CN104549658A - Application method of cold field plasma discharge assisted high energy ball milled powder and plasma assisted high energy ball milling device - Google Patents
Application method of cold field plasma discharge assisted high energy ball milled powder and plasma assisted high energy ball milling device Download PDFInfo
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/14—Mills in which the charge to be ground is turned over by movements of the container other than by rotating, e.g. by swinging, vibrating, tilting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/06—Selection or use of additives to aid disintegrating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
- B02C23/24—Passing gas through crushing or disintegrating zone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/18—Use of auxiliary physical effects, e.g. ultrasonics, irradiation, for disintegrating
- B02C2019/183—Crushing by discharge of high electrical energy
Abstract
The invention provides an application method of cold field plasma discharge assisted high energy ball milled powder and a plasma assisted high energy ball milling device using the cold field plasma discharge assisted high energy ball milling method. The method comprises the following steps: utilizing dielectric barrier discharge to generate plasmas, introducing a dielectric barrier discharge electrode bar into a high-speed vibrating ball-milling tank, on one hand, requiring a solid insulating medium on the outer layer of the electrode bar to simultaneously bear high-voltage discharge and mechanical shock failure of the grinding ball, and on the other hand, requiring the high-speed vibrating ball milling device to uniformly process the powder. The method is based on the ordinary ball milling technology; the processing efficiency and the effect of the ball mill can be greatly improved by the following steps: under a non-heat-balance discharge condition of the pressure that the discharge space pressure is set to be about 102-106 Pa, introducing the discharge plasmas to input another effective energy to the processed powder, promoting the powder to be processed to be subjected to combined action of the mechanical stress effect and the heat effect of the external electric field, and further accelerating refining of the powder and promoting the alloying progress.
Description
Technical field
The invention belongs to machine-building and powder metallurgical technology, relate to a kind of high-energy ball milling device, be specifically related to a kind of awkward silence at a meeting plasma auxiliary high-energy ball mill apparatus and prepare the application of carbide alloy, lithium ion battery, hydrogen storing alloy powder powder material.
Background technology
The method that common high-energy ball milling prepares alloy powder is one of technology that prepared by current nano and micro materials and mechanical alloying is the most frequently used, generally utilize high energy ball mill to rotate or vibrate metal or alloy powder fining to receiving micro-meter scale, that is: the ball grinder two or more powder being put into simultaneously high energy ball mill carries out ball milling, a powder abrasive particle is through calendering, pressing, pulverize, the repetitive process (i.e. cold welding-pulverizing-cold welding repeatedly carry out) of pressing again, powder grain and the continuous refinement of particle size can be made, finally can obtain micron superfine alloy powder of receiving that microstructure and composition is evenly distributed.Usual high energy ball mill is just simple by rotating or vibrating ball grinding jar, utilizes the mechanical energy of abrading-ball in ball grinder to process powder, namely only has mechanical stress fields to facilitate powder to have an effect.But the application of current mechanical alloying mainly concentrates on planetary and stirring ball mill aspect, and this mechanical alloying exists the shortcomings such as energy consumption is large, efficiency is low.
Plasma generator is generally under negative pressure (vacuum), and apply high-frequency electric field to reacting gas environment, gas ionizes under the excitation of high-frequency electric field, produces plasma.The activity of these ions is very high, and its energy is enough to destroy nearly all chemical bond, causes chemical reaction, thus the structure of material surface, composition and group are changed, be met the surface of actual requirement at the material surface of any exposure.Meanwhile, plasma reaction speed is fast, treatment effeciency is high, and modification occurs over just material surface, does not affect the performance of material internal bulk material, is desirable surface modification means.Plasma surface modification has been widely used in the material of the shapes such as film-form, bulk and graininess, and difform material must adopt different plasma treatment modes, as film-form material (comprising film, fabric, non-woven fabrics, silk screen etc.), because it can baling, therefore Reel-to-reel type batch process can be adopted; Lump material, owing to putting one by one, is therefore applicable to multi-layer planar Electrode treatment.And the application of plasma in process powder particle is less, the difficulty be particularly incorporated in high-energy ball milling machine by plasma is larger.This is mainly owing to two aspects: one is because powder is piled up, reunion between particulate, makes the microparticle surfaces be not exposed in plasma atmosphere can not get process, is difficult to realize particulate and all processes, cause particulate process incomplete, uneven, poor processing effect; Two is that in high-energy ball milling tank, the high velocity impact of abrading-ball and the acting in conjunction of electrion are serious to the destruction of sparking electrode, and electrode life-span in ball grinder is very short.Therefore, a kind of device of effective plasma auxiliary high-energy ball-milling treatment powder body material is needed badly.
CN 1718282 A discloses a kind of high energy ball mill method with plasma aid, how it improves and to realize the effect that plasma discharge assists ball milling on general milling machine basis if mainly describing, but do not do open further for the selection of the concrete structure of main ball mill, the structural design of ball discharge grinding jar, particularly medium blocking discharge electrode rod with design.And in fact, plasma auxiliary high-energy ball mill additional plasma electrical source, ball discharge grinding jar and medium blocking discharge electrode rod etc. in there is various technical barrier, particularly electrode bar is introduced in the process of ball grinder, exist cooperatively interact, the problem such as localized high intensity disruptive discharge and plasma discharge strength control, and electrode bar self has the various problems affecting the life-span being limited to materials and structures and bringing, be all that foregoing invention patent is unsolved.
CN 101239334 A and CN1011239336 A individually discloses a kind of plasma auxiliary high-energy roller ball mill device and a kind of plasmaassisted stirring ball mill device, it mainly converts in conventional rollers and agitating ball mill, but this two kinds of ball mill mechanical energy are less, grinding efficiency is low, not only be difficult to the adjustment realizing long scope ballmilling energy, and be not suitable for the high efficiency thinning effect under plasmaassisted.And oscillatory type ball mill device can realize the long range regulation of ballmilling energy jointly by the amplitude of exciting block and drum's speed of rotation two aspects simultaneously.
CN 101239335 A discloses a kind of plasma auxiliary high-energy planetary ball mill device, and it is on conventional planetary Ball Mill Foundation, adds the electrode bar being circumscribed with plasma electrical source, improve the grinding efficiency of planetary ball mill in the ball grinder that luck of being expert at turns.But realize rotation and the revolution of ball grinder because planetary ball mill is confidential, the electrode extremely unstable introduced in ball grinder; In addition, be arranged on the collision of the electrode bar in ball grinder to abrading-ball and produce serious inhibition, inhibition is produced to the ball milling advantage of planetary structure.
CN 102500451 A and CN 202398398 U discloses a kind of auxiliary ball milling dielectric barrier discharge electrode rod, and it is sheathed tubulose polytetrafluoroethylene (PTFE) block media layer in tubular conductive electrode layer, obviates threaded engagement between two pipes; And it is all on the ball grinder of through hole that this electrode bar can only be applied with two ends.In actual process and assemble process, this cooperation can not avoid residual air infringement to electrode bar in discharge process all the time, and the actual life of its electrode bar cannot increase substantially.
US 6126097 and US 6334583 discloses a kind of planet ball high-energy ball milling device and prepares the method for nanometer powder, describe a kind of structure of common planetary formula ball mill and the application in prepared by nanometer powder thereof, but this patent of invention is only confined to planetary ball mill field, and do not relate to the application of additional plasma electric field.
