CN113388792B - Biomedical amorphous magnesium alloy powder, composite material and preparation process - Google Patents
Biomedical amorphous magnesium alloy powder, composite material and preparation process Download PDFInfo
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Abstract
The invention provides biomedical amorphous magnesium alloy powder, a composite material and a preparation process, and relates to the technical field of biomedical magnesium alloy. The amorphous magnesium alloy powder comprises the following components in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca. The biomedical amorphous magnesium alloy composite material is prepared from the biomedical amorphous magnesium alloy powder serving as raw material powder. The biomedical amorphous magnesium alloy powder can be prepared into an amorphous magnesium alloy composite material through a selective laser melting process (SLM), and the amorphous magnesium alloy of a large-size block with a complex shape is prepared according to actual requirements while an amorphous structure of the amorphous magnesium alloy powder is kept.
Description
Technical Field
The invention relates to the technical field of biomedical magnesium alloy, in particular to a biomedical magnesium alloy composite material and a preparation process thereof.
Background
Mg is one of the macroelements which are essential elements for the human body, and is the second metal element to Ca, K and Na. Mg and its alloy have the features of low density, high specific strength, low elastic modulus, etc. Meanwhile, Mg is easy to corrode and degrade in various body fluid environments, and the medical clinical purpose that the metal implant gradually degrades in vivo until finally disappears is achieved. Therefore, the attractive potential of Mg and its alloy as a degradable biomedical implant material in orthopedic applications is receiving more social attention. When the Mg-Mg alloy and-Mg alloy can stimulate and promote bone healing after being implanted into human body without causing acute reaction or obvious reaction.
However, the standard electrode potential for Mg is very low, about-2.37V (vs SCE), which makes Mg and its alloys less corrosion resistant and degrade too quickly. Usually less than the time required for bone tissue to heal (more than 12 weeks) while releasing excess H during its degradation2A balloon is formed under the skin, which may hinder the interaction of the implant and the bone tissue to some extent, and affect the healing of the bone tissue. Particularly, in the Mg alloy, the alloy elements and Mg form precipitation phases to form galvanic corrosion with a Mg matrix, the corrosion rate of the Mg alloy is accelerated, and the mechanical property of the Mg alloy is reduced due to surface defects caused by the formed pitting corrosion.
In contrast, the magnesium-based amorphous alloy has a large number of cavities due to irregular atomic arrangement, and atomic distribution has uniformity and single-phase property, so that crystal boundaries do not exist, defects are reduced, and the corrosion resistance and mechanical properties of the material are improved. However, since the amorphous alloy is formed by rapidly solidifying a metal melt, there is a technical bottleneck in preparing large-sized complex-structure parts in the forming and manufacturing process. In recent years, the manufacture of bulk amorphous biomagnesium alloys has mainly employed copper mold casting molding and thermoplastic molding. The copper mold casting forming method is to inject magnesium alloy melt into a copper mold cavity to realize direct forming of the bulk amorphous magnesium alloy, for example, the Liquidmetal company successfully realizes preparation of the bulk amorphous magnesium alloy by adopting a die-casting forming technology. However, the fast cooling rate of the copper mold severely affects the fluidity of the alloy melt, which presents challenges to the preparation of complex parts. The thermoplastic forming method mainly utilizes the superplasticity of amorphous alloy in a supercooled liquid region, adopts forming technologies such as stamping, injection molding, blow molding and extrusion and realizes the near-net forming of parts with the dimension from nanometer to centimeter, but the method is only suitable for the stamping forming of micro parts and is difficult to be used for forming large-size complex structural parts.
Disclosure of Invention
The invention provides biomedical amorphous magnesium alloy powder and composite material and a preparation process thereof, in order to realize large-size and complex-shape bulk amorphous magnesium alloy.
The application provides a biomedical amorphous magnesium alloy powder, which adopts the following technical scheme:
the amorphous magnesium alloy powder consists of the following components in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca.
By adopting the alloy component range, amorphous magnesium alloy powder can be prepared, and the amorphous magnesium alloy composite material can be prepared by utilizing a 3D printing technology, such as a selective laser melting process (SLM), so that the amorphous magnesium alloy of a large-size block with a complex shape can be prepared according to actual requirements while the amorphous structure of the amorphous magnesium alloy powder is kept.
Preferably, the amorphous magnesium alloy powder is spherical powder, and the particle size of the powder is 15-105 μm.
By adopting the technical scheme, the good fluidity of the spherical powder is utilized to improve the powder spreading uniformity in the laser melting process, so that the uniformity of the internal organization structure of the finally prepared amorphous magnesium alloy composite material is ensured, and the particle size range of the powder is 15-105 mu m, so that the powder is easier to flow and be formed by laser melting.
Preferably, the amorphous magnesium alloy powder is spherical powder, and the particle size of the powder is 15-75 μm.
By adopting the technical scheme, the amorphous magnesium alloy composite material is prepared by selecting the amorphous magnesium alloy powder with the powder particle size of 15-75 microns as a raw material and adopting a laser melting process, the amorphous structure of the powder is better reserved, and meanwhile, the amorphous magnesium alloy composite material has the advantages of less crystal phase, low degradation rate and excellent corrosion and degradation resistance.
The application provides a preparation process of biomedical amorphous magnesium alloy powder, which comprises the following steps:
s1, the raw materials in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca is prepared;
s2, smelting the prepared raw materials to prepare a target master alloy;
and S3, atomizing the target master alloy to prepare powder, so as to obtain the amorphous magnesium alloy powder.
By adopting the technical scheme, the amorphous magnesium alloy powder can be prepared, the process is simple, the operation is easy, and the method is suitable for industrial application and popularization.
Preferably, the melting temperature in step S2 is 720 to 750 ℃.
By adopting the technical scheme, the raw materials can be fully melted, meanwhile, the raw material loss is avoided, and the target alloy with the target components is obtained.
Preferably, the airflow pressure of the atomized powder in the step S3 is 1.8-2.2 MPa, and the airflow speed is 300-340 m/S.
By adopting the technical scheme, the spherical powder with the target particle size can be obtained, the particle size of the spherical powder is uniform, and the flowability and uniformity of powder paving in the subsequent laser melting process are improved.
The biomedical amorphous magnesium alloy composite material is prepared from the biomedical amorphous magnesium alloy powder serving as raw material powder, and the phase structure of the amorphous magnesium alloy composite material comprises an amorphous phase and an optional crystalline phase, wherein the optional crystalline phase is an Mg phase, or the optional crystalline phase is an Mg phase and a Ca phase2Mg5Zn13Phase, Ca2Mg6Zn3And (4) phase.
By adopting the technical scheme, the corrosion resistance and the mechanical property of the magnesium alloy can be improved, the magnesium-based amorphous alloy has a large number of cavities due to irregular atomic arrangement, the atomic distribution has uniformity and single-phase property, no crystal boundary exists, and the defects are reduced, so that the corrosion resistance and the mechanical property of the material are improved.
Preferably, the phase structure of the amorphous magnesium alloy composite material comprises an amorphous phase and an Mg phase, the Mg phase is an alpha-Mg microcrystalline structure, and the alpha-Mg microcrystalline structure accounts for 15% of the volume ratio of the composite material.
By adopting the technical scheme, the crystal phase comprises the Mg phase, so that the crystal phase composition of the amorphous magnesium alloy composite material is reduced, and the defects caused by different crystal phases such as the Mg phase and the Ca are improved2Mg5Zn13Phase, Ca2Mg6Zn3Phase, and their preparationGalvanic corrosion is caused by the potential difference of the amorphous structure, and the alpha-Mg microcrystalline structure has good plasticity, so that the mechanical property of the amorphous magnesium alloy composite material is further improved.
The application provides a preparation process of a biomedical amorphous magnesium alloy composite material, which is prepared by adopting the biomedical amorphous magnesium alloy powder as a raw material and adopting a selective laser melting process.
By adopting the technical scheme, the large-size and complex-shape bulk amorphous magnesium alloy can be conveniently prepared according to actual requirements without being limited by casting forming and thermoplastic forming, and the method is simple in process and easy to industrially apply and popularize.
Preferably, the parameters of the selective laser melting process are: the laser spot is 70 μm, the laser scanning speed is 80-100 mm/s, the laser power is 80-110W, the scanning times are 1-3 times, and the scanning interval is 0.06-0.08 mm.
By adopting the technical scheme, the amorphous magnesium alloy composite material can be prepared, the amorphous structure of the raw amorphous powder can be better reserved, and the corrosion resistance and the mechanical property of the amorphous magnesium alloy material are improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the biomedical amorphous magnesium alloy powder can be used for preparing amorphous magnesium alloy powder, can be used for preparing amorphous magnesium alloy composite materials by utilizing a 3D printing technology, such as a selective laser melting process (SLM), and can be used for preparing amorphous magnesium alloy blocks with large sizes and complex shapes according to actual requirements while keeping the amorphous structure of the amorphous magnesium alloy powder.
2. The preparation process of the biomedical amorphous magnesium alloy powder provided by the application can be used for preparing the amorphous magnesium alloy powder, is simple in process, easy to operate and suitable for industrial application and popularization.
3. The biomedical amorphous magnesium alloy composite material provided by the application can improve the corrosion resistance and mechanical property of magnesium alloy, and the magnesium-based amorphous alloy has a large number of cavities due to irregular atomic arrangement, has uniformity and single-phase property of atomic distribution, does not have crystal boundary, and reduces defects, thereby improving the corrosion resistance and mechanical property of the material.
4. According to the preparation process of the biomedical amorphous magnesium alloy composite material, the amorphous magnesium alloy composite material can be prepared, the amorphous structure of the raw amorphous powder can be well reserved, and the corrosion resistance and the mechanical property of the amorphous magnesium alloy material are improved.
Drawings
Fig. 1 is an XRD spectrum of the target master alloy prepared in example 1 of the present application.
FIG. 2 is an optical microscopic image of the target master alloy prepared in example 1 of the present application.
Fig. 3 is an SEM image of the amorphous magnesium alloy powder prepared in example 1 of the present application.
Fig. 4 is an XRD spectrum of the amorphous magnesium alloy powder prepared in example 1 of the present application.
Fig. 5 is an XRD spectrum of the amorphous magnesium alloy composite material prepared in example 1 of the present application.
Fig. 6 is an SEM image of the amorphous magnesium alloy powder produced in example 2 of the present application.
Fig. 7 is an XRD spectrum of the amorphous magnesium alloy powder prepared in example 2 of the present application.
Fig. 8 is an XRD spectrum of the amorphous magnesium alloy composite material prepared in example 2 of the present application.
Fig. 9 is an XRD spectrum of the amorphous magnesium alloy powder prepared in example 3 of the present application.
Fig. 10 is an XRD spectrum of the amorphous magnesium alloy composite material prepared in example 3 of the present application.
Fig. 11 is an XRD spectrum of the amorphous magnesium alloy composite material prepared in example 4 of the present application.
Fig. 12 is an optical microscopic image of an amorphous magnesium alloy composite material produced in example 4 of the present application.
Fig. 13 is an XRD spectrum of the amorphous magnesium alloy composite material prepared in example 5 of the present application.
Fig. 14 is an XRD spectrum of the amorphous magnesium alloy composite material prepared in example 6 of the present application.
Fig. 15 is an XRD spectrum of the amorphous magnesium alloy composite material prepared in example 7 of the present application.
Detailed Description
The common biomedical magnesium alloy at present mainly comprises Mg-Ca, Mg-Zn, Mg-Mn, Mg-Sr and Mg-RE alloy, and the alloy subjected to alloying treatment has good biocompatibility and has no adverse effect on tissues. The Mg-Zn-Ca alloy has higher specific strength and specific rigidity, the elastic modulus is similar to that of human skeleton, and the Mg-Zn-Ca alloy has good biocompatibility, so that the Mg-Zn-Ca alloy is a research hotspot in the field of medical alloys at present. However, since the ability of magnesium alloys to form an amorphous structure is affected by the alloy system, Mg-Zn-Ca alloys belong to alloy systems that have a weak ability to form an amorphous structure. In order to obtain an amorphous structure of Mg-Zn-Ca alloy, patent document No. CN109161766B discloses a biological magnesium alloy containing an amorphous fused layer and a method for preparing the same, the amorphous fused layer is obtained on a magnesium-zinc-calcium alloy block by a laser melting process, a fiber laser is used to collect heat to a relatively high temperature at a local position of the surface of the magnesium alloy to melt the magnesium alloy, and then the melted metal surface is rapidly quenched and solidified by means of the heat absorption and conduction heat effect of a relatively cold metal matrix, thereby forming an amorphous layer.
However, for a bulk amorphous magnesium alloy with a large size and a complex shape, the ability of each part of the bulk to conduct heat is different, and it cannot be guaranteed that an amorphous layer with a uniform thickness is formed on the surface of the bulk, and once the amorphous layer at a thinner position is corroded and broken down, the corrosion degradation of the whole bulk is accelerated.
In order to realize the large-size and complex-shape bulk amorphous magnesium alloy, the application provides an amorphous magnesium alloy powder, and a selective laser melting process in a 3D printing technology, wherein CO is adopted2The laser prints and forms highly complex parts layer by layer without any die, thereby realizing great design freedom and breaking through amorphous MThe forming capability of the g-Zn-Ca alloy is limited, thereby realizing the preparation of large-size block amorphous alloy parts with complex shapes.
The amorphous magnesium alloy powder, the amorphous magnesium alloy composite material, and the production process of the present invention will be described in detail below.
1. Amorphous magnesium alloy powder
The amorphous magnesium alloy powder is magnesium alloy powder with an amorphous structure. The method mainly takes an Mg-Zn-Ca alloy system as an example to research the influence of the amorphous magnesium alloy powder and the influence of the amorphous magnesium alloy powder on the preparation of an amorphous magnesium alloy composite material or device. The amorphous magnesium alloy powder consists of the following components in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca. The following steps can be also included: mg: 55-65 at.%; 30-35 at.% Zn; ca balance, total of alloy constituents 100 at.%. The amorphous magnesium alloy powder can also cover other magnesium alloy systems.
The amorphous magnesium alloy powder is used for preparing amorphous magnesium alloy composite materials or devices and the like, and can be prepared by adopting processes such as 3D printing forming, powder sintering forming, powder injection forming, hot isostatic pressing forming and the like.
The amorphous magnesium alloy powder adopts atomization equipment to heat a target master alloy to be molten, the overheating is kept at 100-150 ℃, and a metal liquid flow with the diameter of 5-6 mm is formed; and introducing argon through an annular nozzle, wherein the airflow pressure is 1.8-2.2 MPa, and the airflow speed is 300-340 m/s, so as to obtain the amorphous magnesium alloy powder. The prepared powder is spherical powder, the diameter of the powder is 15-105 mu m, can be 15-45 mu m, can be 45-53 mu m, can be 15-75 mu m, can be 75-105 mu m, preferably 15-75 mu m, the sphericity of the powder is high, the fluidity is good, and the powder spreading uniformity is good. The laser printing device is suitable for 3D laser printing forming. The atomization process is in an oxygen-free and closed-loop device environment, so that powder is prevented from being oxidized in the preparation process, high-purity argon (the purity is 99.9 vol%) is used as inert gas to sweep alloy melt, and simultaneously, along with the rapid condensation process, the liquid alloy is atomized into amorphous spherical powder with high circularity.
Smelting and preparing a target master alloy, namely firstly, carrying out raw material proportioning according to the alloy with the following design components: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca. The following steps can be also included: mg: 55-65 at.%; 30-35 at.% Zn; ca balance, total of alloy constituents 100 at.%. The Mg in the raw materials can be 57%, 58-60 at%, 62%, 63-65 at%, and the Zn can be 30-32 at%; 33 at.%, 34-35 at.%, and the balance Ca, the total amount of alloy components being 100 at.%. After surface oxides are removed through pretreatment, smelting is carried out under the protective atmosphere, the smelting temperature is 720-750 ℃, the alloy is fully melted to form magnesium alloy melt, and the magnesium alloy melt is poured into a preheated metal mold to obtain the target master alloy.
2. Amorphous magnesium alloy composite material
The amorphous magnesium alloy composite material takes biomedical amorphous magnesium alloy powder prepared by a gas atomization method as raw material powder, and adopts high-energy CO2The laser beam selectively melts the amorphous alloy powder. And (3) constructing a three-dimensional solid model by using a computer, and setting a layered model generated along the Z direction and scanning path programs of each layer, wherein the powder laying thickness of each layer is 0.5-1 mm. After the laser scan is complete, the work plane is lowered, the next layer of metal powder is deposited on its top surface, and a new layer is then laser scanned. And repeating the process to finally print the required parts. The laser scanning process parameters are as follows: the laser spot is 70 μm; the laser scanning speed is 80-100 mm/s, and can be 80mm/s, 85mm/s, 90mm/s, 95mm/s and 100 mm/s; the laser power is 80-110W, and can be 80W, 85W, 90W, 95W, 100W, 105W and 110W; the scanning times are 1-3 times, and can be 1 time, 2 times and 3 times; the scanning interval is 0.06-0.08 mm, and can be 0.06mm, 0.07mm or 0.08 mm.
The following is a detailed description with reference to examples.
Example 1
The pure magnesium ingot, the pure zinc ingot and the magnesium-calcium 30 intermediate alloy ingot are proportioned according to the components in the target master alloy, and the target master alloy comprises the following components: mg: 60 at.%; zn: 35 at.%; ca:5 at.%, and the surface of the metal stock is polished to remove oxides from the surface of the metal stock, and then placed in an oven and dried at 110 ℃ for 2 h.
Introducing CO2And SF6Under the protection of mixed atmosphere, CO2The gas flow rate is set to 10ml/min, SF6Setting the gas flow as 40ml/min, putting the magnesium ingot into a resistance furnace for melting, setting the melting temperature as 720 ℃, preserving the temperature for 10 minutes after the magnesium ingot is completely melted, and adding the preheated pure zinc ingot and the magnesium-calcium 30 intermediate alloy ingot into the magnesium melt. After the added pure zinc ingot and the magnesium-calcium 30 intermediate alloy ingot are fully melted, stirring for 2 minutes to ensure the full mixing of the alloy elements. And then standing for 20 minutes, skimming, and pouring the alloy liquid into a preheated metal mold to obtain the target master alloy. The XRD pattern of the target master alloy is shown in figure 1, and the XRD pattern shows that characteristic peaks of a plurality of phases appear in the target master alloy after smelting, and the master alloy comprises Mg phase and Ca phase2Mg5Zn13，Mg2Zn11，Ca2Mg6Zn3，MgZn2. FIG. 2 is an optical morphology of the target master alloy, and it can be seen from FIG. 2 that the α -Mg matrix contains a large amount of pale white massive CaMgZn phase and gray acicular MgZn phase.
Putting the target master alloy into atomization equipment, heating the target master alloy to be molten, keeping the target master alloy overheated at 150 ℃, and forming a metal liquid flow with the diameter of 5-6 mm; and introducing argon through an annular nozzle, wherein the airflow pressure is 2.0MPa, and the airflow speed is 320m/s, so as to obtain the magnesium alloy powder. The diameter of the prepared amorphous magnesium alloy powder is 15-75 μm, as shown in fig. 3, which is an SEM morphology of the magnesium alloy powder prepared by the gas atomization method used in example 1, and as can be seen from fig. 3, the magnesium alloy powder is spherical powder, has a high sphericity, and has a small amount of intergrowth satellite ball powder.
Fig. 4 is an XRD pattern of the magnesium alloy powder prepared in example 1 of the present application, and it can be seen from fig. 4 that the phase structure of the magnesium alloy powder has a crystalline phase: mg phase, Ca2Mg5Zn13Phase, Ca2Mg6Zn3Phase, Mg2Zn11Phase, and MgZn2The phase disappeared and a broadened diffraction peak appeared, which is an obvious amorphous characteristic, and thus, the magnesium alloy powder prepared in example 1 was an amorphous magnesium alloy powder.
Taking the amorphous magnesium alloy powder prepared in the example 1 as an original powder, selectively melting the amorphous magnesium alloy powder by adopting a high-energy laser beam, scanning the magnesium alloy powder layer by layer, lowering a printing working plane after completing one layer of laser scanning, laying a next layer of magnesium alloy powder on the top surface of the printing working plane, and then scanning a new layer of magnesium alloy powder by laser. The above process is repeated in this way, and finally the required parts are printed. The laser adopts CO2The laser has laser spot of 70 μm, scanning interval of 0.07mm, laser power of 110W, laser scanning speed of 100mm/s, and powder spreading thickness of each layer of powder of about 0.5 mm. Fig. 5 is an XRD diffraction pattern of the magnesium alloy composite material prepared by selective laser melting of amorphous magnesium alloy powder of example 1. As can be seen from fig. 5, compared to the XRD patterns of fig. 1 and 4, the magnesium alloy composite material contains crystalline phases in addition to the amorphous phase: mg phase, Ca2Mg5Zn13Phase of Ca2Mg6Zn3And (4) phase(s). The amorphous magnesium alloy composite material prepared in example 1 is subjected to a soaking experiment to collect the release volume of gas, and the degradation rate of the amorphous alloy (Song GL, Atrens A, Stjohn D.an moisture evolution method for the degradation of the corrosion rate of magnesium alloy, Magnes. Technol. (Ed. Hryn, TMS) 2001; 255-262.) is calculated according to the hydrogen release rate, so that the degradation rate is 0.61mm/y (mm/year).
Example 2
The difference between the embodiment 2 and the embodiment 1 is that in the target master alloy gas atomization powder preparation step, the airflow pressure is 1.8MPa, the airflow speed is 300m/s, and the diameter of the obtained magnesium alloy powder is 75-105 μm. FIG. 6 is an SEM morphology of the magnesium alloy powder prepared in example 2. As can be seen from fig. 6, the magnesium alloy powder prepared in example 2 is spherical powder, has a higher sphericity, has a narrower particle size distribution than the powder obtained in example 1, and has an increased number of symbiotic satellites. Fig. 7 is an XRD spectrum of the magnesium alloy powder prepared in example 2 of the present application, which still obtains an obvious broadened diffraction peak, indicating that the obtained powder is also an amorphous magnesium alloy powder.
Fig. 8 is an XRD diffraction pattern of the magnesium alloy composite material prepared in example 2. As can be seen from FIG. 8, the alloy contains Mg phase, Ca, in addition to amorphous phase2Mg5Zn13Phase of Ca2Mg6Zn3In contrast to the XRD pattern of example 1, the characteristic peak intensity of the aforementioned crystal phase was significantly increased, indicating that the proportion of the crystal phase was increased. The main reason for the analysis is that the grain size of the amorphous magnesium alloy powder used in the laser melting process is larger than that in example 1, so that the amorphous magnesium alloy powder cannot be completely melted in the laser melting process, and is affected by heat transfer, so that atoms are more easily nucleated, and the crystal phase is increased. The degradation rate of the block alloy is 0.94mm/y (millimeter/year), and the degradation rate is obviously increased because the powder has overlarge particle size and narrower particle size distribution, and in the laser melting process, part of powder is not well combined, and micro-pores exist, so that the degradation is further accelerated.
Example 3
The difference between the embodiment 3 and the embodiment 1 is that in the step of atomizing and pulverizing the mother alloy cast ingot, the airflow pressure is 2.2MPa, the airflow speed is 340m/s, and the diameter of the obtained magnesium alloy powder is 15-45 μm. Fig. 9 is an XRD spectrum of the magnesium alloy powder prepared in example 3, and it can be seen from fig. 9 that the magnesium alloy powder is still amorphous. The shape of the magnesium alloy powder is detected to find that the amorphous magnesium alloy powder is also spherical powder, has higher sphericity and reduces the number of symbiotic satellite balls.
Fig. 10 is an XRD pattern of the magnesium alloy composite material prepared in example 3. As can be seen from FIG. 10, the Mg phase, Ca, still appears2Mg5Zn13Phase of Ca2Mg6Zn3In the case of the phase combination, it is worth mentioning that the amorphous diffraction peak of example 3 is significantly broadened compared to example 1, indicating that the amorphous structure is more prominent. The main reason for the analysis is laser ablationCompared with the method in the embodiment 1, the grain diameter of the amorphous magnesium alloy powder adopted in the process is reduced, so that the melting speed of the amorphous powder is increased, the crystallization speed is inhibited, and more amorphous structures are reserved in the laser melting process. However, as the particle size of the powder is further reduced, magnesium is easily burned off during laser melting, and a foreign phase such as Ca is easily generated2Mg5Zn13Phase of Ca2Mg6Zn3The phase of the phase is correspondingly increased. The degradation rate of the magnesium alloy composite material in test example 3 was 0.76mm/y (mm/year).
Example 4
Example 4 differs from example 1 in that the laser power in the laser ablation process is 90W.
Fig. 11 is an XRD diffraction pattern of the magnesium alloy composite material prepared in example 4. As can be seen from fig. 11, the crystalline phase only shows the Mg phase, and the amorphous diffraction peak of example 4 is significantly broadened compared to example 1, indicating that the amorphous structure is more significant. The main reason for the analysis is that the power used in the laser melting process is reduced compared to that in example 1, the burning loss of the magnesium element is reduced, so that the magnesium element is burned and more remains, the crystalline phase only forms the Mg phase, and no other crystalline phase is formed, and meanwhile, the laser melting power is reduced, so that the crystallization rate is slowed down, and the amorphous state of the powder is largely retained. The degradation rate of the amorphous magnesium alloy composite material is tested to be 0.29mm/y (millimeter/year), and the degradation rate is obviously reduced because the crystalline phase in the amorphous block is obviously reduced, the galvanic corrosion between the crystalline phase and the amorphous phase is reduced, meanwhile, the amorphous phase is better retained after the powder is prepared into the block, and the degradation rate of the block is further reduced because the amorphous phase has more obvious corrosion resistance.
Fig. 12 is an optical microscopic image of the amorphous magnesium alloy composite material of example 4. From fig. 12, it is found that the texture structure of the amorphous magnesium alloy composite material comprises an amorphous matrix and alpha-Mg microcrystals distributed in the amorphous matrix, and the volume percentage of the alpha-Mg microcrystals is 15%.
Example 5
Example 5 differs from example 4 in that the laser power in the laser ablation process is 80W.
FIG. 13 is an XRD pattern of an amorphous magnesium alloy material prepared in example 5. As can be seen from the XRD pattern, Mg phase, Ca, appears in the alloy2Mg5Zn13Phase of Ca2Mg6Zn3A phase of phase. Compared with example 4, the increase of the crystalline phase of example 5 is mainly caused by the further reduction of the power used in the laser melting process, the amorphous powder is only partially melted, and the degradation rate of the tested bulk alloy is 0.68mm/y (mm/year) due to the crystallization of the internal part of the powder.
Example 6
Example 6 differs from example 4 in that the laser scanning speed in the laser melting process is 80 mm/s.
Figure 14 is an XRD pattern of the bulk alloy prepared in example 6. As can be seen from FIG. 14, Mg phase, Ca, appears in the crystalline phase2Mg5Zn13Phase of Ca2Mg6Zn3Phase, the crystalline phase of example 6 increased compared to example 4, mainly due to the slower scanning speed used in the laser melting process, the gradual transformation of the alloy from the amorphous to the crystalline state with the decrease of the scanning speed, and Ca in the alloy2Mg5Zn13Phase of Ca2Mg6Zn3The phases also increase gradually. The degradation rate of the test bulk alloy was 0.63mm/y (mm/year).
Example 7
Example 7 differs from example 4 in that the number of laser scans in the laser ablation process was 3.
Fig. 15 is an XRD diffraction pattern of the magnesium alloy composite material prepared in example 7. As can be seen from FIG. 15, Mg phase, Ca, appears in the crystalline phase2Mg5Zn13Phase of Ca2Mg6Zn3Phase, the crystalline phase of example 7 increased compared to example 4, which was mainly a 3-pass sweep, accumulating heat of the alloy and increasing the crystalline phase. The degradation rate of the test bulk alloy was 0.71mm/y (mm/year).
Comparative example 1
The difference from example 1 is that the design composition of the master alloy is 50:40:10 in atomic ratio of magnesium, zinc and calcium. As can be seen from the XRD pattern of the powder prepared by atomization, Mg phase and Ca phase appear in addition to amorphous phase2Mg5Zn13Phase of Ca2Mg6Zn3The corrosion rate of the magnesium alloy material prepared by the atomized powder is 2.2 mm/y.
Comparative example 2
The difference from example 1 is that the design composition of the master alloy is such that the atomic ratio of magnesium, zinc and calcium is 70:20: 10. As can be seen from the XRD pattern of the powder prepared by atomization, besides a small amount of amorphous phase, a large amount of Mg phase and Ca phase appear in the powder2Mg5Zn13Phase of Ca2Mg6Zn3The corrosion rate of the magnesium alloy material prepared by the atomized powder is 3.6 mm/y.
The above are all preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, so: all equivalent changes made according to the mechanism, shape and principle of the invention are covered by the protection scope of the invention.
Claims (5)
1. A biomedical amorphous magnesium alloy composite material is characterized in that: the magnesium alloy powder is prepared from amorphous magnesium alloy powder serving as raw material powder, wherein the amorphous magnesium alloy powder comprises the following components in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca, wherein the amorphous magnesium alloy powder is prepared by the following steps:
s1, the raw materials in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca is prepared;
s2, smelting the prepared raw materials to prepare a target master alloy;
s3, atomizing the target master alloy to prepare powder to obtain amorphous magnesium alloy powder;
s3, atomizing to prepare powder, wherein the airflow pressure is 2.0MPa, and the airflow speed is 320 m/S;
the amorphous magnesium alloy powder is spherical powder, the particle size of the powder is 15-75 mu m, and the phase structure of the amorphous magnesium alloy composite material is an amorphous phase and an Mg phase.
2. The biomedical amorphous magnesium alloy composite material according to claim 1, characterized in that: the Mg phase is an alpha-Mg microcrystalline structure, and the alpha-Mg microcrystalline structure accounts for 15% of the volume ratio of the composite material.
3. The biomedical amorphous magnesium alloy composite material according to claim 1, characterized in that: the melting temperature in step S2 is 720-750 ℃.
4. A preparation process of biomedical amorphous magnesium alloy composite material is characterized by comprising the following steps: the amorphous magnesium alloy composite material is prepared by taking amorphous magnesium alloy powder as raw material powder through a selective laser melting process, wherein the amorphous magnesium alloy powder comprises the following components in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca, wherein the amorphous magnesium alloy powder is prepared by the following steps:
s1, the raw materials in atomic percentage: mg: 55-65 at.%; 30-35 at.% Zn; 5-10 at.% of Ca is prepared;
s2, smelting the prepared raw materials to prepare a target master alloy;
s3, atomizing the target master alloy to prepare powder to obtain amorphous magnesium alloy powder;
s3, atomizing to prepare powder, wherein the airflow pressure is 2.0MPa, and the airflow speed is 320 m/S;
the amorphous magnesium alloy powder is spherical powder, the particle size of the powder is 15-75 mu m, and the phase structure of the prepared amorphous magnesium alloy composite material is an amorphous phase and an Mg phase.
5. The preparation process of the biomedical amorphous magnesium alloy composite material according to claim 4, which is characterized by comprising the following steps of: the parameters of the selective laser melting process are as follows: the laser spot is 70 μm, the laser scanning speed is 100mm/s, the laser power is 90W, the scanning times is 1 time, and the scanning interval is 0.07 mm.
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