for preparing silica-calcium silicate glass ceramics, this invention has the following advantages:

[0032] 1. For the first time, the gel system of hydantoin epoxy resin and diethylenetriamine was applied to the gel injection molding process of silica-calcium silicate glass ceramics. Furthermore, by using a two-component method, the raw materials were pre-mixed evenly in components A and B, which improved the uniformity of the resin and curing agent slurry.

[0033] 2. Through gel casting molding process, the components can not only undergo cross-linking and curing reaction under air conditions, but also the curing process can be controlled by controlling the change of external ambient temperature. Furthermore, the two-component method avoids curing during the mixing process, and achieves control over the timing and process of curing. The resulting green body is uniformly cured, has high strength, and good integrity.

[0034] 3. The silica-alkali-calcium silicate glass-ceramic products prepared by this invention have the advantages of high density, good mechanical properties, and excellent comprehensive performance, and are suitable for use in structural parts, appearance parts, etc. Detailed Implementation

[0035] To better understand the above technical solutions, exemplary embodiments of the present invention will be described in more detail below. While exemplary embodiments of the present invention are set forth in this specification, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that the present invention can be understood more clearly and thoroughly, and that the scope of the present invention can be fully conveyed to those skilled in the art.

[0036] This invention provides a glass-ceramic product comprising component A and component B; wherein component A, by weight, comprises the following raw materials:

[0037]

[0038] Component B, by weight, includes the following raw materials:

[0039]

[0040] In this embodiment, the solvent is deionized water or an organic solvent.

[0041] In this embodiment, the organic solvent is one or more of ethanol, tert-butanol, or ethylene glycol.

[0042] In this embodiment, the dispersant is one or two of sodium polyacrylate, ammonium polyacrylate, and polydimethyldiallylammonium chloride.

[0043] In this embodiment, the defoamer is n-octanol, isooctanol, or a polyether defoamer.

[0044] In this embodiment, the particle size of the silica-calcium silicate microcrystalline glass powder is 1–20 μm.

[0045] On the other hand, the present invention also provides a method for preparing glass-ceramic articles, which includes the following steps:

[0046] S1: The silica-calcium silicate microcrystalline glass powder, solvent, dispersant, diethylenetriamine, ethylene glycol diglycidyl ether, defoamer, and thickener are mixed evenly to form a slurry, which is called component A;

[0047] S2: The silica-calcium silicate microcrystalline glass powder, solvent, dispersant, hydantoin epoxy resin, defoamer, and thickener are mixed evenly to form a slurry, which is called component B;

[0048] S3: Mix components A and B evenly in proportion to form a slurry, degas it under vacuum, pour it into a mold, demold it after curing, heat and dry it, then sinter it, and cool it to obtain a glass-ceramic product.

[0049] In this embodiment, in S1 and S2, the A and B components are mixed and then ball-milled using a drum ball milling method, with a ball-to-material ratio of 3:1 to 4:1 and a milling time of 1 to 5 hours.

[0050] In this embodiment, in S3, the solid content of the mixture of components A and B is preferably 50.0-60.0 vol%, the viscosity is <1 Pa·s, the curing temperature is 20-60℃, and the curing time is 2-24 h.

[0051] In this embodiment, during the drying process in step S3, the heating rate is 5-10°C / h, and the temperature is raised to the final drying temperature of 60-80°C and held for 24-48 hours. During the sintering process, the temperature is raised to 400-600°C at a rate of 0.5-1°C / min and held for 1-3 hours, and then raised to 850-1000°C at a rate of 5-10°C / min for sintering. The sintering time is 30 minutes to 4 hours.

[0052] In this embodiment, silicon dioxide is used as the thickener.

[0053] The present invention will be further described below with reference to specific embodiments:

[0054] Example 1

[0055] This invention provides a glass-ceramic product and its preparation method, comprising component A and component B;

[0056] Component A, by weight, includes the following raw materials: 60 parts of silica-calcium silicate microcrystalline glass powder, 18 parts of solvent, 1.2 parts of dispersant, 1 part of ethylene glycol diglycidyl ether, 1 part of diethylenetriamine, 0.07 parts of defoamer, and 0.03 parts of thickener;

[0057] Component B, by weight, includes the following raw materials: 60 parts of silica-calcium silicate microcrystalline glass powder, 18 parts of solvent, 1.2 parts of dispersant, 4 parts of hydantoin epoxy, 0.07 parts of defoamer, and 0.03 parts of thickener.

[0058] In this embodiment, the preparation method includes the following steps:

[0059] S1: Mix the silica-calcium silicate microcrystalline glass powder, solvent, dispersant, diethylenetriamine, ethylene glycol diglycidyl ether, defoamer and thickener evenly according to the proportion to form a slurry;

[0060] S2: Mix the silica-calcium silicate microcrystalline glass powder, solvent, dispersant, hydantoin epoxy resin, defoamer and thickener evenly according to the proportion to form a slurry;

[0061] S3: The two slurries mentioned above are ball-milled separately. After ball milling, the two slurries are thoroughly mixed and then vacuum degassed. The degassed mixed slurry is then injected into a mold and cured at 20°C for 24 hours. After demolding, the mold is then heated and dried at a rate of 10°C / h until the final drying temperature of 80°C is reached and held for 48 hours. The heating and air drying method of this invention can further ensure that the moisture in the wet blank evaporates evenly and slowly, preventing the sample from bending, deforming or cracking during the drying process. During sintering, the temperature is increased to 600°C at 1°C / min and held for 3 hours. Then, the temperature is increased to 1000°C at 10°C / min and sintered for 30 minutes to obtain a silica-calcium silicate glass-ceramic product.

[0062] Example 2

[0063] This invention provides a glass-ceramic product and its preparation method, comprising component A and component B;

[0064] Component A, by weight, includes the following raw materials: 70 parts of silica-calcium silicate microcrystalline glass powder, 23 parts of solvent, 1.4 parts of dispersant, 2 parts of ethylene glycol diglycidyl ether, 1.5 parts of diethylenetriamine, 0.07 parts of defoamer, and 0.03 parts of thickener;

[0065] Component B, by weight, includes the following raw materials: 70 parts of silica-calcium silicate microcrystalline glass powder, 24 parts of solvent, 1.3 parts of dispersant, 5 parts of hydantoin epoxy, 0.07 parts of defoamer, and 0.03 parts of thickener.

[0066] In this embodiment, the preparation method includes the following steps:

[0067] S1: Mix the silica-calcium silicate microcrystalline glass powder, solvent, dispersant, diethylenetriamine, ethylene glycol diglycidyl ether, defoamer and thickener evenly according to the proportion to form a slurry;

[0068] S2: Mix the silica-calcium silicate microcrystalline glass powder, solvent, dispersant, hydantoin epoxy resin, defoamer and thickener evenly according to the proportion to form a slurry;

[0069] S3: The two slurries mentioned above are ball-milled separately. After ball milling, the two slurries are thoroughly mixed and then vacuum degassed. The degassed mixed slurry is then injected into a mold and cured at 30°C for 13 hours. After demolding, the mold is then heated and dried at a rate of 7°C / h until the final drying temperature of 75°C is reached and held for 36 hours. The heating and air drying method of this invention can further ensure that the moisture in the wet blank evaporates evenly and slowly, preventing the sample from bending, deforming or cracking during the drying process. During sintering, the temperature is increased to 500°C at 0.7°C / min and held for 2 hours. Then, the temperature is increased to 900°C at 8°C / min and sintered for 2.5 hours to obtain a silica-calcium silicate glass-ceramic product.

[0070] Example 3

[0071] This invention provides a glass-ceramic product and its preparation method, comprising component A and component B;

[0072] Component A, by weight, includes the following raw materials: 80 parts of silica-calcium silicate microcrystalline glass powder, 28 parts of solvent, 1.5 parts of dispersant, 3 parts of ethylene glycol diglycidyl ether, 2 parts of diethylenetriamine, 0.07 parts of defoamer, and 0.03 parts of thickener.

[0073] Component B, by weight, includes the following raw materials: 80 parts of silica-calcium silicate microcrystalline glass powder, 28 parts of solvent, 1.5 parts of dispersant, 6 parts of hydantoin epoxy, 0.07 parts of defoamer, and 0.03 parts of thickener.

[0074] In this embodiment, the preparation method includes the following steps:

[0075] S1: Mix the silica-calcium silicate microcrystalline glass powder, solvent, dispersant, diethylenetriamine, ethylene glycol diglycidyl ether, defoamer and thickener evenly according to the proportion to form a slurry;

[0076] S2: Mix the silica-calcium silicate microcrystalline glass powder, solvent, dispersant, hydantoin epoxy resin, defoamer and thickener evenly according to the proportion to form a slurry;

[0077] S3: The two slurries mentioned above are ball-milled separately. After ball milling, the two slurries are thoroughly mixed and then vacuum degassed. The degassed mixed slurry is then injected into a mold and cured at 60°C for 2 hours. After demolding, the mold is then heated and dried at a rate of 5°C / h until the final drying temperature of 60°C is reached and held for 24 hours. The heating and air drying method of this invention can further ensure that the moisture in the wet blank evaporates evenly and slowly, preventing the sample from bending, deforming or cracking during the drying process. During sintering, the temperature is increased to 400°C at 0.5°C / min and held for 3 hours. Then, the temperature is increased to 850°C at 5°C / min and sintered for 4 hours to obtain a silica-calcium silicate glass-ceramic product.

