EP3208356B1 - Magnesiumlegierung, magnesiumlegierungsplatte, magnesiumlegierungsteil und verfahren zur herstellung einer magnesiumlegierung - Google Patents
Magnesiumlegierung, magnesiumlegierungsplatte, magnesiumlegierungsteil und verfahren zur herstellung einer magnesiumlegierung Download PDFInfo
- Publication number
- EP3208356B1 EP3208356B1 EP15851242.6A EP15851242A EP3208356B1 EP 3208356 B1 EP3208356 B1 EP 3208356B1 EP 15851242 A EP15851242 A EP 15851242A EP 3208356 B1 EP3208356 B1 EP 3208356B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- magnesium alloy
- inclusive
- particles
- melt
- compounds
- 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.)
- Not-in-force
Links
- 229910000861 Mg alloy Inorganic materials 0.000 title claims description 191
- 238000004519 manufacturing process Methods 0.000 title claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 113
- 229910052782 aluminium Inorganic materials 0.000 claims description 68
- 239000002245 particle Substances 0.000 claims description 68
- 229910052748 manganese Inorganic materials 0.000 claims description 66
- 239000000155 melt Substances 0.000 claims description 56
- 238000001816 cooling Methods 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 15
- 238000009749 continuous casting Methods 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 description 135
- 239000000463 material Substances 0.000 description 68
- 229910045601 alloy Inorganic materials 0.000 description 41
- 239000000956 alloy Substances 0.000 description 41
- 229910018131 Al-Mn Inorganic materials 0.000 description 37
- 229910018461 Al—Mn Inorganic materials 0.000 description 37
- 238000005096 rolling process Methods 0.000 description 33
- 239000000523 sample Substances 0.000 description 28
- 238000013507 mapping Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- 238000005266 casting Methods 0.000 description 23
- 238000005336 cracking Methods 0.000 description 23
- 230000001133 acceleration Effects 0.000 description 18
- 230000035882 stress Effects 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 238000012545 processing Methods 0.000 description 12
- 239000011362 coarse particle Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 10
- 239000002344 surface layer Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 230000001186 cumulative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005728 strengthening Methods 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000009864 tensile test Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007712 rapid solidification Methods 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 230000003685 thermal hair damage Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- INCHANCIPURAPN-NTEUORMPSA-N 2-[(E)-(pyridin-2-ylhydrazinylidene)methyl]benzenethiol Chemical compound Sc1ccccc1\C=N\Nc1ccccn1 INCHANCIPURAPN-NTEUORMPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- 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
-
- 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
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
- 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
-
- 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
Definitions
- the present invention relates to a magnesium alloy suitable for a constituent material of housings, various parts, etc., to a magnesium alloy sheet suitable for raw materials (primary-processed materials) for secondary-processed materials such as housings and various parts, to a magnesium alloy structural member suitable for secondary-processed materials such as housings and various parts, and to a method for producing the magnesium alloy.
- the present invention relates to a magnesium alloy, a magnesium alloy sheet, and a magnesium alloy structural member that are excellent in impact resistance, mechanical properties, and plastic formability and also excellent in productivity.
- Magnesium alloys which are lightweight and excellent in specific strength and specific rigidity, have been increasingly used as constituent materials of various parts such as parts of automobiles and housings of mobile electronic-electric devices such as cellular phones and laptop computers.
- Magnesium alloys are lighter than many other metals, have high specific strength, and also have excellent impact absorption ability. Since various elements are added to active Mg (magnesium), these magnesium alloys also have excellent corrosion resistance and are preferable for the constituent materials of the above-described various parts. Among these magnesium alloys, Mg-Al-based alloys containing Al (aluminum), in particular, are excellent in strength and corrosion resistance and are preferable for the constituent materials described above.
- PTL 1 discloses a magnesium alloy sheet that is composed of a magnesium alloy containing Al and Mn (manganese) and is excellent in impact resistance and mechanical properties not only at ordinary temperature but also at low temperature.
- This magnesium alloy sheet contains compounds containing Al and Mn (mainly precipitates in crystal. These may be hereinafter referred to as Al-Mn crystallized phases).
- the Al-Mn crystallized phases are very fine and are very small in amount and preferably are not substantially present. Therefore, in this magnesium alloy sheet, cracking etc. caused by coarse Al-Mn crystallized phases are unlikely to occur. Therefore, the magnesium alloy sheet is excellent in impact resistance and mechanical properties and also excellent in plastic formability such as press formability.
- EP 2 453 031 discloses magnesium alloy plate for housings which discloses Al-Mn particles in the microstructure.
- magnesium alloy excellent in impact resistance, mechanical properties such as strength, proof stress, and elongation, and plastic formability such as rolling formability and press formability and also excellent in productivity.
- the magnesium alloy sheet disclosed in PTL 1 is excellent in impact resistance etc. as described above.
- the temperature of a melt of the alloy is set to be relatively high, i.e., 700°C.
- the Al-Mn crystallized phases are formed and grow most easily when the temperature of the melt of the magnesium alloy containing Al and Mn is around 630°C, particularly lower than 630°C. Therefore, when the temperature of the melt of the alloy is sufficiently higher than 630°C, preferably higher than 690°C, the formation and growth of the Al-Mn crystallized phases can be effectively prevented.
- One object of the present invention is to provide a magnesium alloy excellent in impact resistance, mechanical properties, and plastic formability and also excellent in productivity.
- Another object of the present invention is to provide a magnesium alloy sheet excellent in impact resistance, mechanical properties, and plastic formability and also excellent in productivity.
- Still another object of the present invention is to provide a magnesium alloy structural member excellent in impact resistance and mechanical properties and also excellent in productivity.
- Yet another object of the present invention is to provide a magnesium alloy production method that can produce a magnesium alloy excellent in impact resistance, mechanical properties, and plastic formability with high productivity.
- a magnesium alloy according to one aspect of the present invention contains, in mass%, from 1% to 12% inclusive of Al and from 0.1% to 5% inclusive of Mn and has a structure in which particles of a compound containing Al and Mn are dispersed.
- the average diameter of the particles of the compound is from 0.3 ⁇ m to 1 ⁇ m inclusive, and the area ratio of the particles of the compound is from 3.5% to 25% inclusive.
- a magnesium alloy production method includes the step of subjecting a melt of a magnesium alloy containing, in mass%, from 1% to 12% inclusive of Al and from 0.1% to 5% inclusive of Mn to continuous casting.
- the temperature of the melt immediately before it comes into contact with a mold is from 630°C to 675°C inclusive, and the cooling rate of the melt is 560°C/second or higher.
- the above magnesium alloy is excellent in impact resistance, mechanical properties, and plastic formability and also excellent in productivity.
- the above magnesium alloy production method can produce a magnesium alloy excellent in impact resistance, mechanical properties, and plastic formability with high productivity.
- the present inventors have produced magnesium alloys having compositions containing Al and Mn and capable of providing, in particular, excellent strength and corrosion resistance under various production conditions to examine the structure of a magnesium alloy excellent in impact resistance, mechanical properties, and plastic formability. Then the inventors have found that a magnesium alloy having a structure in which compounds containing Al and Mn (Al-Mn crystallized phases) and having a size within a specific range are contained in an amount within a specific range can have impact resistance, mechanical properties, and plastic formability substantially comparable to those of a magnesium alloy containing only a very small amount of the above-described compounds or substantially no such compounds.
- the magnesium alloy when the magnesium alloy has a structure containing a certain amount of the above-described compounds and these compounds are relatively fine and distributed uniformly, the magnesium alloy can have impact resistance, mechanical properties, and plastic formability substantially comparable to those of a magnesium alloy containing only a very small amount of the above-described compounds or substantially no such compounds.
- the inventors have also found that the magnesium alloy having the above-described specific structure can be produced by a specific casting process including performing continuous casting such that the temperature of the melt of the alloy before it comes into contact with the mold is set to be as low as possible and that the rate of cooling is very high. In this production method, the melt of the alloy is maintained at a relatively low temperature.
- the average diameter of the particles of the compound is measured using an image observed under an optical microscope.
- the area ratio of the particles of the compound is measured by a compositional mapping of a cross section of the magnesium alloy by an FE-EPMA at an electron gun acceleration voltage of 5 kV or 15 kV. The details of the measurement method will be described later.
- the above magnesium alloy contains Al and Mn in amounts within the specific ranges and is therefore excellent in strength and also excellent in corrosion resistance.
- the particles of the compound containing Al and Mn are present in a certain amount within the specific range, the particles are fine. Therefore, even when the magnesium alloy receives an impact of, for example, dropping or is subjected to plastic forming such as rolling or press forming, the particles are unlikely to serve as starting points of cracking etc., so that the magnesium alloy is excellent in impact resistance, plastic formability, and mechanical properties such as strength proof stress, and elongation.
- the magnesium alloy has a dispersion strengthened structure in which the above-described fine particles of the compound are dispersed.
- This dispersion strengthened structure increases the proof stress, and therefore the magnesium alloy is resistant to denting and is excellent in impact resistance.
- the magnesium alloy having the above-described specific composition and structure can be produced by, for example, a specific casting step described later and is therefore also excellent in productivity.
- the melt of the magnesium alloy containing Al and Mn in amounts within the specific ranges is used, and this allows the magnesium alloy produced to have excellent strength and corrosion resistance.
- the temperature of the melt is set to be lower than the temperature conventionally used. At the set temperature, compounds containing Al and Mn (Al-Mn crystallized phases) are easily formed.
- the cooling rate is set to be very high, so that the time during which the material is held at around 630°C in the course of solidification can be shortened. Therefore, with the above magnesium alloy production method, only an appropriate amount of the Al-Mn crystallized phases can be formed in the alloy.
- the growth of the particles of the Al-Mn crystallized phases is suppressed, so that relatively fine particles of the Al-Mn crystallized phases, typically particles of the Al-Mn crystallized phases having an average diameter of 1 ⁇ m or less, are present.
- relatively fine particles of the Al-Mn crystallized phases typically particles of the Al-Mn crystallized phases having an average diameter of 1 ⁇ m or less.
- the particles of the Al-Mn crystallized phases grow.
- a structure in which coarse particles having a maximum diameter of 2.5 ⁇ m or more are unevenly distributed may be obtained. These coarse particles can serve as starting points of cracking etc. Since Al and Mn are contained in the coarse particles, the amounts of Al and Mn necessary for fine particles may not remain, so that the amount of the fine particles present may not be sufficient. In this case, the dispersion strengthening effect of the fine Al-Mn crystallized phases may not be obtained sufficiently. Therefore, in a magnesium alloy in which coarse Al-Mn crystallized phases are present locally, impact resistance, mechanical properties, and plastic formability may deteriorate.
- the magnesium alloy produced can be excellent in impact resistance and mechanical properties such as strength and proof stress because of dispersion strengthening by the particles of the Al-Mn crystallized phases that are generally harder than the magnesium alloy serving as the matrix phase.
- the particles of the Al-Mn crystallized phases are fine, and these fine particles are unlikely to serve as starting points of cracking etc. Therefore, the magnesium alloy produced can also be excellent in toughness such as elongation, impact resistance, and plastic formability.
- a magnesium alloy, a magnesium alloy sheet, a magnesium alloy structural member, and a magnesium alloy production method according to an embodiment of the present invention will be described one by one.
- the unit of the content of each element is percent by mass.
- the magnesium alloy has a composition containing at least both Al and Mn as additive elements.
- the magnesium alloy may contain, in addition to the composition containing Al and Mn, a second additive element described later, so long as a specific amount of compounds containing Al and Mn (Al-Mn crystallized phases) having a specific size can be formed in the production process.
- the balance is Mg and inevitable impurities, and the content of Mg is more than 50%.
- the content of Al is from 1% to 12% inclusive.
- excellent mechanical properties such as strength and excellent corrosion resistance, in particular, are obtained.
- the larger the content of Al within the above range the higher the strength and the corrosion resistance. Therefore, the content of Al may be 3% or more, 5% or more, 5.5% or more, and 7% or more.
- a magnesium alloy containing Al in an amount of from 8.3% to 9.5% inclusive e.g., an ASTM standard AZ91 alloy, has mechanical properties and corrosion resistance superior to those of a magnesium alloy containing Al in an amount of about 3%, e.g., an ASTM standard AZ31 alloy. The lower the content of Al within the above range, the more easily plastic forming such as bending can be performed.
- the content of Al may be 7% or less and particularly 4% or less.
- the content of Al that provides a good balance between strength and workability may be from 5.5% to 12% inclusive.
- Part of Al in the alloy is present as compounds such as intermetallic compounds typified by compounds containing Al and Mn and compounds containing Al and Mg, and the other part is dissolved in Mg to form a solid solution.
- the content of Mn is from 0.1% to 5% inclusive.
- Mn is contained within the above range, excellent corrosion resistance is obtained.
- the larger the content of Mn the more easily the compounds containing Al and Mn are formed and grow. In this case, the amount of solute Al tends to decrease, and coarse compound particles tend to be present. Therefore, the content of Mn may be 2% or less, 1.5% or less, and particularly 1% or less.
- a Mn content of from 0.2% to 0.5% inclusive is expected to effectively suppress excessive formation and growth of the above compounds.
- the second additive element may be at least one element selected from Zn (zinc), Ca (calcium), Si (silicon), Be (beryllium), Sr (strontium), Y(yttrium), Ag (silver), Sn (tin), Zr (zirconium), Ce (cerium), Au (gold), and rare-earth elements (excluding Y and Ce).
- the specific content of Zn may be from 0.2% to 7.0% inclusive, and the specific content of Ca may be from 0.2% to 6.0% inclusive.
- the specific content of Si may be from 0.2% to 1.0% inclusive, and the specific content of Be may be from 0.0001% to 0.002% inclusive.
- the specific content of Sr may be from 0.2% to 7.0% inclusive, and the specific content of Y may be from 1.0% to 6.0% inclusive.
- the specific content of Ag may be from 0.5% to 3.0% inclusive, and the specific content of Sn may be from 0.01% to 2.0% inclusive.
- the specific content of Zr may be from 0.1% to 1.0% inclusive, and the specific content of Ce may be from 0.05% to 1.0% inclusive.
- the specific contents of rare-earth elements (excluding Y and Ce) may be from 1.0% to 3.5% inclusive.
- the second additive element contained can provide the following effects: various excellent properties including mechanical properties such as strength and elongation (e.g., Zn, Zr, etc.), high-temperature strength and creep resistance (e.g., Si, rare-earth elements, Ag, etc.), and flame resistance (e.g., Ca etc.); a reduction in crystal size; and suppression of hot cracking (e.g., Zr etc.).
- mechanical properties such as strength and elongation (e.g., Zn, Zr, etc.), high-temperature strength and creep resistance (e.g., Si, rare-earth elements, Ag, etc.), and flame resistance (e.g., Ca etc.); a reduction in crystal size; and suppression of hot cracking (e.g., Zr etc.).
- Specific production conditions described later may be used to produce a magnesium alloy having a composition including Al and Mn in amounts within the above specific ranges and further including the second additive element.
- the compounds containing Al and Mn and having a specific size are contained
- composition of the magnesium alloy containing Al and Mn include the following.
- the AZ-based alloys contain, in addition to Al and Mn, from 0.2% to 1.5% inclusive of Zn as the second additive element.
- Al content in the AZ-based alloys increases, the mechanical properties such as strength and proof stress and corrosion resistance tend to be improved.
- the plastic formability tends to be improved.
- the magnesium alloy in the embodiment has a structure in which relatively fine particles formed of compounds containing Al and Mn are uniformly dispersed.
- the compounds containing Al and Mn are crystallized phases that are formed mainly during casting. These crystallized phases have high hardness. When the crystallized phases are once formed, it is difficult to change their size and content during a production process after the casting. Therefore, in the magnesium alloy in the embodiment, specific casting conditions described later, for example, are used to control the size and content of the above-described compounds (crystallized phases).
- Examples of the compounds containing Al and Mn include intermetallic compounds containing only Al and Mn and intermetallic compounds containing iron (Fe) etc. in addition to Al and Mn. Fe contained in the latter intermetallic compounds is an inevitable impurity.
- the compositions of these compounds can be examined by component analysis using energy dispersive X-ray analysis (EDX) or Auger electron spectroscopy (AES).
- the compounds containing Al and Mn are present as particles in the matrix of the magnesium alloy in the embodiment.
- the average diameter of the particles of the compounds is from 0.3 ⁇ m to 1 ⁇ m inclusive. When the average particle diameter is within the above range, the particles of the compounds can well function as a dispersion strengthening material for the structure and are less likely to serve as starting points of cracking, so that the magnesium alloy is excellent in impact resistance, mechanical properties, and plastic formability.
- the average particle diameter can be from 0.3 ⁇ m to 0.9 ⁇ m inclusive and particularly from 0.35 ⁇ m to 0.8 ⁇ m inclusive.
- the maximum diameter of the compounds containing Al and Mn is less than 2.5 ⁇ m.
- coarse particles of 2.5 ⁇ m or more are not present, cracking originating from such coarse particles is unlikely to occur, and deterioration of impact resistance, mechanical properties, and plastic formability caused by such coarse particles can be suppressed.
- a reduction in the amount of fine particles due to the presence of these coarse particles can be suppressed, so that an appropriate amount of fine particles can be contained. Therefore, the magnesium alloy can be excellent in impact resistance, mechanical properties, and plastic formability.
- the smaller the compounds the smaller the number of coarse particles serving as the starting points of cracking, and the more easily a structure containing an appropriate amount of fine particles is obtained.
- the maximum diameter is preferably 2 ⁇ m or less, more preferably 1.5 ⁇ m or less, still more preferably 1.2 ⁇ m or less, and yet more preferably 1 ⁇ m or less.
- the average particle diameter of the above compounds is within the above range and the maximum diameter of the above compounds is less than 2.5 ⁇ m and preferably 2 ⁇ m or less, the variations in size of the above compounds are small, and the size is uniform. Therefore, in this form, variations in characteristics due to the variations in size of the above compounds can also be suppressed, and good characteristics can be achieved.
- the content of the compounds containing Al and Mn is determined by the area ratio of the compounds in a cross section of the magnesium alloy, and the area ratio is from 3.5% to 25% inclusive.
- the area ratio is 3.5% or more, a sufficient amount of the above compounds is present in the magnesium alloy, and the dispersion strengthening effect of the particles of the compounds can be preferably obtained.
- the area ratio is 25% or less, an appropriate amount of the above compounds is present, and the embrittlement of the alloy due to the presence of an excessive amount of the above compounds, a reduction in corrosion resistance due to a reduction in the amount of solute Al, etc. are suppressed, so that the magnesium alloy is excellent in impact resistance, mechanical properties, and plastic formability.
- the area ratio is measured as follows. A cross section of the magnesium alloy is taken, and an observation field described below (e.g., a square region of 195 ⁇ m ⁇ 195 ⁇ m) is selected in the cross section. A compositional mapping by FE-EPMA is performed on the observation field to determine the distribution of the concentration of Mn. Assume that substantially all the Mn in the observation field is present as the compounds containing Al and Mn. Then the area ratio of Mn in the observation field is regarded as the area ratio of the compounds containing Al and Mn. Specifically, the distribution of the Mn concentration determined by the compositional mapping is used to determine the area ratio of the above compounds. A specific computation method will be described later.
- a region of the magnesium alloy that extends inwardly from its surface to a depth of 30% of the thickness of the magnesium alloy is referred to as a surface layer region, and the above-described observation field is selected in this surface layer region.
- the reason that the observation field is selected in the surface layer region is that a region that undergoes cracking and directly receives an impact of, for example, dropping may generally be the surface layer region.
- the distribution of the Mn concentration varies depending on the acceleration voltage of an electron gun used in the FE-EPMA. As the acceleration voltage increases, the amount of information obtained tends to increase, and the concentration (level) of Mn tends to increase. Specifically, the value of the area ratio may vary depending on the magnitude of the acceleration voltage. To measure the area ratio, the acceleration voltage of the electron gun is 15 kV or less.
- the area ratio when the compositional mapping by the FE-EPMA is performed on the observation field in the cross section using an electron gun acceleration voltage of 15 kV is 9.5% or more, from 10% to 25% inclusive, and particularly from 15% to 24% inclusive.
- the area ratio when the compositional mapping by the FE-EPMA is performed on the observation field in the cross section using an electron gun acceleration voltage of 5 kV is from 3.5% to 15% inclusive, from 4.0% to 12% inclusive, and particularly from 5.0% to 10% inclusive.
- the magnesium alloy has a fine crystalline structure.
- a structure in which the average crystal grain size satisfies 10 ⁇ m or less is a structure in which the average crystal grain size satisfies 10 ⁇ m or less.
- the average crystal grain size is 10 ⁇ m or less, substantially no coarse crystal grains are present, and the occurrence of cracking due to coarse crystal grains can be reduced. Therefore, in this form, the magnesium alloy is more excellent in impact resistance, mechanical properties such as strength and elongation, and plastic formability.
- the smaller the crystal grains the more effectively the occurrence of cracking due to coarse crystal grains can be reduced.
- the average crystal grain size may be, for example, 6 ⁇ m or less and particularly 4 ⁇ m or less.
- the lower limit of the average crystal grain size may be, for example, 2 ⁇ m and particularly 1 ⁇ m.
- plastic forming such as rolling after casting.
- Representative examples of the magnesium alloy having a fine crystalline structure include rolled sheets and press-formed sheets obtained by subjecting the rolled sheets to press forming. It is expected that the crystal grain size can be further reduced easily by increasing the cooling rate in the casting step (560°C/second or higher and particularly 600°C/second or higher) or adding the second additive element described above.
- Specific forms of the magnesium alloy in the embodiment are classified by their production process as follows.
- Cast material (2) Primary-processed material (such as a rolled material) prepared by subjecting the cast material to plastic forming (primary processing) such as rolling.
- Primary processing such as rolling.
- Treated material prepared by subjecting the primary-processed material to various types of treatment such as polishing, leveling, heat treatment performed for the purpose of, for example, removal of strain, anticorrosive treatment (chemical conversion treatment, anodic oxidation treatment), treatment for decoration purposes (cutting such as diamond cut finishing and hairline finishing, etching, shot blasting, etc.), and coating treatment.
- Secondary-processed material (a magnesium alloy structural member in the embodiment) prepared by subjecting the primary-processed material or the above treated material to plastic forming (secondary processing) such as press forming.
- Secondary-treated material (a magnesium alloy structural member in the embodiment) prepared by subjecting the secondary-processed material to surface treatment such as anticorrosive treatment, coating, or processing for decoration.
- their average crystal grain size is smaller than that of the cast material as described above, and cracking etc. are less likely to occur. Therefore, they can be used as raw materials for secondary-processed materials such as press-formed materials.
- the entire portion of the primary-processed material is subjected to plastic forming and is therefore a plastically formed portion.
- the secondary-processed material may be in such a form that only part of the raw material is subjected to plastic forming to form a plastically formed portion (e.g., a press-formed material having a bent portion) or may be in such a form that the entire portion of the raw material is subjected to plastic forming (e.g., a processed material bent into a cylindrical shape).
- the shape of the magnesium alloy in the embodiment include a sheet having first and second surfaces parallel to each other (a magnesium alloy sheet in the embodiment).
- the first and second surfaces are typically flat surfaces but may be subjected to, for example, bending to form bent surfaces.
- the planar shape of the sheet is typically rectangular, but the sheet may be punched into a circular shape or any other shape.
- the sheet may have any of the following forms classified by their production process described above: (1) a cast material, (2) a primary-processed material (such as a rolled sheet), (3) a treated material, (4) a secondary-processed material, and (5) a surface-treated material.
- Specific examples of the shape of the secondary-processed material include a member including a bottom portion and side wall portions extending from the bottom portion and having a rectangular U-shaped cross section (a member having a sheet portion).
- the thickness of the sheet may be 5 mm or less.
- the thickness of the sheet is the average distance between the first and second surfaces.
- the thickness can be easily made uniform over the entire sheet and can be further reduced easily.
- the thickness may be about 3 mm or less and particularly 2.5 mm or less. The larger the thickness of the sheet, the higher the strength and stiffness.
- the thickness of the sheet is small (preferably 2 mm or less, more preferably 1.5 mm or less, and still more preferably 1.2 mm or less), a thin and lightweight primary-processed material and secondary-processed material can be formed.
- the lower limit of the thickness of the sheet may be 0.1 mm or more and particularly 0.3 mm or more.
- the thickness of the final sheet may be selected by controlling the casting conditions, the rolling conditions, etc. according to its desired application purpose. In forms other than the forms in which the thickness is uniform over the entire sheet and the entire member, portions with different thicknesses may be present (e.g., a form in which a through hole is provided and a form in which a groove or a protrusion is provided).
- the magnesium alloy in the embodiment is excellent in mechanical properties such as strength, proof stress, and elongation.
- at least one of a tensile strength (room temperature) of 270 MPa or more, a 0.2% proof stress (room temperature) of 200 MPa or more, and a rupture elongation (room temperature) of 5% or more is satisfied.
- all the three are satisfied.
- Examples of such a form include the magnesium alloy subjected to the above-described plastic forming such as rolling, i.e., the primary-processed material and the secondary-processed material.
- At least one of a tensile strength of from 280 MPa to 450 MPa inclusive, a 0.2% proof stress of from 230 MPa to 350 MPa inclusive, and a rupture elongation of from 5% to 15% inclusive can be satisfied, and preferably all the three can be satisfied. However, this depends on the composition, the production process, etc.
- the magnesium alloy in the embodiment is less likely to be dented when the alloy receives an impact of, for example, dropping.
- the amount of dent is small and is less than 0.63 mm.
- the magnesium alloy in the embodiment has been subjected to the above-described plastic forming such as rolling, i.e., is a primary-processed material or a secondary-processed material, the amount of dent is further small and is 0.6 mm or less and particularly 0.55 mm or less.
- the method includes a specific casting step in order to form a structure in which compounds having specific compositions, i.e., compounds containing Al and Mn, are contained in a specific amount and have a specific size.
- this casting step includes the following three conditions: (1) Continuous casting is performed. (2) The temperature of the melt is set to be relatively low. (3) The cooling rate of the melt is set to be very high. The casting step will next be described in detail, and then steps after the casting will be described.
- a melt of a magnesium alloy having a specific composition containing Al and Mn within the specific ranges described above is prepared, and then continuous casting is performed.
- rapid solidification can be performed. Therefore, the amount of oxide and the amount of segregation can be reduced, and the formation of coarse crystallized phases can be easily reduced.
- the size of the compounds containing Al and Mn can be easily controlled to the above-described specific value.
- Specific examples of the continuous casting process include a twin-roll process.
- the twin-roll process is suitable for production of a cast sheet. In the twin-roll process, the cooling rate can be increased by reducing the thickness of the cast sheet (to preferably 5 mm or less), reducing the temperature of the rolls (to preferably 100°C or lower), changing the material of the rolls, etc.
- the temperature of the melt before it comes into contact with a mold is from 630°C to 675°C inclusive.
- the reason that the lower limit is defined as above is that, when the temperature of the melt is lower than 630°C, the compounds containing Al and Mn are very easily formed.
- the reason that the upper limit is defined as above is that, when the temperature is higher than 675°C, productivity becomes low because the temperature of the melt is excessively high.
- the compounds containing Al and Mn can be preferably formed during the solidification process and contained in an appropriate amount (the specific amount described above). To form the above compounds sufficiently, it is preferable that the temperature of the melt is as low as possible.
- the temperature of the melt is 635°C or higher, 640°C or higher, and particularly 645°C or higher, excessive formation and coarsening of the above compounds can be easily suppressed, and the amount and size of the above compounds can be easily controlled. Therefore, it is expected that the productivity can be improved.
- the melting temperature tends to increase. The temperature of the melt is controlled within the above range according to the composition.
- the melt Before the melt comes into contact with the mold, the melt is held in facilities such as a melting furnace, a conveying launder, and a holding furnace.
- facilities such as a melting furnace, a conveying launder, and a holding furnace.
- the temperature of the melt in these facilities for holding the melt is set to be uniform, i.e., to a temperature selected within the range of from 630°C to 675°C inclusive, the temperature can be easily controlled. Since this temperature range is relatively lower than the conventional range, thermal damage to the facilities can be easily reduced, and the service life of the facilities can be extended. From this point of view, it is expected to improve the productivity and reduce the cost.
- the above melt having a relatively low temperature is rapidly cooled at a cooling rate of 560°C/second or higher.
- retention time at around 630°C that is within a temperature range in which the compounds containing Al and Mn are easily formed in the solidification process is sufficiently short.
- excessive formation and coarsening of the above compounds can be effectively suppressed, and a structure in which the above compounds are present in a certain amount and are relatively fine can be preferably formed.
- the higher the cooling rate the more preferable.
- the cooling rate may be 600°C/second or higher, 620°C/second or higher, and particularly 650°C/second or higher.
- the cast material obtained by the above-described rapid solidification has a dispersion strengthened structure in which the above compounds having the above-described specific size are uniformly dispersed in at least the surface layer region of the cast material. In this structure, the crystals are also fine.
- the DAS is denoted by d AZ
- Test pieces with different compositions and sizes are used to determine the relation between the DAS and the cooling rate in advance, and correlation data is produced. Good workability is obtained when the cooling conditions are controlled using this correlation data such that a desired cooling rate is achieved.
- Examples of the method for achieving a cooling rate of 560°C/second or higher include the following.
- the surface temperature of the mold is reduced (e.g., to 100°C or lower and particularly 80°C or lower).
- a forced cooled mold such as a water-cooled mold is used. In this case, the surface temperature of the mold can be maintained low.
- the size of the cast material is reduced. For example, when the cast material is a cast sheet, its thickness is 5 mm or less, 4.5 mm or less, and particularly 4 mm or less.
- a mold formed of a material having high cooling ability is used. For example, when a mold formed of a material with high thermal conductivity is used, the cooling rate can be increased because of the high heat radiation performance of the mold.
- the casting step (including the cooling step) is performed in an inert gas atmosphere in order to prevent, for example, oxidation of the magnesium alloy.
- the above-described cast material (typically a cast sheet) is subjected to at least one rolling pass.
- the magnesium alloy production method in the embodiment includes the casting step described above and the step of subjecting the cast material obtained by the continuous casting to at least one rolling pass (this step may be hereinafter referred to as a rolling step).
- the at least one rolling pass is warm rolling at a rolling temperature of from 200°C to 400°C inclusive.
- the number of passes in the rolling step, a rolling reduction per pass, the total rolling reduction, etc. may be appropriately selected such that a rolled sheet with a desired thickness is obtained.
- a rolled structure (typically a recrystallized structure) can be obtained instead of a cast structure.
- a rolled structure typically a recrystallized structure
- the following effects are expected.
- a fine structure having an average crystal grain size of 20 ⁇ m or less and particularly 10 ⁇ m or less is easily obtained.
- the occurrence of internal defects and surface defects such as segregation, shrinkage cavities, and pores during casing can be reduced, and a good surface texture can be obtained.
- the formation of a fine recrystallized structure easily allows the strength and corrosion resistance to be further improved.
- the rolled sheet obtained through the above-described rolling step has a dispersion strengthened structure in which at least its surface layer region has a finer crystalline structure and the compounds containing Al and Mn having the above-described specific size are uniformly dispersed.
- the production method may further include, after the rolling step, the step of performing at least one additional process such as the above-described polishing, leveling, anticorrosive treatment, coating, processing for decoration purposes, and heat treatment for the purpose of, for example, removal of strain.
- one exemplary form of the magnesium alloy production method in the embodiment includes the above-described casting step, the above-described rolling step, and the step of subjecting at least part of the raw material subjected to the rolling step to plastic forming (secondary processing).
- the plastic forming (secondary processing) include press forming (deep drawing, punching, upsetting, etc.), forging, and bending.
- the plastic forming is performed as warm working at a processing temperature of from 200°C to 280°C inclusive. This is because since the plastic formability of the raw material (typically the above rolled sheet) is improved, the plastic forming (secondary processing) can be performed with high precision. With the warm working, the amount of a coarse recrystallized structure in the structure of the raw material can be reduced, so that the deterioration of the mechanical properties and corrosion resistance can be reduced.
- the plastic forming (secondary processing) may be performed on only part of the raw material or on the entire raw material.
- the production method may further include, after the secondary processing step, the step of performing at least one additional process such as the above-described polishing, anticorrosive treatment, coating, processing for decoration purposes, and heat treatment for the purpose of, for example, removal of strain.
- the magnesium alloy in the embodiment and its production method will be described more specifically by way of a Test Example.
- Magnesium alloys having different compositions shown in Table 1 were used to produce magnesium alloy sheets under various conditions, and these magnesium alloy sheets were subjected to press forming to produce press-formed materials. For each of the magnesium alloy sheets obtained, structural observation, a tensile test (ordinary temperature), an impact resistance test (ordinary temperature), a pass/fail check of press formability, and a pass/fail determination of productivity were performed.
- the content of each element is represented by percent by mass (mass%).
- cast sheets (magnesium alloy sheets), rolled sheets (magnesium alloy sheets), and press-formed materials (magnesium alloy structural members) were produced using a production process including twin-roll continuous casting, rolling, and press forming in this order.
- an ingot of a magnesium alloy having one of the compositions shown in Table 1 was melted in an inert atmosphere to prepare a melt of the alloy.
- the temperature of the melt immediately before it comes into contact with the mold (hereinafter referred to as molten alloy temperature, °C) is shown in Table 1.
- a facility including a melting furnace, a holding furnace for holding the melt, and a conveying unit for conveying the melt from the holding furnace to the mold (a pair of rolls) was used, and the temperature of the melt in the conveying unit is used as the "molten alloy temperature.”
- the temperature of the melt in the conveying unit is the temperature setting of the facility. The melt was brought into contact with the mold (rolls) and thereby solidified to produce a cast sheet having a thickness of 5.0 mm.
- the cooling rate (°C/second) in the casting step is shown in Table 1.
- the cooling rate was changed by controlling the temperature of the rolls, the peripheral speed of the rolls, the rate of casting, etc.
- samples Nos. 1-1 to 1-5, and 1-101 a water-cooled mold was used, and the casting was performed while the rolls were cooled such that the roll temperature was 100°C or lower.
- Each of the cast sheets obtained was subjected to a plurality of warm rolling passes to produce a rolled sheet with a thickness of 0.7 mm.
- the conditions of the warm rolling were a rolling temperature of from 200°C to 400°C inclusive, a rolling reduction per pass of from 5% to 20% inclusive, and a total rolling reduction of 86%.
- Each of the rolled sheets obtained was cut into a 200 mm ⁇ 30 mm piece, and the cut piece was used as a raw material for pressing.
- the raw material was subjected to press forming (square cup drawing) to produce a press-formed material having a rectangular U-shaped cross section and including a top portion and leg portions extending from the top portion.
- the press conditions were a heating temperature of 250°C, and a corner R connecting the top portion and a leg portion was 2 mm.
- each of the cast sheets may be subjected to heat treatment (solution treatment) for homogenization of the structure or aging treatment, subjected to intermediate heat treatment during rolling, or subjected to final heat treatment after final rolling.
- the rolled sheet may be subjected to leveling to improve flatness or may be subjected to polishing to further smoothen the surface.
- FIG. 1 An upper part of Figure 1 shows a secondary electron image obtained by SEM observation of the selected observation field in the rolled sheet of sample No. 1-1, and the lower part shows a binary image obtained by binarizing the secondary electron image.
- Figure 2 is a backscattered electron image obtained by SEM observation of the selected observation field.
- the white particles are uniformly dispersed in the crystalline structure. As also can be seen, a certain amount of the white particles is present, although the white particles are smaller than the ⁇ phase and the amount of the white particles is smaller than the amount of the ⁇ phase. This can also be seen from Figure 2 . As can also be seen in the SEM backscattered electron image shown in Figure 2 , light grey particles and white particles are present. A certain amount of the white particles is present, although the white particles are smaller than the light grey particles and the amount of the white particles is smaller than the amount of the light grey particles. It was therefore found that, in the rolled sheet of sample No.
- the rolled sheets of samples Nos. 1-2 to 1-5 have the same structure as the rolled sheet of sample No. 1-1, i.e., have a fine crystalline structure in which the relatively small Al-Mn crystallized phases are present in a certain amount and are uniformly distributed.
- the above-described white particles in the SEM image (the binary image converted from the secondary electron image) were extracted as the compounds containing Al and Mn (Al-Mn crystallized phases), and the average diameter ( ⁇ m) and the maximum diameter ( ⁇ m) of the extracted particles of the Al-Mn crystallized phases were examined.
- the results are shown in Table 1.
- the diameters of the particles of the Al-Mn crystallized phases were determined as follows. The diameters of circles having the same areas as the extracted particles were determined.
- the average of the diameters of all the particles present in the observation field (a 195 ⁇ m ⁇ 195 ⁇ m square region selected in the above-described surface layer region) was used as the average particle diameter of the Al-Mn crystallized phases.
- the largest value among the diameters of all the particles was used as the maximum diameter of the Al-Mn crystallized phases.
- a compositional mapping by FE-EPMA was produced in the observation field selected in the CP cross section to examine the distribution of the Mn concentration.
- the concentration of Mn was analyzed under two different conditions with different electron gun acceleration voltages. These conditions are shown below.
- Figure 3 shows an FE-EPMA compositional mapping of Mn in the rolled sheet of sample No. 1-1 under conditions (1) with an acceleration voltage of 15 kV.
- a color scale is shown on the right side of Figure 3 .
- the concentration of Mn is represented by a color shade changing from white, pink, red, orange, yellow, green, light blue, blue, to black.
- a color close to white means a high Mn concentration
- a color close to black means a low Mn concentration.
- the level of Mn at a point with the highest Mn concentration is set to 135, and the level of Mn at a point with no Mn is set to 0. Then the concentration of Mn at each point is represented by a value relative to the level 135.
- the percentage of each level is represented as an area ratio (Area %).
- Area % As shown in the compositional mapping in Figure 3 , a large number of regions composed of red-to-blue particle-like clusters are present in a black background.
- the red-to-blue particle-like regions in the compositional mapping were found to be included in the compounds containing Al and Mn (Al-Mn crystallized phases). This may show that Mn in the rolled sheet of sample No. 1-1 is present as the Al-Mn crystallized phases. Therefore, in this case, all the Mn present is treated as compounds with Al.
- Figure 4 is a graph of the frequency of the level of Mn (the number of Mn counts) and the cumulative frequency produced using the compositional mapping (15 kV) of Mn shown in Figure 3 .
- the horizontal axis represents the level of Mn (0 to 135, the level is shown up to 110 in Figure 4 ).
- the left vertical axis represents the frequency of the level of Mn, and the right vertical axis represents the cumulative frequency (%) of the level of Mn.
- the cumulative frequency at a level of Mn is equivalent to the area ratio (Area %) at this level.
- the average S Level of the levels of Mn was computed and found to be S Level ⁇ 10, and the overall concentration of Mn was found to be very small. Therefore, when regions in which the level of Mn is about the average S Level are treated as noise, Mn may be more suitably extracted. Specifically, the compounds containing Al and Mn (Al-Mn crystallized phases) may be more suitably extracted.
- the standard deviation ⁇ Level of the levels of Mn was determined. Then the average S Level + 3 ⁇ Level was used as a threshold value, and regions in which the level of Mn was equal to or larger than the average S Level + 3 ⁇ Level were treated as the Al-Mn crystallized phases.
- a left part of Figure 5 shows an FE-EPMA compositional mapping of Mn in the rolled sheet of sample No. 1-1 when conditions (2) with an acceleration voltage of 5 kV were used, and the right part shows an SEM image (backscattered electron image) in the same observation field.
- the concentration of Mn is represented by a color shade, as in Figure 3 .
- the level of Mn at a point with the highest Mn concentration is set to 55, and the level of Mn at a point with no Mn is set to 0.
- the percentage of each level is represented by an area ratio (Area %).
- the irradiation energy of the electron gun is smaller than that of conditions (1), and the amount of information about Mn is smaller than that under conditions (1), so that the maximum level of Mn is small, i.e., 55.
- the color shade of Mn can be observed, and red-to-blue particle-like clusters are present, as in the compositional mapping in Figure 3 .
- the red-to-blue particle-like regions in the compositional mapping were found to be the compounds containing Al and Mn (Al-Mn crystallized phases).
- Figure 6 is a graph of the frequency of the level of Mn (the number of Mn counts) and the cumulative frequency produced using the compositional mapping (5 kV) of Mn shown the left part of Figure 5 .
- the horizontal axis represents the level of Mn (0 to 55, the level is shown up to 50 in Figure 6 ).
- the left vertical axis represents the frequency of the level of Mn, and the right vertical axis represents the cumulative frequency (%) of the level of Mn. Also in this case, the average S Level of the levels of Mn and the standard deviation ⁇ Level were determined.
- the average S Level + 3 ⁇ Level was used as a threshold value, and the cumulative frequency (%) in a portion in which the level was equal to or larger than the average S Level + 3 ⁇ Level (12 in this case) was determined as the area ratio (%, 5 kV) of the compounds containing Al and Mn (Al-Mn crystallized phases). The results are shown in Table 1.
- the metallographic structure of the top portion substantially free from bending etc. was observed in the same manner as in the rolled sheet.
- the top portion was found to have a fine crystalline structure as fine as that of the rolled sheet, and the compounds containing Al and Mn (Al-Mn crystallized phases) were dispersed in the structure.
- the average crystal grain size, the average diameter of the above compounds, their maximum diameter, and their area ratio were equivalent to those of the rolled sheet. Therefore, the top portion is considered to have substantially the same structure as that of the rolled sheet.
- the metallographic structure was observed in the same manner as in the rolled sheet.
- the cast sheet was found to have a fine crystalline structure although the crystal grains were larger than those in the rolled sheet.
- at least their surface layer region was found to have a structure in which the compounds containing Al and Mn were uniformly dispersed.
- the average diameter of the above compounds, their maximum diameter, and their area ratios (15 kV and 5 kV) were examined and found to be equivalent to those of the rolled sheet. This shows that the above compounds present in the cast sheets are substantially maintained in the rolled sheets of samples Nos. 1-1 to 1-5.
- Plate-shaped pieces of 30 mm ⁇ 30 mm were cut from the rolled sheets (thickness: 0.7 mm) of the samples obtained, and the cut plate-shaped pieces were used as test pieces.
- the depth of the circular hole 21 was set such that a cylindrical rod 10 described layer could be inserted sufficiently into the circular hole 21.
- a test piece 1 was places so as to close the circular hole 21.
- the maximum diameter of the above compounds is 1.2 ⁇ m or less. This allows the occurrence of cracking etc. originating from the above compounds to be effectively suppressed.
- the crystals are also fine, and the average crystal grain size is 10 ⁇ m or less. This also allows the occurrence of cracking etc. originating from coarse crystal grains to be effectively suppressed. This may be the reason that excellent impact resistance, mechanical properties, and plastic formability are achieved.
- the area ratio of the compounds containing Al and Mn in each of samples Nos. 1-1 to 1-5 was higher than that in each of samples Nos. 1-101 and 1-201, irrespective of whether the acceleration voltage of the electron gun for the analysis by the FE-EPMA was 5 kV or 15 kV. A sufficient amount of the compounds containing Al and Mn was found to be present.
- a magnesium alloy excellent in impact resistance, mechanical properties, plastic formability, and also productivity can be produced by setting the temperature of the melt immediately before it comes into contact with the mold to be relatively low, i.e., from 630°C to 690°C inclusive, and then rapidly cooling the melt at a cooling rate of 560°C/second or higher, as described above.
- a magnesium alloy having impact resistance, mechanical properties, and plastic formability can be produced with high productivity by controlling the temperature of the melt and its cooling rate within the above ranges, so long as the compounds containing Al and Mn are contained in the above-described specific amount and have the specific average particle diameter.
- sample No. 1-201 Although the temperature of the melt was very high, the cooling rate was very slow, i.e., less than 550°C/second. It was found that, in sample No. 1-201, although the amount of the compounds containing Al and Mn was smaller than that in sample No. 1-1, coarse particles (2.5 ⁇ m or more) were present. In sample No. 1-201, its impact resistance, mechanical properties, and plastic formability are worse than those of sample No. 1-1 having the same composition as sample No. 1-201. The reason for these results may be that the retention time in the temperature range of around 630°C in which the above compounds are easily formed and grow during solidification is long.
- sample No. 1-101 the temperature of the melt was high, and the cooling rate was also high. Therefore, the amount of the compounds containing Al and Mn was very small. In sample No. 1-101, the impact resistance, in particular, was worse than that of sample No. 1-1 having the same composition. This may be because the dispersion strengthening by the fine compounds was insufficient.
- the press-formed material was also excellent in impact resistance and mechanical properties.
- the reasons for this may be that at least part of the press-formed material substantially maintains the structure of the rolled sheet, i.e., the at least part of the press-formed material has a fine crystalline structure and the compounds containing Al and Mn having the specific size are uniformly dispersed in this structure.
- the present invention is not limited to the above-described examples.
- the present invention is defined by the scope of the claims and is intended to include any modifications within the scope of the claims and meaning equivalent to the scope of the claims.
- the composition (the types of the additive elements and their contents), the shape and size (thickness, length, width, etc.) of the magnesium alloy sheet, the production conditions (the specifications of the mold, the temperature of the mold, the molten alloy temperature, the cooling rate, the thickness of the cast sheet, etc. in the casting conditions) may be appropriately changed.
- the magnesium alloy and magnesium alloy sheet of the present invention can be preferably used as raw materials for plastically formed members (magnesium alloy structural members) subjected to various types of plastic forming such as press forming, bending, and forging.
- the magnesium alloy sheet can be preferably used as raw materials for members desirably having characteristics such as lightweight, small thickness, high strength, and vibration damping ability, and examples of such members include: exterior members such as housings and covers of various electronic-electric devices (personal computers (PCs), tablet PCs, cellular phones such as smartphones and folding cellular phones, digital cameras, etc.); structural members and constituent members of transportation apparatuses such as automobiles and aircrafts; bags; and various protective cases.
- PCs personal computers
- tablet PCs tablet PCs
- cellular phones such as smartphones and folding cellular phones, digital cameras, etc.
- structural members and constituent members of transportation apparatuses such as automobiles and aircrafts
- bags and various protective cases.
- the magnesium alloy and magnesium alloy structural member of the present invention can be preferably used for, for example, the above described exterior members such as housings, the structural members and constituent members of the transportation apparatuses, bags, and protective cases.
- the magnesium alloy production method of the present invention can be preferably used to produce magnesium alloys such as the above-described magnesium alloy sheet and the above-described magnesium alloy structural member.
Landscapes
- 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)
Claims (5)
- Magnesiumlegierung umfassend, in Massenprozent, von einschließlich 1 % bis einschließlich 12 % Al und von einschließlich 0,1 % bis einschließlich 5 % Mn, und gegebenenfalls eines oder mehrere der folgenden: von einschließlich 0,2 % bis einschließlich 7,0 % Zn, von einschließlich 0,2 % bis einschließlich 6,0 % Ca, von einschließlich 0,2 % bis einschließlich 1,0 % Si, von einschließlich 0,0001 % bis einschließlich 0,002 % Be, von einschließlich 0,2 % bis einschließlich 7,0 % Sr, von einschließlich 1,0 % bis einschließlich 6,0 % Y, von einschließlich 0,5 % bis einschließlich 3,0 % Ag, von einschließlich 0,01 % bis einschließlich 2,0 % Sn, von einschließlich 0,1 % bis einschließlich 1,0 % Zr, von einschließlich 0,05 % bis einschließlich 1,0 % Ce und von einschließlich 1,0 % bis einschließlich 3,5 % Seltenerdelemente mit Ausnahme von Y und Ce, wobei der Rest Mg und unvermeidbare Verunreinigungen sind und der Gehalt von Mg mehr als 50 % beträgt,
wobei die Magnesiumlegierung eine Struktur aufweist, in welcher Teilchen einer Verbindung, die Al und Mn enthält, dispergiert sind, wobei die Verbindungen, die Al und Mn enthalten, intermetallische Verbindungen sind, die nur Al und Mn und gegebenenfalls Fe als eine unvermeidbare Verunreinigung enthalten,
ein mittlerer Durchmesser der Teilchen der Verbindung von einschließlich 0,3 µm bis einschließlich 1 µm beträgt,
ein Flächenverhältnis der Teilchen der Verbindung von einschließlich 3,5 % bis einschließlich 25 % beträgt, und
ein maximaler Durchmesser der Teilchen der Verbindung weniger als 2,5 µm beträgt. - Magnesiumlegierung gemäß Anspruch 1, wobei eine mittlere Kristallkorngröße der Magnesiumlegierung 10 µm oder weniger beträgt.
- Magnesiumlegierungsblech, das aus der Magnesiumlegierung gemäß Anspruch 1 oder Anspruch 2 gebildet ist.
- Magnesiumlegierungsstrukturelement, das aus der Magnesiumlegierung gemäß Anspruch 1 oder Anspruch 2 gebildet ist, wobei das Magnesiumlegierungsstrukturelement in wenigstens einem Teil davon einen plastisch geformten Bereich aufweist, der einer plastischen Formgebung unterworfen wird.
- Verfahren zum Herstellen einer Magnesiumlegierung gemäß Anspruch 1, wobei das Verfahren den Schritt umfasst, dass eine Schmelze einer Magnesiumlegierung einem kontinuierlichen Gießen unterworfen wird, wobei die Magnesiumlegierung, in Massenprozent, von einschließlich 1 % bis einschließlich 12 % Al und von einschließlich 0,1 % bis einschließlich 5 % Mn enthält,
wobei die Temperatur der Schmelze, unmittelbar bevor die Schmelze mit einer Form in Berührung kommt, von einschließlich 630 °C bis einschließlich 675 °C beträgt, und
eine Kühlgeschwindigkeit der Schmelze 560 °C/Sekunde oder höher beträgt.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014211259A JP6465338B2 (ja) | 2014-10-15 | 2014-10-15 | マグネシウム合金、マグネシウム合金板、マグネシウム合金部材、及びマグネシウム合金の製造方法 |
PCT/JP2015/076885 WO2016059950A1 (ja) | 2014-10-15 | 2015-09-24 | マグネシウム合金、マグネシウム合金板、マグネシウム合金部材、及びマグネシウム合金の製造方法 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3208356A1 EP3208356A1 (de) | 2017-08-23 |
EP3208356A4 EP3208356A4 (de) | 2017-11-08 |
EP3208356B1 true EP3208356B1 (de) | 2018-10-24 |
Family
ID=55746498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15851242.6A Not-in-force EP3208356B1 (de) | 2014-10-15 | 2015-09-24 | Magnesiumlegierung, magnesiumlegierungsplatte, magnesiumlegierungsteil und verfahren zur herstellung einer magnesiumlegierung |
Country Status (6)
Country | Link |
---|---|
US (1) | US20170283915A1 (de) |
EP (1) | EP3208356B1 (de) |
JP (1) | JP6465338B2 (de) |
KR (1) | KR20170068431A (de) |
CN (1) | CN106715736A (de) |
WO (1) | WO2016059950A1 (de) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6649665B2 (ja) * | 2015-10-19 | 2020-02-19 | 権田金属工業株式会社 | マグネシウム合金製造方法、マグネシウム合金圧延材、およびマグネシウム合金成形体 |
JP6760584B2 (ja) * | 2016-06-24 | 2020-09-23 | 不二ライトメタル株式会社 | マグネシウム合金の押し出し加工部材 |
KR101889018B1 (ko) | 2016-12-23 | 2018-09-20 | 주식회사 포스코 | 마그네슘 합금 판재 및 이의 제조방법 |
WO2019039502A1 (ja) * | 2017-08-24 | 2019-02-28 | キヤノン株式会社 | 反射光学素子およびステレオカメラ装置 |
JP2019174781A (ja) | 2017-08-24 | 2019-10-10 | キヤノン株式会社 | 反射光学素子およびステレオカメラ装置 |
US11268173B2 (en) | 2017-11-17 | 2022-03-08 | Sumitomo Electric Industries, Ltd. | Magnesium alloy and magnesium alloy member |
KR102043786B1 (ko) * | 2017-12-26 | 2019-11-12 | 주식회사 포스코 | 마그네슘 합금 판재 및 이의 제조방법 |
WO2020197527A1 (en) * | 2019-03-22 | 2020-10-01 | Hewlett-Packard Development Company, L.P. | Covers for electronic devices |
CN111455243A (zh) * | 2020-05-21 | 2020-07-28 | 东北大学 | 一种高Mn含量的Mg-Ca-Mn-Al-Zn系变形镁合金及其制备方法 |
CN114908278A (zh) * | 2021-02-08 | 2022-08-16 | 通用汽车环球科技运作有限责任公司 | 镁合金和锻造组件 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2359961B1 (de) * | 2004-06-30 | 2017-09-06 | Sumitomo Electric Industries, Ltd. | Verfahren zur Herstellung eines Produktes aus einer Magnesiumlegierung |
KR100993840B1 (ko) * | 2008-01-30 | 2010-11-11 | 포항공과대학교 산학협력단 | 고강도 마그네슘 합금 판재 및 그 제조방법 |
JP2010156007A (ja) * | 2008-12-26 | 2010-07-15 | Mitsubishi Alum Co Ltd | 耐食性及び表面処理性に優れるマグネシウム合金板材とその製造方法 |
JP2011006754A (ja) * | 2009-06-26 | 2011-01-13 | Sumitomo Electric Ind Ltd | マグネシウム合金板 |
JP5648885B2 (ja) * | 2009-07-07 | 2015-01-07 | 住友電気工業株式会社 | マグネシウム合金板、マグネシウム合金部材、及びマグネシウム合金板の製造方法 |
JP5522400B2 (ja) * | 2009-12-11 | 2014-06-18 | 住友電気工業株式会社 | マグネシウム合金材 |
JP2011236497A (ja) * | 2010-04-16 | 2011-11-24 | Sumitomo Electric Ind Ltd | 耐衝撃部材 |
JP2012077320A (ja) * | 2010-09-30 | 2012-04-19 | Mitsubishi Alum Co Ltd | 曲げ加工用マグネシウム合金板材およびその製造方法ならびにマグネシウム合金パイプおよびその製造方法 |
WO2012066986A1 (ja) * | 2010-11-16 | 2012-05-24 | 住友電気工業株式会社 | マグネシウム合金板、及びその製造方法 |
JP5522000B2 (ja) * | 2010-11-22 | 2014-06-18 | 住友電気工業株式会社 | マグネシウム合金部材 |
JP5880811B2 (ja) * | 2011-06-22 | 2016-03-09 | 住友電気工業株式会社 | マグネシウム合金鋳造材、マグネシウム合金鋳造コイル材、マグネシウム合金展伸材、マグネシウム合金接合材、マグネシウム合金鋳造材の製造方法、マグネシウム合金展伸材の製造方法、及びマグネシウム合金部材の製造方法 |
-
2014
- 2014-10-15 JP JP2014211259A patent/JP6465338B2/ja not_active Expired - Fee Related
-
2015
- 2015-09-24 KR KR1020177004623A patent/KR20170068431A/ko not_active Application Discontinuation
- 2015-09-24 CN CN201580049782.0A patent/CN106715736A/zh active Pending
- 2015-09-24 US US15/506,622 patent/US20170283915A1/en not_active Abandoned
- 2015-09-24 WO PCT/JP2015/076885 patent/WO2016059950A1/ja active Application Filing
- 2015-09-24 EP EP15851242.6A patent/EP3208356B1/de not_active Not-in-force
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
US20170283915A1 (en) | 2017-10-05 |
KR20170068431A (ko) | 2017-06-19 |
EP3208356A4 (de) | 2017-11-08 |
EP3208356A1 (de) | 2017-08-23 |
JP2016079451A (ja) | 2016-05-16 |
JP6465338B2 (ja) | 2019-02-06 |
WO2016059950A1 (ja) | 2016-04-21 |
CN106715736A (zh) | 2017-05-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3208356B1 (de) | Magnesiumlegierung, magnesiumlegierungsplatte, magnesiumlegierungsteil und verfahren zur herstellung einer magnesiumlegierung | |
EP2548984B1 (de) | Aluminiumlegierungsmaterial für einen speicherbehälter für hochdruck-wasserstoffgas | |
JP5880811B2 (ja) | マグネシウム合金鋳造材、マグネシウム合金鋳造コイル材、マグネシウム合金展伸材、マグネシウム合金接合材、マグネシウム合金鋳造材の製造方法、マグネシウム合金展伸材の製造方法、及びマグネシウム合金部材の製造方法 | |
JP4189687B2 (ja) | マグネシウム合金材 | |
EP3395458B1 (de) | Blech aus magnesiumlegierung und verfahren zur herstellung davon | |
EP2453031B1 (de) | Magnesiumlegierungsplatte | |
JP5522400B2 (ja) | マグネシウム合金材 | |
EP2447381A1 (de) | Platte aus magnesiumlegierung | |
WO2010103971A1 (ja) | マグネシウム合金部材 | |
JP2017160542A (ja) | マグネシウム合金鋳造材、マグネシウム合金鋳造コイル材、マグネシウム合金展伸材、マグネシウム合金部材、マグネシウム合金接合材、及びマグネシウム合金鋳造材の製造方法 | |
JPWO2019013226A1 (ja) | マグネシウム基合金展伸材及びその製造方法 | |
EP3561098B1 (de) | Blech aus einer magnesiumlegierung und herstellungsverfahren dafür | |
EP2535435B1 (de) | Magnesiumlegierungsblech | |
JP6869119B2 (ja) | Cu−Ni−Al系銅合金板材および製造方法並びに導電ばね部材 | |
JP3996340B2 (ja) | ホウ素およびマグネシウム含有Al基合金並びにその製造方法 | |
JP5757104B2 (ja) | マグネシウム合金材及びその製造方法 | |
US20170349979A1 (en) | Aluminum alloy sheet | |
CN112771189A (zh) | 镁合金板材及其制造方法 | |
CA3032801C (en) | Method for producing deformed semi-finished products from aluminium-based alloys | |
US11739400B2 (en) | Magnesium alloy and method for manufacturing the same | |
EP3643802A1 (de) | Blech aus einer magnesiumlegierung und herstellungsverfahren dafür | |
JP6136037B2 (ja) | マグネシウム合金鋳造材、マグネシウム合金鋳造コイル材、マグネシウム合金展伸材、マグネシウム合金接合材、マグネシウム合金鋳造材の製造方法、マグネシウム合金展伸材の製造方法、及びマグネシウム合金部材の製造方法 | |
EP4141136A1 (de) | Magnesiumlegierung, magnesiumlegierungsplatte, magnesiumlegierungsstange, herstellungsverfahren dafür und magnesiumlegierungselement | |
RU2579861C1 (ru) | Способ получения деформированных полуфабрикатов из сплава на основе алюминия | |
KR20200035629A (ko) | 마그네슘 합금 판재 및 그 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170313 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20171010 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B21B 3/00 20060101ALI20171004BHEP Ipc: C22C 23/02 20060101AFI20171004BHEP Ipc: B22D 21/04 20060101ALI20171004BHEP Ipc: B22D 11/06 20060101ALI20171004BHEP Ipc: C22F 1/00 20060101ALI20171004BHEP Ipc: C22F 1/06 20060101ALI20171004BHEP Ipc: C22C 23/00 20060101ALI20171004BHEP |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20180413 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1056740 Country of ref document: AT Kind code of ref document: T Effective date: 20181115 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015018900 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20181024 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1056740 Country of ref document: AT Kind code of ref document: T Effective date: 20181024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190224 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190124 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190124 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190224 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20190125 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015018900 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20190725 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602015018900 Country of ref document: DE Representative=s name: MAIER, LL.M., MICHAEL C., DE Ref country code: DE Ref legal event code: R082 Ref document number: 602015018900 Country of ref document: DE Representative=s name: BOULT WADE TENNANT LLP, DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 602015018900 Country of ref document: DE Representative=s name: BOULT WADE TENNANT LLP, DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190924 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190930 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190924 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190930 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20190930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190930 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20190924 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190930 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20190924 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20150924 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20210818 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20181024 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602015018900 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230401 |