CN111411284A - Cobalt-nickel-iron-based hard alloy material and preparation method thereof - Google Patents
Cobalt-nickel-iron-based hard alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a cobalt-nickel-iron-based hard alloy and a preparation method thereof, belonging to the field of powder metallurgy. FeCoNi is used as a binding phase, Cr, W, V, Nb and the like are used as a small amount of alloy elements, and Fe, Co and Ni element powder, alloy element powder and carbide powder are mixed, subjected to ball milling, dried and granulated, pressed and formed, dewaxed and sintered to prepare a series of novel binder hard alloys with low cost and high performance; adopting tungsten carbide powder with the average grain diameter of 0.4-16 mu m, the grain size distribution of 0.2-18 mu m and the content of 65-95% (weight ratio), and obtaining high-quality cobalt-nickel-iron-based hard alloy from fine grains to ultra-coarse grains, wherein the low-pressure sintering temperature is 1350-1480 ℃, the pressure is 5-10 MPa, and the time is 0.5-2 h; the hardness of the cobalt-nickel-iron-based hard alloy material prepared by the method reaches the level of pure cobalt hard alloy, the bending strength and the fracture toughness are both improved by 5-20% compared with the pure cobalt hard alloy, and the industrial requirement is met. The production cost of the invention is far lower than that of the existing product, and important conditions are provided for industrial popularization and application; meanwhile, the WC granularity range covered by the invention is wide, and the application range of the product can cover hard alloy cutters, mining tools, shield products and PCB micro-drills.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a cobalt-nickel-iron-based hard alloy material and a preparation method thereof.
Background
Cemented carbides consist of a refractory metal hard compound and a binder metal. The hard alloy combines the advantages of high-hardness refractory metal carbide and bonding metal with better ductility, has a series of excellent performances of high strength and hardness, good wear resistance, good red hardness, small thermal expansion coefficient, high elastic modulus, good chemical stability and the like, and is widely applied to the fields of cutting tools, mine tools, wear-resistant parts and the like.
The common hard phases in cemented carbide are mainly WC, TiC, TaC, NbC, VC and the like, the WC is taken as the main component, and metal Co has good wettability and cohesiveness to the hard phases such as WC and the like, so that Co is usually selected as the binder phase in cemented carbide. However, Co is expensive, scarce, and has toxicity and pollution problems. Therefore, the environment-friendly hard alloy with excellent performance and low cost becomes an important research field.
In recent years, a new type of cemented carbide using ferronickel or cobalt-nickel-iron alloy as a binder phase instead of cobalt has attracted much attention from researchers at home and abroad [ 1-4 ]. However, the cobalt-nickel-iron-based hard alloy in the prior art has the problems of poor mechanical property and narrow size range of tungsten carbide grains. Therefore, it is very important to design and develop a cobalt-nickel-iron-based hard alloy material with wide range of grain size, hardness and high bending strength.
High-entropy alloys have been recently reported to be composed of 5 or more kinds of alloy components at an equal atomic ratio or a nearly equal atomic ratio, and have properties such as high strength, high toughness, and high corrosion resistance [ 5 to 7 ]. However, the high-entropy alloy usually contains 25% of Cr, which can greatly reduce the carbon balance interval of the hard alloy, increase the sintering difficulty, and promote the formation of carbide intermediate phase, thus causing the problems of irregular grain shape, reduced toughness and the like of the material. The project adds a large amount of iron and a small amount of W, Cr, V, Nb and other elements on the basis of cobalt-nickel enrichment by means of the concept of high-entropy alloy and adopting the component proportion with non-equal atomic ratio, thereby ensuring that the material has good strength and hardness, improving the sintering process range and toughness of the material and reducing the cost of the material.
Reference documents:
[1]Garcia J.Influence of Fe–Ni–Co binder composition on nitridationof cemented carbides[J].
InternationalJournal of Refractory Metals&Hard Materials,2012,30(1):114-120.
[2]Gao Y,Luo B H,He K J,et al.Effect of Fe/Ni ratio on themicrostructure and properties of WC-Fe-Ni-Co cemented carbides[J].CeramicsInternational,2017:S0272884217323544.
[3]Chang S H,Chang P Y.Investigation into the sintered behavior andproperties of nanostructuredWC–Co–Ni–Fe hard metal alloys[J].MaterialsScience and Engineering:A,2014,606:150-156.
[4]Schubert W D,Fugger M,Wittmann B,et al.Aspects of sintering ofcemented carbides with Fe-based binders[J].International Journal ofRefractory Metals and Hard Materials,2015,49:110-123.
[5]Erik Hlmstrom,Raquel Lizarraga,David Linder,et al.High entropyalloys:Substituting for cobalt in cutting edge technology,Applied MaterialsToday,2018,12:322-329
[6]C.S.Chen,C.C.Yang,H.Y.Chai et al.Journal of Refractory Metals andHard Materials,2014,43:200-204
[7]P.F.Zhou,D.H.Xiao,T.C.Yuan.Powder Metallurgy,2017,60:1-6
disclosure of Invention
The invention aims to provide a cobalt-nickel-iron-based hard alloy with a wide WC grain size range and a preparation method thereof, wherein the cobalt-nickel-iron-based hard alloy provided by the invention has the advantages that the average grain diameter is 0.4-16 mu m, the grain size distribution is 0.2-18 mu m, and the hardness, the bending strength and the fracture toughness are high.
In order to achieve the above object, the present invention provides the following technical solutions:
co powder: 2.5-12%, preferably 3.5-8.5%;
ni powder: 2.5-12%, preferably 3.5-8.5%;
fe powder: 0.5 to 10%, preferably 0.5 to 5.5%;
WC powder: 65-95%, preferably 89.5-93.9%;
powder W: 0.2 to 2.0%, preferably 0.3 to 1.5%;
Cr2C3: 0.1 to 8.0%, preferably 0.5 to 5.5%;
VC: 0.1 to 5.0%, preferably 0.1 to 3.5%;
NbC: 0.1 to 6.0%, preferably 0.3 to 5.5%;
the sum of all the alloy components is 100 percent.
The preparation method of the cobalt-nickel-iron-based hard alloy material comprises the following steps:
s1, material preparation: mixing tungsten carbide powder, cobalt powder, nickel powder, iron powder, tungsten powder and carbide powder of Cr, V and Nb according to the weight percentage, adding a forming agent, carrying out wet grinding treatment, and uniformly mixing to obtain wet grinding slurry; the particle size of the tungsten carbide powder in the wet grinding slurry is 0.2-18 mu m;
s2, filtering, screening, drying and granulating the wet-milled slurry of the S1;
s3, press forming: pressing and forming the material particles subjected to the screen wiping and screening to obtain a semi-finished product;
s4, sintering and forming: and (4) sintering the pressed semi-finished product in a sintering furnace, and cooling to obtain the finished product.
Wherein the average grain size of WC is 0.4-16 μm; the average particle size of the cobalt powder is 1.0-1.5 mu m; the average particle size of the nickel powder is 1.5-2.5 mu m; the average grain diameter of the iron powder is 2.5-3.5 mu m; the average grain diameter of the tungsten powder is 0.5-1.5 mu m; cr (chromium) component2C3The average particle size of the VC and NbC powder is 0.1 to 1.0 μm.
Mixing and ball milling processes: the forming agent is a butadiene rubber solution, and the addition amount of the forming agent is 7.8-8.2% of the weight of the hard alloy powder. Mixing different powders with forming agent, adding hard powder in roller ball millWet grinding the mass alloy balls, wherein the processing technological parameters are as follows: the ball material ratio is (4-8): 1, the ball milling medium is gasoline, tungsten carbide, cobalt powder, nickel powder, iron powder, tungsten powder and Cr2C3The raw material liquid-solid ratio prepared from VC and NbC powder is 250-300 ml/kg, the ball milling time is 24-72 hours, and the ball milling rotating speed is 30-40 r/min.
Drying and granulating: in order to improve the uniformity and the formability of the powder, the slurry after ball milling is dried in a spray drying device or is granulated by vacuum drying and vibration; the drying temperature is 60-200 ℃, and the atmosphere is nitrogen or vacuum.
And (3) pressing and forming: the granulated powder granules are pressed into various product shapes, and the specific mode comprises cold isostatic pressing, unidirectional pressing or bidirectional pressing; the pressure intensity of the pressing forming is 100-200 MPa.
Dewaxing and sintering: the binder of the pressed product needs to be removed at 600-900 ℃ in vacuum or protective atmosphere, and then low-pressure sintering densification is carried out, wherein the specific process comprises the following steps: and introducing argon gas at 5-10 MPa, sintering at 1350-1480 ℃, keeping the temperature for 30-120 min, and cooling to room temperature to obtain the hard alloy material.
More preferably, the tungsten carbide powder has a particle size distribution of 0.5 to 16.0 μm.
