CN110722168B - Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy - Google Patents

Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy Download PDF

Info

Publication number
CN110722168B
CN110722168B CN201910816971.6A CN201910816971A CN110722168B CN 110722168 B CN110722168 B CN 110722168B CN 201910816971 A CN201910816971 A CN 201910816971A CN 110722168 B CN110722168 B CN 110722168B
Authority
CN
China
Prior art keywords
magnesium alloy
phase
powder
needle
shaped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910816971.6A
Other languages
Chinese (zh)
Other versions
CN110722168A (en
Inventor
高成德
帅词俊
王丽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201910816971.6A priority Critical patent/CN110722168B/en
Publication of CN110722168A publication Critical patent/CN110722168A/en
Application granted granted Critical
Publication of CN110722168B publication Critical patent/CN110722168B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B22F10/366—Scanning parameters, e.g. hatch distance or scanning strategy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Automation & Control Theory (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention relates to a method for preparing a needle-shaped second phase to improve the degradation resistance of a medical magnesium alloy. The magnesium alloy comprises an AZ61 matrix and acicular Al uniformly distributed in the matrix4A Ce phase. The preparation method comprises the following steps: ball-milling Ce powder and AZ61 powder to obtain mixed powder, and preparing needle-shaped Al-containing powder by SLM4A magnesium alloy of Ce phase. On one hand, the invention can obviously refine the matrix grains and the acicular Al4Ce phase structure, on the other hand, the solid solubility of solute elements is increased, and Mg is inhibited17Al12And (4) separating out a second phase. Needle-like Al formed4The Ce phase has smaller potential difference and larger resistance with the matrix, and can inhibit galvanic corrosion; and Al4The Ce consumes Al in the alloy in the forming process and can also reduce and refine the original Mg in the alloy17Al12And thus reduce galvanic corrosion, which in combination improve the resistance of magnesium alloys to degradation, thereby facilitating their use in degradable implants.

