CN103482623B - Method for preparing nano diamonds by using direct-current arc process - Google Patents
Method for preparing nano diamonds by using direct-current arc process Download PDFInfo
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- CN103482623B CN103482623B CN201310401410.2A CN201310401410A CN103482623B CN 103482623 B CN103482623 B CN 103482623B CN 201310401410 A CN201310401410 A CN 201310401410A CN 103482623 B CN103482623 B CN 103482623B
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Abstract
The invention discloses a method for preparing nano diamonds by using a direct-current arc process, belonging to the technical field of preparation of carbon-related nano materials. The method is characterized in that direct-current arc hydrogen plasma is used as a heat source, graphite is used as a carbon source, nickel is used as a catalyst and silicon is used as a nucleation substance to synthesize diamond nano-particles. High-temperature hydrogen plasma is used for evaporating a block composite target material to form atomic and ionic states of raw material components, a silicon carbide cluster crystal nucleus is formed and atoms are induced to form a diamond phase during condensation, carbon atoms separated out from a supersaturated nickel-carbon solid solution become growth substances for the diamond phase, and a nano diamond blank is obtained through passivation. The remaining impurities including metals, graphite, amorphous carbon, silicon carbide and the like are removed through purification processes including acid treatment, high-temperature oxidation, rinsing and the like so as to obtain high-purity diamond nano-particles. The method disclosed by the invention has the effects and benefits that the preparation process is simple, the synthesis is performed under a normal pressure condition, and the low cost, low energy consumption and large-scale production of the diamond nano-particles are realized.
Description
Technical field
The invention belongs to carbon to be correlated with technical field of nanometer material preparation.Be carbon source in particular to one with graphite, nickel is catalyzer, silicon is forming core material, utilize DC arc plasma for thermal source, the method for synthesizing nanometer diamond particle under high-temperature pressure condition.
Background technology
Diamond is widely used in science and technology and chemical industrial field owing to having unique physicochemical property.Nano diamond also has the characteristic of nano material except having adamantine essential property, and application prospect is very wide.
Nano diamond main preparation methods has: high pressure-temperature synthesis method, namely produces continuous high temperature with direct current or alternating-current by graphite, and the temperature of reaction is generally 2300-2500 DEG C, and pressure is 12-25GPa.This method needs strict control pressure and temperature condition, proposes higher requirement to equipment; Explosion method, utilize oxygen negative explosive to carry out the formation of Nano diamond, the reaction times is short, and reaction process is complicated, restive and have certain danger; Chemical Vapor deposition process, with liquid phase or gas phase carbonaceous material for carbon source, at deposited on substrates carbon atom growing nano diamond.The method output is lower, and quality also can be restricted; Pulsed laser deposition, can carry out under room temperature or low temperature, and sedimentation velocity is fast, and effective, do not introduce impurity, be convenient to prepare composite parts film, but the capacity usage ratio of laser technology only has 20%, energy dissipation is more serious.Applying of above technology all serves certain active effect to the adamantine Quality and yield of raising, but also there is limitation separately, shortcomings such as such as there is severe reaction conditions, yield poorly, purity is low, therefore develops a kind of high-level efficiency, the novel method of synthesizing nano diamond of less energy-consumption has great importance.
Summary of the invention
The object of this invention is to provide a kind of method that direct current arc method prepares Nano diamond, utilize and automatically control direct-current plasma equipment (China Patent No.: 200410021190.1), take graphite as carbon source, high temperature (about 3000K) hydrogen plasma utilizing ionization hydrogen to be formed is thermal source, anode graphite is made to be evaporated to atom, ion state carbon component, at catalyzer, under the effect of nucleus and condensation atmosphere, through forming core, growth process, final formation diamond nano particle, be difficult to reach to solve the reaction conditions existed in existing diamond technology of preparing, reaction process is complicated, generation diamond yields poorly, the shortcomings such as purity is low.
Technical scheme of the present invention is:
Use and automatically control DC arc plasma equipment, with micron order Graphite Powder 99, nickel powder and silicon powder mixture briquetting, as anode composite target material, wherein nickel as catalyzer, silicon as diamond nucleation seed crystal material.Using graphite rod as negative electrode, in a certain proportion of reactive gas and rare gas element mixed atmosphere, evaporate block material target, obtain Nano diamond stock, after purified technique, obtain diamond nano particle.Concrete technology step is:
1. using the micron order Graphite Powder 99 of certain mass ratio, nickel powder and silicon powder mixture briquetting as anode composite target material, put into crucible and be placed on electric arc furnace copper seat, by negative electrode graphite rod just to above crucible material block, keep 3-5mm gap.
2. reaction chamber internal pressure is evacuated to 10 by device systems
-2pa, passes into certain proportion activity and inert mixed gas, cools.Between two electrodes, produce high temperature hydrogen plasma body after striking, regulate two interpole gaps to keep arc stability, the block material target in evaporator crucible.
3. evaporate block material target and form gaseous state smog, be deposited on reaction chamber water wall gradually, form nano-powder.After to be evaporated, deposition process completes, carry out Passivation Treatment, collect nano-powder and namely obtain Nano diamond stock.
4. above-mentioned stock powder being inserted mass concentration per-cent is in the dust technology of 5-20%, fully stirs, and dissolves and removes metallic impurity.After powder precipitation, upper solution is poured out, again add dust technology and stir, repeatedly carry out 3-6 time, then by rinsed with deionized water to neutral, after drying, obtain the powder of preliminary purification.
5. the preliminary purification powder obtained in step 4 being inserted a small amount of mass concentration per-cent is in the vitriol oil of 70%, is heated to 200 DEG C, and instilling concentration is subsequently the concentrated nitric acid of 65%, and titration speed is about 60 droplets/minute.By rinsed with deionized water to neutral, after drying, obtain the powder be further purified.
6. the purifying powder will obtained in step 5, carries out high temperature oxidation process in pure oxygen atmosphere, removes the impurity such as residue graphite, amorphous carbon, silicon carbide.
7. step 4-6 is repeated 3 to 5 times, obtain the high-purity diamond nanoparticle of abundant purifying.
In above-mentioned processing step 1-7:
Nickel catalyzator described in technical scheme, refers in raw materials evaporate process and forms supersaturation Ni-C sosoloid, in condensation process, separate out carbon atom, as the carbon growth substance that diamond is formed mutually;
Micron order Graphite Powder 99 described in technical scheme, refers to the carbon raw material of synthesizing nano diamond in evaporative process and the carbon raw material of silicon carbide nucleus;
Forming core seed crystal material described in technical scheme, refers to that first silicon form the SiC embryos with diamond lattic structure in evaporative process with carbon atom, and the carbon atom that induction is separated out is grown to diamond phase;
The micron order Graphite Powder 99 of the certain mass ratio described in step 1, nickel powder and silica flour mixture, the scope of its mass ratio C:Ni:Si is in 3:18 ~ 38:1 ~ 2;
Certain proportion mixed gas described in step 2, reactive gas refers to one or its combination of hydrogen, methane, ethane, acetylene, ethene, propylene, propine, propane, butane, butylene, rare gas element refers to one or its combination of argon gas, helium, neon, and reactive gas and inert gas ratio scope are 6 ~ 1:1;
Passivation Treatment described in step 3, refers to and carried out controlled oxidization process with containing the rare gas element of 5% trace oxygen to established nanoparticle surface before exposure air.
High temperature pure oxygen oxide treatment described in step 6, its temperature range is 400-800 DEG C.
Effect of the present invention and benefit are using graphite as forming the carbon growth substance of diamond phase, metallic nickel as catalyzer, silicon as forming core material, achieve the diamond nano particle synthesis under high-temperature pressure, avoid required harsh reaction conditions in prior art; Technique is simple, with the composite target material of micro-powder compacting for raw material, utilize hydrogen plasma thermal source, directly evaporation obtains Nano diamond stock, obtain high-purity diamond nanoparticle through purifying process, yield efficiency relative chemical vapour deposition process etc. has larger lifting; Can realize the low cost of diamond nano particle, less energy-consumption, large-scale production, product can be applicable to the field such as electrochemical electrode, abrasion-resistant coating material.
Accompanying drawing explanation
Accompanying drawing 1 be by embodiment synthesis Nano diamond stock (a) and preliminary purification after (b) XRD contrast collection of illustrative plates.Wherein symbol Δ represents diamond, ◆ represent graphite,
represent nickel, represent nickel dioxide,
represent silicon carbide.
Accompanying drawing 2 is HRTEM figure of the diamond nano particle by embodiment synthesis.
Accompanying drawing 3 be by embodiment synthesis Nano diamond stock (a) and preliminary purification after (b) Raman contrast collection of illustrative plates.
Embodiment
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment
Get mass percent be the micron order nickel powder of 85.5%, the silica flour of 4.5% and 10% Graphite Powder 99 mixture, briquetting after grinding evenly, contains into plumbago crucible as composite anode target.Graphite rod is negative electrode.Reaction chamber internal pressure is evacuated to about 10
-2pa, is filled with hydrogen and argon gas to 10 in the ratio of 6:1
5pa.Open cooling water system, switch on power and the starting the arc, regulate electric current and two interpole gaps to keep arc stability, block target in abundant evaporator crucible, formed gaseous atom, ion and through forming core, grow up, be gathered into nanoparticle after condensation process and be deposited in reaction chamber wall, collect nano-powder through passivation technology.
XRD before and after embodiment gained Nano diamond blank purifying contrasts collection of illustrative plates as shown in Figure 1 (a), (b) shows, shows 2 characteristic peaks having occurred diamond phase after concentrated acid purifying.
As shown in Figure 2, show its lattice parameter is 0.2nm to embodiment gained diamond nano particle HRTEM collection of illustrative plates, is (110) crystal face of cubic diamond.
Raman before and after embodiment gained diamond stock purifying contrasts collection of illustrative plates as shown in Fig. 3 (a) and (b), shows and occurred the Raman peak that diamond is corresponding after concentrated acid purifying.
Claims (1)
1. prepare the method for Nano diamond with direct current arc method for one kind, use direct current arc hydrogen plasma as thermal source, with composite block target for anode and raw material, block material is evaporated in the mixed atmosphere of reactive gas and rare gas element, obtain Nano diamond stock, then obtain high-purity diamond nanoparticle through purifying process, it is characterized in that:
A) composite block target is selected and is consisted of micron order Graphite Powder 99, nickel powder and silicon powder mixture briquetting, the mass ratio range of C:Ni:Si is 3:18 ~ 38:1 ~ 2, wherein micron order nickel powder is as the catalyzer of synthesizing nano diamond, the carbon raw material of micron order Graphite Powder 99 as synthesizing nano diamond and the carbon raw material of silicon carbide nucleus, micron order silica flour is as the silicon raw material of silicon carbide nucleus;
B) reactive gas selects one or its combination of hydrogen, methane, ethane, acetylene, ethene, propylene, propine, propane, butane, butylene, rare gas element selects one or its combination of argon gas, helium, neon, and reactive gas and inert gas ratio scope are 6 ~ 1:1;
C) purifying process selects mass concentration per-cent to be that the dilute nitric acid solution of 5-20% dissolves the metallic impurity removed in diamond stock, the mass concentration per-cent of 200 DEG C is selected to be the vitriol oil of 70%, and instill the concentrated nitric acid that concentration is 65%, titration speed is about 60 droplets/minute, remove the impurity such as metal, graphite in diamond stock, high temperature oxidation carries out in pure oxygen condition, temperature range is 400-800 DEG C, remove the impurity such as residue graphite, amorphous carbon, silicon carbide in diamond stock, repeat 3-5 technique and finally obtain high-purity diamond nanoparticle.
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| CN106564896B (en) * | 2015-10-09 | 2018-08-31 | 江苏天一超细金属粉末有限公司 | A method of extraction diamond |
| CN106006628B (en) * | 2016-07-09 | 2018-06-08 | 大连理工大学 | A kind of method that high-current pulsed electron beam prepares Nano diamond |
| CN106365685B (en) * | 2016-08-29 | 2021-04-02 | 河南飞孟金刚石工业有限公司 | Purification process of white artificial diamond |
| CN106744931B (en) * | 2016-12-09 | 2018-11-02 | 哈尔滨工业大学 | A kind of method that plasma etching graphite prepares diamond particles |
| CN111118471A (en) * | 2020-01-15 | 2020-05-08 | 吉林大学 | Preparation method of high-quality polycrystalline diamond film |
| CN111617700B (en) * | 2020-05-27 | 2022-10-04 | 富耐克超硬材料股份有限公司 | Diamond and preparation method thereof |
| CN111661843B (en) * | 2020-05-27 | 2022-12-13 | 富耐克超硬材料股份有限公司 | Activated nano graphite powder and preparation method thereof |
| CN113809304B (en) * | 2021-09-17 | 2023-03-03 | 青岛科技大学 | Preparation method and application of plasma-based tin dioxide/carbon nanotube composite material |
| CN114540791B (en) * | 2022-03-04 | 2023-05-09 | 杭州超然金刚石有限公司 | Process and equipment for preparing artificial diamond |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084489A (en) * | 1993-08-23 | 1994-03-30 | 复旦大学 | A kind ofly prepare adamantine method from graphite or carbonaceous solid matter |
| CN1105903A (en) * | 1994-01-24 | 1995-08-02 | 成都科技大学 | Method of synthetizing diamond with silicon carbide and metal |
| US5756061A (en) * | 1990-11-13 | 1998-05-26 | White; John L. | Diamond synthesis from silicon carbide |
| CN1260733A (en) * | 1997-04-17 | 2000-07-19 | 德比尔斯工业钻石部门有限公司 | Sintering process for diamond and diamond growth |
| CN102616776A (en) * | 2012-04-09 | 2012-08-01 | 江苏金海丰硬质材料科技有限公司 | Purification method of nano diamond ash material |
| CN102791629A (en) * | 2010-03-16 | 2012-11-21 | 设计材料有限公司 | Method for synthesising diamond |
-
2013
- 2013-09-05 CN CN201310401410.2A patent/CN103482623B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756061A (en) * | 1990-11-13 | 1998-05-26 | White; John L. | Diamond synthesis from silicon carbide |
| CN1084489A (en) * | 1993-08-23 | 1994-03-30 | 复旦大学 | A kind ofly prepare adamantine method from graphite or carbonaceous solid matter |
| CN1105903A (en) * | 1994-01-24 | 1995-08-02 | 成都科技大学 | Method of synthetizing diamond with silicon carbide and metal |
| CN1260733A (en) * | 1997-04-17 | 2000-07-19 | 德比尔斯工业钻石部门有限公司 | Sintering process for diamond and diamond growth |
| CN102791629A (en) * | 2010-03-16 | 2012-11-21 | 设计材料有限公司 | Method for synthesising diamond |
| CN102616776A (en) * | 2012-04-09 | 2012-08-01 | 江苏金海丰硬质材料科技有限公司 | Purification method of nano diamond ash material |
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