CN117069112A - Preparation method and application of metal ceramic or hard alloy - Google Patents

Preparation method and application of metal ceramic or hard alloy Download PDF

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Publication number
CN117069112A
CN117069112A CN202311043910.3A CN202311043910A CN117069112A CN 117069112 A CN117069112 A CN 117069112A CN 202311043910 A CN202311043910 A CN 202311043910A CN 117069112 A CN117069112 A CN 117069112A
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ceramic phase
ceramic
phase
mixed
grain
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李宇涵
王博
南勋
张翰超
王诗阳
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Jiaxing Jirui New Material Technology Co ltd
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Jiaxing Jirui New Material Technology Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/949—Tungsten or molybdenum carbides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention relates to the technical field of manufacturing of metal ceramic composite materials and hard alloy composite materials, in particular to a preparation method and application of metal ceramic or hard alloy. According to the invention, a colloidal suspension cladding method is adopted to prepare first ceramic phase powder (mixed particle size titanium carbonitride or mixed particle size tungsten carbide) containing a certain proportion of coarse and fine particles and having a fine-cladding coarse particle structure, and then the first ceramic phase powder is subjected to wet grinding and mixing with other raw material powder to reconstruct the microstructure of the traditional metal ceramic composite material, so that the dispersion strengthening effect is achieved, and the mechanical property and stability of the material are greatly improved.

Description

Preparation method and application of metal ceramic or hard alloy
Technical Field
The invention relates to the technical field of manufacturing of metal ceramic composite materials and hard alloy composite materials, in particular to a preparation method and application of metal ceramic or hard alloy.
Background
The titanium carbonitride base metal ceramic and the tungsten carbide base hard alloy are composite materials formed by sintering a ceramic hard phase and a metal binding phase, and are widely applied to cutting tools and wear-resistant parts due to the characteristics of high hardness and high strength, and the phase composition, microstructure, preparation process, mechanical property and application fields of the titanium carbonitride base metal ceramic and the tungsten carbide base hard alloy have certain common points and similarities. With the transformation and upgrading of manufacturing industry, the processing demands of some difficult-to-process materials such as high-temperature alloys and titanium alloys are gradually emerging. The hardness of difficult-to-process materials is higher, the strength is higher, and higher requirements are put on the hardness, strength, toughness and red hardness of the cutting tool. However, the current titanium carbonitride-based cermet and tungsten carbide-based cemented carbide matrix materials cannot meet the four requirements at the same time, because: in the prior art, the metal binder phase content of the metal ceramic and the hard alloy is often selected to be increased so as to improve the strength and toughness of the metal ceramic and the hard alloy, or ultrafine grains are formed by adopting the first ceramic phase and/or the second ceramic phase raw materials of ultrafine grains so as to achieve the effects of fine grain strengthening and hardening. However, the direct increase of the metal content can lead to the great reduction of hardness and wear resistance, and the mechanical property advantage of the metal ceramic is deteriorated; because of the characteristics of difficult dispersion and difficult uniform mixing of the superfine raw materials, the microstructure of the material is difficult to be uniform, and the fine grain strengthening and hardening effects cannot be fully realized; and moreover, due to the characteristic of large specific surface area of the superfine raw material, the surface of the superfine raw material is easier to adsorb oxygen to form an oxide layer, the wettability of a ceramic phase and a metal binding phase is greatly reduced due to the existence of the oxide layer, so that defects such as air holes and cobalt pools are formed in the sintering process, the mechanical properties of the metal ceramic and the hard alloy are finally greatly reduced, and the large fluctuation of the size and poor consistency of the mechanical properties of the material before and after sintering are indirectly caused. Therefore, how to skillfully exert the advantages of improving the hardness, strength and toughness of the metal ceramic or hard alloy cutting tool by ultrafine crystals while avoiding the possible adverse factors brought by ultrafine raw materials, and effectively improving the stability of the materials becomes a technical problem to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to provide a preparation method and application of metal ceramic or hard alloy, so as to solve the problems in the prior art. According to the invention, a colloidal suspension cladding method is adopted to prepare first ceramic phase powder (mixed particle size titanium carbonitride or mixed particle size tungsten carbide) containing a certain proportion of coarse and fine particles and having a fine-cladding coarse particle structure, and then the first ceramic phase powder is subjected to wet grinding and mixing with other raw material powder to reconstruct the microstructure of the traditional metal ceramic composite material, so that the dispersion strengthening effect is achieved, and the mechanical property and stability of the material are greatly improved.
