WO2016192177A1 - 一种硬质合金功能梯度材料的成型方法 - Google Patents

一种硬质合金功能梯度材料的成型方法 Download PDF

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WO2016192177A1
WO2016192177A1 PCT/CN2015/084089 CN2015084089W WO2016192177A1 WO 2016192177 A1 WO2016192177 A1 WO 2016192177A1 CN 2015084089 W CN2015084089 W CN 2015084089W WO 2016192177 A1 WO2016192177 A1 WO 2016192177A1
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raw material
alloy raw
mixture
functionally graded
additive
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PCT/CN2015/084089
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English (en)
French (fr)
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徐跃华
袁源
王玉鹏
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西迪技术股份有限公司
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Priority to US15/576,839 priority Critical patent/US20180161879A1/en
Publication of WO2016192177A1 publication Critical patent/WO2016192177A1/zh

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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
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • 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
    • B22F7/06—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 workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—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 workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • 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
    • C22C29/02—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
    • 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
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B22F2003/208—Warm or hot extruding
    • 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
    • B22F2207/00—Aspects of the compositions, gradients
    • B22F2207/01—Composition gradients
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to the field of functionally graded materials, and more particularly to a method of forming a cemented carbide functionally graded material.
  • Composite materials are materials that have new properties on a macroscopic (microscopic) basis by physical or chemical methods from two or more materials of different nature. Various materials complement each other in performance, resulting in synergistic effects, so that the composite material's overall performance is superior to the original composition material to meet various requirements.
  • gradient functional materials are a special type of composite materials. Unlike ordinary composite materials, it uses two (or more) materials with different properties, by continuously changing the two (or A variety of materials have a composition and structure that causes their interface to disappear, causing the properties of the material to slowly change as the composition and structure of the material changes. Since the material composition of the gradient functional material is continuously changed in a certain spatial direction, it can effectively overcome the shortcomings of the conventional composite material.
  • Gradient functional materials can be used as interfacial layers to join incompatible materials, greatly improving bond strength, and can also be used as interfacial layers to reduce residual stress and thermal stress, while eliminating interface intersections and stress freedom in joining materials. The stress singularity of the end point, and it replaces the traditional uniform material, which can enhance the joint strength and reduce the crack driving force.
  • the technical problem to be solved by the present invention is to provide a method for forming a gradient functional material having good wear resistance, toughness, corrosion resistance and high temperature oxidation, and in particular to a cemented carbide functionally graded material. Molding method.
  • the present invention provides a method for molding a cemented carbide functionally graded material, comprising:
  • the composite mold set includes an outer layer high expansion coefficient mold, an intermediate transition layer mold set and an inner layer low expansion coefficient mold;
  • the volume ratio of the alloy raw material in the mixture is 50% to 85%, and the volume ratio of the additive in the mixture is 15% to 50%.
  • the step A) is specifically:
  • a surface layer mixture is obtained; after the additive is mixed with the second alloy raw material, an intermediate layer mixture is obtained; and the additive is mixed with the third alloy raw material to obtain an inner layer mixture.
  • the surface layer has a Vickers particle size of 3 ⁇ m or less
  • the intermediate layer mixture has a Vickers particle size of 0.5 to 5 ⁇ m
  • the inner layer mixture has a Vickers particle size of 3 to 30 ⁇ m.
  • the alloy raw material comprises a hard phase and a soft phase
  • the hard phase is tungsten carbide and the soft phase is cobalt, iron or nickel.
  • the mass content of the hard phase in the first alloy raw material accounts for 93% to 97% of the mass content of the first alloy raw material; and the mass content of the hard phase in the second alloy raw material accounts for The percentage of the mass content of the second alloy raw material is 84% to 95%; and the percentage of the mass content of the hard phase in the third alloy raw material to the mass content of the third alloy raw material is 75% to 90%.
  • the composite pressure is formed into one or more of warm press forming, injection molding, and hot isostatic pressing.
  • the additive comprises one or more of polyethylene, paraffin, polyethylene glycol, polypropylene, polystyrene, stearic acid, dimethyl phthalic acid, dibutyl phthalic acid and EVA. .
  • the degreasing treatment is thermal degreasing and/or solvent degreasing treatment.
  • the sintering is vacuum pressure sintering or hot isostatic pressing.
  • the invention provides a molding method of a cemented carbide functionally graded material.
  • the additive is mixed with the alloy raw material to obtain a mixed material; then the mixture obtained in the above step is placed in a composite mold set, and after composite pressure forming, the obtained a blank; the composite mold set comprises an outer layer high expansion coefficient mold, an intermediate transition layer mold set and an inner low expansion coefficient mold; and finally, the green material is sintered to obtain a cemented carbide functional grade material.
  • the invention adopts the design concept of the functionally graded material of the cemented carbide, and obtains excellent toughness while ensuring excellent wear resistance, corrosion resistance and high temperature resistance of the cemented carbide.
  • the invention also prepares a cemented carbide functionally graded material by means of powder metallurgy, and prepares a cemented carbide gradient functional composite material by using a composite mold constitutive form and a powder metallurgy method, by adjusting the particle size and composition of the alloy powder, the additive ratio, and the composite mold.
  • Shape, different pressure forming methods and process parameters, sintering process can easily prepare a complex shape, continuous change of composition and controllable high wear resistance and excellent combination of toughness and hardness in a large thickness range Alloy functionally graded material.
  • the experimental results show that the cemented carbide functionally graded material prepared by the invention has a transverse rupture strength of 3310 N/mm 2 , a coercive force of 9.3 kA/m, a cobalt magnetic (Com%) of 9.19, and a dense surface layer to the core structure.
  • the composition and hard granules are evenly transitioned without defects such as voids, bubbles and cracks.
  • Example 1 is a metallographic diagram of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite material prepared according to Example 1 of the present invention under a 100-fold microscope;
  • Example 2 is a metallographic diagram of a surface layer of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite material prepared according to Example 1 of the present invention under a microscope of 1500 times;
  • FIG. 3 is a metallographic diagram of an intermediate transition layer G1 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite material prepared in Example 1 of the present invention under a microscope of 1500 times;
  • FIG. 4 is a metallographic diagram of an intermediate transition layer G2 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite prepared according to Example 1 of the present invention under a microscope of 1500 times;
  • FIG. 5 is a metallographic diagram of an intermediate transition layer G3 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite prepared according to Example 1 of the present invention under a 1500-fold microscope;
  • FIG. 6 is a metallographic diagram of an intermediate transition layer G4 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite prepared according to Example 1 of the present invention under a microscope of 1500 times;
  • Example 7 is a metallographic diagram of a core of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite material prepared according to Example 1 of the present invention under a microscope of 1500 times;
  • Example 8 is a schematic structural view of a WC-Co cemented carbide functionally graded composite material prepared in Example 1 of the present invention.
  • the invention provides a molding method of a cemented carbide functionally graded material, comprising:
  • the composite mold set includes an outer layer high expansion coefficient mold, an intermediate transition layer mold set and an inner layer low expansion coefficient mold;
  • the present invention firstly mixes the additive with the alloy raw material to obtain a mixture.
  • the additive is preferably one or more of polyethylene, paraffin, polyethylene glycol, polypropylene, polystyrene, stearic acid, dimethyl phthalic acid, dibutyl phthalic acid, and EVA, Preferably it is polyethylene, paraffin, polyethylene glycol, polypropylene, polystyrene, stearic acid, dimethyl phthalic acid, dibutyl phthalic acid or EVA, most preferably polyethylene, paraffin, polyethylene One or more of an alcohol and stearic acid.
  • the alloy raw material of the present invention is not particularly limited, and may be an alloy raw material for preparing a cemented carbide which is well known to those skilled in the art, and the alloy raw material of the present invention preferably includes a hard phase and a soft phase, the hard material
  • the phase is preferably tungsten carbide, the soft phase, ie the binder phase, preferably one or more of cobalt, iron, molybdenum and nickel, more preferably cobalt, iron or nickel, most preferably cobalt;
  • the alloy raw material preferably further includes an element which can increase the properties of the cemented carbide, preferably one or more of carbon, boron, tungsten, molybdenum, chromium, vanadium, niobium, titanium, nickel, iron and carbides thereof.
  • the volume ratio of the alloy raw material in the mixture in the mixture It is preferably 50% to 85%, more preferably 55% to 80%, most preferably 60% to 75%; and the volume ratio of the additive in the mixture is preferably 15% to 50%, more preferably 25% to ⁇ 45%, most preferably 30% to 40%.
  • the specific steps of the mixing in the present invention are not particularly limited, and may be a mixing process well known to those skilled in the art.
