CN106006628A - Method for preparing nanodiamond by means of high-current pulsed electron beams - Google Patents

Method for preparing nanodiamond by means of high-current pulsed electron beams Download PDF

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CN106006628A
CN106006628A CN201610537883.9A CN201610537883A CN106006628A CN 106006628 A CN106006628 A CN 106006628A CN 201610537883 A CN201610537883 A CN 201610537883A CN 106006628 A CN106006628 A CN 106006628A
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nano
carbon
sized carbon
metal
electron beams
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CN106006628B (en
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张贵峰
郝胜智
黄昊
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Dalian University of Technology
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Dalian University of Technology
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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
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites

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Abstract

The invention belongs to the technical field of advanced material preparation, and provides a method for preparing nanodiamond by means of high-current pulsed electron beams. The method comprises the steps that nanocarbon is selected as a raw material, and a metal catalyst is added through the two processes that 1, the metal catalyst is deposited on the nanocarbon by adopting a chemical plating method, and the nanocarbon plated with the metal catalyst and nanocarbon are mixed; 2, in a carbon containing atmosphere, arc discharge is conducted to evaporate the metal catalyst, and carbon coating metal nanoparticles are obtained; treated mixed powder is pressed into flakes for 1 min to 10 min under the pressure of 20 MPa to 50 MPa and then bombarded 5 times to 15 times through an electron cannon under the condition that the current intensity of the electron beams is 10 kA, the energy of the electron beams is 27 keV, and the pulse width of the electron beams is 3 microseconds to 6 microseconds after being pressed into the flakes, and finally collection and purification are conducted. According to the method, the catalytic effect of the catalyst can be improved to the maximum limit through the adding mode of the metal catalyst; the electron beams are high in energy density, micro-area phase changes are more beneficial for diamond conversation, and the conversion rate is increased.

Description

A kind of high-current pulsed electron beam prepares the method for Nano diamond
Technical field
The invention belongs to advanced material preparing technical field, relate to the interaction of energetic particle beam and material with And the change of material phase structure.After being related specifically to carbon nanomaterial pretreatment, bombard at high-power electron beam Under so that it is the thermodynamics and kinetics condition of high pressure high temperature growth diamond is met at microcosmic, so that carbon material Material is changed into Nano diamond granule.
Background technology
Diamond has a lot of excellent properties, such as high rigidity, high-termal conductivity, high optical transmission, insulating properties etc., Thus at machinery, the energy, electronics, the field such as Aero-Space has broad application prospects.At present, preparation gold The method of hard rock has a lot, has liquid phase method, liquid phase method and solid phase method etc., and the diamond of preparation is mainly with granule Exist with two kinds of forms of thin film.In vapor phase method, hot filament CVD and microwave plasma chemical gas The application of phase sedimentation is the most universal, and the product obtained is diamond thin, by controlling technological parameter and gas Kind, it is possible to obtain nano-diamond film.Common solid phase method has high temperature and high pressure method and laser ablation method etc., The product obtained is based on graininess.Liquid phase method is with carbon containing organic solvent as reactant, under low-temp low-pressure Electrochemical decomposition and obtain diamond thin, this method obtain Diamond Thin Film Quality need to be carried further High.
According to growth mechanism, artificially synthesizing diamond can be divided into balance change and non-equilibrium transformation, vapor phase method It is generally non-equilibrium transformation, the High Temperature High Pressure that solid phase rule is mainly formed with simulation natural diamond with liquid phase method Growth conditions, makes graphite be changed into diamond by equilibrium phase change.Product is many in nanometer, micron or millimeter Grain, in abrasive wear, the field such as electrochemical deposition composite has a extensive future.
High Temperature High Pressure can be carried out at static pressure and dynamic pressure both of which, all by nature diamond growth conditions Inspire.The pressure of static state high-temperature high-pressure process is at 3-10GPa, and temperature is at 1000-2000 DEG C；During dynamic method effect Between short, pressure and temperature can not be controlled by respectively.Under the effect of high energy beam, microcosmos area exists satisfied The superhigh-temperature and-pressure condition of diamond film, such as, with high energy pulse laser method irradiate be placed in gas medium or Graphite in liquid medium or white carbon black target so that it is after high-temperature heating, quenching obtains diamond.The energy of laser is close Degree is about 106W/cm2Magnitude, and the energy density of high-power electron beam can reach 109W/cm2Magnitude, because of This, bombard material with carbon element with high-power electron beam, it is entirely possible to obtains Nano diamond.
Summary of the invention
It is an object of the invention to utilize high energy pulse beam bombardment material with carbon element so that it is be changed into Nano diamond Granule.Energy density about 3 orders of magnitude higher than the energy density of pulse laser of high energy pulse electron beam, electricity The microcosmos area of son bundle bombardment more likely meets graphite under high temperature and high pressure environment and is changed into the thermodynamics of diamond And dynamic conditions.
Technical scheme:
A kind of high-current pulsed electron beam prepares the method for Nano diamond, and step is as follows:
Selection nano-sized carbon is raw material, addition two kinds of techniques of employing of metal solvent:
(1) use chemical plating method to be deposited in nano-sized carbon by metal solvent, the nano-sized carbon of metal solvent will be coated with Mix with nano-sized carbon；
First, the nano-sized carbon after prerinse is carried out roughening treatment, then cleans with deionized water, filter, dry Dry；Secondly, utilize chemical plating fluid nano-sized carbon plating metal on surface ferrum, cobalt, nickel or and alloy 10-30s, Plated nano-sized carbon deionized water is cleaned, filters, dries, the nano-sized carbon of metal solvent must be coated with； Mix being coated with the nano-sized carbon of metal solvent and nano-sized carbon in 5-20% ratio and be scattered in ethanol, sonic oscillation 5-10min, filters, and is dried；Finally, the mixed powder handled well is pressed into lamellar, pressure 20-50MPa, protects Holding 1-10min, be 10kA with high-current pulsed electron beam in electronic beam current intensity after tabletted, energy is 27keV, pulse width is bombarded 5-15 time under conditions of 3-6 μ s, is finally collected purification.
(2) in carbon-containing atmosphere, arc discharge evaporation catalyst metal, it is thus achieved that carbon-clad metal nano particle.
The addition of metal solvent uses DC arc plasma: metal or alloy catalyst is made anode stub, High purity graphite is negative electrode, and reative cell is evacuated to 1 × 10-5After Pa, it is passed through methane 1-5 × 104Pa, is putting Electricity electric current 80-100A, under voltage 30-50V, two interpolars produce arc discharge, collect carbon-clad metal nanoparticle Son；Carbon-clad metal nano particle and nano-sized carbon are mixed in 5-20% ratio and is scattered in ethanol, Under Ultrasonic Vibration Swing 5-10min, filter, be dried；The mixed powder handled well is pressed into lamellar, pressure 20-50MPa, keeps 1-10min, is 10kA with electronics big gun in electronic beam current intensity after tabletted, and energy is 27keV, pulse width Degree bombards 5-15 time under conditions of 3-6 μ s, finally collects purification.
Described nano-sized carbon is CNT, nanometer C60/C70, nano-graphene, nano-graphite etc., wherein, Carbon nanotube diameter is between 2-20nm.