In order to achieve the above object, the present invention provides the following solutions:
according to one of the technical schemes of the invention, the preparation method of the first ceramic phase with the mixed grain size comprises the following steps: preparing a suspension by matching the fine-grain-size first ceramic, evaporating, adding the coarse-grain-size first ceramic phase, evaporating to dryness, and continuously stirring in the whole process to obtain the mixed-grain-size first ceramic phase;
the fine grain size first ceramic phase is fine grain size titanium carbonitride or fine grain size tungsten carbide;
the coarse-grain-diameter first ceramic phase is coarse-grain-diameter titanium carbonitride or coarse-grain-diameter tungsten carbide;
the average grain diameter of the fine grain diameter first ceramic phase is 0.2-0.8 mu m; the first ceramic phase has an average particle size of 2.5 μm to 3.5 μm.
According to the second technical scheme, the mixed grain size first ceramic phase prepared by the preparation method is titanium carbonitride or tungsten carbide.
In the third technical scheme of the invention, the mixed grain size first ceramic phase is applied to the preparation of metal ceramics or hard alloy.
According to a fourth technical scheme, the metal ceramic comprises a first ceramic phase, a second ceramic phase and a metal phase;
the first ceramic phase is the mixed grain size titanium carbonitride;
the second ceramic phase is carbide of elements of sub-groups IV, V and VI;
the metal phase is cobalt and/or nickel.
The fifth technical scheme of the invention is that the hard alloy comprises a first ceramic phase, a second ceramic phase and a metal phase;
the first ceramic phase is the tungsten carbide with the mixed particle size;
the second ceramic phase is carbide of elements of sub-groups IV, V and VI;
the metal phase is cobalt and/or nickel.
The sixth technical scheme of the invention is that the preparation method of the metal ceramic or the hard alloy comprises the following steps:
and uniformly mixing the first ceramic phase, the second ceramic phase and the metal phase, then wet-grinding, drying, pressing into a green body, and then sintering at high temperature to obtain the metal ceramic or the hard alloy.
According to the seventh technical scheme of the invention, the cermet or the hard alloy is applied to preparing pure ceramics, cutting tools or wear-resistant parts.
The technical principle of the invention is as follows:
in a composite material system of metal ceramic or hard alloy, the first ceramic phase is used as a hard 'skeleton' to play a main role on the microstructure of the material, so that the mechanical property of the material is affected. The existing ultra-fine grain technical structure and mixed grain technology can achieve the purposes of strengthening and hardening fine grains by adopting ultra-fine raw materials and mixed grain raw materials to construct an ultra-fine grain or mixed grain microstructure. However, due to the characteristics of difficult dispersion and difficult uniform mixing of the superfine raw materials, the microstructure of the material is difficult to be uniform, and the fine grain strengthening and hardening effects cannot be fully realized; and moreover, due to the characteristic of large specific surface area of the superfine raw material, the surface of the superfine raw material is easier to adsorb oxygen to form an oxide layer, the wettability of a ceramic phase and a metal binding phase is greatly reduced due to the existence of the oxide layer, so that defects such as air holes and cobalt pools are formed in the sintering process, the bending strength and the impact resistance of the metal ceramic or the hard alloy are finally greatly reduced, and the dimensional fluctuation before and after the sintering of the material is indirectly caused, so that the consistency of mechanical properties is poor.
Therefore, the microstructure of the traditional metal ceramic or hard alloy composite material is reconstructed to generate uniform crystal morphology of mixed coarse and fine grains, a dispersion strengthening effect is generated, and the mechanical property advantages of the coarse grains and the fine grains are considered, so that the mechanical property and the stability of the metal ceramic composite material can be obviously improved on the premise of not deteriorating the processing capability of the metal ceramic.
