CN114700495A - A kind of nickel-based composite material with high wear resistance and corrosion resistance without cracking and preparation method thereof - Google Patents

Abstract

The invention discloses a non-cracking, high wear-resistant and corrosion-resistant nickel-based composite material and a preparation method thereof, belonging to the technical field of laser additive manufacturing. At least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder in the powder, both niobium and tantalum are strong carbide forming elements, and will preferentially combine with carbon in the molten pool to form niobium carbide or Tantalum carbide avoids the formation of coarse carbides. At the same time, niobium carbide or tantalum carbide has low Gibbs free energy, and will preferentially grow in the molten pool. At the same time, a certain proportion of reinforced ceramic phase powder can be added to disperse The strengthening effect prevents the hardness of the alloy from being greatly reduced, so that the increase in the plasticity and toughness of the nickel-based composite powder can be achieved by inhibiting the formation of coarse brittle phases and increasing the heterogeneous nucleation particles, which can make the prepared nickel-based composite coating. Cracking and has high wear and corrosion resistance.

Description

A kind of nickel-based composite material with high wear resistance and corrosion resistance without cracking and preparation method thereof

technical field

The invention relates to the technical fields of laser additive manufacturing, laser cladding and laser thermal spraying, in particular to a non-cracking, high wear-resistant and corrosion-resistant nickel-based composite material and a preparation method thereof.

Background technique

At present, when the nickel-based coating is prepared by laser cladding technology in China to improve the wear resistance of the substrate, due to the high hardness of the Ni45 or Ni60 powder used, the resulting coating has poor plasticity and toughness. Defects such as cracks are easily generated during the preparation process, and these defects will greatly reduce the corrosion resistance of the coating, so that the substrate cannot be effectively protected. However, most of the current methods for preparing nickel-based composite materials are relatively complex, or the added elements are relatively high and the price is high, resulting in a substantial increase in the preparation cost. promotion and application of overlay technology.

SUMMARY OF THE INVENTION

The invention provides a non-cracking, high wear-resistant and corrosion-resistant nickel-based composite material and a preparation method thereof, aiming at solving the defects of poor plastic toughness and complicated preparation process of the nickel-based composite material. The modification of nickel-based powder is realized by a simple process, and the preparation process is simplified.

The specific technical scheme provided by the present invention is as follows:

In the first aspect, the present invention provides a non-cracking, high wear and corrosion resistant nickel-based composite material, characterized in that the raw materials of the nickel-based composite material include a mass ratio of 20-30:0.5-2: Nickel-based alloy powder, niobium powder and reinforced ceramic phase powder of 2-6, wherein the powder particle size of the nickel-based alloy powder is 10-150 μm, the single particle size of the niobium powder is 4-6 μm, and the The aggregate size of the niobium powder is 10-150 μm, the reinforced ceramic phase powder includes at least one of niobium carbide powder and niobium boride powder, the single particle size of the reinforced ceramic phase powder is 1-4 μm, and the reinforced ceramic phase powder has a particle size of 1-4 μm. The aggregate size of the ceramic phase powder is 10-150 μm.

In the second aspect, the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. Nickel-based alloy powder, tantalum powder, and reinforced ceramic phase powder, wherein the powder particle size of the nickel-based alloy powder is 10-150 μm, the particle size of a single particle of the tantalum powder is 4-6 μm, and the aggregation of the tantalum powder The size is 10-150 μm, the reinforced ceramic phase powder includes at least one of tantalum carbide powder and tantalum boride powder, the single particle size of the reinforced ceramic phase powder is 1-4 μm, and the reinforced ceramic phase powder The aggregate size is 10-150 μm.

In a third aspect, the present invention provides a nickel-based composite material with no cracking, high wear resistance and corrosion resistance, wherein the raw materials of the nickel-based composite material include 20-30:0.5-2:2-6 by mass ratio. Nickel-based alloy powder, a mixture of niobium powder and tantalum powder, and a reinforced ceramic phase powder, wherein the nickel-based alloy powder has a powder particle size of 10-150 μm, and a single particle particle size of the niobium powder is 4-6 μm, so The aggregated size of the niobium powder is 10-150 μm, the single particle size of the tantalum powder is 4-6 μm, the aggregated size of the tantalum powder is 10-150 μm, and the reinforced ceramic phase powder includes niobium carbide powder, boride At least one of niobium powder, tantalum carbide powder and tantalum boride powder, the single particle size of the reinforced ceramic phase powder is 1-4 μm, and the aggregate size of the reinforced ceramic phase powder is 10-150 μm.

In a fourth aspect, the present invention provides a non-cracking, high wear and corrosion resistant nickel-based composite material, the nickel-based composite material is composed of nickel-based composite materials with a mass fraction ratio of 20-30:0.5-2:2-6 Alloy powder, at least one of niobium powder and tantalum powder, and raw materials composed of reinforced ceramic phase powder are mixed, wherein the nickel-based alloy powder has a powder particle size of 10-150 μm, and a single particle of the niobium powder The particle size is 4-6 μm, the aggregate size of the niobium powder is 10-150 μm, the particle size of a single particle of the tantalum powder is 4-6 μm, the aggregate size of the tantalum powder is 10-150 μm, and the reinforced ceramic phase The powder includes at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder, the single particle size of the reinforced ceramic phase powder is 1-4 μm, and the aggregate size of the reinforced ceramic phase powder 10 to 150 μm.

Optionally, the powder particle size of the nickel-based alloy powder is 17-53 μm, the single particle size of the niobium powder is 4-5 μm, the aggregate size of the niobium powder is 17-53 μm, and the single particle size of the niobium carbide powder is 2-5 μm. 3μm, the aggregate size of niobium carbide powder is 10-20μm, the single particle size of niobium boride powder is 2-3μm, the aggregate size of niobium boride powder is 10-20μm, and the single particle size of tantalum powder is 4-5μm , the aggregate size of tantalum powder is 17-53 μm, the particle size of tantalum carbide powder is 2-3 μm, the aggregate size of tantalum carbide powder is 10-20 μm, the single particle size of tantalum boride powder is 2-3 μm, boron The aggregate size of the tantalum powder is 10-20 μm.

In a fifth aspect, an embodiment of the present invention provides a method for preparing a nickel-based composite material with high wear and corrosion resistance without cracking, the method comprising:

Add at least one of nickel-based alloy powder, niobium powder and tantalum powder with a mass fraction ratio of 20～30:0.5～2:2～6, and reinforced ceramic phase powder into the ball mill jar, and alternate in turn according to forward rotation and reverse rotation. The ball milling is carried out for 200 to 260 minutes in a cyclic ball milling method. The ball milling is restarted after stopping for 3 to 6 minutes after every 10 to 30 minutes of ball milling. 70-100 r/min, the reinforced ceramic phase powder includes at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder.

Optionally, ball milling is carried out for 240 minutes according to the ball milling method in which forward rotation and reverse rotation are alternately cycled, wherein the ball milling is restarted after stopping for 5 minutes after every 20 minutes of ball milling. The rotation speed is 90r/min.

Optionally, the stainless steel ball grinding beads used in the ball milling process include large balls, medium balls and small balls with a mass ratio of 1-2:3-6:2-4, wherein the large balls, medium balls and small balls are of diameter size. The ball-to-material ratio in the ball milling process is 5 to 15:1 for the three sizes of balls that are gradually decreasing; the diameter of the large ball is larger than the diameter of the medium ball and less than 2 times the diameter of the medium ball, and the diameter of the medium ball is larger than the diameter of the small ball and smaller than that of the small ball. 3 times the diameter, the ball-to-material ratio in the ball milling process is 10:1, and the mass ratio of the large balls, medium balls and small balls in the stainless steel ball mill beads used in the ball milling process is 2:5:3.

Optionally, the diameter of the small ball is 1.5 mm, the diameter of the medium ball is 3 mm, and the diameter of the large ball is 5 mm.

Optionally, the forward rotation speed and the reverse rotation speed in the ball milling process are the same, and the nickel 45 powder, the niobium powder and the niobium carbide powder are uniformly mixed after ball milling and show a powder form in which the small particle powder wraps the large particle powder.

In the sixth aspect, the present invention provides a method for preparing a nickel-based composite material with high wear resistance and corrosion resistance without cracking, the method comprising:

Add at least one of nickel-based alloy powder, niobium powder and tantalum powder in a ratio of 20～30:0.5～2:2～6 to the atomizer, strengthen the ceramic phase powder, and then add at least one of nickel-based alloy powder, niobium powder and tantalum powder in a ratio of 20～30:0.5～2:2～6. Atomization or water atomization is prepared into a mixed powder form in which small particle powder wraps large particle powder, wherein the reinforced ceramic phase powder includes niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder. at least one.

The beneficial effects of the present invention are as follows: the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. Including at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder, both niobium and tantalum are strong carbide forming elements, and will preferentially combine with carbon in the molten pool to form niobium carbide or tantalum carbide , to avoid the formation of coarse carbides, and at the same time, niobium carbide or tantalum carbide has a low Gibbs free energy, which will preferentially grow in the molten pool, and a certain proportion of niobium carbide, niobium boride, tantalum carbide or Tantalum boride can play the role of dispersion strengthening to prevent the hardness of the alloy from being greatly reduced. Therefore, by inhibiting the formation of coarse brittle phases and increasing the number of heterogeneous nucleation particles, the plastic and toughness of nickel-based composites can be increased, which solves the problem of nickel-based composites. The defects of poor plasticity and toughness of the material and complicated preparation process can make the prepared nickel-based composite coating not crack and have high wear resistance and corrosion resistance.

Description of drawings

In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without creative effort.

1 is a schematic view of the microscopic morphology of each raw material powder of a nickel-based composite material with high wear resistance and corrosion resistance without cracking according to an embodiment of the present invention;

FIG. 2 is a schematic view of the microscopic morphology of the nickel-based composite material after ball milling according to an embodiment of the present invention.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

The terms "comprising" and "having" and any variations thereof in the description and claims of the present invention are intended to cover non-exclusive inclusion, eg, a process, method, system, product or product comprising a series of steps or units. The apparatus is not necessarily limited to those steps or units expressly listed, but may include other steps or units not expressly listed or inherent to the process, method, product or apparatus.

A nickel-based composite material with high wear resistance and corrosion resistance without cracking according to an embodiment of the present invention will be described in detail below with reference to FIGS. 1 to 2 .

The inventors of the embodiments of the present invention have made creative efforts to observe and analyze the prepared cracked nickel-based coatings, and found out that the cracks of the nickel-based coatings are mainly caused by the precipitation of highly hard and brittle coarse carbides at the grain boundaries. Network carbide dendrites, and then because high-speed laser cladding is an additive manufacturing process with fast heating and rapid cooling, and then under the action of thermal stress caused by strong thermal imbalance, the network carbides crack along the grain boundaries, resulting in coating. The layer cracks, which reduces its corrosion resistance.

