CN110723732A - Preparation method of ultra-dispersed nano-diamond suspension - Google Patents
Preparation method of ultra-dispersed nano-diamond suspension Download PDFInfo
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- 239000000725 suspension Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 103
- 239000010432 diamond Substances 0.000 claims abstract description 103
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000011324 bead Substances 0.000 claims abstract description 26
- -1 aromatic amine compound Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000010296 bead milling Methods 0.000 claims abstract description 4
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 11
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a preparation method of a super-dispersed nano-diamond suspension, which comprises the following steps: (1) diamond pretreatment: adding diamond into an alkali solution, controlling the temperature to be 20-95 ℃, preserving the heat, washing, drying and calcining; (2) preparing a diamond pretreatment solution: ultrasonically dispersing the calcined diamond in deionized water, adding an aromatic amine compound and a nitrite compound to obtain a diamond suspension, and cooling to obtain a diamond pretreatment solution; (3) and (3) wet fine grinding: adding the diamond pretreatment solution into a bead mill with a screen, and performing bead milling to obtain a diamond suspension; (4) centrifugal dispersion: and ultrasonically dispersing the diamond suspension, centrifuging and collecting supernatant to obtain the ultra-dispersed nano diamond suspension. According to the preparation method of the ultra-dispersed nano-diamond suspension, the prepared nano-diamond suspension has the advantages of concentrated diamond particle size distribution, uniform size and no agglomeration.
Description
Technical Field
The invention relates to the field of diamond, in particular to a preparation method of a super-dispersed nano-diamond suspension.
Background
Diamond is an excellent 21 st century material. Because the diamond has the characteristics of excellent thermal conductivity, high hardness, low friction, good optical property, biocompatibility coefficient and the like, the nano-diamond not only inherits the advantages of large-scale diamond particles, but also has the characteristics of nano-materials. Therefore, the nano-diamond has been widely used in various fields such as abrasives, cutting tools, biosensors, electrochemical electrodes, and the like.
The detonation method is the main method for producing nano-diamond at present, and converts graphite in a closed state into diamond through instantaneous high-temperature high-pressure low-oxygen conditions generated by explosion of explosives (such as TNT-RDX mixed explosives). The detonation method has low cost and high speed, but the obtained diamond raw powder has high impurity content (the content can reach 80%). This is due to the non-uniform temperature produced by the detonation process, and the resulting detonation-process diamond has low crystallinity. Besides, the obtained diamond contains a large amount of unconverted graphite and other amorphous carbon, in order to remove impurities in the detonation method diamond, in the prior art (for example, CN 107074555A, a suspension of nano diamond aggregate and nano diamond single-digit nano dispersion liquid) the diamond raw material is put into strong acid, and the oxidation of the strong acid is utilized to remove graphite under the condition of heating. In actual operation, because the content of graphite in diamond raw materials of different batches has large difference, the method has many uncontrollable factors on the technology, large selection span of oxidation time, high requirement on personnel experience and can generate a large amount of strong acid waste liquid, thereby being not beneficial to wide application. In addition, although the particle size diameter of the prepared detonation method diamond particles can reach 3-6 nm, in practice, the obtained nano diamond particles have high specific surface area and serious agglomeration, so the particle size distribution is wide and ranges from nano to millimeter.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a preparation method of the ultra-dispersed nano-diamond suspension, and the prepared nano-diamond suspension has the advantages of concentrated diamond particle size distribution, uniform size and no agglomeration.
The technical scheme of the invention is summarized as follows:
a method for preparing a super-dispersed nano-diamond suspension, wherein the preparation method comprises the following steps:
(1) diamond pretreatment: adding diamond into an alkali solution, controlling the temperature at 20-95 ℃, preserving heat for 1-38 h, washing until the pH value is neutral, drying and calcining;
(2) preparing a diamond pretreatment solution: ultrasonically dispersing the calcined diamond in deionized water, adding an aromatic amine compound and a nitrite compound to obtain a diamond suspension, heating the diamond suspension, preserving heat for a certain time, and cooling to obtain a diamond pretreatment solution;
(3) and (3) wet fine grinding: adding the diamond pretreatment solution into a bead mill with a screen, and collecting diamond suspension flowing out of the screen after the bead mill is used for a certain time;
(4) centrifugal dispersion: and ultrasonically dispersing the diamond suspension, centrifuging and collecting supernatant to obtain the ultra-dispersed nano diamond suspension.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the following steps of 1), preparing diamond by a CVD method; the CVD method is one of a plasma CVD method, a microwave plasma CVD method and a hot wire CVD method. Chemical deposition technology (CVD) is a surface technology that has been commercialized to enable rapid production of nanodiamonds. Since the cost of self-grown diamond is very high, a suitable substrate is generally selected for diamond growth using CVD techniques, and the nanodiamonds are deposited as films on the substrate under high temperature and high pressure conditions, and the process gas for producing the nanodiamonds is mostly a mixed gas containing hydrogen and a carbon-containing gas (e.g., methane) for providing a carbon source during the diamond deposition process. The hydrogen gas may etch non-diamond phases (e.g., graphite, amorphous carbon) formed during the deposition of the nanodiamonds. Therefore, the nano-diamond produced by the CVD technology has high crystallinity and low impurity and defect content, and is an ideal raw material for preparing the nano-diamond solution.
Preferably, the preparation method of the ultra-dispersed nano diamond suspension comprises the following steps of (1) preparing a diamond suspension, wherein the diamond comprises a substrate and a diamond film arranged on the substrate; the diamond film comprises at least one layer of nano-diamond particles; the particle size range of the nano diamond particles is 2-500 nm.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the step (1) of preparing one or two of potassium hydroxide solution and sodium hydroxide solution by mass percentage of 30-40 wt%. The alkali solution may remove the nanodiamond base substrate.
Preferably, the method for preparing the ultra-dispersed nano-diamond suspension comprises the step (1) of calcining under the vacuum degree of less than 10-2mbar, the calcining temperature is 900-1200 ℃, and the calcining time is 0.5-2 h.
Preferably, in the preparation method of the ultra-dispersed nano-diamond suspension, the mass concentration of the diamond suspension in the step (2) is 0.001 to 10 wt%.
Preferably, the method for preparing the ultra-dispersed nano-diamond suspension comprises the following steps of (1) preparing an aniline compound in the step (2), wherein the aniline compound is selected from one or more of p-aminobenzoic acid and aminobenzenesulfonic acid; the nitrite ester compound is isoamyl nitrite; the molar concentrations of the aniline compound and the nitrite compound in the pretreatment liquid are both 10-4～10- 2mol/L. When the aromatic amine compound and the nitrite compound are added into the water in which the diamond particles are dispersed, the diamond particles can be protected, different aromatic functional groups are bridged on the surface of the diamond, and the nano-diamond can be prevented from being agglomerated in the subsequent process.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the step (2) heating the diamond suspension at 40-90 ℃ for 1-38 hours.
Preferably, the preparation method of the ultra-dispersed nano diamond suspension comprises the step (3) of sieving the nano diamond suspension with the aperture of 0.50-500 μm and the rotation speed of a bead mill of 3000-6000 min-1And the bead milling time is 1-8 h. The liquid medium used in the vibrating bead mill is deionized water or an aqueous solution containing aromatic amine compounds and nitrite compounds.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the following steps of (1) preparing the diamond suspension in the step (4), wherein the mass fraction of the diamond suspension in the step (4) is 0.005-3 wt%; the ultrasonic dispersion time is 0.5-1 h, and the power is 200-800W; the rotation speed of the centrifugation is 1000-4000 rpm/min, and the centrifugation time is 0.5-8 h. The purpose of the centrifugation is to remove the crushed ceramic abrasive mixed into the diamond suspension during the vibrating bead milling.
The invention has the beneficial effects that:
(1) the invention relates to a preparation method of a super-dispersed nano-diamond suspension, which selects high-quality nano-diamond film raw materials produced by a CVD technology to prepare a uniform super-dispersed nano-diamond suspension, wherein the diamond particle size distribution of the prepared nano-diamond suspension is centralized, the size is uniform, and the nano-diamond suspension is not agglomerated; in the preparation process of the diamond suspension, no reagent polluting the environment and human body is used, and the prepared nano-diamond suspension can be used as an abrasive, a heat dissipation additive and a diamond electrode liquid crystal and can also be used in the field of biological medicines.
(2) The preparation method of the ultra-dispersed nano-diamond suspension liquid takes the high-quality nano-diamond film produced by the CVD technology as a raw material, and the pollutants such as graphite, carbon, metal and the like contained in the nano-diamond film can be almost ignored. Therefore, the prepared nano-diamond solution has high quality. The base plate at the bottom of the nano-diamond is removed by the alkaline solution, and the aromatic amine compound and the nitrite compound are added into the aqueous solution in which the diamond particles are dispersed, so that the diamond particles can be protected, different aromatic functional groups are bridged on the surface of the diamond, and the re-agglomeration of the nano-diamond in the subsequent process can be prevented.
Drawings
FIG. 1 is a Zeta potential profile of a super dispersed nano-diamond suspension prepared according to example 1 of the present invention;
fig. 2 is a graph showing a particle size distribution of a super-dispersed nanodiamond suspension according to example 1 of the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1:
a preparation method of a super-dispersed nano-diamond suspension comprises the following steps:
(1) adding diamond into 30 wt% potassium hydroxide solution, and microwave dryingImmersing the silicon-based nano-diamond film prepared by plasma CVD in the potassium hydroxide solution, heating to 50 ℃ and preserving heat for 8 hours; the method comprises the steps of collecting nano diamond precipitate, washing the nano diamond precipitate with deionized water for multiple times until the pH value is neutral, drying, taking the dried diamond precipitate, putting the dried diamond precipitate into a heating furnace with a vacuum function, vacuumizing the heating furnace to 10 DEG C-3mbar, heating to 1000 ℃ at a speed of 100 ℃/min, and then preserving heat for 1 h;
(2) ultrasonically dispersing the calcined diamond in deionized water, and adding para aminobenzoic acid and isoamyl nitrite; heating the obtained diamond suspension to 80 ℃, preserving heat for 24 hours, and cooling to obtain diamond pretreatment liquid; wherein the mass fraction of the diamond in the deionized water is 6.05 percent; wherein the concentrations of the p-aminobenzoic acid and the isoamyl nitrite are respectively 0.0083mol/L and 0.0096 mol/L.
(3) Slowly and uniformly dripping the diamond pretreatment liquid into a vibration type bead mill, wherein the liquid medium used by the vibration type bead mill is an aqueous solution containing p-aminobenzoic acid and isoamyl nitrite with the concentrations of 0.0083mol/L and 0.0096mol/L respectively, and the rotating speed of a rotor of the vibration type bead mill is set to 3000min-1The grinding material used by the vibration type bead mill is zirconium dioxide with the average grain diameter of 35 mu m, the vibration type bead mill is connected with a screen, the mesh size of the screen is 1 mu m, and diamond suspension with the mass fraction of 0.05 wt% flowing out of the screen is collected after 4 hours of the vibration type bead mill.
(4) And carrying out ultrasonic separation on the nano-diamond suspension for 0.5h, wherein the power is 500W, the mass fraction of the diamond suspension is 0.005 wt%, centrifuging the nano-diamond suspension subjected to ultrasonic separation at the rotating speed of 2000rpm for 1h, collecting supernatant, and finally obtaining the ultra-dispersed nano-diamond suspension with the particle size of 20-60 nm.
Experimental results as shown in fig. 1 and 2, it can be seen from fig. 1 that the Zeta potential of the ultra-dispersed nanodiamond particles prepared in this example was-55.5 mV, and the outermost charge of the outermost ultra-dispersed nanodiamond particles was negative. The absolute value of the Zeta potential exceeds 30mV, which indicates that the nanodiamond suspension is very stable.
As can be seen from FIG. 2, the particle size of the ultra-dispersed nano-diamond prepared by the example is mainly distributed in the range of 20-60 nm, and the particle size distribution is very centralized, which shows that the obtained nano-diamond is uniform in size.
Example 2:
a preparation method of a super-dispersed nano-diamond suspension comprises the following steps:
(1) adding diamond into 30 wt% of sodium hydroxide solution, immersing the silicon-based nano-diamond film prepared by a plasma CVD method in the sodium hydroxide solution, heating to 20 ℃, and keeping the temperature for 38 hours; the method comprises the steps of collecting nano diamond precipitates, washing the nano diamond precipitates with deionized water for multiple times until the pH value is neutral, drying, taking the dried diamond precipitates, putting the diamond precipitates into a heating furnace with a vacuum function, vacuumizing the heating furnace to 10 DEG C-3mbar, heating to 1100 ℃ at a speed of 100 ℃/min, and then preserving heat for 2 h;
(2) ultrasonically dispersing the calcined diamond in deionized water, and adding aminobenzenesulfonic acid and isoamylnitrite; heating the obtained diamond suspension to 50 ℃, preserving heat for 36 hours, and cooling to obtain diamond pretreatment liquid; wherein the mass fraction of diamond in deionized water is 4.32%; wherein the concentrations of the p-aminobenzoic acid and the isoamyl nitrite are respectively 0.0031mol/L and 0.0075 mol/L.
(3) Slowly and uniformly dripping the diamond pretreatment liquid into a vibration type bead mill, wherein the liquid medium used by the vibration type bead mill is an aqueous solution containing p-aminobenzoic acid and isoamyl nitrite with the concentrations of 0.0031mol/L and 0.0075mol/L respectively, and the rotating speed of a rotor of the vibration type bead mill is set to be 5000min-1The grinding material used by the vibration type bead mill is zirconium dioxide with the average grain diameter of 60 mu m, the vibration type bead mill is connected with a screen, the mesh size of the screen is 1 mu m, and diamond suspension with the mass fraction of 0.07 wt% flowing out of the screen is collected after 6 hours of the vibration type bead mill;
(4) and (3) carrying out ultrasonic dispersion on the nano-diamond suspension for 1h, wherein the power is 600W, the mass fraction of the diamond suspension is 1 wt%, centrifuging the nano-diamond suspension subjected to ultrasonic treatment at the rotating speed of 3000rpm for 1h, and collecting supernatant to finally obtain the ultra-dispersed nano-diamond suspension with the particle size of 10-50 nm.
The Zeta potential of the ultra-dispersed nano-diamond particles prepared by the embodiment is-53.5 mV, the outermost charge of the outermost ultra-dispersed nano-diamond particles is negative charge, and the absolute value of the Zeta potential exceeds 30mV, which indicates that the nano-diamond suspension is very stable; the particle size of the ultra-dispersed nano-diamond prepared by the embodiment is mainly distributed in the range of 10-50 nm, and the particle size distribution is very centralized, which shows that the obtained nano-diamond is uniform in size.
Example 3:
a preparation method of a super-dispersed nano-diamond suspension comprises the following steps:
(1) adding diamond into 30 wt% of sodium hydroxide solution, immersing the silicon-based nano-diamond film prepared by a plasma CVD method in the sodium hydroxide solution, heating to 95 ℃, and preserving heat for 1 h; the method comprises the steps of collecting nano diamond precipitates, washing the nano diamond precipitates with deionized water for multiple times until the pH value is neutral, drying, taking the dried diamond precipitates, putting the diamond precipitates into a heating furnace with a vacuum function, vacuumizing the heating furnace to 10 DEG C-3mbar, heating to 1200 ℃ at a speed of 100 ℃/min, and then preserving heat for 0.5 h;
(2) ultrasonically dispersing the calcined diamond in deionized water, and adding p-aminobenzoic acid, aminobenzenesulfonic acid and isoamylnitrite; heating the obtained diamond suspension to 90 ℃, preserving heat for 1h, and cooling to obtain diamond pretreatment liquid; wherein the mass fraction of the diamond in the deionized water is 0.7 percent; wherein the concentrations of the p-aminobenzoic acid, the aminobenzenesulfonic acid and the isoamyl nitrite are 0.0047mol/L, 0.0051mol/L and 0.0093mol/L respectively.
(3) Mixing diamondThe pretreatment liquid is slowly and uniformly dripped into a vibration type bead mill, the liquid medium used by the vibration type bead mill is an aqueous solution containing para aminobenzoic acid, aminobenzenesulfonic acid and isoamylnitrite with the concentrations of 0.0047mol/L, 0.0051mol/L and 0.0093mol/L respectively, and the rotating speed of a rotor of the vibration type bead mill is set to be 6000min-1The grinding material used by the vibration type bead mill is zirconium dioxide with the average grain diameter of 60 mu m, the vibration type bead mill is connected with a screen, the mesh size of the screen is 10 mu m, and diamond suspension liquid with the mass fraction of 0.25 wt% of diamond flowing out of the screen is collected after 8 hours of the vibration type bead mill;
(4) and (3) carrying out ultrasonic dispersion on the nano-diamond suspension for 1h, wherein the power is 800W, the mass fraction of the diamond suspension is 3 wt%, centrifuging the nano-diamond suspension subjected to ultrasonic treatment at the rotating speed of 1000rpm for 5h, and collecting supernatant to finally obtain the ultra-dispersed nano-diamond suspension with the particle size of 40-60 nm.
The Zeta potential of the ultra-dispersed nano-diamond particles prepared by the embodiment is-60.4 mV, the outermost charge of the outermost ultra-dispersed nano-diamond particles is negative charge, and the absolute value of the Zeta potential exceeds 30mV, which indicates that the nano-diamond suspension is very stable; the particle size of the ultra-dispersed nano-diamond prepared by the embodiment is mainly distributed in the range of 40-60 nm, and the particle size distribution is very centralized, which shows that the obtained nano-diamond is uniform in size.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. A preparation method of a super-dispersed nano-diamond suspension is characterized by comprising the following steps:
(1) diamond pretreatment: adding diamond into an alkali solution, controlling the temperature at 20-95 ℃, preserving heat for 1-38 h, washing until the pH value is neutral, drying and calcining;
(2) preparing a diamond pretreatment solution: ultrasonically dispersing the calcined diamond in deionized water, adding aniline compounds and nitrite compounds to obtain a diamond suspension, heating the diamond suspension, preserving heat for a certain time, and cooling to obtain a diamond pretreatment solution;
(3) and (3) wet fine grinding: adding the diamond pretreatment solution into a bead mill with a screen, and collecting diamond suspension flowing out of the screen after the bead mill is used for a certain time;
(4) centrifugal dispersion: and ultrasonically dispersing the diamond suspension, centrifuging and collecting supernatant to obtain the ultra-dispersed nano diamond suspension.
2. The method for preparing a ultra-dispersed nano-diamond suspension according to claim 1, wherein the diamond in the step 1) is prepared by a CVD method; the CVD method is one of a plasma CVD method, a microwave plasma CVD method and a hot wire CVD method.
3. The method for producing a ultra-dispersed nanodiamond suspension according to claim 2, wherein the diamond includes a substrate and a diamond film provided on the substrate; the diamond film comprises at least one layer of nano-diamond particles; the particle size range of the nano diamond particles is 2-500 nm.
4. The method for preparing the ultra-dispersed nano-diamond suspension according to claim 1, wherein the alkali solution in the step (1) is one or two of a potassium hydroxide solution and a sodium hydroxide solution, and the mass fraction of the alkali solution is 30-40 wt%.
5. The method for preparing a ultra-dispersed nanodiamond suspension according to claim 1, wherein vacuum degree of calcination in step (1) is < 10-2mbar, the calcining temperature is 900-1200 ℃, and the calcining time is 0.5-2 h.
