CN118048568A - Nonmagnetic (Ti, W) C-based metal ceramic and preparation method thereof - Google Patents
Nonmagnetic (Ti, W) C-based metal ceramic and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 17
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Abstract
The invention discloses nonmagnetic (Ti, W) C-based metal ceramic and a preparation method thereof, and relates to the technical field of powder metallurgy, wherein the nonmagnetic (Ti, W) C-based metal ceramic comprises the following components: a binder comprising a Co xCryNiz alloy, wherein x is (0.2-1), y is (0.8-1), and z is (0.2-1), and a matrix material comprising a (Ti, W) C-based ceramic powder. The invention takes Co xCryNiz alloy as a binder to provide toughness and plasticity, takes (Ti, W) C-based ceramic material as a matrix material to provide hardness and strength, and utilizes antiferromagnetic element Cr in Co xCryNiz alloy to weaken the magnetism of the metal ceramic, paramagnetic elements Ti and W in the (Ti, W) C-based ceramic to further weaken the magnetism of the metal ceramic, so that the prepared (Ti, W) C-based metal ceramic has no magnetism and good mechanical property.
Description
Technical Field
The invention relates to the field of powder metallurgy, in particular to nonmagnetic (Ti, W) C-based metal ceramic and a preparation method thereof.
Background
With the continuous progress of science and technology, there is an increasing demand for high-performance, multifunctional cermet materials. Traditional metal ceramic materials are often limited by magnetism, and medium entropy alloy is used as a novel material, and the unique atomic structure and the multi-element composition of the novel material are the focus of attention in the current material research field.
The (Ti, W) C multiple carbide is a solid solution of WC dissolved in TiC, i.e. TiC-WC multiple carbide. The (Ti, W) C-based cermet material is a novel cermet found on the basis of WC-Co cemented carbide and TiC-Ni-based cermet, and is a composite material which usually takes (Ti, W) C as a hard phase, simultaneously adds refractory metal carbide or nitride such as WC, taC and the like, and takes cobalt, nickel and the like as a binder. (Ti, W) C-based cermets are a class of materials that find wide application in the fields of cutting tools and wear resistance, and have excellent hardness, wear resistance and high temperature stability. However, conventional (Ti, W) C-based cermet materials are ferromagnetic, which limits their application in the electronics industry, magnetic material processing, etc.
Disclosure of Invention
The invention mainly aims to provide nonmagnetic (Ti, W) C-based metal ceramic and a preparation method thereof, and aims to solve the problem that the (Ti, W) C-based metal ceramic material in the prior art is ferromagnetic.
To achieve the above object, the present invention provides a non-magnetic (Ti, W) C-based cermet including:
A binder comprising a Co xCryNiz alloy, wherein x is (0.2-1), y is (0.8-1), and z is (0.2-1); and
A matrix material comprising a (Ti, W) C-based ceramic powder.
Optionally, the matrix material further comprises an adjuvant comprising at least one of Mo, tiC, tiN.
Optionally, the mass fraction of the adjuvant is 0-20 wt.%.
Optionally, the mass ratio of the binder to the matrix material is 3 (4.5-12).
Optionally, in the Co xCryNiz alloy, x is 1, y is 1, and z is 1.
The invention also provides a preparation method of the nonmagnetic (Ti, W) C-based metal ceramic, which comprises the following steps:
Mixing Co xCryNiz alloy and (Ti, W) C-based ceramic powder to obtain a metal ceramic mixture, and wet-milling the metal ceramic mixture to obtain a metal ceramic prefabricated material;
drying, sieving and pressing the metal ceramic prefabricated material to obtain a pressed blank of the metal ceramic prefabricated material;
And (3) carrying out vacuum sintering and cooling on the pressed compact of the metal ceramic preform to obtain the nonmagnetic (Ti, W) C-based metal ceramic.
Optionally, in wet milling the cermet mixture, the wet milling method includes placing the cermet mixture in a planetary ball mill for wet ball milling, wherein:
The rotating speed of ball milling is 180-225 r/min; and/or the number of the groups of groups,
The ball milling time is 24-72 hours; and/or the number of the groups of groups,
The ball milling medium comprises absolute ethyl alcohol.
