Dispersion distribution micro-nano double-crystal core ring structure titanium carbonitride-based metal ceramic alloy and preparation method thereof

Abstract

The invention discloses a titanium carbonitride-based metal ceramic alloy with a dispersive distribution micro-nano twin-crystal core ring structure and a preparation method thereof, the metal ceramic alloy comprises hard phase powder, hard phase powder, hard phase powder and hard phase powder, the hard phase powder comprises TiCN powder, TiC powder and WC powder, and the hard phase powder comprises TiC powder, TiC powder and WC powder; binding phase powder and multi-component alloy strengthening powder. According to the core-ring shell composite crystal grain, the core is 50-200 nm superfine TiCN crystal grains (high-hardness phase), and basic strength is provided; according to the annular shell, the core is wrapped with the oriented-growth TiCN whiskers with the large length-diameter ratio, the whisker bridging effect is formed, and the crack path is deflected. And dispersion bicrystal distribution: micron-sized coarse grains and submicron fine grains are in bimodal distribution according to the volume ratio of 7: 3, the coarse grains hinder crack propagation, and the fine grains inhibit grain boundary slippage. In-situ reaction strengthening: MoSiB and other components are added, a MoO / TiO self-lubricating film is generated in high-temperature friction, the wear rate is reduced, and negative wear is realized.

Description

Technical Field

[0001] The present application relates to the technical field of metal ceramic alloy materials, and in particular to a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy and a preparation method thereof. Background Art

[0002] Titanium carbonitride (TiCN)-based cermets are widely used in cutting tools, wear-resistant components, and other applications due to their high hardness, excellent wear resistance, and high-temperature oxidation resistance. Compared to traditional tungsten-cobalt cemented carbide, their red hardness is approximately 30% higher, and their oxidation resistance temperature is increased by over 200°C. While Ti(C, N)-based cermets possess considerable strength and toughness, their hard phase is a polycrystalline sintered material, resulting in brittleness and insufficient toughness. The complex interface between the core and ring in the cermet's hard phase microstructure easily induces interfacial stress and component segregation during the multiphase sintering process, resulting in defects and reduced material strength and toughness. The low toughness of cermet parts hinders their reliability, limiting their application in advanced engineering applications and the primary reason they cannot fully replace WC carbide. In recent years, researchers have conducted extensive research on strengthening and toughening cermets, including phase transformation strengthening, fiber toughening, grain refinement, and nano-modification. However, these methods do not effectively improve the core ring structural defects, which restricts the further improvement of the performance of metal ceramic materials. Summary of the Invention

[0003] In view of this, the present application provides a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy and its preparation method, aiming to improve the problem that the existing technology has no effective improvement on the defects of the microscopic core ring structure of the metal ceramic hard phase, resulting in its high brittleness and insufficient toughness.

[0004] The embodiment of the present application is achieved by dispersively distributing a titanium carbonitride-based cermet alloy with a micro-nano twin-crystal core ring structure, wherein the cermet alloy comprises: Hard phase powder, wherein the hard phase powder includes TiCN powder, TiC powder and WC powder; Binder phase powder, wherein the binder phase powder includes one or more of Fe powder, Ni powder, Co powder, and Mo powder; The multi-component alloy strengthening powder comprises one or more of CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0005] Optionally, the metal ceramic alloy comprises, by mass percentage: 10%~30%TiCN powder; 2% to 15% TiC powder; 2%~15%WC powder; 25%~50%Fe powder; 2%~15%Ni powder; 2%~15%Co powder; 0.5%~8.5% Mo powder; 1.5%~28% multi-element alloy reinforced powder.

[0006] Optionally, the mass percentage of Fe in the multi-component alloy strengthening powder is 20% to 35%. The mass percentage of Co in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Cr in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20% to 35%. Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 1.5% to 20% by mass of the multi-component alloy strengthening powder.

[0007] Optionally, the TiCN powder Fsss particle size is not greater than 4.0 microns; and / or The particle size of the TiC powder Fsss is not greater than 6.0 microns; and / or WC powder Fsss particle size not greater than 4.5 microns; and / or The particle size of the Fe powder Fsss is not greater than 50.0 microns; and / or The Ni powder Fsss particle size is not greater than 4.0 microns; and / or The particle size of the Co powder Fsss is not greater than 4.0 microns; and / or The particle size of the Mo powder Fsss is not greater than 4.0 microns; and / or The particle size of the multi-element alloy strengthening powder Fsss is not greater than 20.0 microns.

[0008] Accordingly, the present invention also provides a method for preparing a dispersed micro-nano twin-crystal core ring structured titanium carbonitride-based cermet alloy, the method comprising: Providing a mixed powder, the mixed powder comprising the hard phase powder, the binder phase powder and the carbon-nitrogen balance powder in the above-mentioned mass percentages; Adding a dispersant and a forming agent to the mixed powder and mixing them evenly to obtain a prepared raw material; ball-milling the prepared raw materials to obtain a mixed slurry; Drying the mixed slurry and pressing to obtain a blank; The blank is sintered to obtain a metal-ceramic alloy.

[0009] Optionally, the dispersant comprises dodecylbenzenesulfonic acid, stearic acid or ethozone; and / or The molding agent comprises rubber, paraffin or PEG; and / or The prepared raw materials are placed into a grinding carbide or stainless steel ball mill of a ball mill, and a solvent is added and ball milled to obtain a mixed slurry, wherein the solvent includes gasoline, ethylene glycol or hexane; and / or After drying, the mixed slurry is filtered through an N-mesh sieve or spray granulated.

[0010] Optionally, the mass fraction of the dispersant in the total amount of the mixed powder is 0.3% to 0.8%; and / or The mass fraction of the molding agent in the total amount of the mixed powder is 2.5% to 8%; and / or The volume mass ratio of the solvent to the mixed powder is 250 ml / Kg to 600 ml / Kg; and / or N mesh is 40 mesh to 120 mesh; and / or The temperature of drying the mixed slurry is 70℃~85℃; and / or The drying time of the mixed slurry is 1.5h~2.5h; and / or The pressing pressure is 150 MPa to 250 MPa; and / or The holding time is 2 min~30 min.

[0011] Optionally, the ball mill is a rolling ball mill, the diameter of the carbide balls is 5.5 mm to 12 mm; the ball-to-material ratio is 3.5 to 8:1; the rotation speed of the ball mill is 38 rpm to 80 rpm; and the ball milling time is 24 h to 80 h.

[0012] Optionally, the blank is loaded into a sintering furnace and sequentially enters a heating and degreasing stage, a solid phase sintering stage, and a liquid phase sintering stage. After the liquid phase sintering is completed, the blank enters a furnace cooling stage, and then the metal ceramic alloy is taken out of the furnace. The heating and degreasing stage is carried out according to the preheating, vacuuming, heating and holding procedures, preheating to T1 temperature, and holding for t1 time; vacuuming to below P1, heating to T2 temperature; heating rate is v1, and holding at T3 temperature for t2 time; in the solid phase sintering stage, the heating rate does not exceed Through v2, the heating temperature is increased from T3 to T4, and kept warm for t3; the heating rate does not exceed v3, the heating temperature is increased from T4 to T5, and kept warm for t4; the heating rate does not exceed v4, the heating temperature is increased from T5 to T6, and kept warm for t5; the heating rate does not exceed v5, the heating temperature is increased from T6 to T7, and kept warm for t6; after the solid phase sintering stage is completed and the liquid phase sintering stage is entered, the temperature is increased to T8 at a heating rate of v6, and kept warm for t7, and argon gas with a pressure of P2 is introduced at the same time.

[0013] Optionally, the T1 is 180° C. to 250° C.; and / or The t1 is 60 min to 150 min; and / or The temperature T2 is 380°C to 480°C; and / or The v1 is 3 ℃ / min to 5 ℃ / min; and / or The temperature T3 is 480°C to 600°C; and / or The t2 is 60 min to 180 min; and / or The v2 does not exceed 10°C / min; and / or The T4 is 750°C to 850°C; and / or The t3 is 60 min to 180 min; and / or The v3 does not exceed 10°C / min; and / or The T5 is 1000°C to 1100°C; and / or The t4 is 60 min to 180 min; and / or The v4 does not exceed 10°C / min; and / or The temperature T6 is 1150°C to 1250°C; and / or The t5 is 120 min to 300 min; and / or The v5 does not exceed 5°C / min; and / or The T7 is 1250°C to 1380°C; and / or The t6 is 60 min to 120 min; and / or The v6 does not exceed 5°C / min; and / or The T8 is 1380°C to 1550°C; and / or The t7 is 60 min to 600 min; and / or The P1 is below 10 Pa; and / or The P2 is 1 MPa to 5 MPa.

[0014] Beneficial effect: The present invention prepares a micro-nano twin-crystal core-ring structure titanium carbonitride-based metal ceramic alloy structure through multi-scale synergistic toughening, which breaks through the limitation of the existing technology that the defects of the microscopic core-ring structure of the metal ceramic hard phase cannot be effectively improved, resulting in its high brittleness and insufficient toughness. Specifically: The present application forms a core-shell composite grain: the core: 50-200nm ultrafine TiCN grains (high hardness phase), providing basic strength, the shell: directionally grown large aspect ratio TiCN whiskers (aspect ratio 5:1~10: 1), the core is wrapped to form a "whisker bridging" effect, deflecting the crack path; a dispersed twin distribution is also formed: micron-sized coarse crystals (1-3μm) and submicron-sized fine crystals (0.2-0.5μm) are distributed in a bimodal manner at a volume ratio of 7:3. The coarse crystals hinder crack propagation, while the fine crystals inhibit grain boundary sliding. In addition, in-situ reaction strengthening is carried out: MoSiB and other components are added to generate a MoO3 / TiO2 self-lubricating film during high-temperature friction, reducing the wear rate and achieving "negative wear" (wear scar thickness is reduced by 5-10%).

[0015] This invention demonstrates breakthroughs in the mechanical properties of a titanium carbonitride-based cermet alloy with a micro-nano twin-crystal core-ring structure. Specifically, it demonstrates: fracture resistance: crack propagation work is doubled, and flexural strength ≥ 2200 MPa (compared to ≤ 1800 MPa for conventional materials); high-temperature stability: hardness remains at HV1200 at 1000°C (compared to below HV800 for conventional materials), due to the twin-crystal structure suppressing grain boundary softening; self-healing and enhanced wear resistance: a Ti4O7 / MoO3 lubricating film is generated during friction, reducing the friction coefficient to 0.15-0.3; and "negative wear" is achieved: the thickening of the surface protective film increases the apparent size of the workpiece by 0.5-1 μm per 10,000 friction cycles. This application reduces raw material costs by 40%: TiCN replaces 50% of tungsten resources, and the solid solution powder preparation temperature is reduced by 200-300°C. Furthermore, the alloy is compatible with injection molding and low-pressure sintering, making it suitable for mass production of complex-shaped cutting tools. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0017] Figure 1 This is a scanning electron microscope image of the dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy obtained in Example 1 of the present application; Figure 2 This is a scanning electron microscope image of the dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy obtained in Example 2 of the present application; Figure 3This is a scanning electron microscope image of the dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy obtained in Example 3 of the present application; Figure 4 This is a scanning electron microscope image of the dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy obtained in Example 4 of the present application; Figure 5 This is a scanning electron microscope image of the dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy obtained in Example 5 of the present application; Figure 6 This is a scanning electron microscope image of the dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy obtained in Example 6 of the present application; Figure 7 This is a scanning electron microscope image of the dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy obtained in Example 7 of the present application; Figure 8 This is a scanning electron microscope image of the dispersedly distributed micro-nano twin crystal core ring structure titanium carbonitride-based metal ceramic alloy obtained in Example 8 of the present application. DETAILED DESCRIPTION

[0018] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work are within the scope of protection of this application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application and are not used to limit the present application.

[0019] In the description of this application, the term "including" means "including but not limited to." The terms first, second, third, etc. are used merely as labels and do not impose numerical requirements or establish a sequence.

[0020] In this application, "and / or" describes the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0021] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can all mean: a, b, c, a~b (i.e., a and b), a~c, b~c, or a~b~c, where a, b, and c can each be single or plural.

[0022] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be understood as a hard limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numbers within the range. For example, the description of a range from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which applies regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0023] The technical solution of this application is as follows: In a first aspect, embodiments of the present application provide a dispersed micro-nano twin-crystal core ring structured titanium carbonitride-based cermet alloy, the cermet alloy comprising: Hard phase powder, wherein the hard phase powder includes TiCN powder, TiC powder and WC powder; Binder phase powder, wherein the binder phase powder includes one or more of Fe powder, Ni powder, Co powder, and Mo powder; The multi-component alloy strengthening powder comprises one or more of CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0024] Furthermore, the metal ceramic alloy comprises, by mass percentage: 10%~30%TiCN powder; 2% to 15% TiC powder; 2%~15%WC powder; 25%~50%Fe powder; 2%~15%Ni powder; 2%~15%Co powder; 0.5%~8.5%Mo powder; 1.5%~28% multi-element alloy reinforced powder.

[0025] Furthermore, the metal ceramic alloy comprises, by mass percentage: 10% to 30% TiCN powder, preferably 12% to 28% TiCN powder, more preferably 15% to 20% TiCN powder; 2% to 15% TiC powder, preferably 4% to 12% TiC powder, more preferably 7% to 10% TiC powder; 2% to 15% WC powder, preferably 4% to 12% WC powder, more preferably 7% to 10% WC powder; 25% to 50% Fe powder, preferably 30% to 45% Fe powder, more preferably 35% to 50% Fe powder. % to 40% Fe powder; 2% to 15% Ni powder, preferably 4% to 12% Ni powder, more preferably 7% to 10% Ni powder; 2% to 15% Co powder, preferably 4% to 12% Co powder, more preferably 7% to 10% Co powder; 0.5% to 8.5% Mo powder, preferably 2.5% to 6.5% Mo powder, more preferably 4% to 5% Mo powder; 1.5% to 28% multi-component alloy strengthening powder, preferably 5% to 22% multi-component alloy strengthening powder, more preferably 10% to 15% multi-component alloy strengthening powder.

[0026] Furthermore, the mass percentage of Fe in the multi-component alloy strengthening powder is 20% to 35%. The mass percentage of Co in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Cr in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20% to 35%. Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 1.5% to 20% by mass of the multi-component alloy strengthening powder.

[0027] Furthermore, the mass percentage of Fe in the multi-component alloy strengthening powder is 20% to 35%, preferably 22% to 33%, and more preferably 25% to 30%; The mass percentage of Co in the multi-component alloy strengthening powder is 20% to 35%, preferably 22% to 33%, and more preferably 25% to 30%; The mass percentage of Cr in the multi-component alloy strengthening powder is 20% to 35%, preferably 22% to 33%, and more preferably 25% to 30%; The mass percentage of Ni in the multi-component alloy strengthening powder is 20% to 35%, preferably 22% to 33%, and more preferably 25% to 30%; Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the balance and together account for 1.5% to 20% by mass of the multi-component alloy strengthening powder, preferably 5% to 17%, more preferably 8% to 12%; Furthermore, the particle size of the TiCN powder Fsss is not greater than 4.0 μm, for example, 0.02 μm, 0.04 μm, 0.06 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.4 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.3 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.8 μm, 3 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, etc. The particle size of the TiC powder Fsss is not greater than 6.0 μm, for example, it can be 0.02 μm, 0.04 μm, 0.06 μm, 0.1 μm, 0.2 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.8 μm, 3 μm, 3.1 μm, 3.2 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 5.6 μm, 5.8 μm, 5.9 μm, etc.; The particle size of the WC powder Fsss is not greater than 4.5 μm, for example, it can be 0.02 μm, 0.04 μm, 0.06 μm, 0.1 μm, 0.2 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.8 μm, 3 μm, 3.1 μm, 3.2 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, 4 μm, 4.2 μm, 4.4 μm, etc.; The particle size of the Fe powder Fsss is not greater than 50.0 μm, for example, it can be 0.02 μm, 0.04 μm, 0.06 μm, 0.1 μm, 0.2 μm, 0.6 μm, 0.8 μm, 1.0 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, 6.0 μm, 7.0 μm, 8.0 μm, 9.0 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 42 μm, 43 μm, 45 μm, 46 μm, 48 μm, 49 μm, etc.; The particle size of the Ni powder Fsss is not greater than 4.0 μm, for example, 0.02 μm, 0.04 μm, 0.06 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.4 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.3 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.8 μm, 3 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, etc.; The particle size of the Co powder Fsss is not greater than 4.0 μm, for example, 0.02 μm, 0.04 μm, 0.06 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.4 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.3 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.8 μm, 3 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, etc.; The particle size of the Mo powder Fsss is not greater than 4.0 μm, for example, 0.02 μm, 0.04 μm, 0.06 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.4 μm, 0.6 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.3 μm, 1.5 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.8 μm, 3 μm, 3.1 μm, 3.2 μm, 3.3 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.7 μm, 3.8 μm, 3.9 μm, etc.; The particle size of the multi-element alloy strengthening powder Fsss is not greater than 20.0 microns, for example, it can be 0.02 microns, 0.04 microns, 0.06 microns, 0.1 microns, 0.2 microns, 0.6 microns, 0.8 microns, 1.0 microns, 2.0 microns, 3.0 microns, 4.0 microns, 5.0 microns, 6.0 microns, 7.0 microns, 8.0 microns, 9.0 microns, 10 microns, 11 microns, 12 microns, 13 microns, 14 microns, 15 microns, 16 microns, 17 microns, 18 microns, 19 microns, 20 microns, etc.

[0028] Second, see Figure 1 The present application also provides a method for preparing a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, the preparation method comprising: S01. Providing a mixed powder, wherein the mixed powder comprises the hard phase powder, the binder phase powder, and the carbon-nitrogen balance powder in the above-mentioned mass percentages; S02, adding a dispersant and a forming agent to the mixed powder, and mixing them evenly to obtain a prepared raw material; S03, ball-milling the prepared raw materials to obtain a mixed slurry; S04, drying the mixed slurry and pressing to obtain a blank; S05. Sintering the blank to obtain a metal-ceramic alloy.

[0029] In the S01: In some embodiments, the cermet alloy comprises, by weight percentage: 10%~30%TiCN powder; 2% to 15% TiC powder; 2%~15%WC powder; 25%~50%Fe powder; 2%~15%Ni powder; 2%~15%Co powder; 0.5%~8.5%Mo powder; 1.5%~28% multi-element alloy reinforced powder.

[0030] Furthermore, the mass percentage of Fe in the multi-component alloy strengthening powder is 20% to 35%. The mass percentage of Co in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Cr in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20% to 35%. Ti, Al, Cu, Si, Ta, Nb and Mn are the remainder and together account for 1.5% to 20% by mass of the multi-component alloy strengthening powder.

[0031] In some embodiments, the TiCN powder Fsss particle size is no greater than 4.0 microns; The particle size of the TiC powder Fsss is not greater than 6.0 μm; The particle size of WC powder Fsss is not greater than 4.5 microns; The particle size of the Fe powder Fsss is not greater than 50.0 μm; The particle size of Ni powder Fsss is not greater than 4.0 μm; The particle size of the Co powder Fsss is not greater than 4.0 μm; The particle size of Mo powder Fsss is not greater than 4.0 μm; The particle size of the multi-element alloy strengthening powder Fsss is not greater than 20.0 microns.

[0032] In the S02: In some embodiments, the dispersant comprises dodecylbenzenesulfonic acid, stearic acid, or ethoxomone.

[0033] In some embodiments, the mass fraction of the dispersant in the total amount of the mixed powder is 0.3%~0.8%, for example, it can be 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, etc. Within the mass fraction range, the mixed powder can be fully dispersed.

[0034] In some embodiments, the molding agent comprises rubber, wax, or PEG.

[0035] In some embodiments, the mass fraction of the forming agent in the total amount of the mixed powder is 2.5% to 8%, for example, it can be 2.5%, 2.8%, 3%, 3.5%, 3.8%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc. Within the mass fraction range, the bonding state between the mixed powders is improved, the strength of the compact is ensured, the pressing performance is improved, and the density of the compact is increased.

[0036] In said S03: In some embodiments, the prepared raw materials are placed into a grinding carbide or stainless steel ball mill jar of a ball mill, and a solvent is added and ball milling is performed to obtain a mixed slurry.

[0037] Further, the solvent includes gasoline, ethylene glycol or hexane.

[0038] Furthermore, the volume mass ratio of the solvent to the mixed powder is 250 ml / Kg~600 ml / Kg, for example, it can be 250 ml / Kg, 280 ml / Kg, 300 ml / Kg, 320 ml / Kg, 350 ml / Kg, 360 ml / Kg, 380 ml / Kg, 400 ml / Kg, 420 ml / Kg, 450 ml / Kg, 480 ml / Kg, 500 ml / Kg, 520 ml / Kg, 550 ml / Kg, 600 ml / Kg, etc. Within the volume mass ratio range, it is conducive to uniform mixing of the mixed powder, dispersant, forming agent and solvent.

[0039] Furthermore, the ball mill is a rolling ball mill, and the diameter of the carbide balls is 5.5 mm to 12 mm, for example, 5.5 mm, 5.8 mm, 6 mm, 6.25 mm, 6.5 mm, 6.85 mm, 7 mm, 7.25 mm, 7.5 mm, 7.85 mm, 8 mm, 8.25 mm, 8.5 mm, 8.75 mm, 9 mm, 9.25 mm, 9.5 mm, 9.85 mm, 10 mm, 10.5 mm, 11 mm, 11.5 mm, 12 mm, 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19 mm, 20 mm, 21 mm, 22 mm, 23 mm, 24 mm, 25 mm mm, etc.; the ball-to-material ratio is 3.5 to 8:1, for example, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, etc.; the speed of the ball mill is 38 rpm to 80 rpm, for example, 38 rpm, 40 rpm, 45 rpm, 50 rpm, 55 rpm, 60 rpm, 65 rpm, 70 rpm, 72 rpm, 75 rpm, 76 rpm, 78 rpm, 80 rpm, etc.; the ball-to-material ratio is 3.5 to 8:1, for example, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, etc.; the ball mill speed is 38 rpm to 80 rpm, for example, 38 rpm, 40 rpm, 45 rpm, 50 rpm, 55 rpm, 60 rpm, 65 rpm, 70 rpm, 72 rpm, 75 rpm, 76 rpm, 78 rpm, 80 rpm, etc.; the ball milling time is 24 h to 80 h, for example, 24 h, 25 h, 30 h, 35 h, 40 h, 45 h, 48 h, 50 h, 55 h, 60 h, 65 h, 70 h, 75h, 80h, etc.

[0040] In said S04: In some embodiments, the mixed slurry is dried and then passed through an N-mesh filter or spray granulated; Furthermore, N mesh is 40 mesh to 120 mesh, for example, it can be 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh, 100 mesh, 110 mesh, 120 mesh, etc.

[0041] Furthermore, the powder after filtering or spray granulation is directly loaded into a mold and pressed into a blank.

[0042] Furthermore, the drying temperature of the mixed slurry is 70°C~85°C, for example, it can be 70°C, 72°C, 74°C, 75°C, 78°C, 80°C, 82°C, 85°C, etc.; the drying time of the mixed slurry is 1.5h~2.5h, for example, it can be 1.5h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.5h, etc.

[0043] Furthermore, the pressing pressure is 150 Mpa~250 Mpa, for example, it can be 150 Mpa, 160 Mpa, 170 Mpa, 180 Mpa, 190 Mpa, 200 Mpa, 210 Mpa, 220 Mpa, 230 Mpa, 240 Mpa, 250 Mpa, etc.

[0044] Furthermore, the holding time is 2 min to 30 min, for example, it can be 2 min, 4 min, 6 min, 8 min, 10 min, 12 min, 14 min, 16 min, 18 min, 20 min, 22 min, 25 min, 26 min, 28 min, 30 min, etc.

[0045] In said S05: In some embodiments, the blank is loaded into a sintering furnace and sequentially enters the heating and degreasing stage, the solid phase sintering stage, and the liquid phase sintering stage. After the liquid phase sintering is completed, the blank enters the furnace cooling stage, and then the metal ceramic alloy is taken out of the furnace.

[0046] Furthermore, the heating and degreasing stage is carried out according to the preheating, vacuuming, heating and heat preservation processes, preheating to T1 temperature, heat preservation time t1; vacuuming to below P1, heating to T2 temperature; heating rate is v1, heat preservation time t2 at T3 temperature; Furthermore, during the solid phase sintering stage, the heating rate does not exceed v2, the heating temperature is increased from T3 to T4, and the temperature is kept at t3; the heating rate does not exceed v3, the heating temperature is increased from T4 to T5, and the temperature is kept at t4; the heating rate does not exceed v4, the heating temperature is increased from T5 to T6, and the temperature is kept at t5; the heating rate does not exceed v5, the heating temperature is increased from T6 to T7, and the temperature is kept at t6; Furthermore, when the solid phase sintering stage is completed and the liquid phase sintering stage is entered, the temperature is raised to T8 at a heating rate of v6 and maintained for t7, while argon gas with a pressure of P2 is introduced.

[0047] Furthermore, the T1 is 180°C to 250°C, for example, it can be 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, etc.

[0048] The t1 is 60 min to 150 min, for example, it can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 150 min, etc.

[0049] The T2 is 380°C to 480°C, for example, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, etc.

[0050] The v1 is 3°C / min to 5°C / min, for example, 3°C / min, 3.2°C / min, 3.5°C / min, 3.8°C / min, 4°C / min, 4.2°C / min, 4.5°C / min, 4.8°C / min, 5°C / min, etc.

[0051] The T3 is 480°C to 600°C, for example, 480°C, 500°C, 520°C, 550°C, 580°C, 600°C, etc.

[0052] The t2 is 60 min to 180 min, for example, it can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, etc.

[0053] The v2 does not exceed 10 ℃ / min, for example, it may be no more than 10 ℃ / min, no more than 9.8 ℃ / min, no more than 9.5 ℃ / min, no more than 9.2 ℃ / min, no more than 9 ℃ / min, no more than 8.5 ℃ / min, no more than 8 ℃ / min, no more than 7.5 ℃ / min, no more than 7 ℃ / min, no more than 6.5 ℃ / min, no more than 6 ℃ / min, no more than 5.5 ℃ / min, no more than 5 ℃ / min, no more than 4 ℃ / min, no more than 3 ℃ / min, no more than 2 ℃ / min, no more than 1 ℃ / min, etc.

[0054] The T4 is 750°C to 850°C, for example, 750°C, 760°C, 780°C, 800°C, 810°C, 820°C, 830°C, 840°C, 850°C, etc.

[0055] The t3 is 60 min to 180 min, for example, it can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, etc.

[0056] The v3 does not exceed 10 ℃ / min, for example, it may be no more than 10 ℃ / min, no more than 9.8 ℃ / min, no more than 9.5 ℃ / min, no more than 9.2 ℃ / min, no more than 9 ℃ / min, no more than 8.5 ℃ / min, no more than 8 ℃ / min, no more than 7.5 ℃ / min, no more than 7 ℃ / min, no more than 6.5 ℃ / min, no more than 6 ℃ / min, no more than 5.5 ℃ / min, no more than 5 ℃ / min, etc.

[0057] The T5 is 1000°C to 1100°C, for example, 1000°C, 1010°C, 1020°C, 1030°C, 1040°C, 1050°C, 1060°C, 1070°C, 1080°C, 1090°C, 1100°C, etc.

[0058] The t4 is 60 min to 180 min, for example, it can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, etc.

[0059] The v4 does not exceed 10 ℃ / min, for example, it may be no more than 10 ℃ / min, no more than 9.8 ℃ / min, no more than 9.5 ℃ / min, no more than 9.2 ℃ / min, no more than 9 ℃ / min, no more than 8.5 ℃ / min, no more than 8 ℃ / min, no more than 7.5 ℃ / min, no more than 7 ℃ / min, no more than 6.5 ℃ / min, no more than 6 ℃ / min, no more than 5.5 ℃ / min, no more than 5 ℃ / min, etc.

[0060] The T6 is 1150°C to 1250°C, for example, it can be 1150°C, 1160°C, 1180°C, 1200°C, 1210°C, 1220°C, 1230°C, 1240°C, 1250°C, etc.

[0061] The t5 is 120 min to 300 min, for example, it can be 120 min, 150 min, 180 min, 200 min, 220 min, 250 min, 260 min, 280 min, 300 min, etc.

[0062] The v5 does not exceed 5°C / min, for example, it may be no more than 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, etc.

[0063] The T7 is 1250°C to 1380°C, for example, it can be 1250°C, 1260°C, 1280°C, 1300°C, 1310°C, 1320°C, 1330°C, 1340°C, 1350°C, 1360°C, 1370°C, 1380°C, etc.

[0064] The t6 is 60 min to 120 min, for example, it can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, etc.

[0065] The v6 does not exceed 5°C / min, for example, it may be no more than 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, etc.

[0066] The T8 is 1380°C to 1550°C, for example, it can be 1380°C, 1400°C, 1420°C, 1450°C, 1480°C, 1500°C, 1520°C, 1550°C, etc.

[0067] The t7 is 60 min to 600 min, for example, it can be 60 min, 80 min, 100 min, 120 min, 150 min, 180 min, 200 min, 220 min, 250 min, 280 min, 300 min, 350 min, 400 min, 450 min, 500 min, 550 min, 600 min, etc.

[0068] The P1 is 0.05Pa, 1Pa, 2Pa, 3Pa, 4Pa, 5Pa, 6Pa, 7Pa, 8Pa, 9Pa, 10Pa, etc.

[0069] The P2 is 1 MPa to 5 MPa, for example, it can be 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa, 5 MPa, etc.

[0070] The present application will be described in detail below through specific examples. The following examples are only some examples of the present application and are not limitations of the present application.

[0071] Example 1 See Figure 1, a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 20% TiCN powder; 7% TiC powder; 7% WC powder; 33% Fe powder; 7% Ni powder; 7% Co powder; 4.5% Mo powder; 14.5% multi-element alloy strengthening powder.

[0072] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0073] The mass percentage of Fe in the multi-component alloy strengthening powder is 25%, The mass percentage of Co in the multi-element alloy strengthening powder is 20%, The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 25%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 10% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 2 μm; The particle size of TiC powder Fsss is 0.6 μm; The particle size of WC powder Fsss is 2 μm; The particle size of Fe powder Fsss is 25 μm; The particle size of Ni powder Fsss is 2 μm; The particle size of Co powder Fsss is 2 μm; The particle size of Mo powder Fsss is 2 μm; The particle size of the multi-element alloy strengthening powder Fsss is 10 μm; A method for preparing a dispersed micro-nano twin-crystal core ring structured titanium carbonitride-based metal ceramic alloy comprises: Step 1. Weighing hard phase powder, binder phase powder, and carbon-nitrogen balance powder according to the above mass percentages and mixing them to obtain a mixed powder, adding a dispersant and a molding agent, and mixing them evenly to obtain a prepared raw material; the dispersant is dodecylbenzenesulfonic acid, and its mass fraction of the total mixed powder is 0.5%; the molding agent is paraffin, and its mass fraction of the total mixed powder is 5.5%; Step 2: The prepared raw materials are loaded into a grinding carbide ball mill of a rolling ball mill, and a solvent is added and ball milled to obtain a mixed slurry, wherein the solvent is ethylene glycol, the volume mass ratio of ethylene glycol to the total amount of the mixed powder is 420 ml / kg, the diameter of the carbide ball is 8.5 mm, and the ball-to-material ratio is 6:1; the ball milling speed of the ball mill is 60 rpm, and the ball milling time is 52 h; Step 3: Dry the mixed slurry (78°C, 2h) and filter through 80 mesh; Step 4: directly put the powder after filtering into the mold and press it into a blank. The pressing pressure is 200 MPa and the holding time is 16 minutes. Step 5, the blank is loaded into the sintering furnace and enters the heating and degreasing stage, the solid phase sintering stage, and the liquid phase sintering stage in sequence. After the liquid phase sintering is completed, it enters the furnace cooling stage, and then the metal ceramic alloy is taken out of the furnace. Among them, the heating and degreasing stage is carried out according to the preheating, vacuuming, heating and holding processes, preheating to 215 ° C, and holding for 105 min; vacuuming to below 5 Pa, heating to 430 ° C; heating rate is 4 ° C / min, and holding at 540 ° C for 120 min; in the solid phase sintering stage, the heating rate does not exceed 5 ° C / min, the heating temperature is increased from 540 ° C to 800 ° C, and holding for 120 min; the heating rate does not exceed 5 ° C / min, the heating temperature is increased from 800 ° C to 1050 ° C, and holding for 120 min; the heating rate does not exceed 5 ° C / min, the heating temperature is increased from 1050 ° C to 1200 ° C, and holding for 210 min; the heating rate does not exceed 3 ° C / min, the heating temperature is heated from 1200 ° C to 1315 ° C, and the temperature is kept at this temperature for 90 min; after the solid phase sintering stage is completed and the liquid phase sintering stage is entered, the temperature is increased to 1465 ° C at a heating rate of 3 ° C / min, and the temperature is kept at this temperature for 330 min, while argon gas with a pressure of 3 MPa is introduced, and the purity of the argon gas is greater than 99.995%.

[0074] Example 2 See Figure 2 , a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 30% TiCN powder; 2% TiC powder; 2% WC powder; 25% Fe powder; 10% Ni powder; 10% Co powder; 8% Mo powder; 13% multi-alloy strengthening powder.

[0075] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0076] The mass percentage of Fe in the multi-component alloy strengthening powder is 20%, The mass percentage of Co in the multi-element alloy strengthening powder is 20%, The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 20% by mass of the multi-element alloy strengthening powder; The particle size of TiCN powder Fsss is 0.4 μm~0.6 μm; The particle size of TiC powder Fsss is 4 μm; The particle size of WC powder Fsss is 0.45 μm; The particle size of Fe powder Fsss is 5 μm; The particle size of Ni powder Fsss is 0.4 μm; The particle size of Co powder Fsss is 0.4 μm; The particle size of Mo powder Fsss is 0.4 μm; The particle size of the multi-element alloy strengthening powder Fsss is 2 microns; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0077] Example 3 See Figure 3 , a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 10% TiCN powder; 15% TiC powder; 15% WC powder; 27% Fe powder; 2% Ni powder; 2% Co powder; 1% Mo powder; 28% multi-alloy strengthening powder.

[0078] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0079] The mass percentage of Fe in the multi-component alloy strengthening powder is 29.5%, The mass percentage of Co in the multi-element alloy strengthening powder is 29%. The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 1.5% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 3 μm; The particle size of TiC powder Fsss is 0.8 μm; The particle size of WC powder Fsss is 2 μm; Fe powder Fsss has a particle size of 0.5 μm; Ni powder Fsss particle size is 0.4 microns; Co powder Fsss particle size is 0.4 microns; Mo powder Fsss particle size is 0.4 microns; The particle size of the multi-element alloy strengthening powder Fsss is 0.2 μm; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0080] Example 4 See Figure 4 , a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 15% TiCN powder; 8% TiC powder; 8% WC powder; 43% Fe powder; 6% Ni powder; 6% Co powder; 4% Mo powder; 10% multi-alloy strengthening powder.

[0081] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0082] The mass percentage of Fe in the multi-component alloy strengthening powder is 22%. The mass percentage of Co in the multi-element alloy strengthening powder is 22%. The mass percentage of Cr in the multi-element alloy strengthening powder is 22%. The mass percentage of Ni in the multi-element alloy strengthening powder is 22%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 12% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 3.5 μm; The particle size of TiC powder Fsss is 5 μm; The particle size of WC powder Fsss is 0.2 μm; The particle size of Fe powder Fsss is 45 μm; The particle size of Ni powder Fsss is 3 μm; The particle size of Co powder Fsss is 3.8 μm; The particle size of Mo powder Fsss is 3.6 μm; The particle size of the multi-element alloy strengthening powder Fsss is 18 μm; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0083] Example 5 See Figure 5 , a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 18% TiCN powder; 4% TiC powder; 4% WC powder; 36% Fe powder; 6% Ni powder; 5% Co powder; 2% Mo powder; 25% multi-alloy strengthening powder.

[0084] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0085] The mass percentage of Fe in the multi-component alloy strengthening powder is 25%, The mass percentage of Co in the multi-element alloy strengthening powder is 25%, The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 10% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 0.6 μm~0.8 μm; The particle size of TiC powder Fsss is 4 μm; The particle size of WC powder Fsss is 4 μm; The particle size of Fe powder Fsss is 40 μm; The particle size of Ni powder Fsss is 3 μm; The particle size of Co powder Fsss is 3 μm; The particle size of Mo powder Fsss is 3 μm; The particle size of the multi-element alloy strengthening powder Fsss is 16 μm; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0086] Example 6 See Figure 6 , a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 22% TiCN powder; 4% TiC powder; 3% WC powder; 39% Fe powder; 3% Ni powder; 3% Co powder; 1% Mo powder; 25% multi-alloy strengthening powder.

[0087] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0088] The mass percentage of Fe in the multi-component alloy strengthening powder is 28%, The mass percentage of Co in the multi-element alloy strengthening powder is 28%, The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 4% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 2 μm; The particle size of TiC powder Fsss is 0.2 μm; The particle size of WC powder Fsss is 1 μm; The particle size of Fe powder Fsss is 10 μm; The particle size of Ni powder Fsss is 2 μm; The particle size of Co powder Fsss is 1 μm; The particle size of Mo powder Fsss is 2 μm; The particle size of the multi-element alloy strengthening powder Fsss is 8 microns; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0089] Figure 6 In the figure, 1-bonding phase alloy, 2-micron core-ring structure grains, 3-nanometer core-ring structure grains.

[0090] Example 7 See Figure 7, a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 25% TiCN powder; 6% TiC powder; 4% WC powder; 40% Fe powder; 4% Ni powder; 5% Co powder; 6% Mo powder; 10% multi-alloy strengthening powder.

[0091] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0092] The mass percentage of Fe in the multi-component alloy strengthening powder is 28%, The mass percentage of Co in the multi-element alloy strengthening powder is 28%, The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 4% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 2 μm; The particle size of TiC powder Fsss is 4 μm; The particle size of WC powder Fsss is 0.6 μm; The particle size of Fe powder Fsss is 18 μm; The particle size of Ni powder Fsss is 0.4 μm; The particle size of Co powder Fsss is 0.4 μm; The particle size of Mo powder Fsss is 0.4 μm; The particle size of the multi-element alloy strengthening powder Fsss is 8 microns; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0093] Example 8 See Figure 8 , a dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy, calculated by mass percentage, includes: 28% TiCN powder; 3% TiC powder; 2% WC powder; 48% Fe powder; 4% Ni powder; 2% Co powder; 0.5% Mo powder; 12.5% ​​multi-alloy strengthening powder.

[0094] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0095] The mass percentage of Fe in the multi-component alloy strengthening powder is 20%, The mass percentage of Co in the multi-element alloy strengthening powder is 30%, The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 10% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 0.2 μm~0.4 μm; The particle size of TiC powder Fsss is 4 μm; The particle size of WC powder Fsss is 1.2 μm; The particle size of Fe powder Fsss is 45 μm; The particle size of Ni powder Fsss is 2 μm; The particle size of Co powder Fsss is 1 μm; The particle size of Mo powder Fsss is 3 μm; The particle size of the multi-element alloy strengthening powder Fsss is 12 microns; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0096] Example 9 A dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy comprises, by mass percentage, 12% TiCN powder; 10% TiC powder; 8% WC powder; 40% Fe powder; 6% Ni powder; 3% Co powder; 1% Mo powder; and 20% multi-element alloy strengthening powder.

[0097] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0098] The mass percentage of Fe in the multi-component alloy strengthening powder is 25%, The mass percentage of Co in the multi-element alloy strengthening powder is 20%, The mass percentage of Cr in the multi-element alloy strengthening powder is 22%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 13% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 1 μm; The particle size of TiC powder Fsss is 0.2 μm; The particle size of WC powder Fsss is 2 μm; The particle size of Fe powder Fsss is 30 μm; The particle size of Ni powder Fsss is 0.4 μm; The particle size of Co powder Fsss is 0.5 μm; The particle size of Mo powder Fsss is 2 μm; The particle size of the multi-element alloy strengthening powder Fsss is 8 microns; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0099] Example 10 A dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy comprises, by mass percentage, 26% TiCN powder; 3% TiC powder; 6% WC powder; 29% Fe powder; 12% Ni powder; 10% Co powder; 6% Mo powder; and 8% multi-element alloy strengthening powder.

[0100] The multi-element alloy strengthening powder includes CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

[0101] The mass percentage of Fe in the multi-component alloy strengthening powder is 35%, The mass percentage of Co in the multi-element alloy strengthening powder is 20%, The mass percentage of Cr in the multi-element alloy strengthening powder is 20%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20%, Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 5% by mass of the multi-component alloy strengthening powder; The particle size of TiCN powder Fsss is 0.6 μm~0.8 μm; The particle size of TiC powder Fsss is 2 μm; The particle size of WC powder Fsss is 2 μm; The particle size of Fe powder Fsss is 25 μm; The particle size of Ni powder Fsss is 1 μm; The particle size of Co powder Fsss is 2 μm; The particle size of Mo powder Fsss is 2 μm; The particle size of the multi-element alloy strengthening powder Fsss is 10 μm; The preparation method of the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy is the same as that of Example 1.

[0102] Example 11 This embodiment differs from embodiment 1 in that: A method for preparing a dispersed micro-nano twin-crystal core ring structured titanium carbonitride-based metal ceramic alloy comprises: Step 1. Weighing hard phase powder, binder phase powder, and carbon-nitrogen balance powder according to the above mass percentages and mixing them to obtain a mixed powder, adding a dispersant and a molding agent, and mixing them evenly to obtain a preliminary raw material; the dispersant is stearic acid, and its mass fraction of the total mixed powder is 0.3%; the molding agent is PEG, and its mass fraction of the total mixed powder is 2.5%; Step 2: The prepared raw materials are loaded into a grinding carbide ball mill of a rolling ball mill, and a solvent is added and ball milled to obtain a mixed slurry, wherein the solvent is gasoline, the volume mass ratio of gasoline to the total amount of the mixed powder is 250 ml / kg, the diameter of the carbide balls is 5.5 mm, and the ball-to-material ratio is 3.5:1; the ball milling speed of the ball mill is 38 rpm, and the ball milling time is 80 h; Step 3: Dry the mixed slurry (70°C, 2.5h) and filter through a 120-mesh sieve; Step 4: directly put the powder after filtering into the mold and press it into a blank. The pressing pressure is 150 MPa and the holding time is 30 minutes. Step 5, the blank is loaded into the sintering furnace and enters the heating and degreasing stage, the solid phase sintering stage, and the liquid phase sintering stage in sequence. After the liquid phase sintering is completed, it enters the furnace cooling stage, and then the metal ceramic alloy is taken out of the furnace. Among them, the heating and degreasing stage is carried out according to the preheating, vacuuming, heating and holding processes, preheating to 180°C and holding for 150 min; vacuuming to below 1 Pa, heating to 380°C; the heating rate is 3°C / min, and holding at 480°C for 180 min; in the solid phase sintering stage, the heating rate does not exceed 3°C / min, the heating temperature is heated from 480°C to 750°C, and holding for 180 min; the heating rate does not exceed 8°C / min, the heating temperature is heated from 750°C to 1000°C, and holding for 180 min; the heating rate does not exceed 7.0°C / min, the heating temperature is heated from 1000°C to 1150°C, and holding for 300 min; the heating rate does not exceed 3 ° C / min, the heating temperature is heated from 1150 ° C to 1250 ° C, and the temperature is kept at this temperature for 120 min; after the solid phase sintering stage is completed and the liquid phase sintering stage is entered, the temperature is raised to 1380 ° C at a heating rate of 2 ° C / min, and the temperature is kept at this temperature for 600 min, while argon gas with a pressure of 6 MPa is introduced, and the purity of the argon gas is greater than 99.995%.

[0103] The rest are the same as in Example 1.

[0104] Example 12 This embodiment differs from embodiment 1 in that: A method for preparing a dispersed micro-nano twin-crystal core ring structured titanium carbonitride-based metal ceramic alloy comprises: Step 1, weighing hard phase powder, binder phase powder and carbon-nitrogen balance powder according to the above mass percentages and mixing them to obtain a mixed powder, adding a dispersant and a molding agent, and mixing them evenly to obtain a prepared raw material; the dispersant is ethosulfanil, and its mass fraction of the total mixed powder is 0.8%; the molding agent is rubber, and its mass fraction of the total mixed powder is 8%; Step 2: The prepared raw materials are loaded into a grinding carbide ball mill of a rolling ball mill, and a solvent is added and ball milled to obtain a mixed slurry, wherein the solvent is hexane, the volume mass ratio of hexane to the total amount of the mixed powder is 600 ml / kg, the diameter of the carbide ball is 12 mm, and the ball-to-material ratio is 8:1; the ball milling speed of the ball mill is 80 rpm, and the ball milling time is 24 h; Step 3: Dry the mixed slurry (85°C, 1.5h) and filter through a 40-mesh sieve; Step 4: directly put the powder after filtering into the mold and press it into a blank. The pressing pressure is 250 MPa and the holding time is 2 minutes. Step 5, the blank is loaded into the sintering furnace and enters the heating and degreasing stage, the solid phase sintering stage, and the liquid phase sintering stage in sequence. After the liquid phase sintering is completed, it enters the furnace cooling stage, and then the metal ceramic alloy is taken out of the furnace. Among them, the heating and degreasing stage is carried out according to the preheating, vacuuming, heating and holding processes, preheating to 250 ° C, and holding for 60 min; vacuuming to below 10 Pa, heating to 480 ° C; the heating rate is 5 ° C / min, and holding at 600 ° C for 60 min; in the solid phase sintering stage, the heating rate does not exceed 9.8 ° C, the heating temperature is increased from 600 ° C to 850 ° C, and holding for 60 min; the heating rate does not exceed 9.5 ° C / min, the heating temperature is increased from 850 ° C to 1100 ° C, and holding for 60 min; the heating rate does not exceed 9.8 ° C / min, the heating temperature is increased from 1100 ° C to 1250 ° C, and holding for 120 min; the heating rate does not exceed 5 ° C / min, the heating temperature is heated from 1250 ° C to 1380 ° C, and the temperature is kept at this temperature for 60 min; after the solid phase sintering stage is completed and the liquid phase sintering stage is entered, the temperature is increased to 1550 ° C at a heating rate of 4.9 ° C / min, and the temperature is kept at this temperature for 60 min, while argon gas with a pressure of 1 MPa is introduced, and the purity of the argon gas is greater than 99.995%.

[0105] The rest are the same as in Example 1.

[0106] The above is a detailed introduction to the dispersed distributed micro-nano twin-crystal core ring structure titanium carbonitride-based metal ceramic alloy and its preparation method provided in the embodiments of the present application. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for technical personnel in this field, based on the ideas of the present application, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. Dispersed distribution micro-nano twin crystal core ring structure titanium carbonitride-based metal ceramic alloy, characterized by: The metal ceramic alloy comprises: Hard phase powder, wherein the hard phase powder includes TiCN powder, TiC powder and WC powder; Binder phase powder, wherein the binder phase powder includes one or more of Fe powder, Ni powder, Co powder, and Mo powder; The multi-component alloy strengthening powder comprises one or more of CoCrNi powder, CoCrNiAlTi powder, FeNiCrMo powder, FeNiCrMoCuNb powder, FeNiCrCuNbSi powder, FeNiCrCuTaSiMn powder and FeNiCrCuNbSiMn powder.

2. The dispersed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy according to claim 1, characterized in that: Measured by mass percentage, the metal ceramic alloy comprises: 10%~30%TiCN powder; 2% to 15% TiC powder; 2%~15%WC powder; 25%~50%Fe powder; 2%~15%Ni powder; 2%~15%Co powder; 0.5%~8.5% Mo powder; 1.5%~28% multi-element alloy reinforced powder.

3. The dispersed micro-nano twin-crystal core-ring structured titanium carbonitride-based cermet alloy according to claim 1 or 2, characterized in that: The mass percentage of Fe in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Co in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Cr in the multi-element alloy strengthening powder is 20% to 35%. The mass percentage of Ni in the multi-element alloy strengthening powder is 20% to 35%. Ti, Al, Mo, Cu, Si, Ta, Nb and Mn are the remainder and together account for 1.5% to 20% by mass of the multi-component alloy strengthening powder.

4. The dispersed micro-nano twin-crystal core-ring structured titanium carbonitride-based cermet alloy according to claim 1 or 2, characterized in that: The TiCN powder Fsss particle size is not greater than 4.0 microns; and / or The particle size of the TiC powder Fsss is not greater than 6.0 microns; and / or WC powder Fsss particle size not greater than 4.5 microns; and / or The particle size of the Fe powder Fsss is not greater than 50.0 microns; and / or The Ni powder Fsss particle size is not greater than 4.0 microns; and / or The particle size of the Co powder Fsss is not greater than 4.0 microns; and / or The particle size of the Mo powder Fsss is not greater than 4.0 microns; and / or The particle size of the multi-element alloy strengthening powder Fsss is not greater than 20.0 microns.

5. A method for preparing a dispersed micro-nano twin-crystal core ring structured titanium carbonitride-based metal ceramic alloy, characterized by: The preparation method comprises: Providing a mixed powder, the mixed powder comprising the hard phase powder, the binder phase powder and the carbon-nitrogen balance powder in the above-mentioned mass percentages; Adding a dispersant and a forming agent to the mixed powder and mixing them evenly to obtain a prepared raw material; ball-milling the prepared raw materials to obtain a mixed slurry; Drying the mixed slurry and pressing to obtain a blank; The blank is sintered to obtain a metal-ceramic alloy.

6. The method for preparing the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy according to claim 5, characterized in that: The dispersant includes dodecylbenzenesulfonic acid, stearic acid or ethoxomone; and / or The molding agent comprises rubber, paraffin or PEG; and / or The prepared raw materials are placed into a grinding carbide or stainless steel ball mill of a ball mill, and a solvent is added and ball milled to obtain a mixed slurry, wherein the solvent includes gasoline, ethylene glycol or hexane; and / or After drying, the mixed slurry is filtered through an N-mesh sieve or spray granulated.

7. The method for preparing the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy according to claim 6, characterized in that: The mass fraction of the dispersant in the total amount of the mixed powder is 0.3% to 0.8%; and / or The mass fraction of the molding agent in the total amount of the mixed powder is 2.5% to 8%; and / or The volume mass ratio of the solvent to the mixed powder is 250 ml / Kg to 600 ml / Kg; and / or N mesh is 40 mesh to 120 mesh; and / or The temperature of drying the mixed slurry is 70℃~85℃; and / or The drying time of the mixed slurry is 1.5h~2.5h; and / or The pressing pressure is 150 MPa to 250 MPa; and / or The holding time is 2 min~30 min.

8. The method for preparing the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy according to claim 6, characterized in that: The ball mill is a rolling type ball mill, the diameter of the carbide balls is 5.5 mm to 12 mm; the ball-to-material ratio is 3.5 to 8:1; the rotation speed of the ball mill is 38 rpm to 80 rpm; and the ball milling time is 24 h to 80 h.

9. The method for preparing the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy according to claim 5, characterized in that: The blank is loaded into the sintering furnace and enters the heating and degreasing stage, solid phase sintering stage, liquid phase sintering stage in sequence. After the liquid phase sintering is completed, it enters the furnace cooling stage, and then the metal ceramic alloy is taken out of the furnace. Among them, the heating and degreasing stage is carried out according to the preheating, vacuuming, heating and insulation processes. Preheating to T1 temperature, insulation time t1; vacuuming to below P1, heating to T2 temperature; heating rate is v1, insulation time t2 at T3 temperature; in the solid phase sintering stage, the heating rate does not exceed v 2. The heating temperature is raised from T3 to T4 and kept at t3; the heating rate does not exceed v3, the heating temperature is raised from T4 to T5 and kept at t4; the heating rate does not exceed v4, the heating temperature is raised from T5 to T6 and kept at t5; the heating rate does not exceed v5, the heating temperature is raised from T6 to T7 and kept at t6; after the solid phase sintering stage is completed and the liquid phase sintering stage is entered, the temperature is raised to T8 at a heating rate of v6 and kept at t7, and argon gas with a pressure of P2 is introduced at the same time.

10. The method for preparing the dispersedly distributed micro-nano twin-crystal core ring structure titanium carbonitride-based cermet alloy according to claim 9, characterized in that: The temperature T1 is 180°C to 250°C; and / or The t1 is 60 min to 150 min; and / or The temperature T2 is 380°C to 480°C; and / or The v1 is 3 ℃ / min to 5 ℃ / min; and / or The temperature T3 is 480°C to 600°C; and / or The t2 is 60 min to 180 min; and / or The v2 does not exceed 10°C / min; and / or The T4 is 750°C to 850°C; and / or The t3 is 60 min to 180 min; and / or The v3 does not exceed 10°C / min; and / or The T5 is 1000°C to 1100°C; and / or The t4 is 60 min to 180 min; and / or The v4 does not exceed 10°C / min; and / or The temperature T6 is 1150°C to 1250°C; and / or The t5 is 120 min to 300 min; and / or The v5 does not exceed 5°C / min; and / or The T7 is 1250°C to 1380°C; and / or The t6 is 60 min to 120 min; and / or The v6 does not exceed 5°C / min; and / or The T8 is 1380°C to 1550°C; and / or The t7 is 60 min to 600 min; and / or The P1 is below 10 Pa; and / or The P2 is 1 MPa to 5 MPa.

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