CN120205816A

CN120205816A - A high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material and a preparation method thereof

Info

Publication number: CN120205816A
Application number: CN202510376937.7A
Authority: CN
Inventors: 张枫凡; 赵亚军; 邹存磊; 张爽; 董闯
Original assignee: Dalian Jiaotong University
Current assignee: Dalian Jiaotong University
Priority date: 2025-03-27
Filing date: 2025-03-27
Publication date: 2025-06-27

Abstract

The invention discloses a high-hardness high-wear-resistance metal-based ceramic particle in-situ reinforced composite material and a preparation method thereof, relates to the technical field of composite engineering materials, and aims to solve the problems that ceramic phases are easy to agglomerate and uneven in distribution caused by large difference of melting points of metal and ceramic in the prior art. The method comprises the steps of mixing metal powder, polysiloxane and a crosslinking catalyst to obtain a mixture, crosslinking, standing and crosslinking to obtain a metal mixed crosslinked material, pyrolyzing the metal mixed crosslinked material to obtain a highly crosslinked material, hot-pressing and sintering the highly crosslinked material to form a pressed sheet, hot-rolling and deforming the pressed sheet at a high temperature, and heat-treating, namely heat-treating the hot-rolled composite material to enable the crosslinked material to be fully ceramic to obtain the metal-based ceramic particle in-situ reinforced composite material.

Description

High-hardness high-wear-resistance metal-based ceramic particle in-situ reinforced composite material and preparation method thereof

Technical Field

The invention relates to the technical field of composite engineering materials, in particular to a high-hardness high-wear-resistance metal-based ceramic particle in-situ reinforced composite material and a preparation method thereof.

Background

The ceramic particle reinforced metal matrix composite is a novel engineering material, and is an important breakthrough in the field of modern material science, and the ceramic particle reinforced metal matrix composite shows a unique prospect in a plurality of engineering material fields by virtue of the excellent comprehensive performance. The innovative material has the performance advantages that the traditional metal materials are difficult to reach, such as 'strength-toughness cooperative improvement', and the like, by uniformly dispersing the ceramic particles with high hardness and high melting point in the metal matrix. The unique performance advantages are mainly that the hardness and the wear resistance of the composite material are obviously improved by introducing the ceramic phase on the basis of keeping good plasticity and thermal conductivity of the metal matrix. The optimization of the performance makes the material suitable for key parts under severe working conditions of high friction and high temperature, such as aerospace, automobile industry and the like, and can also be applied to parts in industries of electronic packaging, energy sources, rail transportation and the like.

The traditional smelting method is used for preparing a metal-based ceramic composite material, ceramic phases are easy to agglomerate and uneven in distribution in a metal matrix due to the difference of melting points of metal and ceramic, so that larger defects are formed in the composite material, the metal-based ceramic composite material is prepared by a melt infiltration method, the porous prefabricated body cannot be uniformly filled with molten metal in the infiltration process, the density of a local area is insufficient or pores exist, the uneven infiltration can reduce the compactness and mechanical properties of the material, particularly in parts with complex shapes, the friction stirring processing method is used for filling cross-linked matters into grooves of the metal matrix, and then friction stirring processing is carried out. In-situ ceramization of the organic matter-metal powder crosslinked mixture is beneficial to uniform mixing of metal particles and ceramic composite materials, and the preparation method for preparing the composite materials by high-pressure torsion is only capable of preparing smaller pieces, and preparation of larger workpieces cannot be realized.

Disclosure of Invention

The invention aims to solve the technical problems that:

The existing method is easy to agglomerate and uneven in distribution of ceramic phase due to larger difference of melting points of metal and ceramic, and only small samples can be prepared.

The invention adopts the technical scheme for solving the technical problems:

the invention provides a preparation method of a high-hardness high-wear-resistance metal-based ceramic particle in-situ reinforced composite material, which comprises the following steps:

step 1, mixing metal powder, polysiloxane and a crosslinking catalyst to obtain a mixture;

step 2, crosslinking, namely standing and crosslinking to obtain a metal mixed crosslinked material;

step 3, pyrolysis, namely carrying out pyrolysis treatment on the metal mixed cross-linked matter to obtain a highly cross-linked matter;

Step 4, hot-press sintering, namely hot-press sintering molding is carried out on the highly crosslinked material to form a tabletting;

step 5, hot rolling, namely performing high-temperature hot rolling deformation treatment on the pressed sheet;

And 6, heat treatment, namely performing heat treatment on the hot-rolled composite material to fully ceramic the cross-linked product in the composite material to obtain the metal-based ceramic particle in-situ reinforced composite material.

Further, in step 1, the polysiloxane is selected from polymethylhydrosiloxane and the crosslinking catalyst is selected from triethylenediamine.

Further, in step 1, the metal powder is copper powder.

Further, in the step 2, the mixture is kept stand and crosslinked at a temperature of 40-60 ℃ for 36-48 hours.

In the step 3, the metal mixed cross-linked compound is subjected to pyrolysis treatment, specifically, the metal mixed cross-linked compound is subjected to pyrolysis treatment for 2 hours under the argon atmosphere at the temperature of 350-660 ℃.

And in the step 4, the temperature for hot-press sintering molding of the highly crosslinked product is 500-660 ℃ and the pressure is not lower than 30MPa.

Further, in the step 5, the temperature of hot rolling deformation treatment of the pressed sheet is 850-1000 ℃.

Further, in the step 6, the temperature of the heat treatment of the hot rolled composite material is 850-1000 ℃ and the time is 2 hours.

Further, the mass ratio of the copper powder to the polymethylhydrosiloxane to the triethylenediamine is (90-98) to (1.9-9.5) to (0.1-0.5).

The invention provides a high-hardness high-wear-resistance metal-based ceramic particle in-situ reinforced composite material, which is prepared by the method according to any one of the technical schemes.

Compared with the prior art, the invention has the beneficial effects that:

The invention adds cross-linked polymer into metal powder, and prepares the composite material with uniform ceramic phase dispersion, submicron-level ceramic particles and high interface bonding strength through in-situ ceramming. The invention volatilizes uncrosslinked polymer through pyrolysis to improve the ceramic conversion rate and reduce impurities, generates ceramic reinforcing phase in situ, forms powder mixture through hot-pressing sintering, uniformly disperses crosslinked polymer in a metal matrix through hot rolling and removes pores, realizes large plastic deformation of the metal matrix to refine grains, effectively reduces internal defects of materials, converts the crosslinked polymer into ceramic in situ through heat treatment, and removes residual stress generated by deformation. The method remarkably improves the hardness and wear resistance of the metal matrix while keeping the good ductility of the material, and is suitable for the fields of special functional materials such as electronic packaging, friction materials and the like.

The production method is simple and feasible, has no material compatibility requirement and special equipment requirement, can rely on the traditional production line to carry out production, has low cost of required raw materials, is nontoxic and environment-friendly in technological process, can be used for preparing isotropic parts with complex structures, can recycle all the constituent elements, and accords with the concept of circular economy.

According to the invention, through reasonably controlling various technological parameters, the finally obtained high-hardness high-wear-resistance composite material provides a more efficient and economical material solution for mechanical manufacturing. Not only is helpful to promote the development of the mechanical industry, but also provides a new thought and method for the technical progress in the related field.

Drawings

FIG. 1 is a flow chart of a method for preparing a metal-based ceramic particle in-situ reinforced composite material in an embodiment of the invention;

FIG. 2 is a schematic diagram of a scanning electron microscope of an in-situ reinforced composite material of metal-based ceramic particles in an embodiment of the invention;

FIG. 3 is a second scanning electron microscope image of the metal matrix ceramic particle in situ reinforced composite material in an embodiment of the invention;

FIG. 4 is a scanning electron microscope image III of an in-situ reinforced composite material of metal-based ceramic particles in an embodiment of the invention;

FIG. 5 is a scanning electron microscope image of a metal material in a comparative example of the present invention;

FIG. 6 is a graph showing the Vickers hardness versus the present invention;

fig. 7 is a graph of wear volume versus the present invention in an example.

Detailed Description

In order that those skilled in the art will better understand the present invention, exemplary embodiments or examples of the present invention will be described below with reference to the accompanying drawings. It is apparent that the described embodiments or examples are only implementations or examples of a part of the invention, not all. All other embodiments or examples, which may be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention based on the embodiments or examples herein.

In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.

In an exemplary embodiment of the present application, the present application provides a method for preparing a high hardness and high wear resistance metal matrix ceramic particle in situ reinforced composite material, as shown in fig. 1, comprising the steps of:

Step 3, pyrolysis, namely carrying out pyrolysis treatment on the crosslinked material to obtain a highly crosslinked material;

In one embodiment of the present application, preferably, the polysiloxane in step 1 is selected from polymethylhydrosiloxanes and the crosslinking catalyst is selected from triethylenediamine.

In one embodiment of the present application, preferably, the metal powder in step 1 is copper powder.

In one embodiment of the present application, the temperature of the mixture in the step 2 is preferably 40 to 60 ℃ and the time is 36 to 48 hours.

In one embodiment of the application, preferably, in the step 3, the metal mixed cross-linked compound is subjected to pyrolysis treatment, specifically, the metal mixed cross-linked compound is subjected to pyrolysis treatment for 2 hours at the temperature of 350-660 ℃ in an argon atmosphere, so that insufficiently cross-linked polymethylhydrosiloxane is removed, the ceramic conversion rate is improved, and impurities are reduced.

In one embodiment of the application, the temperature for hot-press sintering the highly crosslinked material in step 4 is preferably 500-660 ℃ and the pressure is not lower than 30MPa, so as to prevent the sample density of hot-press sintering at too low a temperature from being lower, and the temperature is too high to convert the crosslinked material into ceramic, so that the crosslinked material is easy to break and disperse in the subsequent hot-rolling process. The density of the sample is reduced due to the too low pressure, and graphite is easy to crush due to the too high pressure, so that the pressure is not lower than 30MPa in the embodiment.

In one embodiment of the present application, preferably, the temperature of hot rolling deformation treatment of the pressed sheet in step 5 is 850N1000 ℃, so that the deformation is more than or equal to 80%, and the ceramic particles are further crushed and dispersed under the stress effect, so as to prevent poor plasticity of the pressed sheet caused by too low temperature, and the pressed sheet is easy to crush in the rolling process, and the copper matrix is easy to melt caused by too high temperature.

In one embodiment of the present application, the temperature of the heat-treated composite material after hot rolling in step 6 is preferably 850-1000 ℃ for 2 hours, and the crosslinked material is fully ceramized and the residual stress of the copper matrix after deformation is removed.

In one embodiment of the present application, the mass ratio of copper powder, polymethylhydrosiloxane, and triethylenediamine is preferably (90-98): (1.9-9.5): (0.1-0.5).

In an exemplary embodiment of the present application, the present application provides a high hardness, high wear resistant metal matrix ceramic particle in situ reinforced composite material prepared by a method of preparing a high hardness, high wear resistant metal matrix ceramic particle in situ reinforced composite material.

The advantageous effects of the present invention will be described below with reference to specific examples and comparative examples.

Example 1

Step 1, mixing materials

Step 1.1 weighing 1.9g of polymethylhydrosiloxane, placing in a beaker.

Step 1.2, placing the beaker into a water bath of a heat collection type constant temperature heating magnetic stirrer preheated to 50 ℃.

Step 1.3, the triethylenediamine was put into a sample pulverizer, and the sample pulverizer and a 150-mesh screen were put into a glove box having a humidity of 0.1RH% for drying.

Step 1.4, crushing the triethylene diamine into powder by a small sample crusher at the rotating speed of 10000 r/min.

Step 1.5, sieving the triethylene diamine powder by using a 150-mesh screen.

Step 1.6, weighing 0.1g of sieved triethylene diamine powder.

Step 1.7, adding the weighed triethylenediamine into a beaker containing the polymethylhydrosiloxane, stirring, adding a small amount of absolute ethyl alcohol into the beaker to enable the triethylenediamine to be rapidly dissolved, and mechanically mixing the polymethylhydrosiloxane and the triethylenediamine.

And 1.8, weighing 98g of high-purity copper powder with the particle size of 3-5 mu m.

And 1.9, pouring the high-purity copper powder into a beaker for containing the polymethylhydrosiloxane and the triethylenediamine, and fully stirring to obtain a mixture.

And step 2, crosslinking, namely placing the beaker with the mixture into an electrothermal constant-temperature drying oven preheated to 50 ℃ for standing for 36 hours, and enabling the polymethylhydrosiloxane to be crosslinked in situ in the copper powder to obtain the metal mixed crosslinked material.

Step 3. Pyrolysis

And 3.1, fully grinding the metal mixed cross-linked mixture, and then placing the ground metal mixed cross-linked mixture into a tube furnace.

And 3.3, introducing argon into a tubular furnace, heating to 350 ℃ by programming, pyrolyzing the metal mixed cross-linked compound for 2 hours at 350 ℃, and cooling along with the furnace to remove the polymethyl hydrogen siloxane which is not fully cross-linked, so as to obtain the highly cross-linked compound.

Step 4, hot pressing sintering

And 4.1, selecting a cylindrical graphite die with the diameter of 40mm as a hot-pressed sintering die, and covering carbon paper on the inner surface of the die to prevent adhesion and help demoulding.

And 4.2, uniformly pouring a proper amount of highly crosslinked material into a graphite mold, compacting, and placing into a hot-pressing sintering furnace.

And 4.3, pumping the vacuum degree in the sintering furnace to 3E0Pa before starting the sintering furnace, then programming to 600 ℃, programming to 3.84t, hot-pressing and sintering the highly crosslinked material at 30MPa (the required pressure is calculated according to the size of the die) and 600 ℃ for 10min, cooling to 100 ℃ along with the furnace after sintering, cooling to room temperature in air after taking out, and demolding.

And 4.4, polishing the formed blocky composite material by using sand paper, removing surface carbon paper, and forming a cylindrical tabletting.

Step 5. Hot rolling

And 5.1, placing the cylindrical pressed sheet into a heat treatment furnace preheated to 900 ℃ for heating.

And 5.2, carrying out hot rolling deformation treatment on the pressed sheet by using a rolling mill, wherein the pressed sheet is covered with heat-insulating cotton in the rolling process so as to reduce heat dissipation. The rotating speed of the roller is less than or equal to 100r/min, the single pressing quantity is 0.1mm, and the rolling is carried out in multiple passes, so that the rolling deformation is more than or equal to 80%.

And 6, heat treatment, namely, heat treating the hot-rolled composite material in a vacuum heat treatment furnace at 900 ℃ for 2 hours, cooling along with the furnace, fully ceramifying the crosslinked material, and removing residual stress of the copper matrix after deformation to obtain the ceramic particle in-situ reinforced copper-based composite material shown in figure 2.

And 7, cutting, namely cutting and removing irregular parts of the obtained composite material to obtain a required shape.

Example 2

This embodiment differs from embodiment 1 in that,

In step 1.1, 4.75g of polymethylhydrosiloxane are weighed;

In step 1.6, 0.25g of triethylenediamine powder was weighed;

in the step 1.8, weighing 95g of high-purity copper powder with the particle size of 3-5 mu m;

in step 3.3, the metal mixture cross-link is pyrolyzed at 500 ℃ for 2 hours;

the example finally obtained the ceramic particle in situ reinforced copper matrix composite as shown in figure 3.

Example 3

This embodiment differs from embodiment 1 in that,

In step 1.1, 9.5g of polymethylhydrosiloxane are weighed;

in step 1.6, 0.5g of triethylenediamine powder was weighed;

in the step 1.8, 90g of high-purity copper powder with the particle size of 3-5 mu m is weighed;

in step 3.3, the metal mixture cross-link is pyrolyzed for 2 hours at 450 ℃;

the example finally obtained the ceramic particle in situ reinforced copper matrix composite as shown in fig. 4.

Example 4

This embodiment differs from embodiment 1 in that,

In step 4.3, the highly crosslinked material was hot pressed and sintered at 500℃under 30MPa for 10min.

Example 5

This embodiment differs from embodiment 1 in that,

In step 4.3, the highly crosslinked material was hot pressed and sintered at 30MPa and 550℃for 10min.

Example 6

This embodiment differs from embodiment 1 in that,

In step 5.1, the cylindrical pellets were placed in a heat treatment furnace preheated to 850 ℃.

Example 7

This embodiment differs from embodiment 1 in that,

In step 5.1, the cylindrical pellets are placed into a heat treatment furnace preheated to 1000 ℃ for heating

Example 8

This embodiment differs from embodiment 1 in that,

And 6, performing heat treatment on the hot-rolled composite material in a vacuum heat treatment furnace at 850 ℃ for 2 hours.

Example 7

This embodiment differs from embodiment 1 in that,

And 6, performing heat treatment on the hot-rolled composite material in a vacuum heat treatment furnace at the temperature of 1000 ℃ for 2 hours.

Comparative example 1

And 1, weighing a proper amount of high-purity copper powder with the particle size of 3-5 mu m.

Step 2, hot pressing sintering

And 2.1, selecting a cylindrical graphite die with the diameter of 40mm as a hot-pressed sintering die, and covering carbon paper on the inner surface of the die to prevent adhesion and help demoulding.

And 2.2, pouring the high-purity copper powder into a graphite die, compacting, and putting into a hot-pressing sintering furnace.

And 2.3, pumping the vacuum degree in the sintering furnace to 3E0Pa before starting the sintering furnace, then programming to 600 ℃, programming to 3.84t, hot-pressing and sintering copper powder at 30MPa (the required pressure is calculated according to the die size) and 600 ℃ for 10min, cooling to 100 ℃ along with the furnace after sintering, cooling to room temperature in air after taking out, and demoulding.

And 2.4, polishing the formed copper block by sand paper, removing surface carbon paper, and forming a cylindrical tabletting.

Step 3. Hot rolling

And 3.1, placing the cylindrical pressed sheet into a heat treatment furnace preheated to 900 ℃ for heating.

And 3.2, carrying out hot rolling deformation treatment on the pressed sheet by using a rolling mill, wherein the pressed sheet is covered with heat-insulating cotton in the rolling process so as to reduce heat dissipation. The rotating speed of the roller is less than or equal to 100r/min, the single pressing quantity is 0.1mm, and the rolling is carried out in multiple passes, so that the rolling deformation is more than or equal to 80%.

And 4, heat treatment, namely preserving heat of the material subjected to hot rolling in a vacuum heat treatment furnace at 900 ℃ for 2 hours, cooling along with the furnace, and removing residual stress of the copper matrix after deformation to obtain the metal material shown in figure 5.

The hardness test is carried out on the materials obtained in each embodiment by adopting a Vickers hardness tester, the friction and wear performance of the materials is tested by adopting a multifunctional friction and wear tester, the equipment mode is a ball-disc reciprocating mode, the friction pair is GCr15 balls (diameter is 6.35 mm), the friction mode is linear reciprocating, the loading load is 20N, the experimental time is 10min, the running speed is 3mm/s, the running distance is 6mm, the wear volume is calculated after the test, the friction and wear performance of the samples is tested by adopting the multifunctional friction and wear tester, the friction coefficient is recorded, and the results are shown in the table 1.

TABLE 1

As can be seen from fig. 2 to fig. 4, the method of the invention converts the polymer into ceramic particles in situ, and the obtained composite material has uniform ceramic phase dispersion, ceramic particles reaching submicron level and high interface bonding strength. As can be seen from the data in table 1 and fig. 6 to 7, the in-situ reinforced copper-based composite material with ceramic particles according to the present invention has an abrasion resistance increased by more than 98% compared with the pure copper sample of comparative example 1, a hardness increased by 221.07% at maximum, and a friction coefficient reduced, and thus the in-situ reinforced composite material with metal-based ceramic particles according to the present invention has a significant improvement.

Although the present disclosure is disclosed above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and such changes and modifications would be within the scope of the disclosure.

Claims

1. A method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material, characterized in that it comprises the following steps:

Step 1. Mixing: mixing metal powder, polysiloxane and a cross-linking catalyst to obtain a mixture;

Step 2. Cross-linking: static cross-linking to obtain a metal mixed cross-linked product;

Step 3. Pyrolysis: Pyrolysis the metal mixed cross-linked product to obtain a highly cross-linked product;

Step 4. Hot pressing and sintering: hot pressing and sintering the highly cross-linked material to form a pressed sheet;

Step 5. Hot rolling: subjecting the pressed sheet to high temperature hot rolling deformation treatment;

Step 6. Heat treatment: heat-treating the hot-rolled composite material to fully ceramicize the cross-linked materials therein, thereby obtaining the metal-based ceramic particle in-situ reinforced composite material.

2. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 1, characterized in that the polysiloxane in step 1 is selected from polymethyl hydrogen siloxane, and the cross-linking catalyst is selected from triethylenediamine.

3. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 2, characterized in that the metal powder in step 1 is copper powder.

4. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 3 is characterized in that the temperature of static cross-linking the mixture in step 2 is 40-60°C and the time is 36h-48h.

5. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 4 is characterized in that the metal mixed cross-linked material is subjected to a pyrolysis treatment in step 3, specifically: the metal mixed cross-linked material is subjected to a pyrolysis treatment for 2 hours at a temperature of 350 to 660°C under an argon atmosphere.

6. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 5 is characterized in that the temperature for hot-pressing and sintering the highly cross-linked material in step 4 is 500-660°C and the pressure is not less than 30MPa.

7. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 6, characterized in that the temperature of hot rolling deformation treatment of the pressed sheet in step 5 is 850-1000°C.

8. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 7, characterized in that the temperature of heat treatment of the hot-rolled composite material in step 6 is 850-1000°C and the time is 2 hours.

9. The method for preparing a high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material according to claim 8, characterized in that the mass ratio of copper powder, polymethylhydrogensiloxane and triethylenediamine is: (90-98): (1.9-9.5): (0.1-0.5).

10. A high-hardness and high-wear-resistant metal-based ceramic particle in-situ reinforced composite material, characterized in that the composite material is prepared by the method according to any one of claims 1 to 9.