It is precisely based on the above analysis and findings that the embodiment of the present invention innovatively adds a certain proportion of niobium and niobium carbide to the nickel-based alloy powder. Niobium is a strong carbide forming element, and will preferentially combine with carbon in the molten pool to form niobium carbide. , to avoid the formation of coarse carbides, and at the same time, niobium carbide has a low Gibbs free energy, which will preferentially grow in the molten pool. At the same time, a certain proportion of niobium carbide can play a role in dispersion strengthening to prevent the hardness of the alloy from being greatly reduced. Therefore, by suppressing the formation of coarse and brittle phases and increasing heterogeneous nucleation particles, the increase of the plasticity and toughness of the nickel-based composite material is realized, and the defects of poor plasticity and toughness of the nickel-based composite material and complicated preparation process are solved, which can The prepared nickel-based composite coating does not crack and has high wear resistance and corrosion resistance.

Example 1

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. Nickel-based alloy powder, niobium powder and reinforced ceramic phase powder, wherein the powder particle size of the nickel-based alloy powder is 10-150 μm, the single particle size of the niobium powder is 4-6 μm, and the aggregate size of the niobium powder is 10-150 μm, The reinforced ceramic phase powder includes at least one of niobium carbide powder and niobium boride powder, the single particle size of the reinforced ceramic phase powder is 1-4 μm, and the aggregate size of the reinforced ceramic phase powder is 10-150 μm. The nickel-based alloy powder includes, but is not limited to, nickel 45, nickel 40, nickel 50, nickel 55, nickel 60, etc., which is not limited in the embodiment of the present invention.

In the embodiment of the present invention, the brittle ceramic phase is suppressed by adding Nb or Ta and other strong carbide and boride generating elements (carbide and boride are the main strengthening ceramic phases of nickel-based alloys, and are also the main cause of cracking). Suppresses cracking during coating preparation. Then, through the subsequent aging heat treatment, a new strengthened ceramic phase is generated to further improve the hardness and strength of the coating, and because the higher stress generated during the preparation of the coating is effectively released during high temperature heat treatment, the generation of cracks (crack generation) is avoided. The root cause is brittle phase + higher stress).

Among them, preferably, the raw materials include nickel-based alloy powder, niobium powder and reinforced ceramic phase powder with a mass ratio of 25:1:4, wherein the powder particle size of the nickel-based alloy powder is 17-53 μm, and the niobium powder has a particle size of 17-53 μm. The particle size of a single particle is 4 to 5 μm, and the aggregate size of the niobium powder is 17 to 53 μm. The reinforced ceramic phase powder includes at least one of niobium carbide powder and niobium boride powder, and the single particle size of the reinforced ceramic phase powder is 2 to 53 μm. 3 μm, and the aggregate size of the reinforced ceramic phase powder is 10 to 20 μm.

By optimizing the selection of the powder particle size of the nickel-based alloy powder, niobium powder and niobium carbide powder, the added niobium element can fully reduce the crack sensitivity of the nickel-based composite powder and improve its wear resistance performance. It can play a dispersion strengthening effect on the nickel matrix to ensure that its hardness will not drop too much; appropriate powder particle size selection and ball milling process settings will eventually form a coated powder to ensure the uniformity of powder composition and good fluidity. By optimally selecting the powder particle size of nickel-based alloy powder, niobium powder and niobium carbide powder, the powder morphology of small-particle powder wrapping large-particle powder can be realized, which can further avoid cracking of high-hard nickel-based alloy coating and improve its corrosion resistance. .

Example 2

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. Nickel-based alloy powder, niobium powder and niobium carbide powder, wherein the nickel-based alloy powder has a powder particle size of 10-150 μm, a single particle particle size of the niobium powder is 4-6 μm, and the aggregate size of the niobium powder The particle size of the niobium carbide powder is 10-150 μm, the single particle size of the niobium carbide powder is 1-4 μm, and the aggregate size of the niobium carbide powder is 10-150 μm.

By adding a certain proportion of niobium and niobium carbide to the nickel-based alloy powder, niobium is a strong carbide forming element, and it will preferentially combine with carbon to form niobium carbide in the molten pool, avoiding the formation of coarse carbides, and at the same time, niobium carbide has lower The Gibbs free energy of the alloy will preferentially grow in the molten pool, and at the same time, a certain proportion of niobium carbide can play a role in dispersion strengthening to prevent the hardness of the alloy from being greatly reduced, thereby inhibiting the formation of coarse brittle phases and increasing heterogeneity. The method of forming nucleation particles realizes the increase of the plastic and toughness of the nickel-based composite material, solves the defects of poor plastic and toughness of the nickel-based composite material and complicated preparation process, and can make the prepared nickel-based composite coating not crack and have high performance. Wear and corrosion resistance.

Example 3

The embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. The ceramic phase powder, wherein the powder particle size of the nickel-based alloy powder is 10-150 μm, the single particle size of the tantalum powder is 4-6 μm, the aggregate size of the tantalum powder is 10-150 μm, and the strengthened ceramic phase powder includes tantalum carbide powder and In at least one of the tantalum boride powders, the single particle size of the reinforced ceramic phase powder is 1-4 μm, and the aggregate size of the reinforced ceramic phase powder is 10-150 μm.

In the present invention, a certain proportion of tantalum, tantalum carbide or tantalum boride is added to the nickel-based alloy powder. Tantalum is a strong carbide forming element, and it will preferentially combine with carbon or boron in the molten pool to form tantalum carbide or tantalum boride, so as to avoid The formation of coarse carbides or borides, while tantalum carbide or tantalum boride has a lower Gibbs free energy, will preferentially grow in the molten pool, and a certain proportion of tantalum carbide or tantalum boride can be added. Dispersion strengthening prevents the alloy's hardness from being greatly reduced, so by suppressing the formation of coarse brittle phases and increasing heterogeneous nucleation particles, the increase in the plasticity and toughness of nickel-based composites is achieved, and the poor plasticity and toughness of nickel-based composites is solved. And the defect of the relatively complicated preparation process can make the prepared nickel-based composite coating not crack and have high wear resistance and corrosion resistance.

