CN109012496B - Method for preparing diamond film by shock wave method - Google Patents
Method for preparing diamond film by shock wave method Download PDFInfo
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- CN109012496B CN109012496B CN201811194667.4A CN201811194667A CN109012496B CN 109012496 B CN109012496 B CN 109012496B CN 201811194667 A CN201811194667 A CN 201811194667A CN 109012496 B CN109012496 B CN 109012496B
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- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
- B01J3/062—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies characterised by the composition of the materials to be processed
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- B01J2203/06—High pressure synthesis
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- B01J2203/00—Processes utilising sub- or super atmospheric pressure
- B01J2203/06—High pressure synthesis
- B01J2203/065—Composition of the material produced
- B01J2203/0655—Diamond
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Abstract
The invention provides a method for preparing a diamond film by a shock wave method. Obtaining a second-order graphite intercalation compound by using iodine chloride as an intercalation agent, and performing high-temperature treatment to obtain a double-layer graphene material; uniformly mixing double-layer graphene powder and pure copper powder, pressing into a block, then placing the block into an impact recovery device for impact pressurization, recovering the impacted mixed pressed body, and removing copper by using nitric acid to obtain the diamond film. The double-layer graphene adopted by the method provided by the invention is hardened into the thinnest film with diamond-like hardness in a short time after being impacted, and can be used for protective materials. By using the double-layer graphene as a carbon source, higher diamond conversion rate can be achieved in a lower impact pressure range.
Description
Technical Field
The invention relates to the field of diamond preparation, in particular to a method for preparing a diamond film by using a shock wave method with double-layer graphene as a raw material.
Background
Diamond is a particulate substance composed of elemental carbon, is the highest-hardness substance found in the world at present, and is also an allotrope of graphene, fullerene and carbon nanotubes. Diamond is used for grinding superhard materials such as gems, glass, hard alloys and the like, and is a cutting tool in artware and industry.
Graphene is a two-dimensional material with many excellent properties, having a honeycomb structure composed of a single layer of carbon atoms, having a thickness of only one millionth of the diameter of a human hair, but having a strength superior to steel hundreds of times. The graphene still maintains the hexagonal distribution of carbon atoms in the graphite layer sheet, and the structure still has certain correspondence with the distribution of carbon atoms of diamond, so that the condition of direct phase change exists.
There are many methods for synthesizing diamond, but graphite with good crystallization is generally used as a carbon source for synthesis, because the crystal structure of graphite and diamond have obvious correspondence, and carbon atoms of graphite slightly move under high temperature and high pressure, so that the graphite can be directly converted into diamond. However, during the impact synthesis process, a high diamond conversion rate must be achieved at extremely high impact pressures. The invention patent of China (CN93115929.6) discloses that expanded graphite with enlarged C-axis interlayer spacing, which is regarded as a special porous graphite material, is used as a carbon source for impacting synthetic diamond to achieve higher diamond conversion rate in a lower impact pressure range. By controlling the initial density of the expanded graphite to control the synthesis temperature, a higher synthesis temperature can be achieved at lower pressures than with crystalline graphite. Because the impact loading time is extremely short, the duration time of high pressure is generally not more than ten microseconds, and when the crystalline graphite is adopted for impact synthesis, higher diamond conversion rate can be obtained only under extremely high impact pressure. In order to further increase the yield of diamond, reduce equipment requirements and reduce energy consumption, there is still a need to further reduce the impact pressure and increase the conversion.
Disclosure of Invention
Provides a method for preparing a diamond film by a shock wave method, in particular to a method for preparing the diamond film by the shock wave method by taking double-layer graphene as a raw material, which can achieve higher diamond conversion rate in a lower shock pressure range. Double-layer graphene, which is not already in the category of graphite, can be considered as expanded graphite to the extent that the C-axis interlayer spacing is pulled up to the "limit". The artificial diamond is synthesized by adopting double-layer graphene impact, so that the direct phase change condition is met, and the higher synthesis temperature can be reached under lower pressure, thereby improving the nucleation rate of the diamond.