Preferably, the forming agent is a butadiene rubber solution, and the addition amount of the forming agent is 7.8-8.2% of the weight of the hard alloy powder;
preferably, a ball milling medium adopted by ball milling is gasoline, the liquid-solid ratio of the ball milling is 250-300 m L/kg., the ball milling is carried out in a protective atmosphere, the ball-material ratio of the ball milling is 4-8: 1, the ball milling time is 24-72 hours, and the ball milling rotating speed is 30-40 r/min.
Preferably, drying is further performed after the ball milling, and the drying mode comprises spray drying or vacuum drying; the drying temperature is preferably 100-120 ℃.
Preferably, the compression molding mode is bidirectional compression; the pressure intensity of the pressing forming is 100-150 MPa.
Preferably, the dewaxing is carried out in vacuum or in an atmosphere, preferably, the atmosphere is nitrogen-hydrogen mixed gas, and the temperature is 850-900 ℃; sintering is carried out in the argon protection, the sintering pressure is 5-7 MPa, the sintering temperature is 1400-1450 ℃, and the heat preservation time is 60-90 min. Compared with the prior art, the invention has the beneficial effects that:
the invention adopts cobalt, nickel and iron as main elements to replace cobalt in a specific proportion range to prepare the novel hard alloy material, and the problem of limited cobalt resource is effectively solved because nickel and iron ore are rich and cheap.
W, Cr is adopted in the invention2C3Alloying elements are added in modes of VC, NbC and the like, so that carbon balance and sintering process parameters can be effectively adjusted, the mechanical property of the hard alloy is remarkably improved, and the use requirement is met.
The invention adopts the butadiene rubber solution as the forming agent and degreases in the nitrogen-hydrogen mixed atmosphere before sintering, thereby ensuring to remove impurities brought by the binder and effectively protecting the pressed compact from being oxidized and polluted. The invention is applicable to various hard alloys with tungsten carbide granularity of 0.4-16 mu m in a wide range, and covers the performance of cobalt-nickel-iron-based hard alloys from fine grains to ultra-coarse grains. Particularly, when the WC gradient granularity design is adopted, the characteristics of excellent comprehensive performance of hardness and toughness can be shown.
The invention can obtain the cobalt-nickel-iron-based hard alloy with different grain sizes by scientifically and reasonably designing the binder phase composition and optimizing the process, wherein the hardness of the obtained cobalt-nickel-iron-based hard alloy material is 87.5-91 HRA, the bending strength is 1772-3213 MPa, and the fracture toughness is 12.5-18.0 MPa.m1/2The hardness of the alloy reaches the hardness of the pure Co hard alloy, and the strength and the fracture toughness are improved by 10-20%.
In the invention, when the raw materials used by the hard alloy are as follows: 4 wt% of Co powder, 3.2 wt% of Ni powder, 0.8 wt% of Fe powder, 90.5-91.9 wt% of WC powder, 0.1-1.5 wt% of W powder, and Cr powder2C30.5 to 1.5 wt% of powder, 0.3 to 1.5 wt% of NbC powder, and 0.1 to 0.5 wt% of VC powder. And the particle size distribution of the WC powder is 0.8-15.8 μm, the average particle size of Co powder is 1.0-1.5 μm, the average particle size of nickel powder is 1.5-2.5 μm, the average particle size of iron powder is 2.5-3.5 μm, the average particle size of tungsten powder is 0.5-1.5 μm, Cr is2C3And when the average particle size of the VC and NbC powder is 0.1-1.0 mu m, adopting the following preparation method:
s1, burdening, namely burdening tungsten carbide, cobalt powder, nickel powder, iron powder and tungsten powder according to the weight percentage, adding a forming agent, carrying out wet grinding treatment and uniformly mixing to obtain wet grinding slurry, wherein the forming agent is a butadiene rubber solution, the addition amount of the butadiene rubber solution is 8 percent of the weight of the hard alloy powder, and the wet grinding treatment process parameters are that the ball-to-material ratio is 4: 1, a ball grinding medium is gasoline, the liquid-solid ratio of the gasoline to the raw material is 300m L/kg, the ball grinding time is 24 hours, and the ball grinding rotating speed is 35 r/min;
s2, filtering and screening the wet grinding slurry of S1, and performing vacuum drying at 100 ℃;
s3, press forming: performing compression molding on the material particles subjected to the screen wiping and screening by adopting a bidirectional compression mode under the condition that the pressure is 100-150 MPa to obtain a semi-finished product;
s4, dewaxing, sintering and forming: keeping the temperature of 900 ℃ for 60-90min in the nitrogen-hydrogen mixed gas, and removing the binder; introducing argon gas at 5MPa, sintering at a low pressure of 1430-1450 ℃, keeping the temperature for 1-1.5 h, and cooling to room temperature to obtain a hard alloy material; under the condition of the same content of the binder phase, the performance of the obtained product of the obtained hard alloy is far superior to that of the existing product containing iron and nickel, and the performance of the obtained product in the aspects of strength and toughness is superior to that of pure cobalt hard alloy.