Preferably, the raw materials include nickel-based alloy powder, tantalum powder and reinforced ceramic phase powder with a mass ratio of 25:1:4, wherein the powder particle size of the nickel-based alloy powder is 17-53 μm, and a single particle of the tantalum powder The particle size is 4 to 5 μm, the aggregate size of the tantalum powder is 17 to 53 μm, the reinforced ceramic phase powder includes at least one of tantalum carbide powder and tantalum boride powder, and the particle size of a single particle of the reinforced ceramic phase powder is 2 to 3 μm, The aggregate size of the reinforced ceramic phase powder is 10-20 μm.

By optimally selecting the powder particle size of nickel-based alloy powder, tantalum powder, tantalum carbide powder or tantalum boride powder, the added tantalum element can fully reduce the crack sensitivity of nickel-based composite powder and improve its wear resistance performance. The addition of tantalum carbide and tantalum boride can disperse and strengthen the nickel matrix to ensure that its hardness will not drop too much; appropriate powder particle size selection and ball milling process settings will eventually form coated powder to ensure powder composition. uniformity and good fluidity. By optimizing the powder particle size of nickel-based alloy powder, niobium powder and niobium carbide powder, the powder morphology of small-particle powder wrapping large-particle powder can be realized, which can further avoid cracking of high-hard nickel-based alloy coating and improve its corrosion resistance. .

Example 4

The embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. The mixture of powders and the reinforced ceramic phase powder, wherein the powder particle size of the nickel-based alloy powder is 10-150 μm, the single particle size of the niobium powder is 4-6 μm, the aggregate size of the niobium powder is 10-150 μm, and the single particle size of the tantalum powder is 10-150 μm. The particle size is 4-6 μm, the aggregate size of the tantalum powder is 10-150 μm, the reinforced ceramic phase powder includes at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder, and the reinforced ceramic phase powder is The particle size of the single particle is 1-4 μm, and the aggregate size of the reinforced ceramic phase powder is 10-150 μm.

In the embodiment of the present invention, the brittle ceramic phase is suppressed by adding strong carbide and boride generating elements such as niobium or tantalum (carbide and boride are the main strengthening ceramic phases of nickel-based alloys, and are also the main reason for cracking). Suppresses cracking during coating preparation. Then, through the subsequent aging heat treatment, a new strengthened ceramic phase is generated to further improve the hardness and strength of the coating, and because the higher stress generated during the preparation of the coating is effectively released during high temperature heat treatment, the generation of cracks (crack generation) is avoided. The root cause is brittle phase + higher stress).

By adding a certain proportion of niobium, tantalum and reinforced ceramic phase powder to the nickel-based alloy powder, the reinforced ceramic phase powder includes at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder, niobium and tantalum boride powder. Tantalum is a strong carbide forming element. It will preferentially combine with carbon in the molten pool to form niobium carbide or tantalum carbide to avoid the formation of coarse carbides. At the same time, niobium carbide or tantalum carbide has low Gibbs free energy. The molten pool will preferentially grow up, and at the same time, a certain proportion of niobium carbide, niobium boride, tantalum carbide or tantalum boride can play a role in dispersion strengthening to prevent the alloy hardness from being greatly reduced, thereby inhibiting the formation of coarse brittle phases. The method of increasing the heterogeneous nucleation particles realizes the increase of the plasticity and toughness of the nickel-based composite material, solves the defects of poor plasticity and toughness of the nickel-based composite material and complicated preparation process, and can make the prepared nickel-based composite coating not crack and Has high wear and corrosion resistance.

Preferably, the powder particle size of the nickel-based alloy powder is 17-53 μm, the single particle size of the niobium powder is 4-5 μm, the aggregate size of the niobium powder is 17-53 μm, and the single particle size of the niobium carbide powder is 2-3 μm , the aggregate size of niobium carbide powder is 10～20μm, the particle size of niobium boride powder is 2～3μm, the aggregate size of niobium boride powder is 10～20μm, the particle size of tantalum powder is 4～5μm, The aggregate size of the tantalum powder is 17-53 μm, the single particle size of the tantalum carbide powder is 2-3 μm, the aggregate size of the tantalum carbide powder is 10-20 μm, and the single particle size of the tantalum boride powder is 2-3 μm. The aggregate size of the tantalum powder is 10-20 μm.

By optimally selecting the powder particle size of nickel-based alloy powder, niobium powder, niobium carbide powder, niobium boride powder, tantalum powder, tantalum carbide powder and tantalum boride powder, the added niobium and tantalum elements can fully reduce the nickel-based composite The crack sensitivity of the powder improves its wear resistance performance, and the addition of any one of niobium carbide, niobium boride, tantalum carbide and tantalum boride can play a dispersion strengthening effect on the nickel matrix and ensure its hardness. It will not drop too much; proper powder particle size selection and ball milling process settings will eventually form a coated powder to ensure uniformity of powder composition and good flowability. By optimizing the selection of powder particle sizes of nickel-based alloy powder, niobium powder, niobium carbide powder, niobium boride powder, tantalum powder, tantalum carbide powder and tantalum boride powder, the powder morphology of small particle powder wrapped with large particle powder can be further Avoid cracking of high-hard nickel-based alloy coatings and improve their corrosion resistance.

Example 5

The embodiment of the present invention provides a nickel-based composite material with no cracking, high wear resistance and corrosion resistance, which is composed of nickel-based alloy powder, niobium powder and tantalum powder with a mass fraction ratio of 20-30:0.5-2:2-6 At least one raw material composed of reinforced ceramic phase powder is mixed and formed, wherein the powder particle size of the nickel-based alloy powder is 10-150 μm, the single particle size of the niobium powder is 4-6 μm, and the aggregate size of the niobium powder is 10 to 150 μm, the single particle size of the tantalum powder is 4 to 6 μm, the aggregate size of the tantalum powder is 10 to 150 μm, and the reinforced ceramic phase powder includes niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder. At least one, the single particle size of the reinforced ceramic phase powder is 1-4 μm, and the aggregate size of the reinforced ceramic phase powder is 10-150 μm.

In the embodiment of the present invention, the brittle ceramic phase is suppressed by adding strong carbide and boride generating elements such as niobium or tantalum (carbide and boride are the main strengthening ceramic phases of nickel-based alloys, and are also the main reason for cracking). Suppresses cracking during coating preparation. Then, through the subsequent aging heat treatment, a new strengthened ceramic phase is generated to further improve the hardness and strength of the coating, and because the higher stress generated during the preparation of the coating is effectively released during high temperature heat treatment, the generation of cracks (crack generation) is avoided. The root cause is brittle phase + higher stress).

By adding a certain proportion of niobium, tantalum and reinforced ceramic phase powder to the nickel-based alloy powder, the reinforced ceramic phase powder includes at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder, niobium and tantalum boride powder. Tantalum is a strong carbide forming element. It will preferentially combine with carbon in the molten pool to form niobium carbide or tantalum carbide to avoid the formation of coarse carbides. At the same time, niobium carbide or tantalum carbide has low Gibbs free energy. The molten pool will preferentially grow up, and at the same time, a certain proportion of niobium carbide, niobium boride, tantalum carbide or tantalum boride can play a role in dispersion strengthening to prevent the alloy hardness from being greatly reduced, thereby inhibiting the formation of coarse brittle phases. The method of increasing the heterogeneous nucleation particles realizes the increase of the plasticity and toughness of the nickel-based composite material, solves the defects of poor plasticity and toughness of the nickel-based composite material and complicated preparation process, and can make the prepared nickel-based composite coating not crack and Has high wear and corrosion resistance.

Example 6

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. Nickel 45 powder, niobium powder and niobium carbide powder, wherein the powder particle size of nickel 45 powder is 18-55 μm, the single particle size of niobium powder is 4-6 μm, the aggregate size of niobium powder is 10-150 μm, and the niobium carbide powder has a particle size of 18-55 μm. The particle size of the single particle is 1-4 μm, and the aggregate size of the niobium carbide powder is 10-150 μm.

By adding a certain proportion of niobium and niobium carbide to the nickel-based alloy powder, niobium is a strong carbide forming element, and it will preferentially combine with carbon to form niobium carbide in the molten pool, avoiding the formation of coarse carbides, and at the same time, niobium carbide has lower The Gibbs free energy of the alloy will preferentially grow in the molten pool, and at the same time, a certain proportion of niobium carbide can play a role in dispersion strengthening to prevent the hardness of the alloy from being greatly reduced, thereby inhibiting the formation of coarse brittle phases and increasing heterogeneity. The method of forming nucleation particles realizes the increase of the plastic and toughness of the nickel-based composite material, solves the defects of poor plastic and toughness of the nickel-based composite material and complicated preparation process, and can make the prepared nickel-based composite coating not crack and have high performance. Wear and corrosion resistance.

Example 7

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. Nickel 45 powder, niobium powder and niobium carbide powder, wherein, the powder particle size of nickel 45 powder is 17-53 μm, the single particle size of niobium powder is 4-5 μm, the aggregate size of niobium powder is 17-53 μm, and the niobium carbide powder has a particle size of 17-53 μm. The particle size of the single particle is 2-3 μm, and the aggregate size of the niobium carbide powder is 10-20 μm.

By optimizing the powder particle size of nickel 45 powder, niobium powder and niobium carbide powder, the added niobium element can fully reduce the crack sensitivity of the nickel-based composite powder and improve its wear resistance performance, while the addition of niobium carbide can It plays the role of dispersion strengthening on the nickel matrix to ensure that its hardness will not drop too much; appropriate powder particle size selection and ball milling process settings will eventually form a coated powder to ensure the uniformity of powder composition and good fluidity. By optimizing the powder particle size of nickel 45 powder, niobium powder and niobium carbide powder, the powder morphology of small particle powder wrapped with large particle powder is realized, which can further avoid the occurrence of cracking of the high-hard nickel-based alloy coating and improve its corrosion resistance.

Example 8

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. The raw materials include nickel 45 powder and niobium powder with a mass ratio of 25:1:4. and niobium carbide powder, wherein the particle size of the nickel 45 powder is 17-53 μm, the single particle size of the niobium powder is 4-5 μm, the aggregate size of the niobium powder is 17-53 μm, and the single particle size of the niobium carbide powder is 2 to 3 μm, and the aggregate size of the niobium carbide powder is 10 to 20 μm.

By optimizing the mass ratio of nickel 45 powder, niobium powder and niobium carbide powder, the modification effect of niobium powder on nickel 45 powder can be ensured, and the crack sensitivity of nickel-based composite powder can be fully reduced after modification, and its wear-resistant particle can be improved. For the wear performance, by optimizing the addition ratio of niobium carbide powder, the dispersion strengthening effect of niobium carbide on the nickel matrix is optimized to ensure that the hardness of the modified nickel 45 powder will not drop too much. The powder and the niobium carbide powder cooperate with each other to realize the increase of the plastic and toughness of the nickel-based composite material, solve the defects of the poor plastic and toughness of the nickel-based composite material and the complicated preparation process, so that the prepared nickel-based composite coating does not crack and Has high wear and corrosion resistance.

