CN108046268A - The method that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder - Google Patents
The method that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder Download PDFInfo
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- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
Argon gas is imported plasma generator by the method that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder first, starts plasma and power supply generation electric arc electric discharge occurs, form stable argon plasma arc；Hydrogen and methane are imported into plasma generator again, electric discharge is mixed with argon plasma and forms plasma jet；Then by the reactor below plasma jet importing plasma generator, while boron trichloride gas are imported from reactor, hitting the rapid completion vapor- phase synthesis that mixes with plasma jet reacts, space generation solid-state B4C and gaseous state HCl；Solid-state B4C forms nano boron carbide powder with quenching deposition on jet-impingement to the cooling wall for cooling down powder collector；Processing step is simple, a step finished product；Without exogenous impurity, boron carbide powder purity obtained is high and epigranular, can be used to prepare ceramic material without post processing, has better comprehensive advantage for plasma reaction ultrahigh in efficiency and gas phase reaction.
Description
Technical field
The present invention relates to technical field of inorganic non-metal material preparation more particularly to a kind of plasma enhanced chemical vapor to synthesize
The method that method prepares high-purity nm boron carbide powder.
Background technology
Boron carbide is due to high rigidity, high-modulus, high-melting-point, the spies such as low-density, wearability are good, acid-alkali-corrosive-resisting is strong
Point, and there is many advantages, such as higher neutron absorption capability and semiconducting electrical conductivity, in refractory material, hard material, work
It is used widely in the fields such as industry ceramics, bulletproof ceramic, nuclear industry, space flight and aviation and semi-conductor industry.Boron carbide ceramics material
It is that prepared by powder, shaping is with being sintered to prepare main technique, since boron carbide is a kind of very strong compound of covalent bond so that it is very
Difficulty is sintered, in order to improve sintering quality, it is necessary to use ultra-fine, high-purity boron carbide powder, the boron carbide powder of nanoscale
Spy of the body due to small-size effect, quantum effect, unsaturated valence effect and electron tunneling effect etc., making it have easy-sintering
Property, it is the important directions that boron carbide powder develops, there is very big Development volue and application prospect.
The industrial producing method of boron carbide powder mainly has self-propagating high-temperature synthetic method（SHS）And carbothermic method, in recent years
Also have laser chemistry gas-phase reaction method, sol-gel carbothermic method etc., self-propagating high-temperature synthetic method mostly using magnesium as
Fluxing agent, also known as magnesiothermy, have many advantages, such as it is energy saving, be swift in response, but shortcoming is the granularity of synthesized boron carbide powder
Remaining magnesium and the oxidation extremely difficult thorough removing of magnesium addition only in micron order and reactant；Carbothermic method is by the chemical combination of boracic
Object and carbon dust are put into containing carbon compound in carbon shirt-circuiting furnace or electric arc furnaces, pass to protective gas synthesizing boron carbide at a certain temperature
Powder, the disadvantages of this method are that energy consumption is big, efficiency is low, the powder diameter of synthesis is big（20~40 μm）And contain and be difficult to what is removed
The impurity such as carbon dust or boric anhydride, the raw material as sintering boron carbide also need to substantial amounts of postprocessing working procedures, considerably increase and be produced into
This；Laser induced diffusion（LICVD）Be using reactant gas molecules to the absorption of specific wavelength laser beam and then
Thermal decomposition or chemical reaction are generated, superfines is formed through nucleating growth, this method production capacity is relatively low, and equipment is expensive, energy consumption
It is big and higher to the purity requirement of reaction raw materials；Sol-gel（sol-gel）Carbothermic method is by inorganic matter or metal alcohol
Salt by solution, colloidal sol, gel and cure, then it is thermally treated synthesis compound method, due to provide boron source boride very
It is difficult to form gel with other inorganic matters or organic matter, therefore with the complex process of this method synthesizing boron carbide and of high cost.
The content of the invention
Technical problem solved by the invention is that providing a kind of plasma enhanced chemical vapor synthetic method prepares high-purity nm
The method of boron carbide powder, to solve the disadvantage that in above-mentioned background technology.
