[go: up one dir, main page]

WO2018159394A1 - Alliage de magnésium et procédé de fabrication d'alliage de magnésium - Google Patents

Alliage de magnésium et procédé de fabrication d'alliage de magnésium Download PDF

Info

Publication number
WO2018159394A1
WO2018159394A1 PCT/JP2018/006088 JP2018006088W WO2018159394A1 WO 2018159394 A1 WO2018159394 A1 WO 2018159394A1 JP 2018006088 W JP2018006088 W JP 2018006088W WO 2018159394 A1 WO2018159394 A1 WO 2018159394A1
Authority
WO
WIPO (PCT)
Prior art keywords
magnesium alloy
solid
solution treatment
treatment
aging
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.)
Ceased
Application number
PCT/JP2018/006088
Other languages
English (en)
Japanese (ja)
Inventor
ミンジェ ビャン
泰祐 佐々木
和博 宝野
ビョンチャン スー
重晴 鎌土
大貴 中田
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.)
National Institute for Materials Science
Original Assignee
National Institute for Materials Science
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
Priority claimed from JP2018027358A external-priority patent/JP7116394B2/ja
Application filed by National Institute for Materials Science filed Critical National Institute for Materials Science
Priority to EP18761653.7A priority Critical patent/EP3572542B1/fr
Priority to US16/488,050 priority patent/US20200239992A1/en
Publication of WO2018159394A1 publication Critical patent/WO2018159394A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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 magnesium alloy and a method for producing the magnesium alloy.
  • Magnesium alloy is known as the lightest metal among practical metals, and its application to railways, aircraft, automobiles, etc. is being studied as a lightweight material to replace aluminum alloys.
  • magnesium alloy wrought material is inferior in strength and workability compared to aluminum alloy.
  • various studies have been conducted including the development of new wrought materials.
  • a conventional wrought magnesium alloy has a strength exceeding 300 MPa by refining crystal grains by strong processing and adding rare earth metal elements and zinc as alloy elements (see, for example, Patent Document 1).
  • Patent Document 1 A conventional wrought magnesium alloy has a strength exceeding 300 MPa by refining crystal grains by strong processing and adding rare earth metal elements and zinc as alloy elements.
  • Patent Document 1 A conventional wrought magnesium alloy has a strength exceeding 300 MPa by refining crystal grains by strong processing and adding rare earth metal elements and zinc as alloy elements.
  • an alloy added with a rare earth metal as an alloy element has excellent strength.
  • the raw material cost becomes high.
  • the primary processing such as hot processing and the secondary processing to the final shape cannot be easily performed, the manufacturing cost is high. Therefore, the possibility of developing a general-purpose material that can be applied to automobiles, railways, and the like is extremely low.
  • Non-Patent Document 1 a wrought material whose strength is improved by refining crystal grains by strong processing is known (see Non-Patent Document 1, for example).
  • Non-Patent Document 1 a wrought material whose strength is improved by refining crystal grains by strong processing.
  • Patent Document 3 An example of developing an alloy having excellent workability at room temperature comparable to an aluminum alloy by adding an alloying element or improving a rolling process has been reported (see Patent Document 3). However, there was a tendency for the strength to decrease as the room temperature processability improved. In addition, the example which improved the intensity
  • an object of the present invention is to provide a highly versatile magnesium alloy and a magnesium alloy manufacturing method that can achieve both workability and strength in a temperature range including normal temperature.
  • the application of an aging treatment is a method for solving the above-mentioned problems.
  • the heat treatment called T6 treatment is a kind of heat treatment process applied to the wrought material obtained by hot or warm working, and is a solution treatment (T4 treatment) in which an alloying element is supersaturated in the alloy.
  • T4 treatment a solution treatment in which an alloying element is supersaturated in the alloy.
  • an aging treatment in which precipitates are dispersed and strengthened to the maximum hardness.
  • T6 treatment When T6 treatment is applied to plastic processed products such as plates and bars, plastic processed products are softened after T4 treatment due to solid solution of precipitates in the parent phase, recovery of the parent phase, recrystallization, and a decrease in crystal orientation. Therefore, moldability can be improved, and strength can be imparted by dispersing fine precipitates at high density by subsequent aging treatment.
  • Such heat treatment cannot be applied because Mg-3Al-1Zn alloy, which is known as a current commercial magnesium alloy plate material, does not age harden.
  • a specific magnesium alloy is used, a T6 treatment is possible. The present inventors have found that it is possible to achieve both workability and strength in a temperature range including normal temperature by utilizing the above, and have reached the present invention.
  • the magnesium alloy of the present invention that achieves the above object is provided with 0.2-2% by mass of Al, 0.2-1% by mass of Mn, 0.2-2% by mass of Zn, and at least 0.1% by mass. 2 to 1% by mass of Ca, the balance being made of Mg and inevitable impurities, and precipitates made of Mg, Ca and Al are dispersed on the (0001) plane of the magnesium matrix.
  • the magnesium alloy of the present invention may further contain precipitates made of Al and Mn.
  • the precipitates made of Mg, Ca and Al have a plate shape, the long side of the plate has a range of 3 to 6 nm, and the number density of the precipitates is 10 20 to 10 24 / mm. 3 is preferred.
  • the average crystal grain size of the magnesium matrix is preferably 20 ⁇ m or less.
  • the integration degree of the (0002) poles in the central portion of the plate thickness of the normalized RD-TD plane of the (0002) pole figure measured by X-ray diffraction is 5.0 or less.
  • the Erichsen value at room temperature is 6.5 mm or more.
  • the 0.2% proof stress of the solution treated material is preferably 120 MPa or more, and the 0.2% proof stress of the magnesium alloy finally subjected to aging treatment after molding is preferably 160 MPa or more.
  • the breaking elongation is preferably 20% or more.
  • the method for producing a magnesium alloy of the present invention comprises the steps 1 of obtaining Mg, Al, Mn, Zn, and Ca to obtain a cast solid, and the step of homogenizing the cast solid to obtain a homogenized solid. 2, a process 3 to obtain a tangible solid by processing the homogenized solid hot or warm, a process 4 to obtain a cooling solid by solution treatment of the tangible solid, an aging treatment of the cooling solid to obtain a magnesium alloy And obtaining a homogenized solid by performing a homogenization treatment at 400 ° C. or more and 500 ° C. or less for a predetermined time in Step 2, and aging at a temperature of 140 to 250 ° C. for a predetermined time in Step 5
  • the magnesium alloy is obtained by processing.
  • a secondary processing step of secondary processing of the cooling solid can be included between Step 4 and Step 5.
  • step 3 it is preferable to perform processing by hot or warm processing.
  • step 5 it is preferable to perform an aging treatment for increasing the hardness of the magnesium alloy.
  • the optical microscope image of the solution treatment material which is the cooling solid of the process 4 in Example 1 of this invention is shown.
  • the (0002) pole figure obtained from the X-ray diffraction of the solution treatment material which is the cooling solid of the process 4 in Example 1 is shown.
  • the tensile stress-strain curve of the solution treatment material which is the cooling solid of the process 4 in Example 1, and the aging treatment material of the process 5 is shown.
  • the aging treatment material of Example 1 was observed with a transmission electron microscope.
  • (A) was obtained from a bright-field TEM image
  • (b) was obtained from [011 (bar) 0] and [112 (bar) 0] orientations.
  • Limited field diffraction image, (c) is a diagram showing a three-dimensional atom map.
  • the aging treatment material of Example 1 was observed with a transmission electron microscope.
  • A is a bright-field TEM image
  • (b) is a HAADF-STEM image (High-angle Annular Dark Field Scanning Transmission Electron Microscopy, high angle scattering annular darkness).
  • (Scanning transmission electron microscope image) is an enlarged view of the HAADF-STEM image of (b)
  • (d) is a diagram showing the results of elemental analysis along the arrow of (c). It is a figure which shows the optical microscope image of the solution treatment material which is a cooling solid of the process 4 in Example 5.
  • FIG. The (0002) pole figure obtained from the X-ray diffraction of the solution treatment material which is the cooling solid of the process 4 in Example 5 is shown.
  • the tensile stress-strain curve of the solution treatment material which is the cooling solid of the process 4 in Example 5, and the aging treatment material of the process 5 is shown. It is a figure which shows the optical microscope image of the solution treatment material which is a cooling solid of the process 4 in Example 7.
  • FIG. The (0002) pole figure obtained from the X-ray diffraction of the solution treatment material which is the cooling solid of the process 4 in Example 7 is shown.
  • the tensile stress-strain curve of the solution treatment material which is the cooling solid of the process 4 in Example 7, and the aging treatment material of the process 5 is shown. It is a figure which shows the optical microscope image of the solution treatment material which is a cooling solid of the process 4 in Example 9.
  • the (0002) pole figure obtained from the X-ray diffraction of the solution treatment material which is the cooling solid of the process 4 in Example 9 is shown.
  • the tensile stress-strain curve of the solution treatment material which is the cooling solid of the process 4 in Example 9, and the aging treatment material of the process 5 is shown.
  • the (0002) pole figure obtained from the X-ray diffraction of the solution treatment material which is the cooling solid of the process 4 in the comparative example 1 is shown.
  • the tensile stress-strain curve of the solution treatment material which is the cooling solid of the process 4 in the comparative example 1 and the aging treatment material of the process 5 is shown.
  • the magnesium alloy of the present invention comprises 0.2-2 mass% Al, 0.2-1 mass% Mn, 0.2-2 mass% Zn, and at least 0.2-1 mass% Ca. And the balance of Mg and inevitable impurities.
  • This magnesium alloy has a magnesium matrix composed of Mg in which Mg or Al, Mn, Zn and Ca are dissolved, and a precipitate containing one or more of Al, Mn, Zn and Ca.
  • the form of the magnesium alloy is not particularly limited, and may be, for example, a form of various materials such as a plate material, or may be a form of an intermediate or a final product.
  • the degree of crystal orientation is reduced by the T4 treatment, and Al, Ca, Zn, and Mn, which are alloy elements that form precipitates, are in solid solution.
  • the average crystal grain size of the magnesium matrix is preferably 20 ⁇ m or less. If the crystal grain size is excessively large, the formation of a deformation twin that becomes the starting point of a crack becomes easy, and the moldability at room temperature is remarkably lowered, which is not preferable.
  • the proportion of Al contained in the magnesium alloy of the present invention is preferably 0.2 to 2% by mass.
  • the Al content is small, it is difficult to obtain useful precipitates to be described later.
  • the precipitated phase is preferably changed to coarse precipitates such as an Al 2 Ca phase that is not effective for strengthening. Absent.
  • the proportion of Mn contained in the magnesium alloy of the present invention is preferably 0.2% by mass or more and 1% by mass or less.
  • Mn content is small, an Al—Mn compound that plays a role in suppressing the coarsening of crystal grains is likely to be formed.
  • Al is used to form the Al—Mn compound. Therefore, it is not preferable because large age hardening is not exhibited.
  • the proportion of Zn contained in the magnesium alloy of the present invention is preferably 0.2% by mass or more and 2% by mass or less. If the Zn content is low, the degree of crystal orientation becomes high, so that excellent room temperature workability cannot be obtained. On the other hand, if the amount is excessive, the melting point of the alloy is lowered, and not only is there a possibility of cracking during cooling after the solution treatment, but also the age-hardening ability is remarkably lowered, which is not preferable.
  • the ratio of Ca contained in the magnesium alloy of the present invention is preferably 0.2% by mass or more and 1% by mass or less.
  • the Ca content is small, it is difficult to obtain useful precipitates described later.
  • the Ca content is excessive, precipitates composed of Al and Ca or Mg and Ca are formed, and formability and ductility are reduced. This is not preferable because it causes a decrease in the thickness.
  • Precipitates in the magnesium alloy of the present invention include precipitates made of Mg, Ca and Al and precipitates made of Al and Mn.
  • Precipitates composed of Mg, Ca, and Al are obtained from Guinier. Preston. It is a nano-sized precipitate called a Zone (GP Zone, GP zone).
  • GP Zone nano-sized precipitate
  • the precipitate (GP Zone) made of Mg, Ca, and Al observed in the aging treatment material of the magnesium alloy may be a plate-like precipitate.
  • This nano-sized plate-like precipitate has, for example, a plate-like long side in the range of 3 to 6 nm, and the elemental composition formula is Mg 2 (Ca, Al). That is, Mg is 67 at% and Ca + Al is 33 at%, but it is not limited to these dimensions and elemental composition formulas.
  • the precipitate composed of Al and Mn is a rod-like Al—Mn-based precipitate.
  • the Al—Mn-based precipitates can be refined by forming precipitates during the homogenization or solution treatment with Al and Mn. Precipitates made of Al and Mn are observed in the solution treatment material and the aging treatment material of the magnesium alloy.
  • the rod-like Al—Mn-based precipitate has a length of about 50 nm to 300 nm and a diameter of about 2 to 20 nm, but is not limited thereto.
  • the number density of precipitates (GP Zone) made of Mg, Ca and Al is preferably 10 20 to 10 24 / mm 3 .
  • the number density of precipitates made of Al and Mn is about 10 20 to 10 21 / mm 3 .
  • the value is about 10 3 to 10 4 mm -3 . Does not significantly affect strength.
  • the degree of orientation of crystal grains is such that the degree of integration of the (0002) plane at the center of the thickness of the normalized RD-TD plane of the (0002) pole figure is less than 5.0. Thereby, the orientation degree of a crystal grain can be made low and the outstanding moldability can be obtained.
  • the magnesium alloy of the present invention preferably has an Erichsen value at room temperature of 6.5 mm or more. Thereby, the workability of the magnesium alloy such as pressing at room temperature can be improved, and the workability in the heated state can be further improved.
  • This Erichsen value (IE value) is determined by the height of the depression until the material breaks by deforming the thin plate by pressing the ball head punch at a constant speed against the thin plate with the outer periphery fixed by the Eriksen test. This is to evaluate the workability of the material.
  • the magnesium alloy of the present invention should have a 0.2% proof stress of 120 MPa or more and a breaking elongation of 20% or more while improving the workability at room temperature.
  • the 0.2% proof stress is also called yield stress.
  • it is desirable that the Vickers hardness is 45HV or more.
  • the 0.2% yield strength of the aging treatment material of the magnesium alloy of the present invention is preferably 160 MPa or more.
  • This manufacturing method includes a step 1 for obtaining a cast solid by melting and casting Mg, Al, Mn, Zn and Ca, a step 2 for obtaining a homogenized solid by homogenizing the cast solid, and a homogenized solid.
  • Step 3 for obtaining a tangible solid by hot working or warm processing
  • Step 4 for obtaining a cooling solid by solution treatment of the tangible solid
  • Step 5 for obtaining a magnesium alloy by aging the cooling solid. It is out.
  • step 1 0.2-2% by mass of Al, 0.2-1% by mass of Mn, 0.2-2% by mass of Zn, and at least 0.2-1% by mass of Ca.
  • a cast solid is produced by melting and casting an alloy component containing Mg and inevitable impurities.
  • the size of the melting furnace and cast solid used for melting is not particularly limited as long as a cast solid having a desired composition can be produced.
  • step 2 the homogenized solid is produced by subjecting the cast solid to a homogenization treatment at a temperature of 400 ° C. to 500 ° C. for a predetermined time.
  • the homogenization treatment the distribution of alloy elements present in the cast solid is homogenized, and precipitates formed during cooling of the molten metal are dissolved in the magnesium matrix.
  • the alloy may melt when heat treatment is started at a temperature of 340 ° C. or higher. For this reason, first, heat treatment is performed at a temperature of less than 340 ° C., the initial melting of the Mg—Zn phase formed during casting is suppressed and Zn is dispersed, and then heat treatment is performed at 400 ° C. to 500 ° C. for a predetermined time. Then, the distribution of Zn is homogenized to obtain a homogenized solid.
  • the conditions for the homogenization treatment are not particularly limited and can be set according to the casting solid and the alloy element components.
  • the alloy elements are dissolved in the magnesium matrix by heat treatment at a predetermined temperature and time. I can do it.
  • step 3 the homogenized solid is processed into a plate material by hot rolling to produce a plate-shaped tangible solid.
  • the homogenized solid is processed into a plate material by setting rolling conditions such as sample temperature, roll temperature, rolling reduction, roll peripheral speed, number of passes, presence or absence of intermediate heat treatment of the sample, temperature and time of intermediate heat treatment.
  • the sample temperature and roll temperature may be lowered to such an extent that the sample does not break during rolling.
  • the rolling reduction may be increased to such an extent that the sample does not break during rolling.
  • the intermediate heat treatment of the sample is a heat treatment performed in the middle of rolling, and may be performed at a high temperature that does not cause cracks in the cooling process and does not cause local melting.
  • the hot or warm working is not particularly limited to rolling, and any stretching method that can produce a fine structure may be used. For example, any method such as forging and extrusion, including twin-roll casting and rolling, may be used. .
  • Step 4 Solution treatment
  • a plate-shaped tangible solid is subjected to a solution treatment, and this is cooled to produce a cooled solid.
  • a tangible solid is heat-treated, so that fine precipitates formed during hot or warm processing are dissolved in a matrix and recrystallized to form a structure.
  • the orientation of crystal grains can be randomly oriented, and excellent formability can be imparted.
  • the solution treatment is performed by holding the solution treatment time from 15 minutes to 24 hours at a solution treatment temperature of 350 to 500 ° C. according to the tangible solid.
  • the longer heat treatment time leads to an increase in manufacturing cost, it is not necessary to perform more time than necessary.
  • Secondary processing process When manufacturing the magnesium alloy of the shape different from the shape of the cooling solid obtained after the solution treatment after the step 4, secondary processing can be performed on the cooling solid.
  • the secondary processing is not particularly limited, and sheet metal processing such as press processing and drawing processing, machining, and the like can be appropriately performed according to a desired shape.
  • sheet metal processing such as press processing and drawing processing, machining, and the like can be appropriately performed according to a desired shape.
  • step 5 the cooling solid is age-hardened by heat treatment to disperse the precipitate deposited on the solution-treated cooling solid, thereby imparting strength to produce the magnesium alloy of the present invention.
  • a significant strengthening of the magnesium alloy can be achieved by using an aging treatment that was not conventionally used in commercial magnesium alloys.
  • an aging treatment is performed at a temperature of 140 to 250 ° C. for a predetermined time.
  • the time for performing the aging treatment is a time for increasing the hardness of the magnesium alloy, preferably a time for maximizing the hardness of the magnesium alloy.
  • the magnesium alloy of the present invention thus produced has a content of 0.2-2% by mass of Al, 0.2-1% by mass of Mn, 0.2-2% by mass of Zn, and at least 0.1% by mass. 2 to 1% by mass of Ca, with the balance being Mg and inevitable impurities, and a precipitate comprising Mg, Ca and Al dispersed on the (0001) plane of the magnesium matrix, preferably further Al and It is an alloy containing precipitates made of Mn.
  • the orientation of crystal grains can be randomly oriented by performing a solution treatment after rolling, thereby imparting excellent formability.
  • the crystallinity of crystal grains is randomly oriented, so that the strength is drastically reduced.
  • a highly versatile magnesium alloy capable of achieving both workability and strength in a temperature range including normal temperature can be obtained.
  • the strength and room temperature workability required as applicable mechanical properties can be realized as an automobile material such as a body panel of an automobile.
  • a conventional commercial magnesium alloy made of a relatively inexpensive alloy element without using expensive and resource-free heavy rare earth metal elements, and with a combination of simple rolling and heat treatment using existing equipment. Excellent moldability and room temperature strength that greatly exceed the plate material can be exhibited. Thereby, for example, it is possible to satisfy the characteristics required for automobile applications.
  • the said embodiment can be suitably changed within the scope of the present invention.
  • a magnesium alloy that has been subjected to a solution treatment after hot or warm processing is subjected to various processes such as drawing and bending to produce a molded body, and then subjected to an aging treatment.
  • the example of strengthening was explained, but it is also possible to produce a magnesium alloy by solution treatment and aging treatment after hot or warm working, and then make various forms such as drawing and bending to produce a molded body It is.
  • a manufacturing method of the magnesium alloy it can be completed in a state where the solution treatment is performed after hot or warm processing and the aging treatment is not performed, and the present invention can be applied as a manufacturing method of the processed material. It is.
  • Example 1 (Process 1: Casting) An alloy having a composition of Mg-1.2Al-0.3Ca-0.4Mn-0.3Zn as shown in A-1 of Table 1 using a high-frequency induction melting furnace (manufactured by ULVAC, FMI-I-20F) Was melted and cast using a mold to produce a cast solid.
  • the numbers described before Al, Ca, Mn, and Zn, which are elements other than Mg, indicate mass% of each element.
  • the thickness of the cast solid was approximately 10 mm.
  • the final rolling step was carried out while performing intermediate heat treatment using a rolling device having a roll peripheral speed of 2 m / min as shown in Table 1.
  • the sample temperature and the roll temperature were set to 100 ° C., and the rolling passage was passed six times at a rolling reduction of 23%. Each time the rolling passage is passed, the final rolling is performed while performing an intermediate heat treatment in which the sample is reheated at 500 ° C. for 5 minutes and air-cooled, whereby the thickness is rolled to 1 mm to produce a tangible solid.
  • Step 4 Solution treatment
  • the solution treatment temperature was 450 ° C.
  • the solution treatment time was 1 hour.
  • the mechanical strength of the obtained cooling solid was measured, as shown in Table 2, the Erichsen value, which is the formability (index Erichsen value) evaluated by the Erichsen test (Tester: Model 111, manufactured by Eriksen), was 7 mm.
  • the Vickers hardness was 47 VHN
  • the 0.2% proof stress was 127 MPa
  • the tensile strength was 223 MPa
  • the elongation at break was 30%.
  • FIG. 1 shows an optical microscope image (Nikon Corporation, Eclipse LV-100) of a solution treatment material that is a cooling solid.
  • the crystal grain size calculated by the intercept method was 12.0 ⁇ m.
  • the crystal grain size was calculated in accordance with the American Society for Testing and Materials (ASTM) linear intercept method (E112-13).
  • FIG. 2 shows a (0002) pole figure obtained by X-ray diffraction of the solution-treated material.
  • the density of the (0002) pole also called maximum random distribution, mrd, or texture strength
  • the texture strength is a scale indicating the relative strength of the (0002) plane texture (1 when randomly oriented).
  • FIG. 3 shows tensile stress-strain curves of the solution-treated material (T4), which is the cooling solid in Step 4, and the aging material (T6) in Step 5. With the aging treatment, the yield strength increased significantly to 187 MPa.
  • FIG. 4 shows an image obtained by observing the aging treatment material of Example 1 with a transmission electron microscope.
  • A is a bright field TEM image
  • (b) is [011 (bar) 0], [112 (bar) 0. ]
  • (c) is a diagram showing a three-dimensional atom map.
  • As the transmission electron microscope a scanning transmission electron microscope (Titan, G2 80-200) manufactured by FEI was used. Due to the linear strain contrast in the bright field TEM image of FIG. P. The presence of Zone was confirmed.
  • a three-dimensional atom probe (also called 3DAP) applies a high voltage to a sample, detects ions evaporating from the surface of the sample with a mass spectrometer, and then detects each detected ion in depth. This is a method of measuring a three-dimensional atomic distribution by continuously detecting in the vertical direction and arranging ions in the detected order.
  • the inventor of the National Institute for Materials Science made the three-dimensional atom probe, and a mass spectrometer (ADLD detector) manufactured by Kameka Corporation was used for ion analysis. From the three-dimensional atom map of FIG. P. It was confirmed that the zone was composed of Mg, Ca, and Al. G. P.
  • a typical element composition formula of Zone is Mg 2 (Ca, Al), and there is a theoretical analysis that Mg is 67 at% and Ca + Al is 33 at%, but it was found that this is in agreement with this theory.
  • FIG. 5 shows the aging treatment material of Example 1 observed with a transmission electron microscope.
  • A is a bright field TEM image
  • (b) is a HAADF-STEM image (High-angle Annular Dark Field Scanning Transmission Electron Microscopy (High-angle scattering annular dark field scanning transmission electron microscope image)
  • (c) is an enlarged view of the HAADF-STEM image of (b)
  • (d) is a diagram showing the results of elemental analysis along the arrow of (c).
  • the elemental analysis was performed using an EDS (EDI elemental analyzer (Super X) manufactured by FEI) attached to a scanning transmission electron microscope manufactured by FEI.
  • EDS EDI elemental analyzer
  • Super X X
  • Example 2 When producing a cooling solid by solution treatment of a tangible solid in step 4, a magnesium alloy is produced in the same manner as in Example 1 except that the solution treatment time is 2 hours as shown in Table 2. did. Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Tables 2 and 3, as in Example 1, a magnesium alloy capable of ensuring workability in the temperature range near room temperature and achieving both workability and strength was obtained. With respect to the sample subjected to the solution treatment of Example 2, the number density of the precipitate composed of Al and Mn (see FIG. 5) observed in Example 1 was measured. The number density was 10 20 to 10 21 mm ⁇ 3. It was about.
  • the number density of precipitates made of Al and Mn was found to be about 10 3 to 10 4 mm ⁇ 3 lower than the number density of GP Zone, which is 10 20 to 10 24 / mm 3 . As a result, it has been found that precipitates made of Al and Mn do not significantly affect the strength of the magnesium alloy as compared with GP Zone.
  • Example 3 When producing a cooling solid by solution treatment of a tangible solid in Step 4, as shown in Table 2, a magnesium alloy was produced in the same manner as in Example 1 except that the solution treatment time was 4 hours. did. Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Tables 2 and 3, as in Example 1, a magnesium alloy capable of ensuring workability in the temperature range near room temperature and achieving both workability and strength was obtained.
  • Example 4 In step 1, as shown in A-2 of Table 1, an alloy having a composition of Mg-1.2Al-0.3Ca-0.4Mn-0.3Zn is melted and cast with a mold to produce a cast solid, The roll temperature in the final rolling process was 200 ° C. In step 5, as shown in Table 3, the aging temperature was 450 ° C. and the aging time was 2 hours. Otherwise, a magnesium alloy was produced in the same manner as in Example 1. Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is apparent from Tables 2 and 3, a magnesium alloy capable of achieving both workability and strength was obtained even when the rolling treatment conditions and the aging treatment conditions were changed.
  • Example 5 When a tangible solid is produced by rolling the homogenized solid in step 3, the sample temperature and roll temperature in the final rolling step are set to 200 ° C. as shown in Table 2 and as shown in Table 2.
  • a magnesium alloy was produced in the same manner as in Example 1 except that when the cooling solid was produced by solution treatment of the tangible solid in Step 4, the solution treatment time was changed to 2 hours.
  • Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is apparent from Tables 2 and 3, a magnesium alloy capable of achieving both workability and strength was obtained even when the rolling treatment conditions and the solution treatment conditions were changed.
  • step 6 In step 1, as shown in B-1 of Table 1, an alloy having a composition of Mg-1.2Al-0.5Ca-0.4Mn-0.3Zn is melted and cast with a mold to produce a cast solid.
  • the cast solid was held at 300 ° C for 4 hours, heated to 450 ° C at a heating rate of 7.5 ° C /, then held for 6 hours, and then water-cooled to room temperature for homogenization. A solid was made.
  • the sample reheating temperature in the final rolling step was 450 ° C.
  • step 5 the aging temperature was 350 ° C. and the aging time was 4 hours as shown in Table 3. Otherwise, a magnesium alloy was produced in the same manner as in Example 1.
  • Tables 2 and 3 show the production conditions, mechanical properties, and microstructure characteristics of the obtained solid. As is clear from Tables 2 and 3, a magnesium alloy capable of achieving both workability and strength was obtained even when the composition, homogenization conditions, rolling treatment conditions, and aging treatment conditions were changed.
  • Example 7 In step 1, as shown in B-1 of Table 1, an alloy having a composition of Mg-1.2Al-0.5Ca-0.4Mn-0.3Zn is melted and cast with a mold to produce a cast solid. In No. 2, the cast solid was held at 300 ° C. for 4 hours, heated to 450 ° C. at a heating rate of 7.5 ° C./h, then held for 6 hours, and then water-cooled to room temperature for homogenization. Solidified solids were prepared. In step 3, the sample reheating temperature in the final rolling step was 450 ° C., and in step 5, the aging time was 0.25 as shown in Table 3. Otherwise, a magnesium alloy was produced in the same manner as in Example 1.
  • FIG. 6 shows an optical microscope image of the solution treatment material that is a cooling solid.
  • the crystal grain size calculated by the intercept method was 9.7 ⁇ m.
  • FIG. 7 shows a (0002) pole figure obtained by X-ray diffraction of the solution-treated material.
  • the degree of integration of the (0002) pole was 3.7 and inclined in the rolling direction.
  • FIG. 8 shows the tensile stress-strain curves of the solution treated material (T4), which is the cooling solid in Step 4, and the aging treated material (T6) in Step 5.
  • Table 3 shows the 0.2% proof stress, tensile strength and elongation (E f ) obtained from the stress-strain curve.
  • the yield strength of the solution-treated material was 142 MPa, and it had excellent room temperature formability with an Erichsen value of 7.5 mm. With subsequent aging, the yield strength increased significantly to 201 MPa. As is clear from the above, a magnesium alloy capable of achieving both workability and strength in a temperature range near room temperature could be obtained.
  • Example 8 In step 1, as shown in B-2 of Table 1, a magnesium alloy was produced in the same manner as in Example 7, except that the sample temperature and roll temperature in the final rolling step were set to 200 ° C. Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Tables 2 and 3, as in Example 7, a magnesium alloy capable of ensuring workability in the temperature range near room temperature and achieving both workability and strength was obtained.
  • step 1 an alloy having a composition of Mg-1.2Al-0.5Ca-0.4Mn-0.8Zn is melted and cast with a mold as shown in C-1 of Table 1, and a cast solid is produced.
  • the cast solid was held at 300 ° C. for 4 hours, heated to 450 ° C. at a heating rate of 7.5 ° C./h, then held for 6 hours, and then water-cooled to room temperature for homogenization. Solidified solids were prepared.
  • step 3 the sample reheating temperature is set to 450 ° C., and as shown in Table 2, when forming a cooling solid by solution treatment of the tangible solid in step 4, the solution treatment temperature is set to 350 ° C.
  • Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Tables 2 and 3, a magnesium alloy capable of achieving both workability and strength was obtained even when the composition, homogenization conditions, rolling treatment conditions, and aging treatment conditions were changed.
  • step 1 an alloy having a composition of Mg-1.2Al-0.5Ca-0.4Mn-0.8Zn is melted and cast with a mold as shown in C-1 of Table 1, and a cast solid is produced.
  • the cast solid was held at 300 ° C. for 4 hours, heated to 450 ° C. at a heating rate of 7.5 ° C./h (hours), then held for 6 hours, and then water-cooled to room temperature. To produce a homogenized solid.
  • step 3 the sample reheating temperature in the final rolling step was 450 ° C., and in step 5, the aging time was 1 h (hours) as shown in Table 3. Otherwise, a magnesium alloy was produced in the same manner as in Example 1.
  • FIG. 9 shows an optical microscope image of the solution treatment material that is a cooling solid.
  • the crystal grain size calculated by the intercept method was 10.7 ⁇ m.
  • FIG. 10 shows a (0002) pole figure obtained by X-ray diffraction of the solution treatment material.
  • the integration degree of the (0002) pole was 3.5.
  • FIG. 11 shows tensile stress-strain curves of the solution treated material (T4), which is the cooling solid in Step 4, and the aging treated material (T6) in Step 5.
  • Table 3 shows the 0.2% yield strength, tensile strength, elongation, and Erichsen value obtained from the stress-strain curve.
  • the yield strength of the solution-treated material was 144 MPa, and it had excellent room temperature formability with an Erichsen value of 7.7 mm. Subsequent aging treatment significantly increased the yield strength to 204 MPa. As is clear from the above, a magnesium alloy capable of achieving both workability and strength in a temperature range near room temperature could be obtained.
  • Example 11 In step 1, as shown in C-2 of Table 1, a magnesium alloy was produced in the same manner as in Example 10 except that the sample temperature and the roll temperature in the final rolling step were set to 200 ° C. Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Tables 2 and 3, as in Example 10, a workability in a temperature range near room temperature can be secured, and a magnesium alloy capable of achieving both workability and strength was obtained.
  • Example 12 In step 1, as shown in D-1 of Table 1, an alloy having a composition of Mg-1.2Al-0.5Ca-0.4Mn-1.6Zn is melted and cast with a mold to produce a cast solid.
  • the cast solid was held at 300 ° C. for 4 hours, heated to 450 ° C. at a heating rate of 7.5 ° C./h (hours), then held for 6 hours, and then water-cooled to room temperature. To produce a homogenized solid.
  • the sample reheating temperature in the final rolling step is set to 450 ° C., and when the cooling solid is produced by solution treatment of the tangible solid in step 4, the solution treatment temperature is as shown in Table 2.
  • the solution treatment time was 4 hours, and in Step 5, the aging time was 1 h (hours) as shown in Table 3. Otherwise, a magnesium alloy was produced in the same manner as in Example 1.
  • FIG. 12 shows an optical microscope image of the solution treatment material that is a cooling solid.
  • the crystal grain size calculated by the intercept method was 8.5 ⁇ m.
  • FIG. 13 shows a (0002) pole figure obtained by X-ray diffraction of the solution-treated material.
  • the integration degree of the (0002) pole was 3.7.
  • FIG. 14 shows the tensile stress-strain curves of the solution treated material (T4), which is the cooling solid in Step 4, and the aging treated material (T6) in Step 5.
  • Table 3 shows the 0.2% yield strength, tensile strength, elongation, and Erichsen value obtained from the stress-strain curve.
  • the yield strength of the solution treatment material was 160 MPa, and the Erichsen value had excellent room temperature moldability with a value of 8.3 mm. Yield strength did not increase much even after aging treatment. As is clear from the above, a magnesium alloy capable of achieving both workability and strength in a temperature range near room temperature could be obtained.
  • Example 13 When the cooling solid is produced by solution treatment of the tangible solid in step 4, the solution treatment temperature is set to 450 ° C. as shown in Table 2, and the aging time is set to 0. 5 as shown in Table 3 in step 5.
  • a magnesium alloy was produced in the same manner as in Example 12 except that the duration was 5 hours (30 minutes).
  • Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Table 2 and Table 3, as in Example 12, a workability in the temperature range near room temperature can be secured, and a magnesium alloy capable of achieving both workability and strength was obtained.
  • Example 14 In Example 1, the sample temperature and the roll temperature in the final rolling process were set to 200 ° C. as shown in D-2 of Table 1, and the solution treatment time was set to 1 hour as shown in Table 2. In the same manner as in No. 12, a magnesium alloy was produced. Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Table 2 and Table 3, as in Example 12, a workability in the temperature range near room temperature can be secured, and a magnesium alloy capable of achieving both workability and strength was obtained.
  • Example 15 When the cooling solid is produced by solution treatment of the tangible solid in step 4, the solution treatment temperature is set to 450 ° C. as shown in Table 2, and the aging time is set to 0. 5 as shown in Table 3 in step 5.
  • a magnesium alloy was produced in the same manner as in Example 12 except that the duration was 25 hours (15 minutes).
  • Tables 2 and 3 show the production conditions and mechanical characteristics of the obtained solid and the characteristics of the microstructure. As is clear from Table 2 and Table 3, as in Example 12, a workability in the temperature range near room temperature can be secured, and a magnesium alloy capable of achieving both workability and strength was obtained.
  • FIGS. 15 to 17 show the production conditions, mechanical properties, and microstructure characteristics of the obtained solid.
  • FIG. 15 shows an optical microscope image of the solution treatment material that is a cooling solid. The crystal grain size calculated by the intercept method was 9.9 ⁇ m.
  • FIG. 16 shows a (0002) pole figure obtained by X-ray diffraction of the solution-treated material. The integration degree of the (0002) pole was 4.0.
  • FIG. 17 shows the tensile stress-strain curves of the solution treated material (T4), which is the cooling solid in Step 4, and the aging treated material (T6) in Step 5.
  • Table 3 shows the 0.2% yield strength, tensile strength, elongation, and Erichsen value obtained from the stress-strain curve. The yield strength of the solution treatment material was 149 MPa, and the Erichsen value was 6.4 mm. Therefore, as apparent from Table 2, the workability was insufficient.
  • step 1 As shown in B-2 of Table 1, an alloy having a composition of Mg-1.2Al-0.5Ca-0.4Mn-0.3Zn is melted and cast with a mold to produce a cast solid.
  • the cast solid was held at 300 ° C. for 4 hours, heated to 450 ° C. at a heating rate of 7.5 ° C./h, then held for 6 hours, and then water-cooled to room temperature for homogenization. Solidified solids were prepared.
  • step 3 the sample temperature and the roll temperature in the final rolling step are set to 200 ° C., and as shown in Table 2, the solution treatment temperature is set to 350 when the tangible solid is solution treated in step 4 to form a cooling solid.
  • a magnesium alloy was produced in the same manner as in Comparative Example 1 except that the solution treatment time was 1 hour at 0 ° C.
  • Table 2 shows the production conditions, mechanical properties, and microstructure characteristics of the obtained solid. As shown in Table 2, the Erichsen value of the solution-treated material of Comparative Example 12 was 5.8 mm, and the workability was clearly insufficient.

Landscapes

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

Abstract

La présente invention concerne un alliage de magnésium qui est très polyvalent et peut présenter à la fois l'aptitude au façonnage et la résistance dans une plage de température comprenant la température ambiante, et un procédé de fabrication de l'alliage de magnésium, l'alliage de magnésium obtenu contenant de 0,2 à 2 % en poids de Al, 0,2 à 1 % en poids de Mn, 0,2 à 2 % en poids de Zn, et au moins 0,2 à 1 % en poids de Ca, le reste comprend Mg et des impuretés inévitables, et un précipité comprenant Mg, Ca et Al est dispersé sur le plan (0001) d'une phase parente de magnésium.
PCT/JP2018/006088 2017-02-28 2018-02-20 Alliage de magnésium et procédé de fabrication d'alliage de magnésium Ceased WO2018159394A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP18761653.7A EP3572542B1 (fr) 2017-02-28 2018-02-20 Alliage de magnésium et son procédé de fabrication
US16/488,050 US20200239992A1 (en) 2017-02-28 2018-02-20 Magnesium alloy and method for manufacturing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2017-037769 2017-02-28
JP2017037769 2017-02-28
JP2018027358A JP7116394B2 (ja) 2017-02-28 2018-02-19 マグネシウム合金及びマグネシウム合金の製造方法
JP2018-027358 2018-02-19

Publications (1)

Publication Number Publication Date
WO2018159394A1 true WO2018159394A1 (fr) 2018-09-07

Family

ID=63371303

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/006088 Ceased WO2018159394A1 (fr) 2017-02-28 2018-02-20 Alliage de magnésium et procédé de fabrication d'alliage de magnésium

Country Status (1)

Country Link
WO (1) WO2018159394A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019151930A (ja) * 2018-03-03 2019-09-12 国立研究開発法人物質・材料研究機構 マグネシウム合金時効処理材とその製造方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3146096A (en) * 1962-11-23 1964-08-25 Dow Chemical Co Weldable high strength magnesium base alloy
JP2002266044A (ja) 2001-03-09 2002-09-18 Aisin Takaoka Ltd マグネシウム合金
JP2004010959A (ja) 2002-06-06 2004-01-15 Mitsui Mining & Smelting Co Ltd マグネシウム合金板の改質方法及びマグネシウム合金板
JP2009120883A (ja) * 2007-11-13 2009-06-04 Mitsubishi Alum Co Ltd マグネシウム合金箔およびその製造方法
CN101629260A (zh) * 2008-07-18 2010-01-20 中国科学院金属研究所 医用可吸收Mg-Zn-Mn-Ca镁合金
JP2010013725A (ja) 2008-06-05 2010-01-21 National Institute Of Advanced Industrial & Technology 易成形性マグネシウム合金板材及びその作製方法
WO2012049990A1 (fr) * 2010-10-12 2012-04-19 住友電気工業株式会社 Filament d'alliage de magnésium et boulon, écrou et rondelle
JP2013079436A (ja) 2011-10-05 2013-05-02 Kumamoto Univ マグネシウム合金及びその製造方法
JP2016169427A (ja) 2015-03-13 2016-09-23 国立研究開発法人物質・材料研究機構 Ｍｇ合金とその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3146096A (en) * 1962-11-23 1964-08-25 Dow Chemical Co Weldable high strength magnesium base alloy
JP2002266044A (ja) 2001-03-09 2002-09-18 Aisin Takaoka Ltd マグネシウム合金
JP2004010959A (ja) 2002-06-06 2004-01-15 Mitsui Mining & Smelting Co Ltd マグネシウム合金板の改質方法及びマグネシウム合金板
JP2009120883A (ja) * 2007-11-13 2009-06-04 Mitsubishi Alum Co Ltd マグネシウム合金箔およびその製造方法
JP2010013725A (ja) 2008-06-05 2010-01-21 National Institute Of Advanced Industrial & Technology 易成形性マグネシウム合金板材及びその作製方法
CN101629260A (zh) * 2008-07-18 2010-01-20 中国科学院金属研究所 医用可吸收Mg-Zn-Mn-Ca镁合金
WO2012049990A1 (fr) * 2010-10-12 2012-04-19 住友電気工業株式会社 Filament d'alliage de magnésium et boulon, écrou et rondelle
JP2013079436A (ja) 2011-10-05 2013-05-02 Kumamoto Univ マグネシウム合金及びその製造方法
JP2016169427A (ja) 2015-03-13 2016-09-23 国立研究開発法人物質・材料研究機構 Ｍｇ合金とその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
W.J.KIMI.B.PARKS.H.HAN, SCRIPTA MATERIALIA, vol. 66, 2012, pages 590 - 593

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019151930A (ja) * 2018-03-03 2019-09-12 国立研究開発法人物質・材料研究機構 マグネシウム合金時効処理材とその製造方法
WO2019172047A1 (fr) * 2018-03-03 2019-09-12 国立研究開発法人物質・材料研究機構 Matériau d'alliage de magnésium traité par vieillissement et son procédé de production
JP2024020485A (ja) * 2018-03-03 2024-02-14 国立研究開発法人物質・材料研究機構 マグネシウム合金溶体化処理材とその使用方法
JP2024020484A (ja) * 2018-03-03 2024-02-14 国立研究開発法人物質・材料研究機構 マグネシウム合金時効処理材とその製造方法

Similar Documents

Publication Publication Date Title
KR102121156B1 (ko) 표면 로핑이 감소되거나 없는 고성형성 자동차 알루미늄 시트 및 제조 방법
CN103339276B (zh) 螺栓用铝合金线、螺栓及其制造方法
JP6810508B2 (ja) 高強度アルミニウム合金板
JP6433380B2 (ja) アルミニウム合金圧延材
JP2024020485A (ja) マグネシウム合金溶体化処理材とその使用方法
JP2017125240A (ja) アルミニウム合金構造部材およびその製造方法、アルミニウム合金板
JP2016222958A (ja) 高強度アルミニウム合金板
JP7116394B2 (ja) マグネシウム合金及びマグネシウム合金の製造方法
JP2017078211A (ja) 高成形性アルミニウム合金板
WO2013180122A1 (fr) Alliage de magnésium, élément en alliage de magnésium et procédé de fabrication de ce dernier, et procédé d'utilisation de l'alliage de magnésium
CN111989415A (zh) 用于具有优异的碰撞性能和高屈服强度的挤压件的6xxx铝合金及其制备方法
Kuchariková et al. Study of the precipitation hardening process in recycled Al-Si-Cu cast alloys
JP2018154869A (ja) プレス成形性、リジングマーク性、ｂｈ性に優れたアルミニウム合金板
JP7076731B2 (ja) マグネシウム合金及びマグネシウム合金の製造方法
JP2004124213A (ja) パネル成形用アルミニウム合金板およびその製造方法
WO2018159394A1 (fr) Alliage de magnésium et procédé de fabrication d'alliage de magnésium
JP2017210673A (ja) ｒ値の異方性が小さいプレス成形用アルミニウム合金板およびその製造方法
JP6843353B2 (ja) Ｍｇ合金とその製造方法
JP6085473B2 (ja) プレス成形性に優れたアルミニウム合金板
JP5435266B2 (ja) 疲労強度，靭性及び光輝性に優れたアルマイト処理用アルミニウム合金展伸材及びその製造方法
JP4996854B2 (ja) 高温高速成形用アルミニウム合金材及びその製造方法、並びにアルミニウム合金成形品の製造方法
JP7760123B2 (ja) マグネシウム合金時効処理材及びその製造方法、並びにそれを使用したｏａ機器、輸送機器及びその部品
CN119194133A (zh) 一种可回收的铝合金及其制造方法和应用
Matvija et al. Study of the precipitation hardening process in recycled Al-Si-Cu cast alloys

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18761653

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018761653

Country of ref document: EP

Effective date: 20190823