CN105776875A - Cobalt-doped glass microsphere and preparation method and application thereof - Google Patents
Cobalt-doped glass microsphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN105776875A CN105776875A CN201610184565.9A CN201610184565A CN105776875A CN 105776875 A CN105776875 A CN 105776875A CN 201610184565 A CN201610184565 A CN 201610184565A CN 105776875 A CN105776875 A CN 105776875A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- glass microsphere
- mixing
- xerogel
- doped glass
- 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
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
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0084—Solid storage mediums characterised by their shape, e.g. pellets, sintered shaped bodies, sheets, porous compacts, spongy metals, hollow particles, solids with cavities, layered solids
-
- 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
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention provides a cobalt-doped glass microsphere and a preparation method and application thereof. The preparation method of the cobalt-doped glass microsphere provided by the invention can be used for producing a cobalt-doped glass microsphere having a light-induced hydrogen release effect, wherein the component of the cobalt-doped glass microsphere is alkali borosilicate glass containing cobalt oxide. The preparation method provided by the invention is a dried gel method. The cobalt-doped glass microsphere is formed by a cobalt-doped dried gel particle through processes such as heat absorption, packaging, foaming, refining and cooling in a vertical highly-dried gel furnace, and the dried gel method has the advantages of simplicity and convenience in operation, high yield, high finished product rate and the like. The cobalt-doped glass microsphere provided by the invention can absorb visible light and form a quick passage for gas molecules after the cobalt-doped glass microsphere is irradiated by light, such that controllable release of hydrogen in the sphere is realized. The cobalt-doped glass microsphere can undergo repetitive gas loading and release, is a high-capacity, high-efficiency, economic and safe hydrogen storage material and has a good application prospect in hydrogen energy storage and transportation.
Description
Technical field
The invention belongs to hydrogen energy source storage art, be specifically related to one and mix cobalt glass microsphere and its preparation method and application.
Background technology
Hydrogen Energy is a kind of green, regenerative resource, will play the part of important role in the energy resource supply of human future.One of the problem needing solution that effectively utilizes of Hydrogen Energy is to set up a kind of suitable supply-conveying-storage-consumption system.The hydrogen storage system setting up a kind of high weight ratio and volume ratio and safety is an important step.The storage of hydrogen should meet: (1) high-energy-density, (2) safety, and loading and the release energy consumption of (3) gas are low and controlled, and (4) are amenable to repeated loading and release, (5) low cost.
Glass microsphere, because having efficient, safe, light, economic, convenient, compressive resistance advantages of higher, is a kind of very promising hydrogen storage vessel.The draw ratio ratio of wall thickness (diameter with) is the glass microsphere of 50 ~ 200, and the weight efficiency of its hydrogen storage is up to 14wt.% ~ 21wt.%, and the blowing pressure is up to 62.1MPa ~ 150MPa.At present in glass microsphere hydrogen storage to be based on hydrogen infiltration rate in glass microsphere spherical shell closely related with temperature.Under high temperature (300 ° of C ~ 400 ° C), hydrogen infiltration rate in glass microsphere spherical shell is greatly increased, thus hydrogen can spread the spherical shell penetrating glass microsphere quickly.Under room temperature, infiltration rate reduces several orders of magnitude, thus hydrogen is limited in glass microsphere, until glass microsphere is reheated to uniform temperature, hydrogen is just released.This traditional inflation and delivery mode because carrying out under high-temperature and high-pressure conditions, and in ball, pressure is more than the twice under room temperature, makes glass microsphere be in relatively hightension state, thus requires big to the compressive resistance of glass microsphere, also can affect the service life of glass microsphere.Additionally, traditional thermal diffusion method danger is relatively big, energy consumption is higher.
