CN110964938B - High-entropy alloy wear-resistant composite material, preparation method and application - Google Patents
High-entropy alloy wear-resistant composite material, preparation method and application Download PDFInfo
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- CN110964938B CN110964938B CN201911402348.2A CN201911402348A CN110964938B CN 110964938 B CN110964938 B CN 110964938B CN 201911402348 A CN201911402348 A CN 201911402348A CN 110964938 B CN110964938 B CN 110964938B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
Abstract
The invention provides a high-entropy alloy wear-resistant composite material, a preparation method and application, and relates to the technical field of wear-resistant composite materials. And sintering the high-entropy alloy matrix and the uniform mixture of the external mixed reinforcing phase subjected to surface metallization pretreatment to prepare the high-entropy alloy wear-resistant composite material. The method carries out metallization pretreatment on the surface of the reinforced particles, can greatly improve the interface metallurgical bonding between the reinforced phase and the matrix, reduces the falling-off phenomenon of the reinforced particles, and indirectly improves the wear resistance of the material.
Description
Technical Field
The invention relates to the technical field of wear-resistant composite materials, in particular to a high-entropy alloy wear-resistant composite material, a preparation method and application.
Background
The high-entropy alloy has the characteristics of high strength, high hardness, high-temperature oxidation resistance, good plasticity, excellent wear resistance and the like, and is one of potential base materials of tool steel. Based on the advantages of the metal matrix composite material, the wear resistance of the high-entropy alloy matrix is greatly improved by adding the hard particles, and the method has very important engineering significance.
In the currently available hard phase reinforced high-entropy alloy composite materials (patents 201810617341.1, 201810508772.4, 201810770406.6, 201810008864.6, 201811145610.5, 201810617466.4, 20161003430.7, 201610030517.4 and the like), the hard phase mainly comprises micro-nano-scale carbides (TiC, WC, NbC, SiC), nitrides (BN), borides (TiB)2) Oxide (TiO, Sc)2O3) And diamond, and the like, and common preparation methods include a vacuum melting method, a laser plating method, a mechanical alloying method, 3D printing, and the like.
The existing high-entropy alloy and composite material still need an effective method to improve the wear resistance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a high-entropy alloy wear-resistant composite material, a preparation method and application.
The invention is realized by the following steps:
a preparation method of a high-entropy alloy wear-resistant composite material comprises the following steps: and sintering the high-entropy alloy matrix and the uniform mixture of the external mixed reinforcing phase subjected to surface metallization pretreatment to prepare the high-entropy alloy wear-resistant composite material.
In order to solve the problems in the prior art, the inventor firstly considers the adding mode of the reinforcing phase, the existing adding mode is divided into an endogenous method and an external method, reinforcing particles prepared by the endogenous method are fine, are well metallurgically combined with a matrix, have a low thermal expansion coefficient, but fine particles are easy to agglomerate, so that local components of the material are not uniform, reinforcing phase particles with the size larger than micron are difficult to generate, and the reinforcing particles are easy to be cut in a large area in the process of material abrasion, so that the disadvantages of greatly improving the hardness and the wear resistance of the high-entropy alloy are solved. In the external addition method, hard particles are directly added, so that residual gaps exist between the external particles and a matrix material, the affinity between the particles and the matrix is low, and the mechanical property is poor.
For the preparation method, in the prior art, when the non-metal reinforced particles are added by using a vacuum melting method, the factors such as thermal expansion and condensation generated in the casting process and the difference of the density, the thermal expansion coefficient and the material interface among materials exist, so that the as-cast high-entropy alloy has the defects of large grain size, obvious internal component segregation, overlarge material internal stress, more gaps, shrinkage cavities and the like; the laser plating method is more suitable for preparing the composite material with the surface layer enhancement effect; the 3D printing has high requirements on the shape and the flowability of the powder, and the input cost is high; in the conventional powder metallurgy process, the powder is usually required to be molded firstly, friction exists between the powder and a mold wall in the process, hard particles have high hardness, the prepared green body has high pore defects, and the subsequent sintering time is long, so that the growth phenomenon of the tissue in the material is obvious, and the mechanical property of the material is reduced.
How to improve the uniform distribution of the reinforcing phase and the interface affinity of the reinforcing phase and the high-entropy alloy matrix through a proper process, reduce the interface defects in the composite material, and further greatly improve the wear resistance of the high-entropy alloy matrix is a key point for preparing the high-entropy alloy composite material.
According to the invention, the surface of the reinforced particle is subjected to metallization pretreatment, so that the problem that the interface has gaps and is not firmly combined when the reinforced particle is directly contacted with a matrix can be greatly improved, the metallurgical bonding of the interface is enhanced, the quality of the composite material is improved, the phenomena of falling off of the reinforced particle and the like in the use process are reduced, and the wear resistance of the material is indirectly improved.
The invention also provides a high-entropy alloy matrix composed of 5 elements, wherein ceramic particles subjected to surface metallization pretreatment and diamond micro powder are jointly used as a reinforcing phase, and Spark Plasma Sintering (SPS) is used as a preparation method to prepare the high-entropy alloy wear-resistant composite material.
According to the invention, ceramic particles and diamond micro powder are used as an additional hybrid reinforcing phase together, and are composed of components of 'diamond micro powder-ceramic particles-samples' in space, so that a 'micro-mesoscopic-macroscopic' size difference effect is cooperatively constructed, the hybrid reinforcing particles are all cross-coated by a matrix in a three-dimensional direction, good component transition and circulation are formed in the composite material, further, the isotropy of the hardness of the high-entropy alloy wear-resistant composite material is improved, and the stability of the performance of the composite material is ensured. Through the multidimensional structure, the wear resistance of the high-entropy alloy wear-resistant composite material is greatly improved.
The surface of the reinforced particles is subjected to metallization pretreatment, so that the interface bonding force between the reinforced phase and the matrix can be greatly improved, the falling-off phenomenon of the reinforced particles is reduced, and the wear resistance of the material is indirectly improved. The invention can shorten the material preparation process and improve the efficiency by using the SPS sintering method, and the prepared composite material has the advantages of abrasion resistance, stable performance and the like, and has wide application prospect in abrasion-resistant materials.
The mixing mode of the additional mixed reinforcing phase and the high-entropy alloy matrix is dry mixing of a V-shaped mixer, the mixing time is 30-300min, preferably 60-180min, and the rotating speed is controlled to be 80-200r/min, preferably 100-150 r/min.
In a preferred embodiment of the present invention, the molecular formula of the high-entropy alloy matrix is axFeCoCrNi, wherein A is Al, Cu or Ti, and X is more than 0 and less than or equal to 2.
In a preferred embodiment of the present invention, X is 0.2-1.5.
The method provided by the invention can be used for preparing the high-entropy alloy wear-resistant composite material by using the conventional matrix with the molecular formula.
In the preferred embodiment of the present invention, the purity of the elemental metal powder is greater than or equal to 99.5%, and the particle size is 100-500 μm.
In a preferred embodiment of the present invention, the particle size of the elemental metal powder is 150-350 μm, and the elemental metal powder is spherical or nearly spherical.
If the particle size of the simple substance metal powder is too small, the rapid ball milling and mixing are not facilitated, and the time for mechanical alloying is prolonged. If the metal simple substance with the diameter of more than 500 mu m is adopted, the time for obtaining the high-entropy alloy mixed powder with the diameter of tens of microns by ball milling is greatly prolonged. Because the ball milling raw materials contain Al and other elements, the ball milling for a long time is easy to generate extremely high temperature, and hidden troubles are brought to the safety production.
The metallization pretreatment of the ceramic particles and the diamond micropowder comprises the steps of modulating the enhanced particles into a mixture by using a binder, and then sequentially drying, vacuum sintering, cooling and separating and dispersing the mixture; the reinforcing particles are a combination of alloy powder, ceramic particles and diamond micropowder.
In the preferred embodiment of the present invention, the alloy powder is a metal alloy powder of a high-entropy alloy matrix.
In a preferred embodiment of the present invention, the binder is any one of water glass, paraffin wax and polyvinyl alcohol.
In the preferred embodiment of the invention, the mixture is spread on graphite paper, dried in a drying oven, sintered in a vacuum sintering furnace, cooled with the furnace, and then the particles are separated by a mortar.
In the preferred embodiment of the present invention, the mass ratio of the binder to the reinforcing particles is 1:100 to 1: 20.
In the preferred embodiment of the invention, the drying temperature of the mixture is 50-80 ℃, and the sintering conditions are as follows: vacuumizing to 10-100Pa, heating to 850-1050 ℃ at the heating rate of 80-150 ℃/min, and keeping the temperature for 30-180 min.
In a preferred embodiment of the present invention, the pre-metallization treatment of the diamond micro-powder comprises coating and sintering the surface of the reinforcing particles with a metal alloy powder containing one or more corresponding high-entropy alloy matrix components.
In a preferred embodiment of the present invention, the diamond micro powder is micron-sized diamond micro powder, and the ceramic particles are millimeter-sized ceramic particles. Through the matching of the micron-sized diamond micro powder and the millimeter-sized ceramic particles, the problem that the reinforcing phase is poorly matched with the matrix in a tough manner when the diamond micro powder is added independently can be solved, and the defects that the hardness range is improved singly and is limited when the ceramic particles are added independently can be overcome. The structural complexity of the composite material can be increased by the cooperation of millimeter scale and micron scale. If only millimeter-sized particles or micron-sized particles are added, the inventors found that only a partial region of the structure can be increased, and that there is a defect. The best effect of flexibility matching can be achieved by adopting the compatibility of particles with different sizes and different hardness gradients, and the isotropy and the performance stability of the composite material tissue can be well ensured on the basis of greatly improving the toughness matching and the wear resistance of the composite material.
In a preferred embodiment of the present invention, the grain size of the ceramic grains after the metallization pretreatment is 1-3mm, preferably 1.2-2.5 mm; the diamond micro powder after the metallization pretreatment has the particle size of 10-50 μm, and preferably 20-40 μm.
In a preferred embodiment of the present invention, the ceramic particles are ZTA ceramic particles, carbide ceramic particles or nitride ceramic particles. The hardness of the high-entropy alloy wear-resistant composite material can be obviously improved by adopting the carbide ceramic particles or the nitride ceramic particles.
In a preferred embodiment of the present invention, ZrO contained in the above ZTA ceramic particles2The mass percentage of the components is 20-80%, preferably 25-60%.
In a preferred embodiment of the application of the invention, in the high-entropy alloy wear-resistant composite material, the additional mixed reinforcing phase accounts for 5-40% of the high-entropy alloy wear-resistant composite material by mass, wherein the ceramic particles account for less than 40% of the high-entropy alloy wear-resistant composite material by mass, and preferably account for 2.5-35% of the high-entropy alloy wear-resistant composite material by mass; the mass percentage of the diamond micro powder in the high-entropy alloy wear-resistant composite material is less than 40%, and preferably 2.5-30%.
The proportion of the added hybrid reinforced phase is 5-40%, and if the proportion exceeds 50%, the added hybrid reinforced phase is not taken as a matrix but taken as a matrix, and is commonly used for hard materials such as cutters, saw blades and the like. The application aims at the high-entropy alloy matrix which is applied to a pipeline wear-resistant part or a mechanical component of a hydraulic power plant.
In a preferred embodiment of the invention, when the external high-entropy alloy matrix is prepared, 5 kinds of elemental metal powders of the elements of the high-entropy alloy matrix are mixed and placed in a planetary high-energy ball mill for ball milling, wherein a ball milling medium is absolute ethyl alcohol, and the addition amount of the ball milling medium is 10-25% of the mass of the high-entropy alloy mixed powder; preferably 12-20%.
Because the 5 high-entropy alloy matrix elements contain Al, Cu or Ti, if a ball milling medium is not added for dry milling, the ball milling temperature is easily overhigh under the impact of high-speed ball milling particles, so that the threat to the safety production is caused. Anhydrous ethanol is selected as a ball milling medium to facilitate the removal of the ball milling medium by heating and evaporation.
In the preferred embodiment of the invention, the ball-to-material ratio in the ball milling process is 3-10: 1; preferably 5-8: 1.
In the preferred embodiment of the present invention, the rotation speed of the ball mill is set to 200-; preferably 250-400 r/min.
In the preferred embodiment of the invention, the ball milling is set to be alternately operated in a positive and negative rotation intermittent mode, and the effective ball milling time is 10-70 h; preferably 30-60 h. And the technological parameters of ball milling are adaptively adjusted according to the element content ratio of the high-entropy alloy matrix.
During preparation of the high-entropy alloy matrix powder, the storage, weighing, proportioning and packaging of the high-entropy alloy matrix powder and the tank body are all completed in a glove box filled with high-purity protective gas, then the tank body is moved and fixed on a planetary high-energy ball mill by using a clamp, and the water content and the oxygen content in the glove box are ensured to be less than 100ppm and less than 100ppm respectively. The protective gas is argon or helium.
In the preferred embodiment of the present invention, the sintering is performed by spark plasma sintering of the homogeneous mixture to obtain the high-entropy alloy wear-resistant composite material.
The spark plasma sintering includes: and placing the uniform mixture in a graphite mold, and performing spark plasma sintering.
In the preferred embodiment of the invention, the vacuum degree of the sintering chamber is set to be less than 20 Pa. Setting the sintering pressure to be 20-50 MPa; preferably 20-30 MPa. The discharge plasma sintering is carried out by heating to 800-1200 ℃ at the heating rate of 80-120 ℃/min and preserving the heat for 3-20 min; preferably, the temperature of the spark plasma sintering is raised to 850-1050 ℃ at the heating rate of 90-105 ℃/min, the sintering pressure is 20-30MPa, and the heat preservation time is 3-12 min.
The sintering process condition is adaptively adjusted according to the theoretical melting point of the external mixed reinforcing phase and the high-entropy alloy matrix.
In a preferred embodiment of the present invention, the molecular formula of the high-entropy alloy matrix is axFeCoCrNi, wherein A is Al, Cu or Ti, and X is more than 0 and less than or equal to 2; preferably, X is 0.2 to 1.5.
The maximum size range of the high-entropy alloy wear-resistant composite material prepared by the preparation method is that the diameter is more than 0mm and less than or equal to 100mm, and the height is more than 0 and less than or equal to h and less than or equal to 30 mm.
The high-entropy alloy wear-resistant composite material or the high-entropy alloy wear-resistant composite material prepared by the preparation method is applied to preparation of a reinforcement module of a complete component or a large wear-resistant component.
In the preferred embodiment of the present invention, the complete member is a hot mold, a cutting tool, a drill or a pipe, and the large wear-resistant member is a grinding roll, a lining plate or a hammer.
The invention has the following beneficial effects:
the invention provides a high-entropy alloy wear-resistant composite material, a preparation method and application. The invention provides a high-entropy alloy matrix, which is prepared by sintering an additional mixed reinforcing phase subjected to surface metallization pretreatment as a reinforcing phase. The invention carries out metallization pretreatment on the surface of the reinforced particles, can greatly improve the interface metallurgical bonding effect between the reinforced phase and the matrix in the SPS sintering process, improves the falling phenomenon of the reinforced particles caused by interface defects, and indirectly improves the wear resistance of the material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow chart of a manufacturing process of example 1 of the present invention;
FIG. 2 is a photograph of a composite material sample and a corresponding matrix in example 1 of the present invention and a comparison of the effect of bonding between the reinforcing particles and the interface (a is a photograph of the composite material sample, and b is a photograph of the matrix sample);
FIG. 3 is a comparison of the micro-topography of the composite samples of example 1 of the present invention and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a high-entropy alloy wear-resistant composite material, and the preparation process is shown in fig. 1 and comprises the following steps in sequence:
(1) the glove box filled with high purity argon shielding gas was checked to ensure that the water content was < 100ppm and the oxygen content was < 100 ppm. In a glove box, according to the formula of AlFeCoCrNi, 65g of elementary metal powder of nearly spherical aluminum, iron, cobalt, chromium and nickel with the purity of 99.5 percent and the average particle size of 300 mu m is respectively weighed. 12.5g of absolute ethyl alcohol is added into a tank body as a ball milling medium, the ball-material ratio is set to be 6:1, and after the tank body is packaged, the tank body is moved and fixed on a planetary high-energy ball mill by a clamp. And (3) starting ball milling, setting the rotating speed of the ball milling to be 300r/min, alternately operating in a positive and negative rotation intermittent mode, setting the effective ball milling time to be 50h, and drying the powder to obtain the high-entropy alloy matrix powder.
(2) Carrying out surface metallization pretreatment on the reinforced particles, which specifically comprises the following steps: weighing ZrO according to the weight percentage of the added mixed hard particles accounting for 35 percent of the composite material227g of ZTA ceramic particles with the effective component content of 40% and the particle size of 1.5-2.5mm, wherein the ZTA ceramic particles are in irregular shapes; weighing 8g of diamond micropowder with the granularity of 30 mu m, adding 1.75g of water glass serving as a binder according to the mass ratio of the binder to the mixed reinforced particles of 1:20, uniformly stirring, adding proper amount of high-entropy alloy matrix alloy powder to form a mixture, placing the mixture in a drying oven, keeping the temperature at 80 ℃ for 24 hours, and then placing in a vacuum sintering furnace for plating and sintering metal powder on the surfaces of the particles, wherein the sintering conditions are as follows: vacuumizing to 20Pa, heating to 900 ℃ at the heating rate of 100 ℃/min, and preserving the temperature for 120min to obtain the externally added mixed hard particles.
And (3) placing the high-entropy alloy matrix powder prepared in the step (1) and the added mixed hard particles in the step (2) into a V-shaped mixer for dry mixing, wherein the mixing time is 120min, and the set rotating speed is 120r/min, so that uniform mixture powder is obtained.
(3) And (3) putting the uniform mixture powder obtained in the step (2) into a graphite die, vacuumizing until the vacuum degree of a sintering cavity is less than 20Pa, the sintering pressure is 30MPa, heating to 950 ℃ at the heating rate of 105 ℃/min, preserving heat for 5min, and cooling a sample along with a furnace to obtain the high-entropy alloy wear-resistant composite material with the addition of the hard particle increasing phase.
(4) The high-entropy alloy wear-resistant composite material sample prepared in the step (3) is shown in figure 2, wherein a in figure 2 is the high-entropy alloy wear-resistant composite material sample, and b is the AlFeCoCrNi high-entropy alloy matrix sample prepared under the same process conditions.
And (3) carrying out a three-body abrasion performance test on the high-entropy alloy abrasion-resistant composite material sample prepared in the step (3) and the AlFeCoCrNi high-entropy alloy matrix sample prepared under the same process conditions by using an MMH-5 type three-body abrasive abrasion tester. Carrying out ultrasonic cleaning, drying and weighing on the sample every 2 hours, wherein the total test time is 10 hours, and the weight of the sample after each abrasion is as follows in sequence: g0、G1、G2、G3、G4、G5And the abrasion resistance of the sample is represented by comparing the final weight loss rate of the sample.
Weight loss rate (total weight loss/G)0) X 100%, total weight loss G0–G5。
The test results are shown in table 1, and it can be known from table 1 that the wear weight loss rate of the high-entropy alloy matrix sample is 6.7 times that of the composite material, that is, the abrasion resistance of the composite material is 6.7 times that of the matrix material, and the abrasion performance of the high-entropy alloy abrasion-resistant composite material prepared in the embodiment is greatly improved.
Table 1 table of sample weighing data for example 1.
Example 2
The embodiment provides a preparation method of a high-entropy alloy wear-resistant composite material, which comprises the following steps of:
(1) the glove box filled with high purity argon shielding gas was checked to ensure that the water content was < 100ppm and the oxygen content was < 100 ppm. In a glove box, according to the formula Al0.2The method comprises the following steps of proportioning FeCoCrNi, weighing 70g of simple substance metal powder of nearly spherical aluminum, iron, cobalt, chromium and nickel with the purity of 99.5% and the average particle size of 100 mu m, adding 12.5g of absolute ethyl alcohol as a ball milling medium, wherein the ball-material ratio is 8:1, and moving and fixing a tank body on a planetary high-energy ball mill by using a clamp after the tank body is packaged. And (3) starting ball milling, setting the ball milling rotation speed to be 400r/min, performing positive and negative rotation intermittent alternate operation, performing effective ball milling for 60 hours, and drying the powder to obtain the high-entropy alloy matrix powder.
(2) Carrying out surface metallization pretreatment on the reinforced particles, which specifically comprises the following steps: weighing ZrO according to the weight percentage of the added mixed hard particles accounting for 30 percent of the composite material220g of irregular ZTA ceramic particles with the active ingredient content of 30 percent and the particle size of 2-3 mm; weighing 10g of diamond micropowder with the granularity of 20 mu m, adding 0.83g of water glass serving as a binder according to the mass ratio of the binder to the mixed reinforced particles of 1:25, uniformly stirring, adding proper amount of high-entropy alloy matrix alloy powder to form a mixture, placing the mixture in a drying box, keeping the temperature at 60 ℃ for 24 hours, and then placing in a vacuum sintering furnace for plating and sintering metal powder on the surfaces of the particles, wherein the sintering conditions are as follows: vacuumizing to 30Pa, heating to 900 ℃ at the heating rate of 105 ℃/min, and preserving the temperature for 100min to obtain the externally added mixed hard particles.
And (3) putting the high-entropy alloy matrix powder prepared in the step (1) and the added mixed hard particles prepared in the step (2) into a V-shaped mixer for dry mixing for 90min at a rotating speed of 100r/min to obtain uniform mixture powder.
(3) And (3) putting the uniform mixture powder obtained in the step (2) into a graphite die, vacuumizing until the vacuum degree of a sintering cavity is less than 20Pa, the sintering pressure is 20MPa, heating to 1050 ℃ at the heating rate of 110 ℃/min, preserving the temperature for 5min, and cooling a sample along with a furnace to obtain the high-entropy alloy wear-resistant composite material reinforced by the additionally-added mixed hard particles.
(4) Simultaneously carrying out abrasion testing on the high-entropy alloy wear-resistant composite material sample prepared in the step (3) by utilizing an MMH-5 type three-body abrasive material abrasion testing machineAl prepared under the same process conditions0.2And carrying out three-body abrasion performance test on the FeCoCrNi high-entropy alloy matrix sample. Carrying out ultrasonic cleaning, drying and weighing on the sample every 2 hours, wherein the total test time is 10 hours, and the weight of the sample after each abrasion is as follows in sequence: g0、G1、G2、G3、G4、G5And the abrasion resistance of the sample is represented by comparing the final weight loss rate of the sample.
Weight loss rate (total weight loss/G)0) X 100%, total weight loss G0–G5。
The test results are shown in table 2, and it can be known from table 2 that the abrasion weight loss ratio of the high-entropy alloy matrix sample is 5.30 times that of the composite material, that is, the abrasion resistance of the composite material is 5.30 times that of the matrix material, and the abrasion performance is greatly improved.
Table 2 table of sample weighing data for example 2.
Example 3
The embodiment provides a preparation method of a high-entropy alloy wear-resistant composite material, which comprises the following steps of:
(1) the glove box filled with high purity argon shielding gas was checked to ensure that the water content was < 100ppm and the oxygen content was < 100 ppm. In a glove box, according to the molecular formula of TiFeCoCrNi, 80g of simple substance metal powder of nearly spherical titanium, iron, cobalt, chromium and nickel with the purity of 99.5 percent and the granularity of 200 mu m is weighed, 10g of absolute ethyl alcohol is added as a ball milling medium, the ball-material ratio is 5:1, then a tank body is packaged, the tank body is moved and fixed on a planetary high-energy ball mill by a clamp for ball milling, the ball milling rotation speed is 500r/min, the positive and negative rotation intermittent type alternate operation is carried out, the effective ball milling is carried out for 30h, and the high-entropy alloy matrix powder is prepared after the powder is dried.
(2) Carrying out surface metallization pretreatment on the reinforced particles, which specifically comprises the following steps: weighing ZrO according to the weight percentage of the added mixed hard particles accounting for 20 percent of the composite material2The content of the components is 20 percent, and the particle size is12.5g of irregular ZTA ceramic particles with the diameter of 2-2.5 mm; 7.5g of diamond micropowder with a particle size of 30 μm was weighed. Adding 0.67g of polyvinyl alcohol as a binder according to the mass ratio of the binder to the mixed reinforced particles being 1:30, uniformly stirring, then adding proper amount of high-entropy alloy matrix alloy powder to form a mixture, placing the mixture in a drying box, keeping the temperature at 80 ℃ for 24 hours, and then placing the mixture in a vacuum sintering furnace for plating and sintering metal powder on the surfaces of the particles, wherein the sintering conditions are as follows: vacuumizing to 20Pa, heating to 950 ℃ at the heating rate of 105 ℃/min, and preserving the temperature for 80min to obtain the externally added mixed hard particles.
And (3) placing the high-entropy alloy matrix powder prepared in the step (1) and the added mixed hard particles in the step (2) into a V-shaped mixer for dry mixing for 120min at a rotating speed of 150r/min to obtain uniform mixture powder.
(3) And (3) putting the uniform mixture powder obtained in the step (2) into a graphite die, vacuumizing until the vacuum degree of a sintering cavity is less than 20Pa, the sintering pressure is 30MPa, heating to 1000 ℃ at the heating rate of 90 ℃/min, preserving heat for 5min, and cooling a sample along with a furnace to obtain the high-entropy alloy wear-resistant composite material reinforced by additionally mixed hard particles.
(4) The method comprises the following steps of utilizing an MMH-5 type three-body abrasive wear testing machine, simultaneously carrying out three-body wear performance testing on the composite material sample and a TiFeCoCrNi high-entropy alloy matrix sample prepared under the same process conditions, carrying out ultrasonic cleaning, drying and weighing on the sample every 2 hours, carrying out the test for 10 hours, wherein the weight of the sample after each wear is as follows in sequence: g0、G1、G2、G3、G4、G5And the abrasion resistance of the sample is represented by comparing the final weight loss rate of the sample.
Weight loss rate (total weight loss/G)0) X 100%, total weight loss G0–G5。
The test results are shown in table 3, and it can be known from table 3 that the abrasion weight loss ratio of the high-entropy alloy matrix sample is 3.89 times of that of the composite material, that is, the abrasion resistance of the composite material is 3.89 times of that of the matrix material, and the abrasion performance is greatly improved.
Table 3 table of sample weighing data for example 3.
Example 4
The embodiment provides a preparation method of a high-entropy alloy wear-resistant composite material, which comprises the following steps of:
(1) the glove box filled with high purity argon shielding gas was checked to ensure that the water content was < 100ppm and the oxygen content was < 100 ppm. In a glove box, according to the formula Ti1.5The method comprises the following steps of proportioning FeCoCrNi, weighing 60g of simple substance metal powder of nearly spherical titanium, iron, cobalt, chromium and nickel with the purity of 99.5% and the granularity of 400 mu m, adding 12.5g of absolute ethyl alcohol as a ball milling medium, performing tank body packaging, moving and fixing a tank body on a planetary high-energy ball mill by using a clamp, performing ball milling, wherein the ball milling rotation speed is 300r/min, performing positive and negative rotation intermittent alternate operation, performing effective ball milling for 55h, and drying the powder to obtain the high-entropy alloy matrix powder.
(2) Carrying out surface metallization pretreatment on the reinforced particles, which specifically comprises the following steps: weighing ZrO according to the total proportion of the added mixed hard particles being 40wet DEG of the composite material235g of irregular ZTA ceramic particles with the component content of 60 percent and the particle size of 1.5-1.8 mm; 5g of diamond fine powder having a particle size of 10 μm was weighed. Adding 2g of polyvinyl alcohol as a binder according to the mass ratio of the binder to the mixed reinforced particles of 1:20, uniformly stirring, then adding proper amount of high-entropy alloy matrix alloy powder to form a mixture, placing the mixture in a drying box, keeping the temperature at 100 ℃ for 20 hours, and then placing the mixture in a vacuum sintering furnace to perform plating sintering on metal powder on the surfaces of the particles, wherein the sintering conditions are as follows: vacuumizing to 20Pa, heating to 1000 ℃ at the heating rate of 100 ℃/min, and preserving the temperature for 60min to obtain the externally added mixed hard particles.
And (3) putting the high-entropy alloy matrix powder obtained in the step (1) and the added mixed hard particles obtained in the step (2) into a V-shaped mixer for dry mixing for 200min at a rotating speed of 100r/min to obtain uniform mixture powder.
(3) And putting the mixed powder into a graphite mold, vacuumizing until the vacuum degree of a sintering cavity is less than 20Pa, the sintering pressure is 25MPa, heating to 950 ℃ at the heating rate of 80 ℃/min, preserving heat for 10min, and cooling a sample along with a furnace to obtain the high-entropy alloy wear-resistant composite material reinforced by additionally mixed hard particles.
(4) An MMH-5 type three-body abrasive abrasion tester is utilized to simultaneously carry out abrasion testing on the composite material sample and Ti prepared under the same process conditions1.5The three-body abrasion performance test is carried out on the FeCoCrNi high-entropy alloy matrix sample, the sample is subjected to ultrasonic cleaning, drying and weighing once every 2 hours, the total test time is 10 hours, and the weight of the sample after each abrasion is as follows in sequence: g0、G1、G2、G3、G4、G5And the abrasion resistance of the sample is represented by comparing the final weight loss rate of the sample.
Weight loss rate (total weight loss/G)0) X 100%, total weight loss (G) ═ G0–G5。
The test results are shown in table 4, and it can be known from table 4 that the abrasion weight loss ratio of the high-entropy alloy matrix sample is 7.73 times of that of the composite material, that is, the abrasion resistance of the composite material is 7.73 times of that of the matrix material, and the abrasion performance is greatly improved.
Table 4 table of sample weighing data for example 4.
Example 5
The embodiment provides a preparation method of a high-entropy alloy wear-resistant composite material, which comprises the following steps of:
(1) the glove box filled with high purity argon shielding gas was checked to ensure that the water content was < 100ppm and the oxygen content was < 100 ppm. In a glove box, according to the formula Cu0.5FeCoCrNi proportioning, weighing 90g of simple substance metal powder of nearly spherical copper, iron, cobalt, chromium and nickel with the purity of 99.5 percent and the granularity of 500 mu m, adding 19.3g of absolute ethyl alcohol as a ball milling medium, wherein the ball-material ratio is 3:1, then carrying out tank body encapsulation, moving and fixing the tank body on a planetary high-energy ball mill by utilizing a clamp, and carrying out ball millingThe ball milling speed is 500r/min, the positive and negative rotation intermittent alternate operation is carried out, the ball milling is effectively carried out for 70h, and the high-entropy alloy matrix powder is prepared after the powder is dried.
(2) Carrying out surface metallization pretreatment on the reinforced particles, which specifically comprises the following steps: weighing ZrO according to the total proportion of the added mixed hard particles being 10wet DEG of the composite material23g of irregular tungsten carbide particles with the component content of 30 percent and the particle size of 1-1.2 mm; weighing 7g of diamond micropowder with the granularity of 20 mu m, adding 0.2g of paraffin as a binder according to the mass ratio of 1:50 of the binder to the mixed reinforced particles, uniformly stirring, adding proper amount of high-entropy alloy matrix alloy powder to form a mixture, placing the mixture in a drying box, keeping the temperature at 50 ℃ for 20 hours, and then placing in a vacuum sintering furnace to perform plating and sintering on metal powder on the surfaces of the particles, wherein the sintering conditions are as follows: vacuumizing to 40Pa, heating to 900 ℃ at the heating rate of 90 ℃/min, and preserving the temperature for 80min to obtain the externally added mixed hard particles.
And (3) placing the high-entropy alloy matrix powder obtained in the step (1) and the added mixed hard particles obtained in the step (2) into a V-shaped mixer for dry mixing for 300min at a rotating speed of 100r/min to obtain uniform mixture powder.
(3) And putting the mixed powder into a graphite mold, vacuumizing until the vacuum degree of a sintering cavity is less than 20Pa, the sintering pressure is 25MPa, heating to 1000 ℃ at the heating rate of 120 ℃/min, preserving heat for 5min, and cooling a sample along with a furnace to obtain the high-entropy alloy wear-resistant composite material reinforced by additionally mixed hard particles.
(4) An MMH-5 type three-body abrasive abrasion tester is utilized to simultaneously test the composite material sample and the Cu prepared under the same process conditions0.5The three-body abrasion performance test is carried out on the FeCoCrNi high-entropy alloy matrix sample, the sample is subjected to ultrasonic cleaning, drying and weighing once every 2 hours, the total test time is 10 hours, and the weight of the sample after each abrasion is as follows in sequence: g0、G1、G2、G3、G4、G5And the abrasion resistance of the sample is represented by comparing the final weight loss rate of the sample.
Weight loss rate (total weight loss/G)0) X 100%, total weight loss G0–G5。
The test results are shown in table 5, and it can be known from table 5 that the abrasion weight loss ratio of the high-entropy alloy matrix sample is 1.57 times that of the composite material, that is, the abrasion resistance of the composite material is 1.57 times that of the matrix material, and the abrasion performance is improved.
Table 5 table of sample weighing data for example 5.
Comparative example 1
The difference between the comparative example and the example 1 is that in the step (2), the surface metallization pretreatment is not carried out on the added mixed hard particles ZTA ceramic particles and the diamond micropowder, and the process parameters such as the rest addition amount, the particle size and the like are the same as those in the example 1.
Experimental results show that if the surface of the reinforced particles is not subjected to metallization pretreatment and is directly mixed with high-entropy alloy matrix powder for SPS sintering, the reinforced particles without good conductivity can block effective connection and sintering between the reinforced particles and the matrix and between the alloy powder, and the preparation of the composite material is basically difficult to realize. As can be seen from the graph (a) in fig. 3, the sintered sample of example 1 forms a clean and dense bonding interface between the reinforcing particles and the matrix, and the matrix alloy is completely sintered, while as can be seen from the graph (b) in fig. 3, the sintered sample of comparative example 1 cannot form bonding between the reinforcing particles and the matrix, has a large number of voids, and the matrix portion maintains the original powder form, and no solid phase sintering process occurs.
Comparative example 2
The difference between the comparative example and the example 1 is that in the step (2), the surface metallization pretreatment is not carried out on the mixed hard particle ZTA ceramic particles, the metallization pretreatment is carried out on the diamond micropowder, and the process parameters such as the rest addition amount, the particle size and the like are the same as the example 1. The test results are as follows.
Experimental results show that the added mixed hard particles ZTA ceramic particles do not undergo surface metallization pretreatment, but only the diamond micro powder undergoes metallization pretreatment, so that the abrasion resistance of the composite material is reduced.
Comparative example 3
The comparative example is different from example 1 in that in step (2), the addition of the hybrid hard particle diamond micropowder does not perform surface metallization pretreatment, ZTA ceramic particles perform metallization pretreatment, and the rest of the process parameters such as addition amount, particle size and the like are the same as those of example 1. The test results are as follows.
Experimental results show that the added mixed hard particles ZTA ceramic particles do not undergo surface metallization pretreatment, but only do the ZTA ceramic particles undergo metallization pretreatment, so that the abrasion resistance of the composite material is reduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (19)
1. The preparation method of the high-entropy alloy wear-resistant composite material is characterized by comprising the following steps of: sintering the high-entropy alloy matrix and the uniform mixture of the external mixed reinforcing phase subjected to surface metallization pretreatment to prepare the high-entropy alloy wear-resistant composite material;
the preparation method comprises the steps of preparing an additional hybrid enhanced phase, wherein the preparation of the additional hybrid enhanced phase comprises the steps of mixing ceramic particles subjected to metallization pretreatment and diamond micro powder subjected to metallization pretreatment; the metallization pretreatment of the ceramic particles and the diamond micropowder comprises the steps of modulating the enhanced particles into a mixture by using a binder, and then sequentially drying, vacuum sintering, cooling and separating and dispersing the mixture; the reinforcing particles are a composition of alloy powder, ceramic particles and diamond micropowder;
the alloy powder is metal alloy powder of a high-entropy alloy matrix; the binder is any one of water glass, paraffin and polyvinyl alcohol;
the drying temperature of the mixture prepared by the reinforced particles is 50-100 ℃, and the sintering conditions are as follows: vacuumizing to 10-100Pa, heating to 850-;
the diamond micro powder is micron-sized diamond micro powder, and the ceramic particles are millimeter-sized ceramic particles; the mass ratio of the binder to the reinforcing particles is 1: 20-100; the granularity of the ceramic particles after the metallization pretreatment is 1-3mm, and the granularity of the diamond micro powder after the metallization pretreatment is 10-50 mu m;
the mass percentage of the additional mixed reinforcing phase in the high-entropy alloy wear-resistant composite material is 5-40%, wherein the mass percentage of the ceramic particles in the high-entropy alloy wear-resistant composite material is less than 40%, and the mass percentage of the diamond micropowder in the high-entropy alloy wear-resistant composite material is less than 40%.
2. The preparation method according to claim 1, wherein the drying, vacuum sintering, cooling and then separating and dispersing the mixture is as follows:
and dispersing and flatly paving the mixture on graphite paper, drying the graphite paper in a drying box, then placing the graphite paper in a vacuum sintering furnace for sintering, cooling the mixture along with the furnace, and then separating particles by using a mortar.
3. The production method according to claim 2, wherein the mass ratio of the binder to the reinforcing particles is 1:20 to 50.
4. The method according to claim 2, wherein the drying temperature of the mixture prepared from the reinforcing particles is 50 to 80 ℃, and the sintering conditions are as follows: vacuumizing to 20-70Pa, heating to 900-1000 ℃ at the heating rate of 90-120 ℃/min, and keeping the temperature for 60-120 min.
5. The method of claim 1, wherein the ceramic particles after the metallization pretreatment have a particle size of 1.2 to 2.5 mm; the granularity of the diamond micro powder after the metallization pretreatment is 20-40 mu m.
6. The production method according to claim 5, wherein the ceramic particles are ZTA ceramic particles, carbide ceramic particles or nitride ceramic particles.
7. The production method according to claim 6, wherein ZrO contained in the ZTA ceramic particles2The mass percentage of the components is 20-80%.
8. The production method according to claim 7, wherein ZrO contained in the ZTA ceramic particles2The mass percentage of the components is 25-60%.
9. The preparation method according to claim 1, further comprising preparing a high-entropy alloy matrix, wherein the preparing of the high-entropy alloy matrix comprises mixing elemental metal powders of 5 high-entropy alloy matrix elements, and mechanically alloying to obtain the high-entropy alloy matrix;
the molecular formula of the high-entropy alloy matrix is AxFeCoCrNi, wherein A is Al, Cu or Ti, and X is more than 0 and less than or equal to 2;
the purity of the simple substance metal powder is more than or equal to 99.5 percent, and the granularity is 500 mu m.
10. The method of claim 9, wherein X is 0.2 to 1.5;
11. the method as claimed in claim 9, wherein the elemental metal powder has a particle size of 150-350 μm; the shape of the simple substance metal powder is spherical or nearly spherical.
12. The preparation method according to claim 9, wherein in the preparation of the high-entropy alloy matrix, the simple substance metal powders of 5 high-entropy alloy matrix elements are mixed, placed in a ball mill for ball milling, and added with a ball milling medium;
the addition amount of the ball milling medium is 10-25% of the mass of the high-entropy alloy mixed powder; the ball milling medium is absolute ethyl alcohol; the ball-material ratio in the ball milling process is 3-10: 1; the rotating speed of the ball milling is 200-500 r/min; the ball milling is set to be operated alternately in a positive and negative rotating intermittent mode, and the effective ball milling time is 10-70 h.
13. The preparation method of claim 12, wherein the addition amount of the ball milling medium is 12-20% of the mass of the high-entropy alloy mixed powder;
the ball-material ratio in the ball milling process is 5-8: 1;
the rotating speed of the ball milling is 250-400 r/min;
the effective ball milling time is 30-60 h.
14. The preparation method according to claim 1, wherein in the high-entropy alloy wear-resistant composite material, the mass percentage of the ceramic particles in the high-entropy alloy wear-resistant composite material is 2.5-35%; the diamond micropowder accounts for 2.5-30% of the high-entropy alloy wear-resistant composite material by mass percent.
15. The preparation method according to claim 1, wherein the sintering is carried out by spark plasma sintering of the homogeneous mixture to obtain the high-entropy alloy wear-resistant composite material.
16. The method of claim 15, wherein the spark plasma sintering comprises: placing the uniform mixture in a graphite mold, and performing spark plasma sintering;
the vacuum degree of the sintering cavity is less than 20 Pa;
the sintering pressure is 20-50 MPa;
the discharge plasma sintering is carried out by heating to 800-1200 ℃ at a heating rate of 80-120 ℃/min and preserving the heat for 3-20 min.
17. The method as claimed in claim 16, wherein the spark plasma sintering is performed at a temperature rising rate of 90-105 ℃/min to 850-1050 ℃, a sintering pressure of 20-30MPa, and a holding time of 3-12 min.
18. A high-entropy alloy wear-resistant composite material prepared by the preparation method according to any one of claims 1 to 17, wherein the maximum size range of the high-entropy alloy wear-resistant composite material is that the diameter is more than 0mm and less than phi and less than 100mm, and the height is more than 0 and less than h and less than 30 mm.
19. Use of the high-entropy alloy wear-resistant composite material prepared by the preparation method according to any one of claims 1 to 17 or the high-entropy alloy wear-resistant composite material according to claim 18 in preparation of a reinforcement module of a complete member or a large wear-resistant member;
the complete component is a hot die, a cutting tool, a drill bit or a pipeline, and the large wear-resistant component is a grinding roller, a lining plate or a hammer.
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| CN107663607B (en) * | 2017-09-12 | 2019-06-28 | 中南大学 | A kind of high-entropy alloy holds the composite material and preparation method and application of abrasive grain |
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