CN112195463A - AlCoCrFeNi/NbC gradient high-entropy alloy coating material prepared by laser cladding and method - Google Patents
AlCoCrFeNi/NbC gradient high-entropy alloy coating material prepared by laser cladding and method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
Abstract
The invention designs a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material which comprises a substrate and an AlCoCrFeNi/NbC gradient high-entropy alloy coating, wherein the AlCoCrFeNi/NbC gradient high-entropy alloy coating contains AlCoCrFeNi high-entropy alloy and NbC ceramic particles, the atomic ratio of all elements in the high-entropy alloy is Al to Co to Cr to Fe to Ni is 1 to 1, the NbC content is continuously and gradiently changed from an inner layer to a top layer in the AlCoCrFeNi/NbC gradient high-entropy alloy coating, and the mass fractions of the NbC content are respectively 0-5 wt%, 5-15 wt% and 15-25 wt%. The cladding coating prepared on the carbon steel substrate has high hardness and wear resistance on the surface, good metallurgical bonding is formed between the cladding layers and the substrate, the toughness of the bonding position is good, the residual stress and crack driving force are small, and the prepared part is beneficial to prolonging the service life and widening the range of working conditions.
Description
Technical Field
The invention belongs to the field of laser cladding, and particularly relates to a preparation method of an AlCoCrFeNi/NbC gradient coating.
Background
The high-entropy alloy is an alloy composed of 5 or more main elements mixed in terms of the amount of the same substance or the amount of a near substance, generally has a simple solid solution composition, is not easy to form a brittle intermetallic compound, and can combine excellent properties such as high hardness and wear resistance.
The gradient cladding coating can avoid the performance mutation between the cladding layer and the substrate by continuously changing the material composition, thereby obtaining lower stress, defect and fracture tendency. Therefore, the gradient alloy material has longer service life and wider application range.
Application publication No. CN 107675046A proposes a light-weight high-strength aluminum-magnesium-copper high-entropy alloy and a preparation method thereof, and the designed high-entropy alloy has a component atom expression of AlxMgyCuzZnvSiwWherein x + y + z + v + w is 100, x is 55-90, y is 7-35, z is 1-5, v is 1-5, and w is 0.3-1. The preparation method comprises the steps of vacuum induction melting and direct pouring to obtain an alloy ingot. The high-entropy alloy prepared by the method has large segregation and internal stress, has more defects such as air holes, cracks and the like, and still belongs to aluminum magnesium alloy.
Application publication No. CN 107881501A proposes an additive composition for preparing alloy powder for a high-entropy alloy coating, the raw materials of the additive composition comprise at least three of carbon, manganese, silicon, boron starch and cellulose, and the additive is coated on the surface of a substrate before cladding, so that the performance of the high-entropy alloy coating can be improved. But the dosage of the additive can not be quantitatively analyzed, which causes difficulty in controlling the performance of the high-entropy alloy coating.
Application publication No. CN 106319260A proposes a high-melting-point high-entropy alloy and a preparation method of a coating thereof, wherein the high-entropy alloy consists of CoCrMoNbTi, and the atomic molar ratio of the components is as follows: (0.8-1.1), (0-1.1); in addition, the preparation method of the alloy laser cladding coating comprises the steps of powder preparation, ball milling, powder presetting and laser cladding. The high-entropy alloy coating prepared by the method has poor toughness, large crack driving force and residual stress, and is easy to generate cracks to cause the failure of the prepared parts.
Therefore, in order to prepare a cladding coating with good surface hardness and wear resistance, good cladding layer toughness and small internal stress and fracture tendency, it is necessary to develop a gradient high-entropy alloy cladding coating.
Disclosure of Invention
The invention aims to provide a method for laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy aiming at the defects of preparing a single-layer high-entropy alloy coating by different process methods. The method can be used for preparing the cladding layer which is in good metallurgical bonding with the substrate on the substrate, can obviously improve the toughness between the substrate and the cladding layer and between the cladding layer and the cladding layer, and reduces the residual stress and the crack driving force at the interface. The method has simple process and easy control of the thickness of the coating.
The invention relates to a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material, wherein a coating is coated on a substrate, the total thickness of the coating is 1.5-3.0 mm, and the coating is composed of high-entropy alloy and NbC; the high-entropy alloy comprises the following elements in atomic ratio: co, Cr, Fe, Ni, 1:1:1: 1; the content of NbC in the coating is increased in a gradient manner from the contact surface of the substrate and the coating to the surface of the coating; the coating is prepared by laser cladding.
As a preferred scheme, the invention relates to a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material, wherein the coating is divided into 2-3 sub-coatings, and the coating is divided into a first sub-coating, a second sub-coating and a third sub-coating along the contact surface of a substrate and the coating to the surface of the coating; after the subcoating is determined, the content of NbC in the subcoating is a fixed value and is uniformly distributed. The content of NbC in the first subcoating is 0-5 wt%, the content of NbC in the second subcoating is 5-15 wt%, the content of NbC in the third subcoating is 15-25 wt%, and the content of NbC in any two subcoats is not equal.
As a preferred scheme, the invention relates to a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material, wherein the thickness of a first subcoating layer is 0.5-0.8 mm, the thickness of a second subcoating layer is 0.5-0.8 mm, and the thickness of a third subcoating layer is 0.8-1.2 mm.
As a preferred scheme, the invention discloses a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material, wherein the thickness of a first subcoating layer is as follows: thickness of the second subcoat: the thickness of the third coating layer is 0.5-1.0: 0.5-1.0: 0.5 to 1.2, preferably 0.5 to 0.8: 0.5-0.8: 0.8-1.2. Through the optimal design of the thickness of each sub-layer and the thickness proportion and the components of each sub-layer, the residual stress can be reduced to the maximum extent, and the surface strength can be improved.
The invention relates to a preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material; the method comprises the following steps:
step one, preparing powder required by each sublayer;
uniformly mixing NbC ceramic particles with different mass fractions with high-entropy alloy raw material powder respectively; obtaining powder required by the first sublayer, powder required by the second sublayer and powder required by the third sublayer; the high-entropy alloy raw material consists of Al, Co, Cr, Fe and Ni according to the atomic ratio of 1:1:1:1: 1;
step two, layer-by-layer laying and laser cladding
2.1, laying the first sublayer raw material powder on a substrate, and carrying out laser cladding to obtain a first sublayer;
2.2 laying the second sublayer raw material powder on the first sublayer, and carrying out laser cladding to obtain a second sublayer;
2.3 laying the third sublayer raw material powder on the second sublayer, and carrying out laser cladding to obtain a third sublayer;
cooling the third sub-layer.
The invention relates to a preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material; in the first step, the raw material powder of the high-entropy alloy is element powder, and the purity of the element powder is more than or equal to 99.5%.
As a preferred scheme, the invention discloses a preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material; in the first step of the method,
preparing Al powder, Co powder, Cr powder, Fe powder and Ni powder with equal atomic ratio; NbC/(Al powder, Co powder, Cr powder, Fe powder and Ni powder) in a mass ratio of A; NbC powder is prepared according to the proportion; adding the prepared powder into a ball mill, and performing ball milling and mixing to obtain powder required by a first sublayer; a is greater than 0 and less than or equal to 0.05;
preparing Al powder, Co powder, Cr powder, Fe powder and Ni powder with equal atomic ratio; preparing NbC powder according to the mass ratio of NbC/(Al powder + Co powder + Cr powder + Fe powder + Ni powder) of 0.05-0.15; adding the prepared powder into a ball mill, and performing ball milling and mixing to obtain powder required by a second sublayer;
preparing Al powder, Co powder, Cr powder, Fe powder and Ni powder with equal atomic ratio; preparing NbC powder according to the mass ratio of NbC/(Al powder, Co powder, Cr powder, Fe powder and Ni powder) of 0.15-0.25; adding the prepared powder into a ball mill, and performing ball milling and mixing to obtain powder required by a third layer;
the powder required by the first sublayer, the powder required by the second sublayer and the powder required by the third sublayer have unequal NbC content;
the ball-milling mixed powder is prepared by adopting a low-energy ball milling method, and the method comprises the following specific steps: mixing ceramic powder weighed according to mass fraction and AlCoCrFeNi high-entropy alloy powder, adding the mixture into a ball milling tank, vacuumizing, carrying out low-energy ball milling, controlling the mass ratio of ball materials to be 5: 1-10: 1, the rotating speed to be 100-150 r/min, the ball milling time to be 1-2 h, uniformly mixing the two kinds of powder at the rotating speed of preferably 100r/min in order to prevent Al powder from aggregating and growing in the ball milling process, and cooling for 30 minutes after the ball milling is finished, and taking out the powder; the ball milling tank is a vacuum stainless steel tank, a hard alloy tank or an agate tank, the balls are stainless steel balls, hard alloy balls or zirconia balls, and the process control agent is absolute ethyl alcohol, n-heptane, stearic acid or no ball milling medium is added. The powder elements after ball milling are uniformly distributed and are suitable for being used as laser cladding powder.
As a preferred scheme, the invention discloses a preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material; the granularity of the Al powder, the Co powder, the Cr powder, the Fe powder and the Ni powder is 100-300 meshes, and the particle size of the NbC powder is 1-8 mu m.
As a preferred scheme, the invention discloses a preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material; the substrate is a substrate with a clean and dry surface. The substrate is preferably 45# steel. When the method is applied to industry, the surface of the substrate is subjected to oil and rust removal treatment. The common oil and rust removing treatment comprises the following steps: and (3) polishing or sandblasting the substrate by using #400 to #800 sandpaper, and then cleaning impurities and oil stains on the surface by using absolute ethyl alcohol or acetone.
As a preferred scheme, the invention discloses a preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material; during laser cladding, the laser is a laser 4.4KW high-power semiconductor fiber coupled laser, the laser power is 800-.
The wear resistance of the AlCoCrFeNi/NbC gradient high-entropy alloy coating material designed and prepared by the invention is improved by about 32 percent compared with that of a matrix, and the average surface hardness of the AlCoCrFeNi/NbC gradient high-entropy alloy coating material is 654 HV.
The principle is as follows:
in the invention, AlCoCrFeNi/NbC gradient high-entropy alloy is laser-cladded on the surface of a carbon steel substrate, the cladding layer phase structure of the alloy consists of FCC (face centered cubic) and BCC (body centered cubic), and the alloy has high surface hardness and better wear resistance. In addition, the gradient high-entropy alloy coating avoids sudden change of the components of the cladding layer, so that sudden change of the performance can not occur, the toughness of the joint of the cladding layer is good, and cracks are not easy to generate. Meanwhile, the thickness proportion and the components of each sub-coating are optimized, so that the performance of the product can be remarkably improved.
The invention utilizes the relative stability and the similar density of NbC and Fe, designs Fe components in the high-entropy alloy and applies the Fe components to the iron-based substrate, which is beneficial to improving the binding capacity of the coating and the substrate and is also beneficial to the uniform distribution of carbide particles in the coating.
Compared with the prior art, the invention has the following characteristics:
(1) the AlCoCrFeNi/NbC gradient high-entropy alloy coating prepared by the method has the phase structures of FCC (face centered cubic) and BCC (body centered cubic), has higher surface hardness and better wear resistance, and the cladding layer is not easy to generate cracks because the gradient high-entropy alloy coating has better toughness;
(2) compared with a ceramic particle alloy coating added under the same condition, the high-entropy alloy also has good corrosion resistance.
(3) The high-entropy alloy coating prepared by the method has the advantages of low cost, simple operation and easy realization of industrialization.
Drawings
FIG. 1 is a macroscopic texture of a cladding layer according to an embodiment;
FIG. 2 is a cross-sectional hardness curve of the gradient high entropy alloy of one embodiment;
FIG. 3 is a cross-sectional hardness curve of the gradient high entropy alloy of example two;
FIG. 4 is a macroscopic texture profile of the three cladding layers of the example;
FIG. 5 is a cross-sectional hardness curve of the gradient high-entropy alloy of comparative examples I, II and IV;
FIG. 6 shows the abrasion loss of the gradient high-entropy alloy in the first embodiment, the second embodiment, the comparative embodiment and the second embodiment.
Detailed Description
Example one
A preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material comprises the following steps:
(1) selecting Al, Co, Cr, Fe and Ni element powder to be respectively and uniformly mixed with NbC with the mass fraction of 0, 10 wt% and 20 wt% according to equal atomic ratio; the purity of the metal powder is more than 99.5%, the granularity is 100-300 meshes, and the particle size of NbC ceramic particles is 2 microns;
(2) the mixed powder is prepared by adopting a low-energy ball milling method, and the method comprises the following specific steps: respectively adding the mixed powder into a ball milling tank, vacuumizing, controlling the mass ratio of ball materials to be 5:1, the rotating speed to be 100r/min, ball milling time to be 2 hours, uniformly mixing the two kinds of powder, cooling for 30 minutes after ball milling is finished, and taking out the powder; the ball milling tank is a vacuum stainless steel tank, and the ball is a stainless steel ball without adding a ball milling medium.
(3) Pretreating a 45# steel substrate, and specifically, cleaning, drying, polishing or sand blasting by using #400 and #800 abrasive paper, and cleaning impurities and oil stains on the surface by using absolute ethyl alcohol or acetone;
(4) laying AlCoCrFeNi powder configured in the step (1) on the surface of a substrate in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(5) performing laser cladding treatment on the preset layer in the step (4), wherein the laser power is 1000W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(6) polishing the sample obtained in the step (5) by using #400 abrasive paper, paving AlCoCrFeNi +10 wt% NbC powder configured in the step (1) on the surface of the sample in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(7) performing laser cladding treatment on the preset layer in the step (6), wherein the laser power is 900W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(8) polishing the sample obtained in the step (7) by using #400 abrasive paper, paving AlCoCrFeNi +20 wt% NbC powder configured in the step (1) on the surface of the sample in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(9) and (5) carrying out laser cladding treatment on the preset layer in the step (8) according to the same parameters as those in the step (7).
(10) The resulting sample was air cooled to room temperature. The properties of the obtained product were: the distribution of the cross-section sub-layer is shown in figure 1; as can be seen in fig. 2, the surface average hardness is 654 HV; the amount of wear is shown in fig. 6, and the abrasion resistance is improved by about 32% as compared with the matrix. The maximum hardness of the obtained product is 690 HV; and the maximum hardness is positioned at the position of 0.6-0.8mm on the surface of the coating; then, a sharp drop in hardness occurred at 1.2 to 1.3mm and 2.2 to 2.3 mm.
Example two
A preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material comprises the following steps:
(1) selecting Al, Co, Cr, Fe and Ni element powder to be respectively and uniformly mixed with NbC with the mass fraction of 0, 5 wt% and 15 wt% according to equal atomic ratio; the purity of the metal powder is more than 99.5%, the granularity is 100-300 meshes, and the particle size of NbC ceramic particles is 2 microns;
(2) the mixed powder is prepared by adopting a low-energy ball milling method, and the method comprises the following specific steps: respectively adding the mixed powder into a ball milling tank, vacuumizing, controlling the mass ratio of ball materials to be 5:1, the rotating speed to be 100r/min, ball milling time to be 2 hours, and uniformly mixing the two kinds of powder; the ball milling tank is a vacuum stainless steel tank, and the ball is a stainless steel ball without adding a ball milling medium.
(3) Pretreating a 45# steel substrate, and specifically, cleaning, drying, polishing or sand blasting by using #400 and #800 abrasive paper, and cleaning impurities and oil stains on the surface by using absolute ethyl alcohol or acetone;
(4) laying AlCoCrFeNi powder configured in the step (1) on the surface of a substrate in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(5) performing laser cladding treatment on the preset layer in the step (4), wherein the laser power is 1000W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(6) polishing the sample obtained in the step (5) by using #400 abrasive paper, paving AlCoCrFeNi +5 wt% NbC powder configured in the step (1) on the surface of the sample in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(7) performing laser cladding treatment on the preset layer in the step (6), wherein the laser power is 900W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(8) polishing the sample obtained in the step (7) by using #400 abrasive paper, paving AlCoCrFeNi +15 wt% NbC powder configured in the step (1) on the surface of the sample in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(9) and (5) carrying out laser cladding treatment on the preset layer in the step (8) according to the same parameters as those in the step (7).
(10) The resulting sample was air cooled to room temperature. The properties of the obtained product were: the surface average hardness thereof is 503 HV; the amount of wear is shown in fig. 6, and the abrasion resistance is improved by about 22% compared to the matrix. In the coating 1.0-1.2mm and 1.8-2.0mm, a sharp decrease in hardness occurs due to a change in the composition of the subcoat.
Comparative example 1
A preparation method of a laser cladding AlCoCrFeNi high-entropy alloy coating material comprises the following steps:
(1) selecting Al, Co, Cr, Fe and Ni element powder to mix according to equal atomic ratio; the purity of the metal powder is more than 99.5%, and the granularity is 100-300 meshes;
(2) the mixed powder is prepared by adopting a low-energy ball milling method, and the method comprises the following specific steps: respectively adding the mixed powder into a ball milling tank, vacuumizing, controlling the mass ratio of ball materials to be 5:1, the rotating speed to be 100r/min, ball milling time to be 2 hours, and uniformly mixing the powder; the ball milling tank is a vacuum stainless steel tank, and the ball is a stainless steel ball without adding a ball milling medium.
(3) Pretreating a 45# steel substrate, and specifically, cleaning, drying, polishing or sand blasting by using #400 and #800 abrasive paper, and cleaning impurities and oil stains on the surface by using absolute ethyl alcohol or acetone;
(4) laying AlCoCrFeNi powder configured in the step (1) on the surface of a substrate in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(5) performing laser cladding treatment on the preset layer in the step (4), wherein the laser power is 900W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(6) the resulting sample was air cooled to room temperature. The properties of the obtained product were: the surface average hardness is about 210 HV; the amount of wear is shown in fig. 6, and the abrasion resistance is improved by about 8.9% as compared with the matrix.
Comparative example No. two
A preparation method of a laser cladding AlCoCrFeNi/NbC high-entropy alloy coating material comprises the following steps:
(1) uniformly mixing Al, Co, Cr, Fe and Ni element powder with 30 wt% of NbC according to equal atomic ratio; the purity of the metal powder is more than 99.5%, the granularity is 100-300 meshes, and the particle size of NbC ceramic particles is 2 microns;
(2) the mixed powder is prepared by adopting a low-energy ball milling method, and the method comprises the following specific steps: respectively adding the mixed powder into a ball milling tank, vacuumizing, controlling the mass ratio of ball materials to be 5:1, the rotating speed to be 100r/min, ball milling time to be 2 hours, and uniformly mixing the two kinds of powder; the ball milling tank is a vacuum stainless steel tank, and the ball is a stainless steel ball without adding a ball milling medium.
(3) Pretreating a 45# steel substrate, and specifically, cleaning, drying, polishing or sand blasting by using #400 and #800 abrasive paper, and cleaning impurities and oil stains on the surface by using absolute ethyl alcohol or acetone;
(4) laying AlCoCrFeNi +30 wt% NbC powder configured in the step (1) on the surface of a substrate in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(5) performing laser cladding treatment on the preset layer in the step (4), wherein the laser power is 900W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(6) the resulting sample was air cooled to room temperature. The properties of the obtained product were: the highest surface hardness can reach 489HV, and the hardness in the coating is not uniform due to the nonuniform distribution of NbC particles; the amount of wear is shown in fig. 6, and the wear resistance is improved by about 34% compared to the matrix.
Comparative example No. three
A preparation method of a laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material comprises the following steps:
(1) selecting Al, Co, Cr, Fe and Ni element powder to be respectively and uniformly mixed with NbC with the mass fraction of 0, 10 wt% and 20 wt% according to equal atomic ratio; the purity of the metal powder is more than 99.5%, the granularity is 100-300 meshes, and the particle size of NbC ceramic particles is 2 microns;
(2) the mixed powder is prepared by adopting a low-energy ball milling method, and the method comprises the following specific steps: respectively adding the mixed powder into a ball milling tank, vacuumizing, controlling the mass ratio of ball materials to be 5:1, the rotating speed to be 100r/min, ball milling time to be 2 hours, uniformly mixing the two kinds of powder, cooling for 30 minutes after ball milling is finished, and taking out the powder; the ball milling tank is a vacuum stainless steel tank, and the ball is a stainless steel ball without adding a ball milling medium.
(3) Pretreating a 45# steel substrate, and specifically, cleaning, drying, polishing or sand blasting by using #400 and #800 abrasive paper, and cleaning impurities and oil stains on the surface by using absolute ethyl alcohol or acetone;
(4) laying AlCoCrFeNi powder configured in the step (1) on the surface of a substrate in advance, and then compacting to form a preset layer with the thickness of 0.5 mm;
(5) performing laser cladding treatment on the preset layer in the step (4), wherein the laser power is 1000W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(6) polishing the sample obtained in the step (5) by using #400 abrasive paper, paving AlCoCrFeNi +10 wt% NbC powder configured in the step (1) on the surface of the sample in advance, and then compacting to form a preset layer with the thickness of 0.5 mm;
(7) performing laser cladding treatment on the preset layer in the step (6), wherein the laser power is 900W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(8) polishing the sample obtained in the step (7) by using #400 abrasive paper, paving AlCoCrFeNi +20 wt% NbC powder configured in the step (1) on the surface of the sample in advance, and then compacting to form a preset layer with the thickness of 2 mm;
(9) and (5) carrying out laser cladding treatment on the preset layer in the step (8) according to the same parameters as those in the step (7).
(10) The resulting sample was air cooled to room temperature. As shown in fig. 4, the first sub-layer and the second sub-layer of the obtained product have too thin thickness of the pre-fabricated powder, and the thickness of the prepared layer is about 0.2mm or less, so that the transition and bearing functions cannot be achieved; if the coating is prefabricated too thick, the prepared coating has uneven appearance and cannot be directly produced and applied.
Comparative example No. four
Laser cladding AlCoCrFeNi/Al2O3The preparation method of the high-entropy alloy coating material comprises the following steps:
(1) al, Co, Cr, Fe and Ni element powder is selected according to the equal atomic ratio and the mass fraction of 20wt percent2O3Uniformly mixing; the purity of the metal powder is more than 99.5%, the granularity is 100-300 meshes, and Al is2O3The grain diameter of the ceramic particles is 2 mu m;
(2) the mixed powder is prepared by adopting a low-energy ball milling method, and the method comprises the following specific steps: respectively adding the mixed powder into a ball milling tank, vacuumizing, controlling the mass ratio of ball materials to be 5:1, the rotating speed to be 100r/min, ball milling time to be 2 hours, and uniformly mixing the two kinds of powder; the ball milling tank is a vacuum stainless steel tank, and the ball is a stainless steel ball without adding a ball milling medium.
(3) Pretreating a 45# steel substrate, and specifically, cleaning, drying, polishing or sand blasting by using #400 and #800 abrasive paper, and cleaning impurities and oil stains on the surface by using absolute ethyl alcohol or acetone;
(4) mixing the AlCoCrFeNi +20 wt% Al prepared in the step (1)2O3Laying the powder on the surface of a substrate in advance, and then compacting to form a preset layer with the thickness of 1 mm;
(5) performing laser cladding treatment on the preset layer in the step (4), wherein the laser power is 900W, the spot diameter is 4mm, the scanning speed is 4mm/s, and Ar gas is adopted for protection in the cladding process;
(6) the resulting sample was air cooled to room temperature. The properties of the obtained product were: the surface average hardness is about 441 HV; the wear resistance was improved by about 23% as shown in FIG. 6.
It can be seen from examples 1 and 2 and comparative example 1 that the hardness and wear resistance of the coating can be greatly improved by adding ceramic particles into the high-entropy alloy cladding layer, which proves that the optimized scheme of the invention achieves unexpected effects (see fig. 2, 3, 5 and 6).
It can be seen from example 1 and comparative example 2 that when ceramic particles are added into the high-entropy alloy cladding layer, the hardness and wear resistance of the coating are not greatly improved when the ceramic particles exceed 20 wt.%, which proves that the optimized scheme of the invention has certain economic effect (see fig. 2, 5 and 6).
Through the embodiment 1 and the comparative example 3, it can be seen that the proper cladding thickness can greatly affect the forming quality of the cladding layer, which proves that the optimized scheme of the invention has certain practical effect and use value (see fig. 1 and 4).
The improvement of the addition of SiC particles can be maximized by example 1 and comparative example 4, wherein the mass fraction is the same. This is seen to demonstrate the unexpected results achieved by the optimized version of the invention (see figures 2, 5, 6).
Claims (10)
1. A laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material is characterized in that: the coating is coated on a substrate, the total thickness of the coating is 1.5-3.0 mm, and the coating is composed of high-entropy alloy and NbC strengthening phase; the high-entropy alloy comprises the following elements in atomic ratio: co, Cr, Fe, Ni, 1:1:1: 1; the content of NbC in the coating is increased in a gradient manner from the contact surface of the substrate and the coating to the surface of the coating; the coating is prepared by laser cladding.
2. The laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 1, which is characterized in that: the coating is divided into 2-3 sub-coatings, and the coating is divided into a first sub-coating, a second sub-coating and a third sub-coating along the contact surface of the substrate and the coating to the surface of the coating; after the subcoating is determined, the content of NbC in the subcoating is a fixed value and is uniformly distributed. The content of NbC in the first subcoating is 0-5 wt%, the content of NbC in the second subcoating is 5-15 wt%, the content of NbC in the third subcoating is 15-25 wt%, and the content of NbC in any two subcoats is not equal.
3. The laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 2, which is characterized in that: the thickness of the first sub-coating layer is 0.5-0.8 mm, the thickness of the second sub-coating layer is 0.5-0.8 mm, and the thickness of the third sub-coating layer is 0.8-1.2 mm.
4. The laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 3, which is characterized in that: thickness of the first subcoat: thickness of the second subcoat: the thickness of the third coating layer is 0.5-1.0: 0.5-1.0: 0.5 to 1.2, preferably 0.5 to 0.8: 0.5-0.8: 0.8-1.2.
5. A preparation method of the AlCoCrFeNi/NbC gradient high-entropy alloy coating material laser-clad according to any one of claims 1 to 4; it is characterized in that; the method comprises the following steps:
step one, preparing powder required by each sublayer;
uniformly mixing NbC ceramic particles with different mass fractions with high-entropy alloy raw material powder respectively; obtaining powder required by the first sublayer, powder required by the second sublayer and powder required by the third sublayer; the high-entropy alloy raw material consists of Al, Co, Cr, Fe and Ni according to the atomic ratio of 1:1:1:1: 1;
step two, layer-by-layer laying and laser cladding
2.1, laying the first sublayer raw material powder on a substrate, and carrying out laser cladding to obtain a first sublayer;
2.2 laying the second sublayer raw material powder on the first sublayer, and carrying out laser cladding to obtain a second sublayer;
2.3 laying the third sublayer raw material powder on the second sublayer, and carrying out laser cladding to obtain a third sublayer;
cooling the third sub-layer.
6. The preparation method of the laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 5; the method is characterized in that: in the first step, the raw material powder of the high-entropy alloy is element powder, and the purity of the element powder is more than or equal to 99.5%.
7. The preparation method of the laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 5; the method is characterized in that: in the first step of the method,
preparing Al powder, Co powder, Cr powder, Fe powder and Ni powder with equal atomic ratio; and NbC/(Al powder, Co powder, Cr powder, Fe powder and Ni powder) is 0-0.05 by mass ratio; adding the prepared powder into a ball mill, and performing ball milling and mixing to obtain powder required by a first sublayer;
preparing Al powder, Co powder, Cr powder, Fe powder and Ni powder with equal atomic ratio; preparing NbC powder according to the mass ratio of NbC/(Al powder + Co powder + Cr powder + Fe powder + Ni powder) of 0.05-0.15; adding the prepared powder into a ball mill, and performing ball milling and mixing to obtain powder required by a second sublayer;
preparing Al powder, Co powder, Cr powder, Fe powder and Ni powder with equal atomic ratio; preparing NbC powder according to the mass ratio of NbC/(Al powder, Co powder, Cr powder, Fe powder and Ni powder) of 0.15-0.25; adding the prepared powder into a ball mill, and performing ball milling and mixing to obtain powder required by a third layer;
the powder required by the first sublayer, the powder required by the second sublayer and the powder required by the third sublayer have unequal NbC content;
when the materials are mixed by ball milling, the mass ratio of the ball materials is controlled to be 5: 1-10: 1, the rotating speed is 100-150 r/min, and the ball milling time is 1-2 h.
8. The preparation method of the laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 5; the method is characterized in that: the granularity of the Al powder, the Co powder, the Cr powder, the Fe powder and the Ni powder is 100-300 meshes, and the particle size of the NbC powder is 1-8 mu m.
9. The preparation method of the laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 5; the method is characterized in that: the substrate is a substrate with a clean and dry surface. The substrate is preferably 45# steel.
10. The preparation method of the laser cladding AlCoCrFeNi/NbC gradient high-entropy alloy coating material of claim 5; the method is characterized in that: during laser cladding, the laser is a laser 4.4KW high-power semiconductor fiber coupled laser, the laser power is 800-.
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