Drawings
FIG. 1 is a scanning electron micrograph of the microstructure of a cobalt-nickel-iron based cemented carbide prepared in example 1;
FIG. 2 is a scanning electron micrograph of the microstructure of the cobalt-nickel-iron based cemented carbide prepared in example 2;
FIG. 3 is a scanning electron micrograph of the microstructure of the cobalt-nickel-iron based cemented carbide prepared in example 3;
FIG. 4 is a scanning electron micrograph of the microstructure of the cobalt nickel iron based cemented carbide prepared in example 4;
fig. 5 is a scanning electron micrograph of the microstructure of the cobalt-nickel-iron based cemented carbide prepared in example 5.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The embodiment provides a cobalt-nickel-iron-based hard alloy material, which comprises the following alloy components in percentage by weight: co powder: 4%, Ni powder: 3.2%, Fe powder: 0.8%, W powder: 1.5% of Cr2C3Powder: 0.5%, NbC powder: 0.35%, VC powder 0.15%, WC powder: 89.5%, WC average particle size of 0.84 μm, Co powder average particle size of 1.33 μm, Ni powder average particle size of 2.0 μm, Fe powder average particle size of 3.08 μm, W powder average particle size of 1.0 μm, Cr2C3The average particle size of VC and NbC powders was 0.8. mu.m.
The preparation method of the cobalt-nickel-iron-based hard alloy material comprises the following steps:
s1, material preparation: mixing tungsten carbide, cobalt powder, nickel powder, iron powder and Cr2C3VC and NbC powder are mixed according to the weight percentage, a forming agent is added, wet grinding treatment is carried out, and the mixture is uniformly mixed to obtain wet grinding slurry, wherein the forming agent is a butadiene rubber solution, the addition amount of the butadiene rubber solution is 8 percent of the weight of the hard alloy powder, the wet grinding treatment process parameters comprise that the ball-to-material ratio is 4: 1, a ball-milling medium is gasoline, the liquid-to-solid ratio of the gasoline to the raw material is 300m L/kg, and the ball-milling time is 24 hours;
s2, filtering and screening the wet grinding slurry of S1, and performing vacuum drying at 100 ℃;
s3, press forming: performing compression molding on the material particles subjected to the screen wiping and screening by adopting a unidirectional compression mode under the condition that the pressure is 150MPa to obtain a semi-finished product;
s4, dewaxing, sintering and forming: keeping the temperature of 900 ℃ for 80min in the nitrogen-hydrogen mixed gas, and removing the binder; introducing argon gas into a sintering furnace at 5MPa, sintering at low pressure to 1430 ℃, keeping the temperature for 1h, and cooling to room temperature to obtain the hard alloy material. The results of various performance tests on the cobalt-nickel-iron-based hard alloy material of the embodiment are shown in table 1; the scanning electron micrograph is shown in fig. 1, and it can be seen from the figure that the structure of the alloy consists of WC and a binder phase of cobalt-nickel-iron surrounding the WC, wherein the WC is irregular rectangle or triangle.
Example 2
The embodiment provides a cobalt-nickel-iron-based hard alloy material, which comprises the following alloy components in percentage by weight: co powder: 4%, Ni powder: 3.2%, Fe powder: 0.8%, W powder: 0.9% of Cr2C3Powder: 0.5%, NbC powder: 0.4%, VC powder 0.1%, WC powder: 90.1 percent; the average grain size of WC was 2.16 μm, that of Co powder was 1.33 μm, that of Ni powder was 2.0 μm, that of Fe powder was 3.08 μm, that of W powder was 1.0 μm, and that of Cr2C3The average particle size of VC and NbC powders was 0.8. mu.m.
