CN104313380A - Method for preparing high density nanocrystalline hard alloy by step sintering - Google Patents
Method for preparing high density nanocrystalline hard alloy by step sintering Download PDFInfo
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Abstract
The invention provides a method for preparing a high density nanocrystalline hard alloy by step sintering, and belongs to the technical field of novel materials and novel powder metallurgy. The method comprises the following steps: firstly determining the dosage of the raw materials according to the requirements on the content of Co in the final hard alloy based on nanoscale purple tungsten oxide, cobaltous oxide, carbon black and mixed powder of vanadium oxide and chromic oxide as raw materials, mixing the raw materials and performing ball milling, then pressing the raw materials to blocks and conveying the pressed raw materials into a vacuum pump to perform a in-situ reaction to prepare nanometer composite powder with uniform distribution and good dispersity; filling the nanometer composite powder into a high density hard alloy mold, performing discharge plasma sintering, and performing segmented heating, heating up and heat preservation processes to obtain a pre-sintered block with controllable length and size of crystalline grain; finally, putting the pre-sintered block in a high-strength graphite mold to perform high temperature instant discharge plasma quick sintering densification to finally obtain a dense nanocrystalline hard alloy block material. The method provided by the invention can be used for effectively improving the density and mechanical properties of the hard alloy block material.
Description
Technical field
The present invention relates to a kind of preparation method of high-compactness nanocrystalline WC-Co hard alloy, reduced the porosity of Nanograin Cemented Carbide by step sintering, obtain high density and mechanical property, belong to novel material and Novel powder metallurgy technical field.
Background technology
In Wimet, the WC-Co series hard metal tool material that the high-tech area that becomes is indispensable because having high hardness, toughness and bending strength, especially Nanograin Cemented Carbide, shows excellent hardness and toughness over-all properties.But, the preparation of existing WC-Co system nano-crystal Wimet block material still rests on the laboratory study stage, prepare full densification at present, have the Nanograin Cemented Carbide block of hard high-strength concurrently and still there is very large difficulty, the industrial pressing needs to high-performance nano cemented carbide cannot be met.
Researchist adopted the method increasing grain growth inhibitor addition and Fast Sintering to prepare Nanograin Cemented Carbide usually in the past, although reach desired result in hard phase WC grain size in reduction Wimet, the problem that the density of sintering block is lower is but difficult to break through always.
No matter the preparation of Wimet block material adopts solid state sintering or liquid phase sintering, sintering temperature is all more than 1000 DEG C, it is inevitable phenomenon that WC grain is grown up in sintering process, control WC grain Size growth, reducing sintering temperature is inevitable approach, but lower sintering temperature cannot be got rid of again between powder particle and the gas of particle surface absorption, causes the porosity of sintering block higher, density is low, cannot obtain the Nanograin Cemented Carbide with the mechanical property such as high tenacity, high strength.For the preparation research present situation of domestic and international Nanograin Cemented Carbide, we research and develop a kind of adopt high pressure presintering after to carry out fast low temperature densification again the preparation of two-step method technology there is the Nanograin Cemented Carbide block materials of high-compactness, be showed no relevant report both at home and abroad.
Summary of the invention
The object of the present invention is to provide and a kind ofly obtain high-compactness by step sintering, method that nanocrystal organizes WC-Co hard alloy block materials.First the purple tungsten (WO of nanoscale is utilized
2.72), Co
3o
4with carbon black (C) and vanadium oxide (V
2o
3) and chromic oxide (Cr
2o
3) mixed powder be raw material, the amount ratio of above-mentioned raw materials is calculated according to the requirement of Co content in final Wimet block material, after the process of raw material mixing and ball milling, briquetting is also sent in vacuum oven and is carried out the WC-Co-VC/Cr that reaction in－situ obtains distributed components, the median size of favorable dispersity is about 70nm
3c
2composite powder; Secondly by nano WC-Co-VC/Cr
3c
2composite powder loads high-strength sintered-carbide die, carries out discharge plasma sintering, adopts segmentation pressurization, heats up and the technological line be incubated and processing step, obtain having high-compactness and the controllable presintering block of grain growth; Finally the block after presintering is put into high-strength graphite mould and carry out the densification of high temperature, short time plasma discharging Fast Sintering, finally obtain the nearly full-compact nanometer cemented carbide block materials of density more than 99.0%.Low and the environmental protection of the technological line energy consumption of the nanocrystalline WC-Co hard alloy block materials prepared by the present invention, prepared block materials has high density and mechanical property while guarantee nanocrystalline grain size, and the batch for Nanograin Cemented Carbide prepares and industrial application provides important technical foundation.
