WO2021111989A1 - 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 - Google Patents

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 Download PDF

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WO2021111989A1
WO2021111989A1 PCT/JP2020/044106 JP2020044106W WO2021111989A1 WO 2021111989 A1 WO2021111989 A1 WO 2021111989A1 JP 2020044106 W JP2020044106 W JP 2020044106W WO 2021111989 A1 WO2021111989 A1 WO 2021111989A1
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magnesium alloy
aging treatment
hours
treatment material
thermal conductivity
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PCT/JP2020/044106
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English (en)
French (fr)
Japanese (ja)
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ゼハオ リー
泰祐 佐々木
和博 宝野
泰祐 城山
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国立研究開発法人物質・材料研究機構
ＬＧ Ｊａｐａｎ Ｌａｂ株式会社
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Priority to JP2021562614A priority Critical patent/JPWO2021111989A1/ja
Publication of WO2021111989A1 publication Critical patent/WO2021111989A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • 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
    • 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 aging treatment material and a method for producing the same, and further, the present invention relates to an OA device, a transportation device and its parts using the magnesium alloy aging treatment material.
  • Magnesium alloy is known as the lightest metal among practical metals, and examples of applications that can take advantage of its light weight include housings for notebook computers and structural materials for transportation equipment. For these applications, wrought materials such as plate materials and bar materials produced by rolling or extrusion are used. When a plate material is used as a housing for a notebook computer or the like, excellent heat dissipation is required in addition to sufficient mechanical properties for application.
  • Solid solution strengthening is a method of strengthening by solid solution of elements with atomic radii different from the matrix phase into the matrix phase and introducing lattice strain. The larger the amount of solute elements, the larger the amount of solid solution strengthening. Obtainable.
  • Patent Document 1 discloses a magnesium alloy in which Al (aluminum) and a rare earth metal are added to magnesium, the thermal conductivity is 80 W / (m ⁇ K) or more, and the tensile strength is 200 MPa or more. ..
  • the thermal conductivity of pure Mg (magnesium) is 158 W / (m ⁇ K) at room temperature, but the yield strength is very low, less than 100 MPa (see Non-Patent Document 1). Therefore, it has been difficult to improve both strength and thermal conductivity at the same time from such an approach.
  • the intermetallic compound formed on the grain boundaries by the addition of Ca is a compound such as Al 2 Ca containing the alloying element Al.
  • the formation of the intermetallic compound by the addition of Ca was effective in improving the thermal conductivity because the concentration of solute elements in the matrix could be lowered.
  • a common method for imparting excellent thermal conductivity and creep properties to cast alloys made of magnesium alloys is to crystallize the alloying elements as crystallization in the grains or along the grain boundaries. That is the point.
  • the concentration of the alloying element in the matrix decreases, so that excellent thermal conductivity can be imparted.
  • Forming a three-dimensional network see Patent Document 2 by forming crystallized products on grain boundaries has the advantage that it can be used as a strength member, but ductility may be significantly impaired. ..
  • a magnesium alloy capable of achieving both workability and strength is disclosed (see Patent Document 3, Non-Patent Documents 3 and 4).
  • the intermetallic compound formed by adding Ca is very coarse, good ductility cannot be obtained even if such an alloy is stretched to produce a plate material or a bar material. Therefore, it is not preferable as a plate material that needs to be processed into a final shape after the stretching process.
  • the housing and panel material of OA equipment are required to have an alloy having a thermal conductivity of about 120 W / (m ⁇ K) or more for heat dissipation as well as mechanical properties.
  • an alloy having a thermal conductivity of about 120 W / (m ⁇ K) or more for heat dissipation as well as mechanical properties In many applications, there is a strong demand for alloys that exhibit both strength and excellent thermal conductivity at room temperature.
  • the conventional method for producing a magnesium alloy has not been able to obtain a highly versatile magnesium alloy having sufficient strength and thermal conductivity at room temperature.
  • the first object of the present invention is to provide a highly versatile magnesium alloy aging treatment material capable of achieving both high thermal conductivity and strength in a temperature range including room temperature, and the magnesium alloy aging treatment material.
  • a second object is to provide a manufacturing method.
  • a third object is to provide OA equipment using a magnesium alloy aging treatment material, and a fourth purpose is to provide a transportation equipment using a magnesium alloy aging treatment material.
  • the present inventors have newly strengthened the magnesium alloys by precipitating and strengthening the GP zone from the magnesium matrix at a high density by aging treatment.
  • the present invention was conceived with the finding that improvement in thermal conductivity and mechanical strength can be realized.
