CN105731457A - Preparation method of pure single-phase ternary carbide Co3W3C - Google Patents
Preparation method of pure single-phase ternary carbide Co3W3C Download PDFInfo
- Publication number
- CN105731457A CN105731457A CN201610096389.3A CN201610096389A CN105731457A CN 105731457 A CN105731457 A CN 105731457A CN 201610096389 A CN201610096389 A CN 201610096389A CN 105731457 A CN105731457 A CN 105731457A
- Authority
- CN
- China
- Prior art keywords
- powder
- ball
- milling
- dehydrated alcohol
- powder body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a preparation method of pure single-phase ternary carbide Co3W3C and belongs to the field of hard alloy material preparation. Cobalt powder, tungsten powder and carbon powder serve as raw materials and are blended and subjected to intermittent ball milling together with hard alloy balls of different diameters and absolute ethyl alcohol, then cold pressing and a chemical reaction are conducted, and a green body containing the pure single-phase ternary carbide Co3W3C powder is obtained; then intermittent ball milling and crushing are conducted, sieving with a 400-600-mesh mesh screen is conducted, and the Co3W3C powder which is pure in physical phase and uniform in granularity is obtained; the Co3W3C powder is arranged in a die, subjected to cold pressing and forming, placed into a discharging plasma sintering equipment for sintering and cooled to the room temperature, and a Co3W3C block material containing a single physical phase can be obtained. A product obtained through the method is a pure single-phase substance.
Description
Technical field:
The invention belongs to Hardmetal materials preparation field, be specifically related to a kind of Co, W, C double carbide Co3W3The preparation method of C.
Background technology:
Proton Exchange Membrane Fuel Cells (PEMFC) is considered as automobile and portable electric appts ideal source owing to having high power density and relatively low operating temperature.Cathod catalyst is one of critical material in PEMFC, it is desirable to allow PEMFC obtain commercial development, it is necessary to have high efficiency cathod catalyst.The cathod catalyst of current PEMFC is frequently with Pd/C, but its catalysis activity and stability still need to improve.In recent years, the impact of Pd/C catalytic performance has been studied by some scholars for metal carbides, it has been found that add Co in Pd/C3W3C can significantly improve cathod catalyst catalysis Activity and stabill in acid medium (such as the overpotential significantly reducing in reduction process；Significantly improve the electric current density etc. of unit mass).Further, it is also possible to by Co3W3C/C uses separately as cathod catalyst.Visible, Co3W3C has broad application prospects in PEMFC field.
Co3W3C application in PEMFC, can be realized by following two approach: first, prepare single-phase Co3W3C, it is achieved the interpolation of its arbitrary proportion or mix with arbitrary proportion with graphite；Second, prepare Co3W3C/C two-phase mixture.Current Co3W3Preparation method single-phase for C has no report.Co3W3C/C is prepared frequently with the method for hydrometallurgy: first a certain amount of ammonium metatungstate hydrate ((NH4) 6H2W12O40) and natrium cobaltinitrosum (Na3Co (NO2) 6) wiring solution-forming are mixed; it is added thereto to D314 macroporous acrylic anion exchange resin again; after W and the Co ion in solution successfully adsorbs; again the obtained resin containing W and Co ion is sintered 2h (argon shield) at 1400 DEG C; finally carry out mechanical ball milling by sintering obtained block materials, finally give containing Co3W3The powder of C and C.The method has the disadvantage that (1) resin has two effects in preparation process, and one is W and the Co ion in adsorbent solution；Two is for Co3W3The synthesis of C provides carbon source.Co3W3Carbon content is required strict by the preparation of C itself, should ensure that W and the Co ion in solution is adsorbed by resin completely that provide, makes have suitable carbon content in resin again and forms Co to supply Co and W element3W3C, its each elemental composition is difficult to control to.(2) formation Co under hot conditions is made3W3Also have certain carbon content to have more than needed after C, and do not make Co3W3C and C reaction generates the carbide of more high-carbon content, such as W2C, WC etc., its preparation technology is difficult to control to.(3) it is difficult to control to Co3W3The relative amount of C and C.In sum, the cathod catalyst Co in PEMFC is prepared at present3W3C/C backing material, exists that preparation process is loaded down with trivial details, the problem such as composition and technique are difficult to control to, it is difficult to realize industrialization.