The preparation method of the cobalt-nickel-iron-based hard alloy material comprises the following steps:
s1, material preparation: mixing tungsten carbide, cobalt powder, nickel powder, iron powder and Cr2C3VC and NbC powder are mixed according to the weight percentage, a forming agent is added, wet grinding treatment is carried out, and the mixture is uniformly mixed to obtain wet grinding slurry, wherein the forming agent is a butadiene rubber solution, the addition amount of the butadiene rubber solution is 8 percent of the weight of the hard alloy powder, the wet grinding treatment process parameters comprise that the ball-to-material ratio is 4: 1, a ball-milling medium is gasoline, the liquid-to-solid ratio of the gasoline to the raw material is 300m L/kg, and the ball-milling time is 24 hours;
s2, filtering and screening the wet grinding slurry of S1, and performing vacuum drying at 100 ℃;
s3, press forming: pressing and molding the material particles subjected to the screen wiping and screening by adopting a unidirectional pressing mode under the condition that the pressure is 130MPa to obtain a semi-finished product;
s4, dewaxing, sintering and forming: keeping the temperature of 900 ℃ for 80min in the nitrogen-hydrogen mixed gas, and removing the binder; introducing argon gas into a sintering furnace at 5MPa, sintering at 1440 ℃ by adopting low pressure, keeping the temperature for 1h, and cooling to room temperature to obtain the hard alloy material. The results of various performance tests on the cobalt-nickel-iron-based hard alloy material of the embodiment are shown in table 1; the scanning electron micrograph is shown in fig. 2, and it can be seen from the figure that the structure of the alloy consists of WC and a binder phase of cobalt-nickel-iron surrounding the WC, wherein the WC is irregular rectangle or triangle.
Example 3
The embodiment provides a cobalt-nickel-iron-based hard alloy material, which comprises the following alloy components in percentage by weight: co powder: 4%, Ni powder: 3.2%, Fe powder: 0.8%, W powder: 0.6%, WC powder: 91.4 percent; the average particle size of WC was 4.45 μm (average particle size of Co powder was 1.33 μm, average particle size of Ni powder was 2.0 μm, average particle size of Fe powder was 3.08 μm, average particle size of W powder was 1.0 μm, Cr was added to the mixture2C3The average particle size of VC and NbC powders was 0.8. mu.m.
The preparation method of the cobalt-nickel-iron-based hard alloy material comprises the following steps:
s1, material preparation: mixing tungsten carbide, cobalt powder, nickel powder, iron powder and Cr2C3VC and NbC powder are mixed according to the weight percentage, a forming agent is added, wet grinding treatment is carried out, and the mixture is uniformly mixed to obtain wet grinding slurry, wherein the forming agent is a butadiene rubber solution, the addition amount of the butadiene rubber solution is 8 percent of the weight of the hard alloy powder, the wet grinding treatment process parameters comprise that the ball-to-material ratio is 4: 1, a ball-milling medium is gasoline, the liquid-to-solid ratio of the gasoline to the raw material is 300m L/kg, and the ball-milling time is 24 hours;
s2, filtering and screening the wet grinding slurry of S1, and performing vacuum drying at 100 ℃;
s3, press forming: performing compression molding on the material particles subjected to the screen wiping and screening by adopting a unidirectional compression mode under the condition that the pressure is 120MPa to obtain a semi-finished product;
s4, dewaxing, sintering and forming: keeping the temperature of 900 ℃ for 80min in the nitrogen-hydrogen mixed gas, and removing the binder; introducing argon gas into a sintering furnace at 5MPa, sintering at 1440 ℃ by adopting low pressure, keeping the temperature for 1.5h, and cooling to room temperature to obtain the hard alloy material. The results of various performance tests on the cobalt-nickel-iron-based hard alloy material of the embodiment are shown in table 1; the scanning electron micrograph is shown in fig. 3, and it can be seen from the figure that the structure of the alloy consists of WC and a binder phase of cobalt-nickel-iron surrounding the WC, wherein the WC is mostly irregular rectangles or triangles, and is mostly round.
Example 4
The embodiment provides a cobalt-nickel-iron-based hard alloy material, which comprises the following alloy components in percentage by weight: co powder: 4%, Ni powder: 3.2%, Fe powder: 0.8%, W powder: 0.3% of Cr2C3Powder: 0.55%, NbC powder: 0.3%, VC powder 0.15%, WC powder: 90.7 percent; the average grain size of WC was 5.94. mu.m, that of Co powder was 1.33. mu.m, that of Ni powder was 2.0. mu.m, that of Fe powder was 3.08. mu.m, that of W powder was 1.0. mu.m, and that of Cr2C3The average particle size of VC and NbC powders was 0.8. mu.m.
