CN110078376B - Preparation method of porous glass material, porous glass material prepared by method and application of porous glass material - Google Patents
Preparation method of porous glass material, porous glass material prepared by method and application of porous glass material Download PDFInfo
- Publication number
- CN110078376B CN110078376B CN201910313597.8A CN201910313597A CN110078376B CN 110078376 B CN110078376 B CN 110078376B CN 201910313597 A CN201910313597 A CN 201910313597A CN 110078376 B CN110078376 B CN 110078376B
- Authority
- CN
- China
- Prior art keywords
- glass
- porous
- porous glass
- glass material
- glass powder
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
-
- 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
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
Abstract
The invention relates to a preparation method of a porous glass material, the porous glass material prepared by the method and application thereof. The preparation method comprises the following process steps: preparing a base glass from a first acid-resistant level glass and a second acid-resistant level glass; cutting, grinding and polishing the substrate glass; putting the substrate glass into an acid solution for corrosion until the glass with the first acid-resistant level is completely digested, and taking out the substrate glass to obtain a porous glass blank; the porous glass blank is cleaned, dried and processed into a porous glass material with a specific size and shape. The preparation method of the porous glass material is simple to operate and good in process stability, the porous glass material with the micron pore diameter can be prepared by adjusting the particle size and the proportion of the first glass powder and the second glass powder and adjusting the particle size of the matrix glass powder, the concentration of the corrosive liquid and the corrosion process parameters, and the porous glass material is uniform in pore size, high in porosity and high in compressive strength.
Description
Technical Field
The invention relates to the field of glass manufacturing, in particular to a preparation method of a porous glass material, the porous glass material prepared by the method and application of the porous glass material.
Background
The porous glass as a novel porous material has the advantages of interconnected pore structure, high specific surface area, good corrosion resistance, chemical stability at high temperature and excellent structural and functional properties, so the porous glass is suitable for serving as a catalyst, an adsorbent, a refining agent, a drug slow-release agent and a carrier for heterogeneous hybridization, and can be widely applied to the fields of food, environmental protection, chemical engineering, medical treatment, biology, genetic engineering and the like.
In the prior art, the preparation methods of porous glass are various, and mainly comprise a sintering method, a phase separation method, a dipping method, a pore-forming agent method, a sol-gel method and the like. The porous glasses prepared by different methods are very different, wherein the most common porous glass preparation method is a phase separation method, and Na is selected for the method2O-B2O3-SiO2The glass is subjected to phase separation treatment at the high temperature of 550-700 ℃, and then acid leaching is carried out to obtain the porous glass. However, the method also has technical defects, such as long process time of thermal phase separation, difficulty in accurately controlling the component proportion of the glass, difficulty in controlling the size of the phase separation, uneven pore size and porosity distribution of the porous glass obtained by the method, and high process control difficulty. Furthermore, the pore space of the porous glass prepared by the phase separation method is between 10nm and 500nm, but the porous glass with the nanometer pore space in practical application is difficult to meet wide requirements, particularly as a certain immobilized cell carrier, the micron pore structure is favorable for reducing the resistance when reactant molecules enter and product molecules leave, and the pore channel is prevented from being blocked.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a micron-pore-size porous glass material with simple preparation process and good process stability, and the porous glass material prepared by the method has uniform pore size, high porosity and high compressive strength.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. According to the preparation method of the porous glass material provided by the invention, the process steps are as follows:
1) preparing a base glass from a first acid-resistant level glass and a second acid-resistant level glass;
2) cutting, grinding and polishing the substrate glass;
3) putting the substrate glass into an acid solution for corrosion until the glass with the first acid-resistant level is completely digested, and taking out the substrate glass to obtain a porous glass blank;
4) the porous glass blank is cleaned, dried and processed into a porous glass material with a specific size and shape.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the preparation method of the porous glass material comprises the following steps:
A. crushing, grinding and sieving a glass material with a first acid resistance level to obtain first glass powder;
B. crushing, grinding and sieving the glass material with the second acid resistance level to obtain second glass powder;
C. uniformly mixing the first glass powder and the second glass powder according to a proportion to obtain a glass powder mixture;
D. and transferring the glass powder mixture into a mold, sintering at a certain temperature, under a certain pressure and under a certain vacuum condition, cooling to room temperature, and demolding to obtain the matrix glass.
