WO2020067704A1 - Tôle d'alliage de magnésium et procédé de fabrication associé - Google Patents

Tôle d'alliage de magnésium et procédé de fabrication associé Download PDF

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Publication number
WO2020067704A1
WO2020067704A1 PCT/KR2019/012409 KR2019012409W WO2020067704A1 WO 2020067704 A1 WO2020067704 A1 WO 2020067704A1 KR 2019012409 W KR2019012409 W KR 2019012409W WO 2020067704 A1 WO2020067704 A1 WO 2020067704A1
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Prior art keywords
magnesium alloy
alloy plate
weight
plate material
relationship
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Ceased
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PCT/KR2019/012409
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English (en)
Korean (ko)
Inventor
박준호
김재중
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Posco Holdings Inc
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Posco Co Ltd
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Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Priority to JP2021541002A priority Critical patent/JP7274585B2/ja
Priority to US17/280,722 priority patent/US20220010413A1/en
Priority to EP19864451.0A priority patent/EP3859024A4/fr
Priority to CN201980063120.7A priority patent/CN112771189A/zh
Publication of WO2020067704A1 publication Critical patent/WO2020067704A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
    • B21B37/58—Roll-force control; Roll-gap control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Definitions

  • One embodiment of the present invention relates to a magnesium alloy plate and its manufacturing method.
  • Magnesium has a HCP structure with a crystalline structure, and the c / a ratio of the unit cell is higher than that of a material having a different HCP structure, so only the basal slip system ⁇ 0001 ⁇ ⁇ 11-20> can be activated at room temperature.
  • the C-axis of the HCP is aligned with the thickness direction of the rolled sheet material, thereby making it difficult to accommodate the C-axis deformation.
  • the aggregate structure of the magnesium alloy sheet can be dispersed, and activation of the non-bottom slip system can be facilitated. Accordingly, it is intended to secure moldability at the level of aluminum alloy for automobiles.
  • Magnesium alloy plate material which is an embodiment of the present invention, Zn: 0.1 to 1.5% by weight, Gd: 0.08 to 0.7% by weight, residual Mg and other unavoidable impurities with respect to 100% by weight, may satisfy the following relationship 1 .
  • relational expression 1 may be 3.0 or more and 15.0 or less.
  • relational expression 1 may be 3.0 or more and 13.0 or less.
  • Mn 0.3% by weight (excluding 0% by weight) may further include.
  • the magnesium alloy plate material includes a secondary phase, and the number of secondary phases per 40000 ⁇ m 2 of the magnesium alloy plate material may be 1 to 20.
  • the average particle diameter of the secondary phase may be 0.1 to 3 ⁇ m.
  • the average grain size of the magnesium alloy plate material may be 5 to 30 ⁇ m.
  • the limit dome height (LDH) of the magnesium alloy plate may be 10.5 mm or more.
  • the magnesium alloy plate material may have an edge crack of 5 mm or less.
  • the magnesium alloy plate material may have a maximum aggregate strength with respect to the (0001) plane of 4.5 or less.
  • a method of manufacturing a magnesium alloy sheet based on 100% by weight, Zn: 0.1 to 1.5% by weight, Gd: 0.08 to 0.7% by weight, residual Mg and other unavoidable impurities by casting an alloy melt
  • a step of preparing a cast material, a step of homogenizing heat treatment of the cast material, a step of preparing a rolled material by rolling the homogenized heat-treated cast material, and a step of final annealing the rolled material, wherein the alloy molten metal is Equation 1 can be satisfied.
  • relational expression 1 may be 3.0 or more and 15.0 or less.
  • relational expression 1 may be 3.0 or more and 13.0 or less.
  • Mn 0.3% by weight (excluding 0% by weight) or less may be further included.
  • the step of homogenizing heat treatment of the cast material may be performed in a temperature range of 300 to 500 ° C.
  • the step of preparing the rolled material may be rolled in a temperature range of 150 to 350 ° C.
  • it can be rolled at a reduction ratio of more than 0 and 30% or less per rolling.
  • gadolium (Gd) and zinc (Zn) By controlling the relationship between gadolium (Gd) and zinc (Zn), it is possible to secure moldability at the level of an aluminum alloy for automobiles.
  • 1 shows a state diagram of the Mg-Gd binary system.
  • Figure 2 shows the maximum high capacity of Gd according to the added element at 400 °C.
  • Figure 3 shows the observation of the microstructure of each step of Example 1 and Comparative Example 4 with an optical microscope (Optical Microscopy).
  • Figure 4 shows the results of the analysis of the (0001) plane of Examples 2 and 3 and Comparative Example 4 by XRD pole viscosity method.
  • Magnesium alloy plate material which is an embodiment of the present invention, may contain Zn: 0.1 to 1.5% by weight, Gd: 0.08 to 0.7% by weight, residual Mg, and other unavoidable impurities relative to 100% by weight.
  • Zn may include 0.1 to 1.5% by weight. Specifically, it may be 1 to 1.5% by weight.
  • the effect of dispersing the aggregated structure may increase.
  • the Zn element when the Zn element is less than 0.1% by weight, the effect of improving moldability and rollability may be insignificant. On the other hand, if it is added in excess of 1.5% by weight, the mechanical properties and moldability may be deteriorated due to the secondary phase fraction increase and coarsening.
  • Gd may include 0.08 to 0.7% by weight. Specifically, it may be 0.1 to 0.6% by weight. More specifically, it may be 0.1 to 0.5% by weight.
  • Gd elements can be segregated by being employed at grain boundaries or twin boundaries. Segregation means that solute elements are concentrated in a certain area. Accordingly, in one embodiment of the present invention, it may mean that it is concentrated on a twin boundary or a grain boundary. Thus, the Gd element can be segregated at the aforementioned interfaces.
  • the segregated (Ggregated) element gives a solute dragging effect, and can accelerate the dispersion of aggregates during the rolling and heat treatment processes.
  • the aggregated tissue dispersion effect may be better.
  • the size and fraction of the secondary phases of Mg 5 Gd and MgZn may be increased. In this case, the moldability may be adversely affected.
  • the value of the relational expression 1 ([Zn] / [Gd]) which will be described later, exceeds 0.7 wt%, the content of Zn must also exceed 2.1 wt%. Accordingly, mechanical properties and formability may be deteriorated due to an increase in the secondary phase fraction and coarsening.
  • the magnesium alloy plate material may satisfy the following relationship (1).
  • [Zn] and [Gd] mean the weight percent of each element.
  • the ratio of the weight percent of zinc (Zn) to the weight percent of gadolium (Gd) may be 3.0 or more. Specifically, it may be 3.0 or more and 15.0 or less. Specifically, it may be 13.0 or less. Specifically, by controlling the weight ratio of zinc to gadolium as described above, gadolium and zinc are employed together at the grain boundary, and thus a solid solution strengthening effect may be excellent.
  • the weight ratio of zinc to gadolium is less than 3, the amount of gadolium (Gd) and zinc (Zn) elements that are segregated together at grain boundaries and twin boundaries This can be reduced. Due to this, the degree of solution dragging effect of segregated elements may be lowered. That is, as the amount of segregated solid solution increases, the non-bottom slip system is activated, so that the moldability can be improved.
  • the solution segregation (Solute segregation) is usually a high probability of distribution along the base surface can control the base surface slip (slip).
  • the base surface slip slip since there is no effect on the non-surface slip, the difference in the degree of activation between the two slip systems is reduced, and the probability of non-surface slip activation can be increased.
  • the moldability improvement effect may be negligible.
  • the secondary phase fraction increase and secondary phase coarsening may be caused, which may be detrimental to formability and processability.
  • the magnesium alloy plate may further include manganese in an amount of 0.3% by weight or less (excluding 0% by weight).
  • the Mn component forms a Fe-Mn-based compound, and serves to reduce the content of the Fe component in the plate material. That is, it is easy to control Fe impurities.
  • the reason for limiting the upper limit of the Mn component to 0.3% by weight is that when manganese is added in excess of 0.3% by weight, the Gd solid solubility decreases and moldability decreases.
  • moldability when manganese is included in the above range, moldability may be excellent. More specifically, an alloy having a small addition amount of alloying elements may have excellent bending properties, thermal conductivity, and corrosion resistance.
  • the magnesium alloy plate material includes a secondary phase, and the number of secondary phases per 40000 ⁇ m 2 of the magnesium alloy plate material may be 1 to 20.
  • the secondary phase may be Mg 5 Gd, MgZn, or a combination thereof.
  • the average particle diameter of the secondary phase may be 0.1 to 3 ⁇ m.
  • the average particle diameter and number of secondary phases are the results of controlling the composition range and relational expression 1 of the above-described alloying component.
  • the average grain size of the magnesium alloy plate material may be 5 to 30 ⁇ m.
  • moldability when the average grain size of the magnesium alloy sheet is within the above range, moldability may be more excellent. More specifically, if it is smaller than the above range, room temperature moldability may be deteriorated. If it is larger than the above range, moldability may deteriorate at high temperatures.
  • the limit dome height (LDH) of the magnesium alloy plate may be 10.5 mm or more. Specifically, it may be 11.0 mm or more.
  • the limit dome height means a value derived through the Ericsson test at room temperature. Through the limit dome height, the formability of the material can be compared.
  • the magnesium alloy plate material may have an edge crack of 5 mm or less. More specifically, it may be 1 mm or less.
  • the edge crack means a groove formed at the edge of the surface portion of the magnesium alloy plate.
  • the edge crack may be caused when the workability is low. That is, the higher the moldability, the better the workability, so the edge crack can be reduced.
  • the edge crack of the magnesium alloy plate material according to an embodiment of the present invention may be in the above range.
  • the edge crack when the edge crack is within the above range, moldability may be excellent. More specifically, the edge crack may be caused more by the Al 2 Ca secondary phase, but the alloy according to one embodiment of the present invention does not contain the Ca component, so the above-described secondary phase is reduced, so the edge crack is reduced and formability It is possible to provide an excellent magnesium alloy plate material.
  • the magnesium alloy plate material may have a maximum aggregate strength with respect to the (0001) plane of 4.5 or less. Specifically, it may be 1.0 to 4.5 or less.
  • the fraction of the bottom crystal grains may be small, so that the activation of the non-bottom slip system may be easy. Thereby, the magnesium alloy plate material excellent in moldability can be provided.
  • a method of manufacturing a magnesium alloy sheet based on 100% by weight, Zn: 0.1 to 1.5% by weight, Gd: 0.08 to 0.7% by weight, residual Mg and other unavoidable impurities by casting an alloy melt
  • a step of preparing a cast material, a step of homogenizing heat treatment of the cast material, a step of preparing a rolled material by rolling the homogenized heat-treated cast material, and a step of final annealing the rolled material may be included.
  • the reason for limiting the composition and composition of the molten alloy is the same as the reason for limiting the composition and composition of the magnesium alloy plate described above, and thus will be omitted.
  • the molten metal may satisfy the following relational expression 1.
  • the temperature of the alloy molten metal may be 650 to 750 °C.
  • the magnesium alloy can be cast in the above temperature range.
  • the magnesium alloy may not be melted properly.
  • it may be difficult to manage molten metal at temperatures above 750 ° C due to ignition.
  • a step of preparing a cast material by casting the above-described alloy molten metal may be performed.
  • it can be cast through strip casting, gravity casting, or a combination thereof. However, it is not limited to this.
  • the step of homogenizing heat treatment of the cast material may be performed in a temperature range of 300 to 500 ° C. Specifically, it can be carried out for 1 hour or more.
  • gadolium When the temperature is 300 ° C or higher, solid solution of gadolium (Gd) is possible. In addition, the higher the temperature, the higher the amount of gadolium may increase. However, if it exceeds 500 °C, the surface of the cast material may be oxidized. Therefore, it may not be suitable for the mass production process.
  • the step of preparing the rolled material may be performed in a temperature range of 150 to 350 ° C.
  • a temperature of 150 ° C or higher may be secured to allow rolling without edge cracking. Rolling above 350 ° C does not realistically match mass production.
  • It can be rolled at a reduction ratio of more than 0 and 30% or less per rolling.
  • the rolling reduction refers to dividing the difference between the thickness of the material before passing through the rolling roll and the thickness of the material after passing through the rolling roll by dividing by the thickness of the material before passing through the rolling roll and multiplying by 100.
  • rolling may be performed several times at the rolling reduction rate to be rolled to a final target thickness.
  • the preparing of the rolled material may further include an intermediate annealing of the rolled material.
  • the intermediate annealing step may be performed in a temperature range of 300 to 500 ° C.
  • intermediate annealing can be performed after two continuous rolling. Alternatively, intermediate annealing may be performed after three consecutive rollings. Alternatively, it can be rolled without intermediate annealing.
  • the final annealing of the rolled material may be performed in a temperature range of 300 to 500 ° C.
  • Recrystallization can be easily formed by final annealing under the above conditions.
  • the Ericsson value of the magnesium alloy plate manufactured through the above-described process may be 10.5 mm or more. Specifically, it may be 11.0 mm or more.
  • the above value may mean a room temperature formability similar to that of a conventional aluminum metal.
  • the molten metal was cast by a strip casting method to prepare a cast material.
  • the cast material was subjected to a homogenization heat treatment at 400 ° C. for 7 hours.
  • the homogenized heat-treated cast material was rolled at 300 ° C at a rolling reduction rate of about 20% per rolling. Intermediate annealing was also performed in the middle of the rolling. Specifically, it was performed at 400 ° C. for 1 hour.
  • the thickness of the magnesium alloy sheet produced as described above was 0.4 to 1.8 mm.
  • Magnesium alloy plates of 50 to 60 mm in size were used for the width and length, and lubricant was used on the outer surface of the plates to reduce friction between the plate and the spherical punch.
  • the outer periphery of the plate was fixed with a force of 10 kN, and then a speed of 5 mm / min using a dome punch having a diameter of 20 mm. Deformation was applied to the plate. Subsequently, a punch was inserted until the plate material was broken, and then the deformation height of the plate material at the time of fracture was measured.
  • the deformation height of the plate is measured as the Ericsson value or the limit dome height (LDH). From this, the moldability of the plate material can be compared. Specifically, the higher the deformation height of the magnesium alloy plate, the larger the Ericsson value, and may be excellent in moldability.
  • one embodiment of the present invention may not include aluminum.
  • employment of Gd may not be possible.
  • 1 shows a state diagram of the Mg-Gd binary system.
  • Figure 1 is a state diagram of Mg-Zn 0.5 wt% -xGd, it can be seen the high Gd capacity at 400 °C.
  • FIG. 2 can be derived by drawing a state diagram according to each element content.
  • Figure 2 shows the maximum high capacity of Gd according to the added element at 400 °C.
  • FIG. 2 shows the measurement of the amount of Gd that can be employed when the state diagrams of Al, Zn, and Mg 3 elements are prepared as in the Mg-Gd binary system diagram of FIG. 1.
  • an embodiment of the present invention may not include aluminum.
  • aluminum may be present as an impurity level.
  • aluminum may be included in an amount of 0.005% by weight or less.
  • the present embodiment may have a level of moldability similar to that of aluminum.
  • Al5083 has an Ericsson value of about 12 mm at room temperature.
  • Figure 3 shows the observation of the microstructure of each step of Example 1 and Comparative Example 4 with an optical microscope (Optical Microscopy).
  • Example 1 can be visually confirmed that the number of secondary phases is significantly less than that of Comparative Example 4. More specifically, in Example 1, it can be seen that the number of secondary phases per area of 40000 ⁇ m 2 is less than about 20. On the other hand, the comparison 4 can be seen that more than the example of 50 to 100 levels per area.
  • the secondary phase is Mg 5 Gd and MgZn.
  • the particle size of the secondary phase is greater than that of the example, and the fraction of the secondary phase can be confirmed.
  • Figure 4 shows the results of the analysis of the (0001) plane of Examples 2 and 3 and Comparative Example 4 by XRD pole viscosity method.
  • the pole figure is a stereoscopic projection of the direction of the arbitrarily fixed crystal coordinate system to the specimen coordinate system. That is, the poles for the (0001) planes of crystal grains of various orientations can be displayed in a reference coordinate system, and the pole figure can be represented by drawing a density contour line according to the pole density distribution. At this time, the pole is fixed in a specific lattice direction by the Bragg angle, and multiple poles may be displayed for a single crystal.
  • the density distribution value of the contour line represented by the pole figure method is expressed numerically as the maximum aggregate strength for the (0001) plane.
  • the maximum aggregate strength value is smaller, it means that the crystal grains of various orientations are distributed and the fraction of the bottom crystal grains is small, so that the formability is excellent.
  • Example 3 has a slightly higher maximum aggregate strength value than Comparative Example 4.
  • Example 3 has similar poles and shapes as compared with Comparative Example 4.
  • Methods for improving the workability of the magnesium alloy sheet include dispersing aggregates and activating non-bottom slip systems. Specifically, in Example 3 and Comparative Example 4, considering that the pole shape is similar, it can be derived that the orientation of the crystal grains is relatively random.
  • Comparative Example 4 is a case where more than the range of gadolium (Gd) according to an embodiment of the present invention is added. As a result, the Zn / Gd value of Comparative Example 4 was 1.28, resulting in a value of less than 3. That is, it can be seen that Comparative Example 4 does not satisfy the composition of gadolium and the value of relational expression 1 (Zn / Gd) according to one embodiment of the present invention.
  • the value according to Equation 1 is less than 3, the amount of gadolium and zinc segregated together at the grain boundary or the grain boundary may be reduced, and thus the activation of the non-surface slip system may be reduced.
  • the moldability of the alloy plate material with better activation of the non-bottom slip system may be better. Further, the moldability of the alloy plate material having a smaller fraction of the secondary phase and a smaller size may be better.
  • the non-bottom slip system can be activated.
  • the content of the gadolium (Gd) component decreases, the fraction of the secondary phase decreases, so the deformation behavior may be easy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne une tôle d'alliage de magnésium comprenant, pour 100 % en poids d'une tôle d'alliage de magnésium entière, de 0,1 à 1,5 % en poids de Zn, de 0,08 à 0,7 % en poids de Gd, le reste étant constitué de Mg et d'autres impuretés inévitables, et satisfaisant à la relation 1 suivante. [Relation 1] [Zn]/[Gd] ≥ 3,0 ([Zn] et [Gd] correspondant au pourcentage en poids de l'élément correspondant.)
PCT/KR2019/012409 2018-09-28 2019-09-24 Tôle d'alliage de magnésium et procédé de fabrication associé Ceased WO2020067704A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2021541002A JP7274585B2 (ja) 2018-09-28 2019-09-24 マグネシウム合金板材およびその製造方法
US17/280,722 US20220010413A1 (en) 2018-09-28 2019-09-24 Magnesium alloy sheet and manufacturing method therefor
EP19864451.0A EP3859024A4 (fr) 2018-09-28 2019-09-24 Tôle d'alliage de magnésium et procédé de fabrication associé
CN201980063120.7A CN112771189A (zh) 2018-09-28 2019-09-24 镁合金板材及其制造方法

Applications Claiming Priority (2)

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KR1020180116033A KR102178806B1 (ko) 2018-09-28 2018-09-28 마그네슘 합금 판재 및 이의 제조방법
KR10-2018-0116033 2018-09-28

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US (1) US20220010413A1 (fr)
EP (1) EP3859024A4 (fr)
JP (1) JP7274585B2 (fr)
KR (1) KR102178806B1 (fr)
CN (1) CN112771189A (fr)
WO (1) WO2020067704A1 (fr)

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CN117431443A (zh) * 2023-10-19 2024-01-23 东莞宜安科技股份有限公司 一种高强耐蚀镁合金棒材及其制备方法

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CN113444945B (zh) * 2021-07-02 2022-04-26 云南大学 一种具有环形发散织构的高塑性、高成形性镁合金板材及其制备方法
CN113462940B (zh) * 2021-07-02 2022-04-26 云南大学 一种具有室温高成形性的镁合金板材及其制备方法
CN114214550A (zh) * 2021-12-17 2022-03-22 河北科技大学 一种医用镁合金及其制备方法

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