KR101736656B1 - Method for fabrication of porous metal oxides - Google Patents
Method for fabrication of porous metal oxides Download PDFInfo
- Publication number
- KR101736656B1 KR101736656B1 KR1020160010000A KR20160010000A KR101736656B1 KR 101736656 B1 KR101736656 B1 KR 101736656B1 KR 1020160010000 A KR1020160010000 A KR 1020160010000A KR 20160010000 A KR20160010000 A KR 20160010000A KR 101736656 B1 KR101736656 B1 KR 101736656B1
- Authority
- KR
- South Korea
- Prior art keywords
- polymer
- solution
- heat treatment
- mixed solution
- treatment step
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
Description
The present invention relates to a method for producing a porous metal oxide.
Nanoporous structures can be used in various fields depending on their characteristics, and they are under development in each research field.
Conventionally, a method of manufacturing nanoporous metal particles of a certain size by spray pyrolysis to produce nanoporous particles has been developed, but it is disadvantageous in that the polymer particles used as materials are expensive. The solution prepared by mixing the polymer solution with the copper precursor solution was prepared by spray pyrolysis using copper nanoporous structure with various pores according to the solution composition. However, since the polymer solution is sprayed, the nozzle is clogged And when 200 ml of the mixed solution is sprayed, nanoporous copper oxide particles having a very low yield of about 0.3 g are produced.
The present invention provides a method for producing nanoporous copper oxide particles by directly heat-treating a mixed solution in a high-temperature furnace to solve the above problems.
The present invention provides a method for preparing a metal precursor, comprising: preparing a mixed solution of a polymer and a metal precursor; And heating the mixed solution in an oxygen atmosphere in a high-temperature furnace.
In the present invention, the mixed solution of the polymer / metal precursor may be a mixed solution of a solution in which the polymer is dissolved and a solution in which the metal precursor is metal ionized, or a solution in which the polymer is dissolved and the metal precursor is metal ionized.
The oxygen atmosphere may be heating in air and may be an atmosphere in which oxygen is supplied to the air to increase the degree of oxidation.
In the heating step,
A first heat treatment step in which the solvent is vaporized and removed so that the polymer is formed into crystalline particles and the metal precursor becomes a metal oxide;
A second heat treatment step of heating the polymer to a temperature higher than the glass transition temperature so as to expand the crystalline particles to increase the porosity of the metal precursor following the first heat treatment step; And
And a third heat treatment step of performing heat treatment so that the polymer is burned out following the second heat treatment step.
The first, second, and third steps may be separate steps, and the results generated by the first, second, and third steps may be generated sequentially or concurrently by one heating.
The solvent of the solution may be a solvent capable of ionizing the metal precursor and dispersing the polymer in the solution.
The polymer may be a thermoplastic polymer, and preferably the polymer is a polystyrene.
The metal precursor is a metal salt that is metal ionizable to the solvent and is oxidizable by the heat treatment, and is preferably copper nitrate.
The present invention provides a method for preparing porous CuO as a specific example, comprising the steps of preparing a mixed solution by mixing a polymer solution and a copper nitrate solution; A first heat treatment step of heat-treating the mixed solution so that the polymer is formed into crystalline particles and the metal precursor becomes a metal oxide while the solvent of the mixed solution is vaporized and removed in a high temperature furnace; A second heat treatment step subsequent to the first heat treatment step in which the polymer is heated to a temperature higher than the glass transition temperature to expand the crystalline particles to increase the porosity of the metal precursor; And a third heat treatment step of performing heat treatment so that the polymer is burned out following the second heat treatment step.
The production process of the present invention is very simple and 0.3 g of nanoporous copper oxide particles can be prepared with a mixed solution of 10 ml, resulting in a 20-fold increase in yield compared with the conventional method.
The pore size can also be controlled according to the molecular weight of the polymer required for preparing the mixed solution used in the solution heat treatment method.
It was confirmed that the porous metal oxide of the present invention can improve explosion propagation time.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view illustrating a method for producing a porous metal oxide according to the present invention. FIG.
