Zinc-based composite powder material and preparation method thereof

Abstract

The invention provides a zinc-based composite powder material and a preparation method, and belongs to the technical field of metal powder materials and preparation, 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 out of the surface of the zinc-based metal phase, the average protruding height is not greater than 4 microns, and the content of the ceramic phase is 2.0-10.0 wt% of the mass of the metal melt. A composite powder material with a ceramic phase and a zinc-based metal phase is prepared through a rotating disc centrifugal atomization technology, the ceramic phase is partially dispersed in the zinc-based metal phase, the ceramic phase partially protrudes out of the surface of the zinc-based metal phase, and the binding force of a subsequent surface coating and a base body is improved while the fluidity of the powder material is guaranteed.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal powder materials and preparation, and specifically relates to a zinc-based composite powder material and a preparation method thereof. Background Art

[0002] Some inorganic materials, such as hydroxyapatite and bioactive glass, have good biocompatibility and are early implant materials. Among them, hydroxyapatite is close to the composition of bone and can effectively promote the proliferation of bone cells. However, the mechanical properties of these inorganic ceramic materials are poor (especially toughness), resulting in easy fracture during service. Therefore, at present, hydroxyapatite is commonly sprayed on the surface of metal implants to prepare a hydroxyapatite coating, achieving a double improvement in the mechanical properties and bone ingrowth performance of the implants.

[0003] However, there are problems with the coating bonding force in the method of making a coating by spraying. There is a risk of shedding of the hydroxyapatite coating in the body, which will still cause the failure of the implant. Therefore, by compounding inorganic ceramic materials such as hydroxyapatite with metal materials and allowing the inorganic materials to be evenly distributed in the metal matrix, a metal-ceramic composite material is developed, which is a new method to achieve the synergistic improvement of the mechanical properties and osteogenic properties of implant materials. Summary of the Invention

[0004] In view of the above deficiencies in the prior art, the present invention provides a zinc-based composite powder material and a preparation method thereof. A composite powder material with a ceramic phase and a zinc-based metal phase is prepared by a rotating disk centrifugal atomization process. The ceramic phase is partially dispersed in the zinc-based metal phase, and the ceramic phase protrudes from the surface of the zinc-based metal phase, with an average protrusion height not greater than 4 μm. The content of the ceramic phase is 2.0 - 10.0 wt% of the mass of the metal melt, while ensuring the fluidity of the powder material and improving the bonding force between the subsequent surface coating and the substrate.

[0005] In order to achieve the above object, the technical solutions adopted by the present invention are as follows:

[0006] On the one hand, the present invention provides a zinc-based composite powder material. The powder particles of the zinc-based composite powder material 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 protrudes from the surface of the zinc-based metal phase, with an average protrusion height not greater than 4 μm. The content of the ceramic phase is 2.0 - 10.0 wt% of the mass of the metal melt.

[0007] Further, the ceramic phase is one or more of hydroxyapatite, zirconia, tricalcium silicate, bioactive glass, calcium carbonate.

[0008] Further, 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 element, copper element, aluminum element, manganese element, indium element, iron element, lithium element, bismuth element, strontium element, calcium element, rare earth element.

[0009] Furthermore, the content requirements of the target alloying elements are as follows: the content of magnesium element is 0.5 - 20.0%, the content of calcium element is 0.5 - 10.0%, the content of copper element is 0.5 - 6.0%, the content of aluminum element is 0.5 - 10.0%, the content of manganese element is 0.5 - 4.0%, and the content of the remaining elements ≤ 5.0%.

[0010] On the other hand, the present invention provides a method for preparing the above zinc - based composite powder material, including: preparing a metal melt; adding ceramic powder into the metal melt; obtaining a zinc - based composite melt after stirring for a preset time, and the zinc - based composite melt is dropped through a nozzle onto a rotating disk and then thrown out to obtain powder, and the rotating disk has a first temperature; collecting, sieving, and post - treating the obtained powder to obtain the product.

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

[0012] Furthermore, the rotation speed of the rotating disk is 15000 - 50000 rpm.

[0013] Furthermore, after adding the ceramic powder into the metal melt, stir for 10 - 15 min, and keep the melt temperature at Tm~Tm + 150 °C, where Tm is the melting point of the metal melt.

