CN112877578A - Ultra-fine grain hard alloy and preparation method thereof - Google Patents
Ultra-fine grain hard alloy and preparation method thereof Download PDFInfo
- Publication number
- CN112877578A CN112877578A CN201911207010.1A CN201911207010A CN112877578A CN 112877578 A CN112877578 A CN 112877578A CN 201911207010 A CN201911207010 A CN 201911207010A CN 112877578 A CN112877578 A CN 112877578A
- Authority
- CN
- China
- Prior art keywords
- powder
- ultra
- hard alloy
- ball milling
- binder phase
- 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
- 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
- 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
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses an ultra-fine grain hard alloy and a preparation method thereof, wherein the ultra-fine grain hard alloy is mainly prepared from the following raw materials in percentage by mass: 5-8% of binder phase powder and Cr3C20.20 to 0.80 percent of powder, 0.25 to 0.80 percent of Ru powder and 90.40 to 94.55 percent of superfine WC powder. The preparation method comprises the steps of mixing the raw materials, ball-milling, granulating, pressing and sintering to prepare the hard alloy. The invention passes through Cr3C2The composite addition of Ru and Ru ensures the alloy hardness, improves the micromechanical property of the binding phase of the superfine hard alloy, obviously improves the crack expansion resistance and the high-temperature oxidation resistance of the alloy material, realizes the obvious improvement of the bonding abrasion resistance of the hard alloy, and solves the problem of vehicles made of the common high-temperature alloy material in the fields of aerospace, aviation, automobiles, ships and the likeThe cutting processing is difficult.
Description
Technical Field
The invention belongs to the technical field of preparation of superfine hard alloy cutter materials, relates to superfine grain hard alloy and a preparation method thereof, and particularly relates to superfine grain hard alloy suitable for turning high-temperature alloy materials and a preparation method thereof.
Background
The hard alloy is an alloy material prepared from a hard compound of refractory metal and bonding metal through a powder metallurgy process, has the characteristics of high hardness and relatively good strength and toughness, and also has certain excellent properties of heat resistance, corrosion resistance and the like. Because of the characteristics of the hard alloy, in the machine tool industry, the hard alloy cutter is generally known as an industrial tooth, and the hard alloy cutter is mainly used for manufacturing cutting tools and wear-resistant parts and can be widely applied to the machining fields of aerospace, automobiles, energy sources, molds and the like.
In the field of machining of traditional aviation, aerospace, automobile parts and the like, high-temperature alloys represented by nickel-based alloys and other materials are increasingly widely applied. However, the materials require high cutting temperature, sticky chips and poor machinability, and have been a difficult application of cemented carbide tools for a long time.
In addition to the aerospace field, with the progress of metal materials, the performance of traditional materials such as steel, cast iron and stainless steel is also continuously improved, more and more novel metal materials are gradually appeared and popularized, the novel materials generally have the characteristics of high-temperature hardness, high strength, corrosion resistance, deformation resistance and the like, the processing index is low, the requirements on the cutter are not only limited to the requirement that the hard alloy material has high wear resistance and high collapse resistance, and meanwhile, higher requirements are also provided for the wear resistance, the adhesion wear resistance and other properties of the cutter under the high-temperature service condition.
The hard alloy cutter can generate a large amount of heat in the cutting process, particularly, the cutting without cooling liquid (environmental protection) is advocated at present, the cutting temperature is higher, the hardness of the cutter can be sharply reduced, and the service life of the conventional hard alloy cutter is greatly reduced. The hard alloy mainly comprises a hard phase and a binding phase, the hard phase hardly changes along with the rise of temperature, but the binding phase has the problems of oxidation, diffusion and the like, the texture structure of the hard alloy is changed, the hard phase is further peeled off and lost, and finally the failure of the cutter is caused.
In order to solve the above problems, the hard alloy tool material is also continuously advancing. On one hand, a third phase of (TaNbW) C is formed by adding high-melting-point metals such as Ta and Nb, and the high-temperature performance of the cutter material is enhanced; on the other hand, the WC crystal grains are refined, the alloy WC crystal grain size is reduced to be less than 0.2 mu m, the nano hard alloy cutter with high strength and high hardness and double high performance is prepared, and the service life of the cutter is prolonged.
However, the applicant has found that, on the one hand, when the high temperature performance of the tool is improved, the increase of the hard phase such as TaC/NbC/WC can improve the high temperature performance of the alloy material, but the improvement range is very limited. The main reason is that under the service condition of the cutter, the high-temperature performance of the binding phase is far lower than that of the hard phase, and before the hard phase fails, the binding phase causes the failure of the cutter material due to the reduction of the high-temperature performance; on the other hand, by refining the grain size of WC in the alloy, the hardness of the alloy is mainly increased, and the toughness of the alloy material cannot be effectively increased. Therefore, there is a need to develop new cemented carbides to overcome the problems of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, in particular to the technical problems of low high-temperature hardness and poor bonding and abrasion resistance of the existing ultrafine grain hard alloy material, and provides an ultrafine grain hard alloy which can improve the micromechanical property of a hard alloy bonding phase, improve crack expansion resistance and improve bonding and abrasion resistance while ensuring the alloy hardness, and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme.
The ultra-fine grain hard alloy is mainly prepared from the following raw materials in percentage by mass:
preferably, in the above ultra-fine grain cemented carbide, the addition amount of the Ru powder is 5% to 10% of the binder phase powder, and the Cr is present in an amount of 5% to 10% of the binder phase powder3C2The addition amount of the powder is 4-10% of the binder phase powder. Namely, the preferable scheme is: an ultrafine grain hard alloy is prepared from binding phase powder and Cr3C2The powder, Ru powder and superfine WC powder are prepared by taking 100 percent of the total amount of the raw materials, and the mass fraction of the raw materials is that the binder phase powder is 5 to 8 percent, the Ru powder is 5 to 10 percent of the binder phase powder, and the Cr powder is3C24-10% of the bonding phase powder and the balance of superfine WC powder.
In the above ultra-fine grain cemented carbide, preferably, the binder phase powder is one or more of Co powder, Ni powder and Fe powder.
Preferably, the binder phase powder is an ultrafine binder phase powder, and the Fsss particle size of the ultrafine binder phase powder is less than 0.8 μm.
In the above ultra-fine grain cemented carbide, preferably, the grain size of the ultra-fine WC powder is less than 0.5 μm.
The above ultra fine grained cemented carbide is preferably the Cr3C2The Fsss particle size of the powder is less than 1 μm.
Preferably, the purity of the Ru powder is not lower than 99.9%.
As a general technical concept, the present invention also provides a method for preparing the ultra-fine grain cemented carbide, comprising the steps of:
binding phase powder and Cr3C2The powder, the Ru powder and the superfine WC powder are mixed according to the mass fraction, and Cr is firstly mixed3C2Mixing the powder and Ru powder for pre-ball milling, adding the binder phase powder, the superfine WC powder and the forming agent for continuous ball milling, and granulating, forming and sintering after the ball milling is finished to obtain the superfine grain hard alloy.
Preferably, in the above method for preparing an ultra-fine grain cemented carbide, the sintering process is: heating to 300-450 ℃, preserving heat for 3-5 hours to remove the forming agent, then heating to 1200-1300 ℃ in vacuum atmosphere, preserving heat for 20-60 min, then heating to 1400-1460 ℃, adding 4-8 MPa high-pressure argon gas for sintering for 20-60 min, and cooling to room temperature after sintering.
Preferably, the ball milling is performed by wet milling, the ball milling medium is alcohol, the ball milling rod is a YG8 hard alloy ball milling rod with the diameter of 7 mm-12 mm, and the ball milling speed is 60 r/min-64 r/min.
In the preparation method of the ultrafine grain hard alloy, preferably, the time of the pre-ball milling is 1 to 3 hours, and the time of the continuous ball milling is 25 to 45 hours.
In the above method for preparing an ultra-fine grain cemented carbide, preferably, the forming agent is PEG4000 and/or PEG1500, and the forming agent is binder phase powder and Cr3C22 to 3 percent of the total mass of the powder, the Ru powder and the superfine WC powder;
and/or, the granulation is performed by a spray drying method.
In the sintering process, the atmosphere in the forming agent removing process is not required to be special, and the sintering process can be carried out according to the conventional operation.
The ultra-fine grain hard alloy is particularly suitable for turning high-temperature alloy.