Technical problem solved by the invention is realized using following technical scheme：
The method that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder, using plasma chemical gaseous phase are closed
The device that high-purity nm boron carbide powder is prepared into method prepares high-purity nm boron carbide powder, is as follows：
1）Argon gas is imported into plasma generator, starts plasma and power supply generation electric arc electric discharge occurs, form stable argon gas
Plasma arcs；
2）Hydrogen and methane are imported into plasma generator again, electric discharge is mixed with argon plasma and forms plasma jet,
The hydrogen atom and carbon atom that largely ionization ion and the reduction activation of dissociation are high are included in plasma jet；
3）Plasma jet is then imported into reactor below plasma generator, at the same from the boron chloride of reactor into
Stomata imports boron trichloride gas, is uniformly mixed rapidly with plasma jet shock, high temperature and active grain in plasma
C, H atom under the action of son in boron chloride scission of link and jet stream quickly carry out vapor- phase synthesis reaction, space generation solid-state B4C and
Gaseous state HCl；
4）Step 3）The solid-state B of middle generation4C forms nano-sized carbon with quenching deposition on jet-impingement to the cooling wall for cooling down powder collector
Change boron powder；
5）Step 4）In part nano boron carbide powder under the drive of air-flow into water absorb gas solid separation powder collector, powder
It is only absorbed by the water and gas overflowing, nano boron carbide powder is obtained after finally collecting powder and washed, drying.
In the present invention, step 1）In, 1.5~2m of argon flow amount3/ h, 0.3~0.5MPa of pressure start plasma hair
The power that raw power supply generates electric arc electric discharge is 10KW, and electric current is 105~115A, and voltage is 90~100V.
In the present invention, step 2）In, the volume flow ratio of hydrogen and methane is 4~6:1, supply gas pressure 0.3~
0.5MPa, adjusting the power supply of plasma generator makes its output power be 10~100KW.
In the present invention, step 3）In, the volume flow ratio of boron chloride and methane is 4:1, boron chloride heating temperature
40~60 DEG C, 0.3~0.5MPa of boron chloride supply gas pressure.
In the present invention, plasma enhanced chemical vapor synthetic method prepare high-purity nm boron carbide powder device include wait from
Daughter occur power supply, plasma generator, reactor, cooling powder collector, water absorb gas solid separation powder collector, tail gas absorber,
Argon gas source, hydrogen source, methane source of the gas and boron chloride source of the gas, wherein, the plasma generator is by polytetrafluoro insulated with material
The semienclosed container of composition, semienclosed container upper end closed lower ending opening, and cerium tungsten material is provided on semienclosed container top
Manufactured cathode, semienclosed container lower part are provided with anode made of copper product, and cathode occurs power cathode with plasma and connects
It connects, anode occurs positive pole with plasma and is connected；It is equipped with to pass through argon gas in plasma generator cathode bottom simultaneously
Source imports the argon inlet hole of argon gas, is equipped at the top of plasma generator anode and is used to import hydrogen by hydrogen source and passes through first
Alkane source of the gas imports the gaseous mixture air admission hole of methane；Plasma generator is built-in with cooling circulating water system and carries out cooling protection, is
It is operated in atmospheric pressure or the cooling of more anticyclonic plasma generator；The sealing of the lower end of the reactor and plasma generator connects
Connect, reactor head be symmetrical arranged there are two be used for by boron chloride source of the gas import boron trichloride gas boron chloride air inlet
Hole, boron chloride source of the gas are provided outside the boron chloride heating source that heating vaporization is carried out for boron chloride, reactor lower port
It is placed in cooling powder collector, the external jacket for cooling down powder collector is provided with recirculating cooling water system, cools down, and the water is inhaled
Gas solid separation powder collector is received to connect with the outlet of cooling powder collector, and in argon gas source, hydrogen source, methane source of the gas and boron chloride source of the gas
Four source outlet ends are respectively arranged with flowmeter, and the argon gas source is connected to plasma generator cathode after flowmeter measures
Bottom argon inlet hole, the hydrogen source are connected to plasma generator anode top after flowmeter measures respectively with methane source of the gas
The hydrogen in portion and methane mixed gas air admission hole, the boron chloride source of the gas is after the heating vaporization of boron chloride heating source again through flow
The boron chloride air admission hole of reactor head is connected to after meter metering, the water absorbs gas solid separation powder collector and tail gas absorber
Connection.
