CN112961998B - Powder metallurgy preparation method for step-by-step forming cemented carbide hard alloy/steel double-layer structure composite material - Google Patents
Powder metallurgy preparation method for step-by-step forming cemented carbide hard alloy/steel double-layer structure composite material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/04—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 carbonitrides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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Abstract
The invention relates to a powder metallurgy preparation method for a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; belongs to the technical field of composite material preparation. Firstly, respectively mixing a steel powder material and carbide hard alloy powder with a binder, granulating to obtain a steel powder material feed and a carbide hard alloy material feed, and then sequentially injecting the steel powder material feed and the carbide hard alloy material feed into a die cavity step by using an injection molding technology to obtain a product green compact; and removing part of the binder in the green body by catalytic degreasing, and finally sintering and densifying to obtain the carbide hard alloy/steel double-layer structure composite material. The preparation process is simple and controllable, and the obtained product has excellent performance and is convenient for large-scale industrial application.
Description
Technical Field
A powder metallurgy preparation method for a step-by-step molding sintering hard alloy/steel double-layer structure composite material belongs to the technical field of composite material preparation.
Background
The hard alloy has high hardness, strength, wear resistance and corrosion resistance, is used for manufacturing cutting tools, cutters, drilling tools and wear-resistant parts, is widely applied to the fields of war industry, aerospace, machining, metallurgy, petroleum drilling, mine tools, electronic communication, building and the like, and the market demand of the hard alloy is continuously increased along with the development of downstream industries. Due to the fact that the hard alloy is high in brittleness and the limitation of a preparation mode, the large-size and complex hard alloy/steel double-layer structure composite material is difficult to prepare.
At present, the hard alloy/steel double-layer structure composite material is generally prepared by methods such as mechanical connection, cladding and the like. The mechanical connection is to connect carbide hard alloy and steel together by large pressure, and the connection mode is a physical connection mode and has the defects of low strength, easy peeling, poor reliability and the like. Cladding is a preparation method for melting carbide hard alloy and attaching the carbide hard alloy to the surface of steel by using external heat sources such as plasma, laser and the like, and the method is limited in that the shape of the steel is required to be flat and smooth, the steel is easy to deform due to the high temperature of the heat source, and the carbide hard alloy is easy to crack.
Therefore, the research on the preparation method of the carbide hard alloy/steel double-layer structure composite material with simplicity and high efficiency has very high commercial value and application prospect.
Disclosure of Invention
The invention provides a powder metallurgy preparation method for a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material aiming at the defects of the prior art. The invention can effectively solve the problems of bonding strength between carbide hard alloy/steel and post processing difficulty, and can realize the preparation of the carbide hard alloy/steel double-layer structure composite material with high precision and high strength. The distributed injection can avoid the defects formed in the injection process, improve the material utilization rate and save the cost.
The invention relates to a powder metallurgy preparation method for a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; the method comprises the following steps:
step one
Mixing and granulating the powder A and the adhesive A to obtain feed A; the powder A is selected from at least one of carbon steel, stainless steel, iron-based alloy, nickel-based alloy and cobalt-based alloy powder;
uniformly mixing the main material and the auxiliary material to obtain mixed powder B, and mixing and granulating the mixed powder B and the adhesive to obtain feed B; the mixed powder B comprises the following main materials in percentage by mass: the auxiliary materials are 9: 1-5: 5; the main material is selected from at least one of metal carbide and metal carbonitride; the auxiliary material is metal powder with a self-melting point lower than 1400 ℃;
step two
Injecting the feed A into a mold cavity by using an injection molding machine, taking out an injection sample after the feed is cooled, observing the appearance, and placing the injection sample into a second set of mold to inject the feed B after the feed is determined to be correct; obtaining a carbide hard alloy/steel double-layer structure composite material product green body; during injection molding, the injection temperature of the two kinds of feeding materials is 120-180 ℃, the injection pressure is 50-110 MPa, the injection speed is 40-60 g/s, and the mold temperature is 120-140 ℃;
step three
Removing part of the adhesive from the product green body by a catalytic degreasing process, wherein the flow rate of nitric acid is 2-4ml/min, the catalytic temperature is 100-;
step four
Heating to 200-250 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-2 h, heating to 450-500 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-2 h, heating to 800-1000 ℃ at the speed of 5-8 ℃/min, preserving heat for 1-2 h, filling inert gas, heating to 1100-1400 ℃ at the speed of 3-5 ℃/min, preserving heat for 6-10 h, and cooling with the furnace.