  • the present invention is preferably carried out in accordance with the following steps in order to ensure the effects of compression molding and sintering:
  • a surface layer mixture is obtained; after the additive is mixed with the second alloy raw material, an intermediate layer mixture is obtained; and the additive is mixed with the third alloy raw material to obtain an inner layer mixture.
  • the present invention mixes the additive with the first alloy raw material to obtain a surface layer mixture, that is, a fine-size alloy particle powder;
  • the surface layer mixture preferably has a Vickers particle size of 3 ⁇ m or less, more preferably 0.5 to 3 ⁇ m, and more preferably less than It is equal to 2.5 ⁇ m, and most preferably 0.5 to 2 ⁇ m;
  • the mass content of the alloy hard phase is preferably 93% to 97%, more preferably 93.5% by mass of the first alloy raw material.
  • the proportion in the feed is preferably from 40% to 50%, more preferably from 41% to 49%, most preferably from 43% to 47%.
  • the mixing mode of the present invention is not particularly limited, and may be a cemented carbide mixing method well known to those skilled in the art.
  • the present invention is preferably a ball milling; the present invention is not particularly limited to the mixing device, as those skilled in the art A well-known cemented carbide mixing apparatus is sufficient; the other conditions of the mixing of the present invention are not particularly limited, and may be a cemented carbide mixing condition well known to those skilled in the art.
  • the present invention obtains a surface mixture of a certain Freund's particle size by the above-mentioned mixing, thereby obtaining a fine grain structure through subsequent compression molding and sintering, and then using these fine grain structures having a specific particle size and composition for the surface layer of the finished product.
  • High content of hard particles and fine grain structure can give excellent surface wear resistance of cemented carbide functionally graded materials.
  • the invention simultaneously mixes the additive with the second alloy raw material to obtain an intermediate layer mixture, that is, a fine-sized and medium-sized mixed-grained alloy powder; the intermediate layer mixture preferably has a Vickers particle size of 0.5 to 5 ⁇ m;
  • the mass content of the alloy hard phase is preferably 84% to 95% by mass of the second alloy raw material; the above percentage is that the particle content of the alloy hard phase accounts for the total mass of the alloy particle powder.
  • the volume ratio of the additive in the intermediate layer mixture is preferably from 30% to 45%, more preferably from 35% to 44%, most preferably from 40% to 43%;
  • the other components in the intermediate mixture are not particularly limited, and may be added to other well-known raw materials according to production needs or quality requirements by those skilled in the art, and the present invention is preferably in the intermediate layer mixture, that is, the intermediate transition layer mixture.
  • TaC having a mass percentage content of preferably 0.2% to 0.4% is further added, more preferably 0.25% to 0.35%, and most preferably 0.3%.
  • the mixing mode of the present invention is not particularly limited, and may be a cemented carbide mixing method well known to those skilled in the art.
  • the present invention is preferably a ball milling; the present invention is not particularly limited to the mixing device, as those skilled in the art A well-known cemented carbide mixing apparatus is sufficient; the other conditions of the mixing of the present invention are not particularly limited, and may be a cemented carbide mixing condition well known to those skilled in the art.
  • the invention obtains an intermediate transition layer mixture of a certain Freund's particle size by the above mixing, and these small-sized and medium-sized multi-scale alloy powders are subjected to subsequent compression molding and sintering to obtain fine and medium sizes between the surface layer and the inner layer. Mixing the grain structure, then using these medium-sized grain structures for the intermediate transition layer of the finished product, through the control of composition and size, to obtain a continuous transition alloy gradient material with no obvious interface, to ensure that the parts have excellent comprehensive mechanical properties. . Meanwhile, it is also preferred in the present invention to add a certain amount of TaC to suppress the growth of WC fine particles in the subsequent sintering process.
  • the present invention mixes the additive with the third alloy raw material to obtain an inner layer mixture, that is, a large-sized and medium-sized alloy powder;
  • the inner layer mixture preferably has a Vickers particle size of 3 to 30 ⁇ m, more preferably 5 to 25 ⁇ m. More preferably, it is 7-20 ⁇ m, and most preferably 8-15 ⁇ m; in the third alloy raw material, the mass content of the alloy hard phase is preferably 75% to 90% by mass of the third alloy raw material.
  • the volume ratio of the additive in the inner layer mixture is preferably from 15% to 45%, more preferably from 25% to 42%, most preferably from 35% to 40%.
  • the mixing mode of the present invention is not particularly limited, and may be a cemented carbide mixing method well known to those skilled in the art.
  • the present invention is preferably a ball milling; the present invention is not particularly limited to the mixing device, as those skilled in the art A well-known cemented carbide mixing apparatus is sufficient; the other conditions of the mixing of the present invention are not particularly limited, and may be a cemented carbide mixing condition well known to those skilled in the art.
  • the inner layer mixture having a certain particle size is obtained by the above mixing, and the alloy powder having the large size and the medium size is subjected to subsequent compression molding and sintering to obtain a coarse grain structure having a specific particle size and composition, which is used.
  • the inner layer of the finished product to meet the high durability and high toughness of functionally graded materials Can ask.
  • the surface layer mixture, the intermediate layer mixture and the inner layer mixture are obtained, and then the mixture obtained in the above step is separately placed in a composite mold set, and after composite pressure forming, a blank is obtained;
  • the composite mold set preferably includes an outer layer high expansion coefficient mold, an intermediate transition layer mold set and an inner layer low expansion coefficient mold; the present invention has no particular limitation on the number of the different molds mentioned above, and those skilled in the art can according to actual production conditions and product requirements.
  • the intermediate transition layer mold set may be one or more; the composite pressure forming method of the present invention is not particularly limited, and the composite pressure forming method of the functional gradient material well known to those skilled in the art is used.
  • the present invention preferably comprises one or more of warm press forming, injection molding and hot isostatic pressing, more preferably thermoforming, injection molding or hot isostatic pressing; the composite pressure of the present invention
  • the molding conditions are not particularly limited, and the composite pressure forming strip of the functionally graded material well known to those skilled in the art is used.
  • the molding temperature of the present invention is preferably 130 to 145 ° C, more preferably 135 to 140 ° C; and the molding pressure is preferably 2 to 5 MPa, and more preferably 3 to 4 MPa.
  • the overall concept of the above preparation steps of the present invention is that, according to the requirements of the molded parts to be prepared, the outer surface is selected from the first alloy raw material, that is, the first hard alloy material (Y1), and the core (inner layer) is selected.
  • a third cemented carbide material (Y2) obtained by mixing the first cemented carbide material having the first coefficient of thermal expansion ( ⁇ 1) with a specific amount of the additive, and obtaining a surface layer mixture (Y1+T1);
  • An inner layer mixture (Y2+T2) obtained by mixing a third alloy raw material having a coefficient of thermal expansion ( ⁇ 2) with a specific amount of an additive.
  • the first thermal expansion coefficient ( ⁇ 1) is different from the second thermal expansion coefficient ( ⁇ 2), and more preferably the first thermal expansion coefficient is slightly larger than the second thermal expansion coefficient.
  • the invention further forms one or more intermediate layer mixtures by adding a specific amount of additive material (Tn), so that the intermediate layer, that is, the intermediate gradient region of the blank (Y1*n%+Y2*(100-n) %+Tn) transitions between the first alloy material and the third alloy material (Y1, Y2), and forms a continuous transition intermediate gradient composite region between the outer surface and the inner layer, and has a coefficient of thermal expansion ( ⁇ n) It is also between ⁇ 1 and ⁇ 2 and has a uniform transition.
  • Tn additive material
  • the invention realizes the interfaceless transition of the surface high hardness fine particle cemented carbide component and the inner layer high toughness coarse particle cemented carbide component, thereby greatly improving the wear resistance of the molded component. , strength, while reducing the crack driving force of the material.
  • the blank prepared by the above steps is sintered to obtain a functional gradient of the cemented carbide.
  • the method of the present invention is not particularly limited, and may be a sintering method well known to those skilled in the art, and the present invention is preferably vacuum pressure sintering or hot isostatic pressing, more preferably vacuum pressure sintering;
  • the sintering temperature of the pressure sintering is preferably 1380 to 1420 ° C, more preferably 1390 to 1410 ° C, and most preferably 1395 to 1405 ° C;
  • the protective atmosphere of the vacuum pressure sintering is preferably one of nitrogen gas, hydrogen gas and inert gas or A variety.
  • the present invention is not particularly limited to the sintered apparatus, and may be a corresponding sintering apparatus well known to those skilled in the art; the other conditions of the sintering of the present invention are not particularly limited, and the corresponding sintering conditions well known to those skilled in the art are employed. Just fine.
  • the present invention includes other steps before and after the sintering of the blank, and the present invention is not particularly limited, and those skilled in the art can adjust according to actual conditions.
  • the present invention improves the quality and performance of the finished functionally graded material, except for the low melting point in the blank.
  • the volatile additive preferably further comprises a degreasing treatment before sintering; the degreasing treatment is preferably thermal degreasing or solvent degreasing; the thermal degreasing is under a protective atmosphere of nitrogen, hydrogen or an inert gas.
  • the billet is heated and kept at a temperature within a range of 500 ° C to completely remove the additive in the body;
  • the solvent degreasing treatment that is, immersion degreasing, is an additive for removing the body from the body by immersing the body in an organic solvent, specifically Preferably, the body is immersed in gasoline at 55 to 90 ° C for 25 to 60 hours.
  • the other conditions of the above two degreasing treatments of the present invention are not particularly limited, and may be related to conditions well known to those skilled in the art.
  • the present invention prepares a cemented carbide gradient functional composite material having a multi-component and no obvious interface having a large-sized and complex outer structure by one-time sintering.
  • the gradient functional material obtained by sintering forms a gradient grain structure with different interfaces and different grain sizes without obvious interface in the thickness direction, so that the formed cemented carbide material is combined with high hardness, wear resistance, strength and Better comprehensive mechanical properties of toughness.
  • the parts manufactured by the above method of the invention can be widely applied to mechanical movement accessory parts which are widely used in petroleum, chemical, energy, electric power, metallurgy, aerospace and other industries, and which are subjected to friction and wear under high temperature oxidation and corrosion environment. .
  • the blank body after removing the additive of the invention has a regular decreasing distribution from the surface layer to the core porosity; the outer layer, the core (inner layer) and the intermediate gradient transition region during the sintering process of the blank body
  • the axial sintering shrinkage rate (radial layer) of the (intermediate layer) is almost the same, and the fluctuation is only within 0.5 percentage points.
  • the experimental results show that the cemented carbide functionally graded material prepared by the invention has a transverse rupture strength of 3310 N/mm 2 , a coercive force of 9.3 kA/m, a cobalt magnetic (Com%) of 9.19, and a dense surface layer to the core structure.
  • the composition and hard granules are evenly transitioned without defects such as voids, bubbles and cracks. This indicates that the present invention achieves no interface transition of the surface high hardness fine particle cemented carbide component and the inner layer high toughness coarse particle cemented carbide component, and improves the wear resistance and strength of the molded component while reducing The crack driving force of the material.
  • WC particles with a mass percentage of 95% and 5% Co powder are weighed to obtain a first alloy raw material; at the same time, polyethylene, paraffin, polyethylene glycol and stearic acid are prepared to obtain an additive for a surface layer mixture, and the volume thereof is 100%.
  • the fractional content ratios are: 18%, 57%, 23%, and 2%, respectively; then the above additive and the first alloy raw material are subjected to ball mill mixing in a volume ratio of 44:56 to obtain a Fischer particle size of 0.5 to 1.2 ⁇ m. Surface mix.
  • WC particles with a mass percentage of 83.7% to 94.7%, 0.3% TaC particles and the balance of Co powder are weighed to obtain a second alloy raw material; at the same time, polyethylene, paraffin, polyethylene glycol and stearic acid are prepared.
  • the additive for the intermediate layer mixture has a volume percentage ratio of 18 to 20%, 55 to 57%, 22 to 23%, and 2 to 3%, respectively; and then the above additive and the second alloy raw material are in accordance with 42:58
  • one outer layer high expansion coefficient mold four intermediate transition layer mold groups and one inner layer are respectively designed according to respective expansion coefficients.
  • Low expansion coefficient mold one outer layer high expansion coefficient mold, four intermediate transition layer mold groups and one inner layer are respectively designed according to respective expansion coefficients.
  • the surface layer mixture, the intermediate layer mixture and the inner layer mixture were sequentially placed in the above six molds, and subjected to warm press forming under the conditions of a temperature of 135 ° C and a pressure of 4 MPa, and finally a blank was obtained.
  • the billet is heated under the protection of argon to a temperature of 200 ° C for 1 hour; then heated to 250 ° C for 3 hours; then heated to 450 ° C, held for 2.5 hours, and finally naturally cooled to room temperature, completely removed Additives in the body.
  • the green body subjected to the above thermal degreasing step is placed in a vacuum pressure sintering furnace, and after passing through protective nitrogen gas, it is subjected to pressure sintering at a temperature of 1400 ° C, and then cooled and cooled to obtain a cemented carbide function. Gradient material.
  • the blank after removing the additive is distributed regularly from the surface layer to the core porosity.
  • the sintering shrinkage coefficient of the blank from the six layers of different particle sizes and compositions in the surface is 1.237 ⁇ 1.243, which indicates the axial direction of the outer layer, core and intermediate gradient transition zone during the sintering process.
  • the sintering shrinkage rate and the radial sintering shrinkage rate are almost the same, and the fluctuation range is only within 0.5%.
  • Table 1 shows the distribution of WC-Co cemented carbide functionally graded composites prepared in Example 1.
  • Table 2 shows the hardness distribution along the thickness direction of the WC-Co cemented carbide functionally graded composite material prepared in Example 1. .
  • the performance of the cemented carbide functionally graded material prepared in this example was tested.
  • the test results show that the metal-based functionally graded composite material prepared by the invention has a product density of 14.41 g/cm 3 and a transverse rupture strength of 3460 N/mm 2 .
  • the magnetic force was 9.86 kA/m, and the cobalt magnetic (Com%) was 9.82. It can be seen from the above test results that the cemented carbide functionally graded material prepared by the present invention has excellent indexes.
  • FIG. 1 is a metallographic diagram of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite material prepared according to Example 1 of the present invention under a 100-fold microscope.
  • the cemented carbide functionally graded material prepared in this example has a porosity of A02 and B00 observed under a microscope of 100 times.
  • FIG. 2 is a metallographic diagram of a surface layer of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite material prepared according to Example 1 of the present invention under a microscope of 1500 ⁇ ;
  • FIG. 3 is a metallographic diagram of an intermediate transition layer G1 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite material prepared in Example 1 of the present invention under a microscope of 1500 times;
  • FIG. 4 is a metallographic diagram of an intermediate transition layer G2 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite prepared according to Example 1 of the present invention under a microscope of 1500 times;
  • FIG. 5 is a metallographic diagram of an intermediate transition layer G3 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite prepared according to Example 1 of the present invention under a 1500-fold microscope;
  • FIG. 6 is a metallographic diagram of an intermediate transition layer G4 of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite prepared according to Example 1 of the present invention under a microscope of 1500 times;
  • Example 7 is a metallographic diagram of a core of a powder metallurgy product of a WC-Co cemented carbide functionally graded composite prepared in Example 1 of the present invention under a microscope of 1500 times.
  • the surface of the cemented carbide functionally graded material prepared in the present embodiment has a dense transition from the surface layer to the core structure, uniform composition and hard particle size, and no defects such as voids, bubbles and cracks.
  • FIG. 8 is a schematic structural view of a WC-Co cemented carbide functionally graded composite material prepared in Example 1 of the present invention.
  • WC particles with a mass percentage of 94% and 6% Co powder were weighed to obtain a first alloy raw material; at the same time, polyethylene, paraffin, polyethylene glycol and stearic acid were prepared to obtain an additive for a surface layer mixture, and the volume thereof was 100%.
  • the fractional content ratios are: 18%, 57%, 23%, and 2%, respectively; then the above additive and the first alloy raw material are subjected to ball mill mixing according to a volume ratio of 43.5:56.5 to obtain a Fisher's particle size of 0.5 to 1.2 ⁇ m. Surface mix.
  • the additive for the intermediate layer mixture has a volume percentage ratio of 18 to 20%, 55 to 57%, 22 to 23%, and 2 to 3%, respectively; and then the above additive and the second alloy raw material are in accordance with 41.5:58.5.
  • the volume ratio after ball milling, gives four sets of intermediate layer mixtures having a particle size of 0.5 to 5 ⁇ m.
  • one outer layer high expansion coefficient mold four intermediate transition layer mold groups and one inner layer are respectively designed according to respective expansion coefficients.
  • Low expansion coefficient mold one outer layer high expansion coefficient mold, four intermediate transition layer mold groups and one inner layer are respectively designed according to respective expansion coefficients.
  • the surface layer mixture, the intermediate layer mixture and the inner layer mixture were successively charged into the above six molds, and subjected to warm press forming under the conditions of a temperature of 140 ° C and a pressure of 5 MPa, and finally a blank was obtained.
  • the billet is heated under the protection of argon to a temperature of 200 ° C for 1 hour; then heated to 250 ° C for 3 hours; then heated to 450 ° C, held for 2.5 hours, and finally naturally cooled to room temperature, completely removed Additives in the body.
  • the green body subjected to the above thermal degreasing step is placed in a vacuum pressure sintering furnace, and after passing through protective nitrogen gas, it is subjected to pressure sintering at a temperature of 1400 ° C, and then cooled and cooled to obtain a furnace.
  • Cemented carbide functionally graded material is placed in a vacuum pressure sintering furnace, and after passing through protective nitrogen gas, it is subjected to pressure sintering at a temperature of 1400 ° C, and then cooled and cooled to obtain a furnace.
  • the blank after removing the additive is distributed regularly from the surface layer to the core porosity.
  • the sintering shrinkage coefficient of the blank from the six layers of different particle sizes and compositions in the surface is 1.236 ⁇ 1.241, which indicates the axial direction of the outer layer, core and intermediate gradient transition zone during the sintering process.
  • the sintering shrinkage rate and the radial sintering shrinkage rate are almost the same, and the fluctuation range is only within 0.5%.
  • Table 3 shows the distribution of WC-Co cemented carbide functionally graded composites prepared in Example 2.
  • Table 4 shows the hardness distribution along the thickness direction of the WC-Co cemented carbide functionally graded composite material prepared in Example 2. .
  • the performance of the cemented carbide functionally graded material prepared in this example was tested.
  • the test results show that the cemented carbide functionally graded material prepared by the invention has a product density of 14.52 g/cm 3 and a transverse rupture strength of 3280 N/mm 2 .
  • the magnetic force was 9.45 kA/m, and the cobalt magnetic (Com%) was 9.22. It can be seen from the above test results that the cemented carbide functionally graded material prepared by the invention has excellent indexes, the surface layer to the core structure is dense, the composition and the hard particle size are uniformly transitioned, and there are no defects such as pores, bubbles and cracks.
  • WC particles with a mass percentage of 83.7% to 94.7%, 0.3% TaC particles and the balance of Co powder are weighed to obtain a second alloy raw material; at the same time, polyethylene, paraffin, polyethylene glycol and stearic acid are prepared.
  • the additive for the intermediate layer mixture has a volume percentage ratio of 18 to 20%, 55 to 57%, 22 to 23%, and 2 to 3%, respectively; and then the above additive and the second alloy raw material are in accordance with 42.5:57.5.
  • the WC particles and the 14% Co powder with a mass percentage of 86% are weighed to obtain a third alloy raw material; at the same time, polyethylene, paraffin, polyethylene glycol and stearic acid are prepared to obtain an additive for the inner layer mixture, and the volume thereof is The percentage ratios are: 20%, 55%, 22%, and 3%, respectively. Then, the above additive and the third alloy raw material are ball-milled and mixed according to a volume ratio of 40:60 to obtain a particle size of 5 to 9 ⁇ m. Inner layer mixture.
  • one outer layer high expansion coefficient mold four intermediate transition layer mold groups and one inner layer are respectively designed according to respective expansion coefficients.
  • Low expansion coefficient mold one outer layer high expansion coefficient mold, four intermediate transition layer mold groups and one inner layer are respectively designed according to respective expansion coefficients.
  • the surface layer mixture, the intermediate layer mixture and the inner layer mixture were sequentially placed in the above six molds, and subjected to warm press forming under the conditions of a temperature of 130 ° C and a pressure of 6 MPa, and finally a blank was obtained.
  • the green body was then immersed in gasoline at 65 ° C for 60 hours to partially remove the addition of the body. Then, the billet is heated under the protection of argon to a temperature of 200 ° C, and kept for 1 hour; then heated to 250 ° C for 3 hours; then heated to 450 ° C, held for 2.5 hours, and finally cooled to normal temperature. The additive in the body is completely removed.
  • the green body subjected to the above thermal degreasing step is placed in a vacuum pressure sintering furnace, and after passing through protective nitrogen gas, it is subjected to pressure sintering at a temperature of 1400 ° C, and then cooled and cooled to obtain a cemented carbide function. Gradient material.
  • the blank after removing the additive is distributed regularly from the surface layer to the core porosity.
  • the blank shrinkage coefficient of the billet from the six layers of different particle sizes and compositions in the surface is 1.238 ⁇ 1.242, which indicates the axial direction of the outer layer, the core and the intermediate gradient transition zone during the sintering process.
  • the sintering shrinkage rate and the radial sintering shrinkage rate are almost the same, and the fluctuation range is only within 0.5%.
  • Table 5 shows the distribution of the WC-Co cemented carbide functionally graded composite prepared in Example 3.
  • Table 6 shows the hardness distribution along the thickness direction of the WC-Co cemented carbide functionally graded composite material prepared in Example 3. .
  • the performance of the cemented carbide functionally graded material prepared in this example was tested.
  • the test results showed that the cemented carbide functionally graded material prepared by the invention has a product density of 14.47 g/cm 3 and a transverse rupture strength of 3240 N/mm 2 , and the coercivity.
  • the magnetic force is 9.37 kA/m
  • the cobalt magnetic (Com%) is 9.29. It can be seen from the above test results that the cemented carbide functionally graded material prepared by the invention has excellent indexes, the surface layer to the core structure is dense, the composition and the hard particle size are uniformly transitioned, and there are no defects such as pores, bubbles and cracks.

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Abstract

一种硬质合金功能梯度材料的成型方法，首先将添加剂与合金原料混合后，得到混合料；然后将上述步骤得到的混合料放入复合模具组中，进行复合压力成型后，得到坯料；所述复合模具组包括外层高膨胀系数模具，中间过渡层模具组和内层低膨胀系数模具；最后将上述坯料经过烧结后，得到硬质合金功能梯度材料。制备了具有大尺寸、复杂外形结构的多组分无明显界面的硬质合金梯度功能复合材料。经过烧结成型后的梯度功能材料沿厚度方向获得具有不同组分、不同晶粒尺寸的无明显界面的梯度晶粒组织，使成型的硬质合金材料获得了结合高硬度、耐磨性、强度和韧性的较好的综合机械性能。

Description

一种硬质合金功能梯度材料的成型方法
本申请要求于2015年06月05日提交中国专利局、申请号为201510305122.6、发明名称为“一种硬质合金功能梯度材料的成型方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及功能梯度材料技术领域，更具体地说，涉及一种硬质合金功能梯度材料的成型方法。
背景技术
复合材料，是由两种或两种以上不同性质的材料，通过物理或化学的方法，在宏观(微观)上组成具有新性能的材料。各种材料在性能上互相取长补短，产生协同效应，使复合材料的综合性能优于原组成材料而满足各种不同的要求。
在众多的复合材料中，梯度功能材料是比较特殊的一类复合材料，不同于普通的复合材料，它是选用两种(或多种)性能不同的材料，通过连续地改变这两种(或多种)材料的组成和结构，使其界面消失导致材料的性能随着材料的组成和结构的变化而缓慢变化。由于梯度功能材料的材料组分是在一定的空间方向上连续变化的特点，因此，它能有效地克服传统复合材料的不足。梯度功能材料可以用作界面层来连接不相容的两种材料，大大地提高粘结强度，也可以用作界面层减小残余应力和热应力，同时消除连接材料中界面交叉点以及应力自由端点的应力奇异性，而且它代替传统的均匀材料，既可以增强连接强度也可以减小裂纹驱动力。
而随着全球经济的快速发展，在石油、化工、能源、电力、冶金、航空航天等工业中，存在大量在高温、腐蚀等恶劣环境下使用的摩擦运动副零部件，不仅要求材料具有良好的耐磨性，耐蚀性和抗氧化能力，还需要有优异的强韧性。而性质均一的单一材料，往往难于满足上述具有多种应用要求的领域。
因而，如何获得一种，能够具有良好的耐磨性、强韧性、耐腐蚀抗高温氧化的梯度功能材料的研究，一直是复合材料领域的重大课题之一。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种具有良好的耐磨性、强韧性、耐腐蚀抗高温氧化的梯度功能材料的成型方法，尤其是涉及一种硬质合金功能梯度材料的成型方法。
为了解决以上技术问题，本发明提供一种硬质合金功能梯度材料的成型方法，包括：
A)将添加剂与合金原料混合后，得到混合料；
B)将上述步骤得到的混合料放入复合模具组中，进行复合压力成型后，得到坯料；
所述复合模具组包括外层高膨胀系数模具，中间过渡层模具组和内层低膨胀系数模具；
C)将上述坯料经过烧结后，得到硬质合金功能梯度材料。
优选的，所述混合料中，所述合金原料在混合料中的体积比为50％～85％，所述添加剂在混合料中的体积比为15％～50％。
优选的，所述步骤A)具体为：
将添加剂与第一合金原料混合后，得到表层混合料；将添加剂与第二合金原料混合后，得到中间层混合料；将添加剂与第三合金原料混合后，得到内层混合料。
优选的，所述表层混合料的费氏粒度为小于等于3μm，所述中间层混合料的费氏粒度为0.5～5μm，所述内层混合料的费氏粒度为3～30μm。
优选的，所述合金原料包括硬质相和软质相；
所述硬质相为碳化钨，所述软质相为钴、铁或镍。
优选的，所述第一合金原料中硬质相的质量含量占所述第一合金原料的质量含量的百分比为93％～97％；所述第二合金原料中硬质相的质量含量占所述第二合金原料的质量含量的百分比为84％～95％；所述第三合金原料中硬质相的质量含量占所述第三合金原料的质量含量的百分比为75％～90％。
优选的，所述复合压力成型为温压成型、注射成型和热等静压成型中的一种或多种。
优选的，所述添加剂包括聚乙烯、石蜡、聚乙二醇、聚丙烯、聚苯乙烯、硬脂酸、二甲基苯二酸、双丁基苯二酸和EVA中的一种或多种。
优选的，所述坯料进行烧结前，还进行除脂处理；所述除脂处理为热除脂和/或溶剂脱脂处理。
优选的，所述烧结为真空压力烧结或热等静压烧结。
本发明提供一种硬质合金功能梯度材料的成型方法，首先将添加剂与合金原料混合后，得到混合料；然后将上述步骤得到的混合料放入复合模具组中，进行复合压力成型后，得到坯料；所述复合模具组包括外层高膨胀系数模具，中间过渡层模具组和内层低膨胀系数模具；最后将上述坯料经过烧结后，得到硬质合金功能梯度材料。与现有技术相比，本发明将硬质合金采用功能梯度材料的设计理念，在保证硬质合金优良的耐磨性、耐腐蚀性及抗高温性能的同时，还获得优良的强韧性。而且本发明还采用粉末冶金的方式制备硬质合金功能梯度材料，利用复合模具组成型和粉末冶金方法制备硬质合金梯度功能复合材料，通过调整合金粉末颗粒度与成分、添加剂配比、复合模具形状、不同的压力成型方式和工艺参数、烧结工艺，可以在较大厚度尺寸范围内方便地制备出形状复杂的、成分连续变化且可控的具有高耐磨性和优异强韧性结合的硬质合金功能梯度材料。实验结果表明，本发明制备的硬质合金功能梯度材料，横向断裂强度为3310N/mm2，矫顽磁力为9.3kA/m，钴磁(Com％)为9.19，而且表层至心部组织致密、成分和硬质颗粒度均匀过渡，且无孔隙、气泡和裂纹等缺陷。
附图说明
图1为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品在100倍显微镜下的金相图；
图2为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的表层在1500倍显微镜下的金相图；
图3为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G1在1500倍显微镜下的金相图；
图4为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G2在1500倍显微镜下的金相图；
图5为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G3在1500倍显微镜下的金相图；
图6为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G4在1500倍显微镜下的金相图；
图7为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品芯部在1500倍显微镜下的金相图；
图8为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的结构示意图。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明提供一种硬质合金功能梯度材料的成型方法，包括：
A)将添加剂与合金原料混合后，得到混合料；
B)将上述步骤得到的混合料放入复合模具组中，进行复合压力成型后，得到坯料；
所述复合模具组包括外层高膨胀系数模具，中间过渡层模具组和内层低膨胀系数模具；
C)将上述坯料经过烧结后，得到硬质合金功能梯度材料。
本发明首先将添加剂与合金原料混合后，得到混合料。所述添加剂优选为聚乙烯、石蜡、聚乙二醇、聚丙烯、聚苯乙烯、硬脂酸、二甲基苯二酸、双丁基苯二酸和EVA中的一种或多种，更优选为聚乙烯、石蜡、聚乙二醇、聚丙烯、聚苯乙烯、硬脂酸、二甲基苯二酸、双丁基苯二酸或EVA，最优选为聚乙烯、石蜡、聚乙二醇和硬脂酸中的一种或多种。本发明对所述合金原料没有特别限制，以本领域技术人员熟知的用于制备硬质合金的合金原料即可，本发明所述合金原料优选包括硬质相和软质相，所述硬质相优选为碳化钨，所述软质相，即粘结相，优选为钴、铁、钼和镍中的一种或多种，更优选为钴、铁或镍，最优选为钴；所述合金原料优选还包括可以增加所述硬质合金性能的元素，优选为碳、硼、钨、钼、铬、钒、钽、钛、镍、铁及其碳化物中的一种或多种，更优选为碳化钽或碳化钛。所述混合料中，所述合金原料在混合料中的体积比 优选为50％～85％，更优选为55％～80％，最优选为60％～75％；所述添加剂在混合料中的体积比优选为15％～50％，更优选为25％～45％，最优选为30％～40％。
本发明对所述混合的具体步骤没有特别限制，以本领域技术人员熟知的混合过程即可，本发明为保证压模复合和烧结的效果，优选按照以下步骤进行：
将添加剂与第一合金原料混合后，得到表层混合料；将添加剂与第二合金原料混合后，得到中间层混合料；将添加剂与第三合金原料混合后，得到内层混合料。
本发明将添加剂与第一合金原料混合后，得到表层混合料，即细尺寸合金颗粒粉末；所述表层混合料的费氏粒度优选为小于等于3μm，更优选为0.5～3μm，更优选为小于等于2.5μm，最优选为0.5～2μm；所述第一合金原料中，合金硬质相的质量含量占所述第一合金原料的质量含量的百分比优选为93％～97％，更优选为93.5％～96.5％，更优选为94％～96％，最优选为94.8％～95.2％；上述百分比即，合金硬质相的颗粒含量占合金颗粒粉末质量总含量的百分比；所述添加剂在表层混合料中的比例优选为40％～50％，更优选为41％～49％，最优选为43％～47％。
本发明对所述混合的方式没有特别限制，以本领域技术人员熟知的硬质合金混合方式即可，本发明优选为球磨；本发明对所述混合的设备没有特别限制，以本领域技术人员熟知的硬质合金混合设备即可；本发明对所述混合的其它条件没有特别限制，以本领域技术人员熟知的硬质合金混合条件即可。
本发明经过上述混合得到一定费氏粒度的表层混合料，从而经过后续压模和烧结，得到细晶粒组织，然后将这些具有特定颗粒度和成分的细晶粒组织，用于成品表层，这些高含量的硬质颗粒和细小的晶粒组织，能够得到优良的表面耐磨性能的硬质合金功能梯度材料。
本发明同时将添加剂与第二合金原料混合后，得到中间层混合料，即细小尺寸和中等尺寸的混合颗粒度合金粉末；所述中间层混合料的费氏粒度优选为0.5～5μm；所述第二合金原料中，合金硬质相的质量含量占所述第二合金原料的质量含量的百分比优选为84％～95％；上述百分比即，合金硬质相的颗粒含量占合金颗粒粉末质量总含量的百分比；所述添加剂在中间层混合料中的体积比优选为30％～45％，更优选为35％～44％，最优选为40％～43％；本发明对所 述中间混合料中的其他成分没有特别限制，以本领域技术人员根据生产需要或质量要求，加入的熟知的其他原料即可，本发明优选在所述中间层混合料，即中间过渡层混合料中，还加入质量百分数含量优选为0.2％～0.4％的TaC，更优选为0.25％～0.35％，最优选为0.3％。
本发明对所述混合的方式没有特别限制，以本领域技术人员熟知的硬质合金混合方式即可，本发明优选为球磨；本发明对所述混合的设备没有特别限制，以本领域技术人员熟知的硬质合金混合设备即可；本发明对所述混合的其它条件没有特别限制，以本领域技术人员熟知的硬质合金混合条件即可。
本发明经过上述混合得到一定费氏粒度的中间过渡层混合料，将这些具有细小尺寸和中等尺寸的多尺度合金粉末经过后续压模和烧结，得到介于表层和内层的细小尺寸和中等尺寸的混合晶粒组织，然后将这些中等尺寸的晶粒组织，用于成品中间过渡层，通过成分和尺寸的控制，以获得无明显界面的连续过渡合金梯度材料，确保零件具有优良的综合机械性能。同时，本发明还优选加入一定量的TaC，以抑制后续烧结过程中WC细颗粒的长大。
本发明将添加剂与第三合金原料混合后，得到内层混合料，即大尺寸和中等尺寸的合金粉末；所述内层混合料的费氏粒度优选为3～30μm，更优选为5～25μm，更优选为7～20μm，最优选为8～15μm；所述第三合金原料中，合金硬质相的质量含量占所述第三合金原料的质量含量的百分比优选为75％～90％，更优选为77％～88％，更优选为80％～85％，最优选为82％～84％；上述百分比即，合金硬质相的颗粒含量占合金颗粒粉末质量总含量的百分比；所述添加剂在内层混合料中的体积比优选为15％～45％，更优选为25％～42％，最优选为35％～40％。
本发明对所述混合的方式没有特别限制，以本领域技术人员熟知的硬质合金混合方式即可，本发明优选为球磨；本发明对所述混合的设备没有特别限制，以本领域技术人员熟知的硬质合金混合设备即可；本发明对所述混合的其它条件没有特别限制，以本领域技术人员熟知的硬质合金混合条件即可。
本发明经过上述混合得到一定费氏粒度的内层混合料，将这些具有大尺寸和中等尺寸的合金粉末经过后续压模和烧结，得到具有特定颗粒度和成分的粗晶粒组织，将其用于成品内层，进而满足功能梯度材料的高持久和高韧性等性 能要求。
本发明经过上述混合步骤后，得到了表层混合料、中间层混合料和内层混合料，然后将上述步骤得到的混合料分别放入复合模具组中，进行复合压力成型后，得到坯料；所述复合模具组优选包括外层高膨胀系数模具，中间过渡层模具组和内层低膨胀系数模具；本发明对上述不同模具的数量没有特别限制，本领域技术人员可以根据实际生产情况和产品要求进行适应性调整，如，中间过渡层模具组可以为1个，也可以为多个；本发明对所述复合压力成型没有特别限制，以本领域技术人员熟知的功能梯度材料的复合压力成型方法即可，本发明优选包括温压成型、注射成型和热等静压成型中的一种或多种，更优选为温压成型、注射成型或热等静压成型；本发明对所述复合压力成型的条件没有特别限制，以本领域技术人员熟知的功能梯度材料的复合压力成型条件即可，本发明的成型温度优选为130～145℃，更优选为135～140℃；所述成型压力优选为2～5MPa，更优选为3～4MPa。
本发明上述制备步骤的整体构思在于，根据所需制备的成型零部件的要求，外表面选择采用第一合金原料，即第一硬质合金材料(Y1)，其芯部(内层)选择采用第三硬质合金材料(Y2)，将上述具有第一热膨胀系数(α1)的第一硬质合金材料与特定量的添加剂混合后，得到的表层混合料(Y1+T1)；将上述具有第二热膨胀系数(α2)的第三合金原料与特定量的添加剂混合后，得到的内层混合料(Y2+T2)。其中所述第一热膨胀系数(α1)不同于第二热膨胀系数(α2)，更优选为第一热膨胀系数略大于第二热膨胀系数。本发明再通过加入特定含量的添加剂材料(Tn)，形成一种或多种中间层混合料，使所述中间层，即中间梯度区域的坯料(Y1*n％+Y2*(100-n)％+Tn)过渡于所述第一合金材料与第三合金材料(Y1，Y2)中，并在所述外表面与内层之间形成连续过渡的中间梯度复合区域，其热膨胀系数(αn)也介于α1～α2之间，且均匀过渡。
本发明通过上述步骤的设计，实现了表层高硬度细颗粒硬质合金组分和内层高韧粗颗粒硬质合金组分的无界面过渡，进而大幅度的提高了成型零部件的耐磨性、强度，同时又减小了材料的裂纹驱动力。
本发明将上述步骤制备得到的坯料，经过烧结后，得到硬质合金功能梯度 材料；本发明对所述烧结的方法没有特别限制，以本领域技术人员熟知的烧结方法即可，本发明优选为真空压力烧结或热等静压烧结，更优选为真空压力烧结；所述真空压力烧结的烧结温度优选为1380～1420℃，更优选为1390～1410℃，最优选为1395～1405℃；所述真空压力烧结的保护性气氛优选为氮气、氢气和惰性气体中的一种或多种。本发明对所述烧结的设备没有特别限制，以本领域技术人员熟知的相应的烧结设备即可；本发明对所述烧结的其它条件没有特别限制，以本领域技术人员熟知的相应的烧结条件即可。
本发明在所述坯料烧结前后，还包括其他步骤，本发明没有特别限制，本领域技术人员可根据实际情况进行调整，本发明为提高成品功能梯度材料的质量和性能，除坯料内的低熔点挥发性添加剂，优选在烧结前还包括除脂处理；所述除脂处理优选为热除脂或溶剂脱脂处理；所述热除脂为在以氮气、氢气或惰性气体的保护性气氛的条件下，在温度为500℃以内的区间对坯料进行加热、保温完全去除坯体内的添加剂；所述溶剂脱脂处理，即浸泡脱脂，是将坯体在有机溶剂中浸泡部分去除坯体内的添加剂，具体可优选为将坯体放入55～90℃中的汽油中浸泡25～60小时。本发明对上述两种除脂处理的其它条件没有特别限制，以本领域技术人员熟知的相关条件即可。
本发明通过上述步骤，一次性烧结的制备了具有大尺寸、复杂外形结构的多组分无明显界面的硬质合金梯度功能复合材料。经过烧结成型后的梯度功能材料沿厚度方向获得具有不同组分、不同晶粒尺寸的无明显界面的梯度晶粒组织，使成型的硬质合金材料获得了结合高硬度、耐磨性、强度和韧性的较好的综合机械性能。本发明上述方法制造的零部件，可广泛应用于石油、化工、能源、电力、冶金、航空航天等工业中大量存在的、在高温氧化及腐蚀等环境下承受摩擦磨损作用的机械运动副零部件。
经工艺过程控制检测，本发明去除添加剂后的坯体，从表层至心部孔隙率呈梯度递减的规律分布；坯体在烧结过程中，外表层、芯部(内层)、中间梯度过渡区域(中间层)的轴向烧结收缩率和径向烧结收缩率几乎一致，波动仅在0.5个百分点以内。
实验结果表明，本发明制备的硬质合金功能梯度材料，横向断裂强度为3310N/mm2，矫顽磁力为9.3kA/m，钴磁(Com％)为9.19，而且表层至心部 组织致密、成分和硬质颗粒度均匀过渡，且无孔隙、气泡和裂纹等缺陷。这表明，本发明实现了表层高硬度细颗粒硬质合金组分和内层高韧粗颗粒硬质合金组分的无界面过渡，而且提高成型零部件的耐磨性和强度的同时，减小了材料的裂纹驱动力。
为了进一步说明本发明的技术方案，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
实施例1
WC-Co硬质合金功能梯度复合材料的制备
称取质量百分含量为95％的WC颗粒和5％的Co粉末，得到第一合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到表层混合料用添加剂，其体积百分含量比分别为：18％、57％、23％和2％；然后将上述添加剂和第一合金原料按照44:56的体积比，经过球磨混合后，得到费氏粒度为0.5～1.2μm的表层混合料。
称取质量百分含量为83.7％～94.7％的WC颗粒、0.3％的TaC颗粒和余量的Co粉末，得到第二合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到中间层混合料用添加剂，其体积百分含量比分别为：18～20％、55～57％、22～23％和2～3％；然后将上述添加剂和第二合金原料按照42:58的体积比，经过球磨混合后，得到4组费氏粒度为0.5～5μm的中间层混合料。
称取质量百分含量为85％的WC颗粒和15％的Co粉末，得到第三合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到内层混合料用添加剂，其体积百分含量比分别为：20％、55％、22％和3％；然后将上述添加剂和第三合金原料按照40:60的体积比，经过球磨混合后，得到费氏粒度为5～9μm的内层混合料。
然后根据上述表层混合料、内层混合料以及中间层混合料以及零部件外形，按照各自的膨胀系数，分别设计1个外层高膨胀系数模具、4个中间过渡层模具组和1个内层低膨胀系数模具。
将表层混合料、中间层混合料以及内层混合料依次先后装入上述6个模具中，在温度为135℃、压力为4MPa的条件下，进行温压成型，最后得到坯料。
再将上述坯料在氩气的保护下，加热至温度为200℃，保温1小时；再加热至250℃，保温3小时；再加热至450℃，保温2.5小时，最后自然降温至常温，完全去除坯体内的添加剂。
最后将经过上述热除脂步骤的坯体，放入真空压力烧结炉中，通入保护性氮气后，在温度为1400℃的条件下进行加压烧结，然后保温冷却出炉，得到硬质合金功能梯度材料。
经工艺过程控制检测，去除添加剂后的坯体，从表层至心部孔隙率呈梯度递减的规律分布。烧结后，粉坯由表及里的六层不同颗粒尺度和成分的坯料的烧结收缩系数为1.237～1.243，这表明坯体在烧结过程中，外表层、芯部、中间梯度过渡区域的轴向烧结收缩率和径向烧结收缩率几乎一致，波动范围仅在0.5％以内。
对本实施例制备的硬质合金功能梯度材料进行成分分布检测，检测结果参见表1，表1为实施例1制备的WC-Co硬质合金功能梯度复合材料分布。
表1实施例1制备的WC-Co硬质合金功能梯度复合材料分布
Figure PCTCN2015084089-appb-000001
对本实施例制备的硬质合金功能梯度材料进行硬度分布检测，检测结果参见表2，表2为实施例1制备的WC-Co硬质合金功能梯度复合材料实施后成型件沿厚度方向的硬度分布。
表2实施例1制备的WC-Co硬质合金功能梯度复合材料实施后成型件沿厚度方向的硬度分布
Figure PCTCN2015084089-appb-000002
Figure PCTCN2015084089-appb-000003
对本实施例制备的硬质合金功能梯度材料进行性能检测，检测结果表明，本发明制备的金属基功能梯度复合材料的产品密度为14.41g/cm3、横向断裂强度为3460N/mm2，矫顽磁力为9.86kA/m，钴磁(Com％)为9.82。由以上检测结果可知，本发明制备的硬质合金功能梯度材料具有优良的指标。
对本发明实施例1制备的硬质合金功能梯度材料进行金相分析。
参见图1，图1为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品在100倍显微镜下的金相图。
由图1可知，本实施例制备的硬质合金功能梯度材料在100倍显微镜下观察产品的孔隙度为A02、B00。
参见图2～图7，图2为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的表层在1500倍显微镜下的金相图；
图3为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G1在1500倍显微镜下的金相图；
图4为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G2在1500倍显微镜下的金相图；
图5为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G3在1500倍显微镜下的金相图；
图6为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品的中间过渡层G4在1500倍显微镜下的金相图；
图7为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的粉末冶金产品芯部在1500倍显微镜下的金相图。
由图2～图7可知，本实施例制备的硬质合金功能梯度材料的表层至芯部组织致密、成分和硬质颗粒度均匀过渡，且无孔隙、气泡和裂纹等缺陷。
参见图8，图8为本发明实施例1制备的WC-Co硬质合金功能梯度复合材料的结构示意图。
实施例2
WC-Co硬质合金功能梯度复合材料的制备
称取质量百分含量为94％的WC颗粒和6％的Co粉末，得到第一合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到表层混合料用添加剂，其体积百分含量比分别为：18％、57％、23％和2％；然后将上述添加剂和第一合金原料按照43.5:56.5的体积比，经过球磨混合后，得到费氏粒度为0.5～1.2μm的表层混合料。
称取质量百分含量为86.2％～92.2％的WC颗粒、0.3％的TaC颗粒和余量的Co粉末，得到第二合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到中间层混合料用添加剂，其体积百分含量比分别为：18～20％、55～57％、22～23％和2～3％；然后将上述添加剂和第二合金原料按照41.5:58.5的体积比，经过球磨混合后，得到4组费氏粒度为0.5～5μm的中间层混合料。
称取质量百分含量为84％的WC颗粒和16％的Co粉末，得到第三合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到内层混合料用添加剂，其体积百分含量比分别为：20％、55％、22％和3％；然后将上述添加剂和第三合金原料按照40:60的体积比，经过球磨混合后，得到费氏粒度为5～9μm的内层混合料。
然后根据上述表层混合料、内层混合料以及中间层混合料以及零部件外形，按照各自的膨胀系数，分别设计1个外层高膨胀系数模具、4个中间过渡层模具组和1个内层低膨胀系数模具。
将表层混合料、中间层混合料以及内层混合料依次先后装入上述6个模具中，在温度为140℃、压力为5MPa的条件下，进行温压成型，最后得到坯料。
再将上述坯料在氩气的保护下，加热至温度为200℃，保温1小时；再加热至250℃，保温3小时；再加热至450℃，保温2.5小时，最后自然降温至常温，完全去除坯体内的添加剂。
最后将经过上述热除脂步骤的坯体，放入真空压力烧结炉中，通入保护性氮气后，在温度为1400℃的条件下进行加压烧结，然后保温冷却出炉，得到 硬质合金功能梯度材料。
经工艺过程控制检测，去除添加剂后的坯体，从表层至心部孔隙率呈梯度递减的规律分布。烧结后，粉坯由表及里的六层不同颗粒尺度和成分的坯料的烧结收缩系数为1.236～1.241，这表明坯体在烧结过程中，外表层、芯部、中间梯度过渡区域的轴向烧结收缩率和径向烧结收缩率几乎一致，波动范围仅在0.5％以内。
对本实施例制备的硬质合金功能梯度材料进行成分分布检测，检测结果参见表3，表3为实施例2制备的WC-Co硬质合金功能梯度复合材料分布。
表3实施例2制备的WC-Co硬质合金功能梯度复合材料分布
Figure PCTCN2015084089-appb-000004
对本实施例制备的硬质合金功能梯度材料进行硬度分布检测，检测结果参见表4，表4为实施例2制备的WC-Co硬质合金功能梯度复合材料实施后成型件沿厚度方向的硬度分布。
表4实施例2制备的WC-Co硬质合金功能梯度复合材料实施后成型件沿厚度方向的硬度分布
Figure PCTCN2015084089-appb-000005
Figure PCTCN2015084089-appb-000006
对本实施例制备的硬质合金功能梯度材料进行性能检测，检测结果表明，本发明制备的硬质合金功能梯度材料的产品密度为14.52g/cm3、横向断裂强度为3280N/mm2，矫顽磁力为9.45kA/m，钴磁(Com％)为9.22。由以上检测结果可知，本发明制备的硬质合金功能梯度材料具有优良的指标，表层至芯部组织致密、成分和硬质颗粒度均匀过渡，且无孔隙、气泡和裂纹等缺陷。
实施例3
WC-Co硬质合金功能梯度复合材料的制备
称取质量百分含量为96％的WC颗粒和4％的Co粉末，得到第一合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到表层混合料用添加剂，其体积百分含量比分别为：18％、57％、23％和2％；然后将上述添加剂和第一合金原料按照44.5:55.5的体积比，经过球磨混合后，得到费氏粒度为0.5～1.2μm的表层混合料。
称取质量百分含量为83.7％～94.7％的WC颗粒、0.3％的TaC颗粒和余量的Co粉末，得到第二合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到中间层混合料用添加剂，其体积百分含量比分别为：18～20％、55～57％、22～23％和2～3％；然后将上述添加剂和第二合金原料按照42.5:57.5的体积比，经过球磨混合后，得到4组费氏粒度为0.5～5μm的中间层混合料。
称取质量百分含量为86％的WC颗粒和14％的Co粉末，得到第三合金原料；同时将聚乙烯、石蜡、聚乙二醇和硬脂酸配制得到内层混合料用添加剂，其体积百分含量比分别为：20％、55％、22％和3％；然后将上述添加剂和第三合金原料按照40:60的体积比，经过球磨混合后，得到费氏粒度为5～9μm的内层混合料。
然后根据上述表层混合料、内层混合料以及中间层混合料以及零部件外形，按照各自的膨胀系数，分别设计1个外层高膨胀系数模具、4个中间过渡层模具组和1个内层低膨胀系数模具。
将表层混合料、中间层混合料以及内层混合料依次先后装入上述6个模具中，在温度为130℃、压力为6MPa的条件下，进行温压成型，最后得到坯料。
再将上述坯体放入65℃中的汽油中浸泡60小时，部分去除坯体内的添加 剂，而后再将坯料在氩气的保护下，加热至温度为200℃，保温1小时；再加热至250℃，保温3小时；再加热至450℃，保温2.5小时，最后自然降温至常温，完全去除坯体内的添加剂。
最后将经过上述热除脂步骤的坯体，放入真空压力烧结炉中，通入保护性氮气后，在温度为1400℃的条件下进行加压烧结，然后保温冷却出炉，得到硬质合金功能梯度材料。
经工艺过程控制检测，去除添加剂后的坯体，从表层至心部孔隙率呈梯度递减的规律分布。烧结后，粉坯由表及里的六层不同颗粒尺度和成分的坯料的烧结收缩系数为1.238～1.242，这表明坯体在烧结过程中，外表层、芯部、中间梯度过渡区域的轴向烧结收缩率和径向烧结收缩率几乎一致，波动范围仅在0.5％以内。
对本实施例制备的硬质合金功能梯度材料进行成分分布检测，检测结果参见表5，表5为实施例3制备的WC-Co硬质合金功能梯度复合材料分布。
表5实施例3制备的WC-Co硬质合金功能梯度复合材料分布
Figure PCTCN2015084089-appb-000007
对本实施例制备的硬质合金功能梯度材料进行硬度分布检测，检测结果参见表6，表6为实施例3制备的WC-Co硬质合金功能梯度复合材料实施后成型件沿厚度方向的硬度分布。
表6实施例3制备的WC-Co硬质合金功能梯度复合材料实施后成型件沿厚度方向的硬度分布
Figure PCTCN2015084089-appb-000008
Figure PCTCN2015084089-appb-000009
对本实施例制备的硬质合金功能梯度材料进行性能检测，检测结果表明，本发明制备的硬质合金功能梯度材料的产品密度为14.47g/cm3、横向断裂强度为3240N/mm2，矫顽磁力为9.37kA/m，钴磁(Com％)为9.29。由以上检测结果可知，本发明制备的硬质合金功能梯度材料具有优良的指标，表层至芯部组织致密、成分和硬质颗粒度均匀过渡，且无孔隙、气泡和裂纹等缺陷。
以上对本发明提供的一种硬质合金功能梯度材料的成型方法进行了详细的介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员都能够实践本发明，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。本发明专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种硬质合金功能梯度材料的成型方法，包括：
    A)将添加剂与合金原料混合后，得到混合料；
    B)将上述步骤得到的混合料放入复合模具组中，进行复合压力成型后，得到坯料；
    所述复合模具组包括外层高膨胀系数模具，中间过渡层模具组和内层低膨胀系数模具；
    C)将上述坯料经过烧结后，得到硬质合金功能梯度材料。
  2. 根据权利要求1所述的成型方法，其特征在于，所述混合料中，所述合金原料在混合料中的体积比为50％～85％，所述添加剂在混合料中的体积比为15％～50％。
  3. 根据权利要求1所述的成型方法，其特征在于，所述步骤A)具体为：
    将添加剂与第一合金原料混合后，得到表层混合料；将添加剂与第二合金原料混合后，得到中间层混合料；将添加剂与第三合金原料混合后，得到内层混合料。
  4. 根据权利要求3所述的成型方法，其特征在于，所述表层混合料的费氏粒度为小于等于3μm，所述中间层混合料的费氏粒度为0.5～5μm，所述内层混合料的费氏粒度为3～30μm。
  5. 根据权利要求3所述的成型方法，其特征在于，所述合金原料包括硬质相和软质相；
    所述硬质相为碳化钨，所述软质相为钴、铁或镍。
  6. 根据权利要求5所述的成型方法，其特征在于，所述第一合金原料中硬质相的质量含量占所述第一合金原料的质量含量的百分比为93％～97％；所述第二合金原料中硬质相的质量含量占所述第二合金原料的质量含量的百分比为84％～95％；所述第三合金原料中硬质相的质量含量占所述第三合金原料的质量含量的百分比为75％～90％。
  7. 根据权利要求1所述的成型方法，其特征在于，所述复合压力成型为温压成型、注射成型和热等静压成型中的一种或多种。
  8. 根据权利要求1所述的成型方法，其特征在于，所述添加剂包括聚乙烯、石蜡、聚乙二醇、聚丙烯、聚苯乙烯、硬脂酸、二甲基苯二酸、双丁基苯二酸和EVA中的一种或多种。
  9. 根据权利要求1所述的成型方法，其特征在于，所述坯料进行烧结前，还进行除脂处理；所述除脂处理为热除脂和/或溶剂脱脂处理。
  10. 根据权利要求1所述的成型方法，其特征在于，所述烧结为真空压力烧结或热等静压烧结。
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105127432A (zh) * 2015-09-29 2015-12-09 浙江恒成硬质合金有限公司 一种梯度结构硬质合金的制备方法
CN108607999B (zh) * 2018-06-14 2021-04-23 陕西理工大学 多层易焊大梯度硬质合金材料的制备方法
CN109434115B (zh) * 2018-11-13 2021-01-15 歌尔光学科技有限公司 一种多层梯度硬质合金冲头
CN110181059A (zh) * 2018-12-13 2019-08-30 苏州赛特锐精密机械配件有限公司 一种共注射近净成型制超细晶硬质合金刀具坯体的方法
CN110387496B (zh) * 2019-08-26 2021-07-20 广东技术师范大学 一种表层无TiC相的WC-TiC-Co基梯度硬质合金及其制备方法
CN112191840B (zh) * 2020-09-21 2022-06-03 广东正信硬质材料技术研发有限公司 一种硬质合金用成型剂及其制备方法
CN113523278B (zh) * 2021-05-20 2022-11-18 九江金鹭硬质合金有限公司 一种低应力硬质合金模具材料烧结方法
CN114147227B (zh) * 2021-12-10 2022-10-11 哈尔滨理工大学 基于竹纤维细胞壁环形多壁层结构仿生刀具及其制备方法
CN115198130B (zh) * 2022-06-15 2023-04-28 上海离原环境科技有限公司 一种镍基碳化钨合金的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880382A (en) * 1996-08-01 1999-03-09 Smith International, Inc. Double cemented carbide composites
CN1470348A (zh) * 2003-06-18 2004-01-28 北京科技大学 一种钨铜梯度热沉材料及其制备方法
CN101545058A (zh) * 2009-05-07 2009-09-30 合肥工业大学 一种WC-Co梯度硬质合金材料的制备方法
CN102672184A (zh) * 2012-06-05 2012-09-19 赣县世瑞新材料有限公司 矿用纳米稀土表面强化梯度硬质合金复合球齿及其制备方法
CN102794053A (zh) * 2012-08-21 2012-11-28 韶关市贝瑞过滤科技有限公司 梯度多层复合结构粉末烧结滤芯及其生产方法
CN104946914A (zh) * 2015-06-05 2015-09-30 株洲西迪硬质合金科技有限公司 一种金属基功能梯度复合材料的成型方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862660A (en) * 1970-12-10 1975-01-28 Sakabe Industry Co Ltd Durable mold of multilayer construction
GB8622464D0 (en) * 1986-09-18 1986-10-22 British Petroleum Co Plc Graded structure composites
JPH05156319A (ja) * 1991-12-04 1993-06-22 Souzou Kagaku:Kk 径方向に傾斜機能層を形成した円筒状または円柱状セラ ミックスー金属系複合体およびその製造方法。
US5543235A (en) * 1994-04-26 1996-08-06 Sintermet Multiple grade cemented carbide articles and a method of making the same
JPH07310103A (ja) * 1994-05-12 1995-11-28 Takata Kogyosho:Kk 粉末冶金法による傾斜機能材料の製造方法
JP3421479B2 (ja) * 1995-08-09 2003-06-30 株式会社日本製鋼所 傾斜機能材料の製造方法
JP3600350B2 (ja) * 1996-03-07 2004-12-15 株式会社東芝 傾斜機能材料及びその製造方法
WO2005056854A1 (en) * 2003-12-15 2005-06-23 Sandvik Intellectual Property Ab Cemented carbide tools for mining and construction applications and method of making the same
JP5093662B2 (ja) * 2005-12-13 2012-12-12 学校法人日本大学 生体用同心円状傾斜機能材料の製造方法及び装置
US8512808B2 (en) * 2008-04-28 2013-08-20 The Boeing Company Built-up composite structures with a graded coefficient of thermal expansion for extreme environment applications
CN102666054A (zh) * 2009-12-25 2012-09-12 柯尼卡美能达先进多层薄膜株式会社 成型模具以及成型模具的制造方法
SE534696C2 (sv) * 2010-03-26 2011-11-22 Diamorph Ab En funktionell gradientmaterialkomponent och metod för att producera en sådan komponent
CN101838766B (zh) * 2010-06-22 2015-05-20 华中科技大学 一种梯度结构金属陶瓷刀具及其制备方法
PT2900404T (pt) * 2012-09-27 2021-11-16 Allomet Corp Métodos de formação de um artigo metálico ou cerâmico tendo uma nova composição de material de graduação funcional
CN103949647B (zh) * 2014-04-01 2016-06-08 山东大学 一种自扩散梯度功能复合刀具材料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5880382A (en) * 1996-08-01 1999-03-09 Smith International, Inc. Double cemented carbide composites
CN1470348A (zh) * 2003-06-18 2004-01-28 北京科技大学 一种钨铜梯度热沉材料及其制备方法
CN101545058A (zh) * 2009-05-07 2009-09-30 合肥工业大学 一种WC-Co梯度硬质合金材料的制备方法
CN102672184A (zh) * 2012-06-05 2012-09-19 赣县世瑞新材料有限公司 矿用纳米稀土表面强化梯度硬质合金复合球齿及其制备方法
CN102794053A (zh) * 2012-08-21 2012-11-28 韶关市贝瑞过滤科技有限公司 梯度多层复合结构粉末烧结滤芯及其生产方法
CN104946914A (zh) * 2015-06-05 2015-09-30 株洲西迪硬质合金科技有限公司 一种金属基功能梯度复合材料的成型方法

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