Preferably, in the preparation method of the porous glass material, the sieve used for sieving in the steps A and B is 200-1500 meshes; the grain diameter of the first glass powder and the second glass powder is 1-100 mu m.
Preferably, in the preparation method of the porous glass material, before the first glass powder and the second glass powder are mixed in the step C, the first glass powder and the second glass powder are cleaned and dried; the mixing in the step C is dry mixing or wet stirring mixing; the mixing ratio of the first glass powder to the second glass powder is 1: 10-100 by mass.
Preferably, in the method for preparing a porous glass material, the glass powder mixture in step C further includes a flux;the fluxing agent is CaF2The content of the powder or the low-temperature sintered glass powder is less than or equal to 10 percent by mass.
Preferably, in the method for preparing the porous glass material, the sintering temperature of the glass powder mixture in the step D is higher than the glass softening temperature thereof; the vacuum degree of the system during sintering is 0.1-100 Pa, and the pressure borne by the glass powder mixture is 10-50 MPa; the sintering temperature is 600-900 ℃, and the sintering time is 0.5-4 h.
Preferably, the method for preparing a porous glass material, wherein the acid solution in step 3) is at least one selected from nitric acid, hydrochloric acid and sulfuric acid; the concentration of the acid solution is 0.1-1 mol/L; the temperature of the acid solution is between room temperature and 80 ℃ during corrosion, and the corrosion time is between 2 and 8 hours.
Preferably, in the step 4), the porous glass blank is washed for 3 to 5 times by using deionized water, and then is soaked in ethanol, propanol or isopropanol for 15 to 60 min; taking out and drying at the temperature of 80-100 ℃ for 0.5-2 h.
The second objective of the present invention is to provide a porous glass material prepared by the above preparation method, wherein the size of the pore diameter of the porous glass material can be adjusted according to the requirement, and the size and distribution range of the porous particle diameter can be adjusted according to the actual requirement.
The third purpose of the invention is to provide an application of the porous glass material prepared by the preparation method.
By the technical scheme, the preparation method of the porous glass material, the porous glass material prepared by the method and the application of the porous glass material at least have the following advantages:
1. the preparation method of the porous glass material provided by the invention adopts two kinds of glass powder with larger difference in acid resistance stability to mix and sinter to prepare the matrix glass, and then corrodes and processes the matrix glass, and the like. The aperture of the porous glass material prepared by the method is 1-100 mu m, the porosity reaches more than 70 percent, and the compressive strength reaches more than 20 MPa;
2. the preparation method of the porous glass material provided by the invention has the advantages of simple manufacturing process and good process stability, and the pore size distribution and the porosity of the prepared porous glass material are controlled;
3. the porous glass material prepared by the preparation method of the porous glass material is particularly suitable for immobilized enzyme carriers and immobilized cell carriers, separating and purifying organisms and biochemical substances such as microorganisms, proteins, interferon, viruses and the like, and can also be used as drug slow-release agent carriers, bone tissue repair scaffold materials, microfluidic chips, gene sequencing substrates, catalyst carriers, radioactive waste curing substrates, sound absorption materials and the like.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made with reference to the preferred embodiments of a method for preparing a porous glass material, a porous glass material prepared by the method, and embodiments, structures, features and effects thereof applied thereto according to the present invention.
The invention provides a preparation method of a porous glass material, which comprises the following process steps:
1) preparing a base glass from a first acid-resistant level glass and a second acid-resistant level glass;
2) cutting, grinding and polishing the substrate glass;
3) putting the substrate glass into an acid solution for corrosion until the glass with the first acid-resistant level is completely digested, and taking out the substrate glass to obtain a porous glass blank;
4) the porous glass blank is cleaned, dried and processed into a porous glass material with a specific size and shape.
The base glass is prepared from two kinds of glass with larger difference of acid resistance. When the base glass is digested by the acid solution, one glass component is digested or partially digested by the acid, and the other glass component is kept as it is, so that the base glass is formed into a porous glass material, and the technical process of thermal phase separation and acid dissolution of the glass in the preparation of the porous glass material in the prior art is changed. The pore size, distribution uniformity, porosity and the like of the porous glass material prepared by hot phase separation depend on the quality of high-temperature phase separation, the porous glass material is usually required to be kept for several hours to dozens of hours at constant temperature, the preparation process is complex, the process stability is poor, and the size of the prepared porous pore is between 10nm and 500 nm. The preparation method of the porous glass material provided by the invention cancels the thermal phase separation process when the porous glass material is prepared by preparing the new matrix glass, and solves the technical problems of complex process, poor process stability and difficult control of pore size.