The invention adopts the following technical scheme:
a method for preparing a diamond film by a shock wave method comprises the following steps:
(1) iodine chloride is used as an intercalating agent to obtain a second-order graphite intercalation compound, the second-order graphite intercalation compound is subjected to high-temperature treatment, and iodine chloride is decomposed to generate gas to peel off graphite sheets to obtain a double-layer graphene material;
(2) uniformly mixing double-layer graphene powder and pure copper powder, pressing the mixture into a block, putting the block into an impact recovery device for impact pressurization, recovering the impacted mixed pressed body, and removing copper by using nitric acid to obtain the diamond film.
The graphite raw material size of the second-order graphite intercalation compound in the step (1) is 10-150 meshes.
The high-temperature treatment temperature in the step (1) is 800-1200 ℃.
And (3) taking the pure copper powder in the step (2) as a pressure transmission medium, wherein the mass ratio of the double-layer graphene powder to the pure copper powder is 0.1-1.
The impact pressurization pressure in the step (2) is 10-150 GPa, and the duration is less than 10 microseconds.
The nitric acid in the step (2) is a nitric acid aqueous solution with the concentration of 20%.
The invention has the following advantages:
(1) in the method, the double-layer graphene is hardened into diamond in a short time after being impacted, becomes the thinnest film with diamond-like hardness, and can be applied to protective materials.
(2) The impact method using graphite and expanded graphite as carbon sources forms diamond particles, and requires a nucleation process and multi-layer displacement matching. The double-layer graphene adopted by the method can form a diamond film under impact only by slightly moving the position, and can achieve higher diamond conversion rate in a lower impact pressure range.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Fig. 2 is a transmission electron microscope image of double-layer graphene prepared by the method of example 1 of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
(1) And (2) uniformly mixing 60g of iodine chloride and 1g of expanded graphite, filling protective gas Ar gas, sealing in a glass bottle, placing in an oil bath environment at 160 ℃, and heating for 48 hours to prepare the second-order graphite intercalation compound.
(2) The graphite intercalation compound is quickly taken out of the glass bottle and filtered, and then put into a quartz boat and heated to 800 ℃ for 5 min. And after the reaction is finished, taking out the sample, and cleaning the sample to obtain the double-layer graphene powder aggregate.
(3) 1g of double-layer graphene powder and 5g of 200-mesh pure copper powder are uniformly mixed, pressed into a block, and then placed into an impact recovery device for impact pressurization, wherein the impact pressurization pressure is 20GPa, and the duration time is less than 10 microseconds.
(4) And recovering the impacted mixed pressed body, and adding a nitric acid aqueous solution with the concentration of 20% to remove copper to obtain the diamond film.
FIG. 1 is a process flow diagram of the present embodiment.
Fig. 2 is a transmission electron microscope image of double-layer graphene prepared in this example.
Example 2
(1) And (2) uniformly mixing 60g of iodine chloride and 1g of expanded graphite, filling protective gas Ar gas, sealing in a glass bottle, placing in an oil bath environment at 160 ℃, and heating for 48 hours to prepare the second-order graphite intercalation compound.
(2) The graphite intercalation compound is quickly taken out of the glass bottle and filtered, and then put into a quartz boat and heated to 800 ℃ for 5 min. And after the reaction is finished, taking out the sample, and cleaning the sample to obtain the double-layer graphene powder aggregate.
(3) 1g of double-layer graphene powder and 2g of 200-mesh pure copper powder are uniformly mixed, pressed into a block, and then placed into an impact recovery device for impact pressurization, wherein the impact pressurization pressure is 20GPa, and the duration time is less than 10 microseconds.
(4) And recovering the impacted mixed pressed body, and adding a nitric acid aqueous solution with the concentration of 20% to remove copper to obtain the diamond film.
Example 3
(1) And (2) uniformly mixing 60g of iodine chloride and 1g of expanded graphite, filling protective gas Ar gas, sealing in a glass bottle, placing in an oil bath environment at 160 ℃, and heating for 48 hours to prepare the second-order graphite intercalation compound.
(2) The graphite intercalation compound is quickly taken out of the glass bottle and filtered, and then put into a quartz boat and heated to 800 ℃ for 5 min. And after the reaction is finished, taking out the sample, and cleaning the sample to obtain the double-layer graphene powder aggregate.
(3) 1g of double-layer graphene powder and 5g of 200-mesh pure copper powder are uniformly mixed, pressed into a block, and then placed into an impact recovery device for impact pressurization, wherein the impact pressurization pressure is 40GPa, and the duration time is less than 10 microseconds.
(4) And recovering the impacted mixed pressed body, and adding a nitric acid aqueous solution with the concentration of 20% to remove copper to obtain the diamond film.
Example 4
(1) And (2) uniformly mixing 60g of iodine chloride and 1g of expanded graphite, filling protective gas Ar gas, sealing in a glass bottle, placing in an oil bath environment at 160 ℃, and heating for 48 hours to prepare the second-order graphite intercalation compound.
(2) The graphite intercalation compound is quickly taken out of the glass bottle and filtered, and then put into a quartz boat and heated to 1000 ℃ for 5 min. And after the reaction is finished, taking out the sample, and cleaning the sample to obtain the double-layer graphene powder aggregate.
(3) 1g of double-layer graphene powder and 5g of 200-mesh pure copper powder are uniformly mixed, pressed into a block, and then placed into an impact recovery device for impact pressurization, wherein the impact pressurization pressure is 20GPa, and the duration time is less than 10 microseconds.
(4) And recovering the impacted mixed pressed body, and adding a nitric acid aqueous solution with the concentration of 20% to remove copper to obtain the diamond film.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (6)
1. A method for preparing a diamond film by a shock wave method comprises the following steps:
(1) iodine chloride is used as an intercalating agent to obtain a second-order graphite intercalation compound, the second-order graphite intercalation compound is subjected to high-temperature treatment, and iodine chloride is decomposed to generate gas to peel off graphite sheets to obtain a double-layer graphene material;
(2) uniformly mixing double-layer graphene powder and pure copper powder, pressing the mixture into a block, putting the block into an impact recovery device for impact pressurization, recovering the impacted mixed pressed body, and removing copper by using nitric acid to obtain the diamond film.
2. The process of claim 1, wherein the graphite feedstock size of the second order graphite intercalation compound of step (1) is 10-150 mesh.
3. The method as claimed in claim 1, wherein the high temperature treatment temperature in step (1) is 800-1200 ℃.
4. The method of claim 1, wherein the pure copper powder is used as a pressure transmission medium in the step (2), and the mass ratio of the double-layer graphene powder to the pure copper powder is 0.1-1.
5. The method according to claim 1, wherein the impact pressurization pressure in the step (2) is 10-150 GPa for less than 10 μ s.
6. The method of claim 1, wherein the nitric acid in step (2) is a 20% aqueous nitric acid solution.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103328A (en) * | 1993-11-27 | 1995-06-07 | 大连理工大学 | Expansion graphite method for explosion synthesis of diamond |
| CN105776201A (en) * | 2016-04-07 | 2016-07-20 | 东南大学 | Method for low-temperature and low-pressure nano-diamond synthesis by using oxidized graphene powder |
| CN108314025A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of preparation method of bilayer graphene intercalation compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110006837A1 (en) * | 2009-06-02 | 2011-01-13 | Feng Wang | Graphene Device, Method of Investigating Graphene, and Method of Operating Graphene Device |
| CN103482610A (en) * | 2012-06-14 | 2014-01-01 | 海洋王照明科技股份有限公司 | Graphene preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103328A (en) * | 1993-11-27 | 1995-06-07 | 大连理工大学 | Expansion graphite method for explosion synthesis of diamond |
| CN105776201A (en) * | 2016-04-07 | 2016-07-20 | 东南大学 | Method for low-temperature and low-pressure nano-diamond synthesis by using oxidized graphene powder |
| CN108314025A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of preparation method of bilayer graphene intercalation compound |
Non-Patent Citations (1)
| Title |
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| Ultrahard carbon film from epitaxial two-layer graphene;Yang Gao et al.;《nature nanotechnology》;20180228(第13期);第133-139页 * |
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