CN113149429A - High borosilicate glass containing metal nanoparticles and preparation method thereof - Google Patents
High borosilicate glass containing metal nanoparticles and preparation method thereof Download PDFInfo
- Publication number
- CN113149429A CN113149429A CN202110211821.XA CN202110211821A CN113149429A CN 113149429 A CN113149429 A CN 113149429A CN 202110211821 A CN202110211821 A CN 202110211821A CN 113149429 A CN113149429 A CN 113149429A
- Authority
- CN
- China
- Prior art keywords
- parts
- borosilicate glass
- high borosilicate
- glass containing
- containing metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
- C03C3/105—Glass compositions containing silica with 40% to 90% silica, by weight containing lead containing aluminium
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a high-efficiency, simple and stable-performance method for synthesizing high borosilicate glass containing metal nano particles. Mixing the following components in percentage by mass: 940-997 parts of high borosilicate glass batch, 0.2-10 parts of metal compound micro powder with the particle size of 200-1600 meshes and 2-50 parts of reducing agent to obtain a premix; carrying out melt heat treatment on the premix at 1450-1800 ℃ for 1-4 h under a protective atmosphere A, annealing at 400-550 ℃ for 30-90 min, and cooling to room temperature; and (3) irradiating the glass containing the metal ions by X-rays at room temperature for 30-120 min, then carrying out heat treatment at 400-700 ℃ for 30-90 min under the protective atmosphere B, and cooling to room temperature to obtain the high borosilicate glass containing the metal nanoparticles. The invention can prepare the high borosilicate glass composite material containing metal nano particles with good stability.
Description
(I) technical field
The invention relates to a high borosilicate glass composite material containing metal nano particles and a preparation method thereof.
(II) background of the invention
Metal nanoparticles (e.g., Au, Ag, Cu, etc.) are of particular interest because of their unique surface plasmon resonance effects, quantum size effects, and localized field effects. The metal nano-particles are introduced into the glass matrix, and the local field intensity is increased due to the excitation of surface plasmon of the metal nano-particles, so that the metal nano-particles can generate better nonlinear optical properties and have wide application prospects in the field of optical devices with specific optical functions.
Researches find that the size, the particle size distribution, the crystallization degree and the like of metal nano particles have great influence on the nonlinear optical properties of the materials, and the type of a glass matrix also has great influence on the materials. At present, the glass substrate is generally selected from common soda-lime silicate series glass with poor optical, thermal and mechanical properties, and the effect and the application range of the material are limited. The high borosilicate glass has excellent properties (such as good transparency, low glass transition temperature (Tg), high density, high thermal expansion coefficient (easy to manufacture optical fiber), suitable bandwidth, good infrared transmittance, etc.), and is more suitable as a matrix of a glass material containing metal nanoparticles. Common methods for generating metal nanoparticles in traditional soda-lime-silica glass with a loose network structure include an ion implantation method, an ion exchange method, a sol-gel method, a fusion heat treatment method and the like, but because the network structure of high borosilicate glass is compact, the nanoparticles synthesized by the traditional process have poor uniformity and poor stability and controllability.
In view of the above problems, it is important to develop a method for preparing nano metal particles with good uniformity and stability in high borosilicate glass.
Disclosure of the invention
Aiming at the problems in the prior art, the invention provides a high-efficiency, simple and convenient method for synthesizing high borosilicate glass containing metal nano particles with stable performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of high borosilicate glass containing metal nano particles, which comprises the following steps:
(1) mixing the following components in parts by mass: 940-997 parts (preferably 975-994 parts) of high borosilicate glass batch, 0.2-10 parts (preferably 0.8-5 parts) of metal compound micro powder with the particle size of 200-1600 meshes and 2-50 parts (preferably 5-20 parts) of reducing agent to obtain a premix; the metal compound of the metal compound micro powder is AgNO3、HAuCl4·4H2O、Cu2One in OOne or more kinds; the reducing agent is SnO or Sb2O5、CeO2One or more of; the high borosilicate glass batch is composed of the following components in parts by mass: 780-850 parts of silicon dioxide (SiO)2) 170-270 parts of boric acid (H)3BO3) 68-172 parts of sodium carbonate (Na)2CO3) 0 to 76 parts of aluminum hydroxide (Al (OH)3) And 0-90 parts of calcium carbonate (CaCO)3)；
(2) Carrying out fusion heat treatment on the premix in the step (1) at 1450-1800 ℃ for 1-4 h under a protective atmosphere A, injecting the obtained glass melt into a mold, annealing at 400-550 ℃, keeping the temperature for 30-90 min, and cooling to room temperature to obtain glass containing metal ions;
(3) and (3) irradiating the glass containing the metal ions in the step (2) with X-ray (CuKa, lambda is 0.15416nm, 50kV and 50mA) at room temperature for 30-120 min, then carrying out heat treatment at 400-700 ℃ in a protective atmosphere B for 30-90 min, and cooling to obtain the high borosilicate glass containing the metal nanoparticles.
Preferably, the high borosilicate glass batch material in the step (1) has the composition of 788 parts of silicon dioxide (SiO)2) 226 parts of boric acid (H)3BO3) 97 portions of sodium carbonate (Na)2CO3)30 parts of aluminum hydroxide (Al (OH)3) 5 parts of calcium carbonate (CaCO)3)。
Preferably, the metal compound of the metal compound micropowder in the step (1) is AgNO3、Cu2One or two of O, and AgNO is especially preferable3。
Preferably, the reducing agent in the step (1) is SnO or CeO2One or two of them.
Preferably, the protective atmosphere A in the step (2) or the protective atmosphere B in the step (3) is a nitrogen or argon atmosphere.
Preferably, the temperature of the melting heat treatment in the step (2) is 1500-1750 ℃ and the time is 1-2 h.
Preferably, the X-ray irradiation time of the glass powder containing metal ions in the step (3) is 30-60 min, and the glass powder is subjected to heat treatment at 500-600 ℃ for 30-60 min in a protective atmosphere B.
Compared with the prior art, the invention has the beneficial effects that: the high borosilicate glass composite material containing metal nano particles with good stability can be prepared, the preparation process is efficient and simple, and the high borosilicate glass composite material is suitable for preparing various metal nano particles.
(IV) description of the drawings
FIG. 1 shows a graph containing 0.08% AgNO3And 1.5% SnO were annealed at 400 ℃ for 60min after X-ray irradiation.
FIG. 2 shows a graph containing 0.15% AgNO3And 1.0% SnO was annealed at 600 ℃ for 60min after X-ray irradiation.
FIG. 3 shows a graph containing 0.08% AgNO3And 1.5% SnO was annealed at 600 ℃ for 60min after X-ray irradiation.
FIG. 4 shows a composition containing Ag+The common glass is annealed for 60min at 420 ℃ and 560 ℃ respectively after being irradiated by X-rays.
(V) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto. The borosilicate glass batch materials selected in the following examples were introduced into the respective groups by selecting reagent grade SiO2、H3BO3、Na2CO3、Al(OH)3And CaCO3Weighing 788g of SiO2、226g H3BO3、97g Na2CO3、30g Al(OH)3And 5g of CaCO3And uniformly mixing to obtain the high borosilicate glass batch. The theoretical mass composition (wt%) of the high borosilicate glass is SiO2:78.8；B2O3:12.8；Na2O:5.7；Al2O3:2.0；CaO:0.3。
Example 1:
a method for synthesizing metal nanoparticles in high borosilicate glass, characterized by: the preparation method comprises the following steps:
(1) 98.42g of a high borosilicate glass batch with 0.1259g of AgNO3Then adding 1.7g of SnO reducing agent into the mixture, mixing the mixture in equal proportion, grinding and mixing the mixture in a ceramic mortarMixing for 30min to obtain 99.1g of mixture;
(2) performing melt heat treatment on the mixture at 1700 ℃ for 1h in nitrogen atmosphere, pouring glass in a mold, annealing and cooling, keeping the temperature at 550 ℃ for 60min, and cooling to room temperature to obtain the metal ion (Ag) containing material+) The high borosilicate glass of (1).