The direct addition of the fine-grain size first ceramic phase can lead to uneven distribution of coarse and fine grains after sintering, so that the mechanical property and processing capacity of the metal ceramic (or hard alloy) are reduced, and the strength stability of the metal ceramic (or hard alloy) is difficult to be favorably influenced. In order to achieve the technical purpose, the invention firstly prepares the fine particle size first ceramic phase suspension, wherein dispersant HPMA (hydrolyzed polymaleic anhydride) is added to enable the fine particle size first ceramic phase suspension to be evaporated to a target viscosity range and to effectively prevent agglomeration in the evaporation process, then oxalic acid, ionic surfactant anion polyacrylamide and coarse particle size first ceramic phase are sequentially added, as oxalic acid is dissolved and precipitated on the first ceramic phase and the surface activity of polyacrylamide on coarse particle size first ceramic phase, oxalic acid can be precipitated in situ on coarse particle size first ceramic phase, the fine particle size first ceramic phase is firmly coated on the surface of coarse particle size first ceramic phase, mixed particle size first ceramic phase powder containing a certain proportion of coarse and fine particles and having a fine particle structure is obtained after evaporation, and as the surface is dissolved and precipitated again, the newly generated surface damages the original oxide layer of superfine powder, the surface of the active ceramic phase has the function of improving the wettability of metal binding phase, and then the active ceramic phase is mixed with other metal binder phase to obtain the metal binder through wet grinding, and then the metal binder is sintered and mixed with other metal ceramic materials.
In the sintering process, HPMA, oxalic acid and ionic surfactant anionic polyacrylamide are completely decomposed at a first temperature step corresponding to the sintering process, the coarse and fine grains of the first ceramic phase are gradually converted into coarse and fine grains in the continuous heating process, and the distribution of the coarse and fine grains is still maintained in the sintering process, so that the continuous and uniform distribution of the coarse and fine grain structures is realized after the sintering is completed. The technical purpose of reconstructing the microstructure of the traditional metal ceramic (or hard alloy) composite material, greatly improving the mechanical property and the stability thereof and further prolonging the service life of the cutter is achieved.
The invention discloses the following technical effects:
the invention provides a new preparation method of metal ceramic or hard alloy, which improves the strength, strength stability and toughness of the metal ceramic (or hard alloy) on the premise of not reducing the processing performance of the metal ceramic (or hard alloy). Because of the improvement of strength, strength stability and toughness and the combination of other excellent performances, the metal ceramic (or hard alloy) composite material not only has greater potential in the machining field, but also is expected to expand the application prospect as a die material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron micrograph of a mixed particle size titanium carbonitride prepared in example 1.
FIG. 2 is a graph showing the calculation of the Weber modulus of flexural strength of the mixed-crystal titanium carbonitride-based cermet prepared in example 1.
Fig. 3 is a scanning electron micrograph of the surface crystal morphology of the cemented tungsten carbide of mixed crystal prepared in example 17 after sintering.
Fig. 4 is a scanning electron micrograph of the mixed-crystal tungsten carbide-based cemented carbide prepared in example 17 after HV30 test.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
In one aspect, the invention provides a method for preparing a mixed particle size first ceramic phase, comprising the steps of: preparing a suspension by matching the fine-grain-size first ceramic, evaporating, adding the coarse-grain-size first ceramic phase, evaporating to dryness, and continuously stirring in the whole process to obtain the mixed-grain-size first ceramic phase;
the fine grain size first ceramic phase is fine grain size titanium carbonitride or fine grain size tungsten carbide;
the coarse grain size first ceramic phase is coarse grain size titanium carbonitride or coarse grain size tungsten carbide.
The average grain diameter of the fine grain diameter first ceramic phase is 0.2-0.8 mu m; the average grain size of the coarse grain size first ceramic phase is 2.5-3.5 mu m; the mass ratio of the coarse grain size first ceramic phase to the fine grain size first ceramic phase is 1 (5-10).
The stirring speed is 300r/min.
In the invention, the solvent of the suspension is water and/or ethanol; the suspension also comprises a dispersing agent; the evaporation is concretely carried out until the viscosity of the suspension is 1100-1300Pas; the step of adding the coarse particle size first ceramic phase further comprises adding oxalic acid and an ionic surfactant.
The mass ratio of the solvent to the fine particle size first ceramic phase is 2:1.
The addition amount of the dispersing agent is 0.15% +/-0.01% of the mass of the fine particle size first ceramic phase.
The evaporating temperature is 70-100 ℃; the evaporating temperature is 70-100 ℃.
The addition amount of oxalic acid is 5mol% of the solvent; the addition amount of the ionic surfactant is 0.1% +/-0.01% of the total mass of the coarse-grain-diameter first ceramic phase and the fine-grain-diameter first ceramic phase.
When the target viscosity of the fine particle size first ceramic phase suspension is higher than 1300Pas, insufficient particle dispersion can cause uneven coating; below 1100Pas, it may be difficult for the fine-grain size first ceramic phase to effectively coat the coarse-grain size first ceramic phase. When the ratio of the coarse grain size first ceramic phase to the fine grain size first ceramic phase in the mixed grain size first ceramic phase is lower than the limit ratio of the invention, the fine grain size raw material powder is agglomerated, uniform mixed crystal morphology cannot be formed after sintering, and when the ratio is higher than the limit ratio of the invention, the fine grain size raw material powder cannot completely cover the coarse grain size raw material powder, and the mechanical property of the metal ceramic is deteriorated.
In the present invention, the dispersant is hydrolyzed polymaleic anhydride; the ionic surfactant is anionic polyacrylamide.
According to the invention, the first ceramic phase powder containing a certain proportion of coarse and fine particles and having a fine-packet coarse particle structure is prepared by a colloidal suspension cladding method, and then is subjected to wet grinding and mixing with other raw material powder, so that the microstructure of the traditional metal ceramic composite material is reconstructed, uniform crystal morphology with mixed coarse and fine grains is generated, the dispersion strengthening effect is achieved, the mechanical property advantages of the coarse grains and the fine grains are considered, and the comprehensive performance and the stability of the material are greatly improved.
The invention also provides a mixed grain size first ceramic phase prepared by the preparation method, wherein the mixed grain size first ceramic phase is mixed grain size titanium carbonitride or mixed grain size tungsten carbide.
In another aspect, the invention provides the use of the mixed grain size first ceramic phase described above in the preparation of a cermet or cemented carbide.
In another aspect, the present invention provides a cermet comprising a first ceramic phase, a second ceramic phase, and a metallic phase;
the first ceramic phase is the mixed grain size titanium carbonitride;
the second ceramic phase is carbide of elements of sub-groups IV, V and VI;
the metal phase is cobalt and/or nickel.
In another aspect, the present invention provides a cemented carbide comprising a first ceramic phase, a second ceramic phase, and a metallic phase;
the first ceramic phase is the tungsten carbide with the mixed particle size;
the second ceramic phase is carbide of elements of sub-groups IV, V and VI;
the metal phase is cobalt and/or nickel.
The second ceramic phase is Mo 2 C、WC、TaC、NbC、VC、Cr 3 C 2 At least one of (a) and (b); more preferably, the second ceramic phase is Mo 2 C. One or more of WC, taC and NbC, and VC, cr 3 C 2 At least one of them.
In the invention, the metal ceramic or the hard alloy contains 40-65% of a first ceramic phase, 10-20% of a metal phase and the balance of a second ceramic phase according to mass percentage.
In another aspect, the present invention provides a method for preparing the above cermet or cemented carbide, comprising the steps of:
and uniformly mixing the first ceramic phase, the second ceramic phase and the metal phase, then wet-grinding, drying, pressing into a green body, and then sintering at high temperature to obtain the metal ceramic or the hard alloy.
In the invention, the high-temperature sintering is one of vacuum sintering, argon or nitrogen atmosphere sintering, argon or nitrogen gas pressure sintering and hot isostatic pressing sintering;
the vacuum sintering is specifically as follows: heating to 500-750 ℃ in vacuum with the pressure lower than 100Pa, preserving heat for 0.5-2 h, heating to 1300-1580 ℃ and preserving heat for 0.5-2 h, and cooling to room temperature along with the furnace after sintering;
the argon or nitrogen atmosphere sintering specifically comprises the following steps: heating to 750-800 ℃ in argon or nitrogen atmosphere of 0.6-4 kPa, preserving heat for 0.5-2 h, and finally preserving heat for 0.5-2 h at 1400-1600 ℃ to finish sintering and cooling to room temperature along with the furnace;
the argon or nitrogen gas pressure sintering is specifically as follows: heating to 800-850 ℃ in argon or nitrogen atmosphere with the pressure of 2-8 MPa, preserving heat for 0.5-2 h, and finally, heating to 1480-1600 ℃ and preserving heat for 0.5-2 h, and cooling to room temperature along with the furnace after sintering;
the hot isostatic pressing sintering is specifically as follows: heating to 650-750 ℃ in vacuum with pressure lower than 100Pa, preserving heat for 0.5-2 h, finally introducing 100-240 MPa nitrogen or argon, heating to 1300-1550 ℃ and preserving heat for 20-70 min, and cooling to room temperature along with the furnace after sintering.
In the present invention, the wet milling specifically includes: the method adopts water or ethanol as a wet grinding solvent, the mass ratio of the solvent to the total mass of the raw materials is (1-3): 1, a hard alloy ball or a steel ball is a grinding medium, the mass ratio of the grinding medium to the total mass of the raw materials is (5-7): 1, the ball milling time is 24-98 h, and the temperature of ball milling slurry is 5-25 ℃; spray drying is adopted for drying.
In the invention, the pressing can be any mode in the ceramic preparation process, preferably one of unidirectional pressing, bidirectional pressing or isostatic pressing, and the pressing pressure is 100-350 MPa.
In another aspect, the invention provides the use of a cermet or cemented carbide as described above for the preparation of pure ceramics, cutting tools or wear parts.
The raw materials used in the examples of the present invention, unless otherwise specified, were all available commercially.
The room temperature described in the present invention, unless otherwise specified, is 25.+ -. 2 ℃.
Example 1
(1) Pre-preparing a mixed grain size first ceramic phase (mixed grain size titanium carbonitride): preparing a fine particle size titanium carbonitride suspension, adopting a vertical heating stirrer as a container, adopting ethanol as a solvent, adding fine particle size titanium carbonitride (the average particle size is 0.5 mu m) into the solvent, adding a dispersing agent HPMA, wherein the mass of the solvent/the mass of the fine particle size titanium carbonitride=2:1, the adding amount of the dispersing agent HPMA is 0.14 percent of the mass of the fine particle size titanium carbonitride, stirring and evaporating, the evaporating temperature is 120 ℃, the stirring speed is 300r/min, and evaporating to the target viscosity 1220Pas; adding coarse-grain-size titanium carbonitride (average grain size is 2.9 mu m, mass ratio of coarse-grain-size titanium carbonitride to fine-grain-size titanium carbonitride is 1:5), ionic surfactant anionic polyacrylamide (the addition amount of the ionic surfactant anionic polyacrylamide is 0.11% of the total mass of the coarse-grain-size titanium carbonitride and the fine-grain-size titanium carbonitride) and oxalic acid (the addition amount of oxalic acid is 5mol% of the solvent) under stirring (300 r/min), and stirring (300 r/min) until the suspension is evaporated to dryness, wherein the evaporating temperature is 200 ℃, and obtaining the mixed-grain-size titanium carbonitride.
(2) Weighing the following raw materials in percentage by mass: 45% of mixed particle size titanium carbonitride prepared in the step (1), 10% of cobalt, 10% of nickel, 15% of WC and the balance of VC (vanadium carbide); the above raw material powder has an average particle diameter of 1 μm to 2 μm except for the mixed particle diameter titanium carbonitride.
(3) Uniformly mixing the powder raw materials in the step (2), placing the mixture in a ball mill, wet-milling, drying, and pressing the mixture into a green body by a press;
wherein wet milling conditions: ethanol is adopted as a wet grinding solvent, the mass of the solvent/raw material (the raw material in the step refers to the total mass of the raw materials, the same applies below) =2:1, a hard alloy ball is adopted as a grinding medium, the mass of the grinding medium/the mass of the raw material=7:1, the ball milling time is 24 hours, and the temperature of ball milling slurry is 5 ℃; drying is spray drying;
pressing conditions: and one-way mould pressing with the pressing pressure of 150MPa.
(4) Heating the obtained green body to 500 ℃ from room temperature by adopting vacuum sintering, preserving heat for 2 hours, continuously heating to 1500 ℃, and preserving heat for 2 hours; the vacuum degree of the sintering environment is kept below 100Pa in the sintering process; and cooling the sintered product to room temperature along with the furnace to obtain the mixed crystal titanium carbonitride base metal ceramic.
FIG. 1 is a scanning electron micrograph of a mixed particle size titanium carbonitride prepared in this example. As can be seen from fig. 1, the mixed grain size titanium carbonitride prepared in the present invention has a fine-packet coarse grain structure.
FIG. 2 is a graph showing the calculation of the Weber modulus of flexural strength of the mixed-crystal titanium carbonitride-based cermet prepared in this example. As can be seen from fig. 2, the weber modulus of the cermet prepared in this example can be greater than 30, indicating excellent strength stability.
Example 2
The difference from example 1 is only that in step (2), the raw materials are composed of, by mass: 55% of titanium carbonitride with mixed particle size, 10% of cobalt, 5% of nickel and Mo 2 C5%, balance Cr 3 C 2 。
In step (3), wet milling conditions: water is adopted as a wet grinding solvent, the mass/raw material of the solvent is=3:1, steel balls are adopted as grinding media, the mass/raw material of the grinding media is=5:1, the ball milling time is 72 hours, and the temperature of ball milling slurry is 25 ℃.
Example 3
The difference from example 1 is only that in step (2), the raw materials are composed of, by mass: 50% of mixed grain size titanium carbonitride, 18% of cobalt, 7% of TaC and the balance of Mo 2 C。
Example 4
The difference from example 1 is only that in step (2), the raw materials are composed of, by mass: carbon of mixed particle size65% of titanium nitride, 16% of nickel and Mo 2 C6%, WC10%, the balance TaC.
Example 5
The difference from example 1 is only that in step (2), the raw materials are composed of, by mass: mixed grain size titanium carbonitride 40%, cobalt 5%, nickel 10%, nbC9% and the balance WC.
Example 6
The only difference from example 1 is that the vacuum sintering in step (4) was replaced with nitrogen atmosphere sintering: heating to 750 ℃ in nitrogen atmosphere of 2kPa for 0.5h, heating to 1510 ℃ for 1.5h, and cooling to room temperature along with the sintering.
Example 7
The only difference from example 1 is that the vacuum sintering in step (4) was replaced with argon gas pressure sintering: heating to 800 ℃ in an argon atmosphere of 5MPa, preserving heat for 1h, heating to 1550 ℃ and preserving heat for 2h, and cooling to room temperature along with the furnace after sintering.
Example 8
The only difference from example 1 is that the stirring process in step (1) was omitted; the results show that omitting this step does not make it possible to obtain the target substance.
Example 9
The only difference from example 1 is that the vacuum sintering in step (4) is replaced by hot isostatic pressing sintering: heating to 700 ℃ in vacuum of less than 100Pa, preserving heat for 2h, finally introducing 120MP argon, heating to 1480 ℃, preserving heat for 70min, and cooling to room temperature along with the sintering.
Example 10
The difference from example 1 was only that in step (1), the mass ratio of coarse grain size titanium carbonitride to fine grain size titanium carbonitride was 1:10, the average grain size of the coarse grain size titanium carbonitride was 2.5 μm, the average grain size of the fine grain size titanium carbonitride was 0.8 μm, the evaporation temperature was 200℃and the evaporation temperature was 300 ℃.
Example 11
The only difference from example 1 is that in step (1), the addition of the dispersant HPMA was omitted.
Example 12
The only difference from example 1 is that in step (1), the target viscosity was 1100Pas.
Example 13 (too low viscosity)
The only difference from example 1 is that in step (1), the target viscosity was 1000Pas.
Example 14 (too high viscosity)
The difference from example 1 was only that in step (1), the target viscosity was 1400Pas.
Example 15 (the mass ratio of coarse grain size titanium carbonitride to fine grain size titanium carbonitride is not in the range of 1:10 to 1:5)
The difference from example 1 is only that in step (1), the mass ratio of coarse grain size titanium carbonitride to fine grain size titanium carbonitride is 1:15.
Example 16 (simultaneous addition of coarse and fine particle size titanium carbonitride)
The difference from example 1 is only that in step (1), fine grain size titanium carbonitride and coarse grain size titanium carbonitride are added simultaneously to the solvent ethanol as follows:
preparation of mixed grain size first ceramic phase (mixed grain size titanium carbonitride): adopting a vertical heating stirrer as a container, adopting ethanol as a solvent, adding fine-grain-size titanium carbonitride (the average grain size is 0.5 mu m) and coarse-grain-size titanium carbonitride (the average grain size is 2.9 mu m, the mass ratio of coarse-grain-size titanium carbonitride to fine-grain-size titanium carbonitride is 1:5) into the solvent, adding a dispersing agent HPMA, wherein the mass of the solvent/the mass of the fine-grain-size titanium carbonitride is=2:1, the adding amount of the dispersing agent HPMA is 0.14 percent of the mass of the fine-grain-size titanium carbonitride, stirring and evaporating, the evaporating temperature is 120 ℃, and the stirring speed is 300r/min, and evaporating to the target viscosity 1220Pas; adding ionic surfactant anionic polyacrylamide (the addition amount of the ionic surfactant anionic polyacrylamide is 0.11% of the total mass of coarse-grain-size titanium carbonitride and fine-grain-size titanium carbonitride) and oxalic acid (the addition amount of oxalic acid is 5mol% of a solvent) under stirring (300 r/min), and stirring (300 r/min) until the suspension is evaporated to dryness, wherein the evaporating temperature is 200 ℃, and obtaining the mixed-grain-size titanium carbonitride.
Example 17
The only difference from example 1 is that in step (1), the mixed grain size first ceramic phase is mixed grain size tungsten carbide; the preparation method of the tungsten carbide with the mixed particle size comprises the following steps:
preparing a fine particle size tungsten carbide suspension, adopting a vertical heating stirrer as a container, adopting ethanol as a solvent, adding fine particle size tungsten carbide (average particle size is 0.5 mu m) into the solvent, adding a dispersing agent HPMA, wherein the mass of the solvent/mass of the fine particle size tungsten carbide=2:1, adding the dispersing agent HPMA accounting for 0.14% of the mass of the fine particle size tungsten carbide, stirring and evaporating, wherein the evaporating temperature is 120 ℃, the stirring speed is 300r/min, and evaporating to the target viscosity 1220Pas; adding coarse particle size tungsten carbide (average particle size is 2.9 mu m, the mass ratio of coarse particle size tungsten carbide to fine particle size tungsten carbide is 1:5), ionic surfactant anionic polyacrylamide (the addition amount of the ionic surfactant anionic polyacrylamide is 0.11% of the total mass of the coarse particle size tungsten carbide and the fine particle size tungsten carbide) and oxalic acid (the addition amount of the oxalic acid is 5mol% of the solvent) under stirring (300 r/min), and stirring (300 r/min) until the suspension is evaporated to dryness, wherein the evaporating temperature is 200 ℃, and obtaining the mixed particle size tungsten carbide.
In the step (2), the raw materials comprise the following components in percentage by mass: 45% of tungsten carbide with mixed particle size, 10% of cobalt, 10% of nickel, 1% of NbC, 1% of TaC and Mo 2 C4%, the remainder VC. Finally preparing the mixed crystal tungsten carbide-based hard alloy.
Fig. 3 is a scanning electron micrograph of the surface crystal morphology of the cemented tungsten carbide of mixed crystal prepared in example 17 after sintering. As can be seen from fig. 3, the mixed-crystal tungsten carbide-based cemented carbide prepared by the method of the present invention has a crystal morphology in which coarse and fine grains are uniformly mixed.
Fig. 4 is a scanning electron micrograph of the mixed-crystal tungsten carbide-based cemented carbide prepared in example 17 after HV30 test. As can be seen from fig. 4, after HV30 hardness test, the mixed crystal tungsten carbide-based cemented carbide prepared by the method of the present invention has no cracks at four corners of the diamond hardness indentation, and the fracture toughness is inversely proportional to the crack length, so that the excellent toughness can be clearly seen.
Example 18 (direct mixing of coarse and Fine particle size titanium carbonitride with other starting materials)
The only difference from example 1 is that the mixed grain size titanium carbonitride was not prepared, i.e., the fine grain size titanium carbonitride, the coarse grain size titanium carbonitride were directly mixed with cobalt, nickel, WC and VC to prepare the cermet.
Effect verification
Mechanical property verification is carried out on the mixed crystal titanium carbonitride base metal ceramic prepared in the examples 1-16 and 18 and the tungsten carbide base hard alloy prepared in the example 17, and a mechanical property test sample adopts a standard B style, and the standards are GBT3851-2015, GBT7997-2014 and JBT12616-2016; the number of samples of the flexural strength weber modulus is 24.
The results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the cermets prepared in examples 1 to 12 (except example 8) of the present invention were excellent in workability and also higher in strength and strength stability and toughness. The metal ceramic and the hard alloy prepared by the method are expected to be widely applied in the field of machining, and have good application prospects as a die material.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (10)

1. A method for preparing a first ceramic phase with mixed grain size, which is characterized by comprising the following steps: preparing a suspension by matching the fine-grain-size first ceramic, evaporating, adding the coarse-grain-size first ceramic phase, evaporating to dryness, and continuously stirring in the whole process to obtain the mixed-grain-size first ceramic phase;
the fine grain size first ceramic phase is fine grain size titanium carbonitride or fine grain size tungsten carbide;
the coarse-grain-diameter first ceramic phase is coarse-grain-diameter titanium carbonitride or coarse-grain-diameter tungsten carbide;
the average grain diameter of the fine grain diameter first ceramic phase is 0.2-0.8 mu m; the first ceramic phase has an average particle size of 2.5 μm to 3.5 μm.
2. The method for producing a mixed particle size first ceramic phase according to claim 1, wherein the solvent of the suspension is water and/or ethanol; the suspension also comprises a dispersing agent; the evaporation is concretely carried out until the viscosity of the suspension is 1100-1300Pas; the step of adding the coarse particle size first ceramic phase further comprises adding oxalic acid and an ionic surfactant.
3. The method of producing a mixed particle size first ceramic phase according to claim 2, wherein the dispersant is hydrolyzed polymaleic anhydride; the ionic surfactant is anionic polyacrylamide.
4. A mixed grain size first ceramic phase prepared by the preparation method according to any one of claims 1 to 3, wherein the mixed grain size first ceramic phase is mixed grain size titanium carbonitride or mixed grain size tungsten carbide.
5. Use of a mixed grain size first ceramic phase according to claim 4 for the preparation of cermets or cemented carbides.
6. A cermet comprising a first ceramic phase, a second ceramic phase, and a metallic phase;
the first ceramic phase is the mixed grain size titanium carbonitride of claim 4;
the second ceramic phase is carbide of elements of sub-groups IV, V and VI;
the metal phase is cobalt and/or nickel.
7. A cemented carbide comprising a first ceramic phase, a second ceramic phase, and a metallic phase;
the first ceramic phase is the mixed grain size tungsten carbide of claim 4;
the second ceramic phase is carbide of elements of sub-groups IV, V and VI;
the metal phase is cobalt and/or nickel.
8. A method of producing a cermet according to claim 6 or a cemented carbide according to claim 7, comprising the steps of:
and uniformly mixing the first ceramic phase, the second ceramic phase and the metal phase, then wet-grinding, drying, pressing into a green body, and then sintering at high temperature to obtain the metal ceramic or the hard alloy.
9. The method of claim 8, wherein the high temperature sintering is one of vacuum sintering, argon or nitrogen atmosphere sintering, argon or nitrogen gas pressure sintering, and hot isostatic pressing sintering.
10. Use of a cermet according to claim 6 or a cemented carbide according to claim 7 for the preparation of pure ceramics, cutting tools or wear parts.
CN202311043910.3A 2023-08-18 2023-08-18 Preparation method and application of metal ceramic or hard alloy Pending CN117069112A (en)

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