Preferably, the preparation method of the porous glass material, wherein the preparation of the matrix glass comprises the following steps:
A. crushing, grinding and sieving a glass material with a first acid resistance level to obtain first glass powder;
B. crushing, grinding and sieving the glass material with the second acid resistance level to obtain second glass powder;
C. uniformly mixing the first glass powder and the second glass powder according to a proportion to obtain a glass powder mixture;
D. and transferring the glass powder mixture into a mold, sintering at a certain temperature, under a certain pressure and under a certain vacuum condition, cooling to room temperature, and demolding to obtain the matrix glass.
The glass material of the first acid resistance level has poor acid resistance, and when the glass material is soaked in an acid solution, the leaching amount of glass components is large. The first acid-resistant level refers to that the acid-resistant stability of the glass material is 4-grade or 5-grade according to the GB/T7962.14-2010 detection method.
The second acid-resistant glass material has good acid resistance, and the leaching amount of the glass component is very small when the glass material is soaked in the acid solution. The second acid resistance level means that the acid resistance stability of the glass material reaches grade 1 or grade 2 according to the detection of the GB/T7962.14-2010 method.
The grinding in the invention refers to ball milling in a ball mill.
Preferably, in the preparation method of the porous glass material, the sieve used for sieving in the steps a and B is 200-1500 meshes; the grain diameter of the first glass powder and the second glass powder is 1-100 mu m.
The grain diameters of the first glass powder and the second glass powder are key control points for preparing the porous glass material with micron aperture. The invention controls the grain diameter of the first glass powder and the second glass powder to be 1-100 mu m, and the first glass powder and the second glass powder are mixed and sintered into base glass with uniform components; and then when the acid solution is used for digestion, the corrosion time and the concentration of the acid solution are limited, so that the first glass powder with poor acid resistance is completely digested, the formed pore size is micron, and the technical problem that the porous glass material with micron pore size is difficult to obtain in the prior art is solved.
Preferably, in the preparation method of the porous glass material, before the first glass powder and the second glass powder are mixed in step C, the first glass powder and the second glass powder are cleaned and dried; the mixing in the step C is dry mixing or wet stirring mixing; the mixing ratio of the first glass powder to the second glass powder is 1: 10-100 by mass.
The mixing ratio of the first glass powder and the second glass powder can be adjusted according to actual needs. The porous glass material with higher porosity can be obtained by improving the proportion of the first glass powder.
Preferably, in the method for preparing a porous glass material, the glass powder mixture in step C further includes a flux; the fluxing agent is CaF2The content of the powder or the low-temperature sintered glass powder is less than or equal to 10 percent by mass.
The flux is intended to provide better fusion of the glass.
Preferably, in the method for preparing a porous glass material, the sintering temperature of the glass powder mixture in step D is higher than the glass softening temperature thereof; the vacuum degree of the system during sintering is 0.1-100 Pa, and the pressure borne by the glass powder mixture is 10-50 MPa; the sintering temperature is 600-900 ℃, and the sintering time is 0.5-4 h.
Preferably, in the method for preparing a porous glass material, the acid solution in step 3) is at least one selected from nitric acid, hydrochloric acid and sulfuric acid; the concentration of the acid solution is 0.1-1 mol/L; the temperature of the acid solution is between room temperature and 80 ℃ during corrosion, and the corrosion time is between 2 and 8 hours.
The concentration of the acid solution and the corrosion time of the acid solution can adjust the size of the pore within a certain range. When the acid solution has a proper concentration and the corrosion time is long enough, the glass with the first acid resistance level can be sufficiently digested, and a porous glass material with larger pore diameter and higher porosity can be obtained.
Preferably, in the step 4), the porous glass blank is washed with deionized water for 3 to 5 times, and then is soaked in ethanol, propanol or isopropanol for 15 to 60 min; taking out and drying at the temperature of 80-100 ℃ for 0.5-2 h.
Soaking with organic solvent to remove part of water to facilitate later drying.
The invention also provides a porous glass material prepared according to the method. The porous glass material has micron pore size, uniform pore size, high porosity and high compressive strength.