Summary of the invention:
For solving above-mentioned technical problem, the invention provides the double carbide Co that a kind of thing is mutually pure3W3The preparation method of C powder and block materials, it is characterised in that comprise the steps of
(1) carrying out proportioning with cobalt powder (granularity 0.8～1.2um), tungsten powder (granularity 0.6～1.2um), carbon dust (granularity 0.4～0.8um) for raw material, wherein cobalt powder and tungsten powder are according to Co3W3The mol ratio of C carries out proportioning, and 1.81wt%～1.92wt% that carbon content is total powder；
(2) step (1) described raw material is configured to W-Co-C mixed powder in proportion, adds together with sintered carbide ball, dehydrated alcohol in hard alloy ball grinder.The weight ratio of sintered carbide ball and W-Co-C mixed powder is (2～4): 1, and Ball-milling Time is 20～30 hours, and rotational speed of ball-mill is 80～120r/min；Wherein, sintered carbide ball comprises 3 kinds, diameter respectively 2～4mm, 5～8mm, 9～12mm, and the every 2～4h of mechanical milling process stops once, and dwell time is 15～30min；
(3) mixed powder after ball milling is dried, colds pressing, cold pressing and forward direction powder adds a certain amount of dehydrated alcohol, the dehydrated alcohol added and the volume ratio of powder body are 1:(15～25), pressure of colding pressing is 3～6MPa, by base substrate vacuum drying 12～20h, then put it into and in vacuum drying oven, carry out chemical reaction, in stove, vacuum is≤0.05Pa, 4～8 DEG C/min of the rate of heat addition, reaction temperature 1230～1300 DEG C, temperature retention time 1～2 hour, obtains pure single-phase double carbide Co after cooling3W3C powder green bodies；
(4) by the Co described in step (3)3W3C powder green bodies carries out ball mill crushing, and dehydrated alcohol is ball-milling medium, and hard alloy bulb diameter is 9～12mm, itself and Co3W3The weight ratio of C base substrate is (5～7): 1, and Ball-milling Time is 30～50 hours, and rotational speed of ball-mill is 140～180r/min, and the every 2～4h of mechanical milling process stops once, and dwell time is 15～30min；
(5) use the mesh screen of 400～600 orders to the Co after ball milling3W3C powder is filtered screening, and dehydrated alcohol is the carrier that sieves, the Co sieved3W3After C is dried, thing Co mutually pure, even-grained can be obtained3W3C powder body；
(6) by step (5) gained Co3W3C powder body loads mould, cold moudling, send into sintering in discharging plasma sintering equipment, sintering process is as follows: heating rate 60-100 DEG C/min, and the first rank are warming up to 500～700 DEG C, is incubated 3～6min, second stage is warming up to 1020 DEG C～1100 DEG C, insulation 5～10min, sintering pressure 30-60MPa, can obtain the Co containing single thing phase after being cooled to room temperature3W3C block materials.
Technical advantage and the effect of the present invention are in that:
(1) mechanical milling process in step (2) uses the sintered carbide ball of 3 kinds of different-diameters.The ball being relatively large in diameter has bigger kinetic energy in mechanical milling process, can effectively by raw material powder mix homogeneously, and the ball that diameter is less has bigger surface area when equal in quality, can effectively reduce the particle diameter of material powder.Lot of experiments is explored and is shown that the raising of powder uniformity contributes to the generation of single thing phase；The reduction of grain diameter, can make granule have high surface energy, thus it is sufficiently conducted to effectively facilitate reaction.On the other hand, it is necessary to control the minimum grain size of powder particle, to reduce spontaneous reunion in mechanical milling process and contingent Powder Oxidation doping in each process procedure.
(2) batch (-type) ball-milling method is adopted, namely the every ball milling a period of time in step (2) and step (4) suspends certain time, abrasive material temperature can be reduced on the one hand, reduce the volatilization of dehydrated alcohol, on the other hand, the batch (-type) ball-milling technology in step (4) can effectively reduce intergranular cold welding phenomenon, additionally, can also prevent Co3W3Phase transition is there is due to heat stability reason in C in mechanical milling process.
(3) due to the Co of preparation3W3C base substrate is very hard, and its shattering process needs big ratio of grinding media to material and longer Ball-milling Time, is therefore easy in mechanical milling process and introduces abrasive dust, with mesh screen to the Co after ball milling3W3C powder sieves, and can effectively eliminate this kind of abrasive dust, it is ensured that Co3W3The pure property of C powder.Due to the Co after ball milling3W3C particle diameter is less, it is easy to reunite, and adopts dehydrated alcohol as the carrier that sieves, can effective discrete particles, increase screening efficiency.
(4) step (3) adds dehydrated alcohol in forward direction powder body of colding pressing, cementation can be played in cold pressure procedure, make powder body in bulk, compared with resinoid bond, dehydrated alcohol has less volatilization temperature, after pressed compact, carry out simple drying process just can remove, and without influence on the carbon content in powder, so more can effectively control the composition of composite powder and follow-up sintering process.
(5) due to Co3W3The heat stability of C own is poor, and discharge plasma sintering can be rapidly completed intensification, sintering and cooling procedure, therefore can retain Co in powder body3W3The Single phase behavior of C.
(6) Co prepared by step of the present invention (5)3W3C double carbide powder, can be used alone and also can mix use with other elements (such as graphite etc.) with arbitrary proportion.
(7) comparing with existing research report, this method is workable, it may be achieved industrialized mass production
(8) adopt the discharge plasma sintering process of the present invention, single-phase Co can be prepared3W3The block materials of C.
Accompanying drawing explanation
Fig. 1 is Co prepared by the present invention3W3The X ray diffracting spectrum of C powder, the Co that wherein (a) is prepared for comparative example 13W3The Co that the X ray diffracting spectrum of C powder, (b) are prepared for embodiment 13W3The Co that the X ray diffracting spectrum of C powder, (c) are prepared for embodiment 23W3The Co that the X ray diffracting spectrum of C powder, (d) are prepared for embodiment 33W3The Co that the X ray diffracting spectrum of C powder, (e) are prepared for comparative example 23W3The X ray diffracting spectrum of C powder.
Fig. 2 is embodiment 3 and the Co of comparative example 3 preparation3W3The X ray diffracting spectrum of C powder, the Co that (f) is prepared for comparative example 33W3The X ray diffracting spectrum of C powder.
Fig. 3 is embodiment 2 and the Co of comparative example 4 preparation3W3The X ray diffracting spectrum of C powder, the Co that (g) is prepared for comparative example 43W3The X ray diffracting spectrum of C powder.
Fig. 4 is Co prepared by the present invention3W3The scanning electron microscope microstructure figure of C powder and block materials, (a) is Co3W3The scanning electron microscope microstructure figure of C powder, (b) are Co3W3The scanning electron microscope microstructure figure of C block materials.
Fig. 5 is the Co of preparation3W3The X ray diffracting spectrum of C block materials, the Co that (h) is prepared for embodiment 43W3The Co that the X ray diffracting spectrum of C block materials, (I) are prepared for embodiment 53W3The Co that the X ray diffracting spectrum of C block materials, (J) are prepared for embodiment 63W3The X ray diffracting spectrum of C block materials.
Detailed description of the invention
Following example further illustrate the present invention, but the present invention is not limited to following example.
Comparative example 1
Be averaged the cobalt powder of granularity respectively 1.0um, the tungsten powder of 1.2um, 0.8um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.94wt%.Mixed-powder, the sintered carbide ball (3mm, 6mm, 10mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 4:1, Ball-milling Time is 20 hours, and rotational speed of ball-mill is 80r/min.Being dried by mixed powder after ball milling, add dehydrated alcohol and cold pressing, pressure is 4MPa, and pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.04Pa, 8 DEG C/min of the rate of heat addition, reaction temperature 1260 DEG C, temperature retention time 1 hour, quickly can obtain double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 7:1, and Ball-milling Time is 30h, and rotational speed of ball-mill is 160r/min, adopts dehydrated alcohol to cross 400 order mesh screens for the carrier that sieves, be then dried after ball milling.
Embodiment 1
Be averaged the cobalt powder of granularity respectively 0.8um, the tungsten powder of 1.0um, 0.6um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.92wt%.Mixed-powder, the sintered carbide ball (4mm, 7mm, 9mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 3:1, Ball-milling Time is 24 hours, and rotational speed of ball-mill is 100r/min.Mixed powder after ball milling is dried, adds dehydrated alcohol and cold pressing, pressure is 6MPa, pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.03Pa, 6 DEG C/min of the rate of heat addition, reaction temperature 1230 DEG C, temperature retention time 2 hours, quickly can obtain pure single-phase double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 6:1, and Ball-milling Time is 40h, and rotational speed of ball-mill is 140r/min.Adopt dehydrated alcohol to cross 500 order mesh screens for the carrier that sieves after ball milling, be then dried.
Embodiment 2
Be averaged the cobalt powder of granularity respectively 0.8um, the tungsten powder of 0.6um, 0.5um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.87wt%.Mixed-powder, the sintered carbide ball (4mm, 8mm, 10mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 2:1, Ball-milling Time is 30 hours, and rotational speed of ball-mill is 120r/min.Mixed powder after ball milling is dried, adds dehydrated alcohol and cold pressing, pressure is 5MPa, pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.04Pa, 5 DEG C/min of the rate of heat addition, reaction temperature 1270 DEG C, temperature retention time 1 hour, quickly can obtain pure single-phase double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 5:1, and Ball-milling Time is 50h, and rotational speed of ball-mill is 180r/min.Adopt dehydrated alcohol to cross 600 order mesh screens for the carrier that sieves after ball milling, be then dried.
Embodiment 3
Be averaged the cobalt powder of granularity respectively 1.0um, the tungsten powder of 0.8um, 0.6um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.81wt%.Mixed-powder, the sintered carbide ball (3mm, 8mm, 10mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 3:1, Ball-milling Time is 30 hours, and rotational speed of ball-mill is 80r/min.Mixed powder after ball milling is dried, adds dehydrated alcohol and cold pressing, pressure is 6MPa, pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.04Pa, 4 DEG C/min of the rate of heat addition, reaction temperature 1300 DEG C, temperature retention time 2 hours, quickly can obtain pure single-phase double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 7:1, and Ball-milling Time is 50h, and rotational speed of ball-mill is 140r/min.Adopt dehydrated alcohol to cross 600 order mesh screens for the carrier that sieves after ball milling, be then dried.
Comparative example 2
Be averaged the cobalt powder of granularity respectively 1.0um, the tungsten powder of 1.0um, 0.4um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.78wt%.Mixed-powder, the sintered carbide ball (4mm, 6mm, 9mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 3:1, Ball-milling Time is 30 hours, and rotational speed of ball-mill is 100r/min.Being dried by mixed powder after ball milling, add dehydrated alcohol and cold pressing, pressure is 6MPa, and pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.04Pa, 8 DEG C/min of the rate of heat addition, reaction temperature 1270 DEG C, temperature retention time 2 hours, quickly can obtain double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 6:1, and Ball-milling Time is 40h, and rotational speed of ball-mill is 150r/min.Adopt dehydrated alcohol to cross 500 order mesh screens for the carrier that sieves after ball milling, be then dried.
Comparative example 3
Essentially identical with comparative example 4, it is distinctive in that, W-Co-C mixed powder ball milling mixed process uses the abrading-ball of single diameter 10mm.
Comparative example 4
Essentially identical with comparative example 3, it is distinctive in that, Co3W3Do not sieve after C ball milling and be just dried.
Embodiment 4
Be averaged the cobalt powder of granularity respectively 1.0um, the tungsten powder of 1.2um, 0.8um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.87wt%.Mixed-powder, the sintered carbide ball (4mm, 7mm, 12mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 3:1, Ball-milling Time is 30 hours, and rotational speed of ball-mill is 80r/min.Mixed powder after ball milling is dried, adds dehydrated alcohol and cold pressing, pressure is 6MPa, pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.04Pa, 8 DEG C/min of the rate of heat addition, reaction temperature 1260 DEG C, temperature retention time 2 hours, quickly can obtain pure single-phase double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 5:1, and Ball-milling Time is 50h, and rotational speed of ball-mill is 180r/min.Adopt dehydrated alcohol to cross 500 order mesh screens for the carrier that sieves after ball milling, be then dried.The Co that will obtain after drying3W3C powder body loads mould, cold moudling, sends in discharging plasma sintering equipment, and sintering process is: 60 DEG C/min of heating rate, first rank are warming up to 500 DEG C, are incubated 5min, and second stage is warming up to 1020 DEG C, insulation 10min, sintering pressure 60MPa, be then quickly cooled to room temperature.