[0078] Based on Examples 1 to 3, it can be determined that the present invention has the following advantages compared with the current methods for preparing silica-calcium silicate glass ceramics:

[0079] 1. For the first time, the gel system of hydantoin epoxy resin and diethylenetriamine was applied to the gel injection molding process of silica-calcium silicate glass ceramics. Furthermore, by using a two-component method, the raw materials were pre-mixed evenly in components A and B, which improved the uniformity of the resin and curing agent slurry.

[0080] 2. Through gel casting molding process, the components can not only undergo cross-linking and curing reaction under air conditions, but also the curing process can be controlled by controlling the change of external ambient temperature. Furthermore, the two-component method avoids curing during the mixing process, and achieves control over the timing and process of curing. The resulting green body is uniformly cured, has high strength, and good integrity.

[0081] 3. The silica-alkali-calcium silicate glass-ceramic products prepared by this invention have the advantages of high density, good mechanical properties, and excellent comprehensive performance, and are suitable for use in structural parts, appearance parts, etc.

[0082] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make modifications, alterations, substitutions and variations to the above embodiments within the scope of the present invention, but as long as they do not depart from the basic idea of ​​the present invention, they are all within the scope of the present invention.

Claims

1. A method for preparing a glass-ceramic product, characterized in that: It includes component A and component B; wherein, component A, by weight, includes the following raw materials: 60-80 parts of silica-calcium silicate microcrystalline glass powder; Solvent: 18-28 parts; Dispersant 1.2~1.5 parts; 1-3 parts of ethylene glycol diglycidyl ether; 1-2 parts of diethylenetriamine; 0.07 parts of defoamer; Thickener 0.03 parts; Component B, by weight, includes the following raw materials: 60-80 parts of silica-calcium silicate microcrystalline glass powder; Solvent: 18-28 parts; Dispersant 1.2~1.5 parts; 4-6 parts of hydantoin epoxy; 0.07 parts of defoamer; Thickener 0.03 parts; The preparation method includes the following steps: S1: The silica-calcium silicate microcrystalline glass powder, solvent, dispersant, diethylenetriamine, ethylene glycol diglycidyl ether, defoamer and thickener are mixed evenly and then ball-milled by roller ball milling to form a slurry, which is called component A. S2: The silica-calcium silicate microcrystalline glass powder, solvent, dispersant, hydantoin epoxy resin, defoamer and thickener are mixed evenly and then ball-milled by roller ball milling to form a slurry, which is called component B. S3: Mix components A and B evenly in a certain proportion to form a slurry, degas under vacuum, and pour into a mold. After curing, demold and then heat and dry at a rate of 5-10℃ / h until the final drying temperature of 60-80℃ is reached and held for 24-48h. Then sinter, heating at 0.5-1℃ / min to 400-600℃ and holding for 1-3h, followed by heating at 5-10℃ / min to 850-1000℃ for sintering. After cooling, the glass-ceramic product is obtained.

2. The method for preparing glass-ceramic products as described in claim 1, characterized in that: The solvent is deionized water or an organic solvent.

3. The method for preparing glass-ceramic products as described in claim 2, characterized in that: The organic solvent is one or more of ethanol, tert-butanol, or ethylene glycol.

4. The method for preparing glass-ceramic products as described in claim 1, characterized in that: The dispersant is one or two of sodium polyacrylate, ammonium polyacrylate, and polydimethyldiallyl ammonium chloride.

5. The method for preparing glass-ceramic products as described in claim 1, characterized in that: The defoamer is n-octanol, isooctanol, or a polyether defoamer.

6. The method for preparing glass-ceramic products as described in claim 1, characterized in that: The particle size of the silica-calcium silicate microcrystalline glass powder is 1~20μm.

7. The method for preparing glass-ceramic products as described in claim 1, characterized in that: In S1 and S2, the ball-to-material ratio is 3:1 to 4:1, and the ball milling time is 1 to 5 hours.

8. The method for preparing glass-ceramic products as described in claim 1, characterized in that: In S3, the solid content of the mixture of components A and B is 50.0~60.0 vol%, the viscosity is <1 Pa • s, the curing temperature is 20~60℃, and the curing time is 2~24 h.

9. The method for preparing glass-ceramic products as described in claim 1, characterized in that: In S3, the sintering time is 30 min to 4 h.

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