At present, the main method preparing glass microsphere has flame method, sessile drop method, Hoppe method and dry gel method etc..Flame method balling-up efficiency is low, and ball-formation quality is poor, thus compressive resistance is not high.And sessile drop method needs glass forming substance to be dissolved in this rigors of water limits the range of choice of glass ingredient, thus limiting the lifting of the multiple performance of glass microsphere.Although Hoppe method has advantage in introducing portion doped chemical, macromole gaseous diffusion process inflation etc., but the sintering process of this method is insufficient to the refinement of glass microsphere, and the compressive resistance of gained glass microsphere is not as good as sessile drop method and dry gel method.Additionally, the process controllability of the method is poor, productivity and yield rate are very low, and the technical difficulty of research and development is big, cost is high, the cycle is long.It is high that dry gel method prepares glass microsphere not only simple, productivity and yield rate, can significantly expand diameter and the wall thickness of glass microsphere, and eliminate the restriction that glass ingredient is selected by additive method, multiple required element can be introduced and realize the doping to glass microsphere, thus giving its specific function or improving its serviceability.
Mixing in the shell of cobalt glass microsphere containing specific functionality ion, can form the gas diffusion paths of inside and outside connection, it is achieved the controlled quick release of hydrogen under room temperature under illumination condition, this phenomenon is called " photic release hydrogen " effect.Photic hydrogen of releasing avoids conventional thermal diffused aeration Problems existing.Dry gel method gained is mixed cobalt glass microsphere and is had balling-up efficiency height, and sphericity is high, the advantages such as diameter, wall thickness and the performance such as compressive resistance, gas retaining are adjustable.At present, there is not been reported to utilize dry gel method preparation to have the photic cobalt glass microsphere of mixing releasing hydrogen effect.
Summary of the invention
The technical problem that the invention solves the problems that is to provide one and mixes cobalt glass microsphere, another technical problem that the invention solves the problems that is to provide a kind of preparation method mixing cobalt glass microsphere, and another technical problem that the invention solves the problems that is to provide a kind of application mixing cobalt glass microsphere.
The present invention mixes cobalt glass microsphere, is characterized in, the described component mixing cobalt glass microsphere is as follows:
SiO2: mass percent is 65.1% ~ 68.8%；
B2O3: mass percent is 15.6% ~ 16.5%；
CoO: mass percent is 0.2% ~ 5.5%；
Li2O: mass percent is 6.5% ~ 6.9%；
Na2O: mass percent is 5.9% ~ 6.2%；
K2O: mass percent is 0.5%；
Al2O3: mass percent is 0.9%；
Said components sum is 100%.
The preparation method mixing cobalt glass microsphere of the present invention, comprises the following steps:
A. will mix cobalt xerogel block and dry 2 hours at 100 ° of C；
B. the cobalt xerogel block of mixing in step a being poured in the agate mortar of vibrosieve and is ground, the amplitude of vibrosieve is 1.1mm ~ 1.2mm, and time of vibration is spaced apart 0.1s, and vibration time is 6min ~ 8min；By the sieve order that aperture is 180 μm, 160 μm, 125 μm, the cobalt xerogel particles of mixing after grinding being sieved, the amplitude of vibrosieve is 0.8mm ~ 0.9mm, and time of vibration is spaced apart 0.1s ~ 0.2s, and vibration time is 5min ~ 7min；The cobalt xerogel particles of mixing of each particle size range is respectively sealed in vial, stores in dry environments；
C. take the cobalt xerogel particles of mixing of gained in step b and dry 3 hours at 105 ° of C；
D. in vertical high-temperature xerogel stove, pass into the heat-conducting gas of 1.0atm, then in-furnace temperature is risen to 1500 ° of C ~ 1550 ° C from room temperature.
E. will step c mix in the charging aperture funnel that cobalt xerogel particles pours vertical high-temperature xerogel stove into, rotatable hopper bottom screw charging；Mix cobalt xerogel particles through heat absorption, encapsulation, foaming, make molten state after refine mix cobalt glass microsphere；The cooled district of cobalt glass microsphere of mixing of molten state solidifies, makes after cooling and mix cobalt glass microsphere；The specimen disc of collecting region is collected and mixes cobalt glass microsphere, needed for obtaining.
The particle size range mixing cobalt xerogel particles described in step c is 125 μm ~ 159 μm or 160 μm ~ 179 μm.
The heating rate of the vertical high-temperature xerogel stove described in step d is 15 ° of C/min；Heat-conducting gas is helium argon mixture gas, and the dividing potential drop of helium is 75% ~ 95%.
The cobalt glass microsphere of mixing of the present invention can be applicable to the controlled quick release of hydrogen in hydrogen energy source transport and field of storage, comprises the following steps:
A. to mixing the inflation of cobalt glass microsphere: mixing cobalt glass microsphere and be placed in aerating device, and pass into the hydrogen of 1.7MPa in plenum chamber, plenum chamber temperature rises to 350 ° of C with 10 ° of C/min speed, and keeps 12h；Again hydrogen gas pressure is increased to 3.4MPa, keep 12h；Finally hydrogen gas pressure is increased to 5.2MPa, keep 12h；Then natural cooling plenum chamber is to room temperature, takes out and mixes cobalt glass microsphere after inflation；
B. inflation after mix the controllable release of gas in cobalt glass microsphere: by inflation after mix in the sample room that cobalt glass microsphere is placed on four-electrode spectrum rga system, mix cobalt glass microsphere after irradiating inflation with the continuous spectrum light source that luminous power is 0.40W ~ 1.11W through Sample Cell windows, control the hydrogen mixed in the cobalt glass microsphere release after inflation.
Cobalt glass microsphere and its preparation method and application of mixing of the present invention has the advantage that
1. its spherical shell of cobalt glass microsphere of mixing prepared by the present invention is contained within functional metal ion, mixes the express passway that can form gas molecule after cobalt glass microsphere absorbs visible ray, it is achieved to the controlled quick release of gas in ball.Additionally, the sphericity mixing cobalt glass microsphere is high, compressive resistance is higher, and gas retaining is good.
2. the present invention adopts dry gel method preparation to mix cobalt glass microsphere, has balling-up efficiency high, the simple advantage of technique.In addition, can also pass through to change the component regulation and control mixing cobalt xerogel particles and mix the character such as the melt temperature of cobalt glass microsphere, viscosity, surface tension, and then control its surface roughness, sphericity, evenness of wall thickness, compressive resistance, gas retaining and photic release the multiple performances such as hydrogen response speed.
Such as, SiO is improved2Content or introduce Al2O3Chemical stability and the mechanical strength of glass can be improved；Add B2O3Chemical stability and the mechanical performance of glass can be improved, reduce the melt temperature of glass, viscosity, surface tension and tendency towards devitrification etc. simultaneously；Improve Li2O、Na2O、K2The content of O can reduce the melt temperature of glass, viscosity and tendency towards devitrification, but also can reduce chemical durability of glass and mechanical strength simultaneously；It is be adjusted in 0.2% ~ 5.5% scope that CoO concentration can release hydrogen response speed at mass percent according to photic needed for practical application.
3. the cobalt glass microsphere of mixing prepared by the present invention is applied to photic release hydrogen, has low energy consumption, efficient, safe, controlled advantage, stores in hydrogen energy source and has potential using value in transport.
Detailed description of the invention
The present invention is described in detail below in conjunction with specific embodiment.
Following example are merely to illustrate the present invention, and are not limitation of the present invention.Relevant person skilled in the art is without departing from the spirit and scope of the present invention, it is also possible to making a variety of changes, replace and modification, therefore equal technical scheme falls within scope of the invention.
Embodiment 1
The present embodiment comprises the following steps:
(1) 6.9Li is selected2O·6.2Na2O·0.5K2O·0.9Al2O3·0.2CoO·16.5B2O3·68.8SiO2(wt.%) cobalt xerogel block of mixing is raw material, dries 2 hours at 100 ° of C, is then ground and sieves.Grinding in vibrosieve, amplitude is 1.2mm, and interval is 0.1s, and milling time is 8min.Cobalt xerogel particles of mixing after grinding is sieved by the sieve successively adopting aperture to be 160 μm and 125 μm, and amplitude is 0.9mm, and interval is 0.2s, and sieving time is 7min；
(2) take the cobalt xerogel particles of mixing that the particle size range of gained in step (1) is 125 μm ~ 159 μm and dry 3 hours at 105 ° of C；
(3) passing into helium argon mixture gas in vertical high-temperature xerogel stove, total gas pressure is 1.0atm, and wherein, the dividing potential drop of helium is 95%；1550 ° of C are risen to from room temperature with the speed in-furnace temperature of 15 ° of C/min.
(4) take gained in step (2) and mix cobalt xerogel particles from vertical high-temperature xerogel stove charging aperture pan feeding, after cooling down from cooling zone collection tray, mix cobalt glass microsphere；
(5) taking the cobalt glass microsphere of mixing of gained in step (4) and be placed in aerating device, pass into the hydrogen of 1.7MPa in plenum chamber, plenum chamber temperature to 350 ° of C, and keeps 12h with 10 ° of C/min ramp；Again hydrogen gas pressure is increased to 3.4MPa, keep 12h；Finally hydrogen gas pressure is increased to 5.2MPa, keep 12h；Then natural cooling plenum chamber temperature is to room temperature, takes out and mixes cobalt glass microsphere after inflation；To mix in the sample room that cobalt glass microsphere is placed on four-electrode spectrum rga system after inflation, after irradiating inflation with the continuous spectrum light source that luminous power is 1.11W through Sample Cell windows, mix cobalt glass microsphere, control the release of hydrogen in ball.
The cobalt glass microsphere of mixing of preparation is blue-tinted transparent, and geometric parameter test display, its diameter is 350 μm ~ 450 μm, and wall thickness is 1.5 μm ~ 3.5 μm；Four-electrode spectrum rga system test shows, mixes cobalt glass microsphere and discharges hydrogen at once once illumination, closes light source, and the release of gas stops at once, and such release and stop release process can iterative cycles, until gas discharges completely in ball.
Embodiment 2
Embodiment 2 is essentially identical with the step of embodiment 1, and the main distinction is, selects 6.7Li2O·6.1Na2O·0.5K2O·
0.9Al2O3·2.3CoO·16.2B2O3·67.3SiO2(wt.%) mixing cobalt xerogel block is raw material.The amplitude of process of lapping vibrosieve is 1.1mm, and interval is 0.1s, and vibration time is 7min.The aperture of sieve used by screening process is 180 μm and 160 μm, and the amplitude of vibrosieve is 0.8mm, and interval is 0.1s, and vibration time is 5min；It is 160 μm ~ 179 μm that gained mixes the size range of cobalt xerogel particles；Mixing the total gas pressure of heat-conducting gas in cobalt glass microsphere preparation process is 1.0atm, and wherein, the dividing potential drop of helium is 80%, and in-furnace temperature is 1550 ° of C；It is photic that to release the power of light source used by hydrogen process be 0.84W.
The cobalt glass microsphere of mixing of preparation is blue-tinted transparent, and geometric parameter test display, its diameter is 400 μm ~ 500 μm, and wall thickness is 1 μm ~ 3 μm.
Embodiment 3
Embodiment 3 is essentially identical with the step of embodiment 1, and the main distinction is to select glass formula 6.5Li2O·5.9Na2O·0.5K2O·
0.9Al2O3·5.5CoO·15.6B2O3·65.1SiO2(wt.%) corresponding cobalt xerogel of mixing is ground and sieves.The amplitude of process of lapping vibrosieve is 1.1mm, and interval is 0.1s, and vibration time is 6min.Sieve aperture used by screening process is 180 μm and 160 μm, and the amplitude of vibrosieve is 0.8mm, and interval is 0.2s, and vibration time is 6min；It is 160 μm ~ 179 μm that gained mixes cobalt xerogel particles size range；Mixing the total gas pressure of furnace gas in cobalt glass microsphere preparation process is 1.0atm, and wherein, the dividing potential drop of helium is 75%, and in-furnace temperature is 1500 ° of C；It is photic that to release the power of light source used by hydrogen process be 0.40W.
The cobalt glass microsphere of mixing of preparation is blue-tinted transparent, and geometric parameter test display, its diameter is 375 μm ~ 475 μm, and wall thickness is 2 μm ~ 3 μm.
Claims (4)
1. mix cobalt glass microsphere for one kind, it is characterised in that the described component mixing cobalt glass microsphere is as follows:
SiO2: mass percent is 65.1% ~ 68.8%；
B2O3: mass percent is 15.6% ~ 16.5%；
CoO: mass percent is 0.2% ~ 5.5%；
Li2O: mass percent is 6.5% ~ 6.9%；
Na2O: mass percent is 5.9% ~ 6.2%；
K2O: mass percent is 0.5%；
Al2O3: mass percent is 0.9%；
Said components sum is 100%.
2. the preparation method mixing cobalt glass microsphere, it is characterised in that comprise the following steps:
A. will mix cobalt xerogel block and dry 2 hours at 100 ° of C；
B. the cobalt xerogel block of mixing in step a being poured in the agate mortar of vibrosieve and is ground, the amplitude of vibrosieve is 1.1mm ~ 1.2mm, and time of vibration is spaced apart 0.1s, and vibration time is 6min ~ 8min；By the sieve order that aperture is 180 μm, 160 μm, 125 μm, the cobalt xerogel particles of mixing after grinding being sieved, the amplitude of vibrosieve is 0.8mm ~ 0.9mm, and time of vibration is spaced apart 0.1s ~ 0.2s, and vibration time is 5min ~ 7min；The cobalt xerogel particles of mixing of each particle size range is respectively sealed in vial, stores in dry environments；
C. take the cobalt xerogel particles of mixing of gained in step b and dry 3 hours at 105 ° of C；
D. in vertical high-temperature xerogel stove, pass into the heat-conducting gas of 1.0atm, then in-furnace temperature is risen to 1500 ° of C ~ 1550 ° C from room temperature；
E. will step c mix in the charging aperture funnel that cobalt xerogel particles pours vertical high-temperature xerogel stove into, rotatable hopper bottom screw charging；Mix cobalt xerogel particles through heat absorption, encapsulation, foaming, make molten state after refine mix cobalt glass microsphere；The cooled district of cobalt glass microsphere of mixing of molten state solidifies, makes after cooling and mix cobalt glass microsphere；The specimen disc of collecting region is collected and mixes cobalt glass microsphere, needed for obtaining.
3. the preparation method mixing cobalt glass microsphere according to claim 2, it is characterised in that the particle size range mixing cobalt xerogel particles described in step c is 125 μm ~ 159 μm or 160 μm ~ 179 μm.
4. the preparation method mixing cobalt glass microsphere according to claim 2, it is characterised in that the heating rate of the vertical high-temperature xerogel stove described in step d is 15 ° of C/min；Heat-conducting gas is helium argon mixture gas, and the dividing potential drop of helium is 75% ~ 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610184565.9A CN105776875B (en) | 2016-03-29 | 2016-03-29 | One kind mixes cobalt glass microballoon and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610184565.9A CN105776875B (en) | 2016-03-29 | 2016-03-29 | One kind mixes cobalt glass microballoon and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105776875A true CN105776875A (en) | 2016-07-20 |
| CN105776875B CN105776875B (en) | 2018-07-03 |
Family
ID=56392246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610184565.9A Expired - Fee Related CN105776875B (en) | 2016-03-29 | 2016-03-29 | One kind mixes cobalt glass microballoon and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105776875B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588521A (en) * | 2016-12-31 | 2017-04-26 | 中国科学技术大学 | Free state hydrogen sensitized emulsion explosive and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020004111A1 (en) * | 2000-05-31 | 2002-01-10 | Asahi Glass Company, Limited | Hollow glass microspheres and process for their production |
| CN101039871A (en) * | 2004-09-21 | 2007-09-19 | 华盛顿萨凡纳河有限公司 | Hollow porous-wall glass microspheres for hydrogen storage |
-
2016
- 2016-03-29 CN CN201610184565.9A patent/CN105776875B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020004111A1 (en) * | 2000-05-31 | 2002-01-10 | Asahi Glass Company, Limited | Hollow glass microspheres and process for their production |
| CN101039871A (en) * | 2004-09-21 | 2007-09-19 | 华盛顿萨凡纳河有限公司 | Hollow porous-wall glass microspheres for hydrogen storage |
Non-Patent Citations (2)
| Title |
|---|
| FANG LI等: "《Influence of titanium doping on the structure and properties of hollow glass microspheres for inertial confinement fusion 》", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 * |
| SRIDHAR DALAI等: "《Effect of Co loading on the hydrogen storage characteristics of hollow glass microspheres 》", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588521A (en) * | 2016-12-31 | 2017-04-26 | 中国科学技术大学 | Free state hydrogen sensitized emulsion explosive and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105776875B (en) | 2018-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1086062A (en) | Method for manufacturing glass frit | |
| CN100526244C (en) | Glass scintillator for thermal neutron detection and its preparation method | |
| CN108530030B (en) | Preparation method of negative ion glazed ceramic tile | |
| US9260340B2 (en) | Luminous nano-glass-ceramics used as white LED source and preparing method of luminous nano-glass-ceramics | |
| CN103467018A (en) | Preparation method for preparing low-density oil well cementing cement briquettes by vermiculites | |
| CN103723910A (en) | Preparation method for porous glass micro beads | |
| CN113503707B (en) | Reminding type gypsum powder drying furnace with high dispersity | |
| CN107739193A (en) | Using the process of three kinds of granularity raw materials, three layers of cloth production foamed ceramic | |
| CN105776876A (en) | Titanium-doped glass microsphere and preparation method and application thereof | |
| CN105800638A (en) | Low-potassium type 3A zeolite molecular sieve and preparation method thereof | |
| CN105776875A (en) | Cobalt-doped glass microsphere and preparation method and application thereof | |
| CN106362677A (en) | Method for preparing doping type carbon dioxide adsorbent ceramic | |
| CN107572539A (en) | A kind of preparation method of plural gel heat-barrier material | |
| CN101209901A (en) | Rare-earth-doped semiconductor-quantum-point-containing transparent glass ceramic luminous material and preparing thereof | |
| CN107857565A (en) | A kind of technique of raw material semidry method grain production foamed ceramic | |
| CN105753459A (en) | Preparation method and products of organic metal complex and aluminum oxide compound | |
| CN105948135A (en) | Monodisperse porous magnetic submicrosphere and preparation method thereof | |
| CN106868480B (en) | A kind of preparation method of the compound target membrane of 6Li-D | |
| CN109437871A (en) | A kind of preparation method of porous positive silicic acid lithium material | |
| CN102093032B (en) | Preparation method of light refractory plate | |
| CN104118980B (en) | A kind of preparation method of the cryogenic foam glass of controllable bore diameter | |
| CN104817274B (en) | Cullet and coal ash for manufacturing are for porous devitrified glass composite plate | |
| CN106630604A (en) | Low-melting-point tellurate glass ceramic, preparation method and application of low-melting-point tellurate glass ceramic | |
| CN106811193B (en) | A kind of Mg2SiO4：The preparation method of Tb Annual doses | |
| CN108358655A (en) | It is a kind of using basalt wire drawing tailing as foam ceramic material of raw material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180703 Termination date: 20200329 |