Zinc-based composite powder material and preparation method

Abstract

The application provides a zinc-based composite powder material and a preparation method, and belongs to the technical field of metal powder materials and preparation. The powder particles of the zinc-based composite powder material comprise a ceramic phase and a zinc-based metal phase. The ceramic phase is distributed in the zinc-based metal phase, and part of the ceramic phase protrudes from the surface of the zinc-based metal phase. The average protruding height is not greater than 4 microns. The content of the ceramic phase is 2.0-10.0 wt% of the mass of the metal melt. The zinc-based composite powder material with the ceramic phase and the zinc-based metal phase is prepared through a rotating disc centrifugal atomization process. Part of the ceramic phase is dispersed in the zinc-based metal phase, and part of the ceramic phase protrudes from the surface of the zinc-based metal phase. The flowability of the powder material is ensured, and the bonding force between the subsequent surface coating and the substrate is improved.

Description

Technical Field

[0001] This invention relates to the field of metal powder materials and preparation technology, specifically to a zinc-based composite powder material and its preparation method. Background Technology

[0002] Some inorganic materials, such as hydroxyapatite and bioglass, possess good biocompatibility and were early implant materials. Hydroxyapatite, in particular, has a composition similar to bone and can effectively promote osteocyte proliferation. However, these inorganic ceramic materials have poor mechanical properties (especially toughness), making them prone to fracture during service. Therefore, currently, hydroxyapatite is often sprayed onto the surface of metal implants to create a hydroxyapatite coating, achieving a dual improvement in implant mechanical properties and bone ingrowth performance.

[0003] However, coating methods using spraying have limitations in terms of adhesion; the hydroxyapatite coating risks detachment within the body, potentially leading to implant failure. Therefore, developing metal-ceramic composites by combining inorganic ceramic materials like hydroxyapatite with metallic materials, allowing the inorganic material to be uniformly distributed within the metal matrix, is a novel approach to synergistically improve the mechanical and osteogenic properties of implant materials. Summary of the Invention

[0004] To address the shortcomings of the prior art, this invention provides a zinc-based composite powder material and its preparation method. The composite powder material having a ceramic phase and a zinc-based metal phase is prepared by a rotating disk centrifugal atomization process. The ceramic phase is dispersed in the zinc-based metal phase and protrudes from the surface of the zinc-based metal phase. This method ensures the fluidity of the powder material while improving the adhesion between the subsequent surface coating and the substrate.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] On one hand, the present invention provides a zinc-based composite powder material, wherein the powder particles of the zinc-based composite powder material include a ceramic phase and a zinc-based metal phase, wherein the ceramic phase is distributed in the zinc-based metal phase, and the ceramic phase portion protrudes from the surface of the zinc-based metal phase with an average protrusion height of no more than 4 μm, and the content of the ceramic phase is 2.0-10.0 wt% of the mass of the molten metal.

[0007] Furthermore, the ceramic phase is one or more of hydroxyapatite, zirconium oxide, tricalcium silicate, bioglass, and calcium carbonate.

[0008] Furthermore, the zinc-based metal phase is zinc or a zinc alloy; in the zinc alloy, the target alloying element is one or more of magnesium, copper, aluminum, manganese, indium, iron, lithium, bismuth, strontium, calcium, and rare earth elements.

[0009] Furthermore, the target alloying elements are required to have the following contents: magnesium 0.5-20.0%, calcium 0.5-10.0%, copper 0.5-6.0%, aluminum 0.5-10.0%, manganese 0.5-4.0%, and the contents of other elements ≤5.0%.

[0010] On the other hand, the present invention provides a method for preparing the above-mentioned zinc-based composite powder material, comprising: preparing a metal melt; adding ceramic powder to the metal melt; stirring for a preset time to obtain a zinc-based composite melt, wherein the zinc-based composite melt drips through a nozzle onto a rotating disk and is then ejected to obtain powder, wherein the rotating disk has a first temperature; and collecting, sieving, and post-processing the obtained powder to obtain the final product.

[0011] Furthermore, the average particle size of the ceramic powder is 100-500 nm.

[0012] Furthermore, the rotational speed of the rotating disk is 15,000-50,000 rpm.

[0013] Furthermore, after adding ceramic powder to the molten metal, the mixture is stirred for 10-15 minutes, maintaining the melt temperature at Tm to Tm+150℃, where Tm is the melting point of the molten metal.