The preparation method of the cobalt-nickel-iron-based hard alloy material comprises the following steps:
s1, material preparation: mixing tungsten carbide, cobalt powder, nickel powder, iron powder and Cr2C3VC and NbC powder are mixed according to the weight percentage, a forming agent is added, wet grinding treatment is carried out, and the mixture is uniformly mixed to obtain wet grinding slurry, wherein the forming agent is a butadiene rubber solution, the addition amount of the butadiene rubber solution is 8 percent of the weight of the hard alloy powder, the wet grinding treatment process parameters comprise that the ball-to-material ratio is 4: 1, a ball-milling medium is gasoline, the liquid-to-solid ratio of the gasoline to the raw material is 300m L/kg, and the ball-milling time is 24 hours;
s2, filtering and screening the wet grinding slurry of S1, and performing vacuum drying at 100 ℃;
s3, press forming: performing compression molding on the material particles subjected to the screen wiping and screening by adopting a unidirectional compression mode under the condition that the pressure is 100MPa to obtain a semi-finished product;
s4, dewaxing, sintering and forming: keeping the temperature of 900 ℃ for 80min in the nitrogen-hydrogen mixed gas, and removing the binder; introducing argon gas into a sintering furnace at 5MPa, sintering at 1450 ℃ by adopting low pressure, keeping the temperature for 1h, and cooling to room temperature to obtain the hard alloy material. The results of various performance tests on the cobalt-nickel-iron-based hard alloy material of the embodiment are shown in table 1; the scanning electron micrograph is shown in fig. 4, and it can be seen from the figure that the structure of the alloy consists of WC and a binder phase of cobalt-nickel-iron surrounding the WC, wherein the WC is irregular rectangle or triangle and partial circle.
Example 5
The embodiment provides a cobalt-nickel-iron-based hard alloy material, which comprises the following alloy components in percentage by weight: co powder: 4%, Ni powder: 3.2%, Fe powder: 0.8%, W powder: 0.1% of Cr2C3Powder: 0.55%, NbC powder: 0.25%, VC powder 0.15%, WC powder: 90.9 percent; the average grain size of WC was 15.81. mu.m, that of Co powder was 1.33. mu.m, that of Ni powder was 2.0. mu.m, that of Fe powder was 3.08. mu.m, that of W powder was 1.0. mu.m, and that of Cr2C3The average particle size of VC and NbC powders was 0.8. mu.m.
The preparation method of the cobalt-nickel-iron-based hard alloy material comprises the following steps:
s1, material preparation: mixing tungsten carbide, cobalt powder, nickel powder, iron powder and Cr2C3VC, NbC powder and the like are mixed according to the weight percentage, a forming agent is added, wet grinding treatment is carried out, and uniform mixing is carried out, so as to obtain wet grinding slurry, wherein the forming agent is a butadiene rubber solution, the addition amount of the butadiene rubber solution is 8 percent of the weight of the hard alloy powder, the wet grinding treatment process parameters are that the ball-to-material ratio is 4: 1, the ball-milling medium is gasoline, the liquid-to-solid ratio of the gasoline to the raw material is 300m L/kg, and the ball-milling time is 24 hours;
s2, filtering and screening the wet grinding slurry of S1, and performing vacuum drying at 100 ℃;
s3, press forming: performing compression molding on the material particles subjected to the screen wiping and screening by adopting a unidirectional compression mode under the condition that the pressure is 100MPa to obtain a semi-finished product;
s4, dewaxing, sintering and forming: keeping the temperature of 900 ℃ for 80min in the nitrogen-hydrogen mixed gas, and removing the binder; introducing argon gas into a sintering furnace at 5MPa, sintering at 1450 ℃ by adopting low pressure, keeping the temperature for 1.5h, and cooling to room temperature to obtain the hard alloy material. . The results of various performance tests on the cobalt-nickel-iron-based hard alloy material of the embodiment are shown in table 1; the scanning electron micrograph is shown in fig. 5, and it can be seen from the figure that the structure of the alloy consists of WC and a binder phase of cobalt-nickel-iron surrounding the WC, wherein the WC is mostly circular and a few irregular rectangles or triangles.
Comparative example 1
The comparison example provides a pure cobalt cemented carbide material, which is mainly characterized by comprising the following alloy components in percentage by weight: co powder: 8%, WC powder: 92 percent; the average grain size of WC is 0.84 μm, and the average grain size of Co powder is 1.33 μm; the preparation method of the pure cobalt hard alloy material refers to the operation steps of example 1.
Comparative example 2
The comparison example provides a pure cobalt cemented carbide material, which is mainly characterized by comprising the following alloy components in percentage by weight: co powder: 8%, WC powder: 92 percent; the average grain size of WC is 2.16 μm, and the average grain size of Co powder is 1.33 μm; the preparation method of the pure cobalt hard alloy material refers to the operation steps of example 2.
Comparative example 3
The comparison example provides a pure cobalt cemented carbide material, which is mainly characterized by comprising the following alloy components in percentage by weight: co powder: 8%, WC powder: 92 percent; the average grain size of WC is 4.45 μm, and the average grain size of Co powder is 1.33 μm; the preparation method of the pure cobalt hard alloy material refers to the operation steps of example 3.
Comparative example 4
The comparison example provides a pure cobalt cemented carbide material, which is mainly characterized by comprising the following alloy components in percentage by weight: co powder: 8%, WC powder: 92 percent; the average grain size of WC is 5.94 μm, and the average grain size of Co powder is 1.33 μm; the preparation method of the pure cobalt hard alloy material refers to the operation steps of example 4.
Comparative example 5
The comparison example provides a pure cobalt cemented carbide material, which is mainly characterized by comprising the following alloy components in percentage by weight: co powder: 8%, WC powder: 92 percent; the average grain size of WC is 15.81 μm, and the average grain size of Co powder is 1.33 μm; the preparation method of the pure cobalt hard alloy material refers to the operation steps of example 5.
Various performance tests are performed on the cobalt-nickel-iron-based hard alloy materials prepared in the embodiments 1 to 5 and the pure cobalt hard alloy materials prepared in the comparative examples 1 to 5, wherein the performance tests comprise cobalt magnetism, coercive force, Rockwell hardness, bending strength and fracture toughness, and specific test results are shown in Table 1.
TABLE 1
As can be seen from the above table, the hardness of the cobalt-nickel-iron-based cemented carbide materials of embodiments 1 to 5 of the present invention is reduced from 91.0HRA to 87.6HRA, the bending strength is increased from 1772MPa to 3213MPa, and the fracture toughness is increased from 12.85MPa m1/2Raised to 17.00MPa m1/2(ii) a In addition, the hardness of the cobalt-nickel-iron-based hard alloy material obtained by the sintering process can be comparable to that of a pure cobalt hard alloy, and the bending strength and the fracture toughness of the cobalt-nickel-iron-based hard alloy material are improved by 5-20% compared with those of the pure cobalt hard alloy.
It should be understood that the above examples are only for clearly illustrating the technical solutions of the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The cobalt-nickel-iron-based hard alloy material is characterized by comprising the following alloy components in percentage by weight:
co powder: 2.5-12%, preferably 3.5-8.5%;
ni powder: 2.5-12%, preferably 3.5-8.5%;
fe powder: 0.5 to 10%, preferably 0.5 to 5.5%;
WC powder: 65-95%, preferably 89.5-93.9%;
powder W: 0.2 to 2.0%, preferably 0.3 to 1.5%;
Cr2C3: 0.1 to 8.0%, preferably 0.5 to 5.5%;
VC: 0.1 to 5.0%, preferably 0.1 to 3.5%;
NbC: 0.1 to 6.0%, preferably 0.3 to 5.5%;
the sum of all the alloy components is 100 percent.
2. The method for preparing the cobalt-nickel-iron-based hard alloy material according to claim 1, comprising the following steps:
s1, material preparation: mixing tungsten carbide powder, cobalt powder, nickel powder, iron powder, tungsten powder and carbide powder of Cr, V and Nb according to the weight percentage, adding a forming agent, carrying out wet grinding treatment, and uniformly mixing to obtain wet grinding slurry; the particle size of the tungsten carbide powder in the wet grinding slurry is 0.2-18 mu m;
s2, filtering, screening, drying and granulating the wet-milled slurry of the S1;
s3, press forming: pressing and forming the material particles subjected to the screen wiping and screening to obtain a semi-finished product;
s4, dewaxing, sintering and forming: and dewaxing the pressed semi-finished product in the atmosphere, and sintering in a sintering furnace to obtain the finished product.
3. The method for preparing a cobalt-nickel-iron-based cemented carbide material according to claim 2, characterized by: the average grain size of the WC is 0.4-16 mu m; the average particle size of the cobalt powder is 1.0-1.5 mu m; the nickel powder is a mixture ofThe average grain diameter is 1.5-2.5 mu m; the average particle size of the iron powder is 2.5-3.5 mu m; the average particle size of the tungsten powder is 0.5-1.5 mu m; the Cr is2C3The average particle size of the VC and NbC powder is 0.1 to 1.0 μm.