Step sintering provided by the invention prepares the method for high-compactness Nanograin Cemented Carbide block materials, it is characterized in that, comprises the following steps:
(1) the raw material V first grain growth inhibitor synthesized
2o
3and Cr
2o
3tungsten WO purple with nanometer
2.72, cobalt oxide Co
3o
4mix with carbon black and carry out even refinement ball-milling processing, milling parameters is: ratio of grinding media to material is 25:1-30:1, and Ball-milling Time is 100-150h, and the mixed powder after ball milling puts into that vacuum reaction stove is obtained comprises grain growth inhibitor VC/Cr
3c
2wC-Co-VC/Cr
3c
2nano composite powder;
(2) by WC-Co-VC/Cr that step (1) prepares
3c
2nano composite powder loads sintered-carbide die precompressed, then put into discharging plasma sintering equipment and carry out cryogenic high pressure presintering, adopt following processing parameter: under sintering pressure 100-300MPa, temperature rises to 100 DEG C from room temperature, temperature rise rate is 10-50 DEG C/min, at 100 DEG C of insulation 10-30min; After insulation terminates, temperature rises to 300 DEG C by 100 DEG C, and temperature rise rate is 10-50 DEG C/min, at 300 DEG C, be incubated 10-30min; After insulation terminates, increase sintering pressure to 300-500MPa, temperature rises to 500-700 DEG C by 300 DEG C at this pressure, and temperature rise rate is 10-100 DEG C/min, at 500-700 DEG C of temperature, be incubated 30-60min;
(3) block in sintered-carbide die step (2) obtained after presintering loads in high-strength graphite mould, put into discharging plasma sintering equipment and carry out second step densification sintering, the processing parameter adopted is: sintering pressure is 70-240MPa, temperature rise rate is 50-100 DEG C/min, sintering temperature is 980-1040 DEG C, 1-3min is incubated at 980-1040 DEG C of temperature, 300 DEG C are cooled to the rate of cooling of 10-100 DEG C/min after insulation terminates, then cool to room temperature with the furnace, finally obtain the Nanograin Cemented Carbide block materials with high-compactness.
In the present invention, the consumption of carbon black guarantees to form WC-Co and grain growth inhibitor VC/Cr
3c
2there is not uncombined carbon simultaneously.
In the Nanograin Cemented Carbide block materials of preparation, the massfraction of grain growth inhibitor is generally 1.0%-2.0%, according to V in concrete numerical value determination raw material
2o
3and Cr
2o
3consumption.
Compared with the preparation method sintering block materials with existing Nanograin Cemented Carbide, essence feature of the present invention and creativeness are embodied in:
(1) existing method is all in WC-Co composite powder end or WC, Co mixed powder, directly add grain growth inhibitor to obtain sintering powdered material, and first the present invention prepares by single step reaction the nano WC-Co-VC/Cr containing grain growth inhibitor that massfraction is controlled, particle diameter is nanoscale
3c
2composite powder, by the WC-Co composite powder end of a step in-situ reaction preparation containing grain growth inhibitor, can reaction generate WC starting stage just makes part C, Cr atom dissolves in Co phase or be present in WC grain surface, thus ensure grain growth inhibitor distributing homogeneity and effectively suppress WC grain to be grown up at subsequent process; By the composite powder of fabricated in situ multiphase coexistence, realize the compound interpolation of chromium, vanadium carbide, can Cr be played
3c
2the hardness that effect effectively promotes the fracture toughness property of Wimet block material, the effect of VC effectively promotes Wimet block material, thus realizing the optimization of material comprehensive mechanical property, the hardness of Wimet block prepared by the present invention reaches 2000kg/mm
2above, fracture toughness property reaches 11.0MPa.m simultaneously
1/2above, the performance data having been reported Nanograin Cemented Carbide prepared by middle discharge plasma sintering has obviously been surmounted.Therefore, compared with existing method, the present invention prepare have in the processing method of sintered powder material, powder characteristics and preparation cycle etc. breakthrough.