In the present invention, it is the direct-current arc power supply that output power is 10~100kW that power supply, which occurs, for the plasma.
In the present invention, the argon inlet hole, gaseous mixture air admission hole are annular line cutting structure.
In the present invention, the tubular reactor that the reactor is formed for external jacket containing water cooling and through hole graphite-pipe.
In the present invention, the cooling powder collector is settling cone by the cylindricality ladle body of top visor containing symmetrical openings, middle part
Shape ladle body and bottom form for accumulated powder tank.
In the present invention, the water, which absorbs, is provided with to connect stretching for cooling powder collector outlet on gas solid separation powder collector
Bottom tube and the air outlet pipe for connecting tail gas absorber.
In the present invention, the bottom tube of stretching stretches into 5cm below the water surface.
In the present invention, the flow is calculated as the spinner flowmeter of air calibration.
In the present invention, the tail gas absorber is tail gas spray absorber.
In the present invention, the argon gas uses always in the reaction, i.e., as purging substitution gas, and does protective gas,
The service life of plasma generator can be extended.
In the present invention, the argon gas, hydrogen, methane, the purity of boron chloride are 99.99%.
Advantageous effect：Using plasma reaction process step of the present invention is simple, can a step finished product；And plasma
The high temperature of generation and a large amount of active particles so that synthetic reaction rate is high, and production efficiency is high；It is non-in gas phase reaction system simultaneously
Product substance is with gas overflowing, and without exogenous impurity, boron carbide powder purity obtained is high；And plasma chemical vapor synthesis is anti-
The solid product that should be generated has the characteristics that space uniform nucleation and jet-impingement disperse to be quenched deposition with cold wall, makes carbon obtained
Change boron powder is ultra-fine and even particle size distribution, boron carbide powder yield can reach more than 68%, and the purity of product is up to 99%
More than, average grain diameter can be used to prepare ceramic material, with traditional handicraft side about between 30~80nm without post processing
Method, which is compared, has better comprehensive advantage.
Description of the drawings
Fig. 1 is the structure diagram of presently preferred embodiments of the present invention.
Fig. 2 is the boron carbide powder product SEM photograph in presently preferred embodiments of the present invention.
Fig. 3 is the boron carbide powder product X-ray diffraction in presently preferred embodiments of the present invention（XRD）Collection of illustrative plates.
Specific embodiment
In order to which the technical means, the creative features, the aims and the efficiencies achieved by the present invention is made to be readily apparent from clearly, tying below
Conjunction is specifically illustrating, and the present invention is further explained.
Referring to the method that the plasma enhanced chemical vapor synthetic method of Fig. 1~Fig. 3 prepares high-purity nm boron carbide powder, use
The device that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder prepares high-purity nm boron carbide powder, described
Plasma enhanced chemical vapor synthetic method prepare high-purity nm boron carbide powder device include plasma occur power supply 1, etc. from
Electronic generator 2, reactor 3, cooling powder collector 4, water absorb gas solid separation powder collector 5, argon gas source 6, hydrogen source 7, methane source of the gas
8th, boron chloride source of the gas 9, flowmeter 10, boron chloride heating source 11, tail gas spray absorber 12, stretch bottom tube 13 and air outlet pipe
14, wherein, it is direct-current arc power supply that power supply 1, which occurs, for the plasma, and output power is adjustable for 10~100kW, the grade from
2 top of electronic generator is rodlike cathode made of cerium tungsten material, and lower part is orificed anode made of copper product, and cathode and anode
The container of a upper end closed lower ending opening is made of polytetrafluoro insulated with material, cathode is connected with direct-current arc power cathode, sun
Pole is connected with direct-current arc positive pole；The cathode bottom of plasma generator 2 is equipped with annular tangent line argon inlet hole for leading to
Cross the importing of argon gas source 6 argon gas, anode top is equipped with annular tangent line hydrogen gas hole for dividing by hydrogen source 7 with methane source of the gas 8
Not Dao Ru hydrogen and methane gaseous mixture air admission hole；Plasma generator 2 carries out cooling guarantor using built-in cooling circulating water system
Shield, for be operated in atmospheric pressure or more anticyclonic direct-current arc heat plasma generator cooling, so there is no need under vacuum into
Row；The reactor 3 is the external jacket containing water cooling and through hole graphite-pipe composition being tightly connected with the lower end of plasma generator 2
Tubular reactor, 3 top of reactor are symmetrically arranged with boron chloride air admission hole for importing tri-chlorination by boron chloride source of the gas 9
Boron gas, the lower port of the reactor 3 are placed in the cooling powder collector 4, and cooling powder collector 4 is regarded by top containing symmetrical openings
The cylindricality ladle body of mirror, middle part are sedimentation shaping conical barrel and bottom is accumulated powder tank composition, and use external jacket recirculating cooling water system
It is cooled down, it is to stretch bottom tube 13 and air outlet pipe comprising what connection cooling powder collector 4 exported that the water, which absorbs gas solid separation powder collector 5,
14 sealing container, wherein stretching bottom tube stretches into 5cm below the water surface, the argon gas source 6 is connected to after the metering of flowmeter 10 etc. from
2 cathode bottom argon inlet hole of electronic generator, the hydrogen source 7 are connected to after the metering of flowmeter 10 respectively with methane source of the gas 8
Gaseous mixture air admission hole at the top of plasma generator anode, the boron chloride source of the gas 9 heat vapour through boron chloride heating source 11
It is connected to the boron chloride air admission hole at 3 top of reactor after change after the metering of flowmeter 10 again, the flowmeter 10 is air mark
Fixed spinner flowmeter, the tail gas spray absorber 12 are connected with air outlet pipe 14；Argon gas is ionized using plasma generator
For plasma arcs, while hydrogen, methane are introduced into plasma arcs and carries out mixing electric discharge and forms high-temperature plasma jet stream,
This jet stream is imported into reactor, then by raw material BCl3Gas by opposite symmetrical boron chloride air admission hole be also introduced into reactor with
Perforative plasma jet mixing, high-temperature hydrogen, methane and BCl3It mixes rapidly and dissociates carry out spatial recomposition, complete gas phase
Synthetic reaction obtains boron carbide powder product, is as follows：
Argon gas is imported into plasma generator 2 first, starts plasma and the generation argon plasma arc of power supply 1 occurs, then will
Hydrogen and methane importing plasma generator 2 mix electric discharge with argon plasma and form plasma jet；Then will etc. from
Daughter jet stream imports the reactor 3 of 2 lower section of plasma generator, while imports trichlorine from the boron chloride air admission hole of reactor 3
Change boron gas, hit to mix rapidly with plasma jet and complete vapor- phase synthesis reaction, space generation solid-state B4C and gaseous state HCl；
Solid-state B4C forms nano boron carbide powder with quenching deposition on jet-impingement to the cooling wall for cooling down powder collector 4；Part nano-sized carbon
Change boron powder and absorb gas solid separation powder collector 5 into water under the drive of air-flow, powder is only absorbed by the water and gas overflowing, is finally received
Nano boron carbide powder is obtained after collection powder and washed, drying；Tail gas HCl is handled by tail gas spray absorber 12；It is specific real
Under applying for example：
Embodiment 1
It is first turned on cooling cycle water and is supplied to plasma generator 2, reactor 3, cooling powder collector 4, then open argon gas source 6, gas
Bottle pressure maintains 0.3MPa, is sent into argon flow amount 1.6m3/ h, purging exchange system 10min；Power supply occurs for open plasma
1, rotatory current adjuster makes current values be in 105A, by starting switch, generates argon plasma torch, at this time voltage number
Value shows about 90V, from observation window it can be seen that argon plasma arc, stablizes 1min；Subsequent rotatory current adjuster, makes electric current liter
To 130 A, hydrogen source 7 and methane source of the gas 8 are opened, storage pressure maintains 0.3MPa, from flowmeter 10（Air is demarcated）Slowly
It is sent into 0.6 m of hydrogen3/ h, 0.6 m of methane3/ h, voltage rises to 130 V at this time, then electric current is adjusted to 200 by rotatory current adjuster
A, plasma jet discharge power is 25KW at this time, and mixing electric discharge forms plasma jet；Boron chloride source of the gas 9 is opened,
By 11 heating system of boron chloride heating source to 40 DEG C of constant temperature, boron chloride supply gas pressure 0.3MPa is slowly sent into boron chloride
About 2.5kg/h；Boron chloride sprays into plasma jet, and plasma chemical vapor is carried out with hydrogen, the methane for wherein ionizing, dissociating
Synthetic reaction, space generation solid-state B4C and gaseous state HCl；Solid-state B4C is quenched on the cooling wall with jet-impingement to cooling powder collector 4
Deposition forms nano boron carbide powder and is settled down to the collection of accumulated powder tank；Part nano boron carbide powder enters under the drive of air-flow
Water absorbs gas solid separation powder collector 5, and powder is only absorbed by the water and gas overflowing, and nanometer is obtained after collecting powder and washed, drying
Boron carbide powder, tail gas HCl are handled by tail gas spray absorber 12；Reaction continues 30min, and accumulated powder tank and water absorb gas solid separation
The boron carbide powder that powder collector 5 is collected amounts to 70g；It is calculated by the supply output ratio of boron chloride, rewinding rate is more than 60%, gained
Boron carbide powder product shows through XRD qualitative analyses and SEM, EDS and ICP detection and analysis：Boron carbide powder grain size for 30~
80nm, purity are more than 99%（Wherein：Oxygen content is less than 0.5%, total metal ion content and is less than 300ppm）.
Embodiment 2
It is first turned on cooling cycle water and is supplied to plasma generator 2, reactor 3, cooling powder collector 4, then open argon gas source 6, gas
Bottle pressure maintains 0.4MPa, is sent into argon flow amount 1.8m3/ h, purging exchange system 10min；Power supply occurs for open plasma
1, rotatory current adjuster makes current values be in 110 A, by starting switch, generates argon plasma torch, at this time voltage number
Value shows about 95V, from observation window it can be seen that argon plasma arc, stablizes 1min；Subsequent rotatory current adjuster, makes electric current liter
To 200A, hydrogen source 7 and methane source of the gas 8 are opened, storage pressure maintains 0.4MPa, from flowmeter 10（Air is demarcated）Slowly send
Enter hydrogen 0.8m3/ h, 0.8 m of methane3/ h, voltage rises to 200V at this time, then electric current is adjusted to 220A by rotatory current adjuster, this
When plasma jet discharge power be 45KW, mixing electric discharge forms plasma jet；Boron chloride source of the gas 9 is opened, by three
11 heating system of boron chloride heating source is to 50 DEG C of constant temperature, boron chloride supply gas pressure 0.4MPa, is slowly sent into boron chloride about
4.5kg/h；Boron chloride sprays into plasma jet, and plasma chemical vapor conjunction is carried out with hydrogen, the methane for wherein ionizing, dissociating
Into reaction, space generation solid-state B4C and gaseous state HCl；Solid-state B4C is heavy with quenching on jet-impingement to the cooling wall for cooling down powder collector 4
Product forms nano boron carbide powder and is settled down to the collection of accumulated powder tank；Part nano boron carbide powder enters water under the drive of air-flow
Gas solid separation powder collector 5 is absorbed, powder is only absorbed by the water and gas overflowing, and nano-sized carbon is obtained after collecting powder and washed, drying
Change boron powder, tail gas HCl is handled by tail gas spray absorber 12；Reaction continues 30min, and accumulated powder tank and water absorb gas solid separation and receives
The boron carbide powder that powder device 5 is collected amounts to 130g；It is calculated by the supply output ratio of boron chloride, rewinding rate is more than 65%.Gained carbon
Change boron powder product through XRD qualitative analyses and SEM, EDS and ICP detection and analysis to show：Boron carbide powder grain size for 30~80nm,
Purity is more than 99%（Wherein：Oxygen content is less than 0.5%, total metal ion content and is less than 300ppm）.
Embodiment 3
It opens cooling cycle water and is supplied to plasma generator 2, reactor 3, cooling powder collector 4, then open argon gas source 6, gas cylinder pressure
Power maintains 0.5MPa, is sent into argon flow amount 2m3/ h, purging exchange system 10min；Power supply 1, rotation occur for open plasma
Current regulator makes current values be in 115A, presses starting switch, generates argon plasma torch, and voltage value is shown at this time
Show about 100V, from observation window it can be seen that argon plasma arc, stablizes 1min；Subsequent rotatory current adjuster, rises to electric current
220A opens hydrogen source 7 and methane source of the gas 8, and storage pressure maintains 0.5MPa, from flowmeter 10（Air is demarcated）Slowly it is sent into
Hydrogen 1.2m3/ h, methane 1.2m3/ h, voltage rises to 220V at this time, then electric current is adjusted to 260A by rotatory current adjuster, at this time etc.
Gas ions jet stream discharge power is 60KW, and mixing electric discharge forms plasma jet；Boron chloride source of the gas 9 is opened, by tri-chlorination
11 heating system of boron heating source is to 60 DEG C of constant temperature, boron chloride supply gas pressure 0.5MPa, is slowly sent into boron chloride about 6kg/h；
Boron chloride sprays into plasma jet, and plasma chemical vapor synthetic reaction is carried out with hydrogen, the methane for wherein ionizing, dissociating,
Space generation solid-state B4C and gaseous state HCl；Solid-state B4C is formed with quenching deposition on jet-impingement to the cooling wall for cooling down powder collector 4
Nano boron carbide powder is simultaneously settled down to the collection of accumulated powder tank；Part nano boron carbide powder absorbs gas under the drive of air-flow into water
Admittedly separating powder collector 5, and powder is only absorbed by the water gas overflowing, nano boron carbide powder is obtained after collecting powder and washed, drying
Body；Tail gas HCl is handled by tail gas spray absorber 12；Reaction continues 30min, and accumulated powder tank and water absorb gas solid separation powder collector 5
The boron carbide powder of collection amounts to 185g；It is calculated by the supply output ratio of boron chloride, rewinding rate is more than 68%.Gained boron carbide
Powder-product shows through XRD qualitative analyses and SEM, EDS and ICP detection and analysis：Boron carbide powder grain size is 30~80nm, purity
More than 99%（Wherein：Oxygen content is less than 0.5%, total metal ion content and is less than 300ppm）.
In the above-described embodiments, discharge with the argon gas starting the arc and with hydrogen, methane blended, form the electricity that temperature is more than 4000 DEG C
Arc plasma jet stream, hydrogen, methane are largely dissociated into the high hydrogen atom and carbon atom of reduction activation at this temperature
（Partial ionization is into ion）；Gaseous state BCl3It is mixed to form the reaction that temperature is more than 2000 DEG C after introducing with plasma jet rapidly
System, under the action of temperature radiation and a large amount of high energy active particles, the quick scission of link of boron chloride simultaneously exists with hydrogen atom, carbon atom
Reduction reaction is completed in space collision restructuring, generates HCl and boron carbide；Since hydrogen, methane, boron chloride system are generally 1150
DEG C can scission of link generate reaction generation boron carbide, therefore, the superhigh temperature and a large amount of high energy active particles generated in plasma
Effect, the efficiency and speed of plasma chemical vapor synthetic reaction are far above traditional approach, and the reaction carried out in reactor 3 is such as
Under：
4BCl3+4H2+CH4→B4C+12HCl；
4BCl3+8H·+C→B4C+12HCl；
Argon gas and " hydrogen and methane " gaseous mixture are respectively from the cathode bottom and anode top of plasma generator 2 with annular tangent line
Mode air inlet, it is ensured that the stability of plasma arcs and plasma jet；Boron chloride is at 3 top of reactor with opposite
Symmetrical mode air inlet increases the uniformity of reaction gas mixing while boron chloride incision kinetic energy is ensured.
In the above-described embodiments, argon flow amount is 1.5~2 m3/ h, the confession air pressure of argon gas, hydrogen, methane, boron chloride
Power is 0.3~0.5MPa, this condition is to ensure plasma arcs（Jet stream）Continuous stability and vapor- phase synthesis react very high
The basis of effect property, guarantee and the relevant jet-impingement rate of granularity；Hydrogen, methane, the volume flow ratio of boron chloride are 4 simultaneously
~6:1:4；Hydrogen is slightly excessive, helps to improve the conversion ratio of boron；And the volume flow ratio of methane and boron chloride remains 1:
4, to avoid free boron or free carbon is generated in boron carbide powder.
When working gas proportioning and constant flow, the discharge power that power supply occurs for plasma, plasma body temperature are heightened
Degree necessarily rises, and hydrogen, the degree of ionization of methane, degree of dissociation also improve therewith, the high energy active particle generated in plasma
Substantial increase, therefore the efficiency and the yield of boron carbide reacted under high power are also significantly increased；Reaction gas is complete in reactor 3
After being reacted into vapor- phase synthesis, the solid-state B of generation4C is in space uniform nucleation and growth process, and with jet-impingement to cooling powder collector 4
Quenching deposits and stops crystal growth on cooling wall, so as to form the boron carbide powder of nano-scale, and is settled along shaping conical barrel
Accumulated powder tank in powder collector bottom；If necessary, the visor window that can be opened on cooling powder collector 4 enters the powder brush that inner wall adheres to
Accumulated powder tank is collected；
After reactant is sprayed from reactor 3, there is part powder to overflow cooling powder collector 4 under the drive of gas, be conducted into
Water absorbs gas solid separation powder collector 5 and carries out gas solid separation, stretches bottom tube 14 and stretches into 5cm below the water surface, you can effectively absorbs what is overflowed
Boron carbide powder, and gas can be easily overflowed, the purpose of gas solid separation is efficiently reached, and resistance, phase will not be caused to reaction gas flow
Than in the screen mesh type, the cloth-bag type gas-solid separator that commonly use, effect is more preferable, reaction is more smooth；The boron carbide powder that water absorbs
It is washed with deionized after collection and the vacuum drying 2h under the conditions of 100 DEG C；After being handled by tail gas spray absorber 12
HCl gases can make hydrochloric acid byproduct use.
The basic principles, main features and the advantages of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. the method that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder, which is characterized in that using etc. from
The device that daughter chemical gas phase synthetic method prepares high-purity nm boron carbide powder prepares high-purity nm boron carbide powder, specific steps
It is as follows：
1）Argon gas is imported into plasma generator, starts plasma and power supply generation electric arc electric discharge occurs, form stable argon gas
Plasma arcs；
2）Hydrogen and methane are imported into plasma generator again, electric discharge is mixed with argon plasma and forms plasma jet；
3）Plasma jet is then imported into reactor below plasma generator, at the same from the boron chloride of reactor into
Stomata imports boron trichloride gas, hits to mix rapidly with plasma jet and completes vapor- phase synthesis reaction, space generation solid-state
B4C and gaseous state HCl；
4）Step 3）The solid-state B of middle generation4C forms nano-sized carbon with quenching deposition on jet-impingement to the cooling wall for cooling down powder collector
Change boron powder；
5）Step 4）In part nano boron carbide powder under the drive of air-flow into water absorb gas solid separation powder collector, powder
It is only absorbed by the water and gas overflowing, nano boron carbide powder is obtained after finally collecting powder and washed, drying.
2. the method that plasma enhanced chemical vapor synthetic method according to claim 1 prepares high-purity nm boron carbide powder,
It is characterized in that, step 1）In, 1.5~2m of argon flow amount3/ h, 0.3~0.5MPa of pressure start plasma and power supply production occur
The power of raw electric arc electric discharge is 10KW, and electric current is 105~115A, and voltage is 90~100V.
3. the method that plasma enhanced chemical vapor synthetic method according to claim 1 prepares high-purity nm boron carbide powder,
It is characterized in that, step 2）In, the volume flow ratio of hydrogen and methane is 4~6:1,0.3~0.5MPa of supply gas pressure, adjust etc.
The power supply of ion generator makes its output power be 10~100KW.
4. the method that plasma enhanced chemical vapor synthetic method according to claim 1 prepares high-purity nm boron carbide powder,
It is characterized in that, step 3）In, the volume flow ratio of boron chloride and methane is 4:1,40~60 DEG C of boron chloride heating temperature,
0.3~0.5MPa of boron chloride supply gas pressure.
5. the method that plasma enhanced chemical vapor synthetic method according to claim 1 prepares high-purity nm boron carbide powder,
It is characterized in that, the device that plasma enhanced chemical vapor synthetic method prepares high-purity nm boron carbide powder includes plasma
Power supply, plasma generator, reactor, cooling powder collector, water absorb gas solid separation powder collector, tail gas absorber, argon gas source, hydrogen
Source of the gas, methane source of the gas and boron chloride source of the gas, the plasma generator are the semiclosed appearance being made of polytetrafluoro insulated with material
Device, semienclosed container upper end closed lower ending opening, and cathode made of cerium tungsten material is provided on semienclosed container top, half seals
It closes lower vessel portion and is provided with anode made of copper product, cathode occurs power cathode with plasma and is connected, anode and plasma
Positive pole connection occurs for body；The argon gas for being used for that argon gas to be imported by argon gas source is equipped in plasma generator cathode bottom simultaneously
Air admission hole, plasma generator anode top, which is equipped with, to be used to import hydrogen by hydrogen source and pass through methane source of the gas to import methane
Gaseous mixture air admission hole；Plasma generator is built-in with cooling circulating water system and carries out cooling protection；The reactor and plasma
The lower end of generator is tightly connected, and reactor head is symmetrical arranged that there are two be used to import boron chloride by boron chloride source of the gas
The boron chloride air admission hole of gas, boron chloride source of the gas be provided outside for boron chloride carry out heating vaporization boron chloride add
Heat source, reactor lower port are placed in cooling powder collector, and the external jacket for cooling down powder collector is provided with recirculating cooling water system, described
Water absorbs gas solid separation powder collector and is connected with the outlet of cooling powder collector, and in argon gas source, hydrogen source, methane source of the gas and boron chloride
Four source outlet ends of source of the gas are respectively arranged with flowmeter, and the water absorbs gas solid separation powder collector and is connected with tail gas absorber.
6. the method that plasma enhanced chemical vapor synthetic method according to claim 5 prepares high-purity nm boron carbide powder,
It is characterized in that, it is the direct-current arc power supply that output power is 10~100kW that power supply, which occurs, for the plasma.
7. the method that plasma enhanced chemical vapor synthetic method according to claim 5 prepares high-purity nm boron carbide powder,
It is characterized in that, the argon inlet hole, gaseous mixture air admission hole are annular line cutting structure.
8. the method that plasma enhanced chemical vapor synthetic method according to claim 5 prepares high-purity nm boron carbide powder,
It is characterized in that, the tubular reactor that the reactor is formed for external jacket containing water cooling and through hole graphite-pipe.
9. the method that plasma enhanced chemical vapor synthetic method according to claim 5 prepares high-purity nm boron carbide powder,
It is characterized in that, the cooling powder collector by the cylindricality ladle body of top visor containing symmetrical openings, middle part for sedimentation shaping conical barrel and
Bottom forms for accumulated powder tank.
10. the method that plasma enhanced chemical vapor synthetic method according to claim 5 prepares high-purity nm boron carbide powder,
It is characterized in that, the water absorbs to be provided on gas solid separation powder collector stretches bottom tube and use for the outlet of connection cooling powder collector
In the air outlet pipe of connection tail gas absorber.
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