Example 9

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking, which is composed of nickel with a mass fraction ratio of 20-30:0.5-2:2-6 The raw materials of 45 powder, niobium powder and niobium carbide powder are mixed by ball milling, wherein the powder particle size of nickel 45 powder is 18-55 μm, the single particle size of niobium powder is 4-6 μm, and the aggregate size of niobium powder is 15 μm. ~60 μm, the single particle size of the niobium carbide powder is 1 to 4 μm, and the aggregate size of the niobium carbide powder is 8 to 25 μm.

By optimizing the raw materials and mixing process of nickel-based composites, only adding niobium powder and niobium carbide powder to nickel-45 powder solves the defects of poor plasticity and toughness and complicated preparation process of nickel-based composites. By adding a very small amount of alloy Element, using a simple ball milling process to realize the powder form of small particle powder wrapping large particle powder, the nickel 45 powder wrapped by niobium powder and niobium carbide powder realizes the modification of nickel-based powder and simplifies the process; The niobium powder outside the powder can reduce the crack sensitivity of the nickel-based composite powder and improve its wear resistance. will drop too much; proper powder particle size selection and ball milling process settings will eventually form a coated powder to ensure uniformity of powder composition and good flowability. To sum up, this strategy can avoid the cracking of high-hard nickel-based alloy coatings and improve their corrosion resistance.

Example 10

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking, which is composed of nickel with a mass fraction ratio of 20-30:0.5-2:2-6 The raw materials of 45 powder, niobium powder and niobium carbide powder are mixed by ball milling. The powder particle size of nickel 45 powder is 17-53 μm, the single particle size of niobium powder is 4-5 μm, and the aggregate size of niobium powder is 17 μm. ~53 μm, the single particle size of the niobium carbide powder is 2 to 3 μm, and the aggregate size of the niobium carbide powder is 10 to 20 μm.

By optimizing the powder particle size of nickel 45 powder, niobium powder and niobium carbide powder, the added niobium element can fully reduce the crack sensitivity of the nickel-based composite powder and improve its wear resistance performance, while the addition of niobium carbide can It plays the role of dispersion strengthening on the nickel matrix to ensure that its hardness will not drop too much; appropriate powder particle size selection and ball milling process settings will eventually form a coated powder to ensure the uniformity of powder composition and good fluidity. By optimizing the powder particle size of nickel 45 powder, niobium powder and niobium carbide powder, the powder morphology of small particle powder wrapped with large particle powder is realized, which can further avoid the occurrence of cracking of the high-hard nickel-based alloy coating and improve its corrosion resistance.

Example 11

Referring to FIG. 1 and FIG. 2 , an embodiment of the present invention provides a non-cracking and high wear-resistant nickel-based composite material, which is composed of nickel 45 powder, niobium powder and niobium carbide with a mass ratio of 25:1:4. The raw materials of the powder are mixed by ball milling, wherein the particle size of the nickel 45 powder is 17-53 μm, the particle size of the niobium powder is 4-5 μm, the aggregate size of the niobium powder is 17-53 μm, and the single particle size of the niobium carbide powder is 17-53 μm. The particle size is 2-3 μm, and the aggregate size of the niobium carbide powder is 10-20 μm.

By optimizing the mass ratio of nickel 45 powder, niobium powder and niobium carbide powder, the modification effect of niobium powder on nickel 45 powder can be ensured, and the crack sensitivity of nickel-based composite powder can be fully reduced after modification, and its wear-resistant particle can be improved. For the wear performance, by optimizing the addition ratio of niobium carbide powder, the dispersion strengthening effect of niobium carbide on the nickel matrix is optimized to ensure that the hardness of the modified nickel 45 powder will not drop too much. The powder and the niobium carbide powder cooperate with each other to realize the increase of the plastic and toughness of the nickel-based composite material, solve the defects of the poor plastic and toughness of the nickel-based composite material and the complicated preparation process, so that the prepared nickel-based composite coating does not crack and Has high wear and corrosion resistance.

Example 12

Based on the same inventive concept, an embodiment of the present invention also provides a method for preparing the above-mentioned nickel-based composite material with high wear resistance and corrosion resistance without cracking, the method comprising:

Add at least one of nickel-based alloy powder, niobium powder and tantalum powder with a mass fraction ratio of 20～30:0.5～2:2～6, and reinforced ceramic phase powder into the ball mill jar, and alternate in turn according to forward rotation and reverse rotation. The ball milling is carried out for 200 to 260 minutes in a cyclic ball milling method. The ball milling is restarted after stopping for 3 to 6 minutes after every 10 to 30 minutes of ball milling. At 70-100 r/min, the reinforced ceramic phase powder includes at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder. Among them, due to the large difference in particle size of at least one of nickel-based alloy powder, niobium powder and tantalum powder, and the reinforced ceramic phase powder, the ball milling method is selected for uniform mixing, and finally the powder of small particle powder wrapped with large particle powder can be realized. form.

Preferably, in the preparation process, ball milling is performed for 240 minutes according to a ball milling method in which forward rotation and reverse rotation are alternately cycled, wherein, after every 20 minutes of ball milling, the ball milling is restarted after stopping for 5 minutes, and the forward rotation speed of the ball mill during the ball milling process is 90r/ min, the reversal speed is 90r/min. By reasonably optimizing the ball milling time and ball milling method, the ball milling is restarted at an interval of 5 minutes after every 20 minutes of ball milling, which can avoid the continuous ball milling that causes the powder temperature to be too high and affects its performance. By stopping every 20 minutes of ball milling 5 minutes, can avoid the performance degradation caused by the high temperature of the powder during the ball milling process.

Preferably, the stainless steel balls used in the ball milling process include large balls, medium balls and small balls with a mass ratio of 1 to 2:3 to 6:2 to 4, wherein the large balls, medium balls and small balls are gradually in diameter and size. For ball milling beads of three decreasing sizes, the ball-to-material ratio in the ball milling process is 5 to 15:1. By optimizing the selection of the size of the ball milling beads, it is possible to avoid the powder particles from being too small after the ball milling is completed. The size and ratio of the ball milling beads are optimally selected. In conjunction with the optimization of the forward and reverse rotation speeds during the ball milling process, the powder can be mixed evenly and avoid the ball milling process. As a result, the particles are too small, which ensures that the small particle powder wraps the large particle powder in a good powder shape after the ball milling is completed.

Preferably, the diameter of the large ball is larger than the diameter of the medium ball and less than 2 times the diameter of the medium ball, the diameter of the medium ball is larger than the diameter of the small ball and less than 3 times the diameter of the small ball, and the ball-to-material ratio in the ball milling process is 10:1. The mass ratio of the large ball, the medium ball and the small ball in the stainless steel ball mill bead is 2:5:3. Among them, the diameter of the small ball is 1.5mm, the diameter of the medium ball is 3mm, and the diameter of the large ball is 5mm. By optimizing the ball milling method and parameter selection, the powder can be mixed evenly, and the particle size caused by the ball milling process can be avoided, and the performance of the powder can be avoided when the temperature is too high.

Preferably, the forward rotation speed and the reverse rotation speed in the ball milling process are the same. Referring to Figures 1 and 2, (a) in Figure 1 is the electron microscope morphology of the nickel 45 powder before ball milling, (b) is Morphology of niobium powder under electron microscope before ball milling, (c) is the electron microscope appearance of niobium carbide powder before ball milling. According to Figure 1, it can be seen that before ball milling, nickel 45 powder, niobium powder and carbide The particle size of niobium powder is quite different and does not appear to be wrapped with each other. Figure 2 shows the powder of nickel 45 powder, niobium powder and niobium carbide powder after being ball-milled and evenly mixed, showing the powder of small particle powder wrapping large particle powder under the electron microscope It can fully improve the plasticity and toughness of Ni45, maintain its certain hardness, and expand the application range of Ni-based powder.

The invention provides a nickel-based composite material with high wear resistance and corrosion resistance without cracking. By adding a certain proportion of niobium and niobium carbide into the nickel-based alloy powder, niobium is a strong carbide forming element, and will preferentially interact with the molten pool in the molten pool. Carbon is combined to form niobium carbide to avoid the formation of coarse carbides. At the same time, niobium carbide has a low Gibbs free energy and will preferentially grow in the molten pool. The hardness of the alloy is greatly reduced, thereby increasing the plastic and toughness of the nickel-based composite material by inhibiting the formation of coarse brittle phases and increasing the heterogeneous nucleation particles, which solves the problem that the plastic and toughness of the nickel-based composite material is poor and the preparation process is complicated. It can make the prepared nickel-based composite coating not crack and have high wear resistance and corrosion resistance.

Example 13

Based on the same inventive concept, an embodiment of the present invention also provides a method for preparing the above-mentioned nickel-based composite material with high wear resistance and corrosion resistance without cracking, the method comprising:

Add at least one of nickel-based alloy powder, niobium powder and tantalum powder in a ratio of 20～30:0.5～2:2～6 to the atomizer, strengthen the ceramic phase powder, and then add at least one of nickel-based alloy powder, niobium powder and tantalum powder in a ratio of 20～30:0.5～2:2～6. Atomization or water atomization is prepared into a mixed powder form in which small particle powder wraps large particle powder, wherein the reinforced ceramic phase powder includes niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder. at least one. Among them, due to the large difference in particle size of nickel-based alloy powder, at least one of niobium powder and tantalum powder, and the reinforced ceramic phase powder, gas atomization or water atomization is selected for uniform mixing, and finally small particle powder can be realized. Powder form that encapsulates large particle powders.

Obviously, those skilled in the art can make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the embodiments of the present invention. Thus, provided that these modifications and variations of the embodiments of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The nickel-based composite material is characterized by comprising nickel-based alloy powder, niobium powder and reinforced ceramic phase powder, wherein the mass part ratio of the nickel-based alloy powder to the niobium powder is 20-30: 0.5-2: 2-6, the particle size of the nickel-based alloy powder is 10-150 mu m, the particle size of a single particle of the niobium powder is 4-6 mu m, the aggregation size of the niobium powder is 10-150 mu m, the reinforced ceramic phase powder comprises at least one of niobium carbide powder and niobium boride powder, the particle size of a single particle of the reinforced ceramic phase powder is 1-4 mu m, and the aggregation size of the reinforced ceramic phase powder is 10-150 mu m.

2. The nickel-based composite material is characterized by comprising nickel-based alloy powder, tantalum powder and reinforced ceramic phase powder, wherein the mass part ratio of the nickel-based alloy powder to the reinforced ceramic phase powder is 20-30: 0.5-2: 2-6, the particle size of the nickel-based alloy powder is 10-150 mu m, the particle size of a single particle of the tantalum powder is 4-6 mu m, the aggregation size of the tantalum powder is 10-150 mu m, the reinforced ceramic phase powder comprises at least one of tantalum carbide powder and tantalum boride powder, the particle size of a single particle of the reinforced ceramic phase powder is 1-4 mu m, and the aggregation size of the reinforced ceramic phase powder is 10-150 mu m.

3. The nickel-based composite material with the characteristics of no cracking, high wear resistance and corrosion resistance is characterized by comprising the following raw materials of nickel-based alloy powder, a mixture of niobium powder and tantalum powder and reinforced ceramic phase powder, wherein the mass part ratio of the nickel-based alloy powder to the mixture of the niobium powder and the tantalum powder is 20-30: 0.5-2: 2-6, wherein the particle size of the nickel-based alloy powder is 10-150 μm, the particle size of a single particle of the niobium powder is 4-6 μm, the aggregation size of the niobium powder is 10-150 mu m, the particle size of a single particle of the tantalum powder is 4-6 mu m, the aggregation size of the tantalum powder is 10-150 mu m, the reinforced ceramic phase powder comprises at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder, the particle size of each single particle of the reinforced ceramic phase powder is 1-4 mu m, and the aggregation size of the reinforced ceramic phase powder is 10-150 mu m.

4. The nickel-based composite material is characterized by being prepared by mixing raw materials consisting of nickel-based alloy powder, at least one of niobium powder and tantalum powder and reinforced ceramic phase powder in a mass part ratio of 20-30: 0.5-2: 2-6, wherein the particle size of the nickel-based alloy powder is 10-150 μm, the particle size of a single particle of the niobium powder is 4-6 μm, the aggregation size of the niobium powder is 10-150 mu m, the single particle diameter of the tantalum powder is 4-6 mu m, the aggregation size of the tantalum powder is 10-150 mu m, the reinforced ceramic phase powder comprises at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder, the particle size of each single particle of the reinforced ceramic phase powder is 1-4 mu m, and the aggregation size of the reinforced ceramic phase powder is 10-150 mu m.

5. The nickel-based composite material according to any one of claims 1 to 4, wherein the nickel powder has a powder particle size of 17 to 53 μm, the niobium powder has a single particle size of 4 to 5 μm, the niobium powder has an aggregate size of 17 to 53 μm, the niobium carbide powder has a single particle size of 2 to 3 μm, the niobium carbide powder has an aggregate size of 10 to 20 μm, the niobium boride powder has a single particle size of 2 to 3 μm, the niobium boride powder has an aggregate size of 10 to 20 μm, the tantalum powder has a single particle size of 4 to 5 μm, the tantalum powder has an aggregate size of 17 to 53 μm, the tantalum carbide powder has a single particle size of 2 to 3 μm, the tantalum carbide powder has an aggregate size of 10 to 20 μm, the tantalum boride powder has a single particle size of 2 to 3 μm, and the tantalum boride powder has an aggregate size of 10 to 20 μm.

6. A method for preparing the non-cracking high-abrasion-resistance and corrosion-resistance nickel-based composite material as claimed in any one of claims 1 to 4, wherein the method comprises the following steps:

adding at least one of nickel-based alloy powder, niobium powder and tantalum powder and reinforced ceramic phase powder in a mass portion ratio of 20-30: 0.5-2: 2-6 into a ball milling tank, and performing ball milling for 200-260 minutes in a ball milling mode of forward rotation and reverse rotation in an alternating circulation mode, wherein after ball milling is performed for 10-30 minutes, the ball milling is started again after stopping for 3-6 minutes at intervals, the forward rotation speed of a ball mill is 70-100 r/min and the reverse rotation speed is 70-100 r/min in the ball milling process, and the reinforced ceramic phase powder comprises at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder.

7. The method for preparing the non-cracking high-abrasion-resistance and corrosion-resistance nickel-based composite material as claimed in claim 6, wherein the ball milling is carried out for 240 minutes in a ball milling mode of forward rotation and reverse rotation in turn and alternately, wherein the ball milling is started again after the ball milling is stopped for 5 minutes at intervals after 20 minutes, the forward rotation speed of a ball mill in the ball milling process is 90r/min, and the reverse rotation speed is 90 r/min.

8. The method for preparing the non-cracking, high-abrasion-resistance and corrosion-resistance nickel-based composite material as claimed in claim 7, wherein the stainless steel ball grinding beads adopted in the ball milling process comprise large balls, medium balls and small balls in a mass ratio of 1-2: 3-6: 2-4, wherein the large balls, the medium balls and the small balls are ball grinding beads with three sizes, the diameters of the ball grinding beads gradually decrease progressively, and the ball-material ratio in the ball milling process is 5-15: 1; the diameter of the large ball is larger than that of the medium ball and is smaller than 2 times of that of the medium ball, the diameter of the medium ball is larger than that of the small ball and is smaller than 3 times of that of the small ball, the ball-material ratio in the ball milling process is 10:1, and the mass ratio of the large ball, the medium ball and the small ball in the stainless steel ball milling bead adopted in the ball milling process is 2:5: 3.

9. The method for preparing the non-cracking, high-abrasion, and corrosion-resistant nickel-based composite material according to claim 8, wherein the forward rotation speed and the reverse rotation speed in the ball milling process are the same, and the nickel-based alloy powder, the niobium powder, and the niobium carbide powder are uniformly mixed after the ball milling process and present a powder form in which large particle powder is wrapped by small particle powder.

10. A method for preparing the non-cracking high-abrasion-resistance and corrosion-resistance nickel-based composite material as claimed in any one of claims 1 to 4, wherein the method comprises the following steps:

adding at least one of nickel-based alloy powder, niobium powder and tantalum powder and reinforced ceramic phase powder into an atomizer according to the mass part ratio of 20-30: 0.5-2: 2-6, and preparing a mixed powder form in which small-particle powder wraps large-particle powder in a gas atomization or water atomization mode, wherein the reinforced ceramic phase powder comprises at least one of niobium carbide powder, niobium boride powder, tantalum carbide powder and tantalum boride powder.

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