The invention have the advantages that: the feed postition of metal solvent can improve catalyst catalysis effect to greatest extent Really；Beam energy density is high, and microcell phase transformation is more beneficial for diamond and changes, and improves conversion ratio.
Detailed description of the invention
Below in conjunction with technical scheme, further illustrate the detailed description of the invention of the present invention.
Embodiment 1:
(1) clean: nano-sized carbon is dispersed in ethanol solution, ultrasonic 8min, after filtration, is placed in 10%NaOH molten Ultrasonic 6min in liquid, repeatedly cleans with deionized water and dries.
(2) roughening treatment: cleaned nano-sized carbon is placed in 160g/L ammonium peroxydisulfate and the mixing of 80ml/L sulphuric acid is thick Change in liquid, electromagnetic agitation 6min under room temperature, it is washed with deionized water after roughening to neutrality, dries stand-by.
(3) chemical nickel plating: chemical nickel-plating liquid includes Nickel dichloride. (30g/L), sodium hypophosphite (10g/L), hydroxyacetic acid Sodium (50g/L), boric acid (5g/L) etc..After chemical nickel plating liquid temp reaches 88-92 DEG C, by roughening treatment After nano-sized carbon be placed in plating solution, deposition 20s after take out, repeatedly clean with deionized water and be dried.
(4) nano-sized carbon of non-nickel plating mixes with the nano-sized carbon of nickel coated, and wherein the percentage by weight of nickel coated nano-sized carbon is 10%, mixed powder is scattered in alcoholic solution, filters after sonic oscillation 6min and be dried.By handle well Mixed powder is pressed into lamellar, pressure 40MPa, keeps 8min.
(5) sheet sample is fixed on target, is evacuated to 6 × 10-3Start after more than Pa to use beam bombardment sample, Bombard 10 times.Wherein, electronic beam current intensity is 10kA, and energy is 27keV, and pulse width is at 4 μ s；Electricity The beam spot area about 30mm of son bundle2。
(6) the nano powder acid of sample and collection being carried out purification processes, clean to neutral with deionized water, vacuum is dried Dry.
Embodiment 2:
(1) using DC arc plasma, with block Ni that purity is 99.99% as anode, graphite rod be the moon Pole.Reative cell is evacuated to 1 × 10-5After Pa, it is passed through methane 1-5 × 104Pa, regulates electrode spacing, adds Enter voltage and produce arc discharge, discharge current 90A, voltage 40V at two interpolars.Metallic is at carbon containing gas Forming core in atmosphere, grows up, and is condensate on water-cooled locular wall, collects nano-powder after Passivation Treatment.
(2) nano-powder that carbon is coated with is scattered in alcoholic solution, filters after sonic oscillation 6min and be dried.At Jiang The nano-powder managed is pressed into lamellar, pressure 30MPa, keeps 6min.
(3) sheet sample is fixed on target, is evacuated to 1 × 10-5Start after more than a to use beam bombardment sample, Bombard 12 times.Wherein, electronic beam current intensity is 10kA, and energy is 27keV, and pulse width is at 5 μ s；Electricity The beam spot area about 30mm of son bundle2。
(4) the nano powder acid of sample and collection being carried out purification processes, clean to neutral with deionized water, vacuum is dried Dry.
Embodiment 3:
(1) clean: nano-sized carbon is dispersed in ethanol solution, ultrasonic 8min, after filtration, is placed in 10%NaOH molten Ultrasonic 6min in liquid, repeatedly cleans with deionized water and dries.
(2) roughening treatment: cleaned carbon nanopowder is placed in 160g/L ammonium peroxydisulfate and the mixing of 80ml/L sulphuric acid In coarsening solution, electromagnetic agitation 6min under room temperature, it is washed with deionized water after roughening to neutrality, dries stand-by.
(3) chemical plating iron: chemical plating iron liquid includes Ferrous ammonium sulfate (16g/L), sodium borohydride (3.2g/L), Fructus Citri Limoniae Acid sodium (60g/L), lactic acid (20g/L), propanoic acid (10g/L), boric acid (2g/L), saccharin (0.5g/L), Glycine betaine (0.2g/L).After chemical plating iron liquid temp reaches 48-52 DEG C, by the carbon nanometer after roughening treatment Powder is placed in plating solution, takes out, repeatedly clean with deionized water and be dried after deposition 30s.
(4) nano-sized carbon that the nano-sized carbon of non-plating iron is coated with ferrum mixes, and wherein the percentage by weight of ferrum coating nano carbon is 15%, mixed powder is scattered in alcoholic solution, filters after sonic oscillation 6min and be dried.By handle well Mixed powder is pressed into lamellar, pressure 40MPa, keeps 8min.
(5) sheet sample is fixed on target, is evacuated to 6 × 10-3Start after more than Pa to use beam bombardment sample, Bombard 10 times.Wherein, electronic beam current intensity is 10kA, and energy is 27keV, and pulse width is at 4 μ s；Electricity The beam spot area about 30mm of son bundle2。
(6) the nano powder acid of sample and collection being carried out purification processes, clean to neutral with deionized water, vacuum is dried Dry.
Embodiment 4:
(1) using DC arc plasma, with block Fe that purity is 99.99% as anode, graphite rod be the moon Pole.Reative cell is evacuated to 1 × 10-5After Pa, it is passed through methane 1-5 × 104Pa, regulates electrode spacing, adds Enter voltage and produce arc discharge, discharge current 90A, voltage 40V at two interpolars.Metallic is at carbon containing gas Forming core in atmosphere, grows up, and is condensate on water-cooled locular wall, collects nano-powder after Passivation Treatment.
(2) nano-powder that carbon is coated with is scattered in alcoholic solution, filters after sonic oscillation 6min and be dried.At Jiang The nano-powder managed is pressed into lamellar, pressure 30MPa, keeps 6min.
(3) sheet sample is fixed on target, is evacuated to 1 × 10-5Start after more than Pa to use beam bombardment sample, Bombard 12 times.Wherein, electronic beam current intensity is 10kA, and energy is 27keV, and pulse width is at 5 μ s；Electricity The beam spot area about 30mm of son bundle2。
(4) the nano powder acid of sample and collection being carried out purification processes, clean to neutral with deionized water, vacuum is dried Dry.

Claims (3)

1. the method that a high-current pulsed electron beam prepares Nano diamond, it is characterised in that step is as follows:
Selection nano-sized carbon is raw material, the addition technique of metal solvent:
Use chemical plating method to be deposited in nano-sized carbon by metal solvent, by be coated with the nano-sized carbon of metal solvent with Nano-sized carbon mixes；
First, the nano-sized carbon after prerinse is carried out roughening treatment, then cleans with deionized water, filter, dry Dry；Secondly, utilize chemical plating fluid nano-sized carbon plating metal on surface ferrum, cobalt, nickel or and alloy 10-30s, Plated nano-sized carbon deionized water is cleaned, filters, dries, the nano-sized carbon of metal solvent must be coated with； Mix being coated with the nano-sized carbon of metal solvent and nano-sized carbon in 5-20% ratio and be scattered in ethanol, sonic oscillation 5-10min, filters, and is dried；
The mixed powder handled well is pressed into lamellar, pressure 20-50MPa, keeps 1-10min, after tabletted Being 10kA with high-current pulsed electron beam in electronic beam current intensity, energy is 27keV, and pulse width is at 3-6 μ s Under conditions of bombard 5-15 time, finally collect purification.
2. the method that a high-current pulsed electron beam prepares Nano diamond, it is characterised in that step is as follows:
Selection nano-sized carbon is raw material, the addition technique of metal solvent:
In carbon-containing atmosphere, arc discharge evaporation catalyst metal, it is thus achieved that carbon-clad metal nano particle；
The addition of metal solvent uses DC arc plasma: metal or alloy catalyst is made anode stub, High purity graphite is negative electrode, and reative cell is evacuated to 1 × 10-5After Pa, it is passed through methane 1-5 × 104Pa, in electric discharge Electric current 80-100A, under voltage 30-50V, two interpolars produce arc discharge, collect carbon-clad metal nano particle； Carbon-clad metal nano particle and nano-sized carbon are mixed in 5-20% ratio and is scattered in ethanol, sonic oscillation 5-10min, filters, and is dried, obtains mixed powder；
The mixed powder handled well is pressed into lamellar, pressure 20-50MPa, keeps 1-10min, after tabletted Being 10kA with high-current pulsed electron beam in electronic beam current intensity, energy is 27keV, and pulse width is at 3-6 μ s Under conditions of bombard 5-15 time, finally collect purification.
Method the most according to claim 1 and 2, it is characterised in that described nano-sized carbon is CNT, receives Rice C60/C70, nano-graphene or nano-graphite, wherein, carbon nanotube diameter is between 2-20nm.
CN201610537883.9A 2016-07-09 2016-07-09 A kind of method that high-current pulsed electron beam prepares Nano diamond Expired - Fee Related CN106006628B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111003705A (en) * 2019-12-25 2020-04-14 大连理工大学 Method for in-situ generation of graphene by irradiation of graphite with high-current pulsed electron beam

Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2006183102A (en) * 2004-12-28 2006-07-13 Shinshu Univ Porous diamond layer, method for producing porous diamond particle and electrode for electrochemistry using them
CN102210999A (en) * 2011-06-10 2011-10-12 东北大学 Method for synthesizing nano diamond by irradiating graphite suspension with high current pulsed electron beam
CN103320829A (en) * 2013-06-06 2013-09-25 大连理工大学 Preparation method of solution used in diamond thin film electrochemical synthesis
CN103482623A (en) * 2013-09-05 2014-01-01 大连理工大学 Method for preparing nano diamonds by using direct-current arc process
US20140057097A1 (en) * 2012-08-22 2014-02-27 National Defense University Method for fabricating coiled nano carbon material, coiled nano carbon layered substrate and coiled nano carbon material thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006183102A (en) * 2004-12-28 2006-07-13 Shinshu Univ Porous diamond layer, method for producing porous diamond particle and electrode for electrochemistry using them
CN102210999A (en) * 2011-06-10 2011-10-12 东北大学 Method for synthesizing nano diamond by irradiating graphite suspension with high current pulsed electron beam
US20140057097A1 (en) * 2012-08-22 2014-02-27 National Defense University Method for fabricating coiled nano carbon material, coiled nano carbon layered substrate and coiled nano carbon material thereof
CN103320829A (en) * 2013-06-06 2013-09-25 大连理工大学 Preparation method of solution used in diamond thin film electrochemical synthesis
CN103482623A (en) * 2013-09-05 2014-01-01 大连理工大学 Method for preparing nano diamonds by using direct-current arc process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111003705A (en) * 2019-12-25 2020-04-14 大连理工大学 Method for in-situ generation of graphene by irradiation of graphite with high-current pulsed electron beam
CN111003705B (en) * 2019-12-25 2021-09-24 大连理工大学 Method for in-situ generation of graphene by irradiation of graphite with high-current pulsed electron beam

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