  • the magnesium alloy aging treatment material of the present invention contains 1% by mass or less of Ca and 3% by mass or less of Zn, and the balance is Mg and unavoidable impurities.
  • the GP zone composed of Ca and Zn is dispersed on the (0001) plane of the magnesium matrix, and the GP zone has a longitudinal direction of 4.0 to 5.0 nm on the (0001) plane. As described above, the number density is in the range of 1 ⁇ 10 20 to 1 ⁇ 10 24 m -3.
  • the magnesium alloy aging treatment material preferably contains Ca of 0.5% by mass or more and 1% by mass or less and Zn of 0.8% by mass or more and 3% by mass or less, and the balance is Mg and unavoidable impurities.
  • the thermal conductivity of the magnesium alloy aging treatment material is preferably 120 W / (m ⁇ K) or more.
  • This magnesium alloy aging treatment material may further contain zirconium or manganese, and may also contain gadolinium or cerium.
  • the method for producing a magnesium alloy aging treatment material of the present invention is: The process of melting Mg, Zn and Ca to obtain a cast solid, A step of homogenizing the cast solid to obtain a homogenized material, and A step of aging the homogenized material to obtain a magnesium alloy aging material, and Including
  • the composition of the magnesium alloy aging treatment material contains 1% by mass or less of Ca and 3% by mass or less of Zn, and the balance is Mg and unavoidable impurities.
  • the above aging treatment is preferably carried out in the temperature range of 140 ° C. to 250 ° C. until the thermal conductivity of the magnesium alloy aging treatment material becomes 120 W / (m ⁇ K) or more.
  • a step of dissolving the homogenizing treatment material to obtain the solution treatment material is inserted.
  • a step of stretching the homogenized treatment material is inserted.
  • the homogenization treatment is preferably carried out at 300 ° C. or higher and 500 ° C. or lower for a predetermined time.
  • the OA equipment of the present invention that achieves the third object has a housing or a panel material using the magnesium alloy aging treatment material.
  • the transportation equipment and its parts of the present invention that achieve the fourth object use the above-mentioned magnesium alloy aging treatment material or are used as its parts.
  • the present invention is capable of achieving both high strength and thermal conductivity in a temperature range including room temperature, a highly versatile magnesium alloy aging treatment material and a method for producing the same, and OA equipment, transportation equipment and the like using the same. Parts can be provided.
  • the magnesium alloy aging treatment material of the present invention is an alloy containing 1% by mass or less of Ca (calcium) and 3% by mass or less of Zn (zinc), and the balance is Mg (magnesium) and unavoidable impurities.
  • Ca of 1% by mass or less is Ca of 1% by mass or less, which is more than 0% by mass.
  • Ca of 3% by mass or less is Zn of 3% by mass or less, which is more than 0% by mass.
  • the Guinier Preston zone (hereinafter referred to as GP zone) composed of Mg, Ca and Zn as the second phase is dispersed and precipitated on the (0001) plane of the magnesium matrix.
  • the GP zone has dimensions of 4.0 to 5.0 nm or more and a number density in the range of 1 ⁇ 10 20 to 1 ⁇ 10 24 m -3.
  • the number density of GP zones is defined as the number of GP zones present per 1 m 3 of the magnesium alloy.
  • the number density of the GP zone can be measured by 3DAP analysis using an atom probe (3DAP) described later.
  • the thermal conductivity of the magnesium alloy aging treatment material is 120 W / (m ⁇ K) or more, and Zr (zirconium) or Mn (manganese) may be contained as a component element. Further, Gd (gadolinium) or Ce (cerium) may be contained.
  • the upper limit value of Ca is preferably 1% by mass or less. It is not preferable to add 1% by mass or more of Ca because it is empirically known that the sample may crack during water quenching after solution treatment, that is, quenching.
  • the concentration of Zn added to Mg In order to obtain excellent thermal conductivity, the lower the concentration of Zn added to Mg, the better. Therefore, there is no lower limit of the concentration of Zn, and an upper limit may be set.
  • the concentration of Zn is preferably more than 0% by mass and 3% by mass or less.
  • the upper limit of the Zn concentration is preferably less than 3% by mass in order to obtain a thermal conductivity of 120 W / (m ⁇ K) from Comparative Example 1 described later.
  • the magnesium alloy aging treatment material of the present invention contains Ca of 0.5% by mass or more and 1% by mass or less and Zn of 0.8% by mass or more and 3% by mass or less, and the balance is Mg and unavoidable. It is desirable that the alloy consists of impurities.
  • Zr or Mn may be added as the grain refiner to be added. From the comparison of Examples 3 and 5 or Examples 6 and 7 described later, it is desirable to add Zr or Mn as a grain refiner. Further, Zr is preferably added as a grain refiner.
  • Ce or Gd is an additive element for improving aging hardening property and controlling the texture during rolling.
  • the addition of the alloying element lowers the thermal conductivity, so it is preferable to keep the addition amount to the minimum necessary.
  • the magnesium alloy is described as a general formula Mg—Ca—X (X is Zn or Al) alloy, it is more appropriate to add Zn as the X element than Al from the comparison between Comparative Examples 1 and 2 and Example 6 described later. Is.
  • FIG. 1 is a flow chart showing a method for producing a magnesium alloy aging treatment material of the present invention.
  • the method for producing a magnesium alloy of the present invention includes a step 1 of melting raw materials such as Mg, Zn, and Ca and then casting to obtain a cast solid, and a homogenization treatment of the cast solid to obtain a homogenized material (also referred to as T4 treatment). ), If necessary, the homogenized treatment material is stretched to obtain a processed material, the processed material is solution-treated to obtain a solution-treated material, and the solution-treated material is obtained. 5 is included in the step 5 of obtaining a magnesium alloy aging treatment material (also referred to as T6 treatment) by aging treatment.
  • T6 treatment magnesium alloy aging treatment material
  • Step 1 Casting
  • step 1 casting is performed after the alloy component containing Ca more than 0% by mass and 1% by mass or less and Zn more than 0% by mass and 3% by mass or less is dissolved and the balance is Mg and unavoidable impurities. Make a solid.
  • Zr or the like may be further added to the magnesium alloy if necessary.
  • the method used for melting may be any method as long as an alloy having a desired composition can be produced.
  • the alloy component can be melted by melting an alloy having a desired composition in an argon atmosphere using a high-frequency induction melting furnace, pouring it into a mold made of iron or the like, and cooling it.
  • the dimensions of the melting furnace and the cast solid used at the time of melting are not particularly limited, and it is sufficient that the cast solid having a desired composition can be produced.
  • Step 2 Homogenization treatment
  • a homogenization treatment a compound formed during segregation of alloy elements existing in the cast alloy and cooling of the molten metal is solid-solved in the matrix phase, and heat treatment is performed to homogenize the distribution of alloy elements.
  • a homogenized solid is produced by subjecting the cast solid to a homogenization treatment at 300 ° C. or higher and 500 ° C. or lower, more preferably 350 ° C. or higher and 450 ° C. or lower for a predetermined time. Details of the conditions are shown in Table 1 described later. In the region where the alloying elements are macrosegregated to a high concentration, the region melts when the heat treatment is performed at a high temperature.
  • the heat treatment at a low temperature may be performed before the heat treatment at a predetermined temperature.
  • the alloy may locally melt, that is, initially melt, when the heat treatment is started at 450 ° C. Therefore, by first heat-treating in the range of 300 ° C. to 350 ° C., the initial melting of the Mg—Zn phase formed during casting is suppressed and Zn is dispersed, and then the heat treatment is performed at 400 ° C. or higher and 500 ° C. or lower for a predetermined time. May be applied to homogenize the distribution of Zn to obtain a homogenized solid.
  • Step 3 is a step of being inserted between the homogenization treatment step 2 and the solution treatment step 4 as needed.
  • the cast material is stretched by rolling or extrusion to form a plate material or a bar material.
  • Process into a processed material This step 3 is not necessarily a necessary step for improving the thermal conductivity.
  • a plate-shaped processed material is produced by processing a homogenized solid into a plate material by hot or warm rolling or the like.
  • the production of the plate material by the stretching process is not limited to hot processing or warm processing, particularly rolling processing, and any other processing method may be used as long as it is a stretching processing method capable of producing a fine structure.
  • Step 4 Solution treatment
  • a plate-shaped tangible solid obtained by rolling or the like is solution-treated, and the solution-treated material is produced by cooling the solid. This is carried out to dissolve the fine precipitates formed during the rolling process in the magnesium matrix and to form a recrystallized structure.
  • the rolling process may be performed in combination with the homogenization process of step 2 and the solution solution process may be omitted.
  • the step 5 of aging the homogenized material to obtain the magnesium alloy aging material is performed.
  • the processed material is heat-treated to dissolve the fine precipitates formed during the hot or warm processing in the matrix and recrystallize them to form a structure.
  • the solution treatment is carried out for 15 minutes to 24 hours in the range of 350 ° C. or higher and 500 ° C. or lower. However, it is not necessary to spend more time than necessary because a longer heat treatment time leads to an increase in manufacturing cost. It can be carried out under various temperature conditions, and the details of the conditions are shown in Table 1 described later.
  • Step 5 Aging process
  • the solution-treated material is aged by heat treatment to disperse the precipitates deposited on the solution-treated processed material and impart strength, whereby the magnesium alloy aging-treated material of the present invention can be obtained.
  • the aging treatment it is possible to significantly strengthen the magnesium alloy and achieve a large thermal conductivity by using an aging treatment which has not been conventionally used in a commercial magnesium alloy.
  • the aging treatment is performed for a predetermined time in a temperature range of 140 ° C. to 250 ° C.
  • the aging treatment is carried out for a time during which the thermal conductivity of the magnesium alloy increases, preferably at least 120 W / (m ⁇ K) or at the maximum.
  • aging treatment is performed at 170 ° C. in an oil bath.
  • the magnesium alloy aging treatment material of the present invention produced in this manner contains Ca more than 0% by mass and 1% by mass or less and Zn more than 0% by mass and 3% by mass or less, and the balance is Mg. It is an alloy composed of unavoidable impurities and nanometer-order precipitates (GP zones) composed of Mg, Ca and Zn dispersed on the (0001) plane of the magnesium matrix.
  • a nanoprecipitate having an interface consistent with the magnesium matrix called a GP zone can be formed at high density.
  • the magnesium alloy aging treatment material of the present invention is a nanoscale precipitate that matches a matching nanoscale precipitate with a magnesium matrix by a combination of a solution treatment and a low-temperature heat treatment called aging treatment. Can be dispersed at high density. As a result, it is possible to manufacture a magnesium alloy aging treatment material having both excellent thermal conductivity and mechanical properties at low cost without using expensive elements.
  • Office automation equipment (called Office Automation, OA equipment) has a housing and a panel material using the magnesium alloy aging treatment material of the present invention.
  • OA equipment is a general term for equipment required for office automation such as companies and offices, and can be applied to OA equipment according to the purpose without particular limitation. Examples of computers include laptop computers, desktop computers, mobile phones (smartphones), personal digital assistants (also called PDAs), copiers, various printers, and facsimiles (FAX).
  • PDAs personal digital assistants
  • FAX facsimiles
  • the housing and panel material processed by stretching the magnesium alloy aging treatment material of the present invention is used, for example, as the housing and panel material of the OA equipment.
  • a panel material made of the magnesium alloy aging treatment material of the present invention may be used for the transportation equipment and its parts.
  • Examples of transportation equipment include automobiles, aircraft, flying objects such as drones, railway vehicles, and the like, and there are no particular restrictions, and they can be appropriately applied according to the purpose.
  • the parts of the transportation equipment are parts using the magnesium alloy aging treatment material of the present invention.
  • the panel material or the like processed by stretching processing such as rolling is, for example, a part such as a luggage retainer used as a panel material of an automobile or a part of a rear seat.
  • Transmission electron microscope image Transmission electron microscope images as a characterization of the microstructure were obtained using a transmission electron microscope (FEI Technai 20 and Titan G 2 80-200).
  • a thin foil test piece for TEM or STEM observation was prepared by punching a disc having a diameter of 3 mm and performing twin jet electropolishing at a voltage of 90 V at about ⁇ 50 ° C.
  • a three-dimensional atom probe (also called 3DAP) applies a high voltage to a needle-shaped sample, detects ions that evaporate from the surface of the sample in an electric field with a mass spectrometer, and detects the individually detected ions. This is a method of measuring a three-dimensional atomic distribution by continuously detecting in the depth direction and arranging ions in the order of detection.
  • the 3DAP analysis was performed in voltage pulse mode at a temperature of 30 K using a local electrode atom probe (LEAP5000XS, manufactured by CAMECA).
  • Sharp needle-shaped samples used for electric field evaporation for 3DAP analysis were prepared by lift-out and annular milling techniques using a SEM focused ion beam device (FIB, FEIHellosG4UX).
  • the number density of the GP zone was measured by the data analysis software of the mass spectrometer (manufactured by CAMECA) used for the 3DAP analysis.
  • the volume of the sample is calculated from the measured sample data.
  • IVAS manufactured by CAMECA was used.
  • the position of the GP zone of the sample is detected using the isoconcentration surface of the data, the number of GP zones is counted, and the volume obtained by first obtaining the number of GP zones.
  • the number density of GP zones was calculated by dividing by.
  • the age hardening response was measured by a Micro Vickers hardness tester (HM-101, manufactured by Mitutoyo) under a load of 300 g.
  • Tensile properties were evaluated at room temperature using a tensile tester (Instron, 5567) at an initial strain rate of 10 -3 s -1.
  • a tensile test piece having a gauge length of 12.5 mm and a width of 5 mm was produced by machining from a solute-treated material and an aging-treated material.
  • the Eriksen value (IE value), which evaluates workability at room temperature, is obtained by pressing a ball head punch against a thin plate whose outer circumference is fixed by an Eriksen test at a constant speed to deform the thin plate and break it into a material. It was measured by the height of the dent until the occurrence of. The Eriksen value was evaluated with a tester (Eriksen, 111 type).
  • Example 1 (1) Alloy composition: Mg-1.0Zn-0.3Ca-0.3Zr (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, and then water-cooled. (3) Solution treatment: 2 hours at 450 ° C. (4) Aging treatment: 6 hours at 170 ° C., 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, at 300 ° C. as a homogenization treatment. After holding for 4 hours, the temperature was raised at 7.5 ° C./h (h is 1 hour), further held at 450 ° C. for 6 hours, and then water-cooled.
  • the thermal conductivity of each of the above samples was measured by the above method, and was aged at 125.2 W / (m ⁇ K), 127.7 W / (m ⁇ K), and 134.8 W / (m ⁇ K), respectively. There was a slight increase in thermal conductivity due to this.
  • Example 2 (1) Alloy composition: Mg-0.8Zn-0.5Ca-0.4Zr (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, and then water-cooled. (3) Solution treatment: 450 ° C. for 1 hour (4) Aging treatment: 170 ° C. for 10 hours, 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, a homogenization treatment at 300 ° C. was 4 After holding for a time, the temperature was raised at 7.5 ° C./h, and after holding at 450 ° C. for 6 hours, it was cooled with water.
  • Example 2 the amount of Ca added was increased as compared with Example 1. It was found that it is necessary to add about 0.5% of Ca to increase the thermal conductivity by the aging treatment.
  • Example 3 (1) Alloy composition: Mg-0.8Zn-0.8Ca-0.4Zr (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, and then water-cooled. (3) Solution treatment: 450 ° C. for 1 hour (4) Aging treatment: 170 ° C. for 16 hours, 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, a homogenization treatment at 300 ° C. was 4 After holding for a time, the temperature was raised at 7.5 ° C./h, and after holding at 450 ° C. for 6 hours, it was cooled with water.
  • Example 3 the amount of Ca added was further increased as compared with Example 2, but the thermal conductivity was lower than that of Example 2. From this, it was found that it is necessary to add about 0.5% of Ca in order to increase the thermal conductivity by the aging treatment.
  • Example 4 (1) Alloy composition: Mg-0.8Zn-0.8Ca-0.3Mn (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, and then water-cooled. (3) Solution treatment: 450 ° C. for 1 hour (4) Aging treatment: 170 ° C. for 16 hours, 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, a homogenization treatment at 300 ° C. was 4 After holding for a time, the temperature was raised at 7.5 ° C./h, and after holding at 450 ° C. for 6 hours, it was cooled with water.
  • Example 4 the alloy composition in which Zr of Example 3 was replaced with Mn was used.
  • Example 5 (1) Alloy composition: Mg-1.6Zn-0.5Ca-0.5Mn-0.2Ce (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, and then water-cooled. (3) Solution treatment: 1 hour at 450 ° C. (4) Aging treatment: 4 hours at 170 ° C., 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, a homogenization treatment at 300 ° C. was 4 After holding for a time, the temperature was raised at 7.5 ° C./h, and after holding at 450 ° C. for 6 hours, it was cooled with water.
  • Example 5 The alloy composition of Example 5 is obtained by adding Ce to Example 4. A thermal conductivity of over 120 W / (m ⁇ K) could be achieved, but the thermal conductivity was lower than in Example 4. From this, it was found that in order to achieve a thermal conductivity exceeding 130 W / (m ⁇ K), the composition of Example 3 or 4 is sufficient, and it is better not to add an extra element.
  • Example 6 (1) Alloy composition: Mg-1.6Zn-0.5Ca-0.4Zr (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, air-cooled to 300 ° C., and then water-cooled. (3) Solution treatment: 450 ° C. for 1 hour (4) Aging treatment: 170 ° C. for 6 hours, 500 hours Samples were prepared according to the above experimental procedure, and held at 300 ° C. for 4 hours as homogenization treatment as shown in Table 1. Later, the temperature was raised at 7.5 ° C./h, kept at 450 ° C.
  • FIG. 2 is a bright field transmission electron microscope image of a magnesium alloy in Example 6, in which (a) is a solution-treated material, (b) is an aging-treated material that has been aged at 170 ° C. for 4 hours, and (c) is 170. An aging treatment material that has been aged at 120 ° C. for 120 hours, and (d) shows an aging treatment material that has been aged at 170 ° C. for 1000 hours.
  • Each brightfield transmission electron microscope image was taken from the zone axis of [112 bar 0].
  • the image shown on the lower side is a corresponding selected area electron diffraction pattern (referred to as SAED pattern), which was taken from the [101 bar 0] ⁇ and [0001] ⁇ directions. As shown in FIG.
  • the solution-treated material contained rod-shaped lumpy particles along the grain boundaries and the inside of the grains, and the particles suppressed the growth of recrystallized particles during the solution treatment. It suggests that. According to Gao et al., The particles are presumed to be Zn 2 Zr 3 phase (see Non-Patent Document 2).
  • the contrast of the SAED pattern is that nm-scale plate-like precipitates are densely distributed on the bottom surface of the Mg matrix.
  • the corresponding SAED patterns of [011 bar 0] ⁇ and [0001] ⁇ are streak along the [0001] ⁇ direction and 1/3 ⁇ 2 bar 110 ⁇ and 2/3 ⁇ compared to the position of the solution treatment material. It shows an extra diffraction spot on the 2 bar 110 ⁇ .
  • the GP zone (Guinier. Preston. Zone), which is a fine precipitate, is dispersed on the bottom surface of the Mg matrix, that is, on the (0001) ⁇ plane of the magnesium matrix. You can see that.
  • a pair of large plate-shaped GP zones having a length of 10-50 nm is precipitated on the (0001) ⁇ plane in the 120-hour aging treatment material.
  • the SAED pattern similar to that of the 4-hour aging treatment material has a matched GP zone even in the 1000-hour aging treatment material.
  • FIG. 3 is a HAADF-STEM image of the aging treatment material of Example 6, in which (a) is an aging treatment material that has been aged for 4 hours, (b) is an aging treatment material that has been aged for 1000 hours, and (c) is (a). ) Is an enlarged view, and (d) is an enlarged view of (b).
  • Each HAADF-STEM image was taken from the crystal zone axis of [112 bar 0]. As shown in FIGS.
  • the GP zone is the bottom surface, that is, the magnesium matrix (0001) ⁇ . Observed as a bright linear contrast along the surface. According to the three-dimensional atom map described later, this precipitate is rich in Ca and / or Zn.
  • the average size of the GP zone is about 3.2 ⁇ 0.4 nm in the 4-hour aging treatment material, and as shown in FIG. 3 (c), (0001). ) It was found that it was a bright atomic sequence of monoatomic layers arranged on the ⁇ plane. On the other hand, as shown in FIG. 3 (b), the average size of GP precipitates is 35 ⁇ 10 nm in the aging treatment material for 1000 hours, and as shown in FIG. 3 (d), it is about 1.3 nm. It was found to be composed of two bright atomic sequences with an interval of.
  • the precipitate observed in the aging treatment material for 1000 hours is different from the GP zone observed in the aging treatment material having a shorter aging treatment time, and the precipitate cannot be called the GP zone. May form. Therefore, it is called a GP precipitate to distinguish it from the GP zone. From this, it was found that the average size of the GP precipitate on the (0001) ⁇ plane increases as the aging treatment time increases.
  • FIG. 4 is a diagram showing a three-dimensional atom map of the magnesium alloy of Example 6, in which (a) is a solution-treated material, (b) is an aging-treated material that has been aged at 170 ° C. for 4 hours, and (c) is 1000 hours. The aging-treated material is shown.
  • FIG. 4D is a diagram showing the concentration distribution of Zn, Ca, and Zr atoms of the aging treatment material of FIG. 4B
  • FIG. 4E is a diagram showing the concentration distribution of Zn, Ca, and Zr atoms of FIG. 4C.
  • Table 3 summarizes the solute concentration in the magnesium matrix, the plane spacing, and the number density of GP zones measured by the three-dimensional atom maps of FIGS. 4 (a) to 4 (c).
  • the Zn, Ca, and Zr atoms of the solution treatment material shown in FIG. 4A have concentrations of 0.412, 0.241, and 0.001 atomic%, respectively, and are chemically uniform solid solutions with a uniform distribution. It shows that there is.
  • the concentration of solute elements in the magnesium matrix tends to decrease with the passage of aging time.
  • a GP zone of 9.9 ⁇ 10 23 m -3 that is, 1 ⁇ 10 24 m -3 , is precipitated in terms of number density, but the GP zone with the passage of aging time. It was found that as the grain becomes coarser, its number density decreases and the particle spacing also increases.
  • FIG. 5 is a diagram showing the relationship between the aging time during isothermal aging at 170 ° C., Vickers hardness, and thermal conductivity in Example 6.
  • the horizontal axis of FIG. 5 is the aging time (hours), the left vertical axis is the Vickers hardness (HV), and the right vertical axis is the thermal conductivity (W / (m ⁇ K)).
  • the Vickers hardness of the solution-treated material is 52.8 ⁇ 1.6 HV, and it shows rapid aging hardening to a peak Vickers hardness of 66.1 ⁇ 1.5 HV by aging treatment for 4 hours. I understand. After 1000 hours of aging, the Vickers hardness drops to 52.3 ⁇ 1.3 HV.
  • the thermal conductivity of the solution-treated material (T4) is 123.3 ⁇ 0.8 W / (m ⁇ K)
  • the thermal conductivity of the aging-treated material (T6) that has been aged for 4 hours is 128.6.
  • the thermal conductivity of the aging treatment material (T6) which increased to ⁇ 0.5 W / (m ⁇ K) and was further aged for 1000 hours, reached a maximum value of 132.7 ⁇ 0.6 W / (m ⁇ K). Reached.
  • FIG. 6 is a diagram showing a tensile stress-strain curve of the magnesium alloy of Example 6.
  • the horizontal axis of the figure is strain (%), and the vertical axis is tensile stress (MPa).
  • Table 4 shows the tensile yield strength, the ultimate tensile yield strength, the elongation, and the thermal conductivity obtained from the stress-strain curve. As shown in FIGS. 6 and 4, the tensile yield strength of the solution-treated material was 181 MPa, the ultimate tensile yield strength was 265 MPa, and the elongation was 28.2%.
  • the Eriksen value measured at room temperature was 8.11 mm.
  • the tensile yield strength of the aging-treated material subjected to the aging treatment for 4 hours was 227 MPa and the ultimate tensile yield strength was 291 MPa, which were higher than those of the solution-treated material.
  • the elongation was 22.6%, which was slightly lower than that of the solution-treated material.
  • the tensile yield strength of the aging treated material subjected to the aging treatment for 1000 hours was 171 MPa, the ultimate tensile yield strength was 242 MPa, and the elongation was 23.8%.
  • FIG. 7 is a diagram showing the relationship between the tensile yield strength and heat conduction in the aging treatment material subjected to the aging treatment for 4 hours in Example 6 and other commercially available wrought alloys.
  • the aging treatment material (T6) subjected to the aging treatment for 4 hours had an excellent balance between the tensile yield strength and the thermal conductivity as compared with other commercially available forged alloys.
  • Example 6 is a case where the Zn concentration of Example 3 is increased from 0.8% by mass to 1.6% by mass.
  • the thermal conductivity is about 120 W / (m ⁇ K), but this is an example showing that the thermal conductivity exceeding 130 W / (m ⁇ K) can be achieved by the aging treatment.
  • the magnesium alloy of the present invention including Example 6, a supersaturated solid solution was formed by quenching the material to be the matrix after the solution treatment, and the solute elements dissolved in the supersaturation by the subsequent aging treatment were dispersed at high density.
  • the mechanical strength of the aging treatment material (T6) is increased by precipitating as a fine GP zone precipitate or GP precipitate.
  • the amount of solute elements such as Ca, Zn, and Zr that are solid-solved in the magnesium matrix decreases, so that the solute elements contribute to the decrease in thermal conductivity.
  • the amount of is reduced.
  • the thermal conductivity could be improved as well as the strength. This principle has already been used for aluminum alloys and the like, and it has been found that the present invention can also be applied to magnesium alloys.
  • Example 7 (1) Alloy composition: Mg-1.6Zn-0.5Ca-0.4Mn (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, air-cooled to 300 ° C., and then water-cooled. (3) Solution treatment: 1 hour at 400 ° C. (4) Aging treatment: 16 hours at 170 ° C., 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, a homogenization treatment at 300 ° C. was 4 After holding for a time, the temperature was raised at 7.5 ° C./h, further held at 450 ° C.
  • Example 7 is an example in which Zr of Example 6 is replaced with Mn.
  • Example 8 (1) Alloy composition: Mg-1.6Zn-0.5Ca-0.4Zr-0.3Gd (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, air-cooled to 300 ° C., and then water-cooled. (3) Solution treatment: 400 ° C. for 1 hour (4) Aging treatment: 170 ° C. for 16 hours, 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, at 300 ° C. as a homogenization treatment. After holding for 4 hours, the temperature was raised at 7.5 ° C./h, further held at 450 ° C.
  • Example 7 is obtained by adding Gd to the alloy composition of Example 6. Thermal conductivity exceeding 120 W / (m ⁇ K) can be achieved by aging treatment, but in order to achieve thermal conductivity exceeding 130 W / (m ⁇ K), it is better not to add extra elements. I found out.
  • Example 9 (1) Alloy composition: Mg-1.6Zn-0.5Ca-0.4Zr (2) Homogenization treatment: After holding at 300 ° C. for 4 hours, the temperature was raised at 7.5 ° C./h, holding at 450 ° C. for 6 hours, air-cooled to 300 ° C., and then water-cooled. (3) Solution treatment: 1 hour at 400 ° C. (4) Aging treatment: 6 hours at 170 ° C., 500 hours Samples were prepared according to the above experimental procedure, and as shown in Table 1, a homogenization treatment at 300 ° C. was 4 After holding for a time, the temperature was raised at 7.5 ° C./h, further held at 450 ° C.
  • Example 9 had the same composition as Example 6, but was homogenized without making a plate-shaped sample.
  • Example 9 is an example showing that the thermal conductivity is not affected even when a rolling step or the like is not performed to prepare a plate-shaped sample.
  • a plate-shaped sample was prepared and solution-treated at 400 ° C. for 2 hours.
  • the thermal conductivity of each sample was measured between the solution-treated material, the aging-treated material which was aged at 170 ° C. for 10 hours, and the aging-treated material which was aged for 500 hours.
  • the thermal conductivity of each of the above samples was 115.3 W / (m ⁇ K), 116.8 W / (m ⁇ K), and 129.5 W / (m ⁇ K), respectively.
  • Comparative Example 1 is an example showing the upper limit of the Zn concentration, and is a case where the amount of Zn added is increased as compared with Example 6. As a result, when 3% by mass of Zn is added, the thermal conductivity can be improved by the aging treatment, but the value higher than 120 W / (m ⁇ K) cannot be obtained by the aging treatment at 170 ° C. for 10 hours.
  • Comparative Example 2 (1) Alloy composition: Mg-3.0Al-0.7Zn-0.4Ca-0.3Mn (2) Solution treatment: A sample was prepared according to the above-mentioned experimental procedure at 400 ° C. for 1 hour, and solution treatment was performed at 400 ° C. for 1 hour. The thermal conductivity was measured for the solution-treated material. As a result, the value of thermal conductivity was 85.6 W / (m ⁇ K). Comparative Example 2 is a case where 90% of Zn of Comparative Example 1 is replaced with Al, and when Zn is replaced with Al, the thermal conductivity is remarkably lowered. Therefore, it is shown that Zn is preferable to Al as an alloying element. ing.
  • Comparative Example 3 is an example showing the upper limit of the Zn concentration, and the amount of Zn added is increased as compared with Examples and Comparative Example 1.

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Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2008016150A1 (fr) * 2006-08-03 2008-02-07 National Institute For Materials Science Alliage de magnésium et son procédé de fabrication
JP2015526592A (ja) * 2012-06-26 2015-09-10 バイオトロニック アクチェンゲゼルシャフト マグネシウム合金、その製造方法およびその使用
WO2019163161A1 (ja) * 2018-02-21 2019-08-29 国立研究開発法人物質・材料研究機構 マグネシウム合金及びマグネシウム合金の製造方法
WO2019172047A1 (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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008016150A1 (fr) * 2006-08-03 2008-02-07 National Institute For Materials Science Alliage de magnésium et son procédé de fabrication
JP2015526592A (ja) * 2012-06-26 2015-09-10 バイオトロニック アクチェンゲゼルシャフト マグネシウム合金、その製造方法およびその使用
WO2019163161A1 (ja) * 2018-02-21 2019-08-29 国立研究開発法人物質・材料研究機構 マグネシウム合金及びマグネシウム合金の製造方法
WO2019172047A1 (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

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