4. The method for preparing a cobalt-nickel-iron-based hard alloy material according to claim 2, wherein the forming agent is a butadiene rubber solution in step S1; the addition amount of the forming agent is 7.8-8.2% of the weight of the hard alloy powder.
5. The method for preparing the cobalt-nickel-iron-based hard alloy material according to claim 2, wherein the wet grinding process parameters in the step S1 are as follows: the ball material ratio is (4-8): 1, the ball milling medium is gasoline, tungsten carbide, cobalt powder, nickel powder, iron powder, tungsten powder and Cr2C3The raw material liquid-solid ratio prepared from VC and NbC powder is 250-300 ml/kg, the ball milling time is 24-72 hours, and the ball milling rotating speed is 30-40 r/min.
6. The method according to claim 2, wherein the drying of step S2 includes spray drying or vacuum drying; the drying temperature is 60-200 ℃.
7. The method for preparing a cobalt-nickel-iron-based cemented carbide material as claimed in claim 2, wherein the step S3 is performed by a press forming method including cold isostatic pressing, uni-directional pressing or bi-directional pressing; the pressure intensity of the pressing forming is 100-200 MPa.
8. The method for preparing the cobalt-nickel-iron-based hard alloy material according to claim 2, wherein in the step S4, the green compact is dewaxed in an atmosphere, and a vacuum or protective atmosphere is adopted, wherein the temperature is 60-900 ℃; and introducing argon gas into the sintering furnace at 5-10 MPa, sintering at the low pressure of 1350-1480 ℃, keeping the temperature for 30-120 min, and cooling to room temperature to obtain the hard alloy material.
9. The method for preparing the cobalt-nickel-iron-based hard alloy material according to any one of claims 2 to 8, wherein the obtained cobalt-nickel-iron-based hard alloy material has a hardness of 87.5 to 91HRA, a bending strength of 1772 to 3213MPa and a fracture toughness of 12.5 to 18.0MPa.m1/2。
10. The method for preparing the cobalt-nickel-iron-based hard alloy material according to claim 9, wherein the hardness of the obtained cobalt-nickel-iron-based hard alloy material is 87.6-91 HRA, the bending strength is 2500-3213 MPa, and the fracture toughness is 14.5-17.5 MPa.m1/2。
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112571003A (en) * | 2020-12-04 | 2021-03-30 | 株洲韦凯切削工具有限公司 | Numerical control blade for fast feed machining and preparation method thereof |
| CN113462946A (en) * | 2021-06-03 | 2021-10-01 | 中南大学 | Cobalt-nickel-iron-chromium-based hard alloy material and preparation method thereof |
| CN114000025A (en) * | 2021-09-14 | 2022-02-01 | 自贡硬质合金有限责任公司 | WC-Co-based alloy with high wear resistance and preparation method thereof |
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| CN115074591A (en) * | 2021-03-16 | 2022-09-20 | 湖南工业大学 | Niobium-chromium-based ultrafine-grained hard alloy and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435322A (en) * | 2016-11-02 | 2017-02-22 | 中南大学 | WC-Fe-Ni-Co-Cr cemented carbide roll collar with low cost and high performance |
| CN109112339A (en) * | 2018-11-09 | 2019-01-01 | 罗纯艳 | Iron nickel for cobalt, titanium for the novel hard alloy of part tungsten production technology |
-
2020
- 2020-04-29 CN CN202010357356.6A patent/CN111411284A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435322A (en) * | 2016-11-02 | 2017-02-22 | 中南大学 | WC-Fe-Ni-Co-Cr cemented carbide roll collar with low cost and high performance |
| CN109112339A (en) * | 2018-11-09 | 2019-01-01 | 罗纯艳 | Iron nickel for cobalt, titanium for the novel hard alloy of part tungsten production technology |
Non-Patent Citations (2)
| Title |
|---|
| 周书助: "《硬质合金生产原理和质量控制》", 31 August 2014, 冶金工业出版社 * |
| 陈爱荣等: "《金属切削原理与刀具》", 30 September 2007, 中国商业出版社 * |
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| CN113462946A (en) * | 2021-06-03 | 2021-10-01 | 中南大学 | Cobalt-nickel-iron-chromium-based hard alloy material and preparation method thereof |
| CN114000025A (en) * | 2021-09-14 | 2022-02-01 | 自贡硬质合金有限责任公司 | WC-Co-based alloy with high wear resistance and preparation method thereof |
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