Compared with the prior art, the invention has the advantages that:
(1) the ultra-fine grain hard alloy of the invention passes through Cr3C2And Ru, and Cr3C2The proportion of Ru is limited, the hardness of the binding phase of the superfine hard alloy cutter is improved, the synchronous improvement of the hardness and the toughness of the alloy material is realized, and particularly the crack propagation resistance of the alloy is improved on the toughness of the alloy. Simultaneously, through Ru and Cr3C2The addition of the superfine hard alloy obviously improves the high-temperature oxidation resistance of the alloy material, solves the problems of high cutting temperature, serious tool bonding abrasion and the like of the common materials in the fields of aerospace and the like of the superfine hard alloy, and improves the turning processing performance of the tool material.
In the invention, the ultrafine grain hard alloy is prepared by Ru (ruthenium) -Cr3C2Compound addition of (2) and p-Cr3C2And the ratio of Ru to the total mechanical property of the cutter material is limited. In conventional ultra-fine cemented carbide, Cr3C2The addition of the powder is mainly to suppress abnormal growth of crystal grains. In the present invention, Cr is added3C2And Ru, first, Cr3C2The addition of the Ru realizes the improvement of toughness and makes up for Cr3C2The toughness is lowered by the addition of (2), and at the same time, Cr3C2And due to the composite addition of Ru, the solid solubility of the binder phase is improved, more solute is added, and the microhardness of the binder phase is obviously improved, so that the comprehensive mechanical property of the alloy is improved.
In the present invention, Cr is used3C2With composite addition of Ru and with Cr3C2The ratio of Ru to the alloy material is limited, so that the high-temperature oxidation resistance of the alloy material can be obviously improved. The local temperature of the cutter material can reach over 800 ℃ under the service condition, and in the conventional hard alloy material, although hard phases with better high temperature performance such as TaC, NbC and the like are added, in the use process, the bonding phase in the alloy usually fails. By Cr, compared with conventional cemented carbide3C2And Ru is added compositely, the high-temperature performance of the binder phase in the alloy is improved, so that the oxidation starting temperature of the alloy material is increased, the oxidation cut-off temperature of the alloy is reduced, the integral oxidation degree of the alloy is obviously reduced, and the oxidation weight of the alloy is increased by less than 40% of that of the conventional alloy at 1000 ℃, so that the cutter material can obviously resist high-temperature oxidation failure under the service condition, and the performance of the binder phase of the hard alloy cutter under the high-temperature service condition is improved.
The addition of Ru improves the phase interface bonding strength of hard phase WC and a binding phase. When the hard alloy material is subjected to external force, the defect points in the material usually become crack sources, and the cracks can be continuously expanded along with the increase of the applied force. Taking Co as an example of the binder phase, the WC/Co phase interface is usually the location with more defects, and the WC/Co phase interface is also usually the interface with the weakest bonding strength in the cemented carbide. The addition of Ru reduces the enrichment of impurity elements at the grain boundary and plays a role in purifying the grain boundary on the one hand, and also reduces the defects of a WC/Co interface on the other hand, and improves the bonding strength of WC and Co phases. Therefore, when the hard alloy turning tool prepared by the invention is used, the generation of internal crack defects of the alloy can be obviously reduced, the propagation rate of generated cracks is reduced, and the bonding abrasion resistance of the alloy is greatly improved.
(2) In the invention, the addition amount of Ru powder is preferably 5-10% of binder phase powder, and Cr is preferably 5-10%3C2The addition amount of the powder is 4-10% of the binder phase powder, and in the proportion range, the binder phase hardness, the alloy crack propagation resistance, the high-temperature oxidation resistance and the like of the ultra-fine grain hard alloy are greatly improved, so that the synchronous improvement of the hardness and the toughness of the alloy material is realized.
(3) The preparation method of the invention prepares the alloy cutter by mixing, ball milling, granulating, pressing and sintering various raw materials according to the powder metallurgy method, and has simple and convenient operation.
(4) The ultrafine grain hard alloy cutter material is particularly suitable for turning high-temperature alloy materials in the fields of aerospace, aviation, automobiles, ships and the like, and can obviously improve the processing performance of the materials.
Drawings
FIG. 1 is a graph showing cracks in fracture toughness of an ultra fine grain cemented carbide according to example 1 of the present invention.
FIG. 2 is a crack pattern of fracture toughness of the ultra fine grain cemented carbide of comparative example 1.
FIG. 3 is a graph comparing the oxidation resistance of the ultra fine grained cemented carbide of example 1 of the present invention with that of the cemented carbide of comparative example 1.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1:
the invention relates to an ultra-fine grain hard alloy which is mainly prepared from the following raw materials in percentage by mass:
in this example, the Fsss particle size of the ultra-fine Co powder is less than 0.8 μm, the grain size of the ultra-fine WC powder is less than 0.5 μm, and Cr is3C2The Fsss particle size of the powder is less than 1 μm, and the purity of the Ru powder is not less than 99.9%.
A method for preparing an ultra-fine grain cemented carbide of the present embodiment includes the following steps:
(1) the total weight of the ingredients is 200kg, wherein 184.11kg of superfine WC powder, 14.0kg of superfine Co powder and Cr are contained in the ingredients3C20.63kg of powder and 1.26kg of Ru powder.
(2) Adding Cr in a wet grinder3C2The method comprises the steps of carrying out pre-ball milling on powder and Ru powder for 2 hours, adding superfine Co powder and superfine WC powder, adding 4kg of PEG4000 forming agent to obtain a mixture, adding 0.35L of alcohol serving as a ball milling medium into each kg of the mixture, wherein a ball milling rod is a YG8 hard alloy ball milling rod with the diameter of phi 10.5mm multiplied by 17mm, continuously carrying out ball milling for 40 hours, and then discharging, wherein the rotation speed of the pre-ball milling and the continuous ball milling is 63 r/min.
(3) After the ball milling is finished, spray drying granulation and compression molding are carried out. Performing high-pressure sintering by using a dewaxing-sintering integrated furnace, heating to 450 ℃, preserving heat for 4 hours to remove a forming agent, heating to 1200 ℃ in a vacuum atmosphere, preserving heat for 60 minutes, heating to 1410 ℃, adding 6MPa high-pressure argon for sintering for 30 minutes, cooling to room temperature after sintering is finished, and obtaining the ultrafine grain hard alloy, namely Ru-Cr3C2The ultra-fine grain hard alloy is added compositely.
Comparative example 1:
a hard alloy and a preparation method, which are basically the same as the embodiment 1, except that: does not contain Ru powder and Cr3C2And (3) pulverizing.
Table 1 raw material comparison of example 1 with comparative document 1
| Raw materials (unit: kg) | Example 1 | Comparative example 1 |
| Superfine WC powder | 184.11 | 186 |
| Co powder | 14.00 | 14 |
| Cr3C2Powder | 0.63 | 0 |
| Ru powder | 1.26 | 0 |
The machined ultra-fine grain cemented carbide tool of example 1 and the machined ultra-fine grain cemented carbide tool of comparative example 1 were subjected to mechanical property testing and used for turning of nickel-based superalloy Ni80, and the tool life was expressed in terms of the number of parts that can be machined with a single cutting edge. The mechanical properties and tool cutting life of the alloys of example 1 and comparative example 1 are as follows:
TABLE 2 comparison of mechanical and application Properties of the alloys of example 1 and comparative example 1
As can be seen from Table 2, the ultra-fine grain cemented carbide produced by the invention has higher bending strength and fracture toughness, higher crack propagation resistance and greatly improved microhardness of the binder phase, and the cutting life is prolonged by more than 80% when a Ni80 high-temperature alloy workpiece is turned.
As shown in fig. 1 and 2, when fracture toughness and cracks were measured by indentation, the ultra fine grain cemented carbide of the present invention generally had shorter crack length and better fracture toughness than comparative example 1, and as shown in fig. 3, the ultra fine grain cemented carbide of the present invention clearly had better high temperature oxidation resistance and higher binder phase microhardness than comparative example 1.
In the invention, Cr3C2The compound is added with Ru, and Cr can pass through3C2The addition of the Ru realizes the refinement of the grain size, improves the hardness of the alloy material, can realize the improvement of the toughness through the addition of the Ru, and makes up for the Cr3C2The toughness is lowered by the addition of (2). By Cr3C2And Ru, the alloy also shows excellent high-temperature oxidation resistance, and can play an obvious role in resisting high-temperature oxidation failure of the cutter material under the service condition. The mechanical property of the binding phase of the hard alloy cutter under the high-temperature service condition is improved.
Example 2
The invention relates to an ultra-fine grain hard alloy which is mainly prepared from the following raw materials in percentage by mass:
in this example, the Fsss particle size of the ultra-fine Co powder is less than 0.8 μm, the grain size of the ultra-fine WC powder is less than 0.5 μm, and Cr is3C2The Fsss particle size of the powder is less than 1 μm, and the purity of the Ru powder is not less than 99.9%.
A method for preparing an ultra-fine grain cemented carbide of the present embodiment includes the following steps:
(1) the total weight of the ingredients is 200kg, wherein 187.40kg of superfine WC powder, 11.0kg of superfine Co powder and Cr are contained in the ingredients3C20.99kg of powder and 0.61kg of Ru powder.
(2) Adding Ru powder and Cr powder into a wet grinder3C2The powder is pre-ball milled for 2 hours, then superfine WC powder and superfine Co powder are added, 4kg of PEG4000 forming agent is added to obtain a mixture, 0.35L of alcohol is added into each kg of the mixture to serve as a ball milling medium, and a ball milling rod is
And (3) continuously ball-milling the YG8 hard alloy ball-milling rod with the diameter of 10.5mm multiplied by 17mm for 45 hours, and then discharging, wherein the rotation speeds of the pre-ball milling and the continuous ball milling are both 63 r/min.
(3) After the ball milling is finished, spray drying granulation and compression molding are carried out. Performing high-pressure sintering by using a dewaxing-sintering integrated furnace, heating to 450 ℃, preserving heat for 4 hours to remove a forming agent, heating to 1200 ℃ in a vacuum atmosphere, preserving heat for 60 minutes, heating to 1410 ℃, adding 6MPa high-pressure argon for sintering for 30 minutes, cooling to room temperature after sintering is finished, and obtaining the ultrafine grain hard alloy, namely Ru-Cr3C2The ultra-fine grain hard alloy is added compositely.
Comparative example 2:
a hard alloy and a preparation method, which are basically the same as the hard alloy in the embodiment 2, and only differ in that: does not contain Ru powder and Cr3C2And (3) pulverizing.
Table 3 raw material comparison of example 2 with comparative document 2
| Raw materials (unit: kg) | Example 2 | Comparative example 2 |
| Superfine WC powder | 187.4 | 189.0 |
| Co powder | 11 | 11.0 |
| Cr3C2Powder | 0.99 | 0 |
| Ru powder | 0.61 | 0 |
The mechanical properties of the machined ultra-fine grain cemented carbide tool of example 2 and the machined ultra-fine grain cemented carbide tool of reference 2 were tested and used for high temperature nickel-based alloy turning of GH4169, and the tool life was expressed in terms of the number of parts that can be machined with a single cutting edge. The mechanical properties and tool cutting life of the alloys of example 2 and comparative example 2 are as follows:
TABLE 4 comparison of mechanical and application Properties of the alloys of example 2 and comparative example 2
| Mechanical property and application property of alloy | Example 2 | Comparative example 2 |
| Vickers hardness (kgf/mm)2) | 1850 | 1800 |
| Flexural Strength TRS (N/mm)2) | 2800 | 2550 |
| Fracture toughness KⅠc(MN/m3/2) | 9.0 | 8.2 |
| Micro hardness of binding phase (MPa) | 600 | 350 |
| Working GH4169 workpiece number (pieces) | 17 | 12 |
As can be seen from Table 4, the ultra-fine grain cemented carbide tool produced by the invention has the advantages that the alloy fracture toughness is obviously improved, the crack expansion resistance is higher, the microhardness of the binder phase is greatly improved, and the cutting life is improved by 50% when a GH4169 nickel-based high-temperature alloy workpiece is turned.
As can be seen from the above, in the present invention, the rare elements Ru and Cr are used as the main elements3C2Is added compositely to realizeThe strengthening of the binder phase represented by Co is realized, the problem of bonding abrasion in the high-temperature alloy turning process is solved, the comprehensive promotion of the mechanical property of the hard alloy cutter under the high-temperature service condition is realized, the service life of the cutter is remarkably prolonged, and the technical problem of difficult turning of common high-temperature alloy materials in the fields of aerospace, aviation, automobiles, ships and the like is solved.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. The ultra-fine grain hard alloy is characterized by being mainly prepared from the following raw materials in percentage by mass:
2. the ultra-fine grained cemented carbide according to claim 1, wherein the Ru powder is added in an amount of 5 to 10% based on the binder phase powder, and the Cr powder is added in an amount of 5 to 10% based on the binder phase powder3C2The addition amount of the powder is 4-10% of the binder phase powder.
3. The ultra fine grained cemented carbide of claim 2, wherein the binder phase powder is one or more of Co powder, Ni powder and Fe powder.
4. The ultra fine grained cemented carbide of claim 3, wherein the binder phase powder is an ultra fine binder phase powder, the Fsss grain size of the ultra fine binder phase powder being less than 0.8 μm.
5. The ultra fine grained cemented carbide according to any one of claims 1 to 4, wherein the grain size of the ultra fine WC powder is less than 0.5 μm; and/or, the Cr3C2The Fsss particle size of the powder is less than 1 μm; and/or the purity of the Ru powder is not lower than 99.9%.
6. A method for preparing the ultra fine grained cemented carbide according to any one of claims 1 to 5, comprising the steps of:
binding phase powder and Cr3C2The powder, the Ru powder and the superfine WC powder are mixed according to the mass fraction, and Cr is firstly mixed3C2Mixing the powder and Ru powder for pre-ball milling, adding the binder phase powder, the superfine WC powder and the forming agent for continuous ball milling, and granulating, forming and sintering after the ball milling is finished to obtain the superfine grain hard alloy.
7. The method of claim 6, wherein the sintering process comprises: heating to 300-450 ℃, preserving heat for 3-5 hours to remove the forming agent, then heating to 1200-1300 ℃ in vacuum atmosphere, preserving heat for 20-60 min, then heating to 1400-1460 ℃, adding 4-8 MPa high-pressure argon gas for sintering for 20-60 min, and cooling to room temperature after sintering.
8. The method for preparing ultra-fine grain cemented carbide of claim 6 or 7, wherein the ball milling is performed by wet milling, the milling medium is alcohol, the ball milling rod is YG8 cemented carbide ball milling rod with diameter of 7 mm-12 mm, and the rotation speed of the ball milling is 60 r/min-64 r/min.
9. The method of claim 8, wherein the pre-ball milling is performed for 1 hour to 3 hours, and the ball milling is performed for 25 hours to 45 hours.
10. The method for preparing ultra-fine grained cemented carbide according to claim 6 or 7, wherein the forming agent is PEG4000 and/or PEG1500, and the forming agent is binder phase powder and Cr3C22 to 3 percent of the total mass of the powder, the Ru powder and the superfine WC powder; and/or, the granulation is performed by a spray drying method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911207010.1A CN112877578A (en) | 2019-11-29 | 2019-11-29 | Ultra-fine grain hard alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911207010.1A CN112877578A (en) | 2019-11-29 | 2019-11-29 | Ultra-fine grain hard alloy and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112877578A true CN112877578A (en) | 2021-06-01 |
Family
ID=76039155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911207010.1A Pending CN112877578A (en) | 2019-11-29 | 2019-11-29 | Ultra-fine grain hard alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112877578A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114427058A (en) * | 2022-01-06 | 2022-05-03 | 四川神工钨钢刀具有限公司 | Hard alloy and manufacturing method thereof |
| CN115896578A (en) * | 2022-10-28 | 2023-04-04 | 株洲硬质合金集团有限公司 | Ultrafine hard alloy cutter material and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004076049A (en) * | 2002-08-13 | 2004-03-11 | Hitachi Tool Engineering Ltd | Hard metal of ultra-fine particles |
| CN1544675A (en) * | 2003-11-17 | 2004-11-10 | 株洲硬质合金集团有限公司 | Process for preparing ultra-fine cemented carbide |
| US20060051618A1 (en) * | 2004-08-20 | 2006-03-09 | Gilles Festeau | PVD coated ruthenium featured cutting tools |
| CN102470446A (en) * | 2009-06-30 | 2012-05-23 | 株式会社图格莱 | Cermet and coated cermet |
| CN104032153A (en) * | 2014-06-06 | 2014-09-10 | 河源正信硬质合金有限公司 | Production method of high-toughness microcrystal hard alloys |
| CN104404337A (en) * | 2014-12-15 | 2015-03-11 | 株洲钻石切削刀具股份有限公司 | Hard alloy and preparation method thereof |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| WO2019215025A1 (en) * | 2018-05-09 | 2019-11-14 | Tribo Hartstoff Gmbh | Workpiece of a hard metal material and method for producing same |
-
2019
- 2019-11-29 CN CN201911207010.1A patent/CN112877578A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004076049A (en) * | 2002-08-13 | 2004-03-11 | Hitachi Tool Engineering Ltd | Hard metal of ultra-fine particles |
| CN1544675A (en) * | 2003-11-17 | 2004-11-10 | 株洲硬质合金集团有限公司 | Process for preparing ultra-fine cemented carbide |
| US20060051618A1 (en) * | 2004-08-20 | 2006-03-09 | Gilles Festeau | PVD coated ruthenium featured cutting tools |
| CN102470446A (en) * | 2009-06-30 | 2012-05-23 | 株式会社图格莱 | Cermet and coated cermet |
| CN104032153A (en) * | 2014-06-06 | 2014-09-10 | 河源正信硬质合金有限公司 | Production method of high-toughness microcrystal hard alloys |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| CN104404337A (en) * | 2014-12-15 | 2015-03-11 | 株洲钻石切削刀具股份有限公司 | Hard alloy and preparation method thereof |
| WO2019215025A1 (en) * | 2018-05-09 | 2019-11-14 | Tribo Hartstoff Gmbh | Workpiece of a hard metal material and method for producing same |
Non-Patent Citations (1)
| Title |
|---|
| 李沐山: "《八十年代世界硬质合金技术进展八十年代世界硬质合金技术进展》", 31 August 1992, 《硬质合金》编辑部 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114427058A (en) * | 2022-01-06 | 2022-05-03 | 四川神工钨钢刀具有限公司 | Hard alloy and manufacturing method thereof |
| CN114427058B (en) * | 2022-01-06 | 2023-11-21 | 四川神工钨钢刀具有限公司 | Hard alloy and manufacturing method thereof |
| CN115896578A (en) * | 2022-10-28 | 2023-04-04 | 株洲硬质合金集团有限公司 | Ultrafine hard alloy cutter material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5427380B2 (en) | Carbide composite material and manufacturing method thereof | |
| CN101824575B (en) | Ultrafine grain wolfram carbide/ cobalt hard alloy and preparation method thereof | |
| US20040134309A1 (en) | Compositions and fabrication methods for hardmetals | |
| CN110923498B (en) | Copper-based powder metallurgy friction material containing metal carbide and metal oxide composite ceramic friction component and preparation method thereof | |
| CN111118376B (en) | High-hardness and high-strength WC-Co-based hard alloy, preparation method thereof and cutting tool | |
| CN111378857B (en) | Preparation method of high-performance ultrafine-grained hard alloy | |
| CN111378860A (en) | Ultra-fine grain hard alloy and preparation method thereof | |
| CN111286664A (en) | Superfine tungsten carbide hard alloy with high-entropy alloy as binder phase and preparation method thereof | |
| CN110438384B (en) | Iron-nickel-based ultrafine-grained hard alloy and preparation method thereof | |
| CN104032153A (en) | Production method of high-toughness microcrystal hard alloys | |
| CN110923535A (en) | Hard alloy and preparation method and application thereof | |
| CN115305401B (en) | High-entropy alloy-high-entropy ceramic combined tungsten carbide hard alloy and preparation method thereof | |
| CN111378886B (en) | Ultra-fine grain hard alloy and preparation method thereof | |
| CN111088445A (en) | Hard alloy and preparation method and application thereof | |
| CN113462946A (en) | Cobalt-nickel-iron-chromium-based hard alloy material and preparation method thereof | |
| CN112743080A (en) | Method for preparing Ti (C, N) -based metal ceramic cutter material with high heat resistance through in-situ integration | |
| CN113549801A (en) | Second-phase reinforced high-entropy binder hard alloy and preparation method thereof | |
| CN112877578A (en) | Ultra-fine grain hard alloy and preparation method thereof | |
| CN108396199B (en) | Cobalt-chromium-nickel alloy material and powder metallurgy preparation method thereof | |
| CN114635069A (en) | High-strength-toughness medium-entropy alloy binding phase Ti (C, N) -based metal ceramic and preparation method thereof | |
| CN102329975A (en) | Super-hard material and preparation method thereof | |
| CN111763865A (en) | Rhenium-containing hard alloy and preparation method and application thereof | |
| CN104388717A (en) | Method for quickly preparing gradient cemented carbide by adding rare-earth elements | |
| CN102766795B (en) | Without magnetic moulding stock and preparation method thereof | |
| CN108411180A (en) | One kind plus ruthenium hard alloy |
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: 20210601 |
|
| RJ01 | Rejection of invention patent application after publication |