CN109943739B - A method for preparing ultrafine-grained WC-Co cemented carbide by plasma ball milling - Google Patents
A method for preparing ultrafine-grained WC-Co cemented carbide by plasma ball milling Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
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- 238000005245 sintering Methods 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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Abstract
The invention discloses a plasma ballA method for preparing ultra-fine grain WC-Co hard alloy by grinding. With WO3And graphite as raw materials, performing discharge ball milling pretreatment by using plasma, then putting the raw materials into a vacuum sintering furnace to synthesize high-purity nano WC powder in situ, finally mixing the nano WC powder with Co, performing ball milling, pressing and sintering to prepare the superfine WC-Co hard alloy. The plasma ball milling is adopted, so that the ball milling time is shortened, the powder activity is greatly improved, and the in-situ synthesis and sintering temperature of the WC phase are obviously reduced. Therefore, the method for preparing the ultra-fine grain hard alloy has low cost, low energy consumption, short flow and simple and convenient process; the prepared hard alloy WC has fine grain size and excellent mechanical property.
Description
Technical Field
The invention belongs to the technical field of hard alloy and powder metallurgy, and particularly relates to a method for preparing ultrafine-grained WC-Co hard alloy by plasma ball milling.
Background
The WC-Co hard alloy is the most developed hard alloy, and is widely applied to the fields of cutting, dies, wear-resistant parts, mine tools and the like due to the high hardness, wear resistance and transverse rupture strength. According to the method, W, C is generally used as a raw material in industry, WC is synthesized by high-temperature carbonization at 1400 ℃, then mixed with Co and ball-milled for a long time to prepare WC-Co composite powder, and then granulation, pressing, dewaxing and finally high-temperature sintering are carried out, wherein after twice high-temperature treatment, WC grows seriously, and the superfine crystal hard alloy is difficult to prepare. In order to reduce the raw material cost and prepare ultra-fine grained hard alloy, cheap WO is also commonly adopted in industry3Instead of the reaction of in-situ synthesis of WC by taking the W simple substance as a raw material and graphite at high temperature, WO is generally used before the reaction in order to realize the complete synthesis of WC phase with high purity3The powder mixed with graphite needs to be ball-milled to activate the powder, but the ball-milling efficiency of the traditional ball-milling method is too low, the ball-milling time is long, and the powder pollution is serious in the ball-milling process. Chinese patent CN101624673A discloses an industrial preparation method for preparing high-performance WC-Co hard alloy, which takes tungsten-cobalt oxide and carbon black as raw materialsThe material is prepared into the hard alloy through common ball milling pretreatment, in-situ synthesis, pressing and sintering. The method adopts the common ball milling with low efficiency, the activity of the powder after ball milling is not high, the required in-situ synthesis temperature is high, the particle size of the synthesized WC powder is large, and the average particle size can reach 210nm only on the basis of adding the grain growth inhibitor. Although the superfine WC hard alloy can be prepared at a lower sintering temperature by applying novel sintering technologies such as microwave sintering and plasma sintering even through common ball-milling pretreatment, compared with the existing production equipment, the price of the novel sintering equipment is quite high, the quantity of materials prepared at one time is very limited, and large-size hard alloy blocks are difficult to prepare, so that the method developed aiming at the equipment can only be applied in a laboratory range and cannot be popularized to actual industrial production. The use of in situ synthesis + low pressure sintering/vacuum sintering remains a common method of industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention mainly aims to provide a method for preparing ultrafine grain WC-Co hard alloy by plasma ball milling. The invention prepares high-activity WO in very short ball milling time3the-C composite powder can obviously reduce the temperature of in-situ synthesis of nano WC powder and the subsequent sintering temperature, and prepare the ultrafine grain WC-Co hard alloy with fine grains.
The technical scheme of the invention is as follows: with WO3And graphite as raw materials, performing discharge ball milling pretreatment by using plasma, then putting the raw materials into a vacuum sintering furnace to synthesize high-purity nano WC powder in situ, finally mixing the nano WC powder with Co, performing ball milling, pressing and sintering to prepare the superfine WC-Co hard alloy. The method has short ball milling time and low in-situ synthesis temperature, can realize rapid in-situ preparation of the superfine WC-Co cemented carbide, and has outstanding industrial application value.
The purpose of the invention is realized by the following technical scheme:
a method for preparing ultra-fine grain WC-Co hard alloy by plasma ball milling comprises the following steps:
(1) mixing WO3And graphite is added into a plasma ball mill and added withoutBall milling is carried out by using water and ethanol as grinding aids to prepare WO3-C composite powder; mixing WO3Heating the-C composite powder, and carrying out in-situ reduction reaction to obtain nano WC powder;
(2) mixing Co with the nano WC powder prepared in the step (1) according to the ratio of WC-X Co, wherein X is 6-12, adding carbon supplement and performing plasma ball milling again to prepare nano WC-Co composite powder;
(3) and (3) pressing and sintering the nano WC-Co composite powder obtained in the step (2) to obtain the superfine WC-Co cemented carbide.
Preferably, WO as described in step (1)3And the graphite by mass part ratio of 80-85: 15 to 20.
Preferably, the absolute ethyl alcohol in the step (1) is added in an amount of WO3And 1-3 wt% of the total mass of graphite.
Preferably, the parameters of the plasma ball mill in the step (1) are as follows: the ball-material ratio is 15: 1-50: 1, the ball milling time is 3 h-10 h, the rotating speed of the ball mill is 960-1400 rpm, and the plasma discharge atmosphere is 5 multiplied by 103～1×105Pa, the dielectric constant of the dielectric barrier layer is 2-10, and the thickness of the dielectric barrier layer is 3-5 mm.
Preferably, the heating temperature in the step (1) is 950-1150 ℃, the heating time is 1-2h, and the heating pressure is 1 × 10-3～1×10-4Pa。
Preferably, WO as described in step (1)3The particle size of (A) is 5 to 10 μm.
Preferably, the amount of the carbon supplement in the step (2) is 0.2-0.3 wt% of the total mass of the nano WC powder and the Co.
Preferably, the particle size of Co in the step (2) is 30-50 μm.
Preferably, the time for performing the plasma ball milling again in the step (2) is 1-3 h.
Preferably, the pressure of the pressing in the step (3) is 100-150 MPa.
Preferably, the sintering temperature in the step (3) is 1350-1410 ℃, and the sintering time is 1-2 h.
Preferably, the sintering in step (3) is trueAir sintering or low-pressure sintering, preferably, the pressure of the low-pressure sintering is 4-5 Mpa, and the pressure of the vacuum sintering is 1 multiplied by 10-3～5×10-3Pa。
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) firstly, a chemical thermodynamic model is applied, and WO is calculated3And the change of Gibbs free energy of the graphite in-situ reduction carbonization reaction in a vacuum state, theoretically analyzes the feasibility of the in-situ reaction, and is based on WO3And calculating the theoretical carbon distribution range by using a graphite reaction equation, and guiding the formulation of the technological parameters of the patent to obtain the high-purity nanocrystalline WC powder.
(2) The invention uses cheap WO3Replaces expensive simple substance W as raw material, can effectively reduce production cost, and simultaneously utilizes graphite and WO3The in-situ reaction characteristic of the method can synthesize nano granular WC powder with high specific surface area and high activity, and the method is ready for preparing the ultrafine grain WC hard alloy.
(3) The invention adopts the plasma discharge ball milling, can obviously improve the ball milling efficiency, shorten the ball milling time and avoid the impurity pollution caused by the ball milling, because the plasma discharge ball milling combines the mechanical energy and the plasma field energy, the plasma ionization electrons adsorb the surface of the powder, and the graphite is easy to form a super-flaky structure under the action of the plasma, thereby increasing the WO3The reaction interface area of/C, so that WO can be significantly refined and activated3And graphite composite powder, effectively reducing WO3And the in-situ reaction temperature of the graphite is controlled, so that the growth of WC at high temperature is avoided, and the nano WC powder is synthesized.
(4) The invention adopts the low-pressure sintering technology to effectively promote the powder densification process, and can prepare the bulk hard alloy close to full densification at lower sintering temperature and heat preservation time, thereby effectively avoiding the WC crystal grains from growing seriously at overhigh sintering temperature or overlong heat preservation time. The size of the final hard alloy WC crystal grain is only 350-450 nm, and the final hard alloy WC crystal grain belongs to the superfine crystal range.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention.
FIG. 2 shows WO prepared in step (1) of example 1 of the present invention3SEM image of composite powder of-C.
FIG. 3 is WO prepared in step (1) of example 3 of the present invention3XRD pattern of composite powder of-C.
FIG. 4 shows the nano-sized WO prepared in step (1) of example 1 of the present invention3DSC-TG pattern of the C composite powder.
Fig. 5 is an XRD pattern of the nano WC powder obtained in step (2) of example 2 of the present invention.
Fig. 6 is an SEM image of the nano WC powder obtained in step (2) of example 2 of the present invention.
FIG. 7 is an XRD pattern of WC-10Co cemented carbide obtained in step (3) of example 2 according to the present invention.
FIG. 8 is an SEM photograph of a WC-8Co cemented carbide produced in step (3) of example 4 according to the present invention.
FIG. 9 is an SEM photograph of the polished WC-8Co cemented carbide obtained in step (3) of example 4 according to the invention.
FIG. 10 is a diagram showing the distribution of WC grain size in the WC-8Co cemented carbide obtained in step (3) in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the argon atmosphere plasma discharge ball milling method of the embodiment, the milling balls are hard alloy milling balls, the tank body is a hard alloy lining stainless steel tank, and the total volume of the milling balls accounts for 30% -50% of the volume of the ball milling tank. The specific diameter size and the number proportion of the grinding balls are as follows, wherein the grinding balls with the diameter of 22mm account for 15%, the grinding balls with the diameter of 15mm account for 25%, the grinding balls with the diameter of 10mm account for 30%, and the grinding balls with the diameter of 6mm account for 30%. The volume of the ball milling powder accounts for 40% of the gap between the milling balls, the material ratio of the milling balls is 15: 1-50: 1, the discharge voltage is 15KV, the discharge current is 1.5A, the vibration excitation block adopts double amplitude of 5mm, and the ball milling speed is 960-1400 rpm.
Example 1
WC-12Co cemented carbide
(1) 85g of WO3Adding 15g of graphite mixed powder into a plasma discharge auxiliary ball mill in argon atmosphere under 1 atmospheric pressure to perform plasma discharge ball milling, and adding WO3And absolute ethyl alcohol accounting for 1 wt% of the total mass of the graphite is used as a grinding aid. The electrode bar takes the king plastic as a medium barrier layer, the thickness is 3mm, the ball-material ratio is 15:1, the ball-milling rotating speed is 960rpm, and the ball-milling time is 6 hours, so that the high-activity nano WO is obtained3-C.
(2) Nano WO obtained in the step (1)3Putting the-C composite powder into a vacuum tube sintering furnace, and vacuumizing to 1 x 10-3Pa, heating to 950 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h to ensure that the graphite and the WO3Fully reacting to obtain the nanometer WC powder.
(3) And (3) proportioning the nano WC powder obtained in the step (2) with Co according to the components of WC-12Co, adding graphite accounting for 0.3% of the total mass of the WC powder and the Co, carrying out plasma ball milling for 3 hours to obtain uniformly mixed WC-Co composite powder, pressing, and carrying out vacuum sintering at 1350 ℃ for 1 hour to obtain the ultrafine grain WC-12Co hard alloy. Wherein the pressing force is 100MPa, and the vacuum sintering pressure is 1 × 10-3Pa。
The WC grain size of the WC-12Co hard alloy prepared in the embodiment is 650-750 nm, the phase composition of the WC and Co is analyzed by XRD, and the density is 98.2%.
Example 2
WC-10Co hard alloy
(1) 80g of W03Mixing 20g of graphite powder, homogenizing and stirring for 3 hr, and mixing with the obtained WO3And placing graphite powder into a plasma discharge auxiliary ball mill in argon atmosphere with 0.05 atmospheric pressure to perform plasma discharge ball milling on the graphite powder, and adding WO3And absolute ethyl alcohol accounting for 1.5 wt% of the total mass of the graphite is used as a grinding aid. The electrode bar takes the king plastic as a medium barrier layer, the thickness is 4mm, the ball-material ratio is 30:1, the ball-milling rotating speed is 1400rpm, and the ball-milling time is 6h, so that the nano WO is obtained3-C composite powder.
(2) Will be provided withThe nanometer WO obtained in the step (1)3Placing the-C composite powder in a vacuum tube sintering furnace, and vacuumizing to 1 x 10-3Pa, heating to 1150 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 2h to ensure that the graphite and the WO3Fully reacting, and obtaining pure nanometer WC powder through XRD analysis.
(3) Proportioning the nano WC powder obtained in the step (2) and Co according to the components of WC-10Co, adding graphite accounting for 0.2 percent of the total mass of the WC powder and the Co, carrying out ball milling for 3 hours by using plasma, finally obtaining uniformly mixed WC-Co composite powder, finally pressing, and carrying out vacuum sintering for 1 hour at 1400 ℃ to obtain the ultrafine grain WC-10Co hard alloy, wherein the pressing force is 120MPa, and the vacuum sintering pressure is 1 x 10-3Pa。
According to XRD analysis, the WC-10Co hard alloy prepared in the embodiment has the phase compositions of WC and Co and the density of 98.5%.
Example 3
WC-8Co hard alloy
(1) 82g of W03Mixing 18g of graphite powder, placing into a plasma discharge auxiliary ball mill in argon atmosphere with 1 atm, performing plasma discharge ball milling, and adding WO3And absolute ethyl alcohol accounting for 2 wt% of the total mass of the graphite is used as a grinding aid. The electrode bar takes ceramic as a medium barrier layer, the thickness of the electrode bar is 5mm, the ball-material ratio is 50:1, the ball-milling rotating speed is 960rpm, and the ball-milling time is 6 hours, so that the nano WO is obtained3-C.
(2) Nano WO obtained in the step (1)3Placing the-C composite powder in a vacuum tube sintering furnace, and vacuumizing to 1 x 10-3Pa, heating to 1150 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h to ensure that the graphite and the WO3Fully reacting, and obtaining the nano WC powder with a phase only containing WC by XRD analysis.
(3) And (3) proportioning the nano WC powder prepared in the step (2) and Co according to the components of WC-8Co, adding graphite accounting for 0.25% of the total mass of the WC powder and the Co, carrying out ball milling for 3 hours by using plasma to obtain uniformly mixed WC-Co composite powder, and finally carrying out pressing and low-pressure sintering at the same sintering temperature of 1350 ℃ for heat preservation for 1 hour to obtain the ultrafine grain WC-8Co hard alloy. Wherein the pressing force is 150MPa, and the low-pressure sintering pressure is 4 MPa.
According to XRD analysis, the WC-8Co hard alloy prepared in the embodiment has the phase compositions of WC and Co and the density of 99.0%.
Example 4
WC-8Co hard alloy
(1) 82g of WO3Mixing 18g of graphite powder, placing into a plasma discharge auxiliary ball mill in argon atmosphere with 1 atm, performing plasma discharge ball milling, and adding WO3And absolute ethyl alcohol accounting for 2 wt% of the total mass of the graphite is used as a grinding aid. The electrode bar takes ceramic as a medium barrier layer, the thickness of the electrode bar is 4mm, the ball-material ratio is 50:1, the ball-milling rotating speed is 960rpm, and the ball-milling time is 10 hours, so that the nano WO is obtained3-C.
(2) Nano WO obtained in the step (1)3Placing the-C composite powder in a vacuum tube sintering furnace, and vacuumizing to 1 x 10-3Pa, heating to 1150 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h to ensure that the graphite and the WO3Fully reacting, and obtaining pure nanometer WC powder through XRD analysis.
(3) And (3) proportioning the nano WC powder obtained in the step (2) and Co according to the components of WC-8Co, adding graphite accounting for 0.25% of the total mass of the WC powder and the Co, adding 2% of paraffin to prepare a molding agent, carrying out plasma ball milling for 1h to obtain uniformly mixed WC-Co composite powder, and finally carrying out pressing and low-pressure sintering at a sintering temperature of 1390 ℃ and keeping the temperature for 1h to obtain the ultrafine-grained WC-8Co hard alloy. Wherein the pressing force is 150MPa, and the low-pressure sintering pressure is 5 MPa.
The grain size of WC in the WC-8Co hard alloy prepared in the embodiment is 450-550 nm, and through XRD analysis, the phase composition of WC and Co is 99.4% in density and 2610MPa in bending strength.
Example 5
WC-8Co hard alloy
(1) 82g of WO3Mixing 18g of graphite powder, placing into a plasma discharge auxiliary ball mill in argon atmosphere with 1 atm, performing plasma discharge ball milling, and adding WO3And 3 wt% of absolute ethyl alcohol of the total mass of the graphiteAnd (4) grinding agent. The electrode bar takes ceramic as a medium barrier layer, the thickness of the electrode bar is 4mm, the ball-material ratio is 50:1, the ball-milling rotating speed is 960rpm, and the ball-milling time is 3 hours, so that the nano WO is obtained3-C.
(2) Nano WO obtained in the step (1)3Placing the-C composite powder in a vacuum tube sintering furnace, and vacuumizing to 1 x 10-3Pa, heating to 1050 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h to ensure that the graphite and the WO are mixed3Fully reacting to obtain the nano WC powder with the average grain diameter of 110 nm.
(3) And (3) proportioning the nano WC powder obtained in the step (2) and Co according to the components of WC-8Co, adding graphite accounting for 0.25% of the total mass of the WC powder and Co, adding 2% of paraffin to prepare a molding agent, carrying out plasma ball milling for 1h to obtain uniformly mixed WC-Co composite powder, and finally carrying out pressing and low-pressure sintering at the sintering temperature of 1410 ℃ and carrying out heat preservation for 1h to obtain the ultrafine grain WC-8Co hard alloy. Wherein the pressing force is 150MPa, and the low-pressure sintering pressure is 5 MPa.
The WC grain size of the WC-8Co hard alloy prepared in the embodiment is 350-450 nm, the phase composition of the WC-8Co hard alloy is WC and Co through XRD analysis, the density is 99.4%, and the bending strength is 2821 MPa.
FIG. 4 shows the nano-sized WO prepared in step (1) of example 1 of the present invention3DSC-TG pattern of the C composite powder. As can be derived from FIG. 4, WO was obtained by plasma ball milling3the-C composite powder has high activity, and the initial temperature drop of in-situ reduction is 851 ℃.
Fig. 6 is an SEM image of the nano WC powder obtained in step (2) of example 2 of the present invention. As can be seen from fig. 6, the in-situ synthesized WC particles are fine and uniformly dispersed, and have a high sphericity.
Fig. 10 is a WC grain size distribution diagram of the WC-8Co hard alloy prepared in step (3) of example 4 of the present invention, and it can be obtained from fig. 10 that the WC grains in the WC-8Co hard alloy prepared by the in-situ reduction method are very fine, and the WC grain size is 450 to 550 nm.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
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| PCT/CN2019/112876 WO2020186752A1 (en) | 2019-03-15 | 2019-10-23 | Method for preparing superfine grain wc-co hard alloy by means of plasma ball milling |
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|---|---|---|---|---|
| CN109943739B (en) * | 2019-03-15 | 2021-02-19 | 华南理工大学 | A method for preparing ultrafine-grained WC-Co cemented carbide by plasma ball milling |
| CN111826568A (en) * | 2020-07-09 | 2020-10-27 | 南昌航空大学 | Preparation method of WC-6Co-graphite self-lubricating cemented carbide |
| CN112723862B (en) * | 2020-12-29 | 2022-11-22 | 太原理工大学 | A simple and low-cost method for preparing high-entropy oxide ceramic materials |
| CN112941352B (en) * | 2021-01-27 | 2022-06-21 | 崇义章源钨业股份有限公司 | Hard alloy and preparation method thereof |
| CN115161505A (en) * | 2022-07-21 | 2022-10-11 | 广东工业大学 | Preparation method of a new type of binder phase cemented carbide |
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| CN116516199A (en) * | 2023-04-10 | 2023-08-01 | 浙江福达合金材料科技有限公司 | Silver tungsten carbide contact material and preparation method thereof |
| CN116969763B (en) * | 2023-09-25 | 2023-12-12 | 成都先进金属材料产业技术研究院股份有限公司 | Graphene-toughened non-bonding-phase WC-based hard alloy and preparation method thereof |
| CN118649764B (en) * | 2024-08-15 | 2024-12-13 | 上海纳琳威科技股份有限公司 | Method and system for improving product dispersibility by adjusting ball-to-material ratio of ball mill |
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| AT410939B (en) * | 2000-12-20 | 2003-08-25 | Treibacher Ind Ag | METHOD FOR THE PRODUCTION OF TUNGSTEN CARBIDE |
| CN1232669C (en) * | 2004-03-12 | 2005-12-21 | 北京工业大学 | Method of WC hard alloy by electric discharge plasma in situ synthesis |
| CN1749422A (en) * | 2005-09-30 | 2006-03-22 | 北京工业大学 | In Situ Synthesis Method of WC－Co Cemented Carbide |
| CN101117673A (en) * | 2007-09-13 | 2008-02-06 | 上海大学 | Preparation method of cemented carbide containing plate-like tungsten carbide grains |
| CN101285134B (en) * | 2008-05-30 | 2011-08-31 | 华南理工大学 | Preparation method for WC-Co cemented carbide |
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| JP6913996B2 (en) * | 2017-03-28 | 2021-08-04 | 日本新金属株式会社 | Manufacturing method of fine tungsten carbide powder |
| CN109943739B (en) * | 2019-03-15 | 2021-02-19 | 华南理工大学 | A method for preparing ultrafine-grained WC-Co cemented carbide by plasma ball milling |
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