The invention also provides application of the porous glass material prepared by the method in the fields of immobilized enzyme carriers, immobilized cell carriers, separation and purification of organisms and biochemical substances such as microorganisms, proteins, interferons, viruses and the like, drug sustained-release agent carriers, bone tissue repair scaffold materials, microfluidic chips, gene sequencing substrates, catalyst carriers, radioactive waste curing substrates, sound absorption materials and the like.
The present invention will be described in further detail with reference to specific examples.
Example 1
A method for preparing porous glass comprises the following steps:
(1) preparing first glass powder: selecting borate glass with acid resistance stability grade 4 (detected according to a GB/T7962.14-2010 method), crushing the borate glass, ball-milling the crushed borate glass in a planetary ball mill at a rotating speed of 300-500 r/min for 30-120 min, and then sieving the crushed borate glass with a 1500-mesh sieve to obtain first glass powder with the particle size of 1-10 mu m.
(2) Preparing second glass powder: selecting silicate glass with acid resistance stability level 2 (detected according to a GB/T7962.14-2010 method), crushing the silicate glass, ball-milling the crushed silicate glass for 30-120 min in a planetary ball mill at the rotating speed of 300-500 r/min, and then sieving the crushed silicate glass with a 1500-mesh sieve to obtain second glass powder with the particle size of 1-10 microns.
(3) Preparation of glass powder mixture
And cleaning and drying the first glass powder and the second glass powder, and uniformly mixing the first glass powder and the second glass powder in a mixer for 30min according to the mass ratio of 1:100 to obtain a glass powder mixture.
(4) Sintering
And transferring the glass powder mixture into a mold, sintering for 1h at 800 ℃, under 40MPa pressure and under 0.1-100 Pa vacuum degree, cooling to room temperature, and demolding to obtain the matrix glass.
(5) Etching of
Putting the matrix glass into 0.5mol/L nitric acid solution, and corroding for 5 hours at 60 ℃ to obtain the porous glass blank with the porous structure.
(6) Machining
And taking out the porous glass blank, rinsing the porous glass blank for 3-5 times by using deionized water, then soaking the porous glass blank in an isopropanol solution for 15 minutes, then drying the porous glass blank in a 90 ℃ drying oven for 1 hour, taking out the porous glass blank, and cutting, grinding and polishing the porous glass to obtain the porous glass material.
Through performance detection, the pore diameter of the porous glass material obtained in the embodiment is 3.6 μm, the porosity is 79%, and the compressive strength is 25.4 MPa.
Example 2
(1) Preparing first glass powder: selecting borate glass with acid resistance stability grade 5 (detected according to a GB/T7962.14-2010 method), crushing the borate glass, ball-milling the crushed borate glass in a planetary ball mill at the rotating speed of 300-500 r/min for 100min, and then sieving the crushed borate glass with a 500-mesh sieve to obtain first glass powder with the particle size of less than 30 mu m.
(2) Preparing second glass powder: selecting silicate glass with acid resistance stability level 1 (detected according to a GB/T7962.14-2010 method), crushing the silicate glass, ball-milling the crushed silicate glass in a planetary ball mill at the rotating speed of 300-500 r/min for 100min, and then sieving the crushed silicate glass with a 500-mesh sieve to obtain second glass powder with the particle size of 30 mu m.
(3) Preparation of glass powder mixture
Cleaning and drying the first glass powder and the second glass powder, adding the first glass powder and the second glass powder into a proper amount of glycerol according to the mass ratio of 1:60, stirring the mixture for 30min at the rotating speed of 40rpm/min, heating the mixture to 200 ℃, and obtaining mixed powder of the first glass powder and the second glass powder after the glycerol is completely volatilized.
(4) Sintering
And transferring the glass powder mixture into a mold, placing the mold into a heating furnace, heating the mixture to 850 ℃ at a constant speed of 20 ℃/min under the pressure of 20MPa, carrying out heat preservation and firing for 30 minutes, then cooling the mixture to 150 ℃ at a constant speed of 40 ℃/min, taking out the mixture, naturally cooling the mixture to room temperature, and taking the material out of the mold to obtain the sintered substrate glass.
(5) Etching of
Putting the matrix glass into 0.6mol/L hydrochloric acid solution, and corroding for 4 hours at 80 ℃ to obtain a porous glass blank with a porous structure;
(6) machining
And taking out the porous glass blank, cleaning the porous glass blank for 3-5 times by using deionized water, then soaking the porous glass blank in an ethanol solution for 30 minutes, then drying the porous glass blank in an oven at 80 ℃ for 45 minutes, taking out the porous glass blank, and cutting, grinding and polishing the porous glass to obtain the porous glass material.
Through performance detection, the pore diameter of the porous glass material obtained in the embodiment is 20.8 μm, the porosity is 76.5%, and the compressive strength is 22.2 MPa.
And further, by adjusting the particle size and the proportion of the first glass powder and the second glass powder and adjusting the particle size of the matrix glass powder, the concentration of the corrosive liquid and the corrosion process parameters, the porous glass material with different pore diameters, different porosities and different compressive strengths can be obtained.
The terms "first", "second", and the like in the technical features of the claims and/or the specification are used for distinguishing names of materials and do not represent superiority or inferiority of performance levels of the materials.
The features of the invention claimed and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to the scope of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the porous glass material is characterized by comprising the following process steps:
1) preparing a base glass from a first acid-resistant level glass and a second acid-resistant level glass; the preparation of the matrix glass comprises the following steps:
A. crushing, grinding and sieving a glass material with a first acid resistance level to obtain first glass powder;
B. crushing, grinding and sieving the glass material with the second acid resistance level to obtain second glass powder;
C. uniformly mixing the first glass powder and the second glass powder according to a proportion to obtain a glass powder mixture;
D. transferring the glass powder mixture into a mold, sintering at a certain temperature, under a certain pressure and under a certain vacuum condition, cooling to room temperature, and demolding to obtain matrix glass; wherein the vacuum degree of the system during sintering is 0.1 Pa-100 Pa, the pressure of the glass powder mixture is 10-50 MPa, and the sintering temperature is 600-900 ℃;
2) cutting, grinding and polishing the substrate glass;
3) putting the base glass in the step 2) into an acid solution for corrosion until the glass with the first acid-resistant level is completely digested, and taking out the glass to obtain a porous glass blank;
4) and cleaning and drying the porous glass blank to obtain the porous glass material.
2. The method for producing a porous glass material according to claim 1,
the sieve used for sieving in the step A and the step B is 200-1500 meshes;
the grain diameter of the first glass powder and the second glass powder is 1-100 mu m.
3. The method for producing a porous glass material according to claim 1,
c, before the first glass powder and the second glass powder are mixed, the first glass powder and the second glass powder are required to be cleaned and dried;
the mixing in the step C is dry mixing or wet stirring mixing;
the mixing ratio of the first glass powder to the second glass powder is 1: 10-100 by mass.
4. The method for producing a porous glass material according to claim 1,
the glass powder mixture of the step C also comprises a fluxing agent;
the fluxing agent is CaF2The content of the powder or the low-temperature sintered glass powder is less than or equal to 10 percent by mass.
5. The method for producing a porous glass material according to claim 1,
the sintering temperature of the glass powder mixture in the step D is higher than the glass softening temperature of the glass powder mixture; the sintering time is 0.5-4 h.
6. The method for producing a porous glass material according to claim 1,
the acid solution in the step 3) is at least one selected from nitric acid, hydrochloric acid and sulfuric acid;
the concentration of the acid solution is 0.1-1 mol/L; the temperature of the acid solution is between room temperature and 80 ℃ during corrosion, and the corrosion time is between 2 and 8 hours.
7. The method for producing a porous glass material according to claim 1,
the cleaning in the step 4) is to clean the porous glass blank for 3 to 5 times by using deionized water, and then soak the porous glass blank in ethanol, propanol or isopropanol for 15 to 60 min;
taking out and drying at the temperature of 80-100 ℃ for 0.5-2 h.
8. A porous glass material prepared according to the method of any one of claims 1 to 7.
9. Use of a porous glass material prepared according to the method of any one of claims 1 to 7 in the field of immobilization and separation of catalyst or drug molecules.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910313597.8A CN110078376B (en) | 2019-04-18 | 2019-04-18 | Preparation method of porous glass material, porous glass material prepared by method and application of porous glass material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910313597.8A CN110078376B (en) | 2019-04-18 | 2019-04-18 | Preparation method of porous glass material, porous glass material prepared by method and application of porous glass material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110078376A CN110078376A (en) | 2019-08-02 |
| CN110078376B true CN110078376B (en) | 2021-11-23 |
Family
ID=67415515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910313597.8A Active CN110078376B (en) | 2019-04-18 | 2019-04-18 | Preparation method of porous glass material, porous glass material prepared by method and application of porous glass material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078376B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452901B (en) * | 2019-08-15 | 2021-07-16 | 芜湖易泽中小企业公共服务股份有限公司 | Immobilized biological reaction filter plate and preparation method and application thereof |
| CN111362582B (en) * | 2020-04-09 | 2021-01-19 | 浙江大学 | Vacuum foaming low-temperature foam glass material and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4966613A (en) * | 1984-11-30 | 1990-10-30 | Ppg Industries, Inc. | Method of producing effective porous glass shapes |
| CA1274255A (en) * | 1987-01-14 | 1990-09-18 | Kirin Beer Kabushiki Kaisha | Method for producing granular multi-cellular glass and the glass produced by the method |
| JPH06227832A (en) * | 1993-02-04 | 1994-08-16 | Ishizuka Glass Co Ltd | Production of spherical glass body |
| CN101555094B (en) * | 2009-05-21 | 2011-06-08 | 天台精工西力玻璃珠有限公司 | Method for manufacturing glass beads by waste glass as well as used additives and electro-thermal rotary furnace thereof |
| WO2013133357A1 (en) * | 2012-03-08 | 2013-09-12 | 日本山村硝子株式会社 | Spherical particle manufacturing method |
| CN103896479B (en) * | 2014-02-27 | 2016-02-10 | 陕西科技大学 | A kind of simple method for preparing of sintered glass |
-
2019
- 2019-04-18 CN CN201910313597.8A patent/CN110078376B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110078376A (en) | 2019-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107663088B (en) | Preparation method of low-temperature sintered acid-alkali-resistant porous silicon carbide ceramic membrane | |
| CN110002725B (en) | Preparation method of porous glass beads, porous glass beads prepared by method and application of porous glass beads | |
| CN111533572B (en) | Preparation method of porous silicon carbide ceramic support | |
| CN110078376B (en) | Preparation method of porous glass material, porous glass material prepared by method and application of porous glass material | |
| CN109824381B (en) | Silicon carbide ceramic membrane and preparation method and application thereof | |
| CN107857577B (en) | Al2O3-ZrO 2-based foamed ceramic and preparation method thereof | |
| WO2017004776A1 (en) | Porous alumina ceramic ware and preparation method thereof | |
| CN104326766A (en) | Preparation method of porous silicon nitride ceramic material with spherical pore structure | |
| CN110732672A (en) | gradient metal-based porous material and preparation method and application thereof | |
| WO2019196180A1 (en) | Spinel-reinforced magnesium oxide-based foam ceramic filter and preparation method therefor | |
| CN110690397A (en) | Fused salt composite electrolyte diaphragm, preparation method and application | |
| CN107698246A (en) | A kind of corundum-mullite base foamed ceramics of multilayer skeleton structure and preparation method thereof | |
| CN110002893A (en) | A kind of preparation method of ceramic super-filtering film | |
| CN108264354A (en) | Multichannel silicon carbide ceramic support body and preparation method thereof | |
| CN111763097B (en) | Method for preparing porous ceramic by using coal gangue | |
| CN104072190B (en) | A kind of preparation method of SiC porous ceramics | |
| CN115364852B (en) | Porous ceramic loaded with nano noble metal oxide catalyst and preparation method and application thereof | |
| CN108046834B (en) | Preparation process of porous ceramic heating body with mosaic structure | |
| CN107020064A (en) | A kind of new packing reclaimed for water-soluble solvent | |
| CN104630771B (en) | A kind of method for preparing porous oxide film in metal carrier surface | |
| CN111470870A (en) | Composite ceramic microsphere and preparation method thereof | |
| CN113737171B (en) | Preparation method of porous tantalum film | |
| CN112957522B (en) | Rigidity-adjustable porous liquid metal bone tissue engineering scaffold and preparation method thereof | |
| CN109534803B (en) | Charged ceramic membrane and preparation method thereof | |
| CN115121788B (en) | Preparation method of nano porous spherical tungsten |
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 |