FIG. 2 (a) is an SEM image of a nanoporous structure prepared by mixing polymer particles and a copper precursor solution, and FIG. 2 (b) is an SEM image of a nanoporous structure prepared by mixing a polymer solution and a copper precursor solution.
3 (a) is an SEM image of a PS-CuO particle sprayed with an atomizer by mixing a polymer solution and a copper precursor solution, and (b) is an SEM image of a nanoporous structure prepared by heat-treating the particles of (a).
4 (a) is an SEM image of PS-CuO particles prepared after mixing 1wt% of polymer solution and 5wt% of copper precursor solution; (b) is an SEM image of nanoporous copper oxide particles pyrolyzed (a); (c) and (e) are SEM images of PS-CuO particles prepared when 2 wt% / 10 wt% and 2 wt% / 15 wt%, respectively; (d) and (f) are SEM images of nanoporous copper oxide particles pyrolyzed (c) and (e).
5 (a) is an SEM image of a copper oxide thin film heat-treated using only a copper nitrate solution; (b) is an SEM image of a nanoporous copper oxide thin film obtained by heat treatment of a polymer solution and a copper nitrate solution (the inset is an HRSEM image)
6 (a) is an SEM image of a nanoporous copper oxide particle obtained by solution-pyrolyzing 1 wt% of a polymer solution and 5 wt% of a copper precursor solution; 10 wt%, 1 wt% / 15 wt%, 2 wt% / 15 wt%, 2 wt% / 10 wt% of the components (b), (c) , And 2 wt% / 15 wt%, respectively.
7 is an XRD graph of nanoporous copper oxide particles prepared by solution pyrolysis.
8 (a) is an SEM image of copper oxide nanoporous particles obtained by solution pyrolysis using a polystyrene solution having a molecular weight of 1,300; (b), (c) and (d) are SEM images of copper oxide nanoporous particles prepared using polystyrene solutions having molecular weights of 13,000, 123,000 and 900,000.
9 (a) is a nanoporous copper oxide particle prepared by subjecting a mixed solution prepared by using polystyrene having a molecular weight of 900,000 to a polymer pyrolysis process at 600 ° C for 10 minutes in a high temperature furnace, wherein (b), (c) (d), (e) and (f) are nanoporous copper oxide particles prepared by heat treatment for 20 minutes, 30 minutes, 60 minutes, 90 minutes and 120 minutes.
10 is a pore size control mechanism according to molecular weight. (A) 1,300, and (b) 900,000, respectively, of a copper nanoporous structure produced by using a polystyrene solution.
11 is a schematic illustration of the porous metal oxide particle generating mechanism of the present invention.
Fig. 12 shows the explosion propagation time of the solid particles and the porous particles.
It is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and similarities. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, the first component may be referred to as a second component, and similarly, the second component may also be referred to as a first component.
The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the term "comprises" or "having" is intended to designate the presence of stated features, elements, etc., and not one or more other features, It does not mean that there is none.
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view illustrating a method for producing a porous metal oxide according to the present invention. FIG. In the method for producing a porous metal of the present invention, a polymer solution in which a polymer (for example, polystyrene) is dissolved in a solvent is prepared and a metal precursor (for example, Cu nitrate) solution in which metal ions are ionized is prepared, A porous metal oxide (for example, CuO) is prepared by preparing a mixed solution, placing the mixed solution in a high-temperature furnace, and then heat-treating the mixed solution in an oxygen atmosphere.
11 is a diagram illustrating a mechanism by which the porous metal oxide of the present invention is produced. As described above, the mixed solution is prepared (410) and heat treated in the high temperature furnace, the solvent of the mixed solution is evaporated, and the polystyrene which is dissolved in the solution state forms a spherical shape (420) And reacts with oxygen in the air to turn into copper oxide (430). When the temperature rises to the glass transition temperature of the polystyrene, the spherical polystyrene is expanded, and the copper oxide is pushed out and removed at the pyrolysis temperature of the polystyrene, forming an empty space between the pushed copper oxide (440). Thereafter, when the heat treatment temperature of 600 ° C is maintained, the polymer is burned (450) and the copper oxide forms pores of a random network structure in the void space through surface diffusion (460).
1. Solution Manufacturing
Toluene (C 6 H 5 CH 3 ) was used to prepare the polymer to be pyrolyzed and to form pores, and a copper precursor solution was prepared using copper nitrate (Cu (NO 3 ) 2 ).
First, 2 g of polystyrene (Alfa Aesar) was dissolved in 100 ml of toluene, stirred for 24 hours, and 10 g of copper nitrate was dissolved in 100 ml of acetone and stirred for 30 minutes to prepare a solution.
The prepared two solutions were immersed in a beaker at a ratio of 1: 1 and mixed using ultrasonic energy for 20 minutes to prepare a mixed solution A (see Table 1).
Polystyrene (Alfa Aesar) having molecular weights of 1,300, 13,000, 123,000 and 900,000 was prepared, and 0.1 g of each polystyrene was dissolved in 5 ml of toluene and stirred for 24 hours. 0.5 g of copper (II) nitrate (NO 3 ) 2 ) was dissolved in 5 ml of acetone and stirred for 30 minutes. 5 ml of the prepared polystyrene solution and 5 ml of the copper precursor solution were mixed for 20 minutes using ultrasonic energy to prepare mixed solutions B, C, D and E (see Table 1).
When the ratio of the polymer in the preparation was 2 wt% or more of the total solution and the proportion of copper nitrate was 15 wt% or more of the total solution, respectively, there was a possibility of precipitation.
2. Fabrication of nanoporous copper oxide particles by thermal decomposition of polymer solution
0.1 g of PS having a molecular weight of 1,300 and 0.5 g of copper (II) nitrate (Cu (NO 3 ) 2 ) were added to 5 ml of toluene and acetone for 24 hours and 30 minutes, respectively, to prepare a copper oxide precursor solution B (Table 1) were transferred to an alumina crucible of 60 x 80 x 20 mm and heated at 600 DEG C for 30 minutes in a high-temperature furnace.
After the temperature of the high temperature furnace was cooled to room temperature, the alumina crucible containing the mixed solution was taken out, and the oxidized nanoporous copper oxide particles were scraped off with a spatula. Unlike the removal of nanoporous copper oxide particles by spray pyrolysis, the nanoporous copper oxide particles can be produced without further heat treatment since burn-out of polystyrene proceeds during the experiment.
In the same way, mixed solutions C, D and E were also tested using PS having molecular weights of 13,000, 123,000 and 900,000. The microporous nanoporous copper oxide prepared by this study was observed by scanning electron microscope (SEM) and its structure was analyzed by X-ray diffraction (XRD) .
3. Fabrication of high-energy materials using nanoporous copper oxide particles
Nanoporous copper oxide particles prepared by solution pyrolysis were mixed with Al nanoparticles (NTbase) at 7: 3, respectively. Nanoporous copper oxide particles and Al nanoparticles prepared by using PS having a molecular weight of 1,300 were dispersed in ethanol and then mixed using ultrasonic energy of 170 W and 40 kHz for 30 minutes. After mixing, the mixture was heat-treated in an oven at 80 ° C for 40 minutes to remove ethanol. The nanoporous copper oxide particles prepared by using PS having a molecular weight of 900,000 were also produced by using ultrasonic waves as in the case of 1,300. In order to compare the explosion characteristics of nanoporous copper oxide particles, the solid copper oxide particles prepared by heating only the copper precursor solution were dispersed in ethanol and then mixed using ultrasonic energy of 170 W and 40 kHz for 30 minutes. The ethanol was removed by heat treatment for 40 minutes.
In order to measure the explosion characteristics of high energy materials made of Al and various copper oxide particles, the explosion propagation velocity during flame ignition was measured. The high-energy material prepared by using the solid high-energy material, PS having the molecular weight of 1,300 and the PS having the molecular weight of 900,000 manufactured by the above-described method is detonated using the tungsten wire, And the burn rate was calculated. The burn rate was calculated by measuring the time the flame propagated from the beginning of the flame to the opposite end with about 1 cm of high energy material of 0.3 mg. At this time, the tungsten wire is connected to a current of 10 V, 60 mA to heat the tungsten wire, and the heated tungsten wire causes the high energy material to explode. The results are confirmed in Fig.
4. Results
(1) Formation of nanoporous copper oxide particles using polymer solution
FIG. 2 (a) is a SEM image of a nanoporous structure prepared by mixing a polymer particle and a copper precursor solution, which is a conventional method for producing nanoporous polymer particles, and FIG. 2 (b) Lt; / RTI > is an SEM image of a nanoporous structure prepared by the method of Example < RTI ID =
The present invention is a method using a relatively inexpensive polymer solution instead of the previously used polymer particles to produce nanoporous copper oxide particles used as a metal oxidizing agent for nano-high energy materials. As shown in FIG. 2, And the nanoporous structure of the nanoporous particles can be manufactured. From this, it can be seen that porous copper oxide similar to the nanoporous copper oxide particles produced using expensive polymer particles can be produced without using polymer particles and using a polymer solution.
(2) Formation of nanoporous copper oxide particles by spray pyrolysis
The nanoporous structure was prepared by spraying a solution prepared by mixing the polymer solution and the copper precursor solution of Table 1 using an atomizer and then burning out the polymer through heat treatment to form a nanoporous structure. It is confirmed that the particles are spherical and the part where the polymer is burned out forms pores and exhibits a porous structure. 3 is referred to.
The nanoporous copper oxide particles have various shapes depending on the concentration of the mixed polymer solution and the copper precursor solution. The concentration of the polymer solution and the concentration of the copper precursor solution were varied depending on the concentration of 1 wt% / 5 wt%, 2 wt% / 10 wt% and 2 wt% / 15 wt%, respectively, of the nanoporous, spherical nanoporous, Sponge-like nanoporous structure was formed. This is confirmed in Fig.
4 (a), 4 (c) and 4 (e) show that the PS-CuO nanoparticles prepared after spraying the mixed solution have different brightness of the particles because the polymer solution and the copper precursor solution are mixed This is because the copper precursor solution is biased to one side and sprayed without mixing evenly as it is sprayed. The nanoporous copper oxide particles were obtained in the case of (a) (Fig. 4 (b)), and in case of (c), spherical nanoporous copper oxide particles were obtained (Fig. 4 (d)). In FIG. 4 (e), only half of the sprayed nanoparticles can be seen to have bright light, so that the heat treated nanoporous copper oxide particles have a hemispherical porous form (FIG. 4 (f)).
This degree of mixing depends on the concentration of the solution of the polymer solution and the concentration of the copper precursor solution. As shown in the SEM image of FIG. 4, various types of nanoporous structures can be manufactured by changing the concentration of the mixed solution.
The nanoporous copper oxide particles prepared by the spray pyrolysis method have a very low yield of about 0.3 g when tested using a 200 ml solution. In order to solve this problem, the present invention provides a method for producing nanoporous copper oxide particles with higher yield by directly pyrolyzing pyrolysis in a high temperature furnace instead of spraying and pyrolyzing a mixture of a polymer solution and a copper precursor solution I suggest.
(3) Formation of nanoporous copper oxide particles by solution pyrolysis
When the nanoporous structure was prepared by spray pyrolysis, it was confirmed that the nozzle clogging occurred at the time of spraying the polymer solution and that the yield was low. In order to improve the nano-porous structure, A new method was devised.
Nanoporous copper oxide particles were prepared by directly heat treating the mixed solution in a high temperature furnace instead of using a heat treatment method in which a mixed solution of a polymer solution and a copper precursor solution was sprayed.
As shown in FIG. 5, when the polymer solution is mixed with the polymer solution different from the heat treated copper oxide thin film by using only the copper nitrate solution without mixing the polymer solution, when the temperature is increased, the solvent evaporates and the polystyrene is thermally decomposed And it was confirmed that the pore size was slightly changed according to the concentration of the polymer solution and the copper precursor solution (FIG. 6).
The concentration of the polymer solution and the copper precursor solution was 1 wt% / 5 wt%, 1 wt% / 10 wt%, 1 wt% / 15 wt%, 2 wt% / 15 wt%, 2 wt% / 10
When the crystal structure of the nanoporous copper oxide particles was analyzed by using XRD, it was found that the crystal structure of the nanoporous copper oxide particles was exactly the same as that of the copper (II) oxide (FIG. 7).
(4) Control of pore size of nanoporous copper oxide particles
In the present invention, copper nanoporous particles were prepared by mixing a solution prepared by dissolving polystyrene having molecular weights of 1,300, 13,000, 123,000 and 900,000 in toluene with a copper precursor solution and then heat-treating the solution.
The experimental conditions were the same except for the molecular weight of polystyrene, and the pore size was different according to the molecular weight when the copper oxide nanoporous particles prepared after the solution heat treatment were compared with each other. 1300, the molecular weight was too small and did not occupy a sufficient degree of mixing to form pores. As a result, it was confirmed that the film had the shape of the whole film. When the molecular weight was 13,000, 123,000, and 900,000, And it was confirmed that it changed evenly. The molecular weight of the polymer solution may be a factor controlling the degree of mixing with the metal precursor solution, and thus the pore size of the nanoporous copper oxide particles produced may vary (FIG. 8).
Referring to Figures 8 (a), 8 (b), 8 (c) and 8 (d), the approximate pore size can be determined by reference to the American Society for Testing and Materials (ASTM) Standard E112 "Standard Methods for Estimating the Average Grain Size for Metals & I guessed it. Five horizontal horizontal lines were randomly drawn on each SEM image and the total length was measured. Then, the lengths of the pore portions were divided by the number of the pore portions. As a result, (a) 231 nm (b) was 96.2 nm, (c) was 78.4 nm, and (d) was 64.8 nm.
Also, it was confirmed that the degree of sintering of the metal oxide varies with the time of thermal decomposition of the polymer at a high temperature even if a polymer solution having the same molecular weight is used, thereby changing the size of the pore. The longer the time of the pyrolysis process, the greater the degree of sintering, the larger the pore size, and the shorter the time, the greater the amount of polymer remaining without pyrolysis (FIG. 9).
Also, the present invention is a pore-forming mechanism that is proposed to explain that the smaller the molecular weight of the polymer is, the larger the pore size. 10 (a) is a view showing a mechanism for producing copper nanoporous particles prepared by solution heat treatment using polystyrene having a molecular weight of 1,300, and FIG. 10 (b) is a view showing a case of using polystyrene having a molecular weight of 900,000 . Referring to FIG. 10 (a), the solvent is removed while heating the mixed solution, and the polymer is gathered to form a spherical shape, and the copper precursor solution reacts with oxygen in the air to convert to copper oxide. The spherical polymer is thermally decomposed after expansion to form an empty space, and the copper oxide is pushed by the expanded polystyrene to form a larger space. The copper oxide then forms pores of the random network structure through surface diffusion. Comparing FIG. 10 (a) with FIG. 10 (b), 1,300, which has a relatively small molecular weight, has a low glass transition temperature and thus is expanded more at 600 ° C. than the polystyrene having a high molecular weight. It can be seen that larger pores are formed when the molecular weight is small.
The size of the pores can be controlled by controlling the molecular weight of the polymer, controlling the size of the pores by controlling the degree of sintering, and controlling the size of the pores.
(5) Explosion characteristics of high energy material using nanoporous copper particles
The explosion experiment was carried out by mixing the nanoporous copper oxide particles prepared in the present invention and solid copper oxide particles heat-treated using only copper precursor solution with Al nanoflower. In the case of solid copper oxide particles, a copper nitrate solution was prepared by heat treatment. In the case of nanoporous copper oxide particles, a mixed solution using polystyrene with molecular weights of 1,300 and 900,000, respectively, was prepared by solution pyrolysis. Each copper oxide particle was mixed with Al nanopowder by ultrasonic at a ratio of 7: 3 wt% and ignited by tungsten wire. Experimental results show that the explosion characteristics of solid particles and nanoporous particles (mw900,000) are not significantly different. Solid particles take a short time to propagate after ignition, but after explosion propagation starts, they propagate faster than nanoporous particles . The explosion propagation time of nano-high-energy materials prepared using polystyrene with molecular weights of 1,300 and 900,000 was found to be 11 times higher than that of 3.03 at 900.3 12). Al nanoparticles used in the manufacture of nano-high-energy materials are 80 to 100 nm in size, compared to copper oxide particles made of nano-high-energy materials with a molecular weight of 900,000. The nanoporous copper oxide particles have a large surface area. Therefore, there is no significant difference in the explosion characteristics between the nano-high energy material made of the solid nanoparticles and the nanoporous copper oxide particles having the larger pore size. The explosion propagation speed also seems to have increased greatly due to the large contact area when blended. In conclusion, the explosion propagation speed did not differ greatly from that of the solid nanoparticle material because the pore was small when the molecular weight was large. However, when the molecular weight was small, the pore size increased and the explosion propagation speed was accelerated.
Claims (8)
And heating the mixed solution under an oxygen atmosphere,
Wherein the heating step comprises:
A first heat treatment step in which the solvent of the mixed solution is vaporized and removed to heat the polymer so that the polymer is crystallized and the metal precursor becomes a metal oxide;
A second heat treatment step of heating the polymer to a temperature higher than the glass transition temperature to heat the polymer so as to expand the crystallization state of the polymer to increase the porosity of the metal precursor following the first heat treatment step; And
And a third heat treatment step subsequent to the second heat treatment step to heat-treat the polymer so that the polymer is burned out.
A method for producing a porous metal oxide.
Wherein the solvent of the mixed solution is a solvent capable of ionizing the metal precursor and capable of dispersing the polymer in a solution.
A method for producing a porous metal oxide.
Wherein the polymer is a thermoplastic polymer.
A method for producing a porous metal oxide.
Wherein the polymer is at least one selected from the group consisting of polystyrene, polymethyl acrylate, polymethyl methacrylate, and polyvinyl benzyl chloride.
A method for producing a porous metal oxide.
Wherein the metal precursor is a metal ion capable of being metal ionized in a solvent of the mixed solution and oxidizable by heat treatment.
A method for producing a porous metal oxide.
Wherein the metal precursor is a copper nitrate.
A method for producing a porous metal oxide.
A first heat treatment step of heat-treating the mixed solution in a high temperature furnace such that the solvent of the mixed solution is vaporized and removed to cause the polymer of the polymer solution to be crystallized and the metal precursor to become a metal oxide;
A second heat treatment step of heating the polymer to a temperature higher than the glass transition temperature to expand the polymer in the crystallized state to increase the porosity of the metal precursor following the first heat treatment step; And
And a third heat treatment step subsequent to the second heat treatment step to heat-treat the polymer so that the polymer is burned out.
A process for producing porous copper oxide (CuO).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160010000A KR101736656B1 (en) | 2016-01-27 | 2016-01-27 | Method for fabrication of porous metal oxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160010000A KR101736656B1 (en) | 2016-01-27 | 2016-01-27 | Method for fabrication of porous metal oxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR101736656B1 true KR101736656B1 (en) | 2017-05-17 |
Family
ID=59048288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160010000A KR101736656B1 (en) | 2016-01-27 | 2016-01-27 | Method for fabrication of porous metal oxides |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101736656B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200053867A (en) * | 2018-11-09 | 2020-05-19 | 한양대학교 에리카산학협력단 | A porous elastic structure, a surface-modified porous elastic structure, and the methods of manufacturing the same |
| KR20200066424A (en) * | 2018-11-30 | 2020-06-10 | 한국생산기술연구원 | Processes for preparation Mesoporous copper oxide |
| KR102370841B1 (en) * | 2021-07-20 | 2022-03-07 | 국방과학연구소 | Highly reactive high energy composite and manufacturing method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047380A1 (en) | 1996-06-12 | 1997-12-18 | Project Earth Industries, Inc. | Acid contacted enhanced adsorbent and/or catalyst and binder system |
| KR101522734B1 (en) | 2013-12-06 | 2015-05-26 | 주식회사 아이엠티에스 | Method of manufacturing copper nanoparticles using polymer solution |
-
2016
- 2016-01-27 KR KR1020160010000A patent/KR101736656B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047380A1 (en) | 1996-06-12 | 1997-12-18 | Project Earth Industries, Inc. | Acid contacted enhanced adsorbent and/or catalyst and binder system |
| KR101522734B1 (en) | 2013-12-06 | 2015-05-26 | 주식회사 아이엠티에스 | Method of manufacturing copper nanoparticles using polymer solution |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200053867A (en) * | 2018-11-09 | 2020-05-19 | 한양대학교 에리카산학협력단 | A porous elastic structure, a surface-modified porous elastic structure, and the methods of manufacturing the same |
| KR102159437B1 (en) | 2018-11-09 | 2020-09-23 | 한양대학교 에리카산학협력단 | A porous elastic structure, a surface-modified porous elastic structure, and the methods of manufacturing the same |
| KR20200066424A (en) * | 2018-11-30 | 2020-06-10 | 한국생산기술연구원 | Processes for preparation Mesoporous copper oxide |
| KR102180500B1 (en) | 2018-11-30 | 2020-11-19 | 한국생산기술연구원 | Processes for preparation Mesoporous copper oxide |
| KR102370841B1 (en) * | 2021-07-20 | 2022-03-07 | 국방과학연구소 | Highly reactive high energy composite and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE102010002124B4 (en) | Graphene Oxide Deoxidation | |
| KR101736656B1 (en) | Method for fabrication of porous metal oxides | |
| JP4839430B2 (en) | Method for producing porous thermoelectric material | |
| WO2004020128A1 (en) | Metallic nickel powder and method for production thereof | |
| JP2005002395A (en) | Porous spherical nickel powder, and its production method | |
| KR20150052652A (en) | Preparation method of yolk-shell structured material by spray drying and yolk-shell structured materials prepared thereby | |
| CN111848153A (en) | Microwave dielectric ceramic, preparation method of microwave dielectric ceramic and communication device | |
| JP4822576B2 (en) | Inorganic hollow powder and method for producing the same | |
| KR102153241B1 (en) | Hollow carbon black having micro-porosity and manufacturing method thereof | |
| Qin et al. | Preparation and characterization of energetic composite films with mutual reactions based on B/PVDF mosaic structure | |
| JP2007090207A (en) | Carbon dioxide absorber and its manufacturing method | |
| KR101754018B1 (en) | Metal Oxides Fabrication Method With the Core and Shell Structure Of Metal Oxide | |
| US8912106B2 (en) | Glass-ceramic composite material | |
| RU2383495C2 (en) | Method of producing complex metal oxides | |
| KR100921649B1 (en) | Method for Manufacturing Artificial Aggregate Having Lightweight and Optimized Blackcore Formation | |
| JP2005239439A (en) | Method of manufacturing carbon microtube | |
| JP2011016718A (en) | Inorganic hollow powder and method for manufacturing the same | |
| KR101478555B1 (en) | Nickel nano powder and method of manufacturing the same using high temperature plasma | |
| KR100281793B1 (en) | Method of light block with waste glass of soda-lime glass silicate | |
| JP2004263205A (en) | Metallic impalpable powder, manufacturing method therefor, and conductive paste using the metallic impalpable powder | |
| JP2005161238A (en) | Production method of nanoparticle or nanostructure | |
| JP4991096B2 (en) | MgO vapor deposition material | |
| RU2733966C1 (en) | Method of producing composite oxide materials | |
| Lee et al. | Effect of HF-treatment on the glass frit upon crystallizing behaviour and microstructure of glass-ceramics | |
| WO2022158127A1 (en) | Method for producing boron nitride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GRNT | Written decision to grant |