CN110723732B - Preparation method of super-dispersed nano-diamond suspension - Google Patents
Preparation method of super-dispersed nano-diamond suspension Download PDFInfo
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- 239000002113 nanodiamond Substances 0.000 title claims abstract description 103
- 239000000725 suspension Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 101
- 239000010432 diamond Substances 0.000 claims abstract description 101
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000011324 bead Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 23
- -1 aromatic amine compounds Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000010296 bead milling Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 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
- 239000000243 solution Substances 0.000 claims description 12
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 9
- 238000005268 plasma chemical vapour deposition Methods 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
- 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
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000004050 hot filament vapor deposition Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000005474 detonation Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229960004050 aminobenzoic acid Drugs 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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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 alkali solution, controlling the temperature at 20-95 ℃, preserving heat, washing, drying and calcining; (2) preparing diamond pretreatment liquid: dispersing calcined diamond in deionized water by ultrasonic, adding aromatic amine compounds and nitrous acid ester compounds to obtain diamond suspension, and cooling to obtain diamond pretreatment liquid; (3) wet fine grinding: adding the diamond pretreatment liquid into a bead mill with a screen, and performing bead milling to obtain a diamond suspension; (4) centrifugal dispersion: and (3) performing ultrasonic dispersion on the diamond suspension, and centrifugally collecting supernatant to obtain the ultra-dispersed nano-diamond suspension. The preparation method of the super-dispersed nano-diamond suspension has the advantages that the diamond particle size distribution of the prepared nano-diamond suspension is concentrated, the size is uniform, and the agglomeration is avoided.
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 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. Accordingly, nanodiamonds have been widely used in various fields such as abrasives, cutting tools, biosensors, electrochemical electrodes, and the like.
Detonation is the main method for producing nano-diamond at present, and graphite in a closed state is converted into diamond by the transient high-temperature high-pressure low-oxygen condition generated by explosion of explosive (such as TNT-RDX mixed explosive). The detonation method has low cost and high speed, but the obtained diamond raw powder has high impurity content (the ratio can reach 80%). This is due to the non-uniform temperature produced by the detonation method, and the resulting detonation method diamond has low crystallinity. In addition, the obtained diamond contains a large amount of unconverted graphite and other amorphous carbon, and in order to remove impurities in the detonation method diamond, in the prior art (for example, CN 107074555A is entitled as a suspension of nano diamond aggregate and nano diamond single digit nano dispersion), diamond raw materials are placed in strong acid, and graphite is removed under the condition of heating by utilizing the oxidizing property of the strong acid. In practical operation, because the graphite content in the diamond raw materials of different batches is greatly different, the pair of technology has the defects of multiple uncontrollable factors, large oxidation time selection span, high requirement on personnel experience and large generation of strong acid waste liquid, and is not beneficial to wide application. In addition, although the diameter of the particle size of the 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 the particle size ranges from nano scale to millimeter.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a preparation method of the super-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 method comprises the following steps:
(1) Diamond pretreatment: adding diamond into 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 diamond pretreatment liquid: dispersing calcined diamond in deionized water by ultrasonic, adding aromatic amine compounds and nitrous acid ester compounds to obtain diamond suspension, heating and preserving the diamond suspension for a certain time, and then cooling to obtain diamond pretreatment liquid;
(3) Wet fine grinding: adding the diamond pretreatment liquid into a bead mill with a screen, and collecting diamond suspension flowing out of the screen after the bead mill is carried out for a certain time;
(4) And (3) centrifugal dispersion: and (3) carrying out ultrasonic dispersion on the diamond suspension, and centrifugally collecting supernatant to obtain the ultra-dispersed nano-diamond suspension.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the step 1), wherein the diamond is prepared by a CVD method; the CVD method is one of a plasma CVD method, a microwave plasma CVD method, and a hot filament CVD method. Chemical deposition (CVD) is a commercially available surface technology that enables rapid production of nanodiamond. Since self-grown diamond is very costly, a suitable substrate is generally selected when diamond is grown by CVD, nanodiamond is deposited on the substrate in the form of a film under high temperature and high pressure, and the gas used to produce nanodiamond is mostly a mixture of hydrogen and a carbon-containing gas (e.g., methane) that is used to provide a carbon source during the deposition of diamond. The hydrogen gas may etch non-diamond phases (e.g., graphite, amorphous carbon) formed during the deposition of the nanodiamond. 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 nano diamond solution.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the steps of forming a diamond film on a 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 an alkali solution which is one or two of potassium hydroxide solution and sodium hydroxide solution, wherein the mass fraction is 30-40 wt%. The alkaline solution may remove the nanodiamond base substrate.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the steps of (1) calcining at a vacuum degree of less than 10 -2 mbar, the calcination temperature is 900-1200 ℃, and the calcination 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 0.001-10wt%.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the following steps of (2) preparing an aniline compound from one or more of para-aminobenzoic acid and aminobenzenesulfonic acid; the nitrous acid ester compound is isoamyl nitrite; the molar concentration of the aniline compound and the nitrous acid ester compound in the pretreatment liquid is 10 -4 ～10 - 2 mol/L. Aromatic amine compound and nitrous oxide added in water for dispersing diamond particlesThe acid ester compound can encapsulate diamond particles, and bridge different aromatic functional groups on the surface of the diamond, so that the re-agglomeration of the nano diamond in the subsequent process can be prevented.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the step (2) of heating the diamond suspension at 40-90 ℃ for 1-38 h.
Preferably, the preparation method of the ultra-dispersed nano-diamond suspension comprises the step (3) that the pore diameter of the screen is in the range of 0.50-500 mu m, and the rotating speed of the bead mill is in the range of 3000-6000 min -1 The bead grinding time is 1-8 h. The liquid medium used in the vibration type bead mill is deionized water or 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 (4) mixing the suspension with the suspension, wherein the mass fraction of the suspension is 0.005-3wt%; the ultrasonic dispersion time is 0.5-1 h, and the power is 200-800W; the rotational speed of the centrifugation is 1000-4000 rpm/min, and the centrifugation time is 0.5-8 h. The purpose of the centrifugal separation is to remove broken ceramic abrasives mixed into the diamond suspension during the vibration bead milling.
The beneficial effects of the invention are as follows:
(1) The preparation method of the super-dispersed nano-diamond suspension adopts high-quality nano-diamond film raw materials produced by a CVD technology to prepare the uniform super-dispersed nano-diamond suspension, and the diamond particle size of the prepared nano-diamond suspension is concentrated in distribution, uniform in size and free from agglomeration; in the preparation process of the diamond suspension, the prepared nano diamond suspension can be used as an abrasive, a heat dissipation additive and a diamond electrode seed crystal liquid without using reagents polluting the environment and human bodies, and can also be used in the field of biological medicine.
(2) According to the preparation method of the ultra-dispersed nano-diamond suspension, the high-quality nano-diamond film produced by a CVD technology is used as a raw material, and pollutants such as graphite, carbon and metal are almost negligible. Therefore, the prepared nano diamond solution has high quality. The base plate at the bottom of the nano-diamond is removed by an alkali solution, and the diamond particles can be coated by adding aromatic amine compounds and nitrous acid ester compounds into the aqueous solution in which the diamond particles are dispersed, so that 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 distribution diagram of a super-dispersed nano-diamond suspension prepared in example 1 of the present invention;
fig. 2 is a particle size distribution diagram of the ultra-dispersed nanodiamond suspension of example 1 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
Example 1:
the preparation method of the ultra-dispersed nano diamond suspension comprises the following steps:
(1) Adding diamond into 30wt% potassium hydroxide solution, immersing the silicon-based nano diamond film prepared by microwave plasma CVD in the potassium hydroxide solution, heating to 50 ℃ and preserving heat for 8 hours; wherein the substrate of the silicon-based nano diamond film is a silicon wafer, the nano diamond film consists of a plurality of layers of diamond particles with the grain diameter of 5-35 nm, nano diamond precipitate is collected and washed by deionized water for a plurality of times until the pH value is neutral, then the nano diamond precipitate is dried, the dried diamond precipitate is taken and put into a heating furnace with a vacuum function, and the heating furnace is vacuumized to 10 -3 mbar, then heating to 1000 ℃ at 100 ℃/min, and preserving heat for 1h;
(2) After the diamond obtained by calcination is dispersed in deionized water by ultrasonic, p-aminobenzoic acid and isoamyl nitrite are added; heating the obtained diamond suspension to 80 ℃, preserving heat for 24 hours, and cooling to obtain a diamond pretreatment liquid; wherein the mass fraction of diamond in deionized water is 6.05%; wherein the concentrations of the para-aminobenzoic acid and the isoamyl nitrite are respectively 0.0083mol/L and 0.0096mol/L.
(3) Diamond is madeThe pretreatment liquid is slowly and evenly dripped into a vibration type bead mill, the liquid medium used by the vibration type bead mill is aqueous solution containing 0.0083mol/L and 0.0096mol/L of p-aminobenzoic acid and isoamyl nitrite respectively, and the rotating speed of a rotor of the vibration type bead mill is set to 3000min -1 The abrasive used in 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 the diamond suspension with the mass fraction of 0.05wt% of diamond flowing out of the screen is collected after 4 hours of the vibration type bead mill.
(4) And (3) 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 0.005wt%, centrifuging the ultrasonic nano-diamond suspension at the rotating speed of 2000rpm for 1h, and collecting supernatant to finally obtain the super-dispersed nano-diamond suspension with the particle size of 20-60 nm.
As shown in fig. 1 and 2, it can be seen from fig. 1 that the Zeta potential of the ultra-dispersed nano-diamond particles prepared in this example is-55.5 mV, and the outermost charge of the outermost ultra-dispersed nano-diamond particles is negative. The absolute value of Zeta potential exceeds 30mV, indicating 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 between 20 and 60nm, and the particle size distribution is very concentrated, which indicates that the obtained nano-diamond has uniform size.
Example 2:
the preparation method of the ultra-dispersed nano diamond suspension comprises the following steps:
(1) Adding diamond into 30wt% sodium hydroxide solution, immersing the silicon-based nano diamond film prepared by the plasma CVD method into the sodium hydroxide solution, heating to 20 ℃ and preserving heat for 38 hours; wherein the substrate of the silicon-based nano diamond film is a silicon wafer, the nano diamond film consists of a plurality of layers of diamond particles with the grain size of 5-35 nm, nano diamond precipitate is collected and washed by deionized water for a plurality of times until the pH value is neutral, and then the silicon-based nano diamond precipitate is dried, and the dried diamond precipitate is put into a vacuumIn the functional heating furnace, the heating furnace is vacuumized to 10 -3 mbar, then heating to 1100 ℃ at 100 ℃/min, and preserving heat for 2 hours;
(2) After the diamond obtained by calcination is dispersed in deionized water by ultrasonic, aminobenzenesulfonic acid and isoamyl nitrite are added; heating the obtained diamond suspension to 50 ℃, preserving heat for 36 hours, and cooling to obtain a diamond pretreatment liquid; wherein the mass fraction of diamond in deionized water is 4.32%; wherein the concentrations of the para-aminobenzoic acid and the isoamyl nitrite are respectively 0.0031mol/L and 0.0075mol/L.
(3) Slowly and uniformly dripping diamond pretreatment liquid into a vibration type bead mill, wherein a liquid medium used by the vibration type bead mill is aqueous solution containing p-aminobenzoic acid and isoamyl nitrite with the concentration 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 5000min -1 The 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 the diamond suspension with the mass fraction of 0.07 weight percent 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 1wt%, centrifuging the ultrasonic nano-diamond suspension at the rotating speed of 3000rpm for 1h, and collecting supernatant to finally obtain the super-dispersion nano-diamond suspension with the particle size of 10-50 nm.
The Zeta potential of the super-dispersed nano-diamond particles prepared by the embodiment is-53.5 mV, the outermost charge of the outermost super-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 super-dispersed nano diamond prepared by the method is mainly distributed at 10-50 nm, and the particle size distribution is very concentrated, which indicates that the obtained nano diamond has uniform size.
Example 3:
the preparation method of the ultra-dispersed nano diamond suspension comprises the following steps:
(1) Diamond of Buddha's warriorAdding stone into 30wt% sodium hydroxide solution, immersing the silicon-based nano diamond film prepared by the plasma CVD method into the sodium hydroxide solution, heating to 95 ℃ and preserving heat for 1h; wherein the substrate of the silicon-based nano diamond film is a silicon wafer, the nano diamond film consists of a plurality of layers of diamond particles with the grain diameter of 5-35 nm, nano diamond precipitate is collected and washed by deionized water for a plurality of times until the pH value is neutral, then the nano diamond precipitate is dried, the dried diamond precipitate is taken and put into a heating furnace with a vacuum function, and the heating furnace is vacuumized to 10 -3 mbar, then heating to 1200 ℃ at 100 ℃/min, and preserving heat for 0.5h;
(2) After the diamond obtained by calcination is dispersed in deionized water by ultrasonic, p-aminobenzoic acid, aminobenzenesulfonic acid and isoamyl nitrite are added; heating the obtained diamond suspension to 90 ℃, preserving heat for 1 hour, and cooling to obtain a diamond pretreatment liquid; wherein the mass fraction of diamond in deionized water is 0.7%; wherein the concentrations of the para aminobenzoic acid, the aminobenzenesulfonic acid and the isoamyl nitrite are respectively 0.0047mol/L, 0.0051mol/L and 0.0093mol/L.
(3) Slowly and uniformly dripping diamond pretreatment liquid into a vibration type bead mill, wherein a liquid medium used by the vibration type bead mill is aqueous solution containing p-aminobenzoic acid, aminobenzenesulfonic acid and isoamyl nitrite with the concentration 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 6000min -1 The 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 the diamond suspension with the mass fraction of 0.25wt% 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 3wt%, centrifuging the ultrasonic nano-diamond suspension at the rotating speed of 1000rpm for 5h, and collecting supernatant to finally obtain the super-dispersion nano-diamond suspension with the particle size of 40-60 nm.
The Zeta potential of the super-dispersed nano-diamond particles prepared by the embodiment is-60.4 mV, the outermost charge of the outermost super-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 super-dispersed nano diamond prepared by the method is mainly distributed at 40-60 nm, and the particle size distribution is very concentrated, which indicates that the obtained nano diamond has uniform size.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. A method for preparing a super-dispersed nano-diamond suspension, which is characterized by comprising the following steps:
(1) Diamond pretreatment: adding diamond into 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 diamond pretreatment liquid: dispersing calcined diamond in deionized water by ultrasonic, adding an aniline compound and a nitrite compound to obtain a diamond suspension, heating and preserving the diamond suspension for a certain time, and then cooling to obtain a diamond pretreatment liquid;
the aniline compound is selected from one or more of para aminobenzoic acid and aminobenzenesulfonic acid; the nitrous acid ester compound is isoamyl nitrite;
(3) Wet fine grinding: adding the diamond pretreatment liquid into a bead mill with a screen, and collecting diamond suspension flowing out of the screen after the bead mill is carried out for a certain time; (4) centrifugal dispersion: and (3) carrying out ultrasonic dispersion on the diamond suspension, and centrifugally collecting supernatant to obtain the ultra-dispersed nano-diamond suspension.
2. The method of preparing a suspension of ultra-dispersed nanodiamond according to claim 1, wherein the diamond in step (1) is prepared by CVD method; the CVD method is one of a plasma CVD method, a microwave plasma CVD method, and a hot filament CVD method.
3. The method of preparing a suspension of ultra-dispersed nanodiamond of claim 2, wherein the diamond comprises a substrate and a diamond film disposed 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 alkaline solution in the step (1) is one or two of potassium hydroxide solution and sodium hydroxide solution, and the mass fraction is 30-40 wt%.
5. The method of preparing a suspension of ultra-dispersed nanodiamond according to claim 1, wherein the vacuum degree of calcination in the step (1) is less than 10 "2 mbar, the calcination temperature is 900 to 1200 ℃ and the calcination time is 0.5 to 2 hours.
6. The method of preparing a suspension of ultra-dispersed nanodiamond according to claim 1, wherein the mass concentration of the suspension of diamond in step (2) is 0.001 to 10wt%.
7. The method for preparing the ultra-dispersed nano-diamond suspension according to claim 1, wherein the molar concentration of the aniline compound and the nitrite compound in the pretreatment liquid is 10 < -4 > to 10 < -2 > mol/L.
8. The method for preparing the ultra-dispersed nano-diamond suspension according to claim 1, wherein the heating temperature of the diamond suspension in the step (2) is 40-90 ℃ and the heat preservation time is 1-38 h.
9. The method for preparing the ultra-dispersed nano-diamond suspension according to claim 1, wherein the screen pore size range of the step (3) is 0.50-500 μm, the rotation speed of the bead mill is 3000-6000 min-1, and 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 rotational speed of the centrifugation is 1000-4000 rpm/min, and the centrifugation time is 0.5-8 h.
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| 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 |
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| 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 |
| 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 |
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