CN109676127B - High-performance TiN-based metal ceramic and preparation method thereof - Google Patents

High-performance TiN-based metal ceramic and preparation method thereof Download PDF

Info

Publication number
CN109676127B
CN109676127B CN201910094134.7A CN201910094134A CN109676127B CN 109676127 B CN109676127 B CN 109676127B CN 201910094134 A CN201910094134 A CN 201910094134A CN 109676127 B CN109676127 B CN 109676127B
Authority
CN
China
Prior art keywords
powder
tin
sintering
temperature
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910094134.7A
Other languages
Chinese (zh)
Other versions
CN109676127A (en
Inventor
甘雪萍
谢丹
吴玉学
周科朝
李志友
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201910094134.7A priority Critical patent/CN109676127B/en
Publication of CN109676127A publication Critical patent/CN109676127A/en
Application granted granted Critical
Publication of CN109676127B publication Critical patent/CN109676127B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1035—Liquid phase sintering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder

Abstract

The invention provides a high-performance TiN-based metal ceramic and a preparation method thereof. The method comprises the following steps: mixing TiN powder with WO3Uniformly mixing the powder, then putting the powder into a hydrogen furnace, introducing water and hydrogen, heating and then reacting to obtain W-coated TiN composite powder; uniformly mixing the composite powder and carbon powder, and then putting the mixture into a vacuum furnace for carbonization to obtain WC coated TiN composite powder; and uniformly mixing the WC-coated TiN composite powder, the metal additive and the forming agent, sequentially sieving, pressing into a blank, degreasing and sintering to obtain the TiN-based metal ceramic. The TiN-based metal ceramic prepared by the method has the characteristics of high density, high hardness, excellent bending resistance, good fracture toughness, low friction coefficient, good wear resistance, excellent oxidation resistance and excellent corrosion resistance, and has very wide market prospect.

Description

High-performance TiN-based metal ceramic and preparation method thereof
Technical Field
The invention belongs to the technical field of inorganic non-metallic materials, and particularly relates to a high-performance TiN-based metal ceramic and a preparation method thereof.
Background
The TiN (titanium nitride) ceramic material has excellent performances of low density, high hardness, high melting point, corrosion resistance, good thermal stability, low friction coefficient and the like, so the TiN ceramic material is considered to be a wear-resistant corrosion-resistant material with research, development and application prospects; in addition, the TiN ceramic material has beautiful golden yellow luster and good gold-substituting decorative effect, and is a very promising decorative material. However, titanium nitride ceramic materials have poor plastic deformability and low toughness, and it is difficult to obtain a dense sintered body, and these defects limit the development and application thereof. At present, TiN ceramic materials are mainly used as coating materials, but the coating materials have the defects of easy peeling, short service life and the like in the using process, so that the preparation of high-performance and high-density TiN block materials has high application value.
The metal ceramic is a composite material with excellent characteristics of ceramic and metal, but the TiN ceramic material has poor wettability with pure metal, and a high-density TiN-based metal ceramic material with excellent comprehensive performance is difficult to obtain after sintering, so that a further improvement on a process method is needed, the cost is reduced, and the comprehensive performance of the material is improved.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects and shortcomings in the background technology, providing a high-performance TiN-based metal ceramic and a preparation method of the TiN-based metal ceramic.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of high-performance TiN-based metal ceramic comprises the following steps:
(1) mixing TiN powder with WO3Mixing the powders uniformly, putting the mixture into a hydrogen furnace, introducing water and hydrogen, heating the mixture, and reacting the mixture, wherein WO is generated in the reaction process3Preferentially reacting with water vapor to generate high-volatility hydrated tungsten hydroxide gas, then reducing the gas by hydrogen at high temperature, and adsorbing the gas on the surfaces of TiN ceramic particles to obtain W-coated TiN composite powder with a prefabricated core-shell structure;
(2) uniformly mixing the W-coated TiN composite powder obtained in the step (1) with carbon powder, and then putting the mixture into a vacuum furnace for carbonization to obtain WC-coated TiN composite powder with a core-shell structure;
(3) and (3) uniformly mixing the WC coated TiN composite powder obtained in the step (2), the metal additive and the forming agent, then sequentially sieving, pressing into a blank, degreasing, sintering, and cooling along with a furnace to obtain the TiN-based metal ceramic.
The above preparation method is preferred, in the step (1), TiN powder and WO3The mass ratio of the powder is 20: 1-5: 1, so that a W particle layer which is uniform and compact and has a certain thickness (10 nm-500 nm) can be coated on the surface of the TiN; in the step (2), the mass ratio of the W-coated TiN composite powder to the carbon powder is 20: 1-15: 1, so that the coated W particles are completely converted into WC, oxygen participating in the system is consumed by reaction, and the system is purified; said step (c) is(3) In the method, the mass ratio of the WC-coated TiN composite powder to the metal additive to the molding agent is that the WC-coated TiN composite powder: metal additive: and (60-90): (10-40): (1-3), the addition ratio of the three components is controlled within the range of the invention, so that the TiN-based metal ceramic with high comprehensive performance is obtained.
In the above production method, it is preferable that the dew point of the aqueous hydrogen gas in the step (1) is-25 ℃ to-30 ℃. According to the preparation method, the dew point of the water hydrogen is controlled within the range of the invention, so that the particle size of the generated W particles can be ensured within a proper range, and the W particles are uniformly and densely coated on the surface of TiN; if the W particle size is beyond the range of the invention, the W particle is promoted to grow, and the coating layer is too thick; if the amount is less than the range of the present invention, the resulting W particles are fine and difficult to coat uniformly.
In the preparation method, preferably, in the step (1), the temperature is increased to 800-1000 ℃, and the reaction time is 1-2 hours. Controlling the reaction temperature and the reaction time in the step (1) within the range of the invention is beneficial to adjusting the growth state of W particles on the surface of TiN powder, and obtaining the W-coated TiN composite powder with uniform and compact coating.
In the preparation method, preferably, in the step (2), the carbonization temperature is controlled to be 1000-1250 ℃, the time is 0.5-1.5 h, and the vacuum degree in a vacuum furnace is less than 10 Pa. Controlling the carbonization parameters in the range of the invention can ensure the reaction to be fully carried out and completely convert the coated W particles into WC.
Preferably, in the steps (1), (2) and (3), a planetary ball mill is adopted for uniform mixing, the ball-material ratio is controlled to be 6: 1-10: 1, the rotating speed is 100-180 r/min, the ball milling time is 12-30 h, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniform mixing, the mixed materials are put into a vacuum drying oven to be dried for 6-8 h at the temperature of 75-85 ℃, and the dried mixed materials are subjected to subsequent treatment. The mixing is carried out by adopting a planetary ball mill, and the mixing parameters are controlled within the range of the invention, so that the powder can be uniformly mixed, the special core-shell structure for coating the powder is not damaged, and the comprehensive performance of the TiN-based metal ceramic is prevented from being influenced.
In the preparation method, preferably, in the step (3), the pressure for pressing the blank is 150-200 Mpa; degreasing is carried out in a hydrogen tube furnace, the temperature rise rate is controlled to be 1-3 ℃/min, the degreasing temperature is controlled to be 400-500 ℃, and the heat preservation time is 40-120 min.
In the above preparation method, preferably, in the step (3), the sintering is vacuum sintering or air pressure sintering; the vacuum sintering is controlled to have the heating rate of 4-5 ℃/min, the sintering temperature of 1450-1550 ℃, the heat preservation time of 1-2 h and the vacuum degree of 10-20 Pa; the temperature rising rate of the air pressure sintering is controlled to be 5 ℃/min, the sintering temperature is 1450-1550 ℃, the heat preservation time is 1-2 h, the sintering atmosphere is argon, and the sintering air pressure is 3-20 MPa. The method adopts a liquid phase sintering mode, the sintering process is a process of carrying out particle rearrangement and dissolution and re-precipitation on ceramic particles by using a metal liquid phase, and the compactness and the comprehensive performance of the composite material can be improved.
In the above preparation method, preferably, in the step (1), the TiN powder has a particle size of 5-20 μm, and WO is3The particle size of the powder is 1-5 mu m; in the step (2), the particle size of the carbon powder is 500 nm-3 μm; in the step (3), the metal additive is nickel powder and/or cobalt powder, the particle size of the nickel powder is 1-5 μm, and the particle size of the cobalt powder is 1-5 μm. The metal additive is selected from nickel powder and cobalt powder, mainly because the metal nickel and cobalt are cheap and easy to obtain, and have good wettability with WC, and the metal additive is easy to compact and improve the comprehensive performance of the metal ceramic after subsequent sintering.
The present invention also provides, as a general inventive concept, a high-performance TiN-based cermet prepared according to the above-described preparation method. The TiN-based cermet has a core-shell structure, WC is coated on the surfaces of TiN particles, and the WC coated TiN particles are uniformly distributed in a three-dimensional network structure formed by a metal phase; the shell phase is a complex solid solution (Ti, W) (C, N) due to solid phase diffusion and dissolution precipitation of the WC phase during sintering. The core-shell structure of the invention can not only improve the wettability, but also inhibit the crystal grains from growing, the thickness of the shell phase can not be too thick or too thin, and the obtained TiN-based cermet has excellent comprehensive performance.
Compared with the prior art, the invention has the advantages that:
(1) according to the preparation method, WC is coated on the surface of TiN, so that a transition layer WC with better toughness is generated between TiN and Ni/Co, and meanwhile, the characteristics of good wettability and easy sintering of liquid phase sintering metal are utilized, so that the wettability between TiN and Ni/Co metal is improved, the compactness of the material is improved, and the TiN-based metal ceramic with excellent comprehensive performance is prepared.
(2) The preparation method disclosed by the invention is simple to operate, low in process cost and suitable for large-scale production.
(3) The TiN-based cermet material has the characteristics that the TiN matrix is uniformly distributed in the Ni and Co composite metal phase, the density is high, the hardness is high, the bending resistance is excellent, the fracture toughness is good, the friction coefficient is low, the wear resistance is good, the oxidation resistance and the corrosion resistance are excellent, the TiN-based cermet material also has a very good gold-replacing decorative effect, can be widely applied to the fields of cutter materials, wear-resistant materials, bearing materials, mold materials and the like, and has very wide market prospects.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM photograph of a TiN-based cermet in example 1 of the present invention;
FIG. 2 is an SEM photograph of a TiN-based cermet in example 2 of the present invention;
FIG. 3 is an SEM photograph of a TiN-based cermet in example 3 of the present invention;
FIG. 4 is an SEM photograph of a TiN-based cermet in example 4 of the present invention;
FIG. 5 is an SEM photograph of a TiN-based cermet in example 5 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the preparation method of the high-performance TiN-based metal ceramic comprises the following steps:
(1) taking TiN powder with average grain size of 5 μm and WO powder with average grain size of 3 μm3Carrying out wet grinding and uniform mixing on the powder in a planetary ball mill according to the mass ratio of 10:1, controlling the ball-material ratio to be 8:1, the rotating speed to be 130r/min, the ball milling time to be 12h, wherein the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, putting the dried mixed powder into a hydrogen furnace, introducing water hydrogen with the dew point of-30 ℃, heating to 800 ℃ for reaction for 60min, and obtaining W-coated TiN composite powder;
(2) mixing the W-coated TiN composite powder obtained in the step (1) and carbon powder with the particle size of 1 mu m according to the mass ratio of 20:1, carrying out wet grinding and uniform mixing in a planetary ball mill, and controlling the ball material ratio to be 8:1, the rotating speed is 130r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, then putting the dried mixed powder into a vacuum furnace for carbonization, wherein the carbonization temperature is 1000 ℃, the carbonization time is 1h, and the vacuum degree in the vacuum furnace is less than 10Pa, so as to obtain WC coated TiN composite powder;
(3) carrying out wet grinding and uniformly mixing on WC-coated TiN composite powder, a metal additive and a forming agent (the mass ratio of the WC-coated TiN composite powder to the metal additive to the forming agent is 70: 30: 2, wherein the metal additive is Ni powder and Co powder, the mass ratio of the Ni powder to the Co powder is 2: 1, the particle size of the Ni powder is 2 microns, and the particle size of the Co powder is 1 micron) in a planet ball mill, and controlling the ball-material ratio to be 8:1, the rotating speed is 130r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniform mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, then sieving the dried mixed powder, pressing into a blank at 200MPa, putting the blank into a hydrogen furnace for degreasing, controlling the heating rate to be 2 ℃/min, heating to 500 ℃ for degreasing for 2h, performing vacuum sintering in the vacuum furnace after degreasing, controlling the heating rate to be 5 ℃/min, the sintering temperature to be 1480 ℃, the heat preservation time to be 1h, the vacuum degree to be 10Pa, and cooling along with the furnace after sintering to obtain the TiN-based metal ceramic.
As shown in fig. 1, the SEM photograph of the TiN-based cermet of this example shows that the metal phase forms a three-dimensional network structure, and WC-coated TiN particles are uniformly distributed in the Ni/Co composite metal phase, so that the TiN-based cermet of this example has a core-shell structure, and the shell phase is a complex solid solution (Ti, W) (C, N) due to solid phase diffusion and dissolution and precipitation of the WC phase during sintering. Through detection, the porosity of the TiN-based cermet prepared in the embodiment is A04B00, the hardness is 88HRA, the bending strength is 2320MPa, and the fracture toughness is 15.6MPam1/2(ii) a Under the condition of dry grinding in a ring block type friction and wear test, the friction coefficient of the material is measured to be 0.396 by being paired with YG10 hard alloy, and the wear rate is measured to be 2.77x 10-7mm3/mm。
Example 2:
the preparation method of the high-performance TiN-based metal ceramic comprises the following steps:
(1) taking TiN powder with average grain size of 5 μm and WO powder with average grain size of 3 μm3Carrying out wet grinding and uniform mixing on the powder in a planetary ball mill according to the mass ratio of 5:1, and controlling the ball material ratio to be 8:1, the rotating speed is 160r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; mixing, drying at 80 deg.C for 6hr, and adding hydrogen into the dried powderIntroducing water hydrogen with dew point of-30 ℃ into a gas furnace, raising the temperature to 800 ℃ for reaction for 60min to obtain W-coated TiN composite powder;
(2) carrying out wet grinding and mixing on the W-coated TiN composite powder obtained in the step (1) and carbon powder with the particle size of 1 mu m in a planetary ball mill according to the mass ratio of 20:1, and controlling the ball material ratio to be 8:1, the rotating speed is 130r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, then putting the dried mixed powder into a vacuum furnace for carbonization, wherein the carbonization temperature is 1000 ℃, the carbonization time is 1h, and the vacuum degree in the vacuum furnace is less than 10Pa, so as to obtain WC coated TiN composite powder;
(3) carrying out wet grinding and uniformly mixing on WC-coated TiN composite powder, a metal additive and a forming agent (the mass ratio of the WC-coated TiN composite powder to the metal additive to the forming agent is 80: 20: 2, wherein the metal additive is Ni powder and Co powder, the mass ratio of the Ni powder to the Co powder is 1: 1, the particle size of the Ni powder is 2 microns, and the particle size of the Co powder is 1 micron) in a planet ball mill, and controlling the ball-material ratio to be 8:1, the rotating speed is 130r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniform mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, then sieving the dried mixed powder, pressing into a blank at 200MPa, putting the blank into a hydrogen furnace for degreasing, controlling the heating rate to be 2 ℃/min, heating to 500 ℃ for degreasing for 2h, performing vacuum sintering in the vacuum furnace after degreasing, controlling the heating rate to be 5 ℃/min, the sintering temperature to be 1480 ℃, the heat preservation time to be 1h, the vacuum degree to be 10Pa, and cooling along with the furnace after sintering to obtain the TiN-based metal ceramic.
As shown in fig. 2, the SEM photograph of the TiN-based cermet of this example shows that the metal phase forms a three-dimensional network structure, and WC-coated TiN particles are uniformly distributed in the Ni/Co composite metal phase, so that the TiN-based cermet of this example has a core-shell structure, and the shell phase is a complex solid solution (Ti, W) (C, N) due to solid phase diffusion and dissolution and precipitation of the WC phase during sintering. The TiN-based cermet prepared in the present example was found to have a porosity of A04B00, a hardness of 91HRA,the bending strength is 2020MPa, and the fracture toughness is 13.6MPam1/2(ii) a Under the condition of dry grinding in a ring block type friction and wear test, the friction coefficient of the material is measured to be 0.402 and the wear rate is measured to be 0.86x 10 by being paired with YG10 hard alloy-7mm3/mm。
Example 3:
the preparation method of the high-performance TiN-based metal ceramic comprises the following steps:
(1) taking TiN powder with average grain size of 5 μm and WO powder with average grain size of 3 μm3Carrying out wet grinding and uniform mixing on the powder in a planetary ball mill according to the mass ratio of 10:1, and controlling the ball material ratio to be 8:1, the rotating speed is 130r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, putting the dried mixed powder into a hydrogen furnace, introducing water hydrogen with the dew point of-30 ℃, heating to 800 ℃ for reaction for 60min, and obtaining W-coated TiN composite powder;
(2) carrying out wet grinding and mixing on the W-coated TiN composite powder obtained in the step (1) and carbon powder with the particle size of 1 mu m in a planetary ball mill according to the mass ratio of 20:1, and controlling the ball material ratio to be 8:1, the rotating speed is 140r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at the temperature of 80 ℃, then putting the dried mixed powder into a vacuum furnace for carbonization at the temperature of 1100 ℃ for 1h, wherein the vacuum degree in the vacuum furnace is less than 10Pa, and obtaining WC coated TiN composite powder;
(3) carrying out wet grinding and mixing on WC-coated TiN composite powder, a metal additive and a forming agent (the mass ratio of the WC-coated TiN composite powder to the metal additive to the forming agent is 70: 30: 2, wherein the metal additive is Ni powder and Co powder, the mass ratio of the Ni powder to the Co powder is 1: 2, the particle size of the Ni powder is 2 mu m, and the particle size of the Co powder is 1 mu m) in a planetary ball mill uniformly, controlling the ball-material ratio to be 8:1, the rotating speed to be 130r/min, the ball milling time to be 12h, using absolute ethyl alcohol as a ball milling medium, and using paraffin as the forming agent; after uniform mixing, the mixed materials are put into a vacuum drying oven to be dried for 6h at the temperature of 80 ℃, then the dried mixed powder is sieved and pressed into a blank at the pressure of 200MPa, the blank is placed in a hydrogen furnace to be degreased, the temperature rise rate is controlled to be 2 ℃/min, the temperature rise is controlled to be 500 ℃ to be degreased for 2h, vacuum sintering is carried out in the vacuum furnace after degreasing, the temperature rise rate is controlled to be 5 ℃/min, the sintering temperature is 1500 ℃, the heat preservation time is 1h, the vacuum degree is 10Pa, and the TiN-based metal ceramic is obtained after sintering and furnace cooling.
As shown in fig. 3, the SEM photograph of the TiN-based cermet of this example shows that the metal phase forms a three-dimensional network structure, and WC-coated TiN particles are uniformly distributed in the Ni/Co composite metal phase, so that the TiN-based cermet of this example has a core-shell structure, and the shell phase is a complex solid solution (Ti, W) (C, N) due to solid phase diffusion and dissolution and precipitation of the WC phase during sintering. Through detection, the TiN-based cermet prepared in the embodiment has the porosity of A04B00, the hardness of 89HRA, the bending strength of 2620MPa and the fracture toughness of 19.6MPam1/2(ii) a Under the condition of dry grinding in a ring block type friction and wear test, the friction coefficient of the material is measured to be 0.462 by being paired with YG10 hard alloy, and the wear rate is measured to be 2.06x 10-7mm3/mm。
Example 4:
the preparation method of the high-performance TiN-based metal ceramic comprises the following steps:
(1) taking TiN powder with average grain size of 10 μm and WO with average grain size of 3 μm3Carrying out wet grinding and uniform mixing on the powder in a planetary ball mill according to the mass ratio of 15:1, and controlling the ball material ratio to be 8:1, the rotating speed is 160r/min, the ball milling time is 16h, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, putting the dried mixed powder into a hydrogen furnace, introducing water hydrogen with the dew point of-30 ℃, heating to 800 ℃ for reaction for 60min, and obtaining W-coated TiN composite powder;
(2) carrying out wet grinding and mixing on the W-coated TiN composite powder obtained in the step (1) and carbon powder with the particle size of 1 mu m in a planetary ball mill according to the mass ratio of 15:1, and controlling the ball material ratio to be 8:1, the rotating speed is 130r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at the temperature of 80 ℃, then putting the dried mixed powder into a vacuum furnace for carbonization at the temperature of 1100 ℃ for 1h, wherein the vacuum degree in the vacuum furnace is less than 10Pa, and obtaining WC coated TiN composite powder;
(3) carrying out wet grinding and uniformly mixing on WC-coated TiN composite powder, a metal additive and a forming agent (the mass ratio of the WC-coated TiN composite powder to the metal additive to the forming agent is 80: 20: 2, wherein the metal additive is Ni powder and Co powder, the mass ratio of the Ni powder to the Co powder is 1: 1, the particle size of the Ni powder is 2 microns, and the particle size of the Co powder is 1 micron) in a planet ball mill, and controlling the ball-material ratio to be 8:1, the rotating speed is 130r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniform mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, then sieving the dried mixed powder, pressing into a blank at 200MPa, putting the blank into a hydrogen furnace for degreasing, controlling the heating rate to be 2 ℃/min, heating to 500 ℃ for degreasing for 2h, performing vacuum sintering in the vacuum furnace after degreasing, controlling the heating rate to be 5 ℃/min, the sintering temperature to be 1480 ℃, the heat preservation time to be 1h, the vacuum degree to be 10Pa, and cooling along with the furnace after sintering to obtain the TiN-based metal ceramic.
The SEM photograph of the TiN-based cermet of this example is shown in fig. 4, which shows that the metal phase forms a three-dimensional network structure, and the WC-coated TiN particles are uniformly distributed in the Ni/Co composite metal phase, and thus the TiN-based cermet of this example has a core-shell structure, and the shell phase is a complex solid solution (Ti, W) (C, N) due to solid phase diffusion and dissolution precipitation of the WC phase during sintering; in the embodiment, the content of WC is relatively high, the content of the metal phase is relatively low, the growth of crystal grains can be well inhibited, and the crystal grains are obviously refined. Through detection, the porosity of the TiN-based cermet prepared in the embodiment is A04B00, the hardness is 90HRA, the bending strength is 2220MPa, and the fracture toughness is 17.6MPam1/2(ii) a Under the condition of dry grinding in a ring block type friction and wear test, the friction coefficient of the material is measured to be 0.426 and the wear rate is measured to be 1.37x 10 by being paired with YG10 hard alloy-7mm3/mm。
Example 5:
the preparation method of the high-performance TiN-based metal ceramic comprises the following steps:
(1) taking TiN powder with average grain size of 10 μm and WO with average grain size of 3 μm3Carrying out wet grinding and uniform mixing on the powder in a planetary ball mill according to the mass ratio of 10:1, and controlling the ball material ratio to be 8:1, the rotating speed is 160r/min, the ball milling time is 16h, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at 80 ℃, putting the dried mixed powder into a hydrogen furnace, introducing water hydrogen with the dew point of-30 ℃, heating to 800 ℃ for reaction for 60min, and obtaining W-coated TiN composite powder;
(2) carrying out wet grinding and mixing on the W-coated TiN composite powder obtained in the step (1) and carbon powder with the particle size of 1 mu m in a planetary ball mill according to the mass ratio of 15:1, and controlling the ball material ratio to be 8:1, the rotating speed is 150r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniformly mixing, putting the mixed material into a vacuum drying oven, drying for 6h at the temperature of 80 ℃, then putting the dried mixed powder into a vacuum furnace for carbonization at the temperature of 1100 ℃ for 1h, wherein the vacuum degree in the vacuum furnace is less than 10Pa, and obtaining WC coated TiN composite powder;
(3) carrying out wet grinding and uniformly mixing on WC-coated TiN composite powder, a metal additive and a forming agent (the mass ratio of the WC-coated TiN composite powder to the metal additive to the forming agent is 80: 20: 2, wherein the metal additive is Ni powder and Co powder, the mass ratio of the Ni powder to the Co powder is 1: 1, the particle size of the Ni powder is 2 microns, and the particle size of the Co powder is 1 micron) in a planet ball mill, and controlling the ball-material ratio to be 8:1, the rotating speed is 150r/min, the ball milling time is 12 hours, the ball milling medium is absolute ethyl alcohol, and the forming agent is paraffin; after uniform mixing, the mixed materials are placed into a vacuum drying oven to be dried for 6h at the temperature of 80 ℃, then the dried mixed powder is sieved and pressed into a blank at the pressure of 200MPa, the blank is placed into a hydrogen furnace to be degreased, the heating rate is controlled to be 2 ℃/min, the temperature is raised to 500 ℃ to be degreased for 2h, after degreasing, the blank is sintered at the pressure in an air pressure furnace, the atmosphere is argon, the heating rate is controlled to be 5 ℃/min, the sintering temperature is 1490 ℃, the heat preservation time is 1h, the sintering pressure is 5MPa, and after sintering, the TiN-based metal ceramic is obtained by furnace cooling.
As shown in fig. 5, it can be seen that the metal phase forms a three-dimensional network structure, and the WC-coated TiN particles are uniformly distributed in the Ni/Co composite metal phase, so that the TiN-based cermet of this example has a core-shell structure, and the WC phase is subjected to solid phase diffusion and dissolution during sintering, and the shell phase is a complex solid solution (Ti, W) (C, N); the TiN-based cermet of the present example has fine crystal grains. Through detection, the TiN-based cermet prepared in the embodiment has the porosity of A04B00, the hardness of 90.6HRA, the bending strength of 2680MPa and the fracture toughness of 18.6MPam1/2(ii) a Under the condition of dry grinding in a ring block type friction and wear test, the friction coefficient of the material is measured to be 0.401 and the wear rate is measured to be 1.24x 10 by being paired with YG10 hard alloy-7mm3/mm。

Claims (10)

1. A preparation method of high-performance TiN-based metal ceramic is characterized by comprising the following steps:
(1) mixing TiN powder with WO3Mixing the powder evenly, TiN powder and WO3The mass ratio of the powder is 20: 1-5: 1, then the powder is placed into a hydrogen furnace, water and hydrogen are introduced, and the reaction is carried out after the temperature is raised to obtain W-coated TiN composite powder;
(2) uniformly mixing the W-coated TiN composite powder obtained in the step (1) with carbon powder, and then putting the mixture into a vacuum furnace for carbonization to obtain WC-coated TiN composite powder;
(3) uniformly mixing the WC coated TiN composite powder obtained in the step (2), the metal additive and the forming agent, then sequentially sieving, pressing into a blank, degreasing, sintering, and cooling along with a furnace to obtain TiN-based metal ceramic; the forming agent is paraffin, the metal additive is nickel powder and/or cobalt powder, the particle size of the nickel powder is 1-5 mu m, and the particle size of the cobalt powder is 1-5 mu m.
2. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the W-coated TiN composite powder to the carbon powder is 20: 1-15: 1; in the step (3), the mass ratio of the WC-coated TiN composite powder to the metal additive to the molding agent is that the WC-coated TiN composite powder: metal additive: molding agent = (60-90): (10-40): (1-3).
3. The production method according to claim 1 or 2, wherein the dew point of the aqueous hydrogen gas in the step (1) is-25 ℃ to-30 ℃.
4. The method according to claim 1 or 2, wherein in the step (1), the temperature is raised to 800-1000 ℃ and the reaction time is 1-2 h.
5. The preparation method according to claim 1 or 2, characterized in that in the step (2), the carbonization temperature is controlled to be 1000-1250 ℃, the carbonization time is 0.5-1.5 h, and the vacuum degree in a vacuum furnace is less than 10 Pa.
6. The preparation method according to claim 1 or 2, characterized in that in the steps (1), (2) and (3), a planetary ball mill is adopted for mixing uniformly, the ball-material ratio is controlled to be 6: 1-10: 1, the rotating speed is 100-180 r/min, the ball milling time is 12-30 h, and the ball milling medium is absolute ethyl alcohol; after uniform mixing, the mixed materials are put into a vacuum drying oven to be dried for 6-8 h at the temperature of 75-85 ℃, and the dried mixed materials are subjected to subsequent treatment.
7. The production method according to claim 1 or 2, wherein in the step (3), the pressure for pressing the green body is 150 to 200 Mpa; degreasing is carried out in a hydrogen tube furnace, the temperature rise rate is controlled to be 1-3 ℃/min, the degreasing temperature is controlled to be 400-500 ℃, and the heat preservation time is 40-120 min.
8. The production method according to claim 1 or 2, wherein in the step (3), the sintering is vacuum sintering or air pressure sintering; the vacuum sintering is controlled to have the heating rate of 4-5 ℃/min, the sintering temperature of 1450-1550 ℃, the heat preservation time of 1-2 h and the vacuum degree of 10-20 Pa; the temperature rising rate of the air pressure sintering is controlled to be 5 ℃/min, the sintering temperature is 1450-1550 ℃, the heat preservation time is 1-2 h, the sintering atmosphere is argon, and the sintering air pressure is 3-20 MPa.
9. The production method according to claim 1 or 2, wherein in the step (1), the TiN powder has a particle size of 5 to 20 μm, WO3The particle size of the powder is 1-5 mu m; in the step (2), the particle size of the carbon powder is 500 nm-3 μm.
10. A high-performance TiN-based cermet prepared by the preparation method according to any one of claims 1 to 9.
CN201910094134.7A 2019-01-30 2019-01-30 High-performance TiN-based metal ceramic and preparation method thereof Active CN109676127B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910094134.7A CN109676127B (en) 2019-01-30 2019-01-30 High-performance TiN-based metal ceramic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910094134.7A CN109676127B (en) 2019-01-30 2019-01-30 High-performance TiN-based metal ceramic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109676127A CN109676127A (en) 2019-04-26
CN109676127B true CN109676127B (en) 2020-07-17

Family

ID=66195274

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910094134.7A Active CN109676127B (en) 2019-01-30 2019-01-30 High-performance TiN-based metal ceramic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109676127B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6042164B2 (en) * 1982-08-04 1985-09-20 日立金属株式会社 Powder manufacturing method
US20070152195A1 (en) * 2005-12-30 2007-07-05 Saint-Gobain Performance Plastics Corporation Electrostatic dissipative composite material
WO2008055496A1 (en) * 2006-11-10 2008-05-15 Dritte Patentportfolio Beteiligungsgesellschaft Mbh & Co. Kg Method for the production of thin layers of metal-ceramic composite materials
CN104846258B (en) * 2015-05-29 2016-08-31 攀枝花学院 The preparation method of iron-based (V, Ti) CN composite granule
CN105385929A (en) * 2015-11-05 2016-03-09 安徽银球轴承有限公司 Self-lubricating metal ceramic bearing good in abrasion resistance and preparing method of self-lubricating metal ceramic bearing
CN105603235B (en) * 2016-01-28 2017-09-01 河南科技大学 A kind of wear-resisting tungsten alloy and preparation method thereof
CN106222511A (en) * 2016-08-22 2016-12-14 合肥东方节能科技股份有限公司 A kind of method of sintering cemented carbide molding guide wheel based on high-energy ball milling method
CN107552802B (en) * 2017-09-26 2021-04-02 中南大学 Titanium carbonitride-based solid solution powder for metal ceramics and preparation method thereof

Also Published As

Publication number Publication date
CN109676127A (en) 2019-04-26

Similar Documents

Publication Publication Date Title
CN106424713B (en) A kind of copper carbon composite and preparation method thereof
CN109161774A (en) Haystellite and preparation method thereof by high-entropy alloy as binder
CN103920887B (en) A kind of method preparing WC-Co powder used for hot spraying
CN108642361B (en) High-strength high-hardness ceramic material and production process thereof
CN108149183B (en) Hard alloy with surface hardness in gradient distribution and preparation method thereof
CN109970464B (en) Preparation method of porous metal oxide
CN101186981A (en) High-intensity high-tenacity super fine crystal WC-10Co hard alloy preparation method
CN112063905B (en) High-performance WC-WCoB-Co complex phase hard alloy and preparation method thereof
CN110819842A (en) Preparation method of formed part based on reduced graphene oxide and copper composite material
CN112813397A (en) Preparation method of molybdenum-sodium alloy plate-shaped target material
CN105198501A (en) Preparation method of carbon/carbon composite material surface metal tungsten gradient coating
CN113122747A (en) Cu- (WC-Y) with excellent mechanical property2O3) Method for preparing composite material
CN106566972B (en) The preparation method of plate-like shape WC grains hard alloy with gradient-structure
CN109053191B (en) Titanium carbonitride based cermet without binder phase and preparation method thereof
CN100522424C (en) Method for preparing superfine carbonyl iron powder in use for high performance magnetic powder core
CN109676127B (en) High-performance TiN-based metal ceramic and preparation method thereof
CN109231990A (en) A kind of preparation method of tungsten carbide-diamond composite
CN108165791B (en) Preparation method of binderless superfine tungsten carbide hard alloy
CN107199346B (en) A kind of industrialized process for preparing of nanometer of W/WC composite powder
CN110527891B (en) Low-cobalt hard alloy surface diamond coating and preparation method thereof
CN101613813A (en) A kind of preparation method of porous iron-based composite powder material
JP2010500477A (en) Mixed powder containing solid solution powder and sintered body using the same, mixed cermet powder containing solid solution powder, cermet using the same, and method for producing them
CN110343899B (en) Double-size hard particle reinforced copper-based composite material and preparation method thereof
CN110405207B (en) Method for preparing graphene reinforced titanium-based composite material by PE-CVD assisted SPS sintering
CN110923493B (en) Preparation process of hole structure SiC/Al composite material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant