CN112760543A - High-strength and high-toughness hard alloy and preparation method and application thereof - Google Patents
High-strength and high-toughness hard alloy and preparation method and application thereof Download PDFInfo
- Publication number
- CN112760543A CN112760543A CN202011566202.4A CN202011566202A CN112760543A CN 112760543 A CN112760543 A CN 112760543A CN 202011566202 A CN202011566202 A CN 202011566202A CN 112760543 A CN112760543 A CN 112760543A
- Authority
- CN
- China
- Prior art keywords
- powder
- stage
- tungsten
- tungsten powder
- single crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
Abstract
The invention provides a high-strength and high-toughness hard alloy which comprises the following components in parts by weight: 85-90 parts of tungsten carbide powder, 20-25 parts of a growth inhibitor, 10-15 parts of a binder and 3-6 parts of an anticorrosive agent, wherein the tungsten carbide powder is prepared by carbonizing tungsten powder, and the tungsten powder is divided into three stages according to the grain size, namely first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder in sequence; the second aspect of the invention provides a preparation method of the high-strength and high-toughness hard alloy; the third aspect of the invention provides the application of the high-strength and high-toughness hard alloy; the high-toughness hard alloy has good impact toughness on the premise of not reducing the hardness, and can ensure that the prepared metal part is not easy to have brittle fracture.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a high-toughness hard alloy and a preparation method and application thereof.
Background
Cemented carbide is an alloy material made from a hard compound of refractory metals and a binder metal by a powder metallurgy process. The hard alloy has a series of excellent performances of high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, particularly high hardness and wear resistance, basically keeps unchanged even at the temperature of 500 ℃, and still has high hardness at the temperature of 1000 ℃. Cemented carbide is widely used as a material for sealing parts and tools, such as turning tools, milling cutters, planing tools, drill bits, boring tools, etc., for cutting cast iron, nonferrous metals, plastics, chemical fibers, graphite, glass, stone and common steel, and also for cutting refractory steel, stainless steel, high manganese steel, tool steel, etc. The cutting speed of the existing novel hard alloy cutter is hundreds times of that of carbon steel.
Most of the hard alloys on the market at present have the condition that the hardness and the impact toughness are mutually contradictory, and the higher the hardness is, the lower the impact toughness is, so that the prepared metal parts are easy to be subjected to brittle fracture under the action of external impact force.
Content of application
The invention aims to provide a high-toughness hard alloy, and simultaneously provides a preparation method and application thereof.
The embodiment of the invention is realized by the following technical scheme:
the invention provides a high-strength and high-toughness hard alloy which comprises the following components in parts by weight: 85-90 parts of tungsten carbide powder, 20-25 parts of a growth inhibitor, 10-15 parts of a binder and 3-6 parts of an anticorrosive agent, wherein the tungsten carbide powder is prepared by carbonizing tungsten powder, and the tungsten powder is divided into three stages according to the grain size, namely first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder in sequence.
The second aspect of the invention provides a preparation method of the high-toughness hard alloy, which comprises the following steps:
s1 preparation of tungsten powder with different grain sizes
Calcining ammonium paratungstate serving as a raw material to obtain tungsten oxide, performing hydrogen reduction reaction on the obtained tungsten oxide to obtain tungsten powder, adding different additives to obtain first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder which are different in grain size in the hydrogen reduction reaction stage of the tungsten oxide, and then compounding the first-stage single crystal tungsten powder, the second-stage single crystal tungsten powder and the third-stage single crystal tungsten powder according to the mass ratio;
s2 preparation of tungsten carbide powder
The tungsten powder compounded in the step S1 is heated after carbon preparation, ball milling and mixing to obtain tungsten carbide powder;
s3 preparation of high-toughness hard alloy
Mixing the tungsten carbide powder prepared in the step S2 with a growth inhibitor, a bonding agent and an anticorrosive agent, and then performing ball milling, drying, molding, sintering and post-treatment to prepare the high-strength and high-toughness hard alloy;
the sintering is divided into four stages, namely a first sintering stage, a second sintering stage, a third sintering stage and a furnace cooling stage, wherein the first sintering stage is heated from room temperature to 2400 ℃ at a heating rate of 20 ℃/min, then the second sintering stage is started, the second sintering stage is heated from 2400 ℃ to 2800 ℃ at a heating rate of 80 ℃/min, the third sintering stage is started after heat preservation is carried out for 5 minutes, the third sintering stage is cooled from 2800 ℃ to 1600 ℃ at a cooling rate of 30 ℃/min, the third sintering stage is started after heat preservation is carried out for 2 hours, the furnace cooling stage is started to be cooled from 1600 ℃ to 200 ℃ at a cooling rate of 20 ℃/min, and the furnace cooling stage is taken out and naturally cooled to normal temperature in the air.
In a third aspect, the invention provides the application of the high-strength and high-toughness hard alloy for manufacturing hard alloy products, wherein the hard alloy products comprise one or more of nozzles, sealing rings, valve seats, shaft sealing bushings and cutters.
The main component of tungsten carbide powder in the high-toughness hard alloy provided by the invention is prepared by carbonizing tungsten powder, the tungsten powder is divided into three stages according to the grain size, and the three stages are roughly small, namely first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder. After the three-stage single crystal tungsten powder is compounded, the obtained tungsten powder mixture has wide grain size distribution, the first-stage single crystal tungsten powder particles with the largest grain size are contacted with each other to form an initial skeleton structure, a plurality of gaps exist in the skeleton structure (namely, between the first-stage single crystal tungsten powder particles), the second-stage single crystal tungsten powder particles with the second grain size are filled into the gaps, so that the gaps are further reduced, the third-stage single crystal tungsten powder particles with the smallest grain size are continuously filled into the reduced gaps, the tungsten powder mixture is preliminarily compacted by utilizing the compact particle packing effect, the internal space (such as pores, cavities and the like) of the tungsten powder mixture is less, and in the roasting process after carbon is matched, the three-stage tungsten powder particles and carbon react to generate tungsten carbide, namely, the three-stage compounded tungsten carbide powder mixture with different grain sizes is formed, and in the subsequent sintering process, tungsten carbide powder with small grain size and other additives are melted into a liquid phase, on one hand, internal pores and cavities are filled, so that the material is more compact in whole and higher in hardness, on the other hand, a protective isolation layer is formed on the surface of tungsten carbide particles with large grain size, because the tungsten carbide particles with large grain size are only partially melted on the surface in the sintering process, the melted part and the protective isolation layer are mutually fused, the tungsten carbide particles which are not melted are not continuously melted after the protective isolation layer is completely formed, after the sintering is finished, a plurality of spherical tungsten carbide particles with large grain size exist in the obtained metal material, the spherical tungsten carbide particles exist among each other and on the surface of the spherical tungsten carbide particles and the protective isolation layer composed of a large amount of tungsten carbide with small grain size and other additives exists, and the grain size of the tungsten carbide particles in the protective isolation layer is smaller, and the arrangement is compact, on one hand, the addition of tungsten carbide is increased through compact accumulation, so that the strength and the hardness of the alloy metal material are improved, on the other hand, the buffer belt is filled among tungsten carbide particles with larger grain sizes, when the metal material is subjected to external impact force, the buffer belt weakens the plastic deformation work and the fracture work of the impact force and then transmits the weakened plastic deformation work and the fracture work to the tungsten carbide particles with larger grain sizes in the metal material, the tungsten carbide particles with larger grain sizes are slightly vibrated, so that the weakened plastic deformation work and the weakened fracture work can be completely absorbed, the impact force can not damage the interior of the metal material, and therefore, the alloy metal material has stronger impact toughness. In addition, because tungsten carbide powder with small grain size and other additives are melted into a liquid phase to fill the internal space in the sintering process, pores or cavities do not exist in the finally prepared metal material, namely, fine defects do not exist in the material, and the impact toughness of the metal material is improved.
The technical scheme of the embodiment of the invention at least has the following advantages and beneficial effects:
the high-toughness hard alloy provided by the invention is compounded by tungsten carbide particles with different grain sizes, the addition of tungsten carbide is increased by close packing so as to improve the strength and hardness of the alloy metal material, and a protective isolation layer is formed on the surface of the tungsten carbide particles with large grain sizes after the tungsten carbide particles with small grain sizes are melted by controlling the temperature in the sintering process, so that the alloy metal material has stronger impact toughness, and the material has excellent impact toughness while ensuring the larger hardness and strength.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a time-temperature map of the high-toughness cemented carbide provided in example 1 of the present invention during sintering.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The specific embodiment provides a high-strength and high-toughness hard alloy which comprises the following components in parts by weight: the tungsten carbide powder is prepared by carbonizing tungsten powder, and the tungsten powder is divided into three stages according to the grain size, namely first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder in sequence.
Preferably, the high-toughness hard alloy comprises the following components in parts by weight: the tungsten carbide powder is prepared by carbonizing tungsten powder, the tungsten powder is divided into three stages according to the grain size, and the three stages are sequentially first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder.
The growth inhibitor comprises one or more of vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide and titanium carbide, and is preferably chromium carbide.
The purpose of adding the growth inhibitor is to prevent tungsten carbide grains with small grain size from growing in the sintering process, and as the tungsten carbide grains are smaller (the powder is finer), the surface area is larger, the activity is larger, and the tungsten carbide grains are easier to grow in the sintering process.
The adhesive comprises nickel powder and/or cobalt powder, preferably a compound mixture of the nickel powder and the cobalt powder, and the mass ratio of the nickel powder to the cobalt powder is 1: (1-2), preferably 1: 1.
The corrosion inhibitor comprises a tantalum-niobium solid solution and/or chromium powder, preferably a compound mixture of the tantalum-niobium solid solution and the chromium powder, and the mass ratio of the tantalum-niobium solid solution to the chromium powder is 1: (0.5-1), preferably 1: 0.5.
The grain size of the first-stage single crystal tungsten powder is 6.2-6.4 microns, the grain size of the second-stage single crystal tungsten powder is 2-2.2 microns, and the grain size of the third-stage single crystal tungsten powder is 0.1-0.3 microns; the mass ratio of the first-stage single crystal tungsten powder to the second-stage single crystal tungsten powder to the third-stage single crystal tungsten powder is 1: (2-4): (4-6).
Wherein, when the tungsten powder and the carbon black are carbonized, the tungsten carbide prepared by carbonizing the tungsten powder has the carbon atom percentage of 0.01 at%.
The arrangement is such that tungsten carbide can be melted smoothly into a liquid phase at a temperature of 2800 ℃ in the fast sintering stage (i.e., the first sintering stage).
The specific embodiment also provides a preparation method of the high-strength and high-toughness hard alloy, which comprises the following steps:
s1 preparation of tungsten powder with different grain sizes
Calcining ammonium paratungstate serving as a raw material to obtain tungsten oxide, and carrying out hydrogen reduction reaction on the obtained tungsten oxide to obtain tungsten powder;
specifically, ammonium paratungstate is placed into a tubular reduction furnace, and is calcined for 20 minutes at 700 ℃ to obtain tungsten oxide, after natural cooling, nitrogen is continuously introduced into the tubular reduction furnace to discharge air, and then the nitrogen is discharged at 2m3And continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain the tungsten powder.
In the step S1, the method further includes adding different additives to the tungsten oxide during the hydrogen reduction reaction to obtain first-stage single crystal tungsten powder with a grain size of 6.2 to 6.4 microns, second-stage single crystal tungsten powder with a grain size of 2 to 2.2 microns, and third-stage single crystal tungsten powder with a grain size of 0.1 to 0.3 microns, and then mixing the first-stage single crystal tungsten powder, the second-stage single crystal tungsten powder, and the third-stage single crystal tungsten powder in a mass ratio of 1: (2-4): (4-6) compounding;
for the preparation of first-stage single crystal tungsten powder with the grain size of 6.2-6.4 microns, a potassium source compound and a manganese source compound are mixed in tungsten oxide, and then hydrogen reduction reaction is carried out, wherein the potassium source compound is potassium carbonate, the manganese source compound is manganese chloride tetrahydrate, and the mass ratio of the tungsten oxide to the potassium carbonate to the manganese chloride tetrahydrate is 1:0.1:0.1, specifically as follows:
in step S1, after the tungsten oxide is obtained by calcining ammonium paratungstate as a raw material, potassium carbonate and manganese chloride tetrahydrate are added to the obtained tungsten oxide in the above-mentioned mass ratio, and after being uniformly mixed, hydrogen reduction reaction is performed, and finally the first-stage single crystal tungsten powder with a larger grain size (6.2 micrometers to 6.4 micrometers) is obtained.
The reason why the grain size of the tungsten powder is increased by adding the potassium carbonate is that the potassium can stay on the surface of the particles for a long time to play a role of a bonding medium, so that the particles are promoted to grow, namely the grain size is increased.
The manganese chloride tetrahydrate is added to change the morphology of the tungsten crystal grains, specifically to passivate the edges and corners of the tungsten crystal grains, the tungsten crystal grains are changed into a nearly spherical body from a regular polyhedral shape, and the crystal grains after the passivation of the edges and corners are not easy to damage when colliding with each other (namely receiving external impact force), namely the impact toughness of the material is increased.
For the preparation of second-stage single crystal tungsten powder with the grain size of 2-2.2 microns, mixing an aluminum source compound and a manganese source compound in tungsten oxide, and then carrying out hydrogen reduction reaction, wherein the aluminum source compound is aluminum chloride, the manganese source compound is manganese chloride tetrahydrate, and the mass ratio of the tungsten oxide to the aluminum chloride to the manganese chloride tetrahydrate is 1:0.1: 0.1;
the reason why the addition of aluminum chloride makes the grain size of the tungsten powder smaller is that Al3+Can form thermally stable Al2O3The film is covered on the surface of the tungsten crystal grains which are reduced to isolate the tungsten crystal grains from the outside, thereby preventing the tungsten crystal grains from growing continuously.
The effect of the manganese chloride tetrahydrate is the same as that of the first-stage single-crystal tungsten powder, and the edges and corners of the tungsten crystal grains are passivated, so that redundant description is omitted.
For the preparation of third-stage single crystal tungsten powder with the grain size of 0.1-0.3 microns, a calcium source compound and a manganese source compound are mixed in tungsten oxide, and then hydrogen reduction reaction is carried out, wherein the calcium reduction compound is calcium chloride, the manganese source compound is manganese chloride tetrahydrate, and the mass ratio of the tungsten oxide to the calcium chloride to the manganese chloride tetrahydrate is 1:0.1: 0.1.
The reason why the addition of calcium chloride makes the grain size of the tungsten powder smaller is that Ca+The method can form stable inclusion segregation to form a brittle phase fracture source at a grain boundary, and the brittle phase fracture source is easy to break in the heating process, so that tungsten powder with smaller grain size is obtained.
The effect of the manganese chloride tetrahydrate is the same as that of the first-stage single-crystal tungsten powder, and the edges and corners of the tungsten crystal grains are passivated, so that redundant description is omitted.
S2 preparation of tungsten carbide powder
The tungsten powder compounded in the step S1 is heated after carbon preparation, ball milling and mixing to obtain tungsten carbide powder;
specifically, the tungsten powder obtained in the step S1 is mixed with carbon black and then ball-milled for 1 hour by using a planetary ball mill, the ball-milling rotation speed is 300 revolutions per minute, the mixture is uniformly mixed and then loaded into a graphite boat, the graphite boat is then put into a graphite tube electric furnace for carbonization, the carbonization temperature is 1500 ℃, the carbonization time is 3 hours, hydrogen is introduced as protective gas during the carbonization process, and the tungsten carbide powder is obtained after the reaction is completed and cooling.
S3 preparation of high-toughness hard alloy
And (4) mixing the tungsten carbide powder prepared in the step (S2) with a growth inhibitor, a bonding agent and an anticorrosive agent, and then performing ball milling, drying, molding, sintering and post-treatment to obtain the high-strength and high-toughness hard alloy.
Specifically, 85-90 parts of tungsten carbide powder prepared in the step S2, 20-25 parts of chromium carbide, 10-15 parts of a binder (the binder is a mixture of nickel powder and cobalt powder with the mass ratio of 1 (1-2)) and 3-6 parts of an anticorrosive agent (the anticorrosive agent is a mixture of a tantalum-niobium solid solution and chromium powder with the mass ratio of 1 (0.5-1)), are mixed with each other, ball milling is carried out for 1 hour by using a planetary ball mill at the ball milling rotation speed of 200 rpm, the mixed powder is transferred into a drying oven to be dried for 3 hours in an environment of 80 ℃ (the temperature is not too high or too low, the temperature is too high, the mixed powder is easily oxidized, the wettability during subsequent sintering is influenced, the temperature is too low, incomplete drying is easily caused), and then the dried mixed powder is poured into a mold to be pressed and molded to obtain a green compact with the thickness of 8 mm, putting the obtained pressed blank into a graphite boat, sending the pressed blank into a vacuum sintering furnace for sintering, wherein the sintering is divided into four stages, as shown in figure 1, namely a first sintering stage, a second sintering stage, a third sintering stage and a furnace cooling stage, the first sintering stage is heated from room temperature to 2400 ℃ at the heating rate of 20 ℃/min, then entering the second sintering stage, the second sintering stage is heated from 2400 ℃ to 2800 ℃ at the heating rate of 80 ℃/min (aiming at melting tungsten carbide with smaller grain size, the melting point of the tungsten carbide is about 2700 ℃ according to the phase diagram of the tungsten carbide), keeping the temperature for 5 minutes and entering the third sintering stage, the third sintering stage is cooled from 2800 ℃ to 1600 ℃ at the cooling rate of 30 ℃/min, keeping the temperature for 2 hours and then entering the furnace cooling stage, the furnace cooling stage is cooled from 1600 ℃ to 200 ℃ at the cooling rate of 20 ℃/min, taking out and naturally cooling to normal temperature in the air.
The high-strength and high-toughness hard alloy provided by the embodiment is used for manufacturing hard alloy products, including nozzles, sealing rings, valve seats, shaft sealing bushings and cutter materials.
Example 1
S1 preparation of tungsten powder
Placing 600 parts of ammonium paratungstate into a tubular reduction furnace, calcining for 20 minutes at 700 ℃ to obtain tungsten oxide, naturally cooling, and dividing 300 parts of tungsten oxide into three groups, wherein each group comprises 100 parts;
uniformly mixing the first group of tungsten oxide with 10 parts of potassium carbonate and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at a speed of 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain first-stage single crystal tungsten powder with the grain size of 6.3 microns;
uniformly mixing the second group of tungsten oxide with 10 parts of aluminum chloride and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at 2m3Introducing hydrogen into the reduction furnace continuously at a speed of/h, raising the temperature to 900 ℃ in a temperature gradient of 90 ℃/10min, and then preservingHeating for 30min to obtain second-stage single crystal tungsten powder with grain size of 2.1 μm;
uniformly mixing the tungsten oxide of the third group with 10 parts of calcium chloride and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain third-stage single crystal tungsten powder with the grain size of 0.2 micron;
and mixing and compounding 20 parts of the first-stage single crystal tungsten powder, 60 parts of the second-stage single crystal tungsten powder and 100 parts of the third-stage single crystal tungsten powder to obtain third-stage mixed tungsten powder.
S2 preparation of tungsten carbide powder
And (2) mixing 150 parts of the three-stage mixed tungsten powder obtained in the step (S1) with 22 parts of carbon black, ball-milling for 1 hour by using a planetary ball mill at the ball-milling rotation speed of 300 r/min, uniformly mixing, loading into a graphite boat, then putting the graphite boat into a graphite tube electric furnace for carbonization at the carbonization temperature of 1500 ℃ for 3 hours, introducing hydrogen as protective gas in the carbonization process, and cooling after the reaction is finished to obtain the tungsten carbide powder.
S3 preparation of high-toughness hard alloy
Mixing 88 parts of the tungsten carbide powder prepared in the step S2 with 23 parts of chromium carbide, 12 parts of a binder (the binder comprises 4 parts of nickel powder and 8 parts of cobalt powder) and 4 parts of an anticorrosive agent (the anticorrosive agent comprises 2 parts of tantalum-niobium solid solution and 2 parts of chromium powder), ball-milling for 1 hour by using a planetary ball mill at the ball-milling rotating speed of 200 revolutions per minute, transferring the mixed powder after ball-milling to a drying box for drying at 80 ℃ for 3 hours, pouring the dried mixed powder into a mould for compression molding to obtain a pressed blank with the thickness of 8 millimeters, putting the pressed blank into a graphite boat for sintering in a vacuum sintering furnace, wherein the sintering is divided into four stages, namely a first sintering stage, a second sintering stage, a third sintering stage and a furnace cooling stage, the first sintering stage is heated from room temperature to 2400 ℃ at the heating rate of 20 ℃/min, and then entering a second sintering stage, wherein the temperature of the second sintering stage is increased from 2400 ℃ to 2800 ℃ at the temperature increase rate of 80 ℃/min, the temperature is maintained for 5 minutes, then entering a third sintering stage, the temperature of the third sintering stage is reduced from 2800 ℃ to 1600 ℃ at the temperature reduction rate of 30 ℃/min, the temperature is maintained for 2 hours, then entering a furnace temperature reduction stage, the temperature of the furnace temperature reduction stage is reduced from 1600 ℃ to 200 ℃ at the temperature reduction rate of 20 ℃/min, and then the material is taken out and naturally cooled to the normal temperature in the air, and then the high-strength and high-toughness hard alloy A1 is obtained after polishing.
Example 2
S1 preparation of tungsten powder
Placing 600 parts of ammonium paratungstate into a tubular reduction furnace, calcining for 20 minutes at 700 ℃ to obtain tungsten oxide, naturally cooling, and dividing 300 parts of tungsten oxide into three groups, wherein each group comprises 100 parts;
uniformly mixing the first group of tungsten oxide with 10 parts of potassium carbonate and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at a speed of 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain first-stage single crystal tungsten powder with the grain size of 6.3 microns;
uniformly mixing the second group of tungsten oxide with 10 parts of aluminum chloride and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain second-stage single crystal tungsten powder with the grain size of 2.1 microns;
uniformly mixing the tungsten oxide of the third group with 10 parts of calcium chloride and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain third-stage single crystal tungsten powder with the grain size of 0.2 micron;
and mixing and compounding 25 parts of the first-stage single crystal tungsten powder, 50 parts of the second-stage single crystal tungsten powder and 100 parts of the third-stage single crystal tungsten powder to obtain third-stage mixed tungsten powder.
S2 preparation of tungsten carbide powder
And (2) mixing 150 parts of the three-stage mixed tungsten powder obtained in the step (S1) with 22 parts of carbon black, ball-milling for 1 hour by using a planetary ball mill at the ball-milling rotation speed of 300 r/min, uniformly mixing, loading into a graphite boat, then putting the graphite boat into a graphite tube electric furnace for carbonization at the carbonization temperature of 1500 ℃ for 3 hours, introducing hydrogen as protective gas in the carbonization process, and cooling after the reaction is finished to obtain the tungsten carbide powder.
S3 preparation of high-toughness hard alloy
Taking 85 parts of the tungsten carbide powder prepared in the step S2, mixing the tungsten carbide powder with 20 parts of chromium carbide, 10 parts of a binder (the binder comprises 5 parts of nickel powder and 5 parts of cobalt powder) and 3 parts of an anticorrosive agent (the anticorrosive agent comprises 2 parts of tantalum-niobium solid solution and 1 part of chromium powder), ball-milling for 1 hour by using a planetary ball mill, wherein the ball-milling speed is 200 revolutions per minute, transferring the mixed powder into a drying box after ball-milling, drying for 3 hours at 80 ℃, pouring the dried mixed powder into a mould, performing compression molding to obtain a green compact with the thickness of 8 millimeters, putting the obtained green compact into a graphite boat, sintering the green compact into a vacuum sintering furnace, wherein the sintering is divided into four stages, namely a first sintering stage, a second sintering stage, a third sintering stage and a furnace cooling stage, the first sintering stage is heated from room temperature to 2400 ℃ at the heating rate of 20 ℃/min, and then entering a second sintering stage, wherein the temperature of the second sintering stage is increased from 2400 ℃ to 2800 ℃ at the temperature increase rate of 80 ℃/min, the temperature is maintained for 5 minutes, then entering a third sintering stage, the temperature of the third sintering stage is reduced from 2800 ℃ to 1600 ℃ at the temperature reduction rate of 30 ℃/min, the temperature is maintained for 2 hours, then entering a furnace temperature reduction stage, the temperature of the furnace temperature reduction stage is reduced from 1600 ℃ to 200 ℃ at the temperature reduction rate of 20 ℃/min, and then the material is taken out and naturally cooled to the normal temperature in the air, and then the high-strength and high-toughness hard alloy A2 is obtained after polishing.
Example 3
S1 preparation of tungsten powder
S1 preparation of tungsten powder
Placing 600 parts of ammonium paratungstate into a tubular reduction furnace, calcining for 20 minutes at 700 ℃ to obtain tungsten oxide, naturally cooling, and dividing 300 parts of tungsten oxide into three groups, wherein each group comprises 100 parts;
uniformly mixing the first group of tungsten oxide with 10 parts of potassium carbonate and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at a speed of 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain first-stage single crystal tungsten powder with the grain size of 6.3 microns;
uniformly mixing the second group of tungsten oxide with 10 parts of aluminum chloride and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain second-stage single crystal tungsten powder with the grain size of 2.1 microns;
uniformly mixing the tungsten oxide of the third group with 10 parts of calcium chloride and 10 parts of manganese chloride tetrahydrate, putting the mixture into a tubular reduction furnace, continuously introducing nitrogen into the tubular reduction furnace to discharge air, and then discharging the air at 2m3Continuously introducing hydrogen into the reduction furnace at a speed of/h, heating to 900 ℃ at a heating gradient of 90 ℃/10min, and then preserving heat for 30min to obtain third-stage single crystal tungsten powder with the grain size of 0.2 micron;
and mixing and compounding 15 parts of the first-stage single crystal tungsten powder, 60 parts of the second-stage single crystal tungsten powder and 90 parts of the third-stage single crystal tungsten powder to obtain third-stage mixed tungsten powder.
S2 preparation of tungsten carbide powder
And (2) mixing 150 parts of the three-stage mixed tungsten powder obtained in the step (S1) with 22 parts of carbon black, ball-milling for 1 hour by using a planetary ball mill at the ball-milling rotation speed of 300 r/min, uniformly mixing, loading into a graphite boat, then putting the graphite boat into a graphite tube electric furnace for carbonization at the carbonization temperature of 1500 ℃ for 3 hours, introducing hydrogen as protective gas in the carbonization process, and cooling after the reaction is finished to obtain the tungsten carbide powder.
S3 preparation of high-toughness hard alloy
Mixing 90 parts of the tungsten carbide powder prepared in the step S2, 25 parts of chromium carbide, 15 parts of a binder (the binder comprises 5 parts of nickel powder and 10 parts of cobalt powder) and 6 parts of an anticorrosive agent (the anticorrosive agent comprises 3 parts of tantalum-niobium solid solution and 3 parts of chromium powder), ball-milling for 1 hour by using a planetary ball mill, wherein the ball-milling speed is 200 revolutions per minute, transferring the mixed powder into a drying box after ball-milling, drying for 3 hours at 80 ℃, pouring the dried mixed powder into a mold, performing compression molding to obtain a pressed blank with the thickness of 8 millimeters, putting the pressed blank into a graphite boat, sintering in a vacuum sintering furnace, wherein the sintering is divided into four stages, namely a first sintering stage, a second sintering stage, a third sintering stage and a furnace cooling stage, the first sintering stage is heated from room temperature to 2400 ℃ at the heating rate of 20 ℃/min, and then entering a second sintering stage, wherein the temperature of the second sintering stage is increased from 2400 ℃ to 2800 ℃ at the temperature increase rate of 80 ℃/min, the temperature is maintained for 5 minutes, then entering a third sintering stage, the temperature of the third sintering stage is reduced from 2800 ℃ to 1600 ℃ at the temperature reduction rate of 30 ℃/min, the temperature is maintained for 2 hours, then entering a furnace temperature reduction stage, the temperature of the furnace temperature reduction stage is reduced from 1600 ℃ to 200 ℃ at the temperature reduction rate of 20 ℃/min, and then the material is taken out and naturally cooled to the normal temperature in the air, and then the high-strength and high-toughness hard alloy A3 is obtained after polishing.
Example 4
The rest characteristics are the same as those of the embodiment 1, except that in the step S3, vanadium carbide is selected as the growth inhibitor, and finally the high-toughness cemented carbide A4 is prepared.
Example 5
The other characteristics are the same as those of the embodiment 1, except that in the step S3, the growth inhibitor is chromium carbide, and finally the high-strength and high-toughness cemented carbide A5 is prepared.
Example 6
The other characteristics are the same as those of the embodiment 1, except that in the step S3, the growth inhibitor is niobium carbide, and finally the high-strength and high-toughness cemented carbide A6 is prepared.
Example 7
The rest characteristics are the same as those of the embodiment 1, except that in the step S3, molybdenum carbide is selected as the growth inhibitor, and finally the high-strength and high-toughness cemented carbide A7 is prepared.
Example 8
The other characteristics are the same as those of the embodiment 1, except that in the step S3, the growth inhibitor is titanium carbide, and finally the high-strength and high-toughness cemented carbide A8 is prepared.
Example 9
The other characteristics are the same as those of the example 1, except that the bonding agent is only nickel powder, and finally the high-toughness cemented carbide A9 is prepared.
Example 10
The other characteristics are the same as those of the embodiment 1, except that the binder is only cobalt powder, and finally the high-toughness cemented carbide A10 is prepared.
Example 11
The other characteristics are the same as those of the embodiment 1, except that the bonding agent is only tantalum-niobium solid solution powder, and finally the high-toughness cemented carbide A11 is prepared.
Example 12
The other characteristics are the same as those of the embodiment 1, except that the adhesive is only chromium powder, and finally the high-toughness cemented carbide A12 is prepared.
Comparative example 1
The remaining characteristics were the same as in example 1, except that ordinary tungsten carbide powder having a grain size of 4 μm was used instead of the tungsten carbide powder in example 1, i.e., step 1 and step 2 were omitted, and finally cemented carbide D1 was obtained.
Comparative example 2
The remaining characteristics were the same as in example 1, except that in step S1, when the three-stage mixed tungsten powder was compounded, the amount of the first-stage single-crystal tungsten powder was 100 parts, the amount of the second-stage single-crystal tungsten powder was 60 parts, and the amount of the third-stage single-crystal tungsten powder was 20 parts, and finally cemented carbide D2 was obtained.
Comparative example 3
The remaining characteristics were the same as those of example 1, except that only the primary single-crystal tungsten powder was used in an amount of 180 parts in step S1, and cemented carbide D3 was finally obtained.
Comparative example 4
The remaining characteristics were the same as those of example 1, except that only the secondary single-crystal tungsten powder was used in an amount of 180 parts in step S1, and cemented carbide D4 was finally obtained.
Comparative example 5
The remaining characteristics were the same as those of example 1, except that only the third-stage single-crystal tungsten powder was used in an amount of 180 parts in step S1, and cemented carbide D5 was finally obtained.
Comparative example 6
The remaining characteristics were the same as in example 1, except that in step S3, when the obtained green compact was placed in a graphite boat and fed into a vacuum sintering furnace to be sintered, sintering was carried out in only one stage at 1600 ℃ for 2 hours, and after sintering, heat was maintained for 30 minutes to finally obtain cemented carbide D6.
Examples of the experiments
The hard alloys obtained in the above examples 1 to 12 and comparative examples 1 to 6 were subjected to an impact toughness and hardness test, wherein the impact toughness test method was as described in the national standard "test method for ordinary temperature impact toughness of hard alloys" (GB/T1817-: test methods (GB/T3849.1-2015), test at normal temperature, and the relevant experimental data are shown in Table 1.
TABLE 1 impact toughness and Rockwell hardness of cemented carbide
As can be seen from the data in Table 1, the impact toughness of the high-toughness cemented carbide A1-A12 prepared by the preparation method provided by the invention can reach 120J/cm2The Rockwell hardness of the alloy can be stabilized to be more than 90HRA, which shows that the alloy has higher hardness and stronger impactAnd (4) toughness.
For D1, because the conventional tungsten carbide powder is selected as the hard phase, the impact toughness and Rockwell hardness are both in a lower range; aiming at D2, the compounding proportion of the three-level mixed tungsten powder is changed, wherein the proportion of large particles is increased, and the proportion of small particles is reduced, so that a small amount of fine cavities exist in the sintered material, and the impact toughness and Rockwell hardness of the material are reduced; for D3-D5, because single-stage particles are adopted, a small amount of fine cavities exist in the sintered material, so that the impact toughness and Rockwell hardness of the material are reduced; for D6, because the sintering is only one stage and the sintering temperature is lower than the melting point of tungsten carbide, the small-particle tungsten carbide is not melted, i.e. the protective isolation layer is not generated and a small amount of fine cavities still exist in the material, thereby reducing the impact toughness and Rockwell hardness of the material.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The high-strength and high-toughness hard alloy is characterized by comprising the following components in parts by weight: 85-90 parts of tungsten carbide powder, 20-25 parts of a growth inhibitor, 10-15 parts of a binder and 3-6 parts of an anticorrosive agent, wherein the tungsten carbide powder is prepared by carbonizing tungsten powder, and the tungsten powder is divided into three stages according to the grain size, namely first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder in sequence.
2. The high strength and toughness hard alloy as recited in claim 1, wherein said growth inhibitor comprises one or more of vanadium carbide, chromium carbide, niobium carbide, molybdenum carbide and titanium carbide.
3. The high strength and toughness cemented carbide of claim 1, wherein the binder comprises nickel powder and/or cobalt powder.
4. The high strength and toughness cemented carbide of claim 1, wherein the corrosion inhibitor comprises tantalum-niobium solid solution and/or chromium powder.
5. The high-toughness hard alloy according to claim 1, wherein the grain size of the first-stage single-crystal tungsten powder is 6.2-6.4 microns, the grain size of the second-stage single-crystal tungsten powder is 2-2.2 microns, and the grain size of the third-stage single-crystal tungsten powder is 0.1-0.3 microns; the mass ratio of the first-stage single crystal tungsten powder to the second-stage single crystal tungsten powder to the third-stage single crystal tungsten powder is 1: (2-4): (4-6).
6. The high strength and toughness cemented carbide according to claim 1, wherein the atomic percent of carbon in tungsten carbide produced by carbonizing tungsten powder is 0.01 at%.
7. The method for preparing the high-toughness hard alloy according to any one of claims 1 to 6, which is characterized by comprising the following steps:
s1 preparation of tungsten powder with different grain sizes
Calcining ammonium paratungstate serving as a raw material to obtain tungsten oxide, performing hydrogen reduction reaction on the obtained tungsten oxide to obtain tungsten powder, adding different additives to obtain first-stage single crystal tungsten powder, second-stage single crystal tungsten powder and third-stage single crystal tungsten powder which are different in grain size in the hydrogen reduction reaction stage of the tungsten oxide, and then compounding the first-stage single crystal tungsten powder, the second-stage single crystal tungsten powder and the third-stage single crystal tungsten powder according to the mass ratio;
s2 preparation of tungsten carbide powder
The tungsten powder compounded in the step S1 is heated after carbon preparation, ball milling and mixing to obtain tungsten carbide powder;
s3 preparation of high-toughness hard alloy
Mixing the tungsten carbide powder prepared in the step S2 with a growth inhibitor, a bonding agent and an anticorrosive agent, and then performing ball milling, drying, molding, sintering and post-treatment to prepare the high-strength and high-toughness hard alloy;
the sintering is divided into four stages, namely a first sintering stage, a second sintering stage, a third sintering stage and a furnace cooling stage, wherein the first sintering stage is heated from room temperature to 2400 ℃ at a heating rate of 20 ℃/min, then the second sintering stage is started, the second sintering stage is heated from 2400 ℃ to 2800 ℃ at a heating rate of 80 ℃/min, the third sintering stage is started after heat preservation is carried out for 5 minutes, the third sintering stage is cooled from 2800 ℃ to 1600 ℃ at a cooling rate of 30 ℃/min, the third sintering stage is started after heat preservation is carried out for 2 hours, the furnace cooling stage is started to be cooled from 1600 ℃ to 200 ℃ at a cooling rate of 20 ℃/min, and the furnace cooling stage is taken out and naturally cooled to normal temperature in the air.
8. The method for producing a high-toughness cemented carbide according to claim 7, wherein in step S1:
preparing first-stage single crystal tungsten powder, namely mixing a potassium source compound and a manganese source compound in tungsten oxide, and then carrying out hydrogen reduction reaction;
preparing second-stage single crystal tungsten powder, namely mixing an aluminum source compound and a manganese source compound in tungsten oxide, and then carrying out hydrogen reduction reaction;
and preparing third-stage single crystal tungsten powder, namely mixing a calcium source compound and a manganese source compound in tungsten oxide, and then carrying out hydrogen reduction reaction.
9. The method for preparing the high-toughness hard alloy according to claim 8, wherein in step S2, the carbon is prepared by reacting 150 parts by weight of tungsten powder and 22 parts by weight of carbon black.
10. The use of the high strength and toughness cemented carbide of any one of claims 1 to 6 in the manufacture of cemented carbide articles including one or more of nozzles, seal rings, valve seats, shaft seal bushings and cutters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011566202.4A CN112760543A (en) | 2020-12-25 | 2020-12-25 | High-strength and high-toughness hard alloy and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011566202.4A CN112760543A (en) | 2020-12-25 | 2020-12-25 | High-strength and high-toughness hard alloy and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112760543A true CN112760543A (en) | 2021-05-07 |
Family
ID=75694589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011566202.4A Pending CN112760543A (en) | 2020-12-25 | 2020-12-25 | High-strength and high-toughness hard alloy and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112760543A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115874101A (en) * | 2022-11-30 | 2023-03-31 | 四川川钨硬质合金有限公司 | Hard alloy powder, hard alloy and application |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1028171A1 (en) * | 1995-11-15 | 2000-08-16 | Sumitomo Electric Industries, Ltd. | Superhard composite material |
| WO2002020403A1 (en) * | 2000-09-06 | 2002-03-14 | H.C. Starck Gmbh | Ultracoarse, monorystalline tungsten carbide and method for producing the same, and hard metal produced therefrom |
| CN101555622A (en) * | 2009-05-08 | 2009-10-14 | 中南大学 | Low temperature catalysis and synthesis method of tungsten monocrystalline whisker |
| CN101899713A (en) * | 2009-05-31 | 2010-12-01 | 北京清大微纳科技有限公司 | Polycrystalline superhard material with gradient nano-micro structure and synthesis method thereof |
| KR20120055026A (en) * | 2010-11-22 | 2012-05-31 | 한국야금 주식회사 | Cemented carbide having good wear resistance and chipping resistance |
| CN107265458A (en) * | 2017-07-01 | 2017-10-20 | 赣州海盛钨钼集团有限公司 | Tungsten powder grading system for extra-coarse grained carbide alloy method |
| WO2019098183A1 (en) * | 2017-11-14 | 2019-05-23 | 株式会社アライドマテリアル | Powder containing tungsten carbide |
| CN109868404A (en) * | 2019-03-27 | 2019-06-11 | 成都川硬合金材料有限责任公司 | A kind of hard alloy axle sleeve and preparation method thereof |
| CN109881072A (en) * | 2019-03-27 | 2019-06-14 | 四川川钨硬质合金有限公司 | A kind of hard alloy seal ring and preparation method thereof |
| CN111187960A (en) * | 2019-12-31 | 2020-05-22 | 株洲硬质合金集团有限公司 | Double-crystal hard alloy and preparation method thereof |
-
2020
- 2020-12-25 CN CN202011566202.4A patent/CN112760543A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1028171A1 (en) * | 1995-11-15 | 2000-08-16 | Sumitomo Electric Industries, Ltd. | Superhard composite material |
| WO2002020403A1 (en) * | 2000-09-06 | 2002-03-14 | H.C. Starck Gmbh | Ultracoarse, monorystalline tungsten carbide and method for producing the same, and hard metal produced therefrom |
| CN101555622A (en) * | 2009-05-08 | 2009-10-14 | 中南大学 | Low temperature catalysis and synthesis method of tungsten monocrystalline whisker |
| CN101899713A (en) * | 2009-05-31 | 2010-12-01 | 北京清大微纳科技有限公司 | Polycrystalline superhard material with gradient nano-micro structure and synthesis method thereof |
| KR20120055026A (en) * | 2010-11-22 | 2012-05-31 | 한국야금 주식회사 | Cemented carbide having good wear resistance and chipping resistance |
| CN107265458A (en) * | 2017-07-01 | 2017-10-20 | 赣州海盛钨钼集团有限公司 | Tungsten powder grading system for extra-coarse grained carbide alloy method |
| WO2019098183A1 (en) * | 2017-11-14 | 2019-05-23 | 株式会社アライドマテリアル | Powder containing tungsten carbide |
| CN109868404A (en) * | 2019-03-27 | 2019-06-11 | 成都川硬合金材料有限责任公司 | A kind of hard alloy axle sleeve and preparation method thereof |
| CN109881072A (en) * | 2019-03-27 | 2019-06-14 | 四川川钨硬质合金有限公司 | A kind of hard alloy seal ring and preparation method thereof |
| CN111187960A (en) * | 2019-12-31 | 2020-05-22 | 株洲硬质合金集团有限公司 | Double-crystal hard alloy and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 王明伟: "《模具材料及表面强化技术》", 31 May 2015, 中国铁道出版社 * |
| 胡亚民: "《材料成形技术基础》", 31 August 2000, 重庆大学出版社 * |
| 陈丽杰等: "氧化钨粉还原碳化机理分析及超细碳化钨粉的制备", 《稀有金属与硬质合金》 * |
| 陈勇志等: "《机械制造工程技术基础》", 28 February 2015, 西南交通大学出版社 * |
| 高辉: "钨粉分级在粗晶碳化钨粉生产中的应用", 《硬质合金》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115874101A (en) * | 2022-11-30 | 2023-03-31 | 四川川钨硬质合金有限公司 | Hard alloy powder, hard alloy and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109252081B (en) | High-entropy alloy binding phase superfine tungsten carbide hard alloy and preparation method thereof | |
| JP5698412B2 (en) | Carbide structures, tool elements, and methods of making them | |
| CA2466866C (en) | Method of making a ceramic body of densified tungsten carbide | |
| CN111378888B (en) | Nano particle interface reinforced Ti (C, N) -based metal ceramic material with high nitrogen content and preparation method thereof | |
| JPS5814390B2 (en) | Manufacturing method of silicon carbide sintered body | |
| KR20030055258A (en) | Ultracoarse, Monocrystalline Tungsten Carbide and Method for Producing the Same, and Hard Metal Produced Therefrom | |
| CN112063905B (en) | High-performance WC-WCoB-Co complex phase hard alloy and preparation method thereof | |
| JPS6241778A (en) | Improvement of composite polycrystal diamond plunged body | |
| CN110204337B (en) | Preparation method of boron carbide ceramic material for aerospace gyroscope bearing and boron carbide ceramic material | |
| CN112760543A (en) | High-strength and high-toughness hard alloy and preparation method and application thereof | |
| CN102924087A (en) | Method for preparing cubic born nitride-silicon carbide composite ceramic material and product thereof | |
| CN114670128A (en) | Nanoscale high-temperature sintered ceramic abrasive and preparation method thereof | |
| CN113151724B (en) | Method for preparing dual-performance DP-Ti (C, N) cermet by adopting oxidation material | |
| CN112143892B (en) | Method for treating oxidation of vanadium-nitrogen alloy product | |
| CN111172443B (en) | High-comprehensive-performance hard alloy cutter material and preparation method thereof | |
| CN111975004A (en) | Manufacturing process of cutting pick for coal mining heading machine | |
| CN113319280A (en) | Metal powder injection molding MIM production process of novel titanium and titanium alloy material | |
| CN112759371A (en) | Titanium nitride coated high-titanium corundum and preparation method and application thereof | |
| CN111945051A (en) | Manufacturing process of bicrystal hard alloy for cutting tooth of coal mining heading machine | |
| RU2533225C2 (en) | Production of nanostructured alloy based on modified tungsten carbide | |
| CN113618068B (en) | Laser additive manufacturing method of high-performance GH3536 nickel-based superalloy without thermal cracks | |
| CN112779452A (en) | Compact light hard alloy and preparation method and application thereof | |
| CN113528918A (en) | Low-cobalt high-strength hard alloy and preparation method thereof | |
| CN109485425A (en) | A kind of tungsten carbide composite and preparation method thereof | |
| CN109518072B (en) | High-vanadium alloy steel carbide additive and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210507 |
|
| RJ01 | Rejection of invention patent application after publication |