CN113480179A - Microcrystalline ceramic articles and methods of making the same - Google Patents
Microcrystalline ceramic articles and methods of making the same Download PDFInfo
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- CN113480179A CN113480179A CN202110888222.1A CN202110888222A CN113480179A CN 113480179 A CN113480179 A CN 113480179A CN 202110888222 A CN202110888222 A CN 202110888222A CN 113480179 A CN113480179 A CN 113480179A
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- microcrystalline ceramic
- microcrystalline
- ceramic product
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
Abstract
The invention discloses a microcrystalline ceramic product and a preparation method thereof, wherein the microcrystalline ceramic product comprises SiO (silicon dioxide) in percentage by mass2+A12O3：65～75％；Na2O+K2O：15～20％；BaO+F+TiO2：5～8％；CaO+B2O3+ ZnO: 5 to 10 percent. The preparation method of the microcrystalline ceramic product carries out technical transformation on the glass melting and forming technology, can meet the technical process requirement of the production of the microcrystalline ceramic wine bottle with little investment, greatly reduces the investment of the technical transformation of equipment, is easy to be widely applied and popularized, and has obvious enterprise benefit and social benefit.
Description
Technical Field
The invention relates to the technical field of ceramic preparation, in particular to a microcrystalline ceramic product and a preparation method thereof.
Background
The microcrystalline ceramic is a new material developed in recent years, and the microcrystalline ceramic wine bottle material is between inorganic glass and ceramic. It is composed of one or more glassy and crystalline phases. The microcrystalline porcelain is obtained by controlling crystallization of base glass. The new crystals obtained in this way precipitate directly from the glassy phase, while the composition of the residual glassy phase also gradually changes.
The microcrystalline ceramic is formed into micron-sized microcrystals in the microcrystalline ceramic through selection of chemical composition of materials, addition of a crystal nucleating agent and control of a heat treatment process. At present, the microcrystalline ceramics are prepared by a sintering method by taking a frit as a raw material; one is a fusion process that employs a glass manufacturing process.
At present, because the microcrystalline ceramic prepared by the method is not improved in the aspects of formula and process, the microcrystalline ceramic has the disadvantages of high energy consumption, strict requirements on equipment, high cost, environmental pollution and poor mechanical property and toughness of materials, and needs to be further improved.
Disclosure of Invention
Therefore, the invention provides a microcrystalline ceramic product and a preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a microcrystalline ceramic product which is prepared from SiO (silicon dioxide) in percentage by mass2+A12O3：65～75％；Na2O+K2O：15～20％；BaO+F+TiO2：5～8％；CaO+B2O3+ZnO：5～10％。
In one embodiment of the invention, the microcrystalline ceramic article has a composition, in terms of mass percent, of SiO2+A12O3：66～74％；Na2O+K2O：16～19％；BaO+F+TiO2：6～7％；CaO+B2O3+ZnO：6～9％。
In one embodiment of the invention, the microcrystalline ceramic article has a composition, in terms of mass percent, of SiO2+A12O3：70％；Na2O+K2O：17.5％；BaO+F+TiO2：6％；CaO+B2O3+ZnO：6.5％。
The invention also provides a method for preparing the microcrystalline ceramic article, which is characterized in that the method comprises the following steps:
melting materials at high temperature, feeding, forming, crystallizing and annealing to form the microcrystalline ceramic product, wherein the microcrystalline ceramic product comprises SiO (silicon dioxide) in percentage by mass2+A12O3：65～75％；Na2O+K2O：15～20％；BaO+F+TiO2：5～8％；CaO+B2O3+ZnO：5～10％。
In one embodiment of the invention, the microcrystalline ceramic article has a composition, in terms of mass percent, of SiO2+A12O3：66～74％；Na2O+K2O：16～19％；BaO+F+TiO2：6～7％；CaO+B2O3+ZnO：6～9％。
In one embodiment of the present invention, the temperature of the high-temperature melting material is 1300-.
In one embodiment of the present invention, the temperature for forming the supply material is 1000-1100 ℃.
In one embodiment of the present invention, the temperature of the crystallization annealing step is 520-.
In one embodiment of the invention, the method further comprises a polishing step, wherein the polishing step is to polish the ceramic product formed by feeding, and the polished ceramic product is subjected to crystallization annealing treatment.
The invention has the following advantages:
the preparation method of the microcrystalline ceramic product carries out technical transformation on the glass melting and forming technology, can meet the technical process requirement of the production of the microcrystalline ceramic wine bottle with little investment, greatly reduces the investment of the technical transformation of equipment, is easy to be widely applied and popularized, and has obvious enterprise benefit and social benefit.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Melting the materials at high temperature: the components are uniformly mixed according to the proportion, the uniform mixture is put into a crucible, and the melting is carried out in an electric furnace or a gas furnace within the temperature range of 1300-1400 ℃ for 5-50h according to the melting difficulty of the glass composition. And cooling the melted high-temperature material to a proper temperature, and feeding and forming.
In the present invention, the high-temperature molten material is formed by a well-known method.
SiO2And Al2O3Is an essential component of the glass of the present invention, and can constitute the network structure of the glass of the present invention by incorporating SiO2And Al2O3SiO in total content2+A12O3Controlling the content of SiO in the glass to 65% or more, so as to obtain excellent glass stability, and improve the crystallinity and four-point bending strength of the glass ceramic and the glass ceramic product2+A12O3Is 68% or more, and SiO is more preferable2+A12O3Is more than 70 percent of SiO2+A12O3Does not exceed 75%. Thus SiO2And A12O3SiO in total content2+A12O3Is 75% or less, preferably 78% or less. In some embodiments, the SiO2+A12O3May be 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%.
Alkali metal oxide Na2O and K2O can promote the melting of glass, reduce the melting temperature of glass, is beneficial to the adjustment of the chemical strengthening process of glass or glass ceramic, has the function of fluxing agent, and Na is added into the invention2O and K2Total content Na of O2O+K2O is controlled to 15% or more to obtain the above effect, and Na is preferable2O+K2O is more than 18 percent. Preferably Na2O+K2O is 20% or less, more preferably Na2O+K2O is 19% or less. In some embodiments, Na2O+K2O can be 16%, 17%, 18%, 19%, 20%.
ZnO can reduce the difficulty of glass melting, but when the content is high, the low-temperature crystallization of glass can be promoted, the crystallinity and the transmittance of glass ceramics and glass ceramic products can be reduced, the haze of the glass ceramics and the glass ceramic products can be increased, and the brightness of products can be improved, so the upper limit of the content is 2%, and the preferred upper limit is 1%. In some embodiments, about 0%, greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2% ZnO may be included.
BaO is a component which is helpful for improving the glass forming performance of the glass, and the content of BaO in the invention is 0-5%, preferably 0-3%, and more preferably 0-1%.
The CaO can increase the hardness of the glass, and as a framework material, the content of the CaO in the invention is 0-5%, preferably 0-3%. In some embodiments, CaO may be included at about 0%, greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%.
TiO2Is an optional component which is helpful for reducing the melting temperature of the glass and improving the chemical stability, and the content of TiO is less than 5 percent in the invention2. Can make the crystallization process of the glass easy to control, and TiO is preferred2The content of (b) is 3% or less, more preferably 1% or less. In some embodiments, it is further preferred that no TiO is present2. In some embodiments, about 0%, greater than 0%, 1%, 1.5%, 2%, 2.5%, 3% TiO may be included2。
B2O3Can improve the network structure of the glass, adjust the chemical strengthening performance of the glass ceramic, is not beneficial to glass forming if the content is excessive, and is easy to crystallize during the forming, B2O3Increase the stability of the material, prevent the cracking of the microcrystalline ceramics, B2O3The upper limit of the content is 5%, preferably 3%, more preferably 1%, and further preferably B is not contained2O3. In some embodiments, about 0%, greater than 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3% B may be included2O3。
The invention provides a microcrystalline ceramic product, which comprises SiO (silicon dioxide) in percentage by mass2+A12O3：65～75％；Na2O+K2O：15～20％；BaO+F+TiO2：5～8％；CaO+B2O3+ZnO：5～10％。
The microcrystalline ceramic product comprises SiO (silicon dioxide) in percentage by mass2+A12O3：70％；Na2O+K2O：17.5％；BaO+F+TiO2：6％；CaO+B2O3+ZnO：6.5％。
The present invention also provides a method of making the microcrystalline ceramic article, the method comprising:
melting materials at a high temperature of 1300-1400 ℃, feeding and forming the materials at a feeding forming temperature of 1000-1100 ℃, polishing the ceramic product formed by feeding, and performing crystallization annealing at a temperature of 520-600 ℃ on the polished ceramic product for 1-4h to form the microcrystalline ceramic product, wherein the composition of the microcrystalline ceramic product is calculated according to mass percentage, and the SiO is2+A12O3：65～75％；Na2O+K2O：15～20％；BaO+F+TiO2：5～8％；CaO+B2O3+ZnO：5～10％。
Example 1
The present embodiments also provide a method of making the microcrystalline ceramic article, the method comprising:
melting a material at a high temperature, wherein the temperature of the material at the high temperature is 1300 ℃, feeding and forming the material at the high temperature, wherein the feeding and forming temperature is 1000 ℃, further polishing the ceramic product formed by feeding, and performing crystallization annealing at 520 ℃ for 1h to form the microcrystalline ceramic product, wherein the microcrystalline ceramic product comprises SiO (silicon dioxide) in percentage by mass2+A12O3：65％；Na2O+K2O：18％；BaO+F+TiO2：7％；CaO+B2O3+ZnO：10％。
Example 2
The present invention also provides a method of making the microcrystalline ceramic article, the method comprising:
the high-temperature melting material is fed and formed at 1350 ℃, wherein the feeding and forming temperature is 1050 ℃, the ceramic product formed by feeding is further polished, and the polished ceramic product is obtainedThen, performing a crystallization annealing step at 560 ℃ for 2.5 hours to form the microcrystalline ceramic product, wherein the microcrystalline ceramic product comprises SiO in percentage by mass2+A12O3：68％；Na2O+K2O：15％；BaO+F+TiO2：8％；CaO+B2O3+ZnO：9％。
Example 3
The present invention also provides a method of making the microcrystalline ceramic article, the method comprising:
melting materials at a high temperature of 1400 ℃, feeding and forming the materials at a feeding forming temperature of 1100 ℃, further polishing the ceramic product formed by feeding, and carrying out crystallization annealing at a temperature of 600 ℃ on the polished ceramic product for 4 hours to form the microcrystalline ceramic product, wherein the microcrystalline ceramic product comprises SiO (silicon dioxide) in percentage by mass2+A12O3：75％；Na2O+K2O：15％；BaO+F+TiO2：5％；CaO+B2O3+ZnO：5％。
Test examples
The microcrystalline ceramic article prepared in example 1 of the present invention has a measured, measured unit: the results of measurements from Ink glass products, Inc., Xixi county are shown in Table 1.
TABLE 1
Test Standard GB/T4548-1995
TABLE 2
Detection standard GB/T4547-2007
| Serial number | Detecting items | Results |
| 1 | Thermal shock resistance (60-25 ℃ heat exchange) | Without damage |
| 2 | Thermal shock resistance (60-25 ℃ heat exchange) | Without damage |
| 3 | Thermal shock resistance (70-25 ℃ heat exchange) | Without damage |
| 4 | Thermal shock resistance (75-25 ℃ heat exchange) | Without damage |
| 5 | Thermal shock resistance (80-25 ℃ heat exchange) | Without damage |
| 6 | Thermal shock resistance (85-25 ℃ heat exchange) | Without damage |
| 7 | Thermal shock resistance (90-25 ℃ heat exchange) | Without damage |
| 8 | Thermal shock resistance (95-25 ℃ heat exchange) | One out of 3 is broken |
The invention manufactures the microcrystal porcelain product consisting of more than one glass phase and more than one crystal phase, has the characteristics of the traditional ceramic wine bottle, and has the advantages of low production cost, no leakage, environmental protection and recycling.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A microcrystalline ceramic product, characterized in that the composition of the microcrystalline ceramic product is, in mass percent, SiO2+A12O3：65～75％；Na2O+K2O：15～20％；BaO+F+TiO2：5～8％；CaO+B2O3+ZnO：5～10％。
2. The microcrystalline ceramic article of claim 1, wherein the microcrystalline ceramic article comprises, in mass percent, SiO2+A12O3：66～74％；Na2O+K2O：16～19％；BaO+F+TiO2：6～7％；CaO+B2O3+ZnO：6～9％。
3. The microcrystalline ceramic article of claim 1,
the microcrystalline ceramic product comprises SiO (silicon dioxide) in percentage by mass2+A12O3：70％；Na2O+K2O：17.5％；BaO+F+TiO2：6％；CaO+B2O3+ZnO：6.5％。
4. A method of making the microcrystalline ceramic article of any of claims 1-3, the method comprising:
melting materials at high temperature, feeding, forming, crystallizing and annealing to form the microcrystalline ceramic product, wherein the microcrystalline ceramic product comprises SiO in percentage by mass2+A12O3：65～75％；Na2O+K2O：15～20％；BaO+F+TiO2：5～8％；CaO+B2O3+ZnO：5～10％。
5. The method of claim 4,
the microcrystalline ceramic product comprises SiO (silicon dioxide) in percentage by mass2+A12O3：66～74％；Na2O+K2O：16～19％；BaO+F+TiO2：6～7％；CaO+B2O3+ZnO：6～9％。
6. The method of claim 4,
the temperature of the high-temperature melting material is 1300-1400 ℃.
7. The method of claim 4,
the feeding and forming temperature is 1000-1100 ℃.
8. The method of claim 4,
the temperature of the crystallization annealing step is 520-600 ℃, and the time of the crystallization annealing is 1-4 h.
9. The method of claim 4, further comprising polishing the feedstock-formed ceramic article, and subjecting the polished ceramic article to a crystallization anneal.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387318B1 (en) * | 1997-12-05 | 2002-05-14 | Alliedsignal, Inc. | Glass-ceramic pressure sensor support base and its fabrication |
| CN105621890A (en) * | 2014-10-25 | 2016-06-01 | 李林君 | Kitchen and toilet table surface glass-ceramic and ceramic composite board formula |
| CN110577365A (en) * | 2019-09-09 | 2019-12-17 | 深圳精匠云创科技有限公司 | Nanocrystalline glass ceramic and preparation method thereof |
| CN112919810A (en) * | 2021-03-23 | 2021-06-08 | 成都光明光电股份有限公司 | Glass-ceramic, glass-ceramic article and method for producing same |
-
2021
- 2021-08-03 CN CN202110888222.1A patent/CN113480179A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6387318B1 (en) * | 1997-12-05 | 2002-05-14 | Alliedsignal, Inc. | Glass-ceramic pressure sensor support base and its fabrication |
| CN105621890A (en) * | 2014-10-25 | 2016-06-01 | 李林君 | Kitchen and toilet table surface glass-ceramic and ceramic composite board formula |
| CN110577365A (en) * | 2019-09-09 | 2019-12-17 | 深圳精匠云创科技有限公司 | Nanocrystalline glass ceramic and preparation method thereof |
| CN112919810A (en) * | 2021-03-23 | 2021-06-08 | 成都光明光电股份有限公司 | Glass-ceramic, glass-ceramic article and method for producing same |
Non-Patent Citations (1)
| Title |
|---|
| 张雪峰等: "一步法热处理对复合尾矿微晶玻璃晶化过程及性能的影响", 《硅酸盐通报》 * |
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