Preferably, the invention relates to a powder metallurgy preparation method of a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; in the first step, the metal powder of carbon steel, stainless steel, iron-based alloy, nickel-based alloy, cobalt-based alloy and the like is prepared by gas atomization, and the particle size of the powder is 5-30 μm, and preferably 10-20 μm. As a further preference, the nickel-based alloy is a nickel-based alloy steel; the cobalt-based alloy is cobalt-based alloy steel.
Preferably, the invention relates to a powder metallurgy preparation method of a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; the granularity of the main material is 5-10 mu m, and the preferable granularity is 5-8 mu m; the particle size of the auxiliary material is 5-30 μm, and the preferable particle size is 10-20 μm.
Preferably, the invention relates to a powder metallurgy preparation method of a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; the main material is selected from tungsten carbide (WC) and chromium carbide (Cr)3C2) At least one of titanium carbide (TiC) and Vanadium Carbide (VC) powder.
Preferably, the invention relates to a powder metallurgy preparation method of a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; in the first step, the adhesive is calculated according to the mass percentage; 70-90% of Polyformaldehyde (POM); 6-12% of polyethylene (PP) and/or Polypropylene (PE); 1-4% of polyethylene wax; 1-5% of polyolefin elastomer (POE); 0.2-1% of a Basff 1098 antioxidant; 0.2-1% of Stearic Acid (SA).
Preferably, the invention relates to a powder metallurgy preparation method of a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; in the first step, when preparing the feed A, the volume ratio of the adhesive to the powder A is controlled to be 42-48%: 58-52%;
preparing feed B, and controlling the volume ratio of the adhesive to the mixed powder B to be 38-40%: 62-60%;
the temperature of the feeding and mixing is 120-160 ℃, and the time is 1-4 h; the rotation speed of the mixing roll is 80-120 r/min.
Preferably, the invention relates to a powder metallurgy preparation method of a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; the inert gas is selected from N2And Ar, or a mixture thereof.
Preferably, the invention relates to a powder metallurgy preparation method of a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; in the product green body obtained in the second step, the part formed by the A feeding accounts for 50-99% of the volume of the product green body.
The invention relates to a powder metallurgy preparation method for a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; the bonding strength of the obtained product is higher than 150MPa, and the hardness of the carbide hard alloy end is more than 1000HV 0.5.
The carbide hard alloy prepared by the invention can be co-sintered with various steels due to more selectivity of auxiliary materials, and has wide material matching property.
The effects or characteristics of the invention are as follows:
by adopting the technical scheme, the carbide hard alloy/steel double-layer structure composite material is prepared based on the metal powder injection molding technology. Firstly, respectively mixing a steel powder material, carbide hard alloy powder and low-melting-point alloy powder with an adhesive, granulating to obtain a steel powder material feed A and a carbide hard alloy material feed B, and then sequentially injecting the steel powder material feed A and the carbide hard alloy material feed B into a die cavity step by using an injection molding technology to obtain a product green compact; and removing part of the adhesive in the green body by catalytic degreasing, and finally sintering and densifying to obtain the carbide hard alloy/steel double-layer structure composite material.
The compatibility of the carbide hard alloy layer and the steel material layer and the sintering temperature are key steps of the invention, and the two links determine the performance of the final product. When the carbide hard alloy material is prepared and fed, different melting point auxiliary materials are selected according to different steel layers to control the final sintering temperature and compatibility. In the sintering process, the invention achieves the target sintering temperature through a multi-stage temperature rise program, and controls the temperature rise rate and the heat preservation time, thereby effectively avoiding the defects of deformation, cracks and the like of the blank body in the temperature rise and sintering processes.
The shrinkage consistency of the carbide hard alloy/steel double-layer structure composite material in the co-sintering process can be controlled by controlling the proportion of the adhesive in the steel powder material feeding and the carbide hard alloy material feeding, and the final product has high precision.
In addition, in the degreasing process, after some adhesives which are difficult to volatilize are removed by catalytic degreasing, a sintering-removing integrated mode is adopted, and the corresponding temperature rise rate and the corresponding heat preservation time are controlled, so that the defects of deformation, falling, cracks and the like of the blank body in the sintering process are avoided.
Compared with the prior art, the carbide hard alloy/steel double-layer structure composite material prepared by the step-by-step injection molding technology has the characteristics that:
(1) the preparation process is simple and convenient, the time consumption is short, and the molding does not need post processing;
(2) the thicknesses of the carbide hard alloy layer and the steel layer can be flexibly and accurately adjusted.
(3) Good binding property after sintering, high hardness of carbide hard alloy layer
(4) The material selection range is wide, and the material can be co-sintered with various steel materials. Can be used for preparing small special-shaped parts.
(5) And step-by-step forming is adopted, so that defects formed in the forming process are effectively avoided, the material utilization rate is improved, and the cost is saved.
(6) The invention expands the preparation range of the carbide hard alloy/steel double-layer structure composite material in the field of powder metallurgy;
(7) the carbide hard alloy/steel double-layer structure composite material prepared by the invention has good bonding property between steel and carbide hard alloy, and the hardness of the carbide hard alloy layer is high.
(8) The invention has wide material selection range and can be co-sintered with various steel products.
In conclusion, the carbide hard alloy/steel double-layer structure composite material prepared by the invention has revolutionary innovation for promoting the development of the preparation process of the existing carbide hard alloy/steel double-layer structure composite material.
Drawings
FIG. 1 is a schematic representation of an injection molded body and a sintered body in example 1;
FIG. 2 is a schematic representation of a sintered compact obtained in example 2 and comparative experiment 2;
FIG. 3 is a schematic diagram of sintered compacts obtained in example 2-1, comparative example 2-1 and comparative example 2-3.
Detailed Description
The invention takes carbide hard alloy/steel double-layer structure composite material as an example to describe the invention in detail, and the process is as follows:
example 1:
A. selecting steel material powder, carbide hard alloy material powder and a binder:
the steel material powder is nickel-based alloy steel Inconel713 powder with the average grain size of 17.6 mu m. The main chemical elements comprise the following components in percentage by mass: 0.04% of C, 12.4% of Cr, 4.5% of Mo, 0.8% of Si, Al: 5.6%, Ti: 0.8%, Nb: 1.8 percent and the balance of Ni.
The carbide hard alloy material powder selects WC + TiC as main materials, wherein the mass fraction of the TiC is 5%, and the average particle size of the main materials is 7.2 mu m; ni60 alloy powder is selected as an auxiliary material, the average particle size is 19.4 mu m, and the mass percentages of main chemical elements are as follows: c: 0.8%, Cr: 16.4%, B: 3.5%, Si: 3.0%, Fe: 14%, Ni: and (4) the balance. According to the mass percentage, the main material and the auxiliary material, namely 13:7, are put into a pot, and are added with a proper amount of absolute ethyl alcohol to be uniformly mixed and dried.
Preparing an adhesive: according to mass percent, Polyformaldehyde (POM): 85 percent; polyethylene (PP): 10 percent; polyolefin elastomer (POE): 3 percent; basf 1098 antioxidant: 1 percent; stearic Acid (SA): 1 percent.
B. Preparing and feeding: mixing the adhesive with nickel-based alloy steel Inconel713 powder according to a volume ratio of 42% to 58%, granulating to prepare a base material feed, wherein the mixing temperature is 155 ℃, the rotating speed of a mixer is 90r/min, and the mixing time is 2 h; mixing the adhesive and carbide hard alloy material powder according to a volume ratio of 40% to 60%, granulating to prepare carbide hard alloy material feed, wherein the mixing temperature is 155 ℃, the rotating speed of a mixing mill is 120r/min, and the mixing time is 3 h;
C. injection molding: firstly, injecting nickel-based alloy steel Inconel713 powder feed into a die cavity of a die by using a metal powder injection molding machine, and taking out an injection blank after the feed is cooled; after the confirmation of no error, the injection blank is put into a second set of die to inject carbide hard alloy material for feeding, and finally the carbide hard alloy/steel double-layer structure composite material green blank is obtained. When in injection molding, the injection temperature is 160 ℃, the injection pressure is 60MPa, the injection speed is 60g/s, and the mold temperature is 140 ℃; the injection blank formed by the nickel-based alloy steel Inconel713 powder accounts for 50 percent of the total volume of the composite material green body;
D. catalytic degreasing: carrying out catalytic degreasing on the product green body by nitric acid to form a pre-degreased blank: the flow rate of nitric acid is 3ml/min, the catalysis temperature is 125 ℃, and the catalysis time is 10 h;
E. and (3) sintering: sintering the product blank after catalytic degreasing in a sintering furnace, heating to 250 ℃ at the speed of 5 ℃/min, preserving heat for 1.5h, then heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and filling inert gas N2Finally, keeping the temperature at 3 ℃/min to 1150 ℃ for 6h, and then cooling with the furnace.
F. Detecting the mechanical properties of a finished product, and obtaining that the average hardness of nickel-base alloy steel Inconel713 in the co-sintered carbide hard alloy/steel double-layer structure composite material is 410HV/0.5, and the average hardness of the carbide hard alloy is 1350 HV/0.5; the interface bonding strength was 180 MPa.
Example 2:
A. selecting steel material powder, carbide hard alloy material powder and a binder:
the steel material powder is martensitic stainless steel 0Cr17Ni4Cu4Nb powder with an average grain size of 12.6 μm. The main chemical elements comprise the following components in percentage by mass: 0.07% of C, 16.8% of Cr, 0.8% of Mn, 0.8% of Si, Ni: 4.5%, Cu: 3.8%, Nb: 0.25 percent and the balance of Fe.
The carbide hard alloy material powder adopts WC as a main material, and the average grain size is 6.8 mu m; Co-Cr alloy powder is selected as an auxiliary material, the average particle size is 10.6 mu m, and the main chemical elements comprise the following components in percentage by mass: c: 1.2%, Cr: 29.5%, W: 3.8%, Si: 1.3%, Fe: 3.2%, Mo: 1.1%, Ni: 2.8%, Co: and (4) the balance. According to the mass percentage, the main material and the auxiliary material are 6:4, put into a pot, added with a proper amount of absolute ethyl alcohol, mixed evenly and dried.
Preparing an adhesive: according to mass percent, Polyformaldehyde (POM): 85 percent; polyethylene (PP): 10 percent; polyolefin elastomer (POE): 3 percent; basf 1098 antioxidant: 1 percent; stearic Acid (SA): 1 percent.
B. Preparing and feeding: mixing the adhesive with martensitic stainless steel 0Cr17Ni4Cu4Nb powder according to a volume ratio of 48% to 52%, granulating to prepare a base material feed, wherein the mixing temperature is 155 ℃, the rotating speed of a mixer is 90r/min, and the mixing time is 2 h; mixing the adhesive and carbide hard alloy material powder according to a volume ratio of 38% to 62%, granulating to prepare carbide hard alloy material feed, wherein the mixing temperature is 155 ℃, the rotating speed of a mixing mill is 120r/min, and the mixing time is 3 h;
C. injection molding: firstly, injecting martensitic stainless steel 0Cr17Ni4Cu4Nb powder feed into a die cavity of a die by using a metal powder injection molding machine, and taking out an injection blank after the feed is cooled; after the confirmation of no error, the injection blank is put into a second set of die to inject carbide hard alloy material for feeding, and finally the carbide hard alloy/steel double-layer structure composite material green blank is obtained. When in injection molding, the injection temperature is 160 ℃, the injection pressure is 60MPa, the injection speed is 60g/s, and the mold temperature is 140 ℃; the injection blank formed by the martensitic stainless steel powder accounts for 50% of the total volume of the composite material green body;
D. catalytic degreasing: carrying out catalytic degreasing on the product green body by nitric acid to form a pre-degreased blank: the flow rate of nitric acid is 3ml/min, the catalysis temperature is 125 ℃, and the catalysis time is 8 h;
E. and (3) sintering: sintering the product blank after catalytic degreasing in a sintering furnace, heating to 250 ℃ at the speed of 5 ℃/min, preserving heat for 1.5h, then heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2h, heating to 1050-1055 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and filling inert gas N2Finally, keeping the temperature at 4 ℃/min to 1260 ℃ for 6h, and then cooling the furnace.
F. Detecting the mechanical property of a finished product, wherein the average hardness of martensitic stainless steel 0Cr17Ni4Cu4Nb alloy in the carbide hard alloy/steel double-layer structure composite material after co-sintering is 280HV/0.5, and the average hardness of the carbide hard alloy is 1200 HV/0.5; the interface bonding strength was 220 MPa.
The above design parameters are only some examples of the present invention, and therefore, the scope of the present invention should not be limited by these examples, and all equivalent changes and modifications made within the scope of the present invention and the specification should be included within the scope of the present invention.
Comparative example 1
The following results were obtained by comparative experiments by varying the volume ratio of the carbide cemented carbide material powder in example 2.
Comparative example 2:
the following results can be obtained by a comparative experiment by changing the co-firing temperature of the carbide cemented carbide/steel double-layer structure composite material in example 2.
Wherein example 2-1 is the product obtained by repeating example 2.
Comparative example 3:
the following results were obtained by comparative experiments by varying the main injection parameters of the carbide cemented carbide/steel dual-layer structure composite material feedstock in example 2.
The comparison shows that the defects of the product can be caused by improper feeding proportion, improper injection parameters, over-high or over-low sintering temperature and heat preservation time, and the performance is further influenced.
The above design parameters are only some examples of the present invention, and therefore, the scope of the present invention should not be limited by these examples, and all equivalent changes and modifications made within the scope of the present invention and the specification should be included within the scope of the present invention.
Claims (9)
1. A powder metallurgy preparation method for a step-by-step formed cemented carbide hard alloy/steel double-layer structure composite material; the method is characterized in that: the method comprises the following steps:
step one
Mixing and granulating the powder A and the adhesive A to obtain feed A; the powder A is selected from at least one of carbon steel, stainless steel, iron-based alloy, nickel-based alloy and cobalt-based alloy powder;
uniformly mixing the main material and the auxiliary material to obtain mixed powder B, and mixing and granulating the mixed powder B and the adhesive B to obtain feed B; the mixed powder B comprises the following main materials in percentage by mass: the auxiliary materials are =9: 1-5: 5; the main material is at least one of metal carbide and metal carbonitride powder; the auxiliary material is metal powder with a self-melting point lower than 1400 ℃;
step two
Injecting the feed A into a mold cavity by using an injection molding machine, taking out an injection sample after the feed is cooled, observing the appearance, and placing the injection sample into a second set of mold to inject the feed B after the feed is determined to be correct; obtaining a carbide hard alloy/steel double-layer structure composite material product green body; when injection molding is carried out, the injection temperature of the two feeds is 120-180 ℃, the injection pressure is 50-110 MPa, the injection speed is 40-60 g/s, and the mold temperature is 120-140 ℃;
step three
Removing part of the adhesive from the product green body by a catalytic degreasing process, wherein the flow rate of nitric acid is 2-4ml/min, the catalytic temperature is 100-;
step four
Heating to 200-250 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-2 h, heating to 450-500 ℃ at the speed of 5-10 ℃/min, preserving heat for 1-2 h, heating to 800-1000 ℃ at the speed of 5-8 ℃/min, preserving heat for 1-2 h, filling inert gas, heating to 1100-1400 ℃ at the speed of 3-5 ℃/min, preserving heat for 6-10 h, and cooling with the furnace.
2. A powder metallurgy preparation method of a step-wise formed cemented carbide/steel two-layer structure composite according to claim 1; the method is characterized in that:
in the first step, the carbon steel, the stainless steel, the iron-based alloy, the nickel-based alloy and the cobalt-based alloy are metal powder prepared by gas atomization, and the particle size of the metal powder is 5-30 microns.
3. A powder metallurgy preparation method of a step-wise formed cemented carbide/steel two-layer structure composite according to claim 1; the method is characterized in that: the granularity of the main material is 5-10 mu m; the particle size of the auxiliary material is 5-30 μm.
4. A powder metallurgy preparation method of a step-wise formed cemented carbide/steel two-layer structure composite according to claim 3; the method is characterized in that: the main material is at least one of tungsten carbide, chromium carbide, titanium carbide and vanadium carbide powder.
5. A powder metallurgy preparation method of a step-wise formed cemented carbide/steel two-layer structure composite according to claim 3; the method is characterized in that: in the first step, the adhesive comprises the following components in percentage by mass: 70-90% of polyformaldehyde; 6-12% of polyethylene and/or polypropylene; 1-4% of polyethylene wax; 1-5% of polyolefin elastomer; 0.2-1% of a Basff 1098 antioxidant; 0.2-1% of stearic acid.
6. A powder metallurgy preparation method of a step-wise formed cemented carbide/steel two-layer structure composite according to claim 1; the method is characterized in that:
in the first step, when preparing the feed A, controlling the volume ratio of the adhesive to the powder A to be 42-48%: 58-52%;
preparing a feed B, and controlling the volume ratio of the adhesive to the mixed powder B to be 38-40%: 62-60%;
the temperature of the feeding and mixing is 120-160 ℃, and the time is 1-4 h; the rotation speed of the mixing roll is 80-120 r/min.
7. A powder metallurgy preparation method of a step-wise formed cemented carbide/steel two-layer structure composite according to claim 1; the method is characterized in that: the inert gas is selected from N2And Ar, or a mixture thereof.
8. A powder metallurgy preparation method of a step-wise formed cemented carbide/steel two-layer structure composite according to claim 1; the method is characterized in that: in the product green body obtained in the second step, the part formed by the A feeding accounts for 50 percent of the volume of the product green body.
9. A powder metallurgy manufacturing method of a step-wise formed cemented carbide/steel two-layer structure composite according to any one of claims 1-7; the method is characterized in that: the bonding strength of the obtained product is higher than 150MPa, and the hardness of the carbide hard alloy end is more than 1000HV 0.5.
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