6. The method for preparing a ultra-dispersed nanodiamond suspension according to claim 1, wherein the mass concentration of the diamond suspension in the step (2) is 0.001-10 wt%.
7. The method for preparing a ultra-dispersed nanodiamond suspension according to claim 1, wherein the aniline compound of step (2) is one or more selected from p-aminobenzoic acid and aminobenzenesulfonic acid; the nitrite ester compound is isoamyl nitrite; the molar concentrations of the aniline compound and the nitrite compound in the pretreatment liquid are both 10-4～10-2mol/L。
8. The preparation method of the ultra-dispersed nano-diamond suspension liquid according to claim 1, wherein the heating temperature of the diamond suspension liquid in the step (2) is 40-90 ℃, and the heat preservation time is 1-38 hours.
9. The method for preparing a ultra-dispersed nano-diamond suspension according to claim 1, wherein the mesh size of the screen in the step (3) is 0.50-500 μm, and the rotation speed of the bead mill is 3000-6000 min-1And the bead milling time is 1-8 h.
10. The method for preparing the ultra-dispersed nano-diamond suspension according to claim 1, wherein the mass fraction of the diamond suspension in the step (4) is 0.005-3 wt%; the ultrasonic dispersion time is 0.5-1 h, and the power is 200-800W; the rotation speed of the centrifugation is 1000-4000 rpm/min, and the centrifugation time is 0.5-8 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114686171A (en) * | 2022-05-19 | 2022-07-01 | 中国振华集团云科电子有限公司 | Suspensible diamond grinding fluid and preparation process thereof |
| CN116589928A (en) * | 2023-05-17 | 2023-08-15 | 耐博检测技术(武汉)有限公司 | Super-dispersed diamond suspension and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238411A (en) * | 2006-03-10 | 2007-09-20 | Naoki Komatsu | Nanodiamond |
| JP2015127364A (en) * | 2013-12-27 | 2015-07-09 | カルボデオン リミティド オサケユイチア | Nanodiamond containing composite and method for producing the same |
| US20160115033A1 (en) * | 2013-05-31 | 2016-04-28 | Carbodeon Ltd Oy | Zeta Positive Hydrogenated Nanodiamond Powder, Zetapositive Single Digit Hydrogenated Nanodiamond Dispersion, and Methods for Producing the Same |
| CN106635336A (en) * | 2016-12-15 | 2017-05-10 | 天长市润达金属防锈助剂有限公司 | Wear-resistant and pressure-resistant nanometer diamond microemulsion cutting fluid |
| CN109422262A (en) * | 2017-08-28 | 2019-03-05 | 深圳先进技术研究院 | A kind of super-dispersed nano diamond dispersion liquid and its preparation method and application |
-
2019
- 2019-09-30 CN CN201910944714.0A patent/CN110723732B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238411A (en) * | 2006-03-10 | 2007-09-20 | Naoki Komatsu | Nanodiamond |
| US20160115033A1 (en) * | 2013-05-31 | 2016-04-28 | Carbodeon Ltd Oy | Zeta Positive Hydrogenated Nanodiamond Powder, Zetapositive Single Digit Hydrogenated Nanodiamond Dispersion, and Methods for Producing the Same |
| JP2015127364A (en) * | 2013-12-27 | 2015-07-09 | カルボデオン リミティド オサケユイチア | Nanodiamond containing composite and method for producing the same |
| CN106635336A (en) * | 2016-12-15 | 2017-05-10 | 天长市润达金属防锈助剂有限公司 | Wear-resistant and pressure-resistant nanometer diamond microemulsion cutting fluid |
| CN109422262A (en) * | 2017-08-28 | 2019-03-05 | 深圳先进技术研究院 | A kind of super-dispersed nano diamond dispersion liquid and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114686171A (en) * | 2022-05-19 | 2022-07-01 | 中国振华集团云科电子有限公司 | Suspensible diamond grinding fluid and preparation process thereof |
| CN116589928A (en) * | 2023-05-17 | 2023-08-15 | 耐博检测技术(武汉)有限公司 | Super-dispersed diamond suspension and preparation method thereof |
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