CN111039565A - Milky white defluorinated glass and preparation method thereof - Google Patents
Milky white defluorinated glass and preparation method thereof Download PDFInfo
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/005—Compositions for glass with special properties for opaline glass
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
Discloses milky white defluorinated glass, which comprises the following chemical components in percentage by weight: SiO 2260.0‑69.0wt％；Al2O31.0‑3.0wt％；B2O36.0‑10.0wt％；CaO 3.0‑5.0wt％；SrO 1.0‑2.5wt％；Li2O 0.5‑2.0wt％；Na2O 3.0‑5.0wt％；K2O1.0-3.0 wt% and mixed opalescent; the latter being selected from P2O5And SnO2Combinations of (a) and (b). The milky white defluorinated glass has high whiteness and chemical stability; while still maintaining a low coefficient of thermal expansion.
Description
Technical Field
The invention belongs to the technical field of glass, and relates to milky white defluorinated glass and a preparation method thereof.
Background
Opal glass is a white opaque glass that finds wide application in construction, bottle, ware, art, and decoration. The glass has dispersed homogeneously therein a large amount of fine particles of several hundred nanometers to about one micron, which have a refractive index different from that of the mother glass. When light irradiates the opal glass, refraction or reflection is generated at the interface of fine particles, so that scattered reflection light and diffused transmission light are generated, and the glass is in an opal color macroscopically. The degree of opalescence (also known as whiteness) and characteristics of opal glasses depend on particle size, number, refractive index difference, and glass thickness.
The typical preparation method of the opal glass is as follows: the opacifier with low solubility is added into the glass batch to separate out crystals. The most commonly used opacifying agents are fluorides such as cryolite, sodium silicofluoride and fluorite, among others. When the glass is melted at high temperature, a small part of fluoride is volatilized, and the solubility of most of fluoride in the glass is reduced, so that supersaturation is achieved, sodium fluoride and calcium fluoride crystals are separated out, and the glass is opaque. However, the dust and exhaust emission of fluoride during raw material treatment and processing is liable to cause environmental pollution; in addition, the reaction of fluoride with silica at high temperatures destroys the silicate network, resulting in a large reduction in the strength of the glass. In order to avoid the above disadvantages, opal fluoride-free (defluorinated) glasses meet the requirements of the current environment-friendly society, and are the development direction of the glass industry, and have become the research direction of common attention of various national scholars and production technicians.
Chinese patent application CN101244889A discloses a fluoride-free environment-friendly opaque glass material and a manufacturing method thereof, wherein the glass material consists of SiO2-Al2O3-B2O3-P2O5-MgO-CaO-SrO-BaO-Li2O-Na2O-K2And O. The preparation method comprises the steps of mixing the raw materials to prepare uniform batch, putting the batch into a corundum crucible, casting and molding after melting and heat preservation, and carrying out heat preservation and annealing. The patent application uses a small amount of phosphate to replace fluoride to generate the opacification effect, does not cause environmental pollution in the industrial production of opacified glass, and can avoid the problems of short service life and safety of a glass kiln caused by fluorine. However, the thermal expansion coefficient of the opacified glass is high, and the chemical stability can only reach II-III level.
Chinese patent application CN110104953A discloses a low-expansion environment-friendly opal glass and a preparation method thereof, and the preparation raw materials comprise the following components by mass percent: 52-56% of quartz sand, 4-5% of alumina, 3.5-4% of zirconia, 7-8% of tungsten oxide, 2-2.5% of ammonium hydrogen phosphate, 12.5-14% of sodium carbonate, 6-7% of calcium carbonate, 2.5-3% of borax pentahydrate and 5-6% of magnesium carbonate. The application of the patent prepares the low-expansion environment-friendly opal glass by a fusion casting method, the temperature shock resistance of the obtained opal glass is not lower than 200, the thermal expansion coefficient is reduced by 1-2 orders of magnitude compared with that of the common opal glass, the process is relatively simple and controllable, and the product quality has better stability. However, while achieving a lower coefficient of thermal expansion, the opal glass of this patent application sacrifices whiteness, while chemical stability is also difficult to meet.
In view of the above technical drawbacks, there is still a need to find a milky white defluorinated glass with high whiteness and chemical stability, while still maintaining a low thermal expansion coefficient, and a preparation method thereof.
Disclosure of Invention
The invention aims to provide milky white defluorinated glass with high whiteness and chemical stability and low thermal expansion coefficient and its preparation process.
In order to achieve the above object, in one aspect, the present invention provides an opal defluorinated glass, the glass composition comprising the following chemical components: SiO 2260.0-69.0wt％；Al2O31.0-3.0wt％；B2O36.0-10.0wt％；CaO 3.0-5.0wt％；SrO 1.0-2.5wt％；Li2O 0.5-2.0wt％；Na2O 3.0-5.0wt％；K2O1.0-3.0 wt% and mixed opalescent; it is characterized in that the preparation method is characterized in that,
the mixed opalescent agent is selected from P2O5And SnO2Combinations of (a) and (b).
Preferably, the glass component comprises the following chemical components: SiO 2261.0-68.0wt％；Al2O31.2-2.8wt％；B2O36.3-9.6wt％；CaO 3.2-4.8wt％；SrO 1.2-2.2wt％；Li2O 0.6-1.8wt％；Na2O3.2-4.8wt％；K2O 1.4-2.8wt％。
More preferably, the glass component comprises the following chemical components: SiO 2261.5-67.0wt％；Al2O31.4-2.6wt％；B2O36.6-9.3wt％；CaO 3.4-4.6wt％；SrO 1.4-2.0wt％；Li2O 0.7-1.5wt％；Na2O3.5-4.6wt％；K2O 1.6-2.6wt％。
And the number of the first and second groups,
most preferably, the glass component comprises the following chemical constituents: SiO 2262.0-66.0wt％；Al2O31.5-2.5wt％；B2O37.0-9.0wt％；CaO 3.5-4.5wt％；SrO 1.5-2.8wt％；Li2O 0.8-1.2wt％；Na2O3.8-4.5wt％；K2O 1.8-2.4wt％。
In one specific embodiment, the glass component comprises the following chemical components: SiO 2264.0wt％；Al2O32.0wt％；B2O38.0wt％；CaO 4.0wt％；SrO 1.6wt％；Li2O 0.8wt％；Na2O 4.2wt％；K2O 2.0wt％。
The opal defluorinated glass according to the invention, wherein P2O5The content is 3.0-7.0 wt%; SnO2The content is 0.5-1.5 wt%.
Preferably, P2O5The content is 3.2-6.0 wt%; SnO2The content is 0.6-1.4 wt%.
More preferably, P2O5The content is 3.4-5.0 wt%; SnO2The content is 0.7-1.3 wt%.
And the number of the first and second groups,
most preferably, P2O5The content is 3.5-4.5 wt%; SnO2The content is 0.8-1.2 wt%.
In a particular embodiment, P2O5The content was 3.8 wt%; SnO2The content was 1.0 wt%.
The opal defluorinated glass according to the invention wherein the glass component further comprises CeO2The content is 0.8-2.5 wt%.
Preferably, CeO2The content is 1.0-2.2 wt%.
More preferably, CeO2The content is 1.2-2.0 wt%.
And the number of the first and second groups,
most preferably, CeO2The content is 1.4-1.8 wt%.
In a specific embodiment, CeO2The content was 1.5 wt%.
The opal defluorinated glass according to the invention, wherein the glass component further comprises ZrO2And WO3The contents are 0.5-2.5 wt% and 4.0-7.0 wt%, respectively.
Preferably, ZrO2And WO3The content is 0.8-2.2 wt% and 4.2-6.5 wt% respectively.
More preferably, ZrO2And WO3The content is 1.0-2.0 wt% and 4.4-6.0 wt% respectively.
And the number of the first and second groups,
most preferably, ZrO2And WO3The contents are 1.2-1.8 wt% and 4.6-5.7 wt%, respectively.
In a specific embodiment, ZrO2And WO3The contents were 1.4 wt% and 5.7 wt%, respectively.
The milky white defluorinated glass provided by the invention comprises the following components in percentage by weight: SiO 2260.0-69.0wt％；Al2O31.0-3.0wt％；B2O36.0-10.0wt％；CaO 3.0-5.0wt％；SrO 1.0-2.5wt％；Li2O 0.5-2.0wt％；Na2O 3.0-5.0wt％；K2O 1.0-3.0wt％；P2O53.0-7.0wt％；SnO20.5-1.5wt％；CeO20.8-2.5wt％；ZrO20.5-2.5wt％；WO34.0-7.0 wt%; and, the balance unavoidable impurities.
Preferably, the glass component consists of the following chemical components: SiO 2261.0-68.0wt％；Al2O31.2-2.8wt％；B2O36.3-9.6wt％；CaO 3.2-4.8wt％；SrO 1.2-2.2wt％；Li2O 0.6-1.8wt％；Na2O3.2-4.8wt％；K2O 1.4-2.8wt％；P2O53.2-6.0wt％；SnO20.6-1.4wt％；CeO21.0-2.2wt％；ZrO20.8-2.2wt％；WO34.2-6.5 wt%; and, the balance unavoidable impurities.
More preferably, the glass component consists of the following chemical constituents: SiO 2261.5-67.0wt％；Al2O31.4-2.6wt％；B2O36.6-9.3wt％；CaO 3.4-4.6wt％；SrO 1.4-2.0wt％；Li2O 0.7-1.5wt％；Na2O3.5-4.6wt％；K2O 1.6-2.6wt％；P2O53.4-5.0wt％；SnO20.7-1.3wt％；CeO21.2-2.0wt％；ZrO21.0-2.0wt％；WO34.4-6.0 wt%; and, the balance unavoidable impurities.
And the number of the first and second groups,
most preferably, the glass component consists ofThe chemical composition comprises the following chemical components: SiO 2262.0-66.0wt％；Al2O31.5-2.5wt％；B2O37.0-9.0wt％；CaO 3.5-4.5wt％；SrO 1.5-2.8wt％；Li2O 0.8-1.2wt％；Na2O3.8-4.5wt％；K2O 1.8-2.4wt％；P2O53.5-4.5wt％；SnO20.8-1.2wt％；CeO21.4-1.8wt％；ZrO21.2-1.8wt％；WO34.6-5.7 wt%; and, the balance unavoidable impurities.
In one specific embodiment, the glass component consists of the following chemical constituents: SiO 2264.0wt％；Al2O32.0wt％；B2O38.0wt％；CaO 4.0wt％；SrO 1.6wt％；Li2O 0.8wt％；Na2O 4.2wt％；K2O 2.0wt％；P2O53.8wt％；SnO21.0wt％；CeO21.5wt％；ZrO21.4wt％；WO35.7wt％。
In another aspect, the present invention further provides a method for preparing the above opal defluorinated glass, wherein the method comprises the following steps:
accurately weighing raw materials of the glass components, mixing and ball-milling the raw materials, and sieving the raw materials with a 200-mesh sieve to obtain a batch mixture;
adding the batch into a crucible, heating the crucible to a melting temperature in a silicon-molybdenum rod electric furnace, and preserving the temperature for a certain time to obtain a clarified and uniform glass melt;
cooling the glass melt liquid to a specific temperature along with a furnace, and pouring the glass melt liquid into a preheated mold for casting and molding;
carrying out heat treatment on the formed glass;
and annealing the glass after heat treatment, and cooling along with the furnace to obtain the milky white defluorinated glass.
The preparation method according to the present invention, wherein the raw material is selected from the group consisting of silicon dioxide, aluminum oxide, boric acid, calcium carbonate, strontium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, ammonium phosphate, tin oxide, cerium oxide, zirconium oxide, and ammonium tungstate.
The preparation method provided by the invention has the advantages that the melting temperature is 1550-.
In a specific embodiment, the melting temperature is 1570 ℃, the holding time is 3h, and the heating rate is 5 ℃/min.
The preparation method of the invention comprises the steps of obtaining the specific temperature of 1300 ℃ and 1350 ℃, and preheating the mold to 450 ℃ and 500 ℃.
In a specific embodiment, the specific temperature is 1320 ℃ and the mold is preheated to 480 ℃.
The preparation method according to the present invention, wherein the heat treatment is: the temperature is reduced from 750 ℃ to 800 ℃ to 50 ℃, and the cooling rate is 4-6 ℃/min.
In a specific embodiment, the heat treatment is: the temperature is reduced from 760 ℃ to 50 ℃, and the cooling rate is 5 ℃/min.
The preparation method comprises the following steps: the annealing temperature is 550-600 ℃, and the heat preservation time is 1-3 h.
In a specific embodiment, the annealing treatment is: the annealing temperature is 580 ℃, and the holding time is 2 h.
Compared with the prior art, the milky white defluorinated glass has the advantages that the whiteness and the chemical stability are higher; while still maintaining a low coefficient of thermal expansion.
Detailed Description
It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include both one and more than one (i.e., two, including two) unless the context clearly dictates otherwise.
References to "comprising," "including," "having," and similar terms in this specification are not intended to exclude the presence of any optional components, steps or procedures, whether or not any optional components, steps or procedures are specifically disclosed. In order to avoid any doubt, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials unless stated to the contrary. In contrast, the term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited. Unless otherwise specified, the term "or" refers to the listed members individually as well as in any combination.
Furthermore, the contents of any referenced patent or non-patent document in this application are incorporated by reference in their entirety, especially with respect to definitions disclosed in the art (where not inconsistent with any definitions specifically provided herein) and general knowledge.
In the present invention, parts are parts by weight unless otherwise indicated, temperatures are indicated in ° c or at ambient temperature, and pressures are at or near atmospheric. There are many variations and combinations of reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Example 1
The chemical components of the milky white defluorinated glass are as follows: SiO 2264.0wt％；Al2O32.0wt％；B2O38.0wt％；CaO 4.0wt％；SrO 1.6wt％；Li2O 0.8wt％；Na2O 4.2wt％；K2O 2.0wt％；P2O53.8wt％；SnO21.0wt％；CeO21.5wt％；ZrO21.4wt％；WO35.7wt％。
The preparation method comprises the following steps:
accurately weighing raw materials of the glass components, mixing and ball-milling the raw materials, and sieving the raw materials with a 200-mesh sieve to obtain a batch mixture; the raw materials are selected from silicon dioxide, aluminum oxide, boric acid, calcium carbonate, strontium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, ammonium phosphate, tin oxide, cerium oxide, zirconium oxide and ammonium tungstate;
adding the batch into a crucible, heating the crucible to a melting temperature in a silicon-molybdenum rod electric furnace, and preserving the temperature for a certain time to obtain a clarified and uniform glass melt; wherein the melting temperature is 1570 ℃, the heat preservation time is 3h, and the heating rate is 5 ℃/min;
cooling the glass melt to 1320 ℃ along with a furnace, and pouring the glass melt into a mold preheated to 480 ℃ for casting and molding;
carrying out heat treatment on the formed glass; the heat treatment comprises the following steps: the temperature is reduced from 760 ℃ to 50 ℃, and the cooling rate is 5 ℃/min.
Annealing the glass after heat treatment, and cooling along with the furnace to obtain the milky white defluorinated glass; the annealing treatment comprises the following steps: the annealing temperature is 580 ℃, and the holding time is 2 h.
Example 2
The chemical components of the milky white defluorinated glass are as follows: SiO 2266.0wt％；Al2O31.5wt％；B2O37.0wt％；CaO 3.5wt％；SrO 1.5wt％；Li2O 1.2wt％；Na2O 3.8wt％；K2O 2.4wt％；P2O53.5wt％；SnO20.8wt％；CeO21.8wt％；ZrO21.8wt％；WO35.2wt％。
The preparation method is the same as example 1.
Example 3
The chemical components of the milky white defluorinated glass are as follows: SiO 2262.0wt％；Al2O32.5wt％；B2O39.0wt％；CaO 4.5wt％；SrO 1.8wt％；Li2O 1.0wt％；Na2O 4.5wt％；K2O 1.8wt％；P2O54.5wt％；SnO21.2wt％；CeO21.4wt％；ZrO21.2wt％；WO34.6wt％。
The preparation method is the same as example 1.
Comparative example 1
No SnO addition2A 1 is to P2O5Adjusting to 4.8 wt%; the amounts of other chemical components and the preparation method are the same as those of example 1.
Comparative example 2
Will P2O5Adjusting the content to 1.0 wt%; SnO2Is adjusted to3.8 wt%; the amounts of other chemical components and the preparation method are the same as those of example 1.
Comparative example 3
No addition of CeO2The amounts of other chemical components and the preparation method are the same as those of example 1.
Comparative example 4
The heat treatment step, the chemical components used and other steps of the preparation method were the same as in example 1.
Performance testing
The whiteness of the glasses of examples 1 to 3 of the present invention and comparative examples 1 to 4 was measured using a WSC-S type whiteness colorimeter (error:. + -. 0.1%). The average thermal expansion coefficient (unit is 10) of the glasses of examples 1 to 3 of the present invention and comparative examples 1 to 4 at 50 to 300 ℃ was measured using a DIL 402 Expedis Classic thermal expansion instrument-7K); the sample used was 4mm × 4mm × 25mm in size and was ground by a polishing machine. Chemical stability is evaluated by using water resistance as an index, and the volumes of 0.01M HCl consumed are 0-0.2mL, 0.2-0.4mL, 0.4-1.7mL, 1.7-4.0mL and 4.0mL or more, respectively, hydrolysis grades I-V, when tested according to DIN 12111.
The results are shown in Table 1.
TABLE 1
As can be seen from the results, examples 1-3 of the present application have improved whiteness and chemical stability over the prior art, while still maintaining a lower coefficient of thermal expansion, as compared to comparative examples 1-4.
Without wishing to be bound by any theory, a specific ratio of P2O5And SnO2、CeO2The combination of specific heat treatment processes leads to the improvement of the technical effects.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (10)
1. The milky white defluorinated glass has the following chemical components: SiO 2260.0-69.0wt％；Al2O31.0-3.0wt％；B2O36.0-10.0wt％；CaO 3.0-5.0wt％；SrO 1.0-2.5wt％；Li2O 0.5-2.0wt％；Na2O 3.0-5.0wt％；K2O1.0-3.0 wt% and mixed opalescent; it is characterized in that the preparation method is characterized in that,
the mixed opalescent agent is selected from P2O5And SnO2Combinations of (a) and (b).
2. The glass of claim 1, wherein P is2O5The content is 3.0-7.0 wt%; SnO2The content is 0.5-1.5 wt%.
3. The glass of claim 1, wherein the glass component further comprises CeO2The content is 0.8-2.5 wt%.
4. The glass of claim 1, wherein the glass component further comprises ZrO2And WO3The contents are 0.5-2.5 wt% and 4.0-7.0 wt%, respectively.
5. The glass of claim 1, wherein the glass composition consists of the following chemical constituents: SiO 2260.0-69.0wt％；Al2O31.0-3.0wt％；B2O36.0-10.0wt％；CaO 3.0-5.0wt％；SrO 1.0-2.5wt％；Li2O0.5-2.0wt％；Na2O 3.0-5.0wt％；K2O 1.0-3.0wt％；P2O53.0-7.0wt％；SnO20.5-1.5wt％；CeO20.8-2.5wt％；ZrO20.5-2.5wt％；WO34.0-7.0 wt%; and, the balance unavoidable impurities.
6. A method for producing an opal defluorinated glass according to any one of claims 1 to 5, comprising the steps of:
accurately weighing raw materials of the glass components, mixing and ball-milling the raw materials, and sieving the raw materials with a 200-mesh sieve to obtain a batch mixture;
adding the batch into a crucible, heating the crucible to a melting temperature in a silicon-molybdenum rod electric furnace, and preserving the temperature for a certain time to obtain a clarified and uniform glass melt;
cooling the glass melt liquid to a specific temperature along with a furnace, and pouring the glass melt liquid into a preheated mold for casting and molding;
carrying out heat treatment on the formed glass;
annealing the heat-treated glass, and furnace-cooling to obtain the milky white defluorinated glass as defined in any one of claims 1 to 5.
7. The preparation method of claim 6, wherein the melting temperature is 1550-.
8. The method as claimed in claim 6, wherein the specific temperature is 1300 ℃ and the mold is preheated to 450 ℃ and 500 ℃.
9. The production method according to claim 6, wherein the heat treatment is: the temperature is reduced from 750 ℃ to 800 ℃ to 50 ℃, and the cooling rate is 4-6 ℃/min.
10. The production method according to claim 6, wherein the annealing treatment is: the annealing temperature is 550-600 ℃, and the heat preservation time is 1-3 h.
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| CN1552650A (en) * | 2003-05-26 | 2004-12-08 | 上海高雅玻璃有限公司 | Lacte glass |
| CN102249540A (en) * | 2011-04-28 | 2011-11-23 | 浙江大学 | Na2O-CaO-SiO2 opaque glass and preparation method thereof |
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| CN109502967A (en) * | 2018-11-22 | 2019-03-22 | 东华大学 | A kind of acid and alkali-resistance free-floride opal glass and its preparation method and application |
| CN110104953A (en) * | 2019-05-22 | 2019-08-09 | 淮阴工学院 | A kind of low bulk environment-friendly type opal glass and preparation method thereof |
| CN110436786A (en) * | 2019-08-19 | 2019-11-12 | 淮阴工学院 | A method of improving phosphate-opal glass whiteness |
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2020
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| CN1552650A (en) * | 2003-05-26 | 2004-12-08 | 上海高雅玻璃有限公司 | Lacte glass |
| CN102249540A (en) * | 2011-04-28 | 2011-11-23 | 浙江大学 | Na2O-CaO-SiO2 opaque glass and preparation method thereof |
| CN102295413A (en) * | 2011-06-14 | 2011-12-28 | 武汉理工大学 | Preparation method of Zr-P fluoride-free opaque glass |
| CN104556688A (en) * | 2014-12-25 | 2015-04-29 | 河北省沙河玻璃技术研究院 | Emulsion opal glass and preparation method thereof |
| US20180099901A1 (en) * | 2016-10-12 | 2018-04-12 | Corning Incorporated | Glass ceramics |
| CN109502967A (en) * | 2018-11-22 | 2019-03-22 | 东华大学 | A kind of acid and alkali-resistance free-floride opal glass and its preparation method and application |
| CN110104953A (en) * | 2019-05-22 | 2019-08-09 | 淮阴工学院 | A kind of low bulk environment-friendly type opal glass and preparation method thereof |
| CN110436786A (en) * | 2019-08-19 | 2019-11-12 | 淮阴工学院 | A method of improving phosphate-opal glass whiteness |
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