[0014] Furthermore, the flow rate of the zinc-based composite melt is 100-120 g / s.

[0015] Furthermore, the first temperature is Tm+30℃~Tm+60℃, where Tm is the melting point of the molten metal.

[0016] Compared with existing technologies, the technical solution provided by this invention brings the following beneficial effects: The zinc-based composite powder material proposed in this invention, through a rotary disc centrifugal atomization process, prepares a ceramic phase portion protruding from the surface of the zinc-based metal phase, with a protrusion height not exceeding 4 μm. Preferably, the average protrusion height is not less than 1 μm and not more than 4 μm, and the D90 particle size of the prepared zinc-based composite powder is not less than 60 μm. That is, when the D90 particle size of the zinc-based composite powder is at least 15 times the protrusion height, the subsequent 3D printing process will not produce powder jamming problems. The reason for limiting the height of the ceramic phase protrusion is that, on the one hand, if the protrusion height of the ceramic phase is higher than 4 μm, it forms a burr structure, which greatly increases the probability of powder jamming during the 3D printing process of the prepared zinc-based composite powder, leading to printing interruption. On the other hand, the protruding ceramic phase has a pinning effect, pinning the subsequently sprayed inorganic coating and preventing the inorganic coating from falling off. Therefore, the protrusion height of the ceramic phase cannot be too low. To ensure the pinning effect, the surface protrusion of the spherical powder must meet certain requirements. It is known that various process parameters, such as the melting process and subsequent solidification behavior, affect the morphology of the final ceramic phase. In this invention, the content of the added ceramic phase is 2.0-10.0 wt% of the metal melt mass, which can greatly improve its pinning effect on the subsequent inorganic coating. The amount of ceramic phase added should not be too small, otherwise the generated ceramic phase protrusion will be too small and unable to effectively pin the subsequent coating. The amount added should not be too large, otherwise it will lead to severe agglomeration and the size of the prepared ceramic phase protrusion will be too large, which will easily cause powder jamming during the 3D printing process. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 Here are SEM images of the zinc-based composite powder material prepared in Example 1 of the present invention: a is a zinc-based ceramic composite powder, and b is a magnified view of the powder surface.

[0019] Figure 2 This is a powder SEM image of the zinc-based composite powder material prepared in Example 2 of the present invention;

[0020] Figure 3 This is a powder SEM image of the zinc-based composite powder material prepared in Example 3 of the present invention;

[0021] Figure 4 This is a powder SEM image of the zinc-based composite powder material prepared in Comparative Example 1 of the present invention. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. The specific embodiments of this invention are not limited to those given herein, and those skilled in the art can make similar improvements without departing from the spirit of this invention. Therefore, this invention is not limited to the disclosed specific embodiments.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used is for describing particular embodiments only and does not limit the scope of the invention.

[0024] This invention provides a zinc-based composite powder material. The powder particles of the zinc-based composite powder material are spherical with protrusions and include a ceramic phase and a zinc-based metal phase. The ceramic phase is distributed in the zinc-based metal phase, and the ceramic phase part protrudes from the surface of the zinc-based metal phase with an average protrusion height of no more than 4 μm. The content of the ceramic phase is 2.0-10.0 wt% of the mass of the molten metal.

[0025] The zinc-based composite powder material proposed in this invention is prepared by a rotary disc centrifugal atomization process, resulting in a ceramic phase protruding from the surface of the zinc-based metallic phase. The protrusion height is no greater than 4 μm, preferably with an average protrusion height of no less than 1 μm and no greater than 4 μm. The D90 particle size of the prepared zinc-based composite powder is no less than 60 μm. In this invention, the particle size refers to the diameter of the spherical matrix. Therefore, when the D90 particle size of the zinc-based composite powder is at least 15 times the protrusion height, powder jamming will not occur. The height of the protruding ceramic phase is the difference between the maximum distance between it and the center of the spherical matrix, and the distance between the surface of the spherical matrix and the center. The height of the protruding ceramic phase is limited for two reasons: firstly, a protrusion height exceeding 4 μm creates a burr structure, significantly increasing the probability of powder jamming during 3D printing and potentially causing printing interruptions; secondly, the protruding ceramic phase has a pinning effect, securing the subsequent inorganic coating and preventing its detachment. Therefore, the protrusion height of the ceramic phase cannot be too small. To ensure the pinning effect, the surface protrusion of the spherical powder must meet certain requirements. It is known that various process parameters, such as the melting process and subsequent solidification behavior, affect the morphology of the final ceramic phase. In this invention, the content of the added ceramic phase is 2.0-10.0 wt% of the metal melt mass, which can greatly improve its pinning effect on the subsequent inorganic coating. The amount of ceramic phase added should not be too small, otherwise the generated ceramic phase protrusion will be too small and unable to effectively pin the subsequent coating. The amount added should not be too large, otherwise it will lead to severe agglomeration and the size of the prepared ceramic phase protrusion will be too large, which will easily cause powder jamming during the 3D printing process.

[0026] It should be noted that the sphericity of the quasi-spherical shape in this application only needs to be 0.6 or higher. The formula for calculating sphericity is common knowledge and will not be elaborated here. The average protrusion height in this invention is obtained by statistically analyzing the heights of at least 20 protrusions, which can be selected from protrusions on one or more powders, and calculating their average value.

[0027] Specifically, the ceramic phase is one or more of hydroxyapatite, zirconium oxide, tricalcium silicate, bioglass, and calcium carbonate. These substances are stable in molten Zn and Zn alloys, with a very low probability of forming intermediate products. Bioglass refers to glass capable of performing specific biological and physiological functions. When implanted into bone defects, bioglass can directly bond with bone tissue, repairing it and restoring its function.

[0028] Specifically, the zinc-based metal phase is zinc or a zinc alloy; in the zinc alloy, the target alloying element is one or more of magnesium, copper, aluminum, manganese, indium, iron, lithium, bismuth, strontium, calcium, and rare earth elements. The total amount of the target alloying element added does not exceed 20 wt%, which will not significantly affect the physical properties of the Zn-based metal melt, and can prepare the zinc-based composite powder material claimed in this invention.

[0029] Specifically, the content requirements for the target alloying elements are as follows: magnesium content is 0.5-20.0%, calcium content is 1.0-10.0%, copper content is 0.2-6.0%, aluminum content is 1.2-10.0%, manganese content is 0.1-4.0%, and the content of other elements is ≤5.0%. Different elements have a certain influence on the physical properties of Zn-based metal melts. In order to avoid drastic changes in physical properties due to the addition of elements, this application limits the content of the target alloying elements.

[0030] To illustrate the inventive aspects of this application, Zn-0.5Mg, Zn-20Mg, and Zn-2Cu are selected as examples.

[0031] This invention also provides a method for preparing the above-mentioned zinc-based composite powder material, comprising:

[0032] S1 is used to prepare metal melts.

[0033] It is preferable to use an intermediate alloy method to select materials, thereby reducing the loss of reactive metals during burning. For example, in the preparation of Zn-0.5Mg in this invention, a combination of Zn-20Mg alloy ingots and pure zinc ingots can be selected to obtain the melt with the final desired composition.

[0034] S2 adds ceramic powder to the molten metal.

[0035] The average particle size of the ceramic powder is 100-500 nm. It should be noted that the average particle size of the ceramic powder added in this application is 100-500 nm, while in the prepared Zn-based composite powder, some ceramic phases protrude up to 4 μm from the surface of the Zn-based metal phase. This is because there is a difference in surface tension between the interior and surface of the Zn-based metal phase. The smaller-sized ceramic powder particles are dispersed within the Zn-based metal phase, while the ceramic phase on the surface of the Zn-based metal phase forms gradually as the droplet solidifies, spreading outwards from the crystallization nucleus. The solidification end drives and aggregates the ceramic powder attached to the surface, thus forming protrusions up to 4 μm in size. Furthermore, the ceramic powder on the droplet surface is prone to agglomeration due to its high surface tension. Therefore, controlling the process is crucial to prevent the formation of protrusions exceeding 4 μm, as process parameters determine the solidification behavior of the Zn-based metal.

[0036] After stirring for a preset time, S3 obtains a zinc-based composite melt. The zinc-based composite melt drips through a nozzle onto a rotating disk and is then ejected as powder. The rotating disk has a first temperature.

[0037] Specifically, stirring for 10-15 minutes at a speed of 20-60 rpm is sufficient, maintaining the melt temperature at Tm to Tm+150℃, where Tm is the melting point of the molten metal. It is known that the melting point can be determined based on a phase diagram. Based on the phase diagram, the melting point of Zn-0.5Mg is 420℃, the melting point of Zn-20Mg is 535℃, and the melting point of Zn-2Cu is 420℃.

[0038] The flow rate of the molten metal is 100-120 g / s, and the first temperature is Tm+30~Tm+60, where Tm is the melting point of the molten metal. The rotational speed of the rotating disk is 15000-50000 rpm. The aforementioned process parameters are crucial for the final zinc-based composite powder material. The flow rate of the zinc-based molten metal determines the impact force between the molten metal and the rotating disk. This determines both the particle size of the final zinc-based composite powder and the interaction between the tiny droplets formed after the impact and the rotating disk. This causes the ceramic phase to protrude from the surface of the zinc-based metal phase, i.e., the ceramic phase is embedded in the zinc-based metal phase, thus forming a strong and reliable connection. Furthermore, the first temperature determines the solidification process of the zinc-based composite molten metal. If the solidification is too fast, the ceramic powder cannot be aggregated, resulting in a small protrusion of the ceramic phase from the zinc-based metal phase. If the solidification is too slow, the ceramic phase protrudes too much from the zinc-based metal phase, which does not meet the requirements. Secondly, the magnitude of the impact force affects the secondary dispersion of the ceramic powder. That is, the zinc-based alloy droplets containing ceramic powder impact the rotating disk, and the rotating disk applies a secondary impact to the ceramic powder in the droplets, thereby dispersing the agglomerated ceramic powder.

[0039] S4 is used to collect, sieve, and post-process the obtained powder.

[0040] Specifically, the powder is collected, sieved, and post-processed under an inert gas protective atmosphere. The protective gas is a gas that does not react with any element or alloy phase in the prepared zinc-based composite powder, preferably nitrogen and / or argon. The collection and sieving of the powder are conventional techniques and are not limited here.

[0041] The post-processing temperature is 0.2Tm to 0.5Tm, and the temperature is maintained for at least 20 minutes to relieve or eliminate the internal stress of the prepared powder.

[0042] This invention employs a rotating disk centrifugal atomization process. By adding ceramic particles to the molten metal and mixing them with the molten metal, the particles undergo secondary mixing and dispersion within the rotating disk channel under centrifugal force, and are finally ejected. This effectively achieves uniform dispersion of ceramic particles within the metal powder, and the prepared powder surface has a ceramic protruding phase. This is a novel preparation method for zinc metal-ceramic composite powders.

[0043] It should be noted that, unless otherwise specified, all measurements in this application are expressed as mass percentages.

[0044] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0045] Example 1

[0046] This embodiment provides a zinc-based composite powder material and its preparation method, including:

[0047] S1. Preparation of the metal melt. A Zn-0.5Mg alloy was prepared as the metal melt. A Zn-20Mg master alloy ingot and a pure Zn ingot were placed in a crucible and melted and held at a temperature of Tm, i.e., 420℃, to achieve the target composition.

[0048] S2. Ceramic powder is added to the molten metal. Hydroxyapatite powder with an average particle size of 200 nm is added at a rate of 10 wt%.

[0049] After stirring for a preset time, S3 obtains a zinc-based composite melt. The zinc-based composite melt drips through a nozzle onto a rotating disk and is then ejected as powder. The rotating disk has a first temperature.

[0050] Stirring for 10 minutes yields a target zinc-based composite melt of Zn-0.5Mg+10wt.%. After stirring, the zinc-based composite melt drips through a funnel onto a rotating disk and is then ejected as powder. The flow rate of the zinc-based composite melt is 100g / s, the rotation speed of the rotating disk is 15000rpm, and the temperature of the rotating disk is 450℃.

[0051] S4 is used to collect, sieve, and post-process the obtained powder.

[0052] The prepared zinc-based composite powder, such as Figure 1 As shown in Figures a and b, after the ceramic phase is incorporated, the zinc-based metal phase surface is embedded with the ceramic phase. The large protrusions on the surface are ceramic particle agglomerates, while other surface flocculent substances are hydroxyapatite. The ceramic particles are uniformly distributed on the surface of the metal powder, proving that the two have achieved good composite properties, and the sphericity of the powder is also guaranteed. Furthermore, the ceramic phase protrudes from the surface of the zinc-based metal phase, with an average protrusion height of not less than 1 μm and not more than 4 μm.

[0053] After testing, its loose density was found to be 3.99 g / cm³. 3 The fluidity was 8.12s / 50g, and no powder jamming occurred during the 3D printing process.

[0054] Example 2

[0055] Unlike Example 1, in this example, hydroxyapatite powder is added in step S2 at a rate of 2 wt%.

[0056] The prepared zinc-based composite powder, such as Figure 2 As shown, the hydroxyapatite content is relatively low, allowing for good integration into the zinc powder. The powder surface is smooth and flat, with only a small amount of ceramic powder adhering to the surface. Furthermore, the ceramic phase protrudes from the zinc-based metal phase surface, with an average protrusion height of not less than 1 μm and not more than 4 μm.

[0057] After testing, its loose bulk density was found to be 4.33 g / cm³. 3 The fluidity was 4.31s / 50g, and no powder jamming occurred during the 3D printing process.

[0058] Example 3

[0059] Unlike Example 1, in this example, hydroxyapatite powder is added in step S2 at a rate of 6 wt%.

[0060] The prepared zinc-based composite powder, such as Figure 3As shown, some ceramic particles agglomerate on the surface, and these agglomerated particles deform under impact. However, the overall composite effect is good. The ceramic phase protrudes from the zinc-based metal phase surface, with an average protrusion height of not less than 1 μm and not more than 4 μm.

[0061] After testing, its loose density was found to be 4.17 g / cm³. 3 The fluidity was 5.54s / 50g, and no powder jamming occurred during the 3D printing process.

[0062] Example 4

[0063] This embodiment provides a zinc-based composite powder material and its preparation method, including:

[0064] S1. Preparation of the metal melt. A Zn-0.5Mg alloy was prepared as the metal melt. A Zn-20Mg master alloy ingot and a pure Zn ingot were placed in a crucible and melted and held at a temperature of 500℃ to achieve the target composition.

[0065] S2. Ceramic powder is added to the molten metal. Hydroxyapatite powder with an average particle size of 300 nm is added at a rate of 10 wt%.

[0066] After stirring for a preset time, S3 obtains a zinc-based composite melt. The zinc-based composite melt drips through a nozzle onto a rotating disk and is then ejected as powder. The rotating disk has a first temperature.

[0067] Stirring for 15 minutes yields a target zinc-based composite melt of Zn-0.5Mg+10wt.%. After stirring, the zinc-based composite melt drips through a funnel onto a rotating disk and is then ejected as powder. The flow rate of the zinc-based composite melt is 110 g / s, the rotation speed of the rotating disk is 30,000 rpm, and the temperature of the rotating disk is 460℃.

[0068] S4 is used to collect, sieve, and post-process the obtained powder.

[0069] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metallic phase, with an average protrusion height of not less than 1 μm and not more than 4 μm. Its loose bulk density is measured to be 4.01 g / cm³. 3 The fluidity was 7.92s / 50g, and no powder jamming occurred during the 3D printing process.

[0070] Example 5

[0071] This embodiment provides a zinc-based composite powder material and its preparation method, including:

[0072] S1. Preparation of the metal melt. A Zn-0.5Mg alloy was prepared as the metal melt. A Zn-20Mg master alloy ingot and a pure Zn ingot were placed in a crucible and melted and held at a temperature of 570℃ to achieve the target composition.

[0073] S2. Ceramic powder is added to the molten metal. Hydroxyapatite powder with an average particle size of 500 nm is added at an amount of 10 wt%.

[0074] After stirring for a preset time, S3 obtains a zinc-based composite melt. The zinc-based composite melt drips through a nozzle onto a rotating disk and is then ejected as powder. The rotating disk has a first temperature.

[0075] Stirring for 15 minutes yields a target zinc-based composite melt of Zn-0.5Mg+10wt.%. After stirring, the zinc-based composite melt drips through a funnel onto a rotating disk and is then ejected as powder. The flow rate of the zinc-based composite melt is 120 g / s, the rotation speed of the rotating disk is 50,000 rpm, and the temperature of the rotating disk is 480℃.

[0076] S4 is used to collect, sieve, and post-process the obtained powder.

[0077] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metallic phase, with an average protrusion height of not less than 1 μm and not more than 4 μm. Its loose bulk density is measured to be 3.87 g / cm³. 3 The fluidity was 8.05s / 50g, and no powder jamming occurred during the 3D printing process.

[0078] Example 6

[0079] This embodiment provides a zinc-based composite powder material and its preparation method, including:

[0080] S1. A Zn-20Mg alloy was prepared as the metal melt, and the holding temperature was 550℃.

[0081] S2. Ceramic powder is added to the molten metal. Tricalcium silicate with an average particle size of 200 nm is added at a rate of 10 wt%.

[0082] After stirring for a preset time, S3 obtains a zinc-based composite melt. The zinc-based composite melt drips through a nozzle onto a rotating disk and is then ejected as powder. The rotating disk has a first temperature.

[0083] Stirring for 10 minutes yields a target zinc-based composite melt of Zn-20Mg + 10wt.%. After stirring, the zinc-based composite melt drips through a funnel onto a rotating disk and is then ejected as powder. The flow rate of the zinc-based composite melt is 100 g / s, the rotation speed of the rotating disk is 15000 rpm, and the temperature of the rotating disk is 580℃.

[0084] S4 is used to collect, sieve, and post-process the obtained powder.

[0085] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metallic phase, with an average protrusion height of not less than 1 μm and not more than 4 μm. Its loose bulk density is measured to be 2.93 g / cm³. 3 The fluidity is 9.20s / 50g, and no powder jamming occurred during the 3D printing process.

[0086] Example 7

[0087] This embodiment provides a zinc-based composite powder material and its preparation method, including:

[0088] S1 is used to prepare a metallic melt. A Zn-2Cu alloy is prepared as the metallic melt, and the holding temperature is 440℃.

[0089] S2. Ceramic powder is added to the molten metal. Calcium carbonate powder with an average particle size of 200 nm is added at an amount of 10 wt%.

[0090] After stirring for a preset time, S3 obtains a zinc-based composite melt. The zinc-based composite melt drips through a nozzle onto a rotating disk and is then ejected as powder. The rotating disk has a first temperature.

[0091] Stirring for 10 minutes yields a target zinc-based composite melt of Zn-2Cu+10wt.%. After stirring, the zinc-based composite melt drips through a funnel onto a rotating disk and is then ejected as powder. The flow rate of the zinc-based composite melt is 100g / s, the rotation speed of the rotating disk is 30000rpm, and the temperature of the rotating disk is 480℃.

[0092] S4 is used to collect, sieve, and post-process the obtained powder.

[0093] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metallic phase, with an average protrusion height of not less than 1 μm and not more than 4 μm. Its loose bulk density is measured to be 4.28 g / cm³. 3 The fluidity is 8.50s / 50g, and no powder jamming occurred during the 3D printing process.

[0094] Comparative Example 1

[0095] Unlike Example 1, in this comparative example, hydroxyapatite powder was added in step S2 at an amount of 12 wt%.

[0096] The prepared zinc-based composite powder, such as Figure 4 As shown, the zinc alloy powder with 15 wt.% hydroxyapatite composite material exhibits significant agglomeration on its surface, and the zinc-based metal phase surface is irregular with an unevenness greater than 4 μm. The ceramic particle distribution is uneven, failing to achieve the expected results. Testing revealed a loose packing density of 3.22 g / cm³. 3 The fluidity was 12.22s / 50g, and no powder jamming occurred during the 3D printing process.

[0097] Comparative Example 2

[0098] Unlike Example 1, in this comparative example, hydroxyapatite powder was added in step S2 at an amount of 1.5 wt%.

[0099] The prepared zinc-based composite powder has very little ceramic phase protruding from the zinc-based metal phase surface, with an average protrusion height of less than 1 μm, which cannot effectively pin the coating in the future.

[0100] Comparative Example 3

[0101] Unlike Example 1, in this comparative example, the temperature of the rotating disk in step S3 is 500°C.

[0102] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metal phase, with an average protrusion height greater than 4 μm, and there is a powder jamming problem during the printing process.

[0103] Comparative Example 4

[0104] Unlike Example 1, in this comparative example, the temperature of the rotating disk in step S3 is 420°C.

[0105] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metal phase, with an average protrusion height of less than 1 μm.

[0106] Comparative Example 5

[0107] Unlike Example 1, in this comparative example, the flow rate of the zinc-based composite melt in step S3 is 90 g / s.

[0108] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metal phase, with an average protrusion height greater than 4 μm.

[0109] Comparative Example 6

[0110] Unlike Example 1, in this comparative example, the flow rate of the zinc-based composite melt in step S3 is 130 g / s.

[0111] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metal phase, with an average protrusion height of less than 1 μm.

[0112] Comparative Example 7

[0113] Unlike Example 1, in this comparative example, hydroxyapatite powder was added in step S2. The average particle size of the hydroxyapatite powder was 600 nm, and the amount added was 10 wt%.

[0114] The prepared zinc-based composite powder has a ceramic phase that protrudes from the surface of the zinc-based metal phase, with an average protrusion height greater than 4 μm.

[0115] As shown in Example 1 and Comparative Example 1, when the amount of hydroxyapatite powder added exceeds 10%, significant agglomeration occurs. This is because the large amount of hydroxyapatite agglomerates, combined with subsequent processes, makes it impossible to achieve secondary dispersion of hydroxyapatite through impact even at a relatively high flow rate of the zinc-based composite melt. This exceeds the process's ability to disperse hydroxyapatite content above 10%. As shown in Example 1 and Comparative Example 2, when too little hydroxyapatite is added, an effective ceramic phase protrusion height cannot be formed, resulting in poor subsequent pinning effect on the coating. As shown in Example 1, Comparative Examples 3 and 4, the temperature of the rotating disk has a significant impact on the performance of the prepared zinc-based composite powder material. This is because the initial temperature determines the solidification process of the zinc-based composite metal melt. A low rotating disk temperature results in excessively rapid solidification of the zinc-based alloy melt, preventing the agglomeration of the ceramic powder and resulting in a smaller protrusion height of the ceramic phase from the zinc-based metal phase. Conversely, a high rotating disk temperature results in excessively slow solidification of the zinc-based alloy melt, leading to an excessively high protrusion height of the ceramic phase, which does not meet the requirements. As shown in Examples 1, 5, and 6, the flow rate of the zinc-based composite melt has a significant impact on the final powder. This is mainly because the impact force itself affects the secondary dispersion of ceramic particles in the melt. A faster flow rate results in a greater impact force and a better secondary dispersion effect; conversely, a lower flow rate results in a smaller impact force and a poorer secondary dispersion effect. As shown in Examples 1 and 7, the average particle size of the hydroxyapatite powder also affects the height of the ceramic phase protruding from the zinc-based metal phase in the final product.

[0116] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A zinc-based composite powder material applied to the field of 3D printing, characterized in that, the powder particles of the zinc-based composite powder material comprise a ceramic phase and a zinc-based metal phase, the ceramic phase is distributed in the zinc-based metal phase, and the ceramic phase partially protrudes from the surface of the zinc-based metal phase, the average protrusion height is not less than 1 µm and not more than 4 µm, and the content of the ceramic phase is 2.0-10.0 wt% of the mass of the metal melt; the D90 particle size of the prepared zinc-based composite powder is not less than 60 µm; the average particle size of the ceramic powder used to generate the ceramic phase is 100-500 nm. 2.The zinc-based composite powder material according to claim 1, characterized in that, the ceramic phase is one or more of hydroxyapatite, zirconia, tricalcium silicate, bioglass, and calcium carbonate. 3.The zinc-based composite powder material according to claim 1, characterized in that, the zinc-based metal phase is zinc or a zinc alloy; in the zinc alloy, the target alloying elements are one or more of magnesium, copper, aluminum, manganese, indium, iron, lithium, bismuth, strontium, calcium, and rare earth elements. 4.The zinc-based composite powder material according to claim 3, characterized in that, the content requirements of the target alloying elements are as follows: the content of magnesium is 0.5-20.0%, the content of calcium is 0.5-10.0%, the content of copper is 0.5-6.0%, the content of aluminum is 0.5-10.0%, the content of manganese is 0.5-4.0%, and the content of the remaining elements is ≤5.0%.

5. The method of producing a zinc-based composite powder material according to any one of claims 1 to 4, characterized in that, including: preparing a metal melt; adding ceramic powder to the metal melt; after stirring for a predetermined time, obtaining a zinc-based composite melt, which is spun off after being dropped through a nozzle to a rotating disc having a first temperature to obtain a powder; after collecting, sieving, and post-processing the obtained powder, the zinc-based composite powder material is obtained; the average particle size of the ceramic powder is 100-500 nm; the rotating disc has a rotating speed of 15000-50000 rpm; the flow rate of the zinc-based composite melt is 100-120 g / s; the first temperature is Tm+30 ℃~Tm+60 ℃, where Tm is the melting point of the metal melt. 6.The preparation method according to claim 5, characterized in that, after adding the ceramic powder to the metal melt, stirring for 10-15 min, and maintaining the melt temperature at Tm~Tm+150 ℃, where Tm is the melting point of the metal melt.

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