CN112853188A - Hard alloy and preparation method and application thereof - Google Patents
Hard alloy and preparation method and application thereof Download PDFInfo
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- CN112853188A CN112853188A CN202011622211.0A CN202011622211A CN112853188A CN 112853188 A CN112853188 A CN 112853188A CN 202011622211 A CN202011622211 A CN 202011622211A CN 112853188 A CN112853188 A CN 112853188A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
- C22C29/067—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 comprising a particular metallic binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/248—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention provides a hard alloy and a preparation method and application thereof. The preparation raw materials of the hard alloy comprise tungsten carbide, a binder, an additive and a forming agent, wherein the dosage of the tungsten carbide is 89-94.5 wt% based on the total weight of the tungsten carbide, the binder and the additive, wherein the tungsten carbide comprises coarse-grain tungsten carbide and medium-coarse-grain tungsten carbide, and the content of the coarse-grain tungsten carbide is 65-85 wt% based on the total weight of the tungsten carbide; the Fisher size of the coarse-crystal tungsten carbide is 16-26 mu m, and the Fisher size of the medium-crystal tungsten carbide is 2-10 mu m. The fracture toughness, the wear resistance and the thermal fatigue resistance of the pavement milling cutter head prepared by the hard alloy are all obviously improved.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a hard alloy and a preparation method and application thereof.
Background
The hard alloy is widely applied to the fields of mining and engineering due to higher wear resistance, heat conductivity and good toughness. The hard alloy is a key material of the road milling cutter, and the performance of the hard alloy determines the service performance and the service life of the milling cutter. The main failure modes of the hard alloy at the front end of the milling tool include cracking, breaking and local peeling caused by cracks besides abrasion, and mainly because the road milling operation conditions are severe, the alloy needs to bear repeated impact, cold and hot alternation and abrasive wear, so that the road milling tool has more severe requirements on the properties of the hard alloy in the aspects of hardness, wear resistance, thermal fatigue performance, impact fatigue and the like. Along with the increasingly modern municipal road surface maintenance, higher requirements are put forward on the performance of the hard alloy, the fracture toughness, the wear resistance and the thermal fatigue resistance of the hard alloy are improved, the problem of failure in advance due to tooth breakage, over-fast abrasion and thermal fatigue is avoided, the frequency of stopping, checking and replacing milling and planing teeth of end user equipment is reduced, and therefore the production efficiency of end users is effectively improved, and the operation cost is reduced.
The conventional method balances the hardness and toughness of the hard alloy by adjusting the grain size and the binder content of WC, thereby meeting the requirements of different working conditions on the material performance, but often considering the difference, the good balance between the performances is difficult to realize. In addition, abrasive wear of the alloy is serious under the working condition of milling and planing of the pavement, the temperature of the working tip of the hard alloy can reach 400 ℃ during milling and planing operation, the binder is very easy to generate crystal form transformation at the temperature, the hardness is reduced, the binder is firstly worn, then the hard phase is peeled or broken, the overall performance of the tool is reduced, and the conventional WC-Co combination is difficult to find an effective scheme which gives consideration to the performance of each aspect.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a hard alloy, a preparation method thereof and application of the hard alloy in pavement milling. The fracture toughness, the wear resistance and the thermal fatigue resistance of the pavement milling cutter head prepared by the hard alloy are all obviously improved.
The invention provides a hard alloy, which is prepared from raw materials including tungsten carbide, a binder, an additive and a forming agent, wherein the tungsten carbide comprises 89-94.5 wt% of coarse-grain tungsten carbide and medium-coarse-grain tungsten carbide, and the content of the coarse-grain tungsten carbide is 65-85 wt% of the total weight of the tungsten carbide; the Fisher size of the coarse-crystal tungsten carbide is 16-26 mu m, and the Fisher size of the medium-crystal tungsten carbide is 2-10 mu m.
In the invention, the judgment standard or the judgment method of the coarse-grain tungsten carbide and the medium-coarse-grain tungsten carbide comprises the following steps: medium-coarse tungsten carbide with the Fisher particle size of 2-10 mu m and coarse tungsten carbide with the Fisher particle size of more than 10 mu m.
According to some preferred embodiments of the cemented carbide according to the present invention, the binder is used in an amount of 5 wt% to 8 wt% and the additive is used in an amount of 0.5 wt% to 3.0 wt%, based on the total weight of the tungsten carbide, the binder and the additive.
According to some preferred embodiments of the cemented carbide according to the invention, the weight ratio of the additive to the binder is not more than 0.1, preferably 0.001 to 0.1.
According to some preferred embodiments of the cemented carbide according to the invention, the binder is cobalt, such as cobalt powder or the like.
According to some preferred embodiments of the cemented carbide of the present invention, the additive contains one or more elements of W, Nb, Re and Si, and preferably the additive is one or more elements of tungsten powder, niobium powder, rhenium powder and silicon powder.
According to some preferred embodiments of the cemented carbide of the present invention, the forming agent is PEG2000 and optionally paraffin wax, preferably the weight ratio of paraffin wax and PEG2000 is (0-2): 1.
According to some preferred embodiments of the cemented carbide according to the invention, the grain size of the cemented carbide is 1 μm to 15 μm. For example, 1.0. mu.m, 1.5. mu.m, 2.0. mu.m, 2.5. mu.m, 3.0. mu.m, 3.5. mu.m, 4.0. mu.m, 4.5. mu.m, 5.0. mu.m, 5.5. mu.m, 6.0. mu.m, 6.5. mu.m, 7.0. mu.m, 7.5. mu.m, 8.0. mu.m, 8.5. mu.m, 9.0. mu.m, 9.5. mu.m, 10.0. mu.m, 10.5. mu.m, 11.0. mu.m, 11.5. mu.m, 12.0. mu.m, 12.5. mu.m, 13.0. mu.m, 13.5. mu.m, 14.0. mu.m, 14.5. mu.m, 15.0. mu.m, and any value therebetween, preferably 2.
According to some preferred embodiments of the cemented carbide according to the invention, the cemented carbide has an average grain size of 1.8 μm to 5.5 μm. For example, 1.8. mu.m, 2.0. mu.m, 2.2. mu.m, 2.4. mu.m, 2.6. mu.m, 2.8. mu.m, 3.0. mu.m, 3.2. mu.m, 3.4. mu.m, 3.6. mu.m, 3.8. mu.m, 4.0. mu.m, 4.2. mu.m, 4.6. mu.m, 4.8. mu.m, 5.0. mu.m, 5.2. mu.m, 5.4. mu.m, 5.5. mu.m, and any value therebetween, preferably the average crystal grain size is 2.4 to 4.6. mu.m.
According to some preferred embodiments of the hard alloy of the present invention, the crystal grains with a grain size of 2.8 μm or less in the hard alloy account for 40% to 60% of the total number of the crystal grains.
According to some preferred embodiments of the hard alloy of the present invention, the grains with a grain size of 2.8 μm or less in the hard alloy account for 45% to 55% of the total number of the grains.
In the present invention, the grain size refers to the size of the main grains observed in the metallographic picture.
In the invention, the average grain size refers to the grain size measured by a GB/T6394-2017 metal average grain size measuring method.
According to some preferred embodiments of the cemented carbide of the present invention, a standard alloy sample made of the cemented carbide has a porosity of no greater than a04B 00.
According to some preferred embodiments of the cemented carbide of the present invention, the standard alloy sample made of cemented carbide has a porosity of a02B 00.
According to some preferred embodiments of the cemented carbide according to the invention, the cemented carbide is used for milling bits, preferably road milling bits.
The second aspect of the present invention provides a method for preparing the cemented carbide, including:
s1, placing the hard phase tungsten carbide, the binder, the additive and the forming agent into a ball mill for ball milling;
s2, drying and granulating the ball-milled raw materials, and pressing and forming into a blank;
s3, firing and molding the green blank into hard alloy;
and S4, carrying out heat treatment on the sintered and molded hard alloy.
According to some preferred embodiments of the preparation method of the present invention, the forming agent is PEG2000 and optionally paraffin, preferably the weight ratio of paraffin to PEG2000 is (0-2): 1.
According to some preferred embodiments of the preparation method of the present invention, the amount of the molding agent is selected from a wide range in order to enable molding.
According to some preferred embodiments of the preparation method of the present invention, in step S1, the ball milling conditions include: the ball-material ratio is (1.5-3) to 1, and the ball milling time is 20-40 h.
According to some preferred embodiments of the preparation method of the present invention, in step S1, alcohol is further added, preferably, the solid-to-liquid ratio of the alcohol to the preparation raw material is 0.14L/kg to 0.24L/kg.
In the invention, the ball material ratio refers to the ratio of the sum of the weights of the tungsten carbide, the adhesive and the additive to the weight of the grinding body; the solid-to-liquid ratio refers to the ratio of the sum of the weight of the tungsten carbide, the binder and the additive to the volume of the alcohol.