Summary of the invention
The present invention seeks to be to overcome mechanical alloying energy consumption large, efficiency is low, pollute heavy shortcoming, utilize dielectric barrier discharge (dielectric barrier discharge, be called for short DBD) to receive much concern unique discharge type as producing the one of plasma, medium blocking discharge electrode rod is incorporated in the ball grinder of vibration at high speed, require that the mechanical shock that the outer field solid dielectric insulation of electrode bar can bear electrion and abrading-ball simultaneously destroys on the one hand, require that the ball mill device of vibration at high speed can make powder-processed uniform in effect on the other hand, provide and a kind ofly effectively improve the novel high-energy ball mill device of material mechanical alloying efficiency and prepare carbide alloy, lithium ion battery, the application process of hydrogen storing alloy powder powder material.On its basis based on general milling technology, by introducing discharge plasma, another kind of effective energy is inputted to handled powder, impel pending powder under mechanical stress effect and extra electric field electric discharge produce plasma acting in conjunction, accelerate the refinement of powder and promote alloying process, thus greatly improving working (machining) efficiency and the action effect of ball mill.
The invention provides a kind of application process of awkward silence at a meeting plasma discharge auxiliary high-energy ball milling powder, the application process of this awkward silence at a meeting plasma high-energy ball milling powder is: be first the different voltage and current using additional awkward silence at a meeting plasma electrical source to input to the ball discharge grinding jar of plasma asistance high-energy ball milling device, by atmosphere system can be controlled, control adjustment is carried out to ball grinder internal atmosphere (gas type and air pressure) again, then the sparking electrode rod in ball discharge grinding jar is allowed to produce intensity controlled corona or glow discharge phenomenon, thus realize implementing plasma field high-energy ball milling to the processed powder in ball discharge grinding jar, the process of Aided Machine alloying.
Present invention also offers the plasma asistance high-energy ball milling device of application awkward silence at a meeting plasma high-energy ball milling powder method, this plasma auxiliary high-energy ball mill device involving vibrations formula high-energy ball milling main frame, additional awkward silence at a meeting plasma electrical source, ball discharge grinding jar, sparking electrode rod, atmosphere system and cooling system six parts can be controlled, the structure of described oscillatory type high-energy ball milling main frame is vibromill form;
Described ball discharge grinding jar comprises connector drum, front shroud, back shroud, grinds tank connected plasma electrical source minus earth pole with ball discharge;
Described sparking electrode rod is cylindrical bar, is jointly made up of the conductive core of its inner iron (copper) material and the insulating outer layer of polytetrafluoroethylmaterial material; Described inner conductive battery core is connected with plasma electrical source positive pole high-pressure stage, and as a pole of plasma discharge, insulating outer layer exists as the dielectric barrier of electric discharge.
A kind of plasma asistance high-energy ball milling device of the present invention, is further characterized in that:
The structure of described oscillatory type high-energy ball milling main frame or be the form of eccentric vibration mill.
Described additional awkward silence at a meeting plasma electrical source 2 adopts the high-voltage ac power of AC-DC-AC mapping mode, civil power is become high frequency electric, wherein the conversion of DC-AC adopts frequency modulation control mode, and operating frequency range is adjustable at 1 ~ 20kHz, and electric power output voltage scope is between 1 ~ 30kV.The insulating outer layer of described cylindrical bar sparking electrode rod, or be high-purity alpha-alumina ceramic material.
The described sparking electrode rod conductive core fastening end of inner iron (copper) material and the insulating outer layer of polytetrafluoroethylmaterial material use threaded engagement, discharge end adopts polished rod structure to coordinate with insulating outer layer, in the fit clearance of conductive core and insulating outer layer, be filled with heat-resistant adhesive, and match with insulating outer layer medium with spherical structure in conductive core top;
Jointly form the insulating outer layer of sparking electrode rod high-purity alpha-alumina ceramic material with the conductive core of described inner iron (copper) material, adopt Direct precipitation mode or differential arc oxidation mode to be shaped;
The sparking electrode rod of the insulating outer layer of described high-purity alpha-alumina ceramic material, or cover has a metal sleeve being with mesh.
Describedly control the top that atmosphere system is arranged on ball discharge grinding jar tank body air inlet/outlet, can and argon gas, nitrogen, ammonia, hydrogen, in all kinds of atmosphere of oxygen, realize plasma and independent regulation and control are implemented to the ball milling effect of processed powder under different air pressure.Cylindrical shell two end flanges of described ball discharge grinding jar is tightly connected with front shroud, back shroud respectively by sealing ring, bolt, and the center of front shroud, back shroud is respectively equipped with the through hole and blind hole that are used for fixing sparking electrode rod.
The embedded stainless steel sleeve of through hole of the front shroud of described ball discharge grinding jar and sealing rubber ring, the blind hole of described back shroud medial surface is embedded with stainless steel sleeve gasket.
Vacuum air valve is equipped with in the front shroud outer face of described ball discharge grinding jar.
The application process of awkward silence at a meeting plasma discharge auxiliary high-energy ball milling powder of the present invention, utilize dielectric barrier discharge as plasma, on the electrode that dielectric overlay is placed at discharge space, when applying sufficiently high alternating voltage on sparking electrode, form the gas between dielectric barrier discharge breakdown electrode, or formed very evenly, careless and sloppy, stable, and the glow discharge seemingly under low pressure, is formed by the unique discharge type of the one of Fast pulsed discharge passage trickle in a large number.Medium blocking discharge electrode rod is incorporated in the ball grinder of vibration at high speed, require that the mechanical shock that the outer field solid dielectric insulation of electrode bar can bear electrion and abrading-ball simultaneously destroys on the one hand, on the other hand require that the ball mill device of high speed vibration can make powder-processed uniform in effect, provide and a kind ofly effectively improve the novel high-energy ball mill device of material mechanical alloying efficiency and prepare the application process of carbide alloy, lithium ion battery, hydrogen storing alloy powder powder material.On its basis based on general milling technology, discharge space air pressure is set to 10
2~ 10
6thermal nonequilibrium discharge condition under about Pa air pressure, by introducing discharge plasma, another kind of effective energy is inputted to handled powder, impel pending powder under mechanical stress effect and additional discharge plasma acting in conjunction, accelerate the refinement of powder and promote alloying process, thus greatly improving working (machining) efficiency and the action effect of ball mill.
Because dielectric barrier discharge plasma of the present invention has the advantage of following uniqueness, when considering to introduce plasma in high-energy ball milling, dielectric barrier discharge plasma is obviously exactly one and preferably selects:
First, dielectric barrier discharge plasma can occur at ambient pressure, meets the condition that ball milling needs carry out under the protective atmosphere of certain pressure;
Secondly, dielectric barrier discharge inhibits the unlimited enhancing of micro discharge due to dielectric layer, make dielectric barrier discharge can not change into spark discharge or arc discharge, guarantee that plasma is not the hot plasma strong to material damage power, thus the scaling loss of ball milling system can be avoided;
Its three, dielectric barrier discharge evenly can spread out at dielectric layer surface, makes the effect of the even accepting medium barrier discharge plasma of ball milling powder physical efficiency;
Finally, under certain condition, dielectric barrier discharge can produce accurate aura or glow discharge, thus can be implemented in efficient ball milling in reaction atmosphere, impel pending powder under mechanical stress effect and additional discharge plasma acting in conjunction, accelerate the refinement of powder and promote alloying process, thus greatly improving working (machining) efficiency and the action effect of ball mill.
Accompanying drawing explanation
Fig. 1 a, Fig. 1 b are inactive state in mechanical milling process of the present invention and ball milling state medium barrier discharge plasma photo;
Fig. 2 is plasma asistance high-energy ball milling apparatus structure schematic diagram of the present invention;
Fig. 3 a and Fig. 3 b is the oscillatory type ball mill bitubular of the present invention mill main frame and eccentric mill main machine structure schematic diagram;
Fig. 4 is plasma asistance high-energy ball milling device ball discharge grinding jar structural representation of the present invention;
Fig. 5 is sparking electrode bar structure schematic diagram of the present invention;
Fig. 6 is ball discharge grinding jar of the present invention and metal sleeve sparking electrode rod scheme of installation is housed;
Fig. 7 is ball discharge grinding jar of the present invention and sparking electrode rod mounting structure schematic diagram;
Fig. 8 is that the present invention can control atmosphere system and ball discharge grinding jar mounting structure schematic diagram;
Fig. 9 is the XRD collection of illustrative plates of the W-C-10Co powder (BPR=50:1) that the different Ball-milling Time of the present invention obtains;
Figure 10 is the W-C-10Co powder heat scan DSC curve of DBDP ball milling 3h of the present invention;
Figure 11 a, Figure 11 b are the ESEM pattern pictures of the W-C-10Co-1.2VC mixed-powder after DBDP auxiliary high-energy ball milling 3h of the present invention.
In figure, 1. oscillatory type high-energy ball milling main frame, 2. additional awkward silence at a meeting plasma electrical source, 3. ball discharge grinding jar, 4. sparking electrode rod, 5. atmosphere system can be controlled, 6. cooling system, 7. abrading-ball, 31. cylindrical shells, 32. front shrouds, 33. back shrouds, 34. plasma electrical source earthing poles, 35. plasma electrical source high-pressure stages, 36. tank body air inlet/outlets, 41. conductive core, 42. insulating outer layer, 311. flange, 312. sealing ring, 313. bolt, 321. through hole, 322. stainless steel sleeves, 323. sealing rubber ring, 324. vacuum air valves, 325. polyfluortetraethylene plate, 326. ceramic wafer, 331. blind hole, 332. stainless steel sleeve gaskets, 333. polyfluortetraethylene plate, 334. ceramic wafer, 411. fastening end, 412. discharge end, 413. spherical structure, 421. metal sleeve, 51. pressure-reducing valves, 52. flowmeters, 56. unloaders, 541. ball valve, 542. ball valve, 551. filter, 552. filter, 571. metal hose, 572. metal hose.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The application process of awkward silence at a meeting plasma discharge auxiliary high-energy ball milling powder of the present invention, first be the different voltage and current using additional awkward silence at a meeting plasma electrical source to input to the ball discharge grinding jar of plasma asistance high-energy ball milling device, by atmosphere system can be controlled, control adjustment is carried out to ball grinder internal atmosphere (gas type and air pressure) again, then the sparking electrode rod in ball discharge grinding jar is allowed to produce intensity controlled corona or glow discharge phenomenon, thus realize implementing plasma field high-energy ball milling to the processed powder in ball discharge grinding jar, the process of Aided Machine alloying.Its principle is: from the angle of energy input, mechanical energy single in former mechanical milling process and plasma organic composite are got up, and strengthens the effective energy input to process powder, carries out Combined Processing to powder.The high-energy particle bombardment ball milling powder that plasma produces, energy is passed to ball milling powder with the form of heat energy, ball milling powder is made to have high temperature rising instantaneously, thus cause that powder is local melting even to gasify, produce so-called " thermal explosion " effect, " thermal explosion " effect of plasma discharge ball milling is relevant with the thermal property of metal material, and fusing point and the boiling point of metal are higher, thermal conductivity factor, specific heat, solution gas heat-transmission are larger, more difficultly bring out " Explosion ".Two active effects that dielectric barrier discharge auxiliary high-energy ball mill device mainly utilizes plasma to bring: fuel factor and excitation effect.Consider in conjunction with powder refining in high-energy ball milling and mechanical alloying two aspect, plasma is incorporated in high-energy ball milling and can produces very large effect to improving Mechanic Alloying Technology.
First be in powder refining.Electron temperature in awkward silence at a meeting plasma is high, but its integral macroscopic temperature is not high, can control below Metal Phase height and even room temperature, it both can realize instantaneous microcell Fast Heating like this, bring out thermal stress, promote that powder is broken, and don't understand disfiguring workpiece and ball milling system; Simultaneously, the thermograde that ball grinder is produced as plasma reactor is very large, powder is sharply heated to high temperature under action of plasma, and the abrading-ball of relative low temperature makes the quick quenching of powder at once, be very beneficial for ultramicro powder synthesis like this, be also very easy to obtain high degree of supersaturation; The more important thing is that plasma is ionized by clean gas and produces, thus thermal source is pure, clean, can not contain unburned carbon black and other impurity completely as chemical flame, this point is very important to preparation high-purity powder.
Next is in mechanical alloying.Due to the fuel factor of plasma, atoms permeating ability will than stronger in general milling, favourable ball milling phase transformation; The more importantly excitation effect that brings of plasma: plasma is the active gaseous material being in highly ionized state, it produces a large amount of ions, electronics, the atom of excitation state and molecule, free radical etc. at reaction chamber underexcitation, and self can provide as lively as a cricket active particle for chemical reaction; And the energy that plasma can utilize electric field to transmit, bombardment sputtering material surface, thus change character and the chemical reactivity of material, make to be strengthened by the powder active of ball milling, under the shock stirring action of abrading-ball, promote the carrying out of powder alloying reaction.That is, by introducing plasma, can realize, close under the condition of room temperature, making to need the alloying reaction that could occur extremely for a long time to become in script general milling process and easily carrying out.
Fig. 1 a, Fig. 1 b are the dielectric barrier discharge plasma photos in mechanical milling process of the present invention.
Plasma asistance high-energy ball milling device of the present invention, as shown in Figure 2, involving vibrations formula high-energy ball milling main frame 1, additional awkward silence at a meeting plasma electrical source 2, ball discharge grinding jar 3, sparking electrode rod 4, atmosphere system 5 and cooling system 6 six parts can be controlled, embodiment as shown in Fig. 3 a of the present invention, the version of oscillatory type high-energy ball milling main frame 1 dual-drum vibration mill, it also can adopt the form of eccentric vibration mill as shown in Figure 3 b.
As shown in Figure 4, ball discharge grinding jar 3 of the present invention comprises connector drum 31, front shroud 32, back shroud 33, the plasma electrical source negative pole 34 be connected with ball discharge grinding jar 3; Sparking electrode rod 4 of the present invention is cylindrical bar, is jointly made up of the conductive core 41 of its inner iron (copper) material and the insulating outer layer 42 of polytetrafluoroethylmaterial material; Described inner conductive battery core 41 is connected with plasma electrical source positive pole 35, and as a pole of plasma discharge, insulating outer layer 42 exists as the dielectric barrier of electric discharge.
As shown in Figure 5, conductive core 41 fastening end 411 of sparking electrode rod 4 inner iron (copper) materials uses threaded engagement with the insulating outer layer 42 of polytetrafluoroethylmaterial material, discharge end 412 adopts polished rod structure to coordinate with insulating outer layer 42, in conductive core 41 with the fit clearance of insulating outer layer 42, be filled with heat-resistant adhesive, and match with insulating outer layer 42 medium with spherical structure 413 in conductive core 41 top; The insulating outer layer 42 jointly forming sparking electrode rod 4 high-purity alpha-alumina ceramic materials with the conductive core 41 of described inner iron (copper) material adopts Direct precipitation mode or differential arc oxidation mode to be shaped.
The insulating outer layer 42 of cylindrical bar sparking electrode rod 4 of the present invention, or be high-purity alpha-alumina ceramic material, according to the sparking electrode rod 4 of the insulating outer layer 42 of high-purity alpha-alumina ceramic material, there is a metal sleeve 421 being with mesh in the outer cover of insulating outer layer 42, as shown in Figure 6.
The additional awkward silence at a meeting plasma electrical source 2 of ion auxiliary high-energy ball mill device of the present invention adopts the high-voltage ac power of AC-DC-AC mapping mode, by it, civil power is become high frequency electric, wherein the conversion of DC-AC adopts frequency modulation control mode, operating frequency range is adjustable at 1 ~ 20kHz, and electric power output voltage scope is between 1 ~ 30kV.
As shown in Figure 7, cylindrical shell 31 liang of end flanges 311 of ball discharge grinding jar 3 of the present invention are tightly connected with front shroud 32, back shroud 33 respectively by sealing ring 312, bolt 313, the center of front shroud 32, back shroud 33 is respectively equipped with the embedded stainless steel sleeve 322 of through hole 321 and the sealing rubber ring 323 of the front shroud 32 being used for fixing sparking electrode rod 4, and the blind hole 331 of back shroud 33 medial surface is embedded with stainless steel sleeve gasket 332; The vacuum air valve 324 of stainless steel material is equipped with in front shroud 32 outer face of ball discharge grinding jar 3.
Plasma asistance high energy ball mill of the present invention as shown in Figure 8, the top that atmosphere system 5 is arranged on ball discharge grinding jar 3 tank body air inlet/outlet 36 can be controlled, with in argon gas, nitrogen, ammonia, hydrogen, all kinds of atmosphere of oxygen under different air pressure, plasma can be realized independent regulation and control implemented to the ball milling effect of processed powder.
Apparatus of the present invention are operated by following steps:
(1) in ball grinder, load abrading-ball and pending powder, and medium blocking discharge electrode rod is arranged on the center of ball grinder, make electrode bar and abrading-ball and pending powder contact, then use the end cap of ball grinder to carry out sealing and fixing;
(2) be evacuated to negative pressure by the ball grinder of vacuum valve to good seal, and then pass into required discharge gas medium by vacuum valve, as: argon gas, nitrogen, argon gas, methane or oxygen etc.Wherein, pass into gas pressure can whole-process control in 0.01 ~ 1MPa scope;
(3) be connected with the positive and negative two-stage of plasma electrical source respectively with electrode bar conductive core by ball grinder tank body, wherein, electrode bar conductive core connects the positive pole of plasma electrical source, and ball grinder tank body connects the negative pole of plasma electrical source;
(4) connect the power supply of plasma, regulate the discharge parameter voltage of plasma electrical source to be 3 ~ 30KV according to discharge gas medium and pressure thereof, frequency is 5 ~ 40KHz, forms electric field, and starts ball mill.Along with the vibration frequency of ball mill or the change of rotating speed, thus change the relative position of abrading-ball in electrode bar and ball grinder, carry out corona discharge or glow discharge plasma auxiliary high-energy ball milling.Wherein, corona plasma mainly uses and adjuvant powders refinement, and glow discharge plasma mainly uses and Aided Machine alloying.
The present invention is relative to prior art, and the design in ball discharge grinding jar, medium blocking discharge electrode rod and atmosphere control system etc., has unique structure and advantage.
Ball discharge grinding jar of the present invention comprises cylindrical shell, front shroud (bilayer), back shroud (bilayer), and ball grinder connects the negative pole of plasma electrical source, the conducting of both sleeve and abrading-ball, overall can see a pole of plasma discharge as; Wherein front shroud and back shroud comprise polytetrafluoroethylene floor and ceramic layer respectively; Ball grinder cylindrical shell is made up of stainless steel casing liner hard alloy layer, for can electric conductor, described forward and backward cover plate all adopts the insulating materials such as double-deck polytetrafluoroethylene (PTFE), lucite and ceramic wafer jointly to make, as polytetrafluoroethylene (PTFE) and ceramic wafer in conjunction with time, the former prevents abrading-ball from smashing as internal layer, and the latter strengthens cover plate intensity as skin; The flange at cylindrical shell two ends is tightly connected with front shroud, back shroud respectively by sealing ring, the bolt of more than 8, and the center of front shroud, back shroud arranges through hole respectively and blind hole is used for fixing electrode bar;
The embedded stainless steel inner ring of through hole of front shroud and sealing rubber ring, the blind hole of back shroud medial surface is also embedded with metal sleeve, and described insert structure effectively avoids electrode bar point discharge to the infringement of forward and backward cover plate;
Front shroud is provided with the vacuum air valve that stainless steel material is made, is convenient to control the vacuum in ball grinder;
The core apparatus of plasmaassisted ball-grinding machine is medium blocking discharge electrode rod, by controlling discharge voltage and the power of plasma, and then the discharge effect of control electrode rod.But, the block media layer of electrode bar is in discharge process, be subject to the mechanical collision of abrading-ball and the destruction of electric field electric discharge simultaneously, work bad border extremely badly, in use usually occurs various forms of destruction: (1) dielectric barrier surface easily generation pin hole or duck eye shape punctures; (2) dielectric barrier easily occurs puncturing cavity in the cooperation place with ball grinder two ends end cap; (3) block media layer because of hot-spot produce cracking and large area burn out.These destructions have had a strong impact on the application that discharge plasma assists ball grinding technique.Solve puncturing and destroying dielectric barrier in electrode layer work, must design and produce electrode bar rational in infrastructure, avoid there is the uneven of discharge electric field and thermal field at block media layer in electric discharge mechanical milling process.Wherein, dielectric barrier weakest link is the position at the shaft shoulder and axle top.This mainly localized high intensity electric field cause block media layer to puncture, and this localized high intensity electric field owing to threaded engagement and cooperation place exist breath remain.
Medium blocking discharge electrode rod of the present invention adopts cylindrical bar, and it is made up of with outer field insulating materials polytetrafluoroethylene (PTFE) or high-purity alpha-alumina pottery etc. jointly the conductive material iron, copper etc. of core.Described inner conductive battery core is connected with plasma electrical source positive pole, and as a pole of plasma discharge, and exterior insulation material is as the dielectric barrier existence of electric discharge.The present invention raising medium blocking discharge electrode rod service life in, specifically comprise following three kinds of structures:
(1) electrode bar described in is made up of jointly inner iron or copper core and outside polytetrafluoroethylene (PTFE), wherein, fastening end and outer teflon insulation with the use of threaded engagement, discharge end adopts polished rod structure (abandoning helicitic texture), and in the fit clearance of electrode layer and polytetrafluoroethylene (PTFE), fully fill heat-resistant adhesive avoid air to exist, top of electrodes adopts spherical structure to match with outer layer insulation medium simultaneously, avoids the electric field that the localized high intensity value that point discharge causes occurs;
(2) electrode bar described in is made up of inner iron or copper core and outside polytetrafluoroethylene (PTFE), wherein, polytetrafluoroethylene (PTFE) (dielectric barrier) is deposited directly to electrode layer, is formed and closely cooperates completely, there is not the dielectric insulation layer in any gap;
(3) electrode bar described in is made up of jointly inner iron or copper core and outside high-purity alpha-alumina pottery, the two adopts the mode such as Direct precipitation or differential arc oxidation to make, wherein, for preventing the cracking destruction of pottery in abrading-ball collision process, the metal sleeve of a band mesh is added between electrode bar and ball grinder, as shown in Figure 6, abrading-ball runs between sleeve and ball grinder.Between electrode bar and ball grinder, add the metal sleeve of a band mesh, abrading-ball is between sleeve and ball grinder, and ball grinder connects the negative pole of plasma electrical source, ball grinder, abrading-ball and sleeve three conducting, overall can see a pole of plasma discharge as.Electrode bar in the middle of the positive pole female connector cylinder of plasma electrical source, electrode bar is still made up of iron, copper core and high-purity alpha-alumina ceramic layer.Such plasma discharge will carry out between sleeve and electrode bar, and the powder of ball milling can be entered in sleeve by the mesh on sleeve and obtain discharge plasma process.The design parameter of metal sleeve 421 is generally: sleeve thickness 3mm, external diameter 40mm, and hole diameter 3mm is less than minimum ball radius.Therefore, in the process of ball milling, powder can free in and out and abrading-ball cannot enter in sleeve, would not produce mechanical impact effect to electrode bar.
From the experimental result of above-mentioned three kinds of sparking electrode rods improved, 1000rpm/min is reached at motor speed, when in tank, abrading-ball weight reaches 7.5kg, the electrode bar life-span prepared by latter two method can reach about 30 ~ 50h, and this is that other ordinary electrode rods are incomparable.
In addition, the present invention, relative to prior art, can control the design in atmosphere system, has unique structure and advantage.This system is achieved through the following technical solutions:
(1) gas passes through pressure and the flow of pressure-reducing valve 51 and flowmeter 52 control inputs.
(2) ball discharge grinding jar 3 setup of entrances and exits ball valve 541 and 542, controls gas and discharges and input.
(3) using filter 551 and 552 for filtering powder, reducing powder because of the discharge of the effect of air-flow, crossing rate precision due to filter and do not reach nanoscale, therefore adopting double filtration mode.
(4) unloader 56 is by adjusting nut above, can when ventilating by the height of adjusting nut the spring pressure in control valve.When gas pressure exceedes spring pressure, spring, by jack-up, is outwards vented (off-load); When gas pressure is less than spring pressure, this valve closes.The object of controlled discharge ball grinder internal pressure is realized with this.
(5) part of installing with ball grinder adopts metal hose 571 and 572, and object reduces the impact of vibrations on other parts of gas circuit (particularly the spring section of unloader).Valve member beyond hose segment all should fix, and reduces the impact of vibrations.
(6) require when using that input air pressure is slightly larger than specified control air pressure, to ensure the flowing of gas and the pure of atmosphere in ball discharge grinding jar.Thus realize the impact of the plasma such as kind and air-flow of gas.
This can control the impact that atmosphere system achieves different air pressure and atmosphere plasma strength of discharge and thickness, thus the different atmosphere parameter provided for the plasmaassisted ball milling of different powder.
The present invention compared with prior art, obtains following advantage and beneficial effect in Mechanical Alloying:
(1) powder heating is fast, and distortion is large, and refinement required time is short.Under same process parameter, the product powder diameter adopting this method to carry out plasmaassisted ball milling can reach nanoscale, and narrow diameter distribution, and the product powder diameter of general milling is at micron order, domain size distribution is wide.
(2) mechanical alloying process is promoted, plasma auxiliary high-energy ball milling, it is the energy of compound plasma on the basis of conventional mechanical energy, this Combined Processing to powder, while efficient refinement powder, must increase surface energy and the interface energy of powder, strengthen the reactivity of powder, and the pure fuel factor of plasma is also favourable to promotion diffusion and alloying reaction.
(3) utilize the inventive method, when discharge gas medium is organic gas, the in-situ-surface modifying to powder can be realized at refinement powder simultaneously.
(4) technique of the present invention is easy to realize, and working (machining) efficiency is high, effectively can shorten powder refining and mechanical alloying required time, economize energy, high-energy ball-milling process can be made to realize real material preparation and produce in enormous quantities, have a extensive future.
Plasmaassisted ball milling can refinement metal-powder more efficient than general milling, and especially plasmaassisted ball milling is the effective way of high-efficiency production of nano metal-powder.Result of the test shows: room temperature general milling iron powder 60h, and iron powder refine to minimum of a value, and this dimension limit is greater than 1 μm;-20 DEG C of low temperature ball milling 30h, iron powder is refine to less than 1 μm; 24kV plasmaassisted grinding efficiency is the highest, only can obtain the nanometer iron powder of average grain diameter 103.9nm with 10h.For aluminium powder and tungsten powder, result is similar with iron powder, general milling 15h, and most of aluminium powder is between 10-50 μm, and plasmaassisted ball milling 15h, obtain the aluminium powder that average grain diameter is 128.7nm; General milling 3h, Tungsten Powder Size is between 0.5-3 μm, and using plasma assists ball milling 3h, obtains the tungsten powder of average grain diameter 101.9nm.In plasmaassisted ball milling simple metal process, what affect plasma " thermal explosion " effect is the thermal property of metal material.Fusing point and the boiling point of metal are higher, and thermal conductivity factor, specific heat, heat of fusion, heat of gasification are larger, more difficultly bring out " Explosion ", and this also directly affects the content of below 10nm powder in plasmaassisted ball milling metal dust.Fusing point as tungsten is high, and below the 10nm tungsten nanoparticle content that plasma generation " thermal explosion " effect obtains only has 10.5%.Although aluminium thermal conductivity ratio iron is large, because its fusing point is too low, below the 10nm aluminum nanoparticles content that plasma generation " thermal explosion " effect obtains is 27.3%, is slightly greater than below 10nm nanoparticle content (25.2%) in iron powder.
Plasmaassisted ball milling can than general milling more efficiently activating reaction powder, promote mechano-chemical reation, as plasmaassisted ball milling W powder+graphite powder only 3h, just energy effective activation powder, follow-up 1100 DEG C of insulation 1h process just makes W powder whole carbonization synthesis particle size at 100nm, average grain size is at the nanometer WC powder body of about 50nm, and carburizing temperature have dropped 500 DEG C than conventional silicon carbide temperature.The activate mechanism of plasmaassisted ball milling, on the one hand that dielectric barrier discharge effect and the shock effect of plasma makes increase in powder self, and more mainly due to the dielectric barrier discharge effect in mechanical milling process, make to define the meticulous composite construction of nanometer scale between reaction powder.This meticulous composite construction can reduce the temperature needed for following reaction on the one hand greatly, reaction can be impelled to carry out on the other hand perfect, make product pure.
Discharge plasma assists ball milling as a kind of new technology, it has and obviously reduces reaction activity, crystal grain thinning, greatly improves powder activity and improve particle distribution uniformity and the combination at interface between reinforcement and matrix, promote solid state ion diffusivity coefficient, bring out low-temp reaction, thus improve the performance of each side of material, be a kind of energy-conservation, efficient material preparation technology.It is by providing a kind of effective energy input that can strengthen process powder, the refinement of powder quick and promotion mechanical alloying process, greatly improve the working (machining) efficiency of ball mill, it is one and relates to the association areas such as machinery, material and electric power, has broader research space.At present, the present invention has wide prospects for commercial application in directions such as carbide alloy, lithium ion battery, hydrogen bearing alloys.
The application process embodiment scheme explanation of awkward silence at a meeting plasma discharge auxiliary high-energy ball milling powder of the present invention
The plasma asistance high energy ball mill of this law invention, sparking electrode rod uses cylindrical bar, it is made up of with outer field insulating materials polytetrafluoroethylene (PTFE) or high-purity alpha-alumina pottery etc. jointly the conductive material iron, copper etc. of core, inner conductive battery core is connected with plasma electrical source positive pole high-pressure stage, as a pole of plasma discharge, and exterior insulation material is as the dielectric barrier existence of electric discharge.And the life-span of electrode bar and performance directly determine the operating efficiency of ball mill, therefore, we to list in patent of the present invention three sections of designed electrode bars and ordinary electrode rod (iron core directly squeeze into have interference fit with in the polytetrafluoroethylene (PTFE) of blind hole), carry out working life contrast.The condition of work adopted is: the discharge voltage of 15KV, the discharge current of 1.5A, and exciting block adopts double-amplitude 8mm, and ratio of grinding media to material adopts 50:1, and abrading-ball adopts carbide alloy or stainless steel material.As shown in table 1.
Embodiment 1:
Step 1, employing internal copper core and outside polytetrafluoroethylene (PTFE) form electrode bar jointly, wherein, fastening end and outer teflon insulation with the use of threaded engagement, discharge end adopts polished rod structure (abandoning helicitic texture), and in the fit clearance of electrode layer and polytetrafluoroethylene (PTFE), fully fills heat-resistant adhesive avoids air to exist, while top of electrodes employing spherical structure match with outer layer insulation medium.Electrode bar is arranged in the ball grinder of 4L, and in ball grinder, load abrading-ball and pending powder, and by the center of medium blocking discharge electrode baseball grinding jar, make electrode bar and abrading-ball and pending powder contact, then use the end cap of ball grinder to carry out sealing and fixing.Wherein, electrode bar diameter is 25mm, and abrading-ball adopts Hardmetal materials, and weigh 7.5 kilograms, ratio of grinding media to material is 50:1;
Step 2, be evacuated to negative pressure by the ball grinder of vacuum valve to good seal, and then pass into required electric discharge argon gas by vacuum valve.Wherein, gas pressure is passed into 0.1MPa;
Step 3, be connected with the positive and negative two-stage of plasma electrical source respectively with electrode bar conductive core by ball grinder tank body, wherein, electrode bar conductive core connects the positive pole of plasma electrical source, and ball grinder tank body connects the negative pole of plasma electrical source; And the discharge voltage of the 15KV adopted, the discharge current of 1.5A, exciting block adopts double-amplitude 8mm, the rotating speed of 1200rpm, starts ball mill.
Result shows, and the service life of electrode bar can reach 20 hours.
Embodiment 2:
Step 1, step 2, with example 1;
Step 3, with example 1, but drum's speed of rotation adopt 960rpm.
Result shows, and the service life of electrode bar can reach 30 hours.
Embodiment 3:
Step 1, with example 1, but ball milling volume adopt 0.15L, electrode bar diameter adopt 20mm, abrading-ball is stainless steel material;
Step 2, with example 1;
Step 3, with example 1, but discharge current adopt 1.0A, drum's speed of rotation adopt 960rpm.
Result shows, and the service life of electrode bar can reach 35 hours.
Embodiment 4:
Step 1, employing internal copper core and outside polytetrafluoroethylene (PTFE) form electrode bar jointly, wherein, are deposited directly on electrode layer by polytetrafluoroethylene (PTFE) (dielectric barrier).Electrode bar is arranged in the ball grinder of 4L, and in ball grinder, load abrading-ball and pending powder, and by the center of medium blocking discharge electrode baseball grinding jar, make electrode bar and abrading-ball and pending powder contact, then use the end cap of ball grinder to carry out sealing and fixing.Wherein, electrode bar diameter is 25mm, and abrading-ball adopts Hardmetal materials, and weigh 7.5 kilograms, ratio of grinding media to material is 50:1;
Step 2, be evacuated to negative pressure by the ball grinder of vacuum valve to good seal, and then pass into required electric discharge argon gas by vacuum valve.Wherein, gas pressure is passed into 0.1MPa;
Step 3, be connected with the positive and negative two-stage of plasma electrical source respectively with electrode bar conductive core by ball grinder tank body, wherein, electrode bar conductive core connects the positive pole of plasma electrical source, and ball grinder tank body connects the negative pole of plasma electrical source; And the discharge voltage of the 15KV adopted, the discharge current of 1.5A, exciting block adopts double-amplitude 8mm, the rotating speed of 1200rpm, starts ball mill.
Result shows, and the service life of electrode bar can reach 15 hours.
Embodiment 5:
Step 1, step 2, with example 4;
Step 3, with example 4, but drum's speed of rotation adopt 960rpm.
Result shows, and the service life of electrode bar can reach 25 hours.
Embodiment 6:
Step 1, with example 4, but ball milling volume adopt 0.15L, electrode bar diameter adopt 20mm, abrading-ball is stainless steel material;
Step 2, with example 4;
Step 3, with example 4, but discharge current adopt 1.0A, drum's speed of rotation adopt 960rpm.
Result shows, and the service life of electrode bar can reach 30 hours.
Embodiment 7:
Step 1, employing internal copper core and external ceramic form electrode bar jointly, and between electrode bar and ball grinder, add the metal sleeve of a band mesh, abrading-ball runs between sleeve and ball grinder.Electrode bar is arranged in the ball grinder of 4L, and in ball grinder, load abrading-ball and pending powder, and by the center of medium blocking discharge electrode baseball grinding jar, make electrode bar and abrading-ball and pending powder contact, then use the end cap of ball grinder to carry out sealing and fixing.Wherein, electrode bar diameter is 25mm, and abrading-ball adopts Hardmetal materials, and weigh 7.5 kilograms, ratio of grinding media to material is 50:1;
Step 2, be evacuated to negative pressure by the ball grinder of vacuum valve to good seal, and then pass into required electric discharge argon gas by vacuum valve.Wherein, gas pressure is passed into 0.1MPa;
Step 3, be connected with the positive and negative two-stage of plasma electrical source respectively with electrode bar conductive core by ball grinder tank body, wherein, electrode bar conductive core connects the positive pole of plasma electrical source, and ball grinder tank body connects the negative pole of plasma electrical source; And the discharge voltage of the 15KV adopted, the discharge current of 1.5A, exciting block adopts double-amplitude 8mm, the rotating speed of 1200rpm, starts ball mill.
Result shows, and the service life of electrode bar can reach 25 hours.
Embodiment 8:
Step 1, step 2, with example 7;
Step 3, with example 7, but drum's speed of rotation adopt 960rpm.
Result shows, and the service life of electrode bar can reach 36 hours.
Embodiment 9:
Step 1, with example 7, but ball milling volume adopt 0.15L, electrode bar diameter adopt 20mm, abrading-ball is stainless steel material;
Step 2, with example 7;
Step 3, with example 7, but discharge current adopt 1.0A, drum's speed of rotation adopt 960rpm.
Result shows, and the service life of electrode bar can reach 40 hours.
Embodiment of the present invention have employed high rotating speed (960 ~ 1200rpm), high abrading-ball packing ratio (accounting for 65 ~ 75% of ball grinder volume) and carbide alloy abrading-ball, increase the oscillation intensity to electrode bar and impulsive force, carry out the service life of test electrode rod.The life-span of never isostructural electrode bar, three kinds of electrode bars designed in the present invention basic close to or reach continuous service life of 30 hours, far away higher than the electrode bar life-span of common process.For the ball milling parameter adopting the slow-speed of revolution, low ratio of grinding media to material, the life-span of electrode bar also will improve greatly.This greatly improves the operational efficiency of ball mill and adds the possibility of commercial Application popularization.
Table 1: the contrast in service life of different structure designs electrode bar
Plasmaassisted ball milling of the present invention is used to prepare the embodiment of carbide alloy
In order to verify feasibility and the odds for effectiveness of apparatus of the present invention further, we have employed high-melting-point, high rigidity WC-Co hard alloy material as ball milling research object.The research that existing high-energy ball milling method prepares nanosized hardmetal powder mainly comprises: powder process, carbonization and shaping three processes, and wherein, powder process and carbonisation are important foundation links prepared by whole WC-Co series hard metal.Its concrete operation step is as follows: (1) first utilizes high-energy ball milling method to prepare ultra-fine W, C mixture; (2) carbonization is carried out to W, C mixture prepared, generate ultrafine tungsten carbide (WC); (3) on the basis of the WC generated, add Co and carry out high-energy ball milling again, WC and Co is mixed.But this method still needs longer Ball-milling Time, and the composite powder decarburization of preparing is serious.Discharge plasma of the present invention is adopted to assist ball grinding method, coordinate compacting sintering, carburizing sintering integration synthetic method can prepare the WC-Co hard alloy with high-strength tenacity, overcome the defect that CEMENTED CARBIDE PRODUCTION process is loaded down with trivial details, energy consumption is large, and effectively improve the degree of purity of product.
Dielectric barrier discharge plasma auxiliary high-energy ball milling is adopted to be achieved through the following technical solutions:
(1) in ball grinder, load the raw material such as W, C, Co grain growth inhibitor of abrading-ball and certain proportioning and the mixed-powder of extra benefit carbon, and be mixed into appropriate ball milling controlling agent (absolute ethyl alcohol etc.);
(2) electrode bar passed ball grinder end cap and implant in ball grinder, fastening ball grinder end cap, is then connected end cap with electrode bar, wherein respectively with the two poles of the earth of plasma electrical source, electrode bar connects the positive pole high-pressure stage of plasma electrical source, and front shroud connects the negative pole earth polar of plasma electrical source;
(3) by vacuum valve, negative pressure to 0.01 ~ 0.1Pa is taken out to airtight ball grinder, or pass into discharge gas medium by vacuum valve again after taking out negative pressure to 0.01 ~ 0.1Pa, until the pressure in this ball grinder is 0.01 ~ 0.1MPa;
(4) power supply of plasma is connected, discharge parameter is regulated according to discharge gas medium and pressure thereof, the voltage of plasma electrical source is made to be 3 ~ 30KV, frequency is 5 ~ 40KHZ, realizes corona discharge, and starts ball mill work, ball grinder and abrading-ball collide motion, thus change the relative position of abrading-ball in electrode bar and ball grinder, carry out dissimilar corona discharge plasma high-energy ball milling, obtain W-C-Co base alloy powder;
(5) by compressing for described W-C-Co base alloy powder, green compact are obtained;
(6) described green compact are sintered in thermal source environment preparation W-C-Co carbide alloy.
For realizing the present invention better, step (1) described W, C, Co, VC or V
2o
5each raw material is according to WC-XCo-YVC or WC-XCo-Y V
2o
5carry out proportioning (interpolation of grain growth inhibitor oxide form is added according to the amount formed needed for corresponding carbide after its carbonization), wherein, the span of X is 3<X<20, the span of Y is 0.09<Y<2.4, and described X, Y are all weight percentage.
In mixed-powder, the amount of C is except the theoretical carbon amounts required for W carbonization, also comprises and additionally mends carbon amounts, and the mass ratio of itself and C raw material is 7.5% ~ 15%.
Described compressing mode is single way stempressing, and unit pressure is 35MPa ~ 1000MPa.
Described thermal source environment is vacuum/low-pressure sintering furnace, and the temperature of thermal source environment is 1320 DEG C ~ 1480 DEG C.
The present invention, compared with the conventional art preparing carbide alloy, has following advantage:
(1) distortion of W, C, Co raw material is large, the refinement time is short, the lamella words time is short, and compared with other ball grinding methods, the method can make powder refining to nanoscale sooner;
(2) the method is conducive to the carrying out of carburizing reagent, after W, C, Co raw material is processed, drastically increase the surface energy of powder, interface energy, reactivity etc., and the fuel factor of plasma for the diffusion between W, C, Co and solid-state reaction favourable, be conducive to the sinter molding of follow-up carbide alloy;
(3) directly W, C, Co alloy powder is pressed into green compact, replaces first by the carbonization of W powder in traditional handicraft by the technology of carburizing sintering integration, then WC, Co mixed-powder is made green sintering forming technique.Only there is the heating process once from room temperature to high temperature in the present invention, and the carbonization of W powder and the heating process of each experience of the sintering of mixed-powder once from room temperature to high temperature in traditional handicraft, thus greatly can reduce energy consumption.
(4) the present invention by adding grain growth inhibitor (VC or V in dielectric barrier discharge plasma ball milling W, C, Co process
2o
5), with in traditional handicraft first by W carbonization, again by grain growth inhibitor and WC, Co-with compared with ball milling, the present invention can increase the distributing homogeneity of grain growth inhibitor, and just can play the inhibitory action of growing up to WC grain in the forming process of WC, that suppresses WC grain to be grown up is effective; Meanwhile, decrease the step of high temperature cabonization, reduce cost to a great extent.
We are when investigating different Ball-milling Time to the affecting of crystallite dimension, and as shown in Figure 9, as can be seen from XRD collection of illustrative plates, DBDP ball milling to the diffraction maximum still mainly W of mixed powder during 6h, and does not have WC to generate, and illustrates that DBDP ball milling 6h is also unlikely to make W carbonization.With the increase of Ball-milling Time, the diffraction maximum generation broadening of W, especially 0.5h broadening clearly.Calculate (211) face of W with Voigt function method, clearly, reach about 43nm, the crystallite dimension of ball milling 1h to 6h decreases, but changes not obvious in the crystallite dimension change of ball milling 0.5h.Illustrate that DBDP ball milling can refinement W crystallite dimension be to a maintenance level rapidly, its efficiency is much higher than common high-energy ball milling.
Observe the DSC curve of the W-C-10Co mixed-powder of DBDP ball milling 3h, as shown in Figure 10, we can find that the endothermic peak of about 650 DEG C be a small amount of WO that carbon reduces because of oxidation generation in ball-milled powder
3with the oxygen of powder surface absorption, generate CO or CO
2effusion.And DSC curve also has an exothermic peak within the scope of 831 ~ 875 DEG C, the carburizing reagent of tungsten may be correspond to.In order to study the phase in version process at this reaction peak, select in Thermal Synthetic Analysis instrument, to heat composite powder 700 DEG C and 900 DEG C.Found that, the XRD spectrum when XRD collection of illustrative plates of the mixed-powder do not heated and the mixed-powder of DBDP ball milling 3h are heated to 700 DEG C is all mainly W peak, but when being heated to 700 DEG C, α-Co peak occurs.This is because with the rising of temperature, the reason of W and Co grain growth.Be also shown in by Figure 10, when mixed-powder is heated to 900 DEG C, have WC to generate, but there is decarburization phase W simultaneously
2c, Co
6w
6c and simple substance W.This process can represent with following reaction equation:
W+C→WC (1)
2W+C→W
2C (2)
6W+6Co+C→Co
6W
6C (3)
Continue to raise heating-up temperature, be heated to 1100 DEG C and be not incubated in DSC, the XRD collection of illustrative plates of the composite powder obtained is understood, mesophase spherule W
2c changes WC into completely, decarburization phase Co
6w
6c is more obvious, still there is a small amount of W.Corresponding reaction equation can be expressed as
W
2C+C→2WC (4)
WC+5W+6Co→Co
6W
6C (5)
Mesophase spherule Co is not had unlike in decarburization phase in version process with other results of study
3w
3the appearance of C, reason may be that the powder activity of DBDP ball milling is higher, ball milling and the oxygen got in powder process in easier absorbed air, and the flowing atmosphere of DSC equipment can take away the CO formed in heating process
2, thus making scarce carbon more serious, powder directly reacts the Co that formation more tends to decarburization
6w
6c phase, and do not generate phosphorus content and compare Co
6w
6the Co that C is high
3w
3c phase.
In addition, when above-mentioned process also proves to complete carburizing reagent in flowing atmosphere, carbon content is wayward, is unfavorable for forming the WC without decarburization phase, should avoid adopting flowing atmosphere to prepare WC-Co composite powder end.Therefore, identical ball-milled powder is adopted in low-pressure sintering furnace, to be heated to 1000 DEG C and to be incubated 1h.Result proves the WC-10Co composite powder that can obtain under such process conditions without decarburization phase.Its reason is low-pressure sintering furnace heating is carry out in closed atmosphere, can not because of CO
2loss and cause scarce carbon.Meanwhile, along with the growth of temperature retention time, uneven carbon spreads further, with Co
6w
6c at high temperature reacts and generates WC and Co, and its reaction equation can be expressed as
Co
6W
6C+5C→6WC+6Co (6)
In addition, based on previous work, we also add grain growth inhibitor with refinement WC grain in WC-Co hard alloy preparation, prepare high-performance carbide.With the addition of the W-C-Co powder of VC as research object, the action effect of DBDP auxiliary high-energy ball milling to the W-C-Co mixed powder that with the addition of grain growth inhibitor is not only refinement simple substance powder, also make graphite fine and closely woven be coated on W particle surface, powder granule is sheet superposition, as shown in fig. lla.The refining efficiency of DBDP auxiliary high-energy ball milling to W powder presents rule first quick and back slow, and the interpolation of VC can promote the refinement of W in mechanical milling process.After 3 hours ball millings, its W crystallite dimension is approximately 23nm.Different sintering process is taked to prepare WC-10Co-0.6VC carbide alloy, find after test properties: sample prepared by low pressure sintering is owing to applying external pressure at holding stage, its liquid phase Co flows fully, not only be filled with the hole caused due to gas effusion preferably, can also be uniformly distributed between hard phase WC, serve good cementation, as shown in figure lib.At 1340 DEG C, load sample prepared by 4MPa pressure, its density reaches 99%, and Rockwell hardness reaches HRA91.8, and cross-breaking strength TRS reaches 3348MPa.The fracture apperance analyzing this sample can find, the fracture mode of carbide alloy is grain boundary fracture.
Above-mentioned embodiment is several example of the present invention, is not used to limit enforcement of the present invention and interest field, and all equivalences made according to the content described in the present patent application scope of patent protection change and modify, and all should be included in the present patent application the scope of the claims.
Claims (12)
1. the application process of an awkward silence at a meeting plasma discharge auxiliary high-energy ball milling powder, the application process of described plasma high-energy ball milling powder is: be first the different voltage and current using additional awkward silence at a meeting plasma electrical source to input to the ball discharge grinding jar of plasma asistance high-energy ball milling device, by atmosphere system can be controlled, control adjustment is carried out to ball grinder internal atmosphere (gas type and air pressure) again, then the sparking electrode rod in ball discharge grinding jar is allowed to produce intensity controlled corona or glow discharge phenomenon, thus realize implementing plasma field high-energy ball milling to the processed powder in ball discharge grinding jar, the process of Aided Machine alloying.
2. a kind of plasma asistance high-energy ball milling device according to claim 1, involving vibrations formula high-energy ball milling main frame (1), additional awkward silence at a meeting plasma electrical source (2), ball discharge grinding jar (3), sparking electrode rod (4), atmosphere system (5) and cooling system (6) six parts can be controlled, it is characterized in that, the structure of described oscillatory type high-energy ball milling main frame (1) is dual-drum vibration mill form;
Described ball discharge grinding jar (3) comprises connector drum (31), front shroud (32), back shroud (33), the plasma electrical source minus earth pole (34) be connected with ball discharge grinding jar (3);
Described sparking electrode rod (4) is cylindrical bar, is jointly made up of the conductive core (41) of its inner iron (copper) material and the insulating outer layer (42) of polytetrafluoroethylmaterial material; Described inner conductive battery core (41) is connected with plasma electrical source positive pole high-pressure stage (35), and as a pole of plasma discharge, insulating outer layer (42) exists as the dielectric barrier of electric discharge.
3. a kind of plasma asistance high-energy ball milling device according to claim 2, is characterized in that, the structure of described oscillatory type high-energy ball milling main frame (1) or be the form of eccentric vibration mill.
4. a kind of plasma asistance high-energy ball milling device according to claim 2, it is characterized in that, described additional awkward silence at a meeting plasma electrical source (2) adopts the high-voltage ac power of AC-DC-AC mapping mode, civil power is become high frequency electric, wherein the conversion of DC-AC adopts frequency modulation control mode, operating frequency range is adjustable at 1 ~ 20kHz, and electric power output voltage scope is between 1 ~ 30kV.
5. a kind of plasma asistance high-energy ball milling device according to claim 2, is characterized in that, the insulating outer layer (42) of described cylindrical bar sparking electrode rod (4), or is high-purity alpha-alumina ceramic material.
6. a kind of plasma asistance high-energy ball milling device according to claim 2, it is characterized in that, conductive core (41) fastening end (411) of described sparking electrode rod (4) inner iron (copper) material and the insulating outer layer (42) of polytetrafluoroethylmaterial material use threaded engagement, discharge end (412) adopts polished rod structure to coordinate with insulating outer layer (42), heat-resistant adhesive is filled with in the fit clearance of conductive core (41) with insulating outer layer (42), and match with insulating outer layer (42) medium with spherical structure (413) in conductive core (41) top.
7. a kind of plasma asistance high-energy ball milling device according to claim 4, it is characterized in that, jointly form the insulating outer layer (42) of sparking electrode rod (4) high-purity alpha-alumina ceramic material with the conductive core (41) of described inner iron (copper) material, adopt Direct precipitation mode or differential arc oxidation mode to be shaped.
8. a kind of plasma asistance high energy ball mill according to claim 4, it is characterized in that, the sparking electrode rod (4) of the insulating outer layer (42) of described high-purity alpha-alumina ceramic material, or cover has a metal sleeve (421) being with mesh.
9. a kind of plasma asistance high energy ball mill according to claim 2, it is characterized in that, describedly control the top that atmosphere system (5) is arranged on ball discharge grinding jar (3) tank body air inlet/outlet (36), with in argon gas, nitrogen, ammonia, hydrogen, all kinds of atmosphere of oxygen under different air pressure, plasma can be realized independent regulation and control implemented to the ball milling effect of processed powder.
10. a kind of plasma asistance high energy ball mill according to claim 2, it is characterized in that, the cylindrical shell (31) two end flanges (311) of described ball discharge grinding jar (3) is tightly connected with front shroud (32), back shroud (33) respectively by sealing ring (312), bolt (313), and the center of front shroud (32), back shroud (33) is respectively equipped with the through hole (321) and blind hole (331) that are used for fixing sparking electrode rod (4).
11. a kind of plasma asistance high energy ball mills according to claim 9, it is characterized in that, the embedded stainless steel sleeve (322) of through hole (321) of the front shroud (32) of described ball discharge grinding jar (3) and sealing rubber ring (323), the blind hole (331) of described back shroud (33) medial surface is embedded with stainless steel sleeve gasket (332); Wherein front shroud (32) comprises polyfluortetraethylene plate (325) and ceramic wafer (326), and back shroud (33) comprises polyfluortetraethylene plate (333) and ceramic wafer (334).
12. a kind of plasma asistance high energy ball mills according to claim 10, is characterized in that, vacuum air valve (324) is equipped with in front shroud (32) outer face of described ball discharge grinding jar (3).
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108712A (en) * | 1994-03-17 | 1995-09-20 | 上海市纺织科学研究院 | Low-temp. plasma-treating technology for wool fiber material and apparatus thereof |
| CN1718282A (en) * | 2005-07-29 | 2006-01-11 | 华南理工大学 | High energy ball mill method with plasma aid |
| CN2780327Y (en) * | 2005-04-07 | 2006-05-17 | 华南理工大学 | Corona plasma auxiliary high energy ball mill |
| CN101181752A (en) * | 2007-12-14 | 2008-05-21 | 华南理工大学 | Method for preparing WC-Co series nano composite hard alloy powder |
| CN102500451A (en) * | 2011-12-23 | 2012-06-20 | 华南理工大学 | Auxiliary ball milling dielectric barrier discharge electrode |
| CN103318840A (en) * | 2013-06-07 | 2013-09-25 | 华南理工大学 | Magnesium-based composite hydrogen-storage material, and preparation method and application thereof |
-
2014
- 2014-12-24 CN CN201410815093.3A patent/CN104549658B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108712A (en) * | 1994-03-17 | 1995-09-20 | 上海市纺织科学研究院 | Low-temp. plasma-treating technology for wool fiber material and apparatus thereof |
| CN2780327Y (en) * | 2005-04-07 | 2006-05-17 | 华南理工大学 | Corona plasma auxiliary high energy ball mill |
| CN1718282A (en) * | 2005-07-29 | 2006-01-11 | 华南理工大学 | High energy ball mill method with plasma aid |
| CN101181752A (en) * | 2007-12-14 | 2008-05-21 | 华南理工大学 | Method for preparing WC-Co series nano composite hard alloy powder |
| CN102500451A (en) * | 2011-12-23 | 2012-06-20 | 华南理工大学 | Auxiliary ball milling dielectric barrier discharge electrode |
| CN103318840A (en) * | 2013-06-07 | 2013-09-25 | 华南理工大学 | Magnesium-based composite hydrogen-storage material, and preparation method and application thereof |
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|---|---|
| CN104549658B (en) | 2017-04-12 |
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