Description

Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy
Technical Field
The invention belongs to the technical field of medical alloy preparation, and particularly relates to a method for preparing a needle-shaped second phase to improve the degradation resistance of a medical magnesium alloy.
Background
Density of magnesium alloy (1.75 g/cm)3) The density of the magnesium alloy is very similar to that of compact bones of a human body, and meanwhile, the elastic modulus (40-45GPa) of the magnesium alloy is relatively close to that (10-40GPa) of human bones, and the magnesium alloy can be matched with bone tissues after being implanted into the human body, so that the stress shielding effect is effectively avoided; meanwhile, the material can be gradually degraded in vivo as an implant material, so that the pain of a patient caused by a secondary operation is avoided; in the degradation process, magnesium released by the magnesium alloy is a trace element necessary for a human body, and can participate in mineral metabolism of bones, promote proliferation and differentiation of bone cells and promote growth and healing of bones. Therefore, the magnesium alloy has wide application prospect in bone repair. However, the standard electrode potential of magnesium is low (-2.36V)sce) And its corrosion product is loosely porous (PBR ═ 0.81), and so thereThe degradation speed in human body is too fast. The magnesium ions are excessively high in concentration, hydrogen is excessively released to form subcutaneous emphysema, mechanical properties are rapidly reduced due to the excessive degradation, the magnesium ions are easy to lose efficacy before bone tissues are healed, and the growth and healing of damaged bones are affected. Therefore, how to improve the corrosion resistance of magnesium and magnesium alloy and control the degradation rate of magnesium and magnesium alloy becomes a difficult problem which needs to be solved urgently in the application of the magnesium and magnesium alloy in the field of biomedicine.
As is known, most magnesium alloys are multiphase alloys, magnesium base body can form micro-couple corrosion with a second phase under a body fluid environment, and the composition, the quantity, the distribution and the like of the second phase play a decisive role in the degradation behavior of the magnesium alloy. The galvanic corrosion is mainly determined by the potential difference between the second phase and the matrix and the resistance of the second phase, and the larger the potential difference between the pair of the micro-couples is, the larger the corrosion tendency is; the smaller the resistance of the second phase, the greater the corrosion current. Second phase (e.g. Mg) in conventional magnesium alloys17Al12Etc.) are distributed in a thick semi-continuous network in the magnesium matrix, and the potential difference between the magnesium matrix and the matrix is large, so that strong micro-galvanic corrosion is usually formed, which is a key factor for the excessive degradation of the magnesium alloy. Therefore, if the second-phase resistance can be increased and the potential difference between the second-phase resistance and the matrix can be reduced, galvanic corrosion can be reduced, and the degradation resistance of the magnesium alloy can be improved.
Disclosure of Invention
In order to overcome the defect of the prior art that the degradation rate of the magnesium alloy is too high, the invention aims to provide a method for preparing a needle-shaped second phase to improve the degradation resistance of the medical magnesium alloy. The invention utilizes a proper amount of needle-shaped second phase to improve the degradation resistance of the medical magnesium alloy.
The invention alloys rare earth element Ce into Mg-6Al-0.5Zn (AZ61) magnesium alloy by Selective Laser Melting (SLM) technology, on one hand, needle-shaped Al is formed4Ce rare earth compound phase uniformly distributed in alloy matrix, Al4The Ce rare earth compound phase has smaller potential difference and larger resistance with the matrix, and can inhibit galvanic corrosion; on the other hand, the combination of Al and Ce consumes Al in the alloy, and can reduce and refine original Mg in the alloy17Al12Phase, thereby reducing galvanic corrosion, which act together to improve magnesium alloy degradationResistance to solution.
The invention relates to a method for preparing a needle-shaped second phase to improve the degradation resistance of medical magnesium alloy; the medical magnesium alloy consists of a matrix magnesium alloy and Ce uniformly distributed in the matrix magnesium alloy, wherein the matrix magnesium alloy is AZ61 magnesium alloy; the mass fraction of Ce in the medical magnesium alloy is 0.2-2.4 wt%; the medical magnesium alloy contains needle-shaped Al4Ce rare earth compound phase, and acicular Al4The Ce rare earth compound phase is uniform in the medical magnesium alloy. Preferably, the mass fraction of Ce is 0.2-2.4 wt%, preferably 0.6-1.8 wt%, and more preferably 1.2 wt%.
The invention relates to a method for preparing a needle-shaped second phase to improve the degradation resistance of medical magnesium alloy; the method comprises the following steps:
(1) mixing Ce powder and AZ61 powder, placing the mixture in a ball mill, and carrying out ball milling under a protective atmosphere to obtain uniformly mixed powder; in the mixed powder, the mass fraction of Ce is 0.2-2.4 wt%;
(2) preparing acicular Al from the mixed powder by SLM4Medical magnesium alloy of Ce rare earth compound phase; obtaining medical magnesium alloy with needle-shaped second phase; in the preparation process, the laser power is controlled to be 70-120W, the scanning speed is controlled to be 100-.
Preferably, in the step (1), the mass fraction of Ce is 0.2-2.4 wt%, preferably 0.6-1.8 wt%, and more preferably 1.2 wt%.
Preferably, in the step (1), the rotation speed of the ball mill is 200-;
preferably, in the step (2), the laser power is controlled to be 70-120W, the scanning speed is controlled to be 400mm/min, the spot diameter is controlled to be 60-100 μm, and the scanning pitch is controlled to be 0.10-0.20mm, more preferably, the laser power is controlled to be 80-110W, the scanning speed is controlled to be 200-400mm/min, the spot diameter is controlled to be 70-90 μm, and the scanning pitch is controlled to be 0.10-0.15mm, and further preferably, the laser power is controlled to be 90W, the scanning speed is controlled to be 300mm/min, the spot diameter is controlled to be 80 μm, and the scanning pitch is controlled to be 0.10 mm.
Preferably, the particle size of the Ce powder is 1 to 5 μm.
Preferably, the particle size of the AZ61 powder is 50-80 μm.
The corrosion current of the magnesium alloy designed and prepared by the invention is less than or equal to 36.25 muA/cm2。
The magnesium alloy designed and prepared by the invention can be applied to the field of biomedicine.
The principle and the advantages of the invention are as follows:
the invention designs a needle-shaped Al-containing alloy for the first time4The medical magnesium alloy containing the Ce rare earth compound phase is simultaneously tried to be alloyed into AZ61 magnesium alloy by adopting SLM technology for the first time to prepare the needle-shaped Al-containing medical magnesium alloy4Medical magnesium alloy of Ce rare earth compound phase. At certain AZ61 and Ce compositions, Ce and Al will preferentially combine to form acicular Al during alloy solidification due to the stronger affinity between Ce and Al than between Mg and Al4Ce rare earth compound phase, Al4The Ce rare earth compound phase and the magnesium alloy matrix have a semi-coherent interface structure, and have a lower potential difference, so that the driving force of galvanic corrosion is small; further, Al4The Ce rare earth compound phase has a needle-like shape, the length-diameter ratio is large, so that the resistance is large, and the electron transfer rate in the galvanic corrosion process can be reduced, thereby effectively reducing the galvanic corrosion and improving the degradation resistance; moreover, the preferential combination of the Al element and the Ce element can consume the Al element in the alloy, thereby refining and reducing the original Mg in the alloy17Al12And the galvanic corrosion between the magnesium alloy and the matrix is reduced, and the degradation resistance of the magnesium alloy is further improved.
Currently, the related research mainly adopts a casting method, and the prepared magnesium alloy has coarse grains, coarse second phase size and uneven distribution, so that the improvement on the degradation behavior is limited. In contrast, the SLM technology has the characteristics of rapid melting and rapid solidification, can obviously refine the matrix structure and improve the solid solubility of solute elements, thereby forming fine Al4Ce rare earth compound phase and matrix structure, further promoting Al4The Ce rare earth compound phase is uniformly distributed in the alloy matrix. Under proper laser technological parameters, the material is preparedTo the whole material, fine crystal grains and uniformly distributed needle-like Al are formed4The Ce rare earth compound phase is rapidly solidified, so that not only can the crystal grains of the magnesium alloy be refined, but also the solid solubility of solute elements in an alloy matrix can be increased, and the Mg content can be reduced17Al12The precipitation of the second phase reduces the galvanic corrosion caused by the precipitation of the second phase, thereby further improving the degradation resistance of the magnesium alloy. When the laser power is too low, the magnesium alloy powder cannot be completely melted, and the prepared magnesium alloy block is loose and porous, so that the degradation of the magnesium alloy can be accelerated; when the laser power is too high, the low-melting-point alloy elements in the magnesium alloy are vaporized, the relative content of the rare earth elements in the alloy is increased, the formed needle-shaped phase becomes coarse and the precipitation amount is increased, so that the micro-galvanic corrosion is increased, and the degradation resistance is reduced.
In the invention, the rare earth element Ce powder and the magnesium alloy powder are mixed by ball milling, and the ball milling process and parameters are optimized, so that the rare earth element Ce powder is prevented from agglomerating and the dispersion of the rare earth element Ce powder is promoted. When the ball milling technological parameters are lower than the selected range, the serious agglomeration phenomenon of the rare earth element Ce occurs, and the needle-shaped Al in the prepared alloy4The Ce rare earth compound has uneven phase distribution, thus deteriorating the degradation performance of the alloy; when the ball milling parameters are higher than the selected range, the powder particles deform and the sphericity is reduced due to the violent collision between the powder and the milling balls in the ball milling process, the powder fluidity in the selective laser melting powder laying process is influenced, the forming quality in the obtained magnesium alloy is poor, even defects are generated, and the alloy degradation resistance is also deteriorated.
Ce element is acicular Al formed in magnesium alloy4The Ce rare earth compound phase is an important element and has the function of refining grains, and the alloy with high, medium and low Ce content contains needle-shaped Al by controlling the content of Ce4A Ce rare earth compound phase. When the content is less than the range selected in the present invention, the amount of acicular phase formed in the magnesium alloy is small and the amount of acicular phase formed in the magnesium alloy is small17Al12The refining effect of the phase is limited, and the second phase is still composed of a large amount of coarse Mg17Al12Phase and small amount of acicular Al4The Ce rare earth compound phase composition has limited improvement on magnesium combination degradation resistance; when the content is higher than that of the inventionWithin the above range, the formed needle phase is coarse and increased in precipitation, the corrosion of the micro-galvanic couple is increased, and the degradation resistance is reduced. Acicular Al in alloy is regulated and controlled by changing Ce content4The content and distribution of the Ce rare earth compound phase achieve the effect of fine and uniform distribution, thereby endowing the magnesium alloy with good degradation resistance.
In conclusion, parameters such as SLM process, ball milling process, Ce content and the like are not selected at will, but are crystallized through numerous experiments and creative labor of the inventor, and the needle-shaped Al-containing crystal is prepared under the synergistic effect of controlling the Ce content, matching with high-speed ball milling and a special SLM process4The Ce rare earth compound phase is uniformly distributed, so that the alloy shows good degradation resistance and is expected to be applied to the field of biomedicine.
Drawings
FIG. 1 is a view showing the appearance of the product obtained in example 1 and comparative example 1 and an AZ61 alloy;
FIG. 2 is a surface topography and a cross-sectional topography of the product obtained in example 1 and the degraded AZ61 alloy
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
Weighing 9.88 g of AZ61 powder (with the particle size of 50-80 μm) and 0.12 g of rare earth element Ce powder (with the particle size of 1-5 μm), placing the AZ61 powder and the rare earth element Ce powder in a ball mill, and carrying out ball milling in a protective atmosphere to obtain uniformly mixed powder, wherein the rotating speed of the ball mill is 350 r/min, and the ball milling time is 3 hours. Preparing acicular Al from the mixed powder by SLM4A Ce-phase medical magnesium alloy; in the preparation process, the laser power is controlled to be 90W, the scanning speed is controlled to be 300mm/min, and the diameter of a light spot is controlled to be 80 mu m.
Tests show that fine crystal grains and needle-shaped Al are formed in the prepared alloy4Ce phase, Al4The Ce phase is uniformly distributed and dispersed in the crystal grains, and simultaneously, the Mg is refined and reduced17Al12Precipitation of the second phase (FIG. 1). Electrochemical tests show that the alloy contains needle-shaped Al compared with AZ61 alloy4The corrosion current of the Ce-phase magnesium alloy is from 40.91 muA/cm of AZ612The reduction is 16.73 mu A/cm2The thickness of the corrosion layer was reduced from 18.1 μm for AZ61 to 6.83 μm (FIG. 2).
Example 2
Weighing 9.88 g of AZ61 powder (with the particle size of 50-80 μm) and 0.12 g of rare earth element Ce powder (with the particle size of 1-5 μm), placing the AZ61 powder and the rare earth element Ce powder in a ball mill, and carrying out ball milling in a protective atmosphere to obtain uniformly mixed powder, wherein the rotating speed of the ball mill is 350 r/min, and the ball milling time is 3 hours. Preparing acicular Al from the mixed powder by SLM4A Ce-phase medical magnesium alloy; in the preparation process, the laser power is controlled to be 70W, the scanning speed is controlled to be 300mm/min, and the diameter of a light spot is controlled to be 80 mu m.
Tests show that fine crystal grains and needle-shaped Al are formed in the prepared alloy4Ce phase, Al4The Ce phase is uniformly distributed and dispersed in the crystal grains, and simultaneously, the Mg is refined and reduced17Al12And (4) separating out a second phase. Electrochemical tests have found that the corrosion current of magnesium alloys containing acicular Al4Ce phase compared to AZ61 alloy is from 40.91 muA/cm of AZ612The reduction is 19.73 mu A/cm2。
Example 3
Weighing 9.76 g of AZ61 powder (with the particle size of 50-80 μm) and 0.24 g of rare earth element Ce powder (with the particle size of 1-5 μm), placing the AZ61 powder and the rare earth element Ce powder in a ball mill, and carrying out ball milling in a protective atmosphere to obtain uniformly mixed powder, wherein the rotating speed of the ball mill is 350 r/min, and the ball milling time is 3 hours. Preparing acicular Al from the mixed powder by SLM4A Ce-phase medical magnesium alloy; in the preparation process, the laser power is controlled to be 90W, the scanning speed is controlled to be 300mm/min, and the diameter of a light spot is controlled to be 80 mu m.
Tests show that fine crystal grains and needle-shaped Al are formed in the prepared alloy4Ce phase, Al4The Ce phase is uniformly distributed and dispersed in the crystal grains, and simultaneously, the Mg is refined and reduced17Al12And (4) separating out a second phase. Electrochemical tests show that the alloy contains needle-shaped Al compared with AZ61 alloy4The corrosion current of the Ce-phase magnesium alloy is from 40.91 muA/cm of AZ612The reduction is 22.34 mu A/cm2。
Example 4
Weighing 9.88 g of AZ61 powder (with the particle size of 50-80 μm) and 0.12 g of rare earth element Ce powder (with the particle size of 1-5 μm), placing the AZ61 powder and the rare earth element Ce powder in a ball mill, and carrying out ball milling in a protective atmosphere to obtain uniformly mixed powder, wherein the rotating speed of the ball mill is 200 revolutions per minute, and the ball milling time is 3 hours. Preparing acicular Al from the mixed powder by SLM4A Ce-phase medical magnesium alloy; in the preparation process, the laser power is controlled to be 90W, the scanning speed is controlled to be 300mm/min, and the diameter of a light spot is controlled to be 80 mu m.
Tests show that fine crystal grains and needle-shaped Al are formed in the prepared alloy4Ce phase, Al4The Ce phase is uniformly distributed and dispersed in the crystal grains, and simultaneously, the Mg is refined and reduced17Al12And (4) separating out a second phase. Electrochemical tests show that the alloy contains needle-shaped Al compared with AZ61 alloy4The corrosion current of the Ce-phase magnesium alloy is from 40.91 muA/cm of AZ612The reduction is 36.25 muA/cm2。
In the process of developing the technology of the invention, the following scheme is also tried, but the performance of the obtained product is far worse than that of the embodiment.
Comparative example 1
The other conditions were the same as in example 1 except that: 9.70 g of AZ61 powder and 0.30 g of rare earth element Ce powder were weighed. Tests show that acicular Al is formed in the prepared alloy4The Ce phase is more and coarser (FIG. 1), and the corrosion current of the alloy is from 40.91 muA/cm of AZ612The rise was 58.72. mu.A/cm2。
Comparative example 2
The other conditions were the same as in example 1 except that: in the preparation process, the laser power is controlled to be 50W, the scanning speed is controlled to be 600mm/min, and the diameter of a light spot is controlled to be 40 mu m. The tests show that the prepared alloy has lower compactness, which is caused by that the laser energy density can not completely melt AZ61 powder and rare earth element powder, and the corrosion current of the alloy is 40.91 muA/cm of AZ612The rise was 78.72. mu.A/cm2。
Comparative example 3
The other conditions were the same as in example 1 except that: the rotating speed of the ball mill is 150 revolutions per minute, and the ball milling time is 2 hours. Tests have found that ZK30 forms in the alloyAcicular Al of (2)4The Ce phase is not uniformly distributed. Electrochemical tests show that the prepared alloy has corrosion current of 40.91 muA/cm from AZ612The rise was 68.72. mu.A/cm2。

Claims (3)

1. A method for preparing a needle-shaped second phase to improve the degradation resistance of medical magnesium alloy; the method is characterized in that: the medical magnesium alloy consists of a matrix magnesium alloy and Ce uniformly distributed in the matrix magnesium alloy, wherein the matrix magnesium alloy is AZ61 magnesium alloy; the mass fraction of Ce in the medical magnesium alloy is 0.2-2.4%; the medical magnesium alloy contains needle-shaped Al4Ce rare earth compound phase, and acicular Al4The Ce rare earth compound phase is uniformly distributed in the medical magnesium alloy;
the method for preparing the needle-shaped second phase to improve the degradation resistance of the medical magnesium alloy comprises the following steps:
(1) mixing Ce powder and AZ61 powder, placing the mixture in a ball mill, and carrying out ball milling under a protective atmosphere to obtain uniformly mixed powder; in the mixed powder, the mass fraction of Ce is 0.2-2.4 wt%; in the step (1), the rotation speed of the ball mill is 300-; the particle size of the Ce powder is 1-5 mu m;
(2) preparing acicular Al from the mixed powder by SLM4Medical magnesium alloy of Ce rare earth compound phase; obtaining medical magnesium alloy with needle-shaped second phase; in the preparation process, the laser power is controlled to be 90W, the scanning speed is controlled to be 300mm/min, the spot diameter is controlled to be 80 mu m, and the scanning interval is controlled to be 0.10 mm.
2. The method for preparing the needle-shaped second phase to improve the degradation resistance of the medical magnesium alloy according to claim 1; the method is characterized in that: in the step (1), the rotating speed of the ball mill is 350 r/min, and the ball milling time is 3 hours.
3. The method for preparing the needle-shaped second phase to improve the degradation resistance of the medical magnesium alloy according to claim 1; the method is characterized in that: the particle size of the AZ61 powder is 50-80 μm.
CN201910816971.6A 2019-08-30 2019-08-30 Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy Active CN110722168B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910816971.6A CN110722168B (en) 2019-08-30 2019-08-30 Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910816971.6A CN110722168B (en) 2019-08-30 2019-08-30 Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy

Publications (2)

Publication Number Publication Date
CN110722168A CN110722168A (en) 2020-01-24
CN110722168B true CN110722168B (en) 2021-11-19

Family

ID=69218735

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910816971.6A Active CN110722168B (en) 2019-08-30 2019-08-30 Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy

Country Status (1)

Country Link
CN (1) CN110722168B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05117798A (en) * 1991-10-22 1993-05-14 Toyota Motor Corp Mg alloy excellent in corrosion resistance
DE102012108089A1 (en) * 2012-08-31 2014-05-15 Gottfried Wilhelm Leibniz Universität Hannover Magnesium alloy used for formation of work samples used as medical device e.g. implant and suture, comprises magnesium and zinc, and rare-earth metal in specified weight ratio
CN105925862A (en) * 2016-06-22 2016-09-07 中南大学 Mg alloy anode material and preparation method thereof
CN109536798A (en) * 2017-09-22 2019-03-29 比亚迪股份有限公司 A kind of antiflaming magnesium alloy and its preparation method and application
CN110066950A (en) * 2019-04-11 2019-07-30 江西理工大学 A kind of magnesium zinc germanium alloy and preparation method thereof with cathode depression effect
CN110064750A (en) * 2019-04-11 2019-07-30 江西理工大学 A kind of Biological magnesium alloy and preparation method thereof containing abundant LPSO structure

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108913969B (en) * 2018-08-10 2020-03-31 江西理工大学 Medical magnesium alloy with uniform and controllable degradation performance and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05117798A (en) * 1991-10-22 1993-05-14 Toyota Motor Corp Mg alloy excellent in corrosion resistance
DE102012108089A1 (en) * 2012-08-31 2014-05-15 Gottfried Wilhelm Leibniz Universität Hannover Magnesium alloy used for formation of work samples used as medical device e.g. implant and suture, comprises magnesium and zinc, and rare-earth metal in specified weight ratio
CN105925862A (en) * 2016-06-22 2016-09-07 中南大学 Mg alloy anode material and preparation method thereof
CN109536798A (en) * 2017-09-22 2019-03-29 比亚迪股份有限公司 A kind of antiflaming magnesium alloy and its preparation method and application
CN110066950A (en) * 2019-04-11 2019-07-30 江西理工大学 A kind of magnesium zinc germanium alloy and preparation method thereof with cathode depression effect
CN110064750A (en) * 2019-04-11 2019-07-30 江西理工大学 A kind of Biological magnesium alloy and preparation method thereof containing abundant LPSO structure

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
稀土对AZ61镁合金组织及室温力学性能的影响;曹凤红等;《铸造》;20090630;第58卷(第6期);第593-597页 *

Also Published As

Publication number Publication date
CN110722168A (en) 2020-01-24

Similar Documents

Publication Publication Date Title
CN108913969B (en) Medical magnesium alloy with uniform and controllable degradation performance and preparation method thereof
TWI493064B (en) Sb-Te based alloy sintered body sputtering target
CN109112361B (en) Biological zinc alloy with fine lamellar eutectic structure and preparation method thereof
CN109172860B (en) Degradable iron-based implant and preparation method thereof
EP3732308B1 (en) Cast iron inoculant and method for production of cast iron inoculant
CN109500396B (en) Intragranular-intergranular composite reinforced biological zinc alloy
CN110064750B (en) Biological magnesium alloy containing rich LPSO structure and preparation method thereof
KR20080063199A (en) Lime-based additive for steel smelting and the preparation method thereof
CN113604695B (en) Method for optimizing additive manufacturing of titanium alloy structure by adding rare earth alloy
CN103695898A (en) Titanium alloy surface metal ceramic composite coating and preparation method thereof
CN111593245A (en) Solid solution type tungsten-based alloy and preparation method thereof
CN107760945A (en) A kind of magnesium alloy with high corrosion drag and bioactivity and preparation method thereof
CN110722168B (en) Method for preparing needle-shaped second phase to improve degradation resistance of medical magnesium alloy
CN110669979B (en) Mesoporous carbon reinforced iron-based composite material and preparation method and application thereof
EP3732305B1 (en) Cast iron inoculant and method for production of cast iron inoculant
CN110541089B (en) Biological Nd-Zn alloy and preparation method thereof
CN108950334B (en) Magnesium-aluminum alloy with continuous eutectic structure and preparation method thereof
CN110157950A (en) A kind of zinc-base medical material and preparation method thereof of redox graphene enhancing
JP3223538B2 (en) Sintered titanium alloy and method for producing the same
CN107760900B (en) A method of preparing corrosion-resistant Biological magnesium alloy
CN110066950B (en) Magnesium-zinc-germanium alloy with cathode inhibition effect and preparation method thereof
CN115582554A (en) Nano cerium oxide enhanced biological magnesium alloy and preparation method thereof
DE102013102917B4 (en) Sinterable and / or meltable ceramic mass, their production and use, and shaped bodies
CN110735065B (en) Composite material composition, titanium alloy product and preparation method thereof
CN109280828B (en) High-strength degradable composite material for implanting instrument and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant