CN111036918B - Metal ceramic with high toughness and thermal fatigue resistance and preparation method thereof - Google Patents

Metal ceramic with high toughness and thermal fatigue resistance and preparation method thereof Download PDF

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CN111036918B
CN111036918B CN201911325997.7A CN201911325997A CN111036918B CN 111036918 B CN111036918 B CN 111036918B CN 201911325997 A CN201911325997 A CN 201911325997A CN 111036918 B CN111036918 B CN 111036918B
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powder
cermet
fine
fatigue resistance
thermal fatigue
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CN111036918A (en
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王洪涛
王家瑞
李宏
熊惟皓
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Tianjin College University Of Science & Technology Beijing
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
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Abstract

The invention provides a cermet with obdurability and thermal fatigue resistance and a preparation method thereof, relates to the technical field of cermet materials, and can obviously improve the obdurability and the thermal fatigue resistance of the cermet, improve the high-temperature comprehensive performance of the cermet and prolong the service life of the cermet; the method comprises the steps of S1, preparing Ti (C, N) and (W, Co) C superfine solid solution powder; s2, preparing Ni-Mo high-distortion solid solution powder by using a mechanical alloying method; the Mo micro powder is nitrogen molecule activated phase Mo; s3, mixing the three kinds of powder with graphite powder to obtain mixed powder, and wet-grinding the mixed powder to prepare mixed slurry; s4, drying, screening and adding polyvinyl alcohol to prepare a uniform mixture; s5, die pressing forming; s6, vacuum degreasing and presintering; s7, vacuum activation sintering; s8, preparing a gradient thermal stress slow release layer on the surface of the metal ceramic matrix. The technical scheme provided by the invention is suitable for the preparation process of the metal ceramic.

Description

Metal ceramic with high toughness and thermal fatigue resistance and preparation method thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of metal ceramic materials, in particular to a metal ceramic with high toughness and thermal fatigue resistance and a preparation method thereof.
[ background of the invention ]
Ti (C, N) cermet is a novel tool and die material developed for processing metal materials in a high-temperature environment. The Ti (C, N) cermet of the metal-based multiphase composite material prepared by the powder metallurgy method has the performance advantages of metal and ceramic materials, has high hardness, high wear resistance, high red hardness, excellent high-temperature creep resistance and chemical stability, has extremely low friction coefficient with metal, is suitable for being used in high-temperature, high-pressure and high-friction working condition environments, and has the service environment temperature of over 1000 ℃, and has obvious advantages compared with the traditional tool and die steel (the safety service temperature of the traditional tool and die steel is generally lower than 700 ℃, and the high-temperature performance of the traditional tool and die steel cannot meet the production requirement of the working condition environment of over 800 ℃). The Ti (C, N) cermet is a novel hot working die material for hot working and forming metal with the temperature of more than 800 ℃.
The hardness of the prepared fine-grain Ti (C, N) -based cermet material reaches HV 1400-1800 MPa, and the fracture toughness reaches 10 MPa.m1/2The elastic modulus is 450GPa, the initial oxidation temperature is 1373-1473K, and the high-temperature comprehensive performance is greatly improved.
However, by its very nature, it is still a brittle material. In service, failure or fracture along the phase interface is the primary form of failure. Due to low toughness and insufficient thermal fatigue resistance, the strength and toughness are quickly attenuated when the high-temperature environment is in service, and early brittle failure is caused under the dual actions of thermal stress and mechanical stress.
Therefore, how to improve the toughness and the thermal fatigue resistance of the Ti (C, N) -based cermet while maintaining red hardness and creep resistance is the key to improve the high-temperature comprehensive performance and prolong the service life of the cermet.
In order to improve the toughness and the thermal fatigue resistance of Ti (C, N) cermet, the current research methods mostly focus on preparing hard or ultra-hard films on the surface of the cermet by a physical method or a chemical method, and the prepared films can play a role in protecting the cermet matrix, but have no obvious effect on improving the toughness and the thermal fatigue resistance of the cermet. The two main deficiencies of these studies are:
firstly, preparing a hard or super-hard film on the surface of Ti (C, N) cermet by a physical vapor deposition method, wherein the prepared film has an obvious phase interface with a matrix and insufficient bonding strength, so that the problem of stress concentration caused by thermal stress is not fundamentally solved, and the effect of improving the toughness and the thermal fatigue resistance of the cermet is not great;
secondly, a chemical vapor deposition method is used for preparing the gradient hard film on the surface of the metal ceramic under the low-pressure condition, but the preparation process is too long (more than 48 h) due to low pressure (less than 1 atmosphere pressure) and insufficient diffusion power, and the prepared film is too thin (less than 2 mu m), so that the stress concentration relief of the film on the thermal stress is limited, and the practical application value is low.
Accordingly, there is a need to develop a cermet having toughness and thermal fatigue resistance and a method for preparing the same to address the deficiencies of the prior art to solve or mitigate one or more of the problems set forth above.
[ summary of the invention ]
In view of the above, the invention provides a cermet with high toughness and thermal fatigue resistance and a preparation method thereof, which can obviously improve the toughness and the thermal fatigue resistance of the cermet, improve the high-temperature comprehensive performance of the cermet and prolong the service life of the cermet.
In one aspect, the invention provides a preparation method of cermet with high toughness and thermal fatigue resistance, which is characterized by comprising the following steps:
s1, preparing Ti (C, N) ultrafine solid solution powder;
s2, preparing (W, Co) C superfine solid solution powder;
s3, mixing Ni micro powder and Mo micro powder by a mechanical alloying method to prepare Ni-Mo high-distortion solid solution powder; wherein the Mo micro powder is nitrogen molecule activated phase Mo;
s4, mixing the solid solution powder prepared in the S1-S3 to obtain first mixed powder, mixing the first mixed powder with graphite powder to obtain second mixed powder, and wet-grinding the second mixed powder to prepare mixed slurry;
s5, drying and screening the mixed slurry, adding polyvinyl alcohol, stirring and mixing uniformly to prepare a mixed material;
s6, molding the mixture to form a pre-sintered blank;
s7, performing vacuum degreasing and presintering on the presintering blank to obtain a presintering body;
s8, carrying out vacuum activated sintering on the pre-sintered body to obtain a fine-grain metal ceramic sintered body;
s9, decomposing nitrogen by taking the fine-grain metal ceramic sintered body as a matrix and utilizing the activation effect of Mo on nitrogen molecules at high temperature and high pressure, and preparing a gradient thermal stress slow release layer on the surface of the fine-grain metal ceramic sintered body;
the order of S1 to S3 is not fixed.
In the aspect and any possible implementation manner described above, there is further provided an implementation manner, in which S1 is specifically configured to mix TiC ultra-fine powder and TiN ultra-fine powder by a high-energy ball milling method to prepare Ti (C, N) ultra-fine solid solution powder containing nano-powder; the mass ratio of the TiC superfine powder to the TiN superfine powder is 2: 1-4: 1.
The above aspects and any possible implementation manners further provide an implementation manner, and the S2 is specifically to mix WC ultrafine powder and Co ultrafine powder by a high energy ball milling method to prepare (W, Co) C ultrafine solid solution powder; the mass ratio of the WC superfine powder to the Co superfine powder is as follows: 5: 1-12: 1;
the mass ratio of the Ni micro powder to the Mo micro powder in the S3 is as follows: 3:1 to 6: 1.
In the aspect and any possible implementation manner described above, a further implementation manner is provided, and the specific process of wet-milling the second mixed powder in S4 is as follows: putting the second mixed powder and the hard alloy grinding balls into a ball milling tank, adding absolute ethyl alcohol while stirring until the absolute ethyl alcohol submerges the second mixed powder for 3-5 cm, and then carrying out ball milling; the ball milling time is 12-48 h, and the rotating speed is 230-300 rpm; the mass ratio of the added hard alloy grinding ball to the second mixed powder is 8: 1.
The above aspect and any possible implementation manner further provide an implementation manner, wherein the addition amount of the polyvinyl alcohol in S5 is: the mass of the polyvinyl alcohol is 3-5% of that of the blending material.
As for the above-mentioned aspect and any possible implementation manner, there is further provided an implementation manner, and the specific process of S7 is: placing the pre-sintered blank at the temperature of 400-650 ℃ and the vacuum degree of 3-6 Pa, keeping for 4-8 h, then heating to 800-1000 ℃ and the vacuum degree of 1-3 Pa, and keeping for 1-2 h;
the vacuum activation sintering of S8 keeps the vacuum degree not less than 1.0 x 10-1Pa, the sintering temperature is 1400-1450 ℃, and the temperature peak heat preservation time is 60-120 min.
As for the above-mentioned aspect and any possible implementation manner, there is further provided an implementation manner, and the specific process of S9 is: and (3) placing the fine-grain metal ceramic sintered body in a hot isostatic pressing furnace, taking nitrogen as a stress medium, keeping the nitrogen pressure at 60-110 MPa, the activation nitriding temperature at 800-1200 ℃, and keeping the temperature for 4-16 h to prepare a gradient thermal stress slow release layer on the surface of the fine-grain metal ceramic sintered body.
In another aspect, the present invention provides a cermet having toughness and thermal fatigue resistance, characterized in that the cermet is prepared by the preparation method as set forth in any one of claims 1 to 7;
the metal ceramic comprises a fine-grain metal ceramic matrix and a gradient thermal stress slow release layer positioned on the surface of the fine-grain metal ceramic matrix;
the hardness of the fine-grained cermet matrix is 88-91 HRA, and the fracture toughness is not less than 12.3 MPa.m1/2(ii) a The gradient thermal stress slow release layer is a pure phase TiN hard film with the thickness of more than 6 mu m, and the hardness of the outer surface of the gradient thermal stress slow release layer is 92-95 HRA.
The above-described aspects and any possible implementations further provide an implementation in which the fine-grained cermet matrix has a "core-shell" structure consisting of a black core phase, a gray ring phase, and a white binder phase.
The above aspect and any possible implementation manner further provide an implementation manner, where the cermet includes the following components in percentage by mass: the alloy comprises, by weight, 10-11% of TiN, 23-38% of TiC, 10-12% of WC, 32-38% of Ni, 6-14% of Mo, 1-2% of Co and 1-2% of graphite powder.
Compared with the prior art, the invention can obtain the following technical effects: the invention improves the preparation process of fine-grain Ti (C, N) cermet, improves the phase interface strength and improves the obdurability; the invention takes the prepared fine-grain Ti (C, N) cermet as a substrate, and a gradient thermal stress slow-release layer is prepared on the surface of the substrate, so that the thermal fatigue resistance of the cermet is improved, the high-temperature comprehensive performance of the cermet is improved, and the service life of the cermet is prolonged.
Of course, it is not necessary for any one product in which the invention is practiced to achieve all of the above-described technical effects simultaneously.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used 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 it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a topographical view of a fine-grained Ti (C, N) cermet provided in accordance with one embodiment of the present invention.
[ detailed description ] embodiments
For better understanding of the technical solutions of the present invention, the following detailed descriptions of the embodiments of the present invention are provided with reference to the accompanying drawings.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In order to solve the problems of low toughness and insufficient thermal fatigue resistance of Ti (C, N) cermet, the cermet with toughness and thermal fatigue resistance and the preparation method thereof begin from two aspects of preparation of the Ti (C, N) cermet and arrangement of a thermal stress slow release layer on the surface of the prepared Ti (C, N) cermet, so that the toughness of the cermet is improved and the thermal fatigue resistance is improved. The morphology of the cermet prepared by the preparation method of the invention is shown in figure 1.
The method specifically comprises the following steps:
1. the preparation of fine-grain Ti (C, N) cermet matrix improves the phase interface strength and improves the toughness;
the preparation method comprises the following specific steps:
preparing Ti (C, N) ultramicro solid solution powder in a high-energy ball milling process; and mixing the TiC superfine powder and the TiN superfine powder by a high-energy ball milling method to prepare Ti (C, N) superfine solid solution powder containing nano powder. The mass ratio of TiC to TiN is 2: 1-4: 1;
preparing (W, Co) C ultramicro solid solution powder in a high-energy ball mill;
and mixing WC ultrafine powder and Co ultrafine powder by a high-energy ball milling method to prepare (W, Co) C ultrafine solid solution powder. The mass ratio of the WC superfine powder to the Co superfine powder is as follows: 5:1 to 12: 1.
Mixing Ni micro powder and Mo micro powder by a mechanical alloying method to prepare Ni-Mo high-distortion solid solution powder; the solid solution powder presets a nitrogen molecule activation phase Mo in a subsequent atmosphere hot isostatic pressing process in a sintering binding phase Ni; the Mo micro powder is nitrogen molecule active phase Mo, and the mass ratio of the Ni micro powder to the Mo micro powder is as follows: ni and Mo are 3: 1-6: 1;
in the application, the grain diameter is 0.2-0.5 mu m, the grain diameter is ultramicro powder, the grain diameter is less than 0.2 mu m, the grain diameter is nanometer powder, and the grain diameter is 0.5-0.8 mu m, and the grain diameter is micro powder.
Mixing the powder prepared in the first step and the third step according to a certain proportion to obtain first mixed powder, and mixing the first mixed powder and graphite powder according to a certain mass ratio to obtain second mixed powder; the mixing proportion of each powder meets the mass percentage requirement of each component of the metal ceramic to be prepared;
absolute ethyl alcohol is used as a wet grinding medium, and ball milling is carried out by a high-energy ball milling method to prepare mixed slurry. And (3) putting the powder and the hard alloy grinding balls into a ball milling tank, adding absolute ethyl alcohol while stirring until the powder is submerged for 3-5 cm, and then carrying out ball milling. The ball milling time is 12-48 h, the mass of the hard alloy balls and the second mixed powder during ball milling is 8:1, and the rotating speed is 230-300 rpm.
Fifthly, drying the mixed slurry, screening the dried mixed slurry, adding a certain proportion of polyvinyl alcohol, mechanically stirring and uniformly mixing to prepare the uniform material. The addition amount of the polyvinyl alcohol is as follows: the mass percentage accounts for 3-5% of the mixed material.
Sixthly, molding the mixed material by a press to form a pre-sintered blank; the molding conditions were: and (3) carrying out die pressing forming under the pressure of 300-350 MPa.
Vacuum degreasing: and (3) degreasing the pre-sintered blank by keeping a certain vacuum degree in a vacuum furnace, and pre-sintering the degreased blank to obtain a pre-sintered body.
The specific process is as follows: preserving the temperature of the pre-sintered blank for 4-8 hours at the temperature of 400-650 ℃ and under the pressure condition of 3-6 Pa of vacuum degree, and carrying out degreasing treatment; and then heating to 800-1000 ℃, performing pre-sintering treatment, keeping the temperature for 1-2 h in the pre-sintering process, and keeping the vacuum degree at 1-3 Pa.
And V, vacuum activation sintering: and (3) maintaining a certain vacuum degree by using a vacuum furnace to carry out activated sintering on the pre-sintered body to obtain a fine-grain Ti (C, N) cermet sintered body, namely the fine-grain Ti (C, N) cermet to be prepared. Vacuum activating sintering to maintain vacuum degree not lower than 1.0 × 10-1Pa, the sintering temperature is 1400-1450 ℃, and the temperature peak heat preservation time is 60-120 min.
The fine-grain Ti (C, N) cermet crystal grain prepared by the method has a core-shell structure, and the shape of the electron microscope microstructure of the core-shell structure is as follows: the inside of the crystal grain is a black core hard phase; the periphery of the black core phase is a gray annular solid solution transition phase; white metal bonding phase is arranged between the crystal grains; the core-shell structure of the crystal grain realizes the gradual transition from an intragranular hard phase to an intercrystalline metal bonding phase, and improves the phase interface strength of the metal ceramic.
The strength of the phase interface of Ti (C, N) cermets is the primary determinant of toughness. Under the condition of keeping high hardness, the effect of improving the interface strength and further improving the obdurability can be achieved by improving the tissue structure of the phase interface. According to the fine grain strengthening theory, the strength and toughness of the material can be effectively improved by refining grains.
The method for preparing the fine-grain Ti (C, N) cermet is a powder metallurgy method, and the subsequent N content is preset by a mechanical alloying method2And (3) cracking an activating element Mo by nitrogen molecules required by atmosphere hot isostatic pressing treatment, and preparing the fine-grain Ti (C, N) cermet by using a powder metallurgy method.
2. The fine-grain Ti (C, N) cermet is taken as a matrix, and a gradient thermal stress slow release layer is prepared on the surface of the matrix, so that the thermal fatigue resistance of the cermet is improved, the high-temperature comprehensive performance of the cermet is improved, and the service life of the cermet is prolonged;
the heat fatigue resistance of the high-temperature material is improved, and the fundamental way is to relieve the thermal stress and avoid the stress concentration. In the case of a multi-phase composite material such as Ti (C, N) cermet, thermal stress is generated mainly due to the difference in expansion coefficient between the constituent phases, and since a phase interface exists between the phases, thermal stress is inevitably generated at the phase interface due to the difference in expansion coefficient under high temperature conditions; in addition, when the hot working material is in service, the surface of the hot working material bears the largest thermal stress, and stress concentration is generated at the surface defect of the material, so that the surface of the material becomes a source for crack germination due to the stress concentration, cracks are easy to germinate, and the thermal fatigue resistance of the material is insufficient;
the invention provides a method for preparing a gradient film structure on the surface of Ti (C, N) cermet, and the components and the structure are in gradient gradual transition within a certain scale from the outside to the inside, so that an obvious interface is eliminated, thereby slowly releasing thermal stress, avoiding stress concentration and improving the thermal fatigue resistance of the Ti (C, N) cermet.
The method for preparing the gradient thermal stress sustained-release layer comprises the following steps: n-containing of Ti (C, N) cermets2And (3) performing atmosphere hot isostatic pressing treatment (namely, performing atmosphere hot isostatic pressing surface activation nitriding treatment), decomposing nitrogen by utilizing the activation effect of Mo on nitrogen molecules at high temperature and high pressure, and preparing a gradient thermal stress slow release layer on the surface of the fine-grain metal ceramic sample. The method specifically comprises the following steps: the method comprises the steps of carrying out nitridation treatment on a fine-grain Ti (C, N) cermet sintered body by using an atmosphere hot isostatic pressing furnace and taking nitrogen as a pressure medium under certain nitrogen pressure and temperature to obtain a thermal stress slow release layer on the surface of the sintered body, and eliminating an obvious phase interface in a certain area close to the surface, so that the thermal stress is slowly released, stress concentration is avoided, the initiation and the expansion of early brittle cracks are effectively inhibited, the toughness and the thermal fatigue resistance of the Ti (C, N) cermet are improved, and the high-temperature comprehensive performance of the Ti (C, N) cermet is improved. Surface activation nitriding treatment by atmosphere hot isostatic pressing: placing the sintered body in a hot isostatic pressing furnace, taking nitrogen as a stress medium, and keeping the nitrogenThe pressure is 60-110 MPa, the activation nitriding temperature is 800-1200 ℃, and the heat preservation time is 4-16 h.
The prepared fine-grain Ti (C, N) cermet comprises the following components in percentage by mass (omega t%): 8-11% of TiN10, 23-38% of TiC, 10-12% of WC, 32-38% of Ni, 6-14% of Mo, 1-2% of Co and 1-2% of graphite powder; the prepared fine-grain Ti (C, N) cermet matrix structure has a core-shell structure and consists of a black core phase, a gray annular phase and a white bonding phase, the matrix hardness is 88-91 HRA, and the fracture toughness is more than or equal to 12.3 MPa.m1/2(ii) a The prepared thermal stress slow release layer is positioned on the surface of the fine-grain metal ceramic matrix, is a pure-phase TiN hard film with the thickness of more than 6 mu m, and has the surface hardness of 92-95 HRA.
Table 1 shows the mass ratios (ω t%) of the four component formulations, and Ti (C, N) -based cermet was prepared and tested for hardness and fracture toughness using the respective process parameters.
TABLE 1 quality ratio of four ingredients (wt%)
Figure BDA0002328391700000121
For the four samples in table 1, the preparation and comparison of the properties were carried out in the examples with different processes.
Example 1:
in the step of mechanical alloying by high-energy ball milling, the rotating speed is 230rpm, and the ball milling time is 12 h.
Before molding, adding 3% polyvinyl alcohol and mixing uniformly; the pressure for the press molding was 300 MPa.
The vacuum degree of the vacuum degreasing step is 3Pa, the temperature is 400 ℃, and the heat preservation time is 4 h.
The vacuum degree of the vacuum activation sintering step is not less than 1.0 multiplied by 10-1Pa, sintering temperature 1400 ℃, and heat preservation time 60 min.
In the step of surface activation nitriding treatment by atmosphere hot isostatic pressing, the sintered body is placed in a hot isostatic pressing furnace, the nitrogen pressure is kept at 60MPa, the activation nitriding temperature is 800 ℃, and the heat preservation time is 4 hours.
In the process, the properties of the prepared Ti (C, N) -based cermet with the four-component formula are shown in Table 2.
TABLE 2 Properties of Ti (C, N) -based cermet prepared under the conditions of example 1
Figure BDA0002328391700000131
Example 2:
in the step of mechanical alloying by high-energy ball milling, the rotating speed is 260rpm, and the ball milling time is 24 hours.
Before molding, adding 4% polyvinyl alcohol and mixing uniformly; the pressure for the press molding was 320 MPa.
The vacuum degree of the vacuum degreasing step is 4Pa, the temperature is 500 ℃, and the heat preservation time is 6 h.
The vacuum degree of the vacuum activation sintering step is not less than 1.0 multiplied by 10-1Pa, sintering temperature 1410 deg.C, and holding time 90 min.
In the step of surface activation nitriding treatment by atmosphere hot isostatic pressing, the sintered body is placed in a hot isostatic pressing furnace, the nitrogen pressure is kept at 80MPa, the activation nitriding temperature is 900 ℃, and the heat preservation time is 8 hours.
In the process, the properties of the prepared Ti (C, N) -based cermet with the four-component formula are shown in Table 3.
TABLE 3 Properties of Ti (C, N) -based cermet prepared under the conditions of example 2
Figure BDA0002328391700000141
Example 3:
in the step of mechanical alloying by high-energy ball milling, the rotating speed is 280rpm, and the ball milling time is 36 h.
Before molding, adding 5% polyvinyl alcohol and mixing uniformly; the pressure for the press molding was 330 MPa.
The vacuum degree of the vacuum degreasing step is 5Pa, the temperature is 600 ℃, and the heat preservation time is 8 h.
The vacuum degree of the vacuum activation sintering step is not less than 1.0 multiplied by 10-1Pa, the sintering temperature is 1430 ℃, and the heat preservation time is 120 min.
In the step of surface activation nitriding treatment by atmosphere hot isostatic pressing, the sintered body is placed in a hot isostatic pressing furnace, the nitrogen pressure is kept at 100MPa, the activation nitriding temperature is 1100 ℃, and the heat preservation time is 12 hours.
In the process, the properties of the prepared Ti (C, N) -based cermet with the four-component formula are shown in Table 4.
TABLE 4 Properties of Ti (C, N) -based cermet prepared under the conditions of example 3
Figure BDA0002328391700000142
Figure BDA0002328391700000151
Example 4:
in the step of mechanical alloying by high-energy ball milling, the rotating speed is 300rpm, and the ball milling time is 48 h.
Before molding, adding 5% polyvinyl alcohol and mixing uniformly; the pressure for the press molding was 350 MPa.
The vacuum degree of the vacuum degreasing step is 6Pa, the temperature is 650 ℃, and the heat preservation time is 8 h.
The vacuum degree of the vacuum activation sintering step is not less than 1.0 multiplied by 10-1Pa, sintering temperature 1450 ℃, and heat preservation time 120 min.
In the step of surface activation nitriding treatment by atmosphere hot isostatic pressing, the sintered body is placed in a hot isostatic pressing furnace, the nitrogen pressure is kept at 110MPa, the activation nitriding temperature is 1200 ℃, and the heat preservation time is 16 h.
In the process, the properties of the prepared Ti (C, N) -based cermet with the four-component formula are shown in Table 5.
TABLE 5 Properties of Ti (C, N) -based cermet prepared under the conditions of example 4
Figure BDA0002328391700000152
The invention is mainly applied to two fields:
the high-temperature performance of the cutting tool material is superior to that of hard alloy, the cutting tool material can finish high-speed cutting on 'difficult-to-machine materials', turning instead of grinding 'and milling instead of grinding' are realized, the metal cutting tool made of the cutting tool material has outstanding anti-breakage performance, wear resistance and machining stability, the red hardness is good, the chip adhesion is prevented, the machining speed is improved by more than 2 times, the dry cutting of the metal material can be finished, and green machining is realized.
Compared with die steel, Ti (C, N) -based cermet has the advantages of high hardness, high temperature resistance, no phase change, small friction coefficient, metal adhesion resistance and the like, and has wide applicability to plastic forming processing of metal materials in a high-temperature environment. Can be used for manufacturing tools and dies such as hot plugs, extrusion dies, wire drawing dies and the like for processing metal hot rolling, hot extrusion, hot stamping and the like.
The embodiments of the present application provide a cermet with high toughness and thermal fatigue resistance and a method for preparing the same. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include/include, but not limited to. "substantially" means within an acceptable error range, within which a person skilled in the art can solve the technical problem and substantially achieve the technical result. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, the use of the phrase "comprising a. -. said" to define an element does not exclude the presence of other like elements in a commodity or system that comprises the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the word "/", herein, generally indicates that the objects associated therewith are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.

Claims (9)

1. A preparation method of cermet with obdurability and thermal fatigue resistance is characterized in that a fine-grain cermet substrate is prepared, and then a gradient thermal stress slow release layer is prepared on the surface of the fine-grain cermet substrate;
when the fine-grain metal ceramic matrix is prepared, a nitrogen molecule activation phase Mo is preset in a sintering bonding phase Ni, and then the nitrogen is decomposed by utilizing the activation effect of Mo on nitrogen molecules at high temperature and high pressure, so that a gradient thermal stress slow release layer is prepared on the surface of the fine-grain metal ceramic matrix;
the preparation method comprises the following steps:
s1, preparing Ti (C, N) ultrafine solid solution powder;
s2, preparing (W, Co) C superfine solid solution powder;
s3, mixing Ni micro powder and Mo micro powder by a mechanical alloying method to prepare Ni-Mo high-distortion solid solution powder; wherein the Mo micro powder is nitrogen molecule activated phase Mo;
s4, mixing the solid solution powder prepared in the S1-S3 to obtain first mixed powder, mixing the first mixed powder with graphite powder to obtain second mixed powder, and wet-grinding the second mixed powder to prepare mixed slurry;
s5, drying and screening the mixed slurry, adding polyvinyl alcohol, stirring and mixing uniformly to prepare a mixed material;
s6, molding the mixture to form a pre-sintered blank;
s7, performing vacuum degreasing and presintering on the presintering blank to obtain a presintering body;
s8, carrying out vacuum activated sintering on the pre-sintered body to obtain a fine-grain metal ceramic matrix;
s9, performing atmosphere hot isostatic pressing surface activation nitriding treatment on the fine-grain cermet matrix, and preparing a gradient thermal stress slow release layer on the surface of the fine-grain cermet matrix;
the order of S1 to S3 is not fixed.
2. The preparation method of cermet with obdurability and thermal fatigue resistance as claimed in claim 1, wherein said S1 is specifically to mix TiC ultra fine powder and TiN ultra fine powder by high energy ball milling method to make Ti (C, N) ultra fine solid solution powder containing nano powder; the mass ratio of the TiC superfine powder to the TiN superfine powder is 2: 1-4: 1;
s2 is specifically that WC ultrafine powder and Co ultrafine powder are mixed by a high-energy ball milling method to prepare (W, Co) C ultrafine solid solution powder; the mass ratio of the WC superfine powder to the Co superfine powder is as follows: 5: 1-12: 1;
the mass ratio of the Ni micro powder to the Mo micro powder in the S3 is as follows: 3: 1-6: 1.
3. The method for preparing cermet having toughness and thermal fatigue resistance according to claim 1, wherein the specific process of wet grinding the second mixed powder in S4 is as follows: putting the second mixed powder and the hard alloy grinding balls into a ball milling tank, adding absolute ethyl alcohol while stirring until the absolute ethyl alcohol submerges the second mixed powder for 3-5 cm, and then carrying out ball milling; the ball milling time is 12-48 h, and the rotating speed is 230-300 rpm; the mass ratio of the added hard alloy grinding balls to the second mixed powder is 8: 1.
4. The method for preparing the cermet having high toughness and thermal fatigue resistance according to claim 1, wherein the addition amount of the polyvinyl alcohol in the S5 is as follows: the mass of the polyvinyl alcohol is 3-5% of that of the blending material.
5. The preparation method of the cermet with high toughness and thermal fatigue resistance according to claim 1, wherein the specific process of S7 is as follows: placing the pre-sintered blank at the temperature of 400-650 ℃ and the vacuum degree of 3-6 Pa, keeping for 4-8 h, then heating to 800-1000 ℃ and the vacuum degree of 1-3 Pa, and keeping for 1-2 h;
the vacuum activation sintering of S8 keeps the vacuum degree not less than 1.0 x 10-1Pa, the sintering temperature is 1400-1450 ℃, and the temperature peak heat preservation time is 60-120 min.
6. The preparation method of the cermet with high toughness and thermal fatigue resistance according to claim 1, wherein the specific process of S9 is as follows: and (3) placing the fine-grain metal ceramic sintered body in a hot isostatic pressing furnace, taking nitrogen as a stress medium, keeping the nitrogen pressure at 60-80 MPa, the activation nitriding temperature at 800-1100 ℃, and keeping the temperature for 4-16 h to prepare a gradient thermal stress slow release layer on the surface of the fine-grain metal ceramic sintered body.
7. A cermet having high toughness and thermal fatigue resistance, characterized in that it is prepared by the process according to any one of claims 1 to 6;
the metal ceramic comprises a fine-grain metal ceramic matrix and a gradient thermal stress slow release layer positioned on the surface of the fine-grain metal ceramic matrix;
the hardness of the fine-grained cermet matrix is 88-91 HRA, and the fracture toughness is not less than 12.3 MPa.m1/2(ii) a The gradient thermal stress slow release layer is a pure phase TiN hard film with the thickness of more than 6 mu m, and the hardness of the outer surface of the gradient thermal stress slow release layer is 92-95 HRA.
8. The cermet having toughness and resistance to thermal fatigue of claim 7, in which the fine-grained cermet matrix has a "core-shell" structure consisting of a black core phase, a grey ring phase and a white binder phase.
9. The cermet with high toughness and thermal fatigue resistance according to claim 7, wherein the cermet comprises the following components in percentage by mass: 10-11% of TiN, 23-38% of TiC, 10-12% of WC, 32-38% of Ni, 6-14% of Mo, 1-2% of Co and 1-2% of graphite powder.
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