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

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

[0016] Compared with the prior art, the technical solution provided by the present invention brings the following beneficial effects: The zinc-based composite powder material proposed by the present invention is prepared by a rotating disk centrifugal atomization process, so that the ceramic phase protrudes from the surface of the zinc-based metal phase, and the protrusion height is not more than 4 μm. Preferably, the average protrusion height is not less than 1 μm and not more than 4 μm. When 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, there will be no powder jamming problem during the subsequent 3D printing process. The reason for limiting the height of the protruding part of the ceramic phase is as follows: on the one hand, when the protrusion height of the ceramic phase is higher than 4 μm, a burr structure is formed, which greatly increases the probability of powder jamming during the 3D printing process of the prepared zinc-based composite powder, resulting in printing interruption. On the other hand, the partially protruding ceramic phase has a pinning effect on the subsequently sprayed inorganic coating to prevent the inorganic coating from falling off. Therefore, the protrusion height of the ceramic phase cannot be too low. In order to ensure the pinning effect, that is, there are certain requirements for the surface protrusion amount of the spherical powder. As is well known, various process parameters such as the melting process and subsequent solidification behavior affect the final morphology of the ceramic phase. The content of the ceramic phase added in the present invention is 2.0-10.0 wt% of the mass of the metal melt, which can greatly improve its pinning effect on the subsequent inorganic coating. The addition amount of the ceramic phase should not be too small, otherwise the generated ceramic phase protrusion is too small to effectively pin the subsequent coating. And the addition amount should not be too large, otherwise serious agglomeration will occur, and the size of the protrusion of the prepared ceramic phase is large, which is easy to cause powder jamming during the 3D printing process. Description of the Drawings

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained according to these drawings.

[0018] Figure 1 It is the powder SEM diagram of the zinc-based composite powder material prepared in Example 1 of the present invention. a is the zinc-based ceramic composite powder, and b is the enlarged view of the powder surface;

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

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

[0021] Figure 4 It is the powder SEM diagram of the zinc-based composite powder material prepared in Comparative Example 1 of the present invention. Detailed Embodiments

[0022] 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 and specific embodiments. The specific embodiments of the present invention are not limited to the specific embodiments given here. Those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the disclosed specific embodiments.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used are only for describing specific embodiments and do not limit the present invention.

[0024] The present invention provides a zinc-based composite powder material. The powder particles of the zinc-based composite powder material are spherical-like 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 a part of the ceramic phase protrudes from the surface of the zinc-based metal phase, with an average protrusion height not greater than 4 μm. The content of the ceramic phase is 2.0-10.0 wt% of the mass of the metal melt.

[0025] For the zinc-based composite powder material proposed by the present invention, through the rotating disk centrifugal atomization process, a ceramic phase is prepared to protrude from the surface of the zinc-based metal phase, and the protrusion height is not greater than 4 μm. Preferably, the average protrusion height is not less than 1 μm and not greater than 4 μm. The D90 particle size of the prepared zinc-based composite powder is not less than 60 μm. The particle size in the present invention is the diameter of the spherical-like matrix, that is, when the D90 particle size of the zinc-based composite powder is at least 15 times the protrusion height, there will be no powder jamming problem. The height of the protruding part of the ceramic phase is the maximum distance between it and the center of the spherical matrix, minus the distance between the surface of the spherical matrix and the center of the sphere. The reason for limiting the height of the protruding part of the ceramic phase is that, on the one hand, when the protrusion height of the ceramic phase is higher than 4 μm, a burr structure is formed, which greatly increases the probability of powder jamming during the 3D printing process of the prepared zinc-based composite powder, resulting in printing interruption. On the other hand, the partially protruding ceramic phase has a pinning effect, pinning the subsequently sprayed inorganic coating to prevent the shedding of the inorganic coating. Therefore, the protruding height of the ceramic phase cannot be too small. To ensure the pinning effect, that is, there are certain requirements for the surface protrusion amount of the spherical powder. As is well known, various process parameters such as the melting process and subsequent solidification behavior affect the final morphology of the ceramic phase. The content of the ceramic phase added in the present invention is 2.0-10.0 wt% of the mass of the metal melt, which can greatly improve its pinning effect on the subsequent inorganic coating. The addition amount of the ceramic phase should not be too small, as too small will result in too small protrusion of the generated ceramic phase and ineffective pinning of the subsequent coating. And the addition amount should not be too large, as too large will lead to serious agglomeration, and the size of the protrusion of the prepared ceramic phase is large, which is likely to cause powder jamming during the 3D printing process.

[0026] It should be noted that the sphericity of the quasi-spherical shape of the present application only needs to be above 0.6. The calculation formula of sphericity is common knowledge and will not be elaborated here. In the present invention, the average protrusion height can be obtained by calculating the average value of the heights of at least 20 protrusions, and the protrusions on one powder or multiple powders can be selected for calculation.

[0027] Specifically, the ceramic phase is one or more of hydroxyapatite, zirconia, tricalcium silicate, bioactive glass, calcium carbonate, etc. The above substances stably exist in the melt of Zn and Zn alloys, and the probability of generating intermediate products is extremely low. Among them, bioactive glass refers to glass that can achieve specific biological and physiological functions. When bioactive glass is implanted into the bone defect site of the human body, it can directly combine with bone tissue and play a role in repairing bone tissue and restoring its function.

[0028] Specifically, 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 element, copper element, aluminum element, manganese element, indium element, iron element, lithium element, bismuth element, strontium element, calcium element, rare earth element, etc. The total addition amount of the target alloying elements does not exceed 20wt%, which will not greatly affect the physical properties of the Zn-based metal melt, and the zinc-based composite powder material required to be protected by the present invention can be prepared.

[0029] Specifically, the content requirements of the target alloying elements are as follows: the content of magnesium element is 0.5 - 20.0%, the content of calcium element is 1.0 - 10.0%, the content of copper element is 0.2 - 6.0%, the content of aluminum element is 1.2 - 10.0%, the content of manganese element is 0.1 - 4.0%, and the content of the remaining elements ≤ 5.0%. Different elements have a certain impact on the physical properties of the Zn-based metal melt. In order to avoid drastic changes in physical properties caused by the addition of elements, the content of the target alloying elements is limited in the present application.

[0030] In order to illustrate the inventive points of the present application, Zn-0.5Mg, Zn-20Mg, and Zn-2Cu are selected as examples for illustration.

[0031] The embodiment of the present invention also provides a preparation method of the above zinc-based composite powder material, including:

[0032] S1 Prepare a metal melt.

[0033] Preferably, the intermediate alloy method is used to select materials to reduce the burning loss of active metals. For example, in the present invention, when preparing Zn-0.5Mg, a material combination of Zn-20Mg alloy ingot and pure zinc ingot can be selected to obtain the melt with the final required composition.

[0034] S2 Add ceramic powder to the metal melt.

[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. In the prepared Zn-based composite powder, some ceramic phases protrude up to 4 μm above the surface of the Zn-based metal phase. The reason for the above is that there are different surface tensions inside and on the surface of the Zn-based metal phase. The ceramic powder with a small particle size inside is dispersed in the Zn-based metal phase, while the formation of the ceramic phase on the surface of the Zn-based metal is due to the fact that during the solidification of the droplet, the solidification diffuses outward from the crystal core and solidifies step by step. The end of the solidification drives and aggregates the ceramic powder attached to the surface, thus forming a protrusion up to 4 μm. Secondly, the ceramic powder on the surface of the droplet is prone to agglomeration due to the large surface tension. In order not to form a protrusion exceeding 4 μm, the control of the process is also very important because the process parameters determine the solidification behavior of the Zn-based metal.

[0036] After stirring for a preset time, a Zn-based composite melt is obtained. The Zn-based composite melt is dropped onto a rotating disk through a nozzle and then thrown out to obtain a powder. The rotating disk has a first temperature.

[0037] Specifically, stirring for 10-15 min is sufficient. The stirring speed is 20-60 rpm, and the melt temperature is maintained at Tm~Tm+150 °C, where Tm is the melting point of the metal melt. As is well known, the melting point can be determined based on the phase diagram. Based on the phase diagram, the melting point of Zn-0.5Mg is 420 °C, the melting point of Zn-20Mg is 535 °C, and the melting point of Zn-2Cu is 420 °C.

[0038] The flow rate of the metal melt is 100-120 g / s, and the first temperature is Tm+30~Tm+60, where Tm is the melting point of the metal melt. The rotation speed of the rotating disk is 15000-50000 rpm. The above process parameters are very important for the finally obtained Zn-based composite powder material. The flow rate of the Zn-based metal melt determines the impact force between the Zn-based metal melt and the rotating disk. On the one hand, it determines the particle size of the finally prepared Zn-based composite powder. On the other hand, it determines the interaction between the tiny droplets formed after the Zn-based metal melt impacts the rotating disk and the rotating disk, making the ceramic phase partially protrude above the surface of the Zn-based metal phase, that is, the ceramic phase is embedded in the Zn-based metal phase, thus forming a firm and reliable connection. And the first temperature determines the solidification process of the Zn-based composite metal melt. If the solidification is too fast, the ceramic powder cannot be aggregated, and the height of the generated ceramic phase protruding above the Zn-based metal phase is small. If the solidification is too slow, the height of the generated ceramic phase protruding above the Zn-based metal phase is too high and does not meet the requirements. Secondly, the magnitude of the impact force affects the secondary dispersion of the ceramic powder, that is, the Zn-based alloy droplet with ceramic powder impacts the rotating disk, and the rotating disk exerts a secondary impact on the ceramic powder in the droplet, thereby secondarily dispersing the agglomerated ceramic powder.

[0039] The obtained powder is obtained after collection, sieving, and post-treatment by S4.

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

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

[0042] The present invention adopts a rotating disk centrifugal atomization process. By adding ceramic particles to the molten metal and mixing them, under the centrifugal force, secondary mixing and dispersion are carried out in the flow channel of the rotating disk and finally thrown out, which can effectively achieve the uniform dispersion of ceramic particles in the metal powder and the surface of the prepared powder has ceramic protruding phases, which is a new preparation method for preparing zinc metal-ceramic composite powder.

[0043] It should be noted that, without special instructions, all measurements in this application are in mass percentages.

[0044] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they cannot be understood as limiting the protection scope of the present invention.

[0045] Example 1

[0046] A zinc-based composite powder material and a preparation method provided in this example include:

[0047] S1 Prepare a metal melt. Prepare a Zn-0.5Mg alloy as the metal melt. Select a Zn-20Mg master alloy ingot and a pure Zn ingot and put them into a crucible for melting and heat preservation to reach the target composition. The heat preservation temperature is Tm, that is, 420°C.

[0048] S2 Add ceramic powder to the metal melt. Add hydroxyapatite powder. The average particle size of the hydroxyapatite powder is 200 nm, and the addition amount is added according to 10 wt%.

[0049] After stirring for a preset time, a zinc-based composite melt is obtained. The zinc-based composite melt is dropped through a nozzle onto a rotating disk and then thrown out to obtain a powder. The rotating disk has a first temperature.

[0050] Stir for 10 minutes to obtain the target zinc-based composite melt of Zn-0.5Mg + 10wt.%. After the zinc-based composite melt after stirring is dropped onto the rotating disk through the nozzle, powder is thrown out. The flow rate of the zinc-based composite melt is 100 g / s, the rotation speed of the rotating disk is 15,000 rpm, and the temperature of the rotating disk is 450 °C.

[0051] S4: Collect, sieve, and post-treat the obtained powder to obtain the product.

[0052] The prepared zinc-based composite powder is as Figure 1 shown in Figures 1a and 1b. It can be seen that after the ceramic is compounded, the ceramic phase is inlaid on the surface of the zinc-based metal phase. The large protrusions on the surface are ceramic particle agglomerations, and the other surface flocs are hydroxyapatite. The ceramic particles are evenly distributed on the surface of the metal powder, proving that good compounding has been achieved between the two, and the sphericity of the powder is also guaranteed. And the ceramic phase protrudes partially from the surface of the zinc-based metal phase, and the average protrusion height is not less than 1 μm and not more than 4 μm.

[0053] After testing, its apparent density is 3.99 g / cm 3 , the fluidity is 8.12 s / 50 g, and no powder jamming occurs during the 3D printing process.

[0054] Example 2

[0055] Different from Example 1, in this example, in step S2, hydroxyapatite powder is added, and the addition amount is 2wt%.

[0056] The prepared zinc-based composite powder is as Figure 2 shown. It can be seen that the content of hydroxyapatite is less, and it can be better compounded into the interior of the zinc powder. The surface of the powder is smooth and flat, and only a small amount of ceramic powder adheres to the surface. And the ceramic phase protrudes partially from the surface of the zinc-based metal phase, and the average protrusion height is not less than 1 μm and not more than 4 μm.

[0057] After testing, its apparent density is 4.33 g / cm 3 , the fluidity is 4.31 s / 50 g, and no powder jamming occurs during the 3D printing process.

[0058] Example 3

[0059] Different from Example 1, in this example, in step S2, hydroxyapatite powder is added, and the addition amount is 6wt%.

[0060] The prepared zinc-based composite powder is as Figure 3As shown, it can be seen that partial agglomeration of ceramic particles appears on the surface, and under the impact, the agglomerated particles are deformed. However, the overall composite effect is good. The ceramic phase protrudes from the surface of the zinc-based metal phase, and the average protrusion height is not less than 1 μm and not more than 4 μm.

[0061] After testing, its loose bulk density is 4.17 g / cm 3 , and the fluidity is 5.54 s / 50 g. There is no powder jamming during the 3D printing process.

[0062] Example 4

[0063] A zinc-based composite powder material and a preparation method provided in this example include:

[0064] S1 Prepare the metal melt. Prepare a Zn-0.5Mg alloy as the metal melt. Select a Zn-20Mg master alloy ingot and a pure Zn ingot and put them into a crucible for melting and holding to reach the target composition. The holding temperature is 500 °C.

[0065] S2 Add ceramic powder to the metal melt. Add hydroxyapatite powder. The average particle size of the hydroxyapatite powder is 300 nm, and the addition amount is added according to 10 wt%.

[0066] S3 After stirring for a preset time, a zinc-based composite melt is obtained. The zinc-based composite melt is dropped onto a rotating disk through a nozzle and then thrown out to obtain powder. The rotating disk has a first temperature.

[0067] Stir for 15 minutes to obtain a target zinc-based composite melt of Zn-0.5Mg + 10 wt.%. After the stirring is completed, the zinc-based composite melt is dropped onto a rotating disk through a nozzle and then thrown out to obtain powder. The flow rate of the zinc-based composite melt is 110 g / s, the rotation speed of the rotating disk is 30000 rpm, and the temperature of the rotating disk is 460 °C.

[0068] S4 The obtained powder is collected, sieved, and post-treated to obtain the product.

[0069] For the prepared zinc-based composite powder, the ceramic phase protrudes from the surface of the zinc-based metal phase, and the average protrusion height is not less than 1 μm and not more than 4 μm. After testing, its loose bulk density is 4.01 g / cm 3 , and the fluidity is 7.92 s / 50 g. There is no powder jamming during the 3D printing process.

[0070] Example 5

[0071] A zinc-based composite powder material and a preparation method provided in this example include:

[0072] S1 Prepare a metal melt. Prepare a Zn-0.5Mg alloy as the metal melt. Select Zn-20Mg master alloy ingots and pure Zn ingots and put them into a crucible for melting and holding to reach the target composition. The holding temperature is 570 °C.

[0073] S2 Add ceramic powder to the metal melt. Add hydroxyapatite powder with an average particle size of 500 nm, and the addition amount is 10 wt%.

[0074] S3 After stirring for a preset time, a zinc-based composite melt is obtained. The zinc-based composite melt is dropped through a nozzle onto a rotating disk and then centrifuged to obtain powder. The rotating disk has a first temperature.

[0075] Stir for 15 minutes to obtain the target zinc-based composite melt of Zn-0.5Mg + 10 wt.%. After the stirring is completed, the zinc-based composite melt is dropped through a nozzle onto a rotating disk and then centrifuged to obtain powder. The flow rate of the zinc-based composite melt is 120 g / s, the rotation speed of the rotating disk is 50000 rpm, and the temperature of the rotating disk is 480 °C.

[0076] S4 Collect, sieve, and post-treat the obtained powder to obtain the product.

[0077] For the prepared zinc-based composite powder, the ceramic phase protrudes from the surface of the zinc-based metal phase, and the average protrusion height is not less than 1 μm and not more than 4 μm. After testing, its loose bulk density is 3.87 g / cm 3 , the fluidity is 8.05 s / 50 g, and no powder jamming occurs during the 3D printing process.

[0078] Example 6

[0079] A zinc-based composite powder material and its preparation method provided in this example include:

[0080] S1 Prepare a metal melt. Prepare a Zn-20Mg alloy as the metal melt, and the holding temperature is 550 °C.

[0081] S2 Add ceramic powder to the metal melt. Add tricalcium silicate with an average particle size of 200 nm, and the addition amount is 10 wt%.

[0082] S3 After stirring for a preset time, a zinc-based composite melt is obtained. The zinc-based composite melt is dropped through a nozzle onto a rotating disk and then centrifuged to obtain powder. The rotating disk has a first temperature.

[0083] Stir for 10 minutes to obtain a target zinc-based composite melt of Zn-20Mg + 10 wt.%. After the zinc-based composite melt is completed stirring, it drops through a nozzle onto a rotating disk and is then spun off to obtain powder. The flow rate of the zinc-based composite melt is 100 g / s, the rotation speed of the rotating disk is 15,000 rpm, and the temperature of the rotating disk is 580 °C.

[0084] S4 Collect, sieve, and post-treat the obtained powder to obtain the product.

[0085] For the prepared zinc-based composite powder, the ceramic phase part protrudes from the surface of the zinc-based metal phase, and the average protrusion height is not less than 1 μm and not more than 4 μm. After testing, its apparent density is 2.93 g / cm 3 , the fluidity is 9.20 s / 50 g, and no powder jamming occurs during the 3D printing process.

[0086] Example 7

[0087] A zinc-based composite powder material and its preparation method provided in this example include:

[0088] S1 Prepare a metal melt. Prepare a Zn-2Cu alloy as the metal melt, and the holding temperature is 440 °C.

[0089] S2 Add ceramic powder to the metal melt. Add calcium carbonate powder, the average particle size of the calcium carbonate powder is 200 nm, and the addition amount is added according to 10 wt%.

[0090] S3 After stirring for a preset time, a zinc-based composite melt is obtained. The zinc-based composite melt drops through a nozzle onto a rotating disk and is then spun off to obtain powder. The rotating disk has a first temperature.

[0091] Stir for 10 minutes to obtain a target zinc-based composite melt of Zn-2Cu + 10 wt.%. After the zinc-based composite melt is completed stirring, it drops through a nozzle onto a rotating disk and is then spun off to obtain powder. The flow rate of the zinc-based composite melt is 100 g / s, the rotation speed of the rotating disk is 30,000 rpm, and the temperature of the rotating disk is 480 °C.

[0092] S4 Collect, sieve, and post-treat the obtained powder to obtain the product.

[0093] For the prepared zinc-based composite powder, the ceramic phase part protrudes from the surface of the zinc-based metal phase, and the average protrusion height is not less than 1 μm and not more than 4 μm. After testing, its apparent density is 4.28 g / cm 3 , the fluidity is 8.50 s / 50 g, and no powder jamming occurs during the 3D printing process.

[0094] Comparative Example 1

[0095] Different from Example 1, in this comparative example, in step S2, hydroxyapatite powder was added, and the addition amount was 12 wt%.

[0096] The prepared zinc-based composite powder is as Figure 4 shown. It can be seen that obvious agglomeration occurred on the surface of the zinc alloy powder with 15 wt.% hydroxyapatite composite added. The surface of the zinc-based metal phase is irregular, and the unevenness is greater than 4 μm. The ceramic particles are unevenly distributed and the expected effect was not achieved. After testing, its loose bulk density is 3.22 g / cm 3 , and the fluidity is 12.22 s / 50 g. There is no powder jamming during the 3D printing process.

[0097] Comparative Example 2

[0098] Different from Example 1, in this comparative example, in step S2, hydroxyapatite powder was added, and the addition amount was 1.5 wt%.

[0099] For the prepared zinc-based composite powder, very few ceramic phase parts protrude from the surface of the zinc-based metal phase, and the average protruding height is less than 1 μm, and it cannot effectively pin the coating subsequently.

[0100] Comparative Example 3

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

[0102] For the prepared zinc-based composite powder, the ceramic phase part protrudes from the surface of the zinc-based metal phase, and the average protruding height is greater than 4 μm, and there is a problem of powder jamming during the printing process.

[0103] Comparative Example 4

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

[0105] For the prepared zinc-based composite powder, the ceramic phase part protrudes from the surface of the zinc-based metal phase, and the average protruding height is less than 1 μm.

[0106] Comparative Example 5

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

[0108] For the prepared zinc-based composite powder, the ceramic phase part protrudes from the surface of the zinc-based metal phase, and the average protruding height is greater than 4 μm.

[0109] Comparative Example 6

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

[0111] For the prepared zinc-based composite powder, the ceramic phase part protrudes from the surface of the zinc-based metal phase, and the average protruding height is less than 1 μm.

[0112] Comparative Example 7

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

[0114] For the prepared zinc-based composite powder, the ceramic phase part protrudes from the surface of the zinc-based metal phase, and the average protruding height is greater than 4 μm.

[0115] It can be seen from Example 1 and Comparative Example 1 that after the addition amount of hydroxyapatite powder is greater than 10%, the agglomeration phenomenon is obvious. The reason is that a large amount of hydroxyapatite agglomerates. Combining with the subsequent process, even at a relatively high flow rate of the zinc-based composite melt, it is impossible to use the impact to perform secondary dispersion on hydroxyapatite, which has exceeded the process's ability to disperse hydroxyapatite with a content of more than 10%. It can be seen from Example 1 and Comparative Example 2 that when too little hydroxyapatite is added, an effective protruding height of the ceramic phase cannot be formed, and subsequent pinning effect on the coating cannot be achieved well. It can be seen from Example 1, Comparative Examples 3 and 4 that the temperature of the rotating disk has a great influence on the performance of the prepared zinc-based composite powder material. The reason is that the first temperature determines the solidification process of the zinc-based composite metal melt. If the temperature of the rotating disk is low, the zinc-based alloy melt solidifies too fast, and it is impossible to aggregate the ceramic powder, and the protruding height of the generated ceramic phase from the zinc-based metal phase is small. If the temperature of the rotating disk is high, the zinc-based alloy melt solidifies too slowly, and the protruding height of the generated ceramic phase from the zinc-based metal phase is too high, which does not meet the requirements. It can be seen from Example 1, Comparative Examples 5 and 6 that the flow rate of the zinc-based composite melt has a great influence on the finally prepared powder. The main reason is that the impact force itself affects the secondary dispersion of ceramic particles in the melt. The faster the flow rate, the greater the impact force, and the better the secondary dispersion effect; while the lower the flow rate, the smaller the impact force, and the worse the secondary dispersion effect. It can be seen from Example 1 and Comparative Example 7 that 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 finally prepared product.

[0116] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A zinc-based composite powder material, characterized in that: 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 partially 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 metal melt.

2. The zinc-based composite powder material according to claim 1, characterized in that: The ceramic phase is one or more of hydroxyapatite, zirconium oxide, 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 element is 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 target alloy element content requirements are: magnesium content of 0.5-20.0%, calcium content of 0.5-10.0%, copper content of 0.5-6.0%, aluminum content of 0.5-10.0%, manganese content of 0.5-4.0%, and the content of other elements is ≤5.0%.

5. The method for preparing the zinc-based composite powder material according to any one of claims 1 to 4, characterized in that: include: preparing a metal melt; adding ceramic powder to the metal melt; After stirring for a preset time, a zinc-based composite melt is obtained, and the zinc-based composite melt drips onto a rotating disk through a nozzle and is then thrown out to obtain powder, wherein the rotating disk has a first temperature; The obtained powder is collected, sieved and post-processed to obtain the product.

6. The preparation method according to claim 5, characterized in that: The average particle size of the ceramic powder is 100-500 nm.

7. The preparation method according to claim 5, characterized in that: The rotating speed of the rotating disk is 15000-50000 rpm.

8. The preparation method according to claim 5, characterized in that: After adding the ceramic powder into the metal melt, stirring is performed for 10-15 minutes, and the melt temperature is maintained at Tm to Tm+150° C., wherein Tm is the melting point of the metal melt.

9. The preparation method according to claim 5, characterized in that: The flow rate of the zinc-based composite melt is 100-120 g / s.

10. The preparation method according to claim 5, characterized in that: The first temperature is Tm+30°C to Tm+60°C, wherein Tm is the melting point of the molten metal.

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