CN110129650B - Metal/carbide core-shell reinforced steel-iron-based composite material and preparation method thereof - Google Patents

Metal/carbide core-shell reinforced steel-iron-based composite material and preparation method thereof Download PDF

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CN110129650B
CN110129650B CN201910402857.9A CN201910402857A CN110129650B CN 110129650 B CN110129650 B CN 110129650B CN 201910402857 A CN201910402857 A CN 201910402857A CN 110129650 B CN110129650 B CN 110129650B
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CN110129650A (en
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钟黎声
白海强
许云华
魏俊哲
邓超
商昭
朱建雷
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Xian University of Technology
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    • 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
    • C22C29/02—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
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    • 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
    • C22C29/10—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 titanium carbide
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium

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Abstract

The invention discloses a metal/carbide core-shell reinforced steel-iron-based composite material, which consists of a metal/carbide core-shell reinforced phase and a steel matrix material, wherein the metal/carbide core-shell takes a high-toughness metal M as a core and a carbide M corresponding to the metal MxCyIs a shell, carbide MxCyThe volume fraction and the shape and the size of the carbide in the shell layer are changed in a gradient way. The invention also discloses a preparation method of the metal/carbide core-shell reinforced steel-iron-based composite material, the core-shell reinforced steel-iron-based composite material prepared by the method is tough inside and hard outside, and the carbide shell layer and the metal core have good interface bonding and wide application range.

Description

Metal/carbide core-shell reinforced steel-iron-based composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a metal/carbide core-shell reinforced steel-iron-based composite material and a preparation method thereof.
Background
With the rapid development of modern industry, tools, dies and structural members working under complex service conditions of high temperature, high speed, wear resistance and the like, such as rolling rings of high-speed rolling mills, rollers of guide wheels, hot working dies and the like, are urgently needed, and the requirement of the service conditions is difficult to meet by the traditional single steel material.
Carbide reinforced steel-base composite materialThe material has excellent toughness, cold and hot workability and weldability of metal materials, and high strength, high hardness, wear resistance and other performances of carbide, so that the material is widely applied to the industries of metallurgy, coal mine, petrochemical industry, aerospace and the like. The wear resistance and strength of the steel-based composite material are improved mainly by changing the volume fraction of the reinforcing phase in the composite material. However, as the volume fraction of reinforcing phase increases, the toughness/plasticity of the composite decreases, with an inverse relationship of toughness and toughness. For example, Jianhong Peng et al, published in 2017 on Journal of Alloys and composites, paper of Improving the mechanical properties of titanium carbide composite by reduced sintering the TaC compositions, produced TaC particle-reinforced iron-based composites with a TaC content of 20-60 wt% using a high energy ball mill followed by a hot press sintering process. As the TaC content increases from 20% to 60%, the yield strength and the maximum compressive strength of the composite increase significantly, and then decrease as the TaC content increases, particularly as the TaC content is 60%, the strain of the TaC/Fe composite decreases sharply. Furthermore, the method is simple. Fangxia Ye et al, in 2014, published in Journal of Materials Engineering and Performance in Volume frame Effect of V8C7 Particulates on Impact Toughness and Wear Performance of V8C7Fe Monolithic Composites by infiltration casting followed by heat treatment8C7A particle reinforced iron-based composite. Studies have shown that with V8C7The particle volume fraction increased from 8% to 33%, the abrasion resistance of the composite was significantly improved, whereas the toughness decreased from 8.06J/cm2 to 4.7J/cm 2.
Due to this inverse relationship between strength and toughness of carbide/steel based composites, their wider application is limited.
Disclosure of Invention
The invention aims to provide a metal/carbide core-shell reinforced steel-iron-based composite material which has better wear resistance and impact toughness.
The invention also aims to provide a preparation method of the metal/carbide core-shell reinforced steel-iron matrix composite.
The first technical scheme adopted by the invention is that the metal/carbide core-shell reinforced steel-iron-based composite material consists of a metal/carbide core-shell reinforced phase and a steel matrix material, wherein the metal/carbide core-shell takes a high-toughness metal M as a core and a carbide M corresponding to the metal M as the corexCyIs a shell, carbide MxCyThe volume fraction and the shape and the size of the carbide in the shell layer are changed in a gradient way.
The present invention is also technically characterized in that,
the composite material comprises the following components in percentage by mass: 2.45 to 16.2 percent of graphite powder, 10 to 30 percent of iron powder and 67.5 to 82 percent of high-toughness metal powder, wherein the total weight percentage of the components is 100 percent.
The composite material comprises the following components in percentage by mass: 70 to 80 percent of carbon steel powder and 20 to 30 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent; the mass percent of carbon in the carbon steel powder is 0.65-1.8%, and the balance is iron.
The high-toughness metal powder is one or more than two of tantalum powder, niobium powder, titanium powder, zirconium powder and vanadium powder.
The second technical scheme adopted by the invention is that the preparation method of the metal/carbide core-shell reinforced steel-iron-based composite material comprises the following steps:
step 1, selection and preparation of material system
A first system: weighing the following components in percentage by mass: 2.45 to 16.2 percent of graphite powder, 10 to 30 percent of iron powder and 67.5 to 82 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent;
the second system is as follows: the composite material comprises the following components in percentage by mass: 70 to 80 percent of carbon steel powder and 20 to 30 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent; the carbon steel powder comprises the following carbon by mass percent: 0.65-1.8% of C, and the balance of iron;
step 2, mixing the materials
Mixing the components weighed in the step 1 by a V-shaped mixer according to a material system, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step (2) by adopting common die pressing or cold isostatic pressing to obtain a pressed compact, wherein the unit pressing pressure is 1.0-1.5 t/cm2；
Step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering to obtain a sintered sample; the final sintering temperature is controlled to be 1000-1150 ℃, and argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process;
and 5, annealing the sintered sample obtained in the step 4 at 450-600 ℃ to obtain the metal/carbide reinforced steel-iron-based composite material.
In the step 1, the high-toughness metal powder is one or more of tantalum powder, niobium powder, titanium powder, zirconium powder and vanadium powder.
In the step 2, when a V-shaped mixer is used for mixing materials, the rotating speed of the V-shaped mixer is 60-90 r/min, and the mixing time is 6-24 h.
Before preforming of a pressed compact, adding 2-4 wt% of paraffin as a forming agent into the mixed powder; before hot-pressing sintering, the pressed blank is subjected to pre-sintering dewaxing, the dewaxing temperature is 500-600 ℃, and the dewaxing time is 0.8-1.2 h.
In the hot-pressing sintering process, the green compact is subjected to heat preservation for 0.3 to 6 hours at the final sintering temperature of 1000 to 1150 ℃, and the unit area pressure of the green compact is kept between 10 and 15 MPa.
The beneficial effect of the invention is that,
(1) the metal/carbide core shell in the metal/carbide core shell reinforced steel-iron based composite material takes high-toughness metal as a core and takes corresponding carbide as a shell, the inner toughness is hard outside, the outer hard carbide shell layer can protect the inner tough metal core, and the inner tough metal core can also support the outer hard carbide shell layer;
(2) the carbide shell layer is not only compact carbide, but also is in gradient distribution in size and distribution;
(3) adopting hot-pressing sintering at near-eutectic temperature, diffusing carbon atoms to the surface of the tough metal at high temperature to generate in-situ reaction, and forming a carbide shell layer on the surface in-situ extension, thereby forming a metal/carbide core shell, wherein the carbide shell layer and the metal core have good interface combination;
(4) the invention adopts a hot-pressing sintering process at near eutectic temperature, can accurately regulate and control the thickness of a carbide shell layer, can prepare a fine crystalline structure at lower temperature, and can obviously reduce the preparation cost and save resources.
Drawings
FIG. 1 is a schematic structural diagram of a Ta/TaC core-shell reinforced iron-based composite material in example 1 of the present invention;
FIG. 2 is a graph showing the results of X-ray diffraction (XRD) analysis of Ta/TaC core-shell reinforced iron-based composite material in example 1 of the present invention;
FIG. 3 is a schematic structural diagram of a Ta/TaC core-shell in example 1 of the present invention;
FIG. 4 is a schematic structural diagram of a V/VC core-shell in embodiment 5 of the present invention.
In the figure, 1 is a core, 2 is a shell, and 3 is a matrix.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention relates to a metal/carbide core-shell reinforced steel-iron-based composite material, which consists of a metal/carbide core-shell reinforced phase and a steel matrix material, wherein the metal/carbide core-shell takes a high-toughness metal M as a core and a carbide M corresponding to the metal M as the corexCyIs a shell, carbide MxCyThe volume fraction and the shape and the size of the carbide in the shell layer are changed in a gradient way.
The composite material comprises two material systems, wherein the first material system comprises the following components in percentage by mass: 2.45 to 16.2 percent of graphite powder, 10 to 30 percent of iron powder and 67.5 to 82 percent of high-toughness metal powder, wherein the total weight percentage of the components is 100 percent. The second one is composed of the following components by mass percent: 70 to 80 percent of carbon steel powder and 20 to 30 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent; the carbon steel powder comprises the following carbon by mass percent: 0.65-1.8% of C, and the balance of iron; the high-toughness metal powder is one or more of tantalum powder, niobium powder, titanium powder, zirconium powder and vanadium powder.
The invention relates to a preparation method of a metal/carbide core-shell reinforced steel-iron matrix composite, which specifically comprises the following steps:
step 1, selection and preparation of material system
A first system: weighing the following components in percentage by mass: 2.45 to 16.2 percent of graphite powder, 10 to 30 percent of iron powder and 67.5 to 82 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent;
the second system is as follows: the composite material comprises the following components in percentage by mass: 70 to 80 percent of carbon steel powder and 20 to 30 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent; the carbon steel powder comprises the following carbon by mass percent: 0.65-1.8% of C, and the balance of iron;
the high-toughness metal powder is one or more of tantalum powder, niobium powder, titanium powder, zirconium powder and vanadium powder;
the relative size K between the diameter R of the metal core and the thickness d of the carbide shell is controlled by adjusting the content of graphite in the raw material, wherein the K is R/d.
Step 2, mixing the materials
Mixing the components weighed in the step 1 by a V-shaped mixer according to a material system, wherein the rotating speed of the V-shaped mixer is 60-90 r/min, the mixing time is 6-24 h, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step (2) by adopting common die pressing or cold isostatic pressing to obtain a pressed blank; before compression molding, 2-4 wt% of paraffin is added into the mixed powder as a forming agent, and during compression molding, the compression pressure is determined according to the pressed area of a pressed blank, and the unit compression pressure is 1.0-1.5 t/cm 2;
step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering, wherein the pressed blank is subjected to pre-sintering dewaxing before hot-pressing sintering, the dewaxing temperature is 500-600 ℃, and the dewaxing time is 0.8-1.2 h; the final sintering temperature of hot-pressing sintering is 1000-1150 ℃, and the heat preservation time is 0.3-6 h at the temperature, thus obtaining a sintered sample; argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process, and the unit area pressure of the pressed compact is kept at 10-15 MPa.
Adopts a hot-pressing sintering process at a near eutectic temperature to realize that carbon atoms diffuse to the surface of the ductile metal at a high temperature to generate an in-situ reaction and form a carbide shell layer M on the surface in an in-situ mannerxCyThereby forming M/MxCyA core-shell structure reinforced steel-based composite material.
And 5, performing stress relief annealing treatment on the sintered sample in the step 4 at 450-600 ℃, wherein the annealing time is 2-6 h, and thus obtaining the metal/carbide core-shell reinforced steel-iron-based composite material. The microstructure of the carbide shell layer is regulated and controlled by adjusting the heat treatment temperature T and the time T, so that the strength and the toughness of the composite material are further regulated and controlled.
Example 1
A preparation method of a Ta/TaC core-shell reinforced iron-based composite material specifically comprises the following steps:
step 1, weighing the following components in percentage by mass: 2.45 percent of graphite powder and 30 percent of iron powder, and the balance of tantalum powder, wherein the granularity of the tantalum powder is 2000 meshes (namely the particle size is about 6.5 mu m), and the sum of the weight percentages of the components is 100 percent;
step 2, mixing materials, namely mixing the components weighed in the step 1 by using a V-shaped mixer, wherein the rotating speed of the V-shaped mixer is 60r/min, the mixing time is 6 hours, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step 2 by adopting common die pressing to obtain a pressed blank; before compression molding, paraffin accounting for 2 wt% of the mixed powder is added into the mixed powder as a forming agent, when compression molding is carried out, the compression pressure is determined according to the pressed area of a pressed compact, and the unit compression pressure is 1.0t/cm2；
Step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering, and performing pre-sintering dewaxing on the pressed blank before hot-pressing sintering, wherein the dewaxing temperature is 550 ℃ and the dewaxing time is 1 h; the final sintering temperature of hot-pressing sintering is 1000 ℃, and the heat preservation time is 4 hours at the temperature, so that a sintered sample is obtained; argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process, and the unit area pressure of a pressed compact is kept at 15 MPa;
and 5, placing the sintered sample obtained in the step 4 in a tube furnace filled with argon gas to carry out stress relief annealing treatment at 450 ℃ for 4 hours to obtain the Ta/TaC core-shell reinforced iron-based composite material.
The prepared Ta/TaC core-shell reinforced iron-based composite material is observed, and the result is as follows:
(1) microstructure of
Referring to fig. 1, 2 and 3, the Ta/TaC core-shell reinforced iron-based composite material prepared in example 1 uses iron as a matrix 3, a Ta/TaC core-shell as a reinforcing phase, a Ta/TaC core-shell uses metal tantalum as a core 1, and TaC as a shell 2, the volume fraction of tantalum carbide in the TaC shell layer gradually increases with the distance from the core, and the morphology and size also change in a gradient manner.
The average diameter of a Ta/TaC core-shell structure in the composite material is measured to be about 6.5 mu m, the average thickness of a TaC shell layer is measured to be about 1.5 mu m, the average diameter of a metal tantalum core is measured to be about 3.5 mu m, and therefore the relative scale K between the diameter of the tantalum core and the thickness of a tantalum carbide shell layer is 2.34.
(2) Mechanical properties
In the Ta/TaC core-shell reinforced iron-based composite material, the hardness of a TaC shell layer can reach 28.3GPa, and the wear test of the Ta/TaC core-shell structure reinforced iron-based composite material shows that the wear rate is only 4.5 multiplied by 10-15m3N, impact toughness of 89.3J/cm2。
Example 2
A preparation method of a Ti/TiC core-shell reinforced iron-based composite material specifically comprises the following steps:
step 1, weighing the following components in percentage by mass: 5.5 percent of graphite powder and 10 percent of iron powder, and the balance of titanium powder, wherein the granularity of the titanium powder is 500 meshes (namely the particle size is about 10 mu m), and the sum of the weight percentages of the components is 100 percent;
step 2, mixing materials, namely mixing the components weighed in the step 1 by using a V-shaped mixer, wherein the rotating speed of the V-shaped mixer is 65r/min, the mixing time is 8 hours, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step (2) by adopting cold isostatic pressing to obtain a pressed blank; before compression molding, paraffin accounting for 2 wt% of the mixed powder is added into the mixed powder as a forming agent, when compression molding is carried out, the compression pressure is determined according to the pressed area of a pressed compact, and the unit compression pressure is 1.0t/cm2；
Step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering, and performing pre-sintering dewaxing on the pressed blank before hot-pressing sintering, wherein the dewaxing temperature is 550 ℃ and the dewaxing time is 1 h; the final sintering temperature of the hot-pressing sintering is 1050 ℃, and the heat preservation time is 3 hours at the temperature, so that a sintered sample is obtained; argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process, and the unit area pressure of a pressed compact is kept at 15 MPa;
and 5, placing the sintered sample obtained in the step 4 in a tube furnace filled with argon gas to carry out stress relief annealing treatment at 600 ℃, wherein the annealing time is 4 hours, and thus obtaining the Ti/TiC core-shell reinforced iron-based composite material.
The prepared Ti/TiC core-shell reinforced iron-based composite material is observed, and the result is as follows:
(1) microstructure of
In the Ti/TiC core-shell reinforced iron-based composite material, the Ti/TiC core shell takes metal titanium as a core and TiC as a shell, the volume fraction of titanium carbide in the TiC shell layer is gradually increased along with the distance from the core, and the shape and size of the titanium carbide are changed in a gradient manner.
Through measurement, the average diameter of a Ti/TiC core-shell structure in the composite material is about 25 mu m, the average thickness of a TiC shell layer is about 4.5 mu m, and the average diameter of a metal titanium core is about 16 mu m, so that the relative scale K between the diameter of the titanium core and the thickness of the titanium carbide shell layer is 3.56.
(2) Mechanical properties
Hardness of TiC shell in Ti/TiC core-shell reinforced iron-based composite materialThe abrasion test of the reinforced iron-based composite material with the Ti/TiC core-shell structure can reach 31.5GPa, and shows that the abrasion rate is only 4.3 multiplied by 10-15m3N, impact toughness of 106.3J/cm2。
Example 3
A preparation method of an Nb/NbC core-shell reinforced iron-based composite material specifically comprises the following steps:
step 1, weighing the following components in percentage by mass: 8.1 percent of graphite powder and 10 percent of iron powder, and the balance of niobium powder, wherein the granularity of the niobium powder is 1000 meshes (namely the particle size is about 13 mu m), and the sum of the weight percentages of the components is 100 percent;
step 2, mixing materials, namely mixing the components weighed in the step 1 by adopting a V-shaped mixer, wherein the rotating speed of the V-shaped mixer is 90r/min, the mixing time is 24 hours, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step (2) by adopting cold isostatic pressing to obtain a pressed blank; before compression molding, paraffin accounting for 3 wt% of the mixed powder is added into the mixed powder as a forming agent, when compression molding is carried out, the compression pressure is determined according to the pressed area of a pressed compact, and the unit compression pressure is 1.2t/cm2；
Step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering, and performing pre-sintering dewaxing on the pressed blank before hot-pressing sintering, wherein the dewaxing temperature is 600 ℃, and the dewaxing time is 1.2 h; the final sintering temperature of the hot-pressing sintering is 1125 ℃, and the heat preservation time is 2h at the temperature, so that a sintered sample is obtained; argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process, and the unit area pressure of a pressed compact is kept at 15 MPa;
and 5, placing the sintered sample obtained in the step 4 in a tube furnace filled with argon gas to carry out stress relief annealing treatment at 450 ℃ for 6 hours to obtain the Nb/NbC core-shell reinforced iron-based composite material.
The prepared Nb/NbC core-shell reinforced iron-based composite material is observed, and the result is as follows:
(1) microstructure of
In the Nb/NbC core-shell reinforced iron-based composite material, the Nb/NbC core shell takes metal niobium as a core and NbC as a shell, the volume fraction of niobium carbide in the NbC shell layer gradually increases along with the distance from the core, and the morphology and the size also change in a gradient manner.
The average diameter of the Nb/NbC core-shell structure in the composite material is measured to be about 13 μm, the average thickness of the NbC shell layer is measured to be about 2.5 μm, and the average diameter of the metal niobium core is measured to be about 8 μm, so that the relative size K between the diameter of the niobium core and the thickness of the niobium carbide shell layer is 3.2.
(2) Mechanical properties
In the Nb/NbC core-shell reinforced iron-based composite material, the hardness of an NbC shell layer can reach 26.5GPa, and the impact toughness of the Nb/NbC core-shell structure reinforced iron-based composite material is 100.6J/cm2。
Example 4
A preparation method of a Zr/ZrC core-shell reinforced steel-based composite material specifically comprises the following steps:
step 1, weighing the following components in percentage by mass: 80 percent of carbon steel powder and 20 percent of zirconium powder, wherein the granularity of the zirconium powder is 3000 meshes (namely the grain diameter is about 5 mu m), and the sum of the weight percentages of the components is 100 percent;
step 2, mixing materials, namely mixing the components weighed in the step 1 by using a V-shaped mixer, wherein the rotating speed of the V-shaped mixer is 60r/min, the mixing time is 8 hours, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step 2 by adopting common die pressing to obtain a pressed blank; before compression molding, paraffin accounting for 4 wt% of the mixed powder is added into the mixed powder as a forming agent, when compression molding is carried out, the compression pressure is determined according to the pressed area of a pressed compact, and the unit compression pressure is 1.5t/cm2；
Step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering, and performing pre-sintering dewaxing on the pressed blank before hot-pressing sintering, wherein the dewaxing temperature is 500 ℃, and the dewaxing time is 0.8 h; the final sintering temperature of hot-pressing sintering is 1150 ℃, and the heat preservation time is 1h at the temperature, so that a sintered sample is obtained; argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process, and the unit area pressure of a pressed compact is kept at 10 MPa;
and 5, placing the sintered sample obtained in the step 4 in a tube furnace filled with argon gas for stress relief annealing treatment at 500 ℃ for 5 hours to obtain the Zr/ZrC core-shell reinforced steel-based composite material.
The prepared Zr/ZrC core-shell reinforced steel-based composite material is observed, and the result is as follows:
(1) microstructure of
In the Zr/ZrC core-shell reinforced steel-based composite material, the Zr/ZrC core shell takes metal zirconium as a core and ZrC as a shell, the volume fraction of zirconium carbide in the ZrC shell layer is gradually reduced along with the distance from the core, and the morphology and the size are also changed in a gradient manner.
The average diameter of the Zr/ZrC core-shell structure in the composite material is measured to be about 2.85 microns, the average thickness of the ZrC shell layer is measured to be about 0.35 microns, the average diameter of the metal zirconium core is measured to be about 2.15 microns, and therefore the relative scale K between the diameter of the zirconium core and the thickness of the zirconium carbide shell layer is 6.14.
(2) Mechanical properties
In the Zr/ZrC core-shell reinforced steel-based composite material, the hardness of a ZrC shell layer can reach 29.6GPa, and the impact toughness of the Zr/ZrC core-shell structure reinforced steel-based composite material is 112.7J/cm2。
Example 5
V/VxCyThe preparation method of the core-shell reinforced steel-based composite material specifically comprises the following steps:
step 1, weighing the following components in percentage by mass: 70 percent of carbon steel powder and 30 percent of vanadium powder, wherein the granularity of the vanadium powder is about 1800 meshes, and the sum of the weight percentages of the components is 100 percent;
step 2, mixing materials, namely mixing the components weighed in the step 1 by using a V-shaped mixer, wherein the rotating speed of the V-shaped mixer is 80r/min, the mixing time is 12 hours, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step (2) by adopting cold isostatic pressing to obtain a pressed blank; adding the mixture into the mixed powder before compression moldingParaffin wax accounting for 3 wt% of the powder is used as a forming agent, the compression pressure is determined according to the pressed area of a pressed compact during compression forming, and the unit compression pressure is 1.2t/cm2；
Step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering, and performing pre-sintering dewaxing on the pressed blank before hot-pressing sintering, wherein the dewaxing temperature is 600 ℃, and the dewaxing time is 1.2 h; the final sintering temperature of the hot-pressing sintering is 1125 ℃, and the heat preservation time is 2h at the temperature, so that a sintered sample is obtained; argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process, and the unit area pressure of a pressed compact is kept at 15 MPa;
step 5, placing the sintered sample in the step 4 into a tube furnace filled with argon gas to carry out stress relief annealing treatment at 450 ℃, wherein the annealing time is 6 hours, and obtaining V/VxCyCore-shell reinforced steel-base composite material.
For the prepared V/VxCyThe core-shell reinforced steel-based composite material is observed, and the result is as follows:
(1) microstructure of
Referring to FIG. 4, V/VxCyIn the core-shell reinforced iron-based composite material, V/VxCyThe core-shell takes vanadium metal as a core 1 and VxCyIs a shell 2, VxCyThe volume fraction of vanadium carbide in the shell layer is gradually reduced along with the distance from the core, and the appearance size is also changed in a gradient manner. At V/VxV is mainly formed at the C interface2C, subsequently converted to V8C7。
Measured, the internal V/V of the composite materialxCyThe average diameter of the core-shell structure is about 3 μm, VxCyThe average thickness of the shell layer is about 0.28 μm, the average diameter of the vanadium metal core is about 2.44 μm, and the relative dimension K between the diameter of the vanadium core and the thickness of the vanadium carbide shell layer is 8.71.
(2) Mechanical properties
V/VxCyIn the core-shell reinforced steel-based composite material, VxCyThe hardness of the shell layer can reach 30.4GPa and V/VxCyCore-shell structureThe impact toughness of the reinforced steel-based composite material is 108.6J/cm2。
Table 1 examples 1 to 5 the ingredients of the raw materials are in the following table wt%
Figure BDA0002060300810000151

Claims (2)

1. A preparation method of a metal/carbide core-shell reinforced steel-iron matrix composite is characterized by comprising the following steps:
step 1, selection and preparation of material system
A first system: weighing the following components in percentage by mass: 2.45 to 16.2 percent of graphite powder, 10 to 30 percent of iron powder and 67.5 to 82 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent;
the second system is as follows: the composite material comprises the following components in percentage by mass: 70 to 80 percent of carbon steel powder and 20 to 30 percent of high-toughness metal powder, wherein the sum of the weight percentages of the components is 100 percent; the carbon steel powder comprises the following carbon by mass percent: 0.65-1.8% of C, and the balance of iron;
the high-toughness metal powder is one or more of tantalum powder, niobium powder, titanium powder, zirconium powder and vanadium powder;
step 2, mixing the materials
Mixing the components weighed in the step 1 by a V-shaped mixer according to a material system, and uniformly mixing to obtain mixed powder;
step 3, performing a green compact
Pressing and forming the mixed powder obtained in the step (2) by adopting common die pressing or cold isostatic pressing to obtain a pressed compact, wherein the unit pressing pressure is 1.0-1.5 t/cm2(ii) a Before the pressed blank is preformed, 2-4 wt% of paraffin is added into the mixed powder to serve as a forming agent;
step 4, hot-pressing sintering
Placing the pressed blank in the step 3 in a hot-pressing sintering furnace for sintering to obtain a sintered sample; the final sintering temperature is controlled to be 1000-1150 ℃, and argon with the purity of more than or equal to 99.9 percent is used as protective gas in the sintering process; before hot-pressing sintering, pre-sintering and dewaxing are carried out on the pressed blank, wherein the dewaxing temperature is 500-600 ℃, and the dewaxing time is 0.8-1.2 h; in the hot-pressing sintering process, the green compact is subjected to heat preservation for 0.3 to 6 hours at the final sintering temperature of 1000 to 1150 ℃, and the unit area pressure of the green compact is kept between 10 and 15 MPa;
and 5, annealing the sintered sample obtained in the step 4 at 450-600 ℃ to obtain the metal/carbide reinforced steel-based composite material, wherein the composite material consists of a metal/carbide core-shell reinforced phase and a steel matrix material, the metal/carbide core-shell takes a high-toughness metal M as a core and a carbide M corresponding to the metal M as a carbide MxCyIs a shell, carbide MxCyThe volume fraction and the shape and the size of the carbide in the shell layer are changed in a gradient way.
2. The preparation method of the metal/carbide core-shell reinforced steel-iron matrix composite material according to claim 1, wherein in the step 2, when a V-shaped mixer is used for mixing, the rotating speed of the V-shaped mixer is 60-90 r/min, and the mixing time is 6-24 h.
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