(3) Finally, the obtained metal ion (Ag) is added+) The high borosilicate glass was irradiated with X-rays (CuK α, λ: 0.15416nm, 50kV, 50mA) at room temperature for 30min, then heat-treated at 400 ℃ for 60min under a nitrogen atmosphere, and then cooled to room temperature, to obtain 61.8g of high borosilicate glass containing metal nanoparticles. The generated metal nanoparticles are characterized by ultraviolet-visible absorption spectrum, as shown in fig. 1, it can be found that the spectral curve shows the characteristic peak of the metal nanoparticles, the wavelength is stable, and the absorption band is about 400nm, under the condition, the metal nanoparticles with good stability can be prepared in the high borosilicate glass.
Example 2:
a method for synthesizing metal nanoparticles in high borosilicate glass, characterized by: the preparation method comprises the following steps:
(1) 98.35g of high borosilicate glass batch and 0.2361g of AgNO3Then adding 1.1g of SnO reducing agent, mixing in equal proportion, and grinding and mixing in a ceramic mortar for 30min to obtain 98.6g of a mixture;
(2) performing melt heat treatment on the mixture at 1700 ℃ for 1h in nitrogen atmosphere, pouring glass in a mold, annealing and cooling, keeping the temperature at 550 ℃ for 60min, and cooling to room temperature to obtain the metal ion (Ag) containing material+) The high borosilicate glass of (1).
(3) Finally, the obtained metal ion (Ag) is added+) The high borosilicate glass was irradiated with X-rays (CuK α, λ: 0.15416nm, 50kV, 50mA) at room temperature for 30min, then subjected to high-temperature heat treatment at 600 ℃ for 60min under a nitrogen atmosphere, and then cooled to room temperature, to obtain 57.2g of high borosilicate glass containing metal nanoparticles. By using ultraviolet-visible absorption spectrum to characterize the produced metal nanoparticles, as shown in fig. 2, it can be found that the spectral curve shows the characteristic peak of the metal nanoparticles,the wavelength is stable, the absorption band is about 404nm, and metal nano-particles with good stability can be prepared in the high borosilicate glass under the condition.
Example 3:
a method for synthesizing metal nanoparticles in high borosilicate glass, characterized by: the preparation method comprises the following steps:
(1) 98.42g of a high borosilicate glass batch with 0.1259g of AgNO3Then adding 1.7g of SnO reducing agent, mixing in equal proportion, and grinding and mixing in a ceramic mortar for 30min to obtain 98.5g of a mixture;
(2) performing melt heat treatment on the mixture at 1700 ℃ for 1h in nitrogen atmosphere, pouring glass in a mold, annealing and cooling, keeping the temperature at 550 ℃ for 60min, and cooling to room temperature to obtain the metal ion (Ag) containing material+) The high borosilicate glass of (1).
(3) Finally, the obtained metal ion (Ag) is added+) The high borosilicate glass was irradiated with X-rays (CuK α, λ: 0.15416nm, 50kV, 50mA) at room temperature for 30min, then subjected to high-temperature heat treatment at 600 ℃ for 60min under a nitrogen atmosphere, and then cooled to room temperature, to obtain 55.7g of high borosilicate glass containing metal nanoparticles. The generated metal nanoparticles are characterized by ultraviolet-visible absorption spectrum, as shown in fig. 3, it can be found that the spectral curve shows the characteristic peak of the metal nanoparticles, the wavelength is stable, and the absorption band is about 400nm, under the condition, the metal nanoparticles with good stability can be prepared in the high borosilicate glass.
Example 4:
a method for synthesizing metal nanoparticles in high borosilicate glass, characterized by: the preparation method comprises the following steps:
(1) 98.8g of a high borosilicate glass batch with 0.5589g of Cu2O, and 0.6g of CeO was added2A reducing agent, which is ground and mixed in a ceramic mortar for 30min to obtain 97.9g of a mixture;
(2) performing melt heat treatment on the mixture at 1750 ℃ for 1.5h in argon atmosphere, pouring glass in a mold, annealing and cooling, keeping the temperature at 550 ℃ for 70min, and cooling to room temperature to obtain the metal-containing materialIon (Cu)+) The high borosilicate glass of (1).
(3) Finally, the obtained metal ion (Cu) is added+) The high borosilicate glass was irradiated with X-rays (CuK α, λ: 0.15416nm, 50kV, 50mA) at room temperature for 40min, then subjected to high-temperature heat treatment at 700 ℃ for 50min under an argon atmosphere, and then cooled to room temperature, to obtain 62.4g of high borosilicate glass containing metal nanoparticles. The generated metal nano-particles are characterized by ultraviolet-visible absorption spectrum, and the spectral curve shows the characteristic peak of the metal nano-particles, the peak shape is stable, and the metal nano-particles with good stability can be prepared in the high borosilicate glass under the condition.
Comparative example 1:
the comparative example adopts common soda-lime-silica glass, and the raw materials introduced into each group select reagent-grade SiO2，Na2CO3，CaCO3And Al (OH)3Weigh 732gSiO2、261gNa2CO3、181gCaCO3And 19gAl (OH)3And mixing to obtain the soda-lime-silica glass batch. The sodium-calcium-silicon glass has the theoretical mass composition (wt%) of SiO2:73.2，Na2O:15.3，CaO:10.2，Al2O3:1.3。
99.92g of ordinary soda-lime-silica glass batch and 0.1259g of AgNO3Grinding and mixing in a ceramic mortar for 30min to obtain 97.3g of a mixture; performing melting heat treatment at 1400 deg.C for 3h, pouring into glass in a mold, annealing, cooling, keeping at 550 deg.C for 70min, and cooling to room temperature to obtain metal ion (Ag)+) The soda-lime-silica glass.
Containing Ag+After the ordinary soda-lime-silica glass is irradiated by X-ray (CuK alpha, lambda is 0.15416nm, 50kV and 50mA) for 30min, Ag atoms are generated, the temperature is heated to 420 ℃ and kept for 60min, 68.7g of soda-lime-silica glass containing Ag nano particles is obtained, and the glass has an obvious absorption peak at about 405 nm. As shown in FIG. 4, in the ordinary soda-lime-silica glass, Ag nano-particles are generated at 420 ℃, the glass has a characteristic yellow color, but when the glass is heated at about 560 ℃, the Ag nano-particles disappear, and an obvious absorption peak at about 405nm is resolved.
The physicochemical properties and characteristic absorption peaks of the Ag nanoparticles of the high borosilicate glass containing Ag nanoparticles are more stable as can be seen by comparing example 2 with comparative example 1.
Although the present invention has been described with reference to preferred embodiments, it will be understood by those skilled in the art that the present invention may be practiced without limitation to the foregoing embodiments and within the scope of the appended claims.
Claims (10)
1. A preparation method of high borosilicate glass containing metal nano particles is characterized by comprising the following steps:
(1) mixing the following components in parts by mass: 940-997 parts of high borosilicate glass batch, 0.2-10 parts of metal compound micro powder with the particle size of 200-1600 meshes and 2-50 parts of reducing agent to obtain a premix; the metal compound of the metal compound micro powder is AgNO3、HAuCl4·4H2O、Cu2One or more of O; the reducing agent is SnO or Sb2O5、CeO2One or more of; the high borosilicate glass batch is composed of the following components in parts by mass: 780-850 parts of silicon dioxide, 170-270 parts of boric acid, 68-172 parts of sodium carbonate, 0-76 parts of aluminum hydroxide and 0-90 parts of calcium carbonate;
(2) carrying out fusion heat treatment on the premix in the step (1) at 1450-1800 ℃ for 1-4 h under a protective atmosphere A, injecting the obtained glass melt into a mold, annealing at 400-550 ℃, keeping the temperature for 30-90 min, and cooling to room temperature to obtain glass containing metal ions;
(3) and (3) irradiating the glass containing the metal ions in the step (2) by using X-rays for 30-120 min at room temperature, then carrying out heat treatment at 400-700 ℃ for 30-90 min under a protective atmosphere B, and cooling to obtain the high borosilicate glass containing the metal nanoparticles.
2. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: the metal compound of the metal compound micro powder in the step (1) is AgNO3、Cu2One or two of O.
3. The method for preparing high borosilicate glass containing metal nanoparticles according to claim 1, wherein the components are mixed in the following parts by mass in step (1): 975-994 parts of high borosilicate glass batch, 0.8-5 parts of metal compound micro powder with the particle size of 200-1600 meshes and 5-20 parts of reducing agent.
4. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: in the step (1), the reducing agent is SnO or CeO2One or two of them.
5. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: the high borosilicate glass batch in the step (1) comprises 788 parts of silicon dioxide, 226 parts of boric acid, 97 parts of sodium carbonate, 30 parts of aluminum hydroxide and 5 parts of calcium carbonate.
6. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: the temperature of the melting heat treatment in the step (2) is 1500-1750 ℃, and the time is 1-2 h.
7. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: the protective atmosphere A in the step (2) or the protective atmosphere B in the step (3) is a nitrogen or argon atmosphere.
8. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: the parameters of X-ray irradiation in step (3) were CuK α, λ 0.15416nm, 50kV, and 50 mA.
9. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: the X-ray irradiation time of the glass powder containing metal ions in the step (3) is 30-60 min.
10. The method of preparing a high borosilicate glass containing metal nanoparticles according to claim 1, wherein: the heat treatment in the step (3) is carried out for 30-60 min at the temperature of 500-600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110211821.XA CN113149429B (en) | 2021-02-25 | 2021-02-25 | High borosilicate glass containing metal nanoparticles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110211821.XA CN113149429B (en) | 2021-02-25 | 2021-02-25 | High borosilicate glass containing metal nanoparticles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113149429A true CN113149429A (en) | 2021-07-23 |
| CN113149429B CN113149429B (en) | 2023-03-31 |
Family
ID=76883407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110211821.XA Active CN113149429B (en) | 2021-02-25 | 2021-02-25 | High borosilicate glass containing metal nanoparticles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149429B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043644A (en) * | 2022-04-13 | 2022-09-13 | 山东电盾科技股份有限公司 | Ceramic hand mold with anti-static function and preparation process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004001729A1 (en) * | 2004-01-13 | 2005-08-04 | Schott Ag | Preparation of red colored borosilicate glass containing reducing agent and colloidal copper useful for decoration, e.g. of church windows |
| CN1830854A (en) * | 2006-03-21 | 2006-09-13 | 武汉理工大学 | Preparation method of colourless transparent glass material capable of forming purple rod stereo pattern inside |
| CN102596841A (en) * | 2009-10-27 | 2012-07-18 | 学校法人东京理科大学 | Light-emitting glass, light-emitting device equipped with the light-emitting glass, and process for producing light-emitting glass |
| CN104817268A (en) * | 2015-04-21 | 2015-08-05 | 同济大学 | Preparation method and luminescent glass capable of efficiently extracting size-controllable Ag nano particles under low-concentration AgNO3 doping condition |
| CN111168079A (en) * | 2020-01-15 | 2020-05-19 | 浙江工业大学 | Method for synthesizing metal nanoparticles based on glass surface |
| CN111491905A (en) * | 2017-10-13 | 2020-08-04 | 阿德莱德大学 | Method for controlling the formation of metal nanoparticles in glass and products thereof |
-
2021
- 2021-02-25 CN CN202110211821.XA patent/CN113149429B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004001729A1 (en) * | 2004-01-13 | 2005-08-04 | Schott Ag | Preparation of red colored borosilicate glass containing reducing agent and colloidal copper useful for decoration, e.g. of church windows |
| CN1830854A (en) * | 2006-03-21 | 2006-09-13 | 武汉理工大学 | Preparation method of colourless transparent glass material capable of forming purple rod stereo pattern inside |
| CN102596841A (en) * | 2009-10-27 | 2012-07-18 | 学校法人东京理科大学 | Light-emitting glass, light-emitting device equipped with the light-emitting glass, and process for producing light-emitting glass |
| CN104817268A (en) * | 2015-04-21 | 2015-08-05 | 同济大学 | Preparation method and luminescent glass capable of efficiently extracting size-controllable Ag nano particles under low-concentration AgNO3 doping condition |
| CN111491905A (en) * | 2017-10-13 | 2020-08-04 | 阿德莱德大学 | Method for controlling the formation of metal nanoparticles in glass and products thereof |
| CN111168079A (en) * | 2020-01-15 | 2020-05-19 | 浙江工业大学 | Method for synthesizing metal nanoparticles based on glass surface |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115043644A (en) * | 2022-04-13 | 2022-09-13 | 山东电盾科技股份有限公司 | Ceramic hand mold with anti-static function and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113149429B (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10391039B2 (en) | Al2O3-free lithium silicate glass composition | |
| CN109987848B (en) | CsPbBr-containing material3Quantum dot superlattice structure glass and preparation method thereof | |
| EP0640571A1 (en) | A wavelength up-conversion glass ceramic and a process for the production thereof | |
| Kukkonen et al. | Nucleation and crystallisation of transparent, erbium III-doped, oxyfluoride glass-ceramics | |
| WO2022151610A1 (en) | Colored microcrystalline glass and preparation method therefor | |
| EP4194415A1 (en) | High-transparency fluorescent glass-ceramic, and preparation method therefor and application thereof | |
| WO2023035704A1 (en) | Preparation method for fluorescent lithium silicate glass ceramic | |
| CN113149429B (en) | High borosilicate glass containing metal nanoparticles and preparation method thereof | |
| CN105130196B (en) | Process for the preparation of a ceramic glass plate, plate obtained by this process and its use | |
| CN112811821B (en) | Rare earth doped YAG high-crystallinity transparent glass ceramics and preparation method thereof | |
| CN106746618A (en) | A kind of ecru devitrified glass and its preparation method and application | |
| CN109354417B (en) | NaTbF is separated out4Nanocrystalline germanosilicate microcrystalline glass and preparation method thereof | |
| CN112174533B (en) | White high-aluminum microcrystalline glass and preparation method thereof | |
| CN112876084B (en) | Quantum dot glass ceramics and preparation method thereof and method for preparing quantum dot glass ceramics product by applying 3D printing technology | |
| CN108623154B (en) | Surface-strengthened transparent glass | |
| CN111252799A (en) | Preparation of YAG Ce by containerless solidification3+Method for mixing amorphous material with aluminum nitride | |
| CN1031826A (en) | Blue discolouration glass | |
| CN107759078A (en) | A kind of heat-insulated coloured glass of antiultraviolet and its production technology | |
| CN116282928B (en) | Gallium/zinc aluminate doped near-infrared tellurium germanate nanocrystalline glass and preparation method thereof | |
| Zheng et al. | Crystallization of CaO–MgO–Al 2 O 3–SiO 2 glass prepared by float process | |
| TANG et al. | Effect of Zinc Oxide on Structure and Transmission Property of MgO–Al 2O 3–SiO 2 Glass-Ceramics | |
| CN1009285B (en) | Black cubic zirconia jewel and manufacture method thereof | |
| CN110002742B (en) | Electronic equipment panel and contain its electronic equipment | |
| CN101205116A (en) | Nd-doped Li2O-Al2O3-SiO2 series transparent laser glass ceramics and method for making same | |
| CN114956578A (en) | Method for preparing high-surface-compressive-stress microcrystalline glass by femtosecond laser |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |