US20140205489A1 - Non-heat treated magnesium alloy sheet with excellent formability at room temperature in which segreation is minimized - Google Patents

Non-heat treated magnesium alloy sheet with excellent formability at room temperature in which segreation is minimized Download PDF

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Publication number
US20140205489A1
US20140205489A1 US14/237,892 US201214237892A US2014205489A1 US 20140205489 A1 US20140205489 A1 US 20140205489A1 US 201214237892 A US201214237892 A US 201214237892A US 2014205489 A1 US2014205489 A1 US 2014205489A1
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Prior art keywords
magnesium alloy
alloy sheet
sheet
heat treatable
ldh
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Abandoned
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US14/237,892
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English (en)
Inventor
Nack-Joon Kim
Myoeng-Shik Shim
Byeong-Chan Suh
Jun-Ho Bae
Dong-Wook Kim
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Academy Industry Foundation of POSTECH
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Academy Industry Foundation of POSTECH
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Assigned to POSTECH ACADEMY-INDUSTRY FOUNDATION reassignment POSTECH ACADEMY-INDUSTRY FOUNDATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAE, JUN-HO, KIM, DONG-WOOK, KIM, NACK-JOON, SUH, BYEONG-CHAN, SHIM, MYOENG-SHIK
Publication of US20140205489A1 publication Critical patent/US20140205489A1/en
Abandoned 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
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • 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
    • 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
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
    • B22D21/04—Casting aluminium or magnesium
    • 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
    • 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

  • the present invention relates to a strip-cast magnesium alloy sheet, and, more particularly, to a non-heat treatable magnesium alloy sheet, which can remarkably reduce a cast defect such as center segregation, inverse segregation or the like by alloy component control, and which can improve room-temperature formability by controlling crystal grain growth in the subsequent heat treatment procedure using a precipitate formed in a rolling procedure.
  • a magnesium alloy which is an alloy for structural materials having low specific gravity, high specific strength and high rigidity, has recently been increasingly used as a material for light portable electronic appliances such as mobile phones, notebooks and the like or as a material for automobiles for improving fuel efficiency.
  • research into magnesium alloys has been restricted to parts for casting.
  • research into the improvement of high-temperature physical properties of magnesium alloys used for automobile engines or gears has attracted considerable attention, whereas research into magnesium alloys for processing, such as magnesium alloy sheets which can be used in more various fields, has not been sufficiently conducted.
  • magnesium alloys For the purpose of various applications of magnesium alloys, demand for magnesium alloy products for processing has increased, and thus many research institutes have conducted research into magnesium alloys for processing. Particularly, among the magnesium alloy products, a magnesium alloy sheet, which is manufactured by twin-roll strip casting, can be applied in various fields, so research into the magnesium alloy sheet has been variously conducted, and the magnesium alloy sheet is commercially available.
  • the present invention has been devised to solve the problems of conventional magnesium alloys for twin-roll strip casting, such as cast defects, low mechanical strength and poor room-temperature formability, and an object of the present invention is to provide a non-heat treatable magnesium alloy sheet, which can reduce a cast defect such as segregation or the like by adjusting the composition of an magnesium alloy and which can obtain suitable mechanical strength and good room-temperature formability without including expensive rare-earth elements by controlling the microstructure of an magnesium alloy.
  • an aspect of the present invention provides a non-heat treatable magnesium alloy sheet, including: 1 ⁇ 3 wt % of aluminum (Al); 0.5 ⁇ 3 wt % of tin (Sn); and a balance of magnesium, wherein the maximum deviation of average Vickers hardness (Hv) thereof, caused by center segregation and inverse segregation, is 10 Hv or less.
  • the magnesium alloy sheet may be formed by twin-roll strip casting, and may have a microstructure of an Mg 2 Sn secondary phase.
  • the Mg 2 Sn secondary phase may have a volume fraction of 5% or less.
  • the magnesium alloy sheet may have a yield strength of 200 MPa or more and a limit dome height (LDH) of 5 mm or more, and preferably 6 mm or more.
  • LDH limit dome height
  • the volume fraction of tension twins inclined at an angle of 85 ⁇ 90° to parent grains may be 5% or more.
  • FIG. 1 is a schematic view showing a twin-roll strip casting apparatus for manufacturing a magnesium alloy sheet according to the present invention
  • FIG. 2 is a view showing the thickness-direction hardness distributions of the magnesium alloy sheet of the present invention and a commercially available AZ31 alloy sheet, each of which was divided into five equal parts;
  • FIG. 3 is a photograph showing the composition distributions of cast structure sections of the magnesium alloy sheet of the present invention and a commercially available AZ31 alloy sheet by EPMA (electron probe X-ray microanalysis);
  • FIG. 4 is a graph showing the results of X-ray diffraction test of the magnesium alloy sheet of the present invention.
  • FIG. 5 is a schematic view showing a method of evaluating the limit dome height (LDH) of the magnesium alloy sheet of the present invention
  • FIG. 6 shows photographs showing the shapes of the magnesium alloy sheet of the present invention (a) and a commercially available AZ31 alloy sheet (b) after the LDH test thereof;
  • FIG. 7 is a view showing the section for analyzing a sample after the LDH test.
  • FIG. 8 shows graphs showing the crystal grain changes of the magnesium alloy sheet of the present invention (a) and a commercially available AZ31 alloy sheet (b).
  • the present invention provides a non-heat treatable magnesium alloy sheet, including: 1 ⁇ 3 wt % of aluminum (Al); 0.5 ⁇ 3 wt % of tin (Sn); and a balance of magnesium, wherein the maximum deviation of average Vickers hardness (Hv) thereof, caused by center segregation and inverse segregation, is 10 Hv or less.
  • the solidification range of a cast material influences the segregation of the cast material and degree thereof.
  • a molten metal is solidified while passing through the set back distance region of rollers during a plating casting process, a liquid region coexisting in a sheet is squeezed from center to surface because the sheet is pressed by two rollers, thus resulting in forming a segregated zone having high composition density on the surface thereof.
  • This phenomenon is referred to as “inverse segregation”.
  • inverse segregation severely occurs in the case of an alloy having a long solidification range.
  • inverse segregation does not easily occur compared to the case of a magnesium alloy having a long solidification range.
  • the present inventors have adjusted the solidification range of a magnesium alloy used in twin-roll strip casting to be within the range where it doesn't have mechanical properties leading to deterioration.
  • an alloy including 1 ⁇ 3 wt % of aluminum (Al), 0.5 ⁇ 3 wt % of tin (Sn) and a balance of magnesium has a solidification range of 30 ⁇ 50K in an equilibrium diagram calculated by Factsage V6.2.
  • This soldification range corresponds to half of that (80 ⁇ 90K) of AZ31, which is a conventional alloy for twin-roll strip casting. Therefore, the magnesium alloy of the present invention has a solidification range of 50K or less, which is similar to that of an aluminum alloy, thus greatly reducing inverse segregation.
  • Degree of segregation can be evaluated by the distribution of alloy composition.
  • center segregation and inverse segregation are highly developed, and thus the distribution of alloy composition in a cast structure appears densely at the center and edge of a sheet.
  • the deviation in the composition of the magnesium alloy of present invention in a thickness direction does not become large.
  • the average deviation in the composition of a commercially available strip-cast AZ31 sheet is 30 ⁇ 50%, whereas the deviation in the composition of the magnesium alloy of the present invention is 10% or less.
  • the magnesium alloy sheet of the present invention exhibits excellent mechanical properties compared to a conventional commercially available AZ31 because of the formation of Mg 2 Sn secondary phases.
  • a heat treatment process for controlling the precipitates is not used, and thus a mechanism for enhancing the mechanical strength of the alloy is restricted.
  • the volume fraction of Mg 2 Sn secondary phases in the magnesium alloy sheet of the present invention is 5% or less, as optical images were measured using an image pro plus 6.0 program.
  • thermo-mechanical treatment such as hot rolling may be used as a mechanism for enhancing mechanical strength.
  • the mechanical strength of AZ31 is rapidly lowered with the passage of annealing time, and this phenomenon becomes remarkable with the increase of annealing temperature.
  • the volume fraction of secondary phases in the magnesium alloy of the present invention is greatly decreased in the homogenization process after casting.
  • secondary phases are distributed in the microstructure thereof again with dynamic precipitation during rolling, and the secondary phase distribution controls crystal grain growth during annealing, thus preventing the mechanical strength of the magnesium alloy from being rapidly lowered.
  • the reasons for limiting the composition ratio of the magnesium alloy to the above range are as follows.
  • the amount of Al is less than 1 wt %, the effect of improving fluidity and the effect of enhancing strength are insufficient, and, when the amount thereof is more than 3 wt %, the solidification range of the molten magnesium alloy is enlarged, and thus the effect of controlling segregation is not sufficient.
  • the amount of Sn is less than 0.5 wt %, the volume fraction of Mg 2 Sn secondary phases in the magnesium alloy is low, the contribution to the improvement of mechanical properties of the magnesium alloy is insufficient, and, when the amount thereof is more than 3 wt %, the homogenization treatment temperature and time increase, and secondary phases formed during a rolling process are locally distributed in the magnesium alloy in large amounts, thus exerting a negative influence on the improvement of formability and elongation.
  • the magnesium alloy sheet according to the present invention exhibits excellent room-temperature formability compared to that of a conventional AZ31 alloy because of tension twins inclined at an angle of 85 ⁇ 90° to parent grains.
  • pure Mg (99.9%), pure Al (99.9%) and pure Sn (99.9%) were melted by a furnace 10 of a twin-roll strip casting apparatus shown in FIG. 1 under a mixed gas atmosphere of CO 2 and SF 6 to prepare a molten metal, and then the molten metal was injected between two cooling rolls 30 using a nozzle 20 to manufacture a magnesium alloy sheet.
  • the distance between the two cooling rolls was maintained about 2 mm
  • the rotation speed of the two cooling rolls was maintained about 4 m/min at the time of injecting the molten metal
  • the cooling rate of the molten metal was maintained 200 ⁇ 300 K/s, thus obtaining a magnesium alloy sheet having a length of about 5 m, a width of about 70 mm and a thickness of about 2 mm.
  • FIG. 2 shows the thickness-direction hardness distributions of a strip-cast AZ31 sheet (Comparative Example) manufacture by POSCO Corporation and an AT33 magnesium alloy sheet (Example 2), wherein samples having a length of 50 cm were respectively divided into five equal parts to obtain samples having a length of 10 cm, and then the hardness of each of the samples was measured in the thickness direction thereof, and wherein the Vickers hardness thereof was measured under conditions of a load of 100 g f and a holding time of 5 seconds.
  • AZ31 sheet locally exhibits high hardness at the center and surfaces thereof, and thus the hardness thereof are entirely non-uniform.
  • AT33 sheet (Example 2) partially shows the hardness deviation to some degree due to segregation, but, entirely, the average deviation of hardness (Hv) thereof is 10 Hv or less, whereas AZ31 shows an average hardness deviation of 10 ⁇ 20 Hv. Consequently, it can be ascertained that the entire hardness distribution of AT33 sheet is uniform compared to that of AZ31 sheet.
  • the sheet manufactured as above was heat-treated as follows. First, the sheet was solution-treated at 400° C. for 3 hours. Subsequently, the solution-treated sheet was preheated to 200° C., and was then hot-rolled by rollers heated to 200° C.
  • the preheated sheet was hot-rolled five times at a reduction ratio of 10% per pass to a final reduction ratio of 50%, thereby finally obtaining a sheet having a thickness of 1 ⁇ 0.7 mm.
  • the above strip-cast and heat-treated magnesium alloy sheet was annealed as shown in Table 1 below, and then the mechanical properties and formability thereof were evaluated.
  • FIG. 5 is a schematic view showing a method of evaluating the limit dome height (LDH) of the magnesium alloy sheet according to an embodiment of the present invention.
  • LH limit dome height
  • a disk-shaped sample having a diameter of 50 mm and a thickness of 0.7 mm was fabricated, inserted between upper and lower dies and then fixed therebetween by a force of 5 kN, and a commonly-known press oil was used as a lubricating oil.
  • the fixed disk-shaped sample was deformed at a deformation rate of 0.1 mm/sec using a spherical punch having a diameter of 27.5 mm until the disk-shaped sample was torn by the movement of the punch, and then the deformation height of the disk-shape sample at this time was measured.
  • the magnesium alloy sheet which is a non-heat treatable magnesium alloy sheet, similarly to AZ31 (typical non-heat treated alloy), is characterized in that its mechanical strength is decreased with the increase of annealing time and annealing temperature, and its elongation and formability (that is, LDH) is increased with the increase of annealing time and annealing temperature.
  • tensile elongation is used as an alternative item to formability, but, as given in Table 1 above, elongation is not absolutely proportional to LDH representing formability. Therefore, it is preferred that a test accompanying an actual forming procedure is conducted compared to when a uniaxial tensile elongation is used as an index representing formability.
  • FIG. 6 shows photographs showing the shapes of an AT alloy sheet sample and a commercially available AZ31 alloy sheet sample after the LDH tests thereof.
  • FIG. 8 shows graphs showing the changes of the most severely deformed top portion of each sample and the non-deformed edge portion of each sample at a crystal direction difference between in a normal direction of a sheet and in a direction of a (0002) basal plane of magnesium hexagonal crystal.
  • the fraction of grains having a high crystal direction difference of the magnesium alloy sheet of the present invention is considerably increased.
  • the fraction of grains having a high crystal direction difference of the AZ31 alloy sheet is slightly increased.
  • the present invention provides a magnesium alloy sheet, which can make a uniform cast structure by controlling alloy elements having a narrow solidification range, which can make up for defects caused by segregation, and which has excellent mechanical strength and formability without using expensive rare-earth elements. Further, the magnesium alloy sheet according to the present invention can be used in various application fields because it is a non-heat treatable magnesium alloy sheet and its yield strength and LDH value are linearly changed depending on annealing time.
  • the magnesium alloy sheet according to the present invention is advantageous in that it can remarkably improve defects, such as inverse segregation, center segregation and the like, occurring in a conventional magnesium alloy sheet prepared by a twin-roll strip casting process due to the change of a solidification range by the addition of alloy elements, and in that its mechanical strength is excellent compared to that of a conventional non-heat treatable strip-cast magnesium alloy sheet even after it is heat-treated to have high formability.
  • the magnesium alloy sheet according to the present invention can exhibit excellent formability without using expensive rare-earth elements added to impart high formability and high strength, thus increasing competitiveness thereof in the light structural materials market.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Continuous Casting (AREA)
  • Metal Rolling (AREA)
US14/237,892 2011-10-20 2012-10-15 Non-heat treated magnesium alloy sheet with excellent formability at room temperature in which segreation is minimized Abandoned US20140205489A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020110107405A KR101342582B1 (ko) 2011-10-20 2011-10-20 편석 현상을 최소화한 상온 성형성이 우수한 비열처리형 마그네슘 합금 판재
KR10-2011-0107405 2011-10-20
PCT/KR2012/008357 WO2013058504A2 (ko) 2011-10-20 2012-10-15 편석 현상을 최소화한 상온 성형성이 우수한 비열처리형 마그네슘 합금 판재

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US (1) US20140205489A1 (ko)
EP (1) EP2770072A4 (ko)
JP (1) JP6099656B2 (ko)
KR (1) KR101342582B1 (ko)
CN (1) CN103781928B (ko)
WO (1) WO2013058504A2 (ko)

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CN103290288B (zh) * 2013-06-26 2015-10-07 重庆大学 一种低成本高塑性变形镁合金及其制备方法
KR101603292B1 (ko) 2014-04-15 2016-03-14 한국신발피혁연구원 초임계 발포 사출용 저비중 동적 가교형 열가소성 탄성체 조성물, 이의 제조방법 및 이를 이용하여 제조된 신발 겉창
KR20160120688A (ko) 2016-08-29 2016-10-18 서울대학교산학협력단 마그네슘 합금 판재 및 이의 제조방법
CN109072359B (zh) * 2017-02-27 2020-09-08 韩国机械研究院 时效热处理型高强度镁合金及其制备方法
WO2018155994A1 (ko) * 2017-02-27 2018-08-30 한국기계연구원 시효열처리형 고강도 마그네슘 합금 및 그 제조방법
CN110031347A (zh) * 2019-04-02 2019-07-19 鞍钢股份有限公司 一种测定弹簧钢盘条偏析的方法

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Publication number Publication date
WO2013058504A2 (ko) 2013-04-25
EP2770072A4 (en) 2015-06-17
EP2770072A2 (en) 2014-08-27
WO2013058504A3 (ko) 2013-05-23
CN103781928A (zh) 2014-05-07
CN103781928B (zh) 2016-08-17
JP2014535005A (ja) 2014-12-25
KR20130043355A (ko) 2013-04-30
JP6099656B2 (ja) 2017-03-22
KR101342582B1 (ko) 2013-12-17

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