Optionally, in the process of drying, sieving and pressing the metal ceramic prefabricated material, the drying mode comprises drying in a vacuum drying oven, wherein the drying temperature is 80-90 ℃; and/or the number of the groups of groups,
The number of the screened screen meshes is 100-200 meshes; and/or the number of the groups of groups,
The pressing pressure is 300-400 MPa.
Optionally, in vacuum sintering the green compact of the cermet preform, the vacuum sintering is performed by placing the green compact in a tube furnace, wherein:
the sintering temperature is 1400-1450 ℃; and/or the number of the groups of groups,
The degree of vacuum for sintering was 10 -1～10-4 Pa.
Optionally, before mixing the Co xCryNiz alloy and the (Ti, W) C-based ceramic powder, ball milling Co, cr and Ni powder is carried out, wherein the ball milling mode comprises the steps of placing the Co, cr and Ni powder into a ball milling tank for ball milling, and the method comprises the steps of:
the rotation speed of ball milling is 300-350 r/min; and/or the number of the groups of groups,
The ball milling time is 24-96 h.
The beneficial effects of the invention are as follows:
The Co xCryNiz alloy is selected as a binder to provide toughness and plasticity, the (Ti, W) C-based ceramic material is selected as a matrix material to provide hardness and strength, and meanwhile, the antiferromagnetic element Cr in the Co xCryNiz alloy is utilized to weaken the magnetism of the metal ceramic, and the paramagnetic elements Ti and W in the (Ti, W) C-based ceramic further weaken the magnetism of the metal ceramic, so that the (Ti, W) C-based metal ceramic prepared by the Co xCryNiz alloy and the (Ti, W) C-based ceramic has excellent non-magnetism and good mechanical property.
Drawings
FIG. 1 is a hysteresis loop diagram of a nonmagnetic (Ti, W) C-based cermet of example 4 of the present invention;
FIG. 2 is a hysteresis loop diagram of nonmagnetic (Ti, W) C-based cermet of example 5 of the present invention;
FIG. 3 is a diagram of the microscopic morphology of the nonmagnetic (Ti, W) C-based cermet of example 4 of the present invention;
FIG. 4 is a graph of the microscopic morphology of the nonmagnetic (Ti, W) C-based cermet of example 5 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
With the continuous progress of science and technology, there is an increasing demand for high-performance, multifunctional cermet materials. Traditional metal ceramic materials are often limited by magnetism, and medium entropy alloy is used as a novel material, and the unique atomic structure and the multi-element composition of the novel material are the focus of attention in the current material research field.
The (Ti, W) C multiple carbide is a solid solution of WC dissolved in TiC, i.e. TiC-WC multiple carbide. The (Ti, W) C-based cermet material is a novel cermet found on the basis of WC-Co cemented carbide and TiC-Ni-based cermet, and is a composite material which usually takes (Ti, W) C as a hard phase, simultaneously adds refractory metal carbide or nitride such as WC, taC and the like, and takes cobalt, nickel and the like as a binder. (Ti, W) C-based cermets are a class of materials that find wide application in the fields of cutting tools and wear resistance, and have excellent hardness, wear resistance and high temperature stability. However, conventional (Ti, W) C-based cermet materials are ferromagnetic, which limits their application in the electronics industry, magnetic material processing, etc.
In view of this, the present invention provides a non-magnetic (Ti, W) C-based cermet comprising:
A binder comprising a Co xCryNiz alloy, wherein x is (0.2-1), y is (0.8-1), and z is (0.2-1); and
A matrix material comprising a (Ti, W) C-based ceramic powder.
In the technical scheme of the invention, the Co xCryNiz alloy is in a liquid phase in the high-temperature process, is filled into (Ti, W) C, and bonds (Ti, W) C ceramic particles to form (Ti, W) C-based cermet. Wherein Co xCryNiz alloy is added as a binder to provide toughness and plasticity, and meanwhile, an antiferromagnetic element Cr is provided. The addition of (Ti, W) C-based ceramic powder provides strength and hardness for the matrix material, and simultaneously provides paramagnetic elements Ti and W, and the elements Cr, ti and W can weaken the magnetism of the material. In some embodiments of the invention, the Dv50 particle size of the (Ti, W) C powder is 1-5 μm. The (Ti, W) C-based metal ceramic prepared by Co xCryNiz alloy and (Ti, W) C-based ceramic powder has uniform tissue distribution, excellent nonmagnetic property and good mechanical property, and can be used in the fields of nonmagnetic dies, magnetic material workpiece processing and the like.
In any embodiment of the invention, the matrix material further comprises an auxiliary agent comprising at least one of Mo, tiC, tiN, wherein the Dv50 particle size of TiC is 10-50 nm and the Dv50 particle size of tin is 10-50 nm.
The adjuvant includes at least one of Mo, tiC, tiN. That is, the auxiliary agent may include any one of Mo, tiC, tiN or two or more kinds of Mo, tiC, tiN, and all of them are within the scope of the present invention. In the technical scheme of the invention, the introduction of a proper amount of Mo can improve the hardness of the metal ceramic and further weaken the magnetism; the introduction of nano TiC and TiN can improve the hardness of the metal ceramic.
In any embodiment of the invention, the mass fraction of the adjuvant is 0 to 20wt.%. The auxiliary agent can influence the tissue structure of the metal ceramic material, and the mass fraction of the auxiliary agent is set to be 0-20 wt.%, which is beneficial to the homogenization of the metal ceramic tissue, the improvement of the hardness of the material and the non-magnetization.
In any embodiment of the present invention, the mass ratio of the binder to the base material is 3 (4.5 to 12). The mass ratio of the binder to the matrix material is 3 (4.5-12), which is favorable for obtaining nonmagnetic (Ti, W) C-based metal ceramic with uniform tissue distribution and good comprehensive performance.
In any embodiment of the present invention, in the Co xCryNiz alloy, x is 1, y is 1, and z is 1. In the Co xCryNiz alloy, co and Ni are ferromagnetic elements, cr is an antiferromagnetic element, and the cermet is rendered nonmagnetic by the presence of a large amount of the antiferromagnetic element Cr. CoCrNi alloy is a typical representation of the Co xCryNiz alloy system, has a single stable face-centered cubic structure, and exhibits excellent fracture toughness at room temperature and low temperature. In some embodiments of the present invention, coCrNi alloys are selected as binders, and the resulting (Ti, W) C-based cermet materials have good toughness and non-magnetic properties.
The invention also provides a preparation method of the nonmagnetic (Ti, W) C-based metal ceramic, which comprises the following steps:
Mixing Co xCryNiz alloy and (Ti, W) C-based ceramic powder to obtain a metal ceramic mixture, and wet-milling the metal ceramic mixture to obtain a metal ceramic prefabricated material;
drying, sieving and pressing the metal ceramic prefabricated material to obtain a pressed blank of the metal ceramic prefabricated material;
And (3) carrying out vacuum sintering and cooling on the pressed compact of the metal ceramic preform to obtain the nonmagnetic (Ti, W) C-based metal ceramic.
The invention selects Co xCryNiz alloy and (Ti, W) C-based ceramic as adhesive, and takes the (Ti, W) C-based ceramic as matrix material, thus preparing nonmagnetic (Ti, W) C-based cermet with excellent comprehensive mechanical property, overcoming the limitation of the traditional (Ti, W) C-based cermet material in terms of magnetism and meeting the demands of wider fields.
In addition, the invention adopts a planetary ball mill to carry out ball milling, so that Co xCryNiz and (Ti, W) C-based powder are fully mixed, and multiple crushing effects on the powder mixture are realized through severe collision between grinding balls. The vacuum liquid phase high temperature calcination makes the metal ceramic prefabricated material fully react, which is beneficial to the reduction of the magnetism of the metal ceramic material because the total amount of carbon, nitrogen and oxygen in the metal ceramic material is low. In the vacuum sintering process, the binder Co xCryNiz is dissolved into a liquid phase and filled into the gaps of the (Ti, W) C ceramic particles, so that the sintered body structure is uniform. The preparation method of the invention fully inhibits the growth of (Ti, W) C crystal grains, so that the (Ti, W) C-based metal ceramic has uniform structure, realizes densification, remarkably improves the comprehensive performance of the metal ceramic, and the prepared metal ceramic has non-magnetism, good mechanical property and uniform structure.
In any embodiment of the present invention, the step of mixing the Co xCryNiz alloy with the (Ti, W) C-based ceramic powder comprises mixing the Co xCryNiz alloy, the (Ti, W) C-based ceramic powder, and an adjuvant comprising at least one of Mo, tiC, tiN.
In any embodiment of the present invention, in wet milling the cermet mixture, the wet milling mode comprises placing the cermet mixture in a planetary ball mill for wet ball milling, wherein: the rotating speed of ball milling is 180-225 r/min. The rotation speed of the ball milling is in the range, which is favorable for fully mixing Co xCryNiz and (Ti, W) C-based powder and reducing impurity mixing.
In any embodiment of the invention, the ball milling time is 24-72 hours. The ball milling time is in the range, which is favorable for improving the mixing efficiency, avoiding agglomeration among particles and being favorable for sintering.
In any embodiment of the invention, the ball milling medium comprises absolute ethanol. The absolute ethyl alcohol is used, so that ingredients are uniformly mixed, and other impurities are prevented from being introduced into the product by utilizing the ethanol for evaporation.
In any embodiment of the present invention, the ball-to-material ratio is (7 to 10): 1. The ball-to-material ratio is in the range, which is favorable for fully mixing ingredients and the grinding balls collide vigorously so as to fully exert the crushing effect.
In any embodiment of the invention, in the steps of drying, sieving and pressing the metal ceramic prefabricated material, the drying mode comprises drying in a vacuum drying oven, wherein the drying temperature is 80-90 ℃. Within this range, the absolute ethanol may be evaporated, allowing the grinding balls and powder to separate.
In any embodiment of the present invention, the number of screen meshes of the screen is 100 to 200 mesh. The grinding balls are separated from the powder by a 100-200 mesh screen.
In any embodiment of the present invention, the pressing pressure is 300 to 400MPa. The pressing pressure is set within the range, so that local gaps can be reduced, powder is pressed into a compact green body, and the problem of layering of the green body is avoided.
In any embodiment of the present invention, in vacuum sintering the green compact of the cermet preform, the vacuum sintering means comprises vacuum sintering the green compact in a tube furnace, wherein: the sintering temperature is 1400-1450 ℃, the heating rate is controlled to be 3-5 ℃/min, and the cold sweat mode is that cooling is carried out at 5 ℃/min and then cooling is carried out along with the furnace after the sintering process is finished. The vacuum sintering temperature in the range is adopted, so that the (Ti, W) C-based metal ceramic material is free from magnetization and has improved mechanical properties.
In any embodiment of the invention, the vacuum degree of the vacuum sintering is 10 -1～10-4 Pa. The vacuum degree of the vacuum sintering is in the range, which is beneficial to deoxidation.
In any embodiment of the invention, prior to mixing the Co xCryNiz alloy with the (Ti, W) C-based ceramic powder, comprising ball milling the Co, cr, ni powder in a ball milling manner comprising placing the Co, cr, ni powder in a ball milling pot, wherein: the rotating speed of ball milling is 300-350 r/min. In this range, co, cr, ni powders are uniformly mixed, and the introduction of impurities is reduced.
In any embodiment of the invention, the ball milling is carried out in a ball milling tank for 24-96 hours. In this range, the mixing efficiency can be improved, and cold welding problems can be prevented.
In any embodiment of the invention, the ball-to-material ratio during ball milling in a ball milling tank is (10-15): 1. Within this range, the polishing efficiency can be improved.
In any embodiment of the present invention, the Dv50 particle size of the Co, cr and Ni powders is 2 to 60 μm. Within this range, the porosity of the Co xCryNiz alloy is advantageously reduced.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention. In the embodiments of the present invention, coCrNi alloys were chosen as the binder.
Example 1
A nonmagnetic (Ti, W) C-based metal ceramic, a binder is CoCrNi alloy, a matrix material is (Ti, W) C-based ceramic, wherein the mass fraction of CoCrNi is 20%, and the mass fraction of (Ti, W) C-based ceramic is 80%.
Example 2
A non-magnetic (Ti, W) C-based metal ceramic, a binder is CoCrNi alloy, a matrix material is (Ti, W) C-based ceramic, an auxiliary agent is Mo and TiC, wherein the mass fraction of CoCrNi is 30%, the mass fraction of (Ti, W) C-based ceramic is 55%, the mass fraction of Mo is 5%, and the mass fraction of TiC is 10%.
Example 3
A nonmagnetic (Ti, W) C-based metal ceramic, a binder is CoCrNi alloy, a matrix material is (Ti, W) C-based ceramic, wherein the mass fraction of CoCrNi is 40%, and the mass fraction of (Ti, W) C-based ceramic is 60%.
Example 4
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) Proportioning and ball milling: weighing and proportioning CoCrNi alloy powder with the mass fraction of 30% and (Ti, W) C powder with the mass fraction of 70%, placing the mixed powder into a ball milling tank for ultrasonic treatment for 20min, and then placing the mixed powder into a planetary ball mill for wet milling, wherein the technological parameters of the wet milling are as follows: the rotation speed of the ball mill is 200rpm, and the ball-material ratio is 7:1, the ball milling medium is absolute ethyl alcohol.
(2) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven, drying at 80 ℃, and then loading the dried powder into a die for sample pressing under the pressure of 300MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: vacuum degree 10 -1-10-4 Pa, sintering temperature 1400 deg.C, and heat preservation time 60min.
(3) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min and then the cooling is carried out along with the furnace, so as to improve the strength and the plasticity of CoCrNi alloy and improve the interface combination of the alloy and a hard phase, and the nonmagnetic (Ti, W) C-based metal ceramic is prepared after cooling.
Example 5
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) Proportioning and ball milling: weighing and proportioning CoCrNi alloy powder with the mass fraction of 30%, (Ti, W) C powder with the mass fraction of 69% and Mo powder with the mass fraction of 1%, placing the mixed powder into a ball milling tank, carrying out ultrasonic treatment for 20min, and then placing the mixed powder into a planetary ball mill for wet milling, wherein the technological parameters of the wet milling are that the ball-material ratio is 7:1, the rotating speed of the ball mill is 200rpm, and the ball milling medium is absolute ethyl alcohol.
(2) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven, drying at 80 ℃, and then loading the dried powder into a die for sample pressing under the pressure of 300MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: vacuum degree 10 -1-10-4 Pa, sintering temperature 1400 deg.C, and heat preservation time 60min.
(3) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after the cooling.
Example 6
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) Weighing and proportioning CoCrNi alloy powder with the mass fraction of 30%, (Ti, W) C powder with the mass fraction of 68% and Mo powder with the mass fraction of 2%, placing the mixed powder in a ball milling tank for ultrasonic treatment for 20min, and then placing the mixed powder in a planetary ball mill for wet milling, wherein the technological parameters of the wet milling are that the ball-material ratio is 7:1, the rotating speed of the ball mill is 200rpm, and the ball milling medium is absolute ethyl alcohol;
(2) Sintering metal ceramic; and (3) placing the ball-milled slurry into an oven, drying at 80 ℃, and then loading the dried powder into a die for sample pressing under the pressure of 300MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: vacuum degree 10 -1-10-4 Pa, sintering temperature 1400 deg.C, and heat preservation time 60min.
(3) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after the cooling.
Example 7
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) Proportioning and ball milling: weighing and proportioning CoCrNi alloy powder with the mass fraction of 30%, (Ti, W) C powder with the mass fraction of 67% and Mo powder with the mass fraction of 3%, placing the mixed powder into a ball milling tank for ultrasonic treatment for 20min, and then placing the mixed powder into a planetary ball mill for wet milling, wherein the technological parameters of the wet milling are as follows: the ball-material ratio is 7:1, the rotating speed of the ball mill is 200rpm, and the ball milling medium is absolute ethyl alcohol.
(2) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven, drying at 80 ℃, and then loading the dried powder into a die for sample pressing under the pressure of 300MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: vacuum degree 10 -1-10-4 Pa, sintering temperature 1400 deg.C, and heat preservation time 60min.
(3) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after the cooling.
Example 8
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) Proportioning and ball milling: weighing and proportioning CoCrNi alloy powder with the mass fraction of 30%, (Ti, W) C powder with the mass fraction of 66% and Mo powder with the mass fraction of 4%, placing the mixed powder into a ceramic ball milling tank for ultrasonic treatment for 20min, and then placing the mixed powder into a planetary ball mill for wet milling, wherein the technological parameters of the wet milling are as follows: the ball-material ratio is 7:1, the rotating speed of the ball mill is 200rpm, and the ball milling medium is absolute ethyl alcohol.
(2) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven, drying at 80 ℃, and then loading the dried powder into a die for sample pressing under the pressure of 300MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: vacuum degree 10 -1-10-4 Pa, sintering temperature 1400 deg.C, and heat preservation time 60min.
(3) And cooling after sintering, wherein the cooling mode is that the cooling rate is 5 ℃ per minute firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after cooling.
Example 9
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) Proportioning and ball milling: weighing and proportioning CoCrNi% of alloy powder with the mass fraction of 30%, 65% (Ti, W) of C powder and 5% of Mo powder, placing the mixed powder into a ceramic ball milling tank for ultrasonic treatment for 20min, and then placing the mixed powder into a planetary ball mill for wet milling, wherein the wet milling process comprises the following parameters: the ball-material ratio is 7:1, the rotating speed of the ball mill is 200rpm, and the ball milling medium is absolute ethyl alcohol.
(2) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven, drying at the temperature of 85 ℃, and then loading the dried powder into a die for sample pressing under the pressure of 300MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: vacuum degree 10 -1-10-4 Pa, sintering temperature 1400 deg.C, and heat preservation time 60min.
(3) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after the cooling.
Example 10
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) CoCrNi alloy powder prefabrication: the high-purity Co, cr and Ni powder (granularity is 15-53 mu m, purity is more than or equal to 99.9%) is 1:1:1, weighing and proportioning, placing the mixed powder in a ceramic ball milling tank, and preparing CoCrNi alloy prefabricated powder by mechanical alloying, wherein the mechanical alloying process parameters are as follows: the ball-to-material ratio is 10:1, the rotating speed of the ball mill is 320rpm, ar gas protective atmosphere is filled in the ball milling tank, and the total ball milling time is 96 hours.
(2) Proportioning and ball milling: weighing and proportioning 30g CoCrNi alloy powder, 60g (Ti, W) C powder and 10g TiN powder, and placing the mixed powder into a ceramic ball mill tank for ultrasonic treatment for 20min. Then placing the mixture into a planetary ball mill for wet milling, wherein the wet milling process parameters are as follows: the ball-to-material ratio is 8:1, the rotating speed of the ball mill is 210rpm, the ball milling medium is absolute ethyl alcohol, and the ball milling time is 72 hours.
(3) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven for drying at the temperature of 85 ℃. And then loading the dried powder into a die for sample pressing, wherein the pressure is 350MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: the vacuum degree is 10 -1-10-4 Pa, the sintering temperature is 1420 ℃, and the heat preservation time is 60min.
(4) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after the cooling.
Example 11
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) CoCrNi alloy powder prefabrication: the high-purity Co, cr and Ni powder (granularity is 15-35 mu m, purity is more than or equal to 99.9%) is 1:1:1, weighing and proportioning, placing the mixed powder in a ceramic ball milling tank, and preparing CoCrNi alloy prefabricated powder by mechanical alloying, wherein the mechanical alloying process parameters are as follows: the ball-to-material ratio is 12:1, the rotating speed of the ball mill is 300rpm, ar gas protective atmosphere is filled in the ball milling tank, and the ball milling time is50 h.
(2) Proportioning and ball milling: weighing and proportioning CoCrNi alloy powder with the mass fraction of 30%, (Ti, W) C powder with the mass fraction of 60% and TiC powder with the mass fraction of 10%, and placing the mixed powder in a ceramic ball milling tank for ultrasonic treatment for 20min. Then placing the mixture into a planetary ball mill for wet milling, wherein the wet milling process parameters are as follows: the ball-to-material ratio is 10:1, the rotating speed of the ball mill is 180rpm, the ball milling medium is absolute ethyl alcohol, and the ball milling time is 24 hours.
(3) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven for drying at 90 ℃. And then loading the dried powder into a die for sample pressing, wherein the pressure is 400MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: vacuum degree 10 -1-10-4 Pa, sintering temperature 1400 deg.C, and heat preservation time 60min.
(4) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after the cooling.
Example 12
A preparation method of nonmagnetic (Ti, W) C-based metal ceramic comprises the following steps:
(1) CoCrNi alloy powder prefabrication: the high-purity Co, cr and Ni powder (granularity is 2-5 mu m, purity is more than or equal to 99.9%) is 1:1:1, weighing and proportioning, placing the mixed powder in a ceramic ball milling tank, and preparing CoCrNi alloy prefabricated powder by mechanical alloying, wherein the mechanical alloying process parameters are as follows: the ball-to-material ratio is 15:1, the rotating speed of the ball mill is 350rpm, ar gas protective atmosphere is filled in the ball milling tank, and the total ball milling time is 24 hours.
(2) Proportioning and ball milling: weighing and proportioning CoCrNi alloy powder with the mass fraction of 30%, (Ti, W) C powder with the mass fraction of 60%, mo powder with the mass fraction of 10% and TiN powder with the mass fraction of 10%, and placing the mixed powder in a ceramic ball milling tank for ultrasonic treatment for 20min. Then placing the mixture into a planetary ball mill for wet milling, wherein the wet milling process parameters are as follows: the ball-to-material ratio is 7:1, the rotating speed of the ball mill is 225rpm, the ball milling medium is absolute ethyl alcohol, and the ball milling time is 36h.
(3) Sintering metal ceramic: and (3) placing the ball-milled slurry into an oven for drying at 90 ℃. And then loading the dried powder into a die for sample pressing, wherein the pressure is 400MPa. The metal ceramic material is prepared by adopting a vacuum sintering mode of a tube furnace, and the sintering process parameters are as follows: the vacuum degree is 10 -1-10-4 Pa, the sintering temperature is 1450 ℃, and the heat preservation time is 60min.
(4) Cooling treatment after sintering: the cooling mode is that the cooling rate is 5 ℃/min firstly and then the cooling is carried out along with the furnace, and the nonmagnetic (Ti, W) C-based metal ceramic is obtained after the cooling.
TABLE 1 composition (mass fraction) of nonmagnetic (Ti, W) C-based cermet of examples 1-12
Comparative example 1
Comparative example 1 was the same as example 1 except that the adhesive CoCrNi alloy was not contained as in example 1.
Since comparative example 1 does not contain CoCrNi alloy, lacks metal binder, and does not prepare cermet material with (Ti, W) C-based ceramic alone, nonmagnetic (Ti, W) C-based cermet cannot be prepared.
Comparative example 2
Comparative example 2 the adhesive was replaced with FeCoCrNi as CoCrNi as in example 1, and the other steps were the same as in example 1.
Since FeCoCrNi of Fe, co, and Ni in comparative example 2 are all ferromagnetic elements, cr is an antiferromagnetic element, and the ferromagnetic elements existing in a large amount make the material prepared in comparative example 2 exhibit ferromagnetism, and thus nonmagnetic (Ti, W) C-based cermet cannot be prepared.
Performance testing
Flexural Strength determination: the materials obtained in examples 1 to 12 and comparative example 2 were subjected to mechanical test analysis, and the flexural strength was measured by a three-point bending test on a universal tester having a span of 14.5 mm.
Hardness measurement: the materials obtained in examples 1 to 12 and comparative example 2 were tested for Rockwell hardness by the Vickers indentation test under the condition of a residence time of 5s measured under an external load of 60 kg.
Initial susceptibility determination: the materials obtained in examples 1-12 and comparative example 2 were tested by Vibrating Sample Magnetometer (VSM) for M-H curves in the range of-20 kOe to 20kOe external magnetic field at room temperature (300K), and the results are shown in Table 2.
TABLE 2 mechanical Property test of the materials obtained in examples 1 to 12 and comparative example 2
As can be seen from Table 2, the (Ti, W) C-based cermets prepared in examples 1 to 12 all had initial magnetic susceptibility less than 10 - 3 emu/g.Oe, and thus the materials prepared in examples 1 to 12 were nonmagnetic, while the materials prepared in comparative example 2 had initial magnetic susceptibility greater than 10 -3 emu/g.Oe and were ferromagnetic. It can also be seen from Table 2 that the (Ti, W) C-based cermets prepared in examples 1 to 12 have excellent mechanical properties.
Vibration Sample Magnetometer (VSM) tests were performed on the (Ti, W) C-based cermets prepared in examples 4 and 5 to obtain hysteresis loop diagrams (M-H curves). Fig. 1 is a hysteresis loop diagram of the material of example 4, fig. 2 is a hysteresis loop diagram of the material of example 5, and it can be seen from fig. 1 and 2 that the M-H curves of the (Ti, W) C-based cermets produced are in a linear relationship, which indicates that the cermets produced in examples 4 and 5 of the present invention have better nonmagnetic properties.
The (Ti, W) C-based cermet obtained in examples 4 and 5 was subjected to microscopic morphological analysis by a scanning electron microscope. Fig. 3 is a microstructure of the material of example 4, and fig. 4 is a microstructure of the material of example 5, and it can be seen from fig. 3 and fig. 4 that the cermet prepared in examples 4 and 5 of the present invention has a relatively uniform tissue distribution.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A non-magnetic (Ti, W) C-based cermet comprising:
A binder comprising a Co xCryNiz alloy, wherein x is (0.2-1), y is (0.8-1), and z is (0.2-1); and
A matrix material comprising a (Ti, W) C-based ceramic powder.
2. The nonmagnetic (Ti, W) C-based cermet according to claim 1, wherein the matrix material further comprises an adjuvant comprising at least one of Mo, tiC, tiN.
3. The non-magnetic (Ti, W) C-based cermet according to claim 2 wherein the adjuvant is present in a mass fraction of 0-20 wt.%.
4. The nonmagnetic (Ti, W) C-based cermet according to claim 1, wherein the mass ratio of binder to matrix material is 3 (4.5-12).
5. The nonmagnetic (Ti, W) C-based cermet according to claim 1, wherein in the Co xCryNiz alloy, x is 1, y is 1, and z is 1.
6. A method for preparing a non-magnetic (Ti, W) C-based cermet according to any of claims 1-5 comprising the steps of:
Mixing Co xCryNiz alloy and (Ti, W) C-based ceramic powder to obtain a metal ceramic mixture, and wet-milling the metal ceramic mixture to obtain a metal ceramic prefabricated material;
drying, sieving and pressing the metal ceramic prefabricated material to obtain a pressed blank of the metal ceramic prefabricated material;
And (3) carrying out vacuum sintering and cooling on the pressed compact of the metal ceramic preform to obtain the nonmagnetic (Ti, W) C-based metal ceramic.
7. The method of preparing a non-magnetic (Ti, W) C-based cermet according to claim 6 wherein, in wet milling the cermet mixture, the wet milling comprises wet ball milling the cermet mixture in a planetary ball mill, wherein:
The rotating speed of ball milling is 180-225 r/min; and/or the number of the groups of groups,
The ball milling time is 24-72 hours; and/or the number of the groups of groups,
The ball milling medium comprises absolute ethyl alcohol.
8. The method for preparing non-magnetic (Ti, W) C-based cermet according to claim 6, wherein in drying the cermet preform, sieving, and pressing, the drying means comprises drying in a vacuum drying oven, wherein the drying temperature is 80-90 ℃; and/or the number of the groups of groups,
The number of the screened screen meshes is 100-200 meshes; and/or the number of the groups of groups,
The pressing pressure is 300-400 MPa.
9. The method of producing a nonmagnetic (Ti, W) C-based cermet according to claim 6, wherein in vacuum sintering the green compact of the cermet preform, the vacuum sintering comprises vacuum sintering the green compact in a tube furnace, wherein:
the sintering temperature is 1400-1450 ℃; and/or the number of the groups of groups,
The degree of vacuum for sintering was 10 -1～10-4 Pa.
10. The method of preparing a nonmagnetic (Ti, W) C-based cermet according to claim 6, wherein prior to mixing the Co xCryNiz alloy with the (Ti, W) C-based ceramic powder, comprising ball milling the Co, cr, ni powder by ball milling the Co, cr, ni powder in a ball milling pot, wherein:
the rotation speed of ball milling is 300-350 r/min; and/or the number of the groups of groups,
The ball milling time is 24-96 h.
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