According to some preferred embodiments of the preparation method of the present invention, in step S2, the drying conditions have a wide range of selection, for example, the drying conditions can be 80 to 120 ℃ for 2 to 12 hours.
According to some preferred embodiments of the preparation method of the present invention, in step S3, the firing conditions include: the temperature is 1360-1580 ℃ and the time is 1-5 h.
According to some preferred embodiments of the preparation method of the present invention, in step S3, the firing conditions include: the temperature is 1440 ℃ to 1520 ℃ and the time is 1h to 2 h.
According to some preferred embodiments of the production method of the present invention, in step S3, the firing is pressure sintering.
According to some preferred embodiments of the preparation method of the present invention, in step S3, pressure sintering is performed in nitrogen and/or inert gas.
According to some preferred embodiments of the preparation method of the present invention, in step S3, Ar gas is used as the pressure medium, and preferably, the partial pressure of Ar gas is 50MPa to 200 MPa.
According to some preferred embodiments of the preparation method of the present invention, after step S3 and before step S4, the method is further cooled, preferably to 20 ℃ to 40 ℃.
According to some preferred embodiments of the preparation method of the present invention, in step S4, the heat treatment conditions include: under the vacuum condition, the temperature is increased from 20 ℃ to 40 ℃ to 500 ℃ to 1000 ℃, the temperature increasing rate is 7 ℃/min to 10 ℃/min, and the heat preservation time is 6 to 12 hours.
According to some preferred embodiments of the preparation method of the present invention, after step S4, the method further includes cooling to 20-40 ℃, and further preferably, the cooling rate is 7-12 ℃/min.
According to some preferred embodiments of the preparation method of the present invention, the tungsten carbide is used in an amount of 89 wt% to 94.5 wt%, based on the total weight of the tungsten carbide, the binder and the additive, wherein the tungsten carbide comprises macrocrystalline tungsten carbide and mesomacrocrystalline tungsten carbide, and the macrocrystalline tungsten carbide is contained in an amount of 65 wt% to 85 wt%, based on the total weight of the tungsten carbide; the Fisher size of the coarse-crystal tungsten carbide is 16-26 mu m, and the Fisher size of the medium-crystal tungsten carbide is 2-10 mu m.
According to some preferred embodiments of the preparation method of the present invention, the macrocrystalline tungsten carbide may be prepared by a high-temperature reduction process, a high-temperature carbonization process, which are conventional in the art, and in the present invention, the macrocrystalline tungsten carbide may be commercially available to satisfy a grain size of 16 μm to 26 μm.
According to some preferred embodiments of the preparation method of the present invention, the medium-coarse tungsten carbide may be commercially available so as to satisfy a grain size of 2 μm to 10 μm.
According to some preferred embodiments of the preparation method of the present invention, the binder is used in an amount of 5 wt% to 8 wt%, and the additive is used in an amount of 0.5 wt% to 3.0 wt%, based on the total weight of the tungsten carbide, the binder, and the additive.
According to some preferred embodiments of the preparation method of the present invention, the weight ratio of the additive to the binder is not more than 0.1, preferably 0.001 to 0.1.
According to some preferred embodiments of the method of manufacturing of the present invention, the binder is cobalt.
According to some preferred embodiments of the preparation method of the present invention, the additive contains one or more elements selected from W, Nb, Re and Si, and preferably the additive is one or more elements selected from tungsten powder, niobium powder, rhenium powder and silicon powder.
According to some preferred embodiments of the preparation method of the present invention, the grain size of the cemented carbide is 1 μm to 15 μm, the average grain size is 1.8 μm to 5.5 μm, wherein the grains with the grain size of 2.8 μm or less account for 40% to 60% of the total number of the grains.
According to some preferred embodiments of the method of manufacturing of the present invention, the grain size of the cemented carbide is 2 μm to 12 μm.
According to some preferred embodiments of the method of manufacturing of the present invention, the cemented carbide has an average grain size of 2.4 μm to 4.6 μm.
According to some preferred embodiments of the preparation method of the present invention, the crystal grains with a grain size of 2.8 μm or less in the hard alloy account for 45% to 55% of the total number of the crystal grains.
According to some preferred embodiments of the method of manufacturing of the present invention, the porosity of the standard alloy specimen made of cemented carbide is not greater than a04B 00.
According to some preferred embodiments of the method of manufacturing of the present invention, the porosity of the standard alloy sample made of cemented carbide is a02B 00.
In a third aspect, the invention provides the use of the cemented carbide or the preparation method in road milling.
The invention has the beneficial effects that:
the invention aims to provide a hard alloy suitable for special working conditions of milling and planing a road surface, which has good matching of hardness and toughness by controlling coarse and fine grain structures, is added with W, Nb, Re and Si which are dissolved in binder Co in a solid solution manner, and controls a strengthening phase to precipitate and separate out in the binder by subsequent heat treatment, and can effectively improve the hardness and toughness of the hard alloy binder, thereby improving the wear resistance of wear-resistant grains of the alloy, and improving the service life of a road surface milling and planing tool by 30% by optimizing the improved hard alloy.
Drawings
Fig. 1 is a metallographic structure photograph of a cemented carbide prepared according to example 1 of the present invention.
Fig. 2 is a metallographic structure photograph of a cemented carbide prepared according to example 2 of the present invention.
Fig. 3 is a metallographic structure photograph of a cemented carbide prepared according to example 3 of the present invention.
Fig. 4 is a metallographic structure photograph of a cemented carbide prepared according to example 10 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.
In the following embodiments, the properties of cemented carbides were tested as follows:
1. density: GB/T3850-2015 compact sintered metal material and hard alloy density determination method;
2. hardness: GB/T3849.1-2015 cemented carbide Rockwell hardness (scale A) first part: an experimental method;
3. strength: GB/T3851-2015 hard alloy transverse rupture strength determination method;
4. grain size: GB/T6394-2017 metal average grain size determination method.
In the following examples, the purity of cobalt powder, silicon powder, tungsten powder, niobium powder, and rhenium powder is 99.9 wt% or more.
[ example 1 ]
S1, adding 130kg of coarse-grain tungsten carbide with Fisher granularity of 20 microns, 57kg of medium-coarse-grain tungsten carbide with Fisher granularity of 6 microns, 12kg of cobalt powder, 0.5kg of silicon powder, 0.5kg of tungsten powder, 2kg of PEG2000 and 2kg of paraffin into a ball mill, simultaneously adding 300kg of ball grinding rod and 32L of alcohol with volume concentration of 100%, ball-milling for 24 hours at the speed of 36rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1480 ℃, filling Ar gas during high-temperature sintering, keeping the Ar gas partial pressure at 100MPa for 2h, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 600 ℃ at a heating rate of 7 ℃/min, preserving heat at 600 ℃ for 12h, cooling, and cooling to 30 ℃ at a cooling rate of 12 ℃/min.
Metallographic examination was carried out on the alloy according to GB/T3488.2-2018, and the metallographic photograph is shown in FIG. 1. As can be seen from FIG. 1, the porosity of the cemented carbide is A02B00, the grain size of the cemented carbide is 2 μm to 6 μm, the average grain size of the cemented carbide is 3.2 μm, and 45% of the total number of grains are grains with a grain size of 2.8 μm or less.
[ example 2 ]
S1, adding 65kg of coarse-grain tungsten carbide with Fisher 'S particle size of 20 microns, 27.5kg of medium-coarse-grain tungsten carbide with Fisher' S particle size of 6 microns, 7kg of cobalt powder, 0.5kg of tungsten powder, 1kg of PEG2000 and 1kg of paraffin into a ball mill, simultaneously adding 150kg of ball grinding rod and 18L of alcohol with volume concentration of 96%, ball-milling for 36 hours at the speed of 32rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, and pressing the dried raw materials into a green body;
s3, sintering the green body at 1520 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and pressure for 2h under the Ar gas partial pressure of 120MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 700 ℃ at a heating rate of 8 ℃/min, preserving the heat at 700 ℃ for 10h, cooling, and cooling to 30 ℃ at a cooling rate of 12 ℃/min.
Metallographic examination was carried out on the alloy according to GB/T3488.2-2018, and the metallographic photograph is shown in FIG. 2. As can be seen from FIG. 2, the porosity of the cemented carbide is A02B00, the grain size of the cemented carbide is 2 μm to 8 μm, the average grain size of the cemented carbide is 3.2 μm, and the grains having a grain size of 2.8 μm or less account for 48% of the total number of the grains.
[ example 3 ]
S1, adding 39kg of coarse-grain tungsten carbide with the Fisher particle size of 20 microns, 16.5kg of medium-coarse-grain tungsten carbide with the Fisher particle size of 6 microns, 4.8kg of cobalt powder, 0.17kg of niobium powder, 0.17kg of rhenium powder, 1kg of PEG2000 and 0.2kg of paraffin into a ball mill, adding 120kg of ball grinding rod and 12L of alcohol with the volume concentration of 92%, ball-milling for 30 hours at the speed of 40rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1480 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and pressure for 2h under the Ar gas partial pressure of 80MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 500 ℃ at a heating rate of 10 ℃/min, preserving heat at 500 ℃ for 10h, cooling, and cooling to 30 ℃ at a cooling rate of 8 ℃/min.
Metallographic examination was carried out on the alloy according to GB/T3488.2-2018, and the metallographic photograph is shown in FIG. 3. As can be seen from FIG. 3, the porosity of the alloy is A02B00, the grain size of the cemented carbide is 2 μm to 9 μm, the average grain size of the cemented carbide is 3.2 μm, and 45% of the total number of grains are grains with the grain size of 2.8 μm or less.
[ example 4 ]
S1, adding 97.5kg of coarse-grain tungsten carbide with Fisher 'S particle size of 20 microns, 41kg of medium-coarse-grain tungsten carbide with Fisher' S particle size of 6 microns, 10.5kg of cobalt powder, 1kg of silicon powder and 3kg of PEG2000 into a ball mill, simultaneously adding 225kg of ball grinding rod and 28L of 94% alcohol by volume concentration, ball-milling for 36 hours at the speed of 36rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1450 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and the pressure for 1h under the Ar gas partial pressure of 150MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 900 ℃ at a heating rate of 7 ℃/min, preserving the heat at 900 ℃ for 10h, cooling, and cooling to 30 ℃ at a cooling rate of 9 ℃/min.
According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 2-8 mu m, the average grain size of the hard alloy is 4.1 mu m, the grain with the grain size less than or equal to 2.8 mu m accounts for 45% of the total number of the grains, and a metallographic photograph is similar to that in the figure 1.
[ example 5 ]
S1, adding 13kg of high-temperature coarse-grain tungsten carbide with Fisher 'S particle size of 20 microns, 5.5kg of medium-coarse-grain tungsten carbide with Fisher' S particle size of 6 microns, 1kg of cobalt powder, 0.02kg of silicon powder, 0.48kg of niobium powder, 0.32kg of PEG2000 and 0.64kg of paraffin into a ball mill, simultaneously adding 50kg of ball grinding rod and 4.5L of 98% alcohol, ball-milling for 28 hours at the speed of 45rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1480 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and pressure for 2h under the Ar gas partial pressure of 180MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 1000 ℃ at a heating rate of 8 ℃/min, preserving heat at 1000 ℃ for 6h, cooling, and cooling to 30 ℃ at a cooling rate of 11 ℃/min.
According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 2-6.5 microns, the average grain size of the hard alloy is 3.6 microns, the grain with the grain size less than or equal to 2.8 microns accounts for 50% of the total number of the grains, and a metallographic photograph is similar to that in figure 1.
[ example 6 ]
S1, adding 188kg of coarse-grain tungsten carbide with the Fisher particle size of 20 microns, 80.1kg of medium-coarse-grain tungsten carbide with the Fisher particle size of 6 microns, 30kg of cobalt powder, 1.9kg of rhenium powder, 4kg of PEG2000 and 2kg of paraffin into a ball mill, simultaneously adding 450kg of ball grinding rod and 54L of fine with the concentration of 92%, ball-milling for 34 hours at the speed of 36rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1520 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and pressure for 2h under the Ar gas partial pressure of 200MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 800 ℃ at a heating rate of 7 ℃/min, preserving heat at 800 ℃ for 8h, cooling, and cooling to 30 ℃ at a cooling rate of 8 ℃/min.
According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 1-5 mu m, the average grain size of the hard alloy is 2.4 mu m, the grain with the grain size less than or equal to 2.8 mu m accounts for 55% of the total number of the grains, and a metallographic photograph is similar to that in the figure 1.
[ example 7 ]
Example 7 is essentially the same as example 1 except that: the weight of the binder cobalt is 5.81 kg; the binder was used in an amount of 3 wt% based on the total weight of tungsten carbide, binder and additives. The porosity of the alloy is A06B06, which indicates that a large amount of pores exist in the alloy, so that the alloy is not dense and the performance of the alloy is reduced.
[ example 8 ]
Example 8 is essentially the same as example 1, except that: the weight of the binder cobalt is 25.64 kg; the binder was used in an amount of 12 wt% based on the total weight of tungsten carbide, binder and additives. The binder content is too high, and the alloy hardness is reduced.
[ example 9 ]
Example 9 is essentially the same as example 1 except that: the weight of the additive is 0.6 kg; the amount of the additive was 0.3 wt% based on the total weight of tungsten carbide, binder and additive, with 0.3kg of Si powder and 0.3kg of W powder. The content of the additive is low, and the strengthening effect of the binder is not obvious.
[ example 10 ]
Example 10 is essentially the same as example 1, except that: the weight of the additive was 9.38kg, and the amount of the additive was 4.5 wt% based on the total weight of tungsten carbide, binder and additive. The additive content is too high, a metallographic photograph is shown in figure 4, and the metallographic structure of the alloy has structural defects such as decarburization and the like.
[ example 11 ]
Example 11 is essentially the same as example 1, except that: the additive is Ni, the weight is 1kg, and the dosage of the additive is 0.5 wt% based on the total weight of the tungsten carbide, the binder and the additive. The binder strength is reduced by adding Ni element.
[ example 12 ]
Example 12 is essentially the same as example 1 except that: the additive is Mo, the weight is 6.15kg, and the dosage of the additive is 3 wt% based on the total weight of the tungsten carbide, the binder and the additive. Mo element is added, and the average grain size of the alloy is 1.2 μm.
[ example 13 ]
The average grain size of the finally prepared hard alloy in the embodiment 13 is 1.6 μm, and the preparation method specifically comprises the following steps:
s1, adding 13kg of coarse-grain tungsten carbide with the Fisher size of 10 microns, 5.7kg of medium-coarse-grain tungsten carbide with the Fisher size of 6 microns, 1.2kg of cobalt powder, 0.05kg of silicon powder, 0.05kg of tungsten powder, 0.2kg of PEG2000 and 0.2kg of paraffin into a ball mill, simultaneously adding 100kg of ball grinding rod and 3.2L of alcohol with the volume concentration of 100%, ball-milling for 50 hours at the speed of 36rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1480 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and pressure for 2h under the Ar gas partial pressure of 120MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 600 ℃ at a heating rate of 7 ℃/min, preserving heat at 600 ℃ for 12h, cooling, and cooling to 30 ℃ at a cooling rate of 12 ℃/min.
According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 0.4-2.5 microns, and the average grain size of the hard alloy is 1.6 microns.
[ example 14 ]
The cemented carbide finally obtained in example 14 had an average grain size of 14 μm.
S1, adding 26kg of coarse-grain tungsten carbide with Fisher 'S particle size of 24 microns, 11.4kg of medium-coarse-grain tungsten carbide with Fisher' S particle size of 10 microns, 2.4kg of cobalt powder, 0.2kg of silicon powder and 0.8kg of PEG2000 into a ball mill, simultaneously adding 5kg of ball grinding rod and 10L of 92% alcohol, ball-milling for 10 hours at the speed of 36rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1450 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and the pressure for 0.5h under the Ar gas partial pressure of 80MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 900 ℃ at a heating rate of 7 ℃/min, preserving heat at 900 ℃ for 8h, cooling, and cooling to 30 ℃ at a cooling rate of 10 ℃/min.
According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A06B06, the grain size of the hard alloy is 4-22 microns, and the average grain size of the hard alloy is 14 microns.
[ example 15 ]
The alloy grain size of the finally obtained cemented carbide in example 15 was 0.5 to 1.8 μm, and the average grain size was 1.2 μm.
S1, adding 5.7kg of coarse-grain tungsten carbide with Fisher 'S particle size of 20 microns, 13kg of medium-coarse-grain tungsten carbide with Fisher' S particle size of 6 microns, 12kg of cobalt powder, 0.05kg of silicon powder, 0.05kg of tungsten powder and 0.4kg of PEG2000 into a ball mill, simultaneously adding 90kg of ball grinding rod and 10L of 92% alcohol by volume concentration, ball-milling for 100 hours at the speed of 40rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1420 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and pressure for 3h under the Ar gas partial pressure of 120MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product from 30 ℃ to 850 ℃ at the heating rate of 8 ℃/min, preserving the heat at 850 ℃ for 7h, cooling, and cooling to 30 ℃ at the cooling rate of 10 ℃/min.
According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 0.5-3.8 microns, and the average grain size of the hard alloy is 1.2 microns.
[ example 16 ]
The alloy grain size of the finally prepared hard alloy in the embodiment 16 is 4-18 μm, and the average grain size is 10 μm.
S1, adding 18.7kg of coarse-grain tungsten carbide with Fisher granularity of 20 microns, 0kg of medium-coarse-grain tungsten carbide with granularity of 6 microns, 12kg of cobalt powder, 0.1kg of tungsten powder, 0.2kg of PEG2000 and 0.2kg of paraffin into a ball mill, simultaneously adding 15kg of ball grinding rod and 40L of 99% alcohol by volume concentration, ball-milling for 14 hours at the speed of 36rpm, and then discharging;
s2, drying the ball-milled raw materials at 80 ℃ for 4 hours, granulating, and pressing to form a green blank;
s3, sintering the green body at 1580 ℃, filling Ar gas during high-temperature sintering, keeping the temperature and the pressure for 2.5 hours at the Ar gas partial pressure of 120MPa, and cooling to 30 ℃;
s4, heating the sintered and molded product at a heating rate of 9 ℃/min to between 30 and 1000 ℃, preserving heat for 7 hours, cooling the product, and cooling the product to between 30 ℃ at a cooling rate of 12 ℃/min.
According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 4-18 mu m, and the average grain size of the hard alloy is 10 mu m.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: 112.2kg of high-temperature coarse-grain tungsten carbide with the grain size of 20 mu m, accounting for 60 wt% of the total weight of the tungsten carbide, and 74.8kg of medium-grain tungsten carbide with the grain size of 6 mu m. According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 2-10 mu m, the average grain size of the hard alloy is 5.0 mu m, and grains with the grain size of less than or equal to 2.8 mu m account for 40% of the total number of the grains.
Comparative example 2
Comparative example 1 is substantially the same as example 1 except that: 168.3kg of high-temperature coarse-grain tungsten carbide with the grain size of 20 mu m accounts for 90 wt% of the total weight of the tungsten carbide, and 18.7kg of medium-grain tungsten carbide with the grain size of 6 mu m. According to GB/T3488.2-2018, metallographic detection is carried out on the alloy, the porosity in the alloy is A02B00, the grain size of the hard alloy is 2-14 mu m, the average grain size of the hard alloy is 6.0 mu m, and grains with the grain size of less than or equal to 2.8 mu m account for 20% of the total number of the grains.
Comparative example 3
The alloy was prepared according to the method of example 1 in CN109487142A, and corresponding property characterization was made.
The hard alloy comprises: 76.4 wt% hard phase WC, 22 wt% binder Co and Ni and 1.6 wt% Cr3C2。
Hard phase adopts two WC raw materials with different Hc, the Hc value of the crude WC raw material is 3.8kA/m, and the crude WC raw material is carbonized at 2400 ℃ and is detected to be W-free in a full-field way under a metallographic microscope2C, the requirement of ball milling wear resistance is met; hc value of the fine WC is 6.6kA/m, and the mass ratio of the coarse WC to the fine WC is 2.6: 1. The mass ratio of Co to Ni is 1: 1.
Mixing hard phase, binder and Cr3C2Mixing to obtain a raw material mixture, adding the raw material mixture into a ball mill at a ball-to-material ratio of 3:1, adding alcohol, wherein the adding amount of the alcohol is 0.28L/1kg of the raw material mixture, the forming agent is paraffin, the dosage of the paraffin is 2.0 percent of the mass of the raw material mixture, the ball milling time is 18 hours, and producing the hard alloy with mixed crystal grain diameter through drying, pressing and low-pressure sintering.
TABLE 1
As can be seen from Table 1, the properties of the cemented carbides prepared in examples 1-6 have an excellent combination of properties. And the low or high dosage of the binder and the additive and the change of additive elements can cause the problem of lowering the comprehensive performance.
Compared with the alloy prepared in the embodiments 1-6, the percentage content of the crystal grains with the grain size less than or equal to 2.8 μm in the alloy prepared in the embodiment 13 is obviously increased, and the comprehensive performance of the alloy is reduced. In example 14, the grain size was too large, the alloy was hard to be densified, and the alloy density and hardness were remarkably reduced.
Comparing examples 1-6 with comparative example 3, under the condition of similar density and average grain size, HRA hardness of the alloy prepared by examples 1-6 is higher than that of comparative example 3, wear resistance of the alloy is better than that of comparative example 3, and bending strength is also higher than that of comparative example 3, which shows that the structure defect of the example is better than that of comparative example 3.
The temperature of 400 ℃ is the possible working temperature of the hard alloy, and the service temperature of the alloy is below 400 ℃ usually due to measures such as water sprinkling and temperature reduction in the pavement milling construction process. At 400 ℃, the red hardness of the hard alloy is better, so the HRA high-temperature hardness of the alloy is basically not changed compared with the room-temperature hardness. In service, the hardness of the binder phase Co is reduced along with the temperature rise, but because the additive elements can play a solid solution strengthening role on the binder phase Co or form a high-temperature stable compound with the Co element to play a precipitation strengthening role on the binder phase, the binder phase Co can be prevented from being worn too fast due to the hardness reduction at the working temperature, and the overall performance of the alloy is improved.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. The hard alloy is prepared from tungsten carbide, binder, additive and forming agent, wherein the tungsten carbide accounts for 89-94.5 wt% of the total weight of the tungsten carbide, the binder and the additive,
wherein, the tungsten carbide comprises coarse-grain tungsten carbide and medium-coarse-grain tungsten carbide; based on the total weight of the tungsten carbide, the content of the coarse-grain tungsten carbide is 65 to 85 weight percent;
the Fisher size of the coarse-crystal tungsten carbide is 16-26 mu m, and the Fisher size of the medium-crystal tungsten carbide is 2-10 mu m.
2. The cemented carbide of claim 1, wherein the binder is present in an amount of 5-8 wt% and the additive is present in an amount of 0.5-3.0 wt%, based on the total weight of tungsten carbide, binder and additive;
preferably, the weight ratio of the additive to the binder is not more than 0.1, preferably 0.001-0.1;
preferably, the binder is cobalt;
preferably, the additive contains one or more elements of W, Nb, Re and Si, and further preferably, the additive is one or more elements of tungsten powder, niobium powder, rhenium powder and silicon powder;
preferably, the forming agent is PEG2000 and optionally paraffin; more preferably, the weight ratio of the paraffin wax to the PEG2000 is (0-2): 1.
3. Cemented carbide according to claim 1 or 2, characterized in that the grain size of the cemented carbide is 1-15 μ ι η, preferably 2-12 μ ι η; the average grain size of the hard alloy is 1.8-5.5 μm, and preferably the average grain size is 2.4-4.6 μm;
preferably, the crystal grains with the grain size less than or equal to 2.8 μm account for 40-60 percent of the total number of the crystal grains, and preferably 45-55 percent;
preferably, the porosity of a standard alloy specimen made with the cemented carbide is no greater than a04B00, preferably a02B 00.
4. Cemented carbide according to any one of claims 1-4, characterized in that it is used for milling bits, preferably road milling bits.
5. A method of making the cemented carbide of any one of claims 1-4 comprising:
s1, placing the hard phase tungsten carbide, the binder, the additive and the forming agent into a ball mill for ball milling;
s2, drying and granulating the ball-milled raw materials, and pressing and forming into a blank;
s3, firing and molding the green blank into hard alloy;
and S4, carrying out heat treatment on the sintered and molded hard alloy.
6. The preparation method according to claim 5, wherein in step S1, the ball milling conditions include: the ball-material ratio is (1.5-3) to 1, the ball milling time is 20-40 h, and the rotating speed is 20-45 rpm;
preferably, alcohol is added during ball milling, and more preferably, the amount of alcohol added is such that the solid-to-liquid ratio is from 0.14L/kg to 0.24L/kg.
7. The method according to claim 5 or 6, wherein in step S2, the drying temperature is 80-120 ℃ and the drying time is 2-12 h.
8. The production method according to any one of claims 4 to 7, wherein in step S3, the firing conditions include: the temperature is 1360-1580 ℃, preferably 1440-1520 ℃; the time is 1h to 5h, and the preferable time is 1h to 2 h;
preferably, in step S3, the firing is pressure sintering, preferably pressure sintering in nitrogen and/or inert gas, and more preferably an Ar partial pressure of 50MPa to 200 MPa;
preferably, after step S3 and before step S4, the method further performs cooling, further preferably, cooling to 20 ℃ to 40 ℃.
9. The production method according to any one of claims 4 to 8, wherein in step S4, the conditions of the heat treatment include: under the vacuum condition, the temperature is increased from 20 ℃ to 40 ℃ to 500 ℃ to 1000 ℃, the temperature increasing rate is 7 ℃/min to 10 ℃/min, and the heat preservation time is 6 to 12 hours;
preferably, after the step S4, the method further comprises cooling to 20-40 ℃, and further preferably, the cooling rate is 7-12 ℃/min.
10. Use of a cemented carbide according to any one of claims 1-4 or a method of manufacturing according to any one of claims 5-9 for road milling.
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| CN114293083A (en) * | 2021-12-30 | 2022-04-08 | 株洲硬质合金集团有限公司 | Hard alloy for plate and preparation method thereof |
| CN115584423A (en) * | 2022-11-04 | 2023-01-10 | 株洲硬质合金集团有限公司 | Composition for preparing low-cobalt ultra-coarse-grain hard alloy, and preparation method and application thereof |
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