(2) in the present invention to nano WC-Co-VC/Cr
3c
2composite powder carries out high pressure low temperature presintering, on the one hand heat treatment in advance is carried out to powder, except there is the effect of removal powder surface adsorbing contaminant, the also local stress of effectively release particles interface and inner existence, is reduced in the motivating force that in subsequent high temperature sintering process, WC grain is grown up while increase presintering block density; On the other hand, sintered-carbide die is adopted to solve the difficult problem that graphite jig cannot reach more than 250MPa ultimate compression strength, thus realize applying enough large pressure at cold stage to powder, to make in nanometer powder between particle and the gas of particle surface absorption is farthest discharged, effectively reduce at the interstitial probability of bulk inner in later stage high-temperature sintering process, thus increase substantially the density of sintering block.
(3) presintering process makes gas in powder substantially be excluded, carry out in plasma discharging Fast Sintering densification process to presintering block, venting exhaust air technique step can be no longer set, and rapid heating, the isothermal treatment for short time directly implemented presintering block, realize within the shortest time the final sintering densification of presintering block, like this, at the grain growth ensureing effectively to suppress while sintering block obtains full densification to cause in temperature-rise period.The density of the nanocrystalline WC-Co hard alloy block materials prepared by present method is all higher than 99.0%, Nanograin Cemented Carbide block materials density significantly more than current report is difficult to the result reaching more than 97.0%, and Nanograin Cemented Carbide block materials prepared by present method possesses excellent hardness and fracture toughness property over-all properties simultaneously.
Accompanying drawing explanation
Nanometer WC-12Co-1.0 (the VC/Cr used in Fig. 1 embodiment
3c
2) the microstructure figure of composite powder;
The scanning electron microscope (SEM) photograph of nanocrystalline WC-12Co Wimet block material microstructure prepared by Fig. 2 the present invention;
The microstructural transmission electron microscope picture of nanocrystalline WC-12Co Wimet block material prepared by Fig. 3 the present invention.
Embodiment
Following instance further illustrates the present invention, but the present invention is not limited to following examples.
Embodiment 1
According to preparing WC-Co-VC/Cr
3c
2grain growth inhibitor VC/Cr in composite powder
3c
2massfraction is 1.0wt.%, VC and Cr
3c
2mass ratio close to 1:1, the raw material V that grain growth inhibitor is synthesized
2o
3and Cr
2o
3tungsten WO purple with nanometer
2.72, cobalt oxide Co
3o
4mix with carbon black and carry out even refinement ball-milling processing, milling parameters is: ratio of grinding media to material is 25:1, and Ball-milling Time is 100h, and the mixed powder after ball milling puts into that vacuum reaction stove is obtained comprises grain growth inhibitor VC/Cr
3c
2wC-Co-VC/Cr
3c
2nano composite powder (see Fig. 1);
By the WC-Co-VC/Cr prepared
3c
2composite powder loads sintered-carbide die precompressed, then put into discharging plasma sintering equipment and carry out cryogenic high pressure presintering, adopt following processing parameter: under sintering pressure 100MPa, temperature rises to 100 DEG C from room temperature, temperature rise rate is 10 DEG C/min, at 100 DEG C of insulation 30min; After insulation terminates, temperature rises to 300 DEG C by 100 DEG C, and temperature rise rate is 10 DEG C/min, at 300 DEG C, be incubated 30min; After insulation terminates, increase sintering pressure to 300MPa, temperature rises to 700 DEG C by 300 DEG C at this pressure, and temperature rise rate is 10 DEG C/min, at 700 DEG C of temperature, be incubated 60min;
Block after above-mentioned the first step presintering is loaded in high-strength graphite mould, put into discharging plasma sintering equipment and carry out second step densification sintering, the processing parameter adopted is: sintering pressure is 70MPa, temperature rise rate is 50 DEG C/min, sintering temperature is 1040 DEG C, 3min is incubated at 1040 DEG C of temperature, 300 DEG C are cooled to the rate of cooling of 10 DEG C/min after insulation terminates, then room temperature is cooled to the furnace, finally obtain the Nanograin Cemented Carbide block materials (see Fig. 2) with high-compactness, its performance perameter is in table 1.
Embodiment 2
According to preparing WC-Co-VC/Cr
3c
2grain growth inhibitor VC/Cr in composite powder
3c
2massfraction is 1.5wt.%, VC and Cr
3c
2mass ratio close to 1:1, the raw material V that grain growth inhibitor is synthesized
2o
3and Cr
2o
3tungsten WO purple with nanometer
2.72, cobalt oxide Co
3o
4mix with carbon black and carry out even refinement ball-milling processing, milling parameters is: ratio of grinding media to material is 28:1, and Ball-milling Time is 130h, and the mixed powder after ball milling puts into that vacuum reaction stove is obtained comprises grain growth inhibitor VC/Cr
3c
2wC-Co-VC/Cr
3c
2nano composite powder;
By the WC-Co-VC/Cr prepared
3c
2composite powder loads sintered-carbide die precompressed, then put into discharging plasma sintering equipment and carry out cryogenic high pressure presintering, adopt following processing parameter: under sintering pressure 200MPa, temperature rises to 100 DEG C from room temperature, temperature rise rate is 30 DEG C/min, at 100 DEG C of insulation 20min; After insulation terminates, temperature rises to 300 DEG C by 100 DEG C, and temperature rise rate is 30 DEG C/min, at 300 DEG C, be incubated 20min; After insulation terminates, increase sintering pressure to 400MPa, temperature rises to 600 DEG C by 300 DEG C at this pressure, and temperature rise rate is 50 DEG C/min, at 600 DEG C of temperature, be incubated 45min;
Block after above-mentioned the first step presintering is loaded in high-strength graphite mould, put into discharging plasma sintering equipment and carry out second step densification sintering, the processing parameter adopted is: sintering pressure is 150MPa, temperature rise rate is 75 DEG C/min, sintering temperature is 1010 DEG C, 2min is incubated at 1010 DEG C of temperature, 300 DEG C are cooled to the rate of cooling of 50 DEG C/min after insulation terminates, then room temperature is cooled to the furnace, finally obtain the Nanograin Cemented Carbide block materials (see Fig. 3) with high-compactness, its performance perameter is in table 1.
Embodiment 3
According to preparing WC-Co-VC/Cr
3c
2grain growth inhibitor VC/Cr in composite powder
3c
2massfraction is 2.0wt.%, VC and Cr
3c
2mass ratio close to 1:1, the raw material V that grain growth inhibitor is synthesized
2o
3and Cr
2o
3tungsten WO purple with nanometer
2.72, cobalt oxide Co
3o
4mix with carbon black and carry out even refinement ball-milling processing, milling parameters is: ratio of grinding media to material is 30:1, and Ball-milling Time is 150h, and the mixed powder after ball milling puts into that vacuum reaction stove is obtained comprises grain growth inhibitor VC/Cr
3c
2wC-Co-VC/Cr
3c
2nano composite powder;
By the WC-Co-VC/Cr prepared
3c
2composite powder loads sintered-carbide die precompressed, then put into discharging plasma sintering equipment and carry out cryogenic high pressure presintering, adopt following processing parameter: under sintering pressure 300MPa, temperature rises to 100 DEG C from room temperature, temperature rise rate is 50 DEG C/min, at 100 DEG C of insulation 10min; After insulation terminates, temperature rises to 300 DEG C by 100 DEG C, and temperature rise rate is 50 DEG C/min, at 300 DEG C, be incubated 10min; After insulation terminates, increase sintering pressure to 500MPa, temperature rises to 500 DEG C by 300 DEG C at this pressure, and temperature rise rate is 100 DEG C/min, at 700 DEG C of temperature, be incubated 30min;
Block after above-mentioned the first step presintering is loaded in high-strength graphite mould, put into discharging plasma sintering equipment and carry out second step densification sintering, the processing parameter adopted is: sintering pressure is 240MPa, temperature rise rate is 100 DEG C/min, sintering temperature is 980 DEG C, 1min is incubated at 980 DEG C of temperature, 300 DEG C are cooled to the rate of cooling of 100 DEG C/min after insulation terminates, then room temperature is cooled to the furnace, finally obtain the Nanograin Cemented Carbide block materials with high-compactness, its performance perameter is in table 1.
The performance perameter of nanocrystalline WC-Co hard alloy block materials prepared by the different embodiment of table 1
Claims (3)
1. prepared a method for high-compactness Nanograin Cemented Carbide block materials by step sintering, it is characterized in that, comprise the following steps:
(1) the raw material V first grain growth inhibitor synthesized
2o
3and Cr
2o
3tungsten WO purple with nanometer
2.72, cobalt oxide Co
3o
4mix with carbon black and carry out even refinement ball-milling processing, milling parameters is: ratio of grinding media to material is 25:1-30:1, and Ball-milling Time is 100-150h, and the mixed powder after ball milling puts into that vacuum reaction stove is obtained comprises grain growth inhibitor VC/Cr
3c
2wC-Co-VC/Cr
3c
2nano composite powder;
(2) by WC-Co-VC/Cr that step (1) prepares
3c
2nano composite powder loads sintered-carbide die precompressed, then put into discharging plasma sintering equipment and carry out cryogenic high pressure presintering, adopt following processing parameter: under sintering pressure 100-300MPa, temperature rises to 100 DEG C from room temperature, temperature rise rate is 10-50 DEG C/min, at 100 DEG C of insulation 10-30min; After insulation terminates, temperature rises to 300 DEG C by 100 DEG C, and temperature rise rate is 10-50 DEG C/min, at 300 DEG C, be incubated 10-30min; After insulation terminates, increase sintering pressure to 300-500MPa, temperature rises to 500-700 DEG C by 300 DEG C at this pressure, and temperature rise rate is 10-100 DEG C/min, at 500-700 DEG C of temperature, be incubated 30-60min;
(3) block in sintered-carbide die step (2) obtained after presintering loads in high-strength graphite mould, put into discharging plasma sintering equipment and carry out second step densification sintering, the processing parameter adopted is: sintering pressure is 70-240MPa, temperature rise rate is 50-100 DEG C/min, sintering temperature is 980-1040 DEG C, 1-3min is incubated at 980-1040 DEG C of temperature, 300 DEG C are cooled to the rate of cooling of 10-100 DEG C/min after insulation terminates, then cool to room temperature with the furnace, finally obtain the Nanograin Cemented Carbide block materials with high-compactness.
2. according to the method for claim 1, it is characterized in that, in the Nanograin Cemented Carbide block materials of preparation, the massfraction of grain growth inhibitor is generally 1.0%-2.0%, according to V in concrete numerical value determination raw material
2o
3and Cr
2o
3consumption.
3. according to the high-compactness Nanograin Cemented Carbide block materials that the method for claim 1 or 2 prepares.
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| CN115821099A (en) * | 2022-11-28 | 2023-03-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of hard alloy |
| CN116334430A (en) * | 2023-03-29 | 2023-06-27 | 北京工业大学 | Preparation method of superfine WC-Co hard alloy based on sol-gel and carbothermic reduction |
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