Embodiment 5
Be averaged the cobalt powder of granularity respectively 1.0um, the tungsten powder of 1.2um, 0.8um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.87wt%.Mixed-powder, the sintered carbide ball (4mm, 6mm, 10mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 3:1, Ball-milling Time is 30 hours, and rotational speed of ball-mill is 100r/min.Mixed powder after ball milling is dried, adds dehydrated alcohol and cold pressing, pressure is 5MPa, pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.04Pa, 8 DEG C/min of the rate of heat addition, reaction temperature 1260 DEG C, temperature retention time 2 hours, quickly can obtain pure single-phase double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 5:1, and Ball-milling Time is 50h, and rotational speed of ball-mill is 180r/min.Adopt dehydrated alcohol to cross 600 order mesh screens for the carrier that sieves after ball milling, be then dried.The Co that will obtain after drying3W3C powder body loads mould, cold moudling, sends in discharging plasma sintering equipment, and sintering process is: 80 DEG C/min of heating rate, first rank are warming up to 600 DEG C, are incubated 3min, and second stage is warming up to 1050 DEG C, insulation 8min, sintering pressure 50MPa, be then quickly cooled to room temperature.
Embodiment 6
Be averaged the cobalt powder of granularity respectively 1.0um, the tungsten powder of 1.2um, 0.8um carbon dust be configured to Co-W-C mixed-powder, wherein carbon content is 1.87wt%.Mixed-powder, the sintered carbide ball (4mm, 6mm, 10mm) of three kinds of different-diameters, dehydrated alcohol addition hard alloy ball grinder will carry out batch (-type) ball milling, the weight ratio of sintered carbide ball and Co-W-C mixed-powder is 3:1, Ball-milling Time is 30 hours, and rotational speed of ball-mill is 120r/min.Mixed powder after ball milling is dried, adds dehydrated alcohol and cold pressing, pressure is 4MPa, pressed compact is placed in vacuum drying oven and carries out chemical reaction, in stove, vacuum is 0.04Pa, 8 DEG C/min of the rate of heat addition, reaction temperature 1300 DEG C, temperature retention time 1 hour, quickly can obtain pure single-phase double carbide Co after cooling3W3C powder green bodies, carries out batch (-type) ball milling by this powder green bodies, and dehydrated alcohol is ball-milling medium, sintered carbide ball and Co3W3The weight ratio of C is 5:1, and Ball-milling Time is 50h, and rotational speed of ball-mill is 180r/min.Adopt dehydrated alcohol to cross 500 order mesh screens for the carrier that sieves after ball milling, be then dried.The Co that will obtain after drying3W3C powder body loads mould, cold moudling, sends in discharging plasma sintering equipment, and sintering process is: 100 DEG C/min of heating rate, first rank are warming up to 700 DEG C, are incubated 6min, and second stage is warming up to 1100 DEG C, insulation 5min, sintering pressure 40MPa, be then quickly cooled to room temperature.
Claims (2)
1. a pure single-phase double carbide Co3W3The preparation method of C powder body material, it is characterised in that comprise the following steps:
(1) with the cobalt powder of granularity 0.8～1.2um, the tungsten powder of granularity 0.6～1.2um, granularity 0.4～0.8um carbon dust carry out proportioning for raw material, wherein cobalt powder and tungsten powder are according to Co3W3The mol ratio of C carries out proportioning, and 1.81wt%～1.92wt% that carbon content is total powder；
(2) step (1) described raw material is configured to W-Co-C mixed powder in proportion, adds together with sintered carbide ball, dehydrated alcohol in hard alloy ball grinder.The weight ratio of sintered carbide ball and W-Co-C mixed powder is (2～4): 1, and Ball-milling Time is 20～30 hours, and rotational speed of ball-mill is 80～120r/min；Wherein, sintered carbide ball is containing 3 kinds of different-diameter respectively 2～4mm, 5～8mm, 9～12mm, and the every 2～4h of mechanical milling process stops once, and dwell time is 15～30min；
(3) mixed powder after ball milling is dried, cold pressing, powder body in bulk after colding pressing for guarantee, a certain amount of dehydrated alcohol need to be added in forward direction powder of colding pressing, the dehydrated alcohol added and the volume ratio of powder body are 1:(15～25), pressure of colding pressing is 3～6MPa, by base substrate vacuum drying 12～20h after pressed compact, then put it into and in vacuum drying oven, carry out chemical reaction, in stove, vacuum is≤0.05Pa, 4～8 DEG C/min of the rate of heat addition, reaction temperature 1230～1300 DEG C, temperature retention time 1～2 hour, can obtain after cooling containing pure single-phase double carbide Co3W3C powder body base substrate；
(4) by the Co described in step (3)3W3C powder body base substrate carries out ball mill crushing, and dehydrated alcohol is ball-milling medium, and hard alloy bulb diameter is 9～12mm, itself and Co3W3The weight ratio of C powder body base substrate is (5～7): 1, and Ball-milling Time is 30～50 hours, and rotational speed of ball-mill is 140～180r/min, and the every 2～4h of mechanical milling process stops once, and dwell time is 15～30min；
(5) use the mesh screen of 400～600 orders to the Co after ball milling3W3C powder is filtered screening, and dehydrated alcohol is the carrier that sieves, the Co sieved3W3After C is dried, thing Co mutually pure, even-grained can be obtained3W3C powder body.
2. a pure single-phase double carbide Co3W3The preparation method of C block materials, it is characterised in that comprise the following steps:
(1) with the cobalt powder of granularity 0.8～1.2um, the tungsten powder of granularity 0.6～1.2um, granularity 0.4～0.8um carbon dust carry out proportioning for raw material, wherein cobalt powder and tungsten powder are according to Co3W3The mol ratio of C carries out proportioning, and 1.81wt%～1.92wt% that carbon content is total powder；
(2) step (1) described raw material is configured to W-Co-C mixed powder in proportion, adds together with sintered carbide ball, dehydrated alcohol in hard alloy ball grinder.The weight ratio of sintered carbide ball and W-Co-C mixed powder is (2～4): 1, and Ball-milling Time is 20～30 hours, and rotational speed of ball-mill is 80～120r/min；Wherein, sintered carbide ball is containing 3 kinds of different-diameter respectively 2～4mm, 5～8mm, 9～12mm, and the every 2～4h of mechanical milling process stops once, and dwell time is 15～30min；
(3) mixed powder after ball milling is dried, cold pressing, powder body in bulk after colding pressing for guarantee, a certain amount of dehydrated alcohol need to be added in forward direction powder of colding pressing, the dehydrated alcohol added and the volume ratio of powder body are 1:(15～25), pressure of colding pressing is 3～6MPa, by base substrate vacuum drying 12～20h after pressed compact, then put it into and in vacuum drying oven, carry out chemical reaction, in stove, vacuum is≤0.05Pa, 4～8 DEG C/min of the rate of heat addition, reaction temperature 1230～1300 DEG C, temperature retention time 1～2 hour, can obtain after cooling containing pure single-phase double carbide Co3W3C powder body base substrate；
(4) by the Co described in step (3)3W3C powder body base substrate carries out ball mill crushing, and dehydrated alcohol is ball-milling medium, and hard alloy bulb diameter is 9～12mm, itself and Co3W3The weight ratio of C powder body base substrate is (5～7): 1, and Ball-milling Time is 30～50 hours, and rotational speed of ball-mill is 140～180r/min, and the every 2～4h of mechanical milling process stops once, and dwell time is 15～30min；
(5) use the mesh screen of 400～600 orders to the Co after ball milling3W3C powder is filtered screening, and dehydrated alcohol is the carrier that sieves, the Co sieved3W3After C is dried, thing Co mutually pure, even-grained can be obtained3W3C powder body；
(6) by mutually pure, even-grained for step (5) gains Co3W3C powder body loads mould, cold moudling, send into sintering in discharging plasma sintering equipment, sintering process is as follows: heating rate 60-100 DEG C/min, and the first rank are warming up to 500～700 DEG C, is incubated 3～6min, second stage is warming up to 1020 DEG C～1100 DEG C, insulation 5～10min, sintering pressure 30-60MPa, can obtain the Co containing single thing phase after being cooled to room temperature3W3C block materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610096389.3A CN105731457B (en) | 2016-02-22 | 2016-02-22 | A kind of pure single-phase double carbide Co3W3C preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610096389.3A CN105731457B (en) | 2016-02-22 | 2016-02-22 | A kind of pure single-phase double carbide Co3W3C preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105731457A true CN105731457A (en) | 2016-07-06 |
| CN105731457B CN105731457B (en) | 2017-10-31 |
Family
ID=56246144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610096389.3A Active CN105731457B (en) | 2016-02-22 | 2016-02-22 | A kind of pure single-phase double carbide Co3W3C preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105731457B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553112A (en) * | 2018-11-12 | 2019-04-02 | 北京工业大学 | A kind of preparation method of single-phase WCoB powder |
| CN109659051A (en) * | 2019-01-02 | 2019-04-19 | 中国原子能科学研究院 | A kind of preparation method of U-Zr-C fuel |
| CN109821652A (en) * | 2018-09-28 | 2019-05-31 | 甘肃虹光电子有限责任公司 | A kind of cathode tungsten powder classification and sorting processing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009007623A (en) * | 2007-06-27 | 2009-01-15 | Kyocera Corp | Small-sized bar-shaped cemented carbide, cutting tool and miniature drill |
| CN103819192A (en) * | 2013-12-11 | 2014-05-28 | 西安交通大学 | Fe, W and C ternary phase carbide Fe3W3C and preparation method thereof |
-
2016
- 2016-02-22 CN CN201610096389.3A patent/CN105731457B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009007623A (en) * | 2007-06-27 | 2009-01-15 | Kyocera Corp | Small-sized bar-shaped cemented carbide, cutting tool and miniature drill |
| CN103819192A (en) * | 2013-12-11 | 2014-05-28 | 西安交通大学 | Fe, W and C ternary phase carbide Fe3W3C and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821652A (en) * | 2018-09-28 | 2019-05-31 | 甘肃虹光电子有限责任公司 | A kind of cathode tungsten powder classification and sorting processing method |
| CN109821652B (en) * | 2018-09-28 | 2021-07-09 | 甘肃虹光电子有限责任公司 | Cathode tungsten powder grading and sorting treatment method |
| CN109553112A (en) * | 2018-11-12 | 2019-04-02 | 北京工业大学 | A kind of preparation method of single-phase WCoB powder |
| CN109553112B (en) * | 2018-11-12 | 2022-03-22 | 北京工业大学 | Preparation method of single-phase WCoB powder |
| CN109659051A (en) * | 2019-01-02 | 2019-04-19 | 中国原子能科学研究院 | A kind of preparation method of U-Zr-C fuel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105731457B (en) | 2017-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102876907B (en) | Preparation method of tungsten carbide-cobalt or tungsten carbide-cobalt-chromium thermal spraying powder | |
| CN106964346B (en) | A kind of palladium/graphene catalyst and preparation method thereof for ten dihydro ethyl carbazole dehydrogenations | |
| CN101658940B (en) | Method for recycling and regenerating hard alloy | |
| CN105731457A (en) | Preparation method of pure single-phase ternary carbide Co3W3C | |
| CN102259186A (en) | Method for producing thin spherical tungsten powder | |
| CN106698427A (en) | Activated carbon, preparation method thereof, and application of activated carbon in supercapacitor electrode | |
| CN103055893B (en) | Supported cobalt platinum superlattices alloy nano particle composite catalyst and preparation method thereof | |
| CN101837463A (en) | Method preparing superfine metallic nickel powder with high frequency plasma | |
| CN102839313B (en) | Nano Cr3C2-WC-Ni composite powder and preparation method thereof | |
| CN104150908A (en) | Titanium-molybdenum carbide ceramic powder and preparation method thereof | |
| CN105126867A (en) | Carbon-supported Pt-Ru-Ni catalyst, preparation method and application thereof | |
| CN1749422A (en) | In-situ synthetic method for WC-Co hard alloy | |
| WO2015124094A1 (en) | Method for preparing tantalum powder for high-reliability, high specific capacity electrolytic capacitor | |
| CN106636844A (en) | Niobium alloy powder suitable for laser 3D printing and preparation method of niobium alloy powder | |
| CN108658038A (en) | One kind being based on LiAlH4Hydrogen storage material and preparation method thereof | |
| CN102134073B (en) | Preparation method of ultrafine tantalum carbide powder | |
| CN101332512B (en) | Preparation method of chromium powder for producing copper-chromium contact | |
| CN103143716B (en) | Preparation method of tungsten powder | |
| CN103205589B (en) | Hard alloy taking Ni-Al intermetallic compound as binding phase and preparation method thereof | |
| CN102031411B (en) | Method for preparing compact W-Cu composite material at low temperature | |
| CN112091208B (en) | Heat conduction copper powder with bimodal distribution characteristics and preparation method and application thereof | |
| CN116618642B (en) | Nickel powder with large particles and low apparent density and preparation method and application thereof | |
| CN117185781A (en) | Indium gallium aluminum oxide powder, target material, powder and preparation method of target material | |
| CN102114542B (en) | Low-temperature sintering method for high-performance Fe-based powder metallurgy parts | |
| CN107245625A (en) | A kind of Tungsten carbide titanium tantalum molybdenum solid-solution powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |