METAL LAMINATE MATERIAL AND METHOD FOR PRODUCING THE SAME
20180265990 ยท 2018-09-20
Assignee
Inventors
- Kouji NANBU (Kudamatsu-shi, Yamaguchi, JP)
- Yusuke HASHIMOTO (Kudamatsu-shi, Yamaguchi, JP)
- Hironao Okayama (Kudamatsu-shi, Yamaguchi, JP)
Cpc classification
C23F4/00
CHEMISTRY; METALLURGY
C21D9/0068
CHEMISTRY; METALLURGY
B32B15/01
PERFORMING OPERATIONS; TRANSPORTING
B32B38/0008
PERFORMING OPERATIONS; TRANSPORTING
B32B2311/00
PERFORMING OPERATIONS; TRANSPORTING
B32B15/013
PERFORMING OPERATIONS; TRANSPORTING
B32B37/18
PERFORMING OPERATIONS; TRANSPORTING
International classification
C23F4/00
CHEMISTRY; METALLURGY
B32B37/18
PERFORMING OPERATIONS; TRANSPORTING
C21D9/00
CHEMISTRY; METALLURGY
Abstract
This invention provides a magnesium laminate material with high heat radiation performance, reduced weight, higher strength, and excellent molding processability. Such metal laminate material has a three-layer-structure of a first stainless steel layer, a magnesium layer and a second stainless steel layer, wherein tensile strength (TS) is 200 to 430 MPa, elongation (EL) is 10% or more, and the surface hardness (Hv) of the first stainless steel layer and the second stainless steel layer is 300 or less.
Claims
1. A metal laminate material having a three-layer-structure of a first stainless steel layer, a magnesium layer and a second stainless steel layer, wherein tensile strength (TS) is 200 to 430 MPa, elongation (EL) is 10% or more, and the surface hardness (Hv) of the first stainless steel layer and the second stainless steel layer is 300 or less.
2. The metal laminate material according to claim 1, wherein the average crystal grain size of the first stainless steel layer and the second stainless steel layer is 1.5 m to 10 m, and the number of shear bands that cross a 10 m line along the sample coordinate system ND is less than 5 in the cross-sectional observation image from the sample coordinate system TD.
3. A method for producing the metal laminate material according to claim 1 comprising: a step of subjecting the first stainless steel plate or foil having surface hardness (Hv) of 300 or less to sputter-etching; a step of subjecting a magnesium plate or foil having surface hardness (Hv) of 50 or more to sputter-etching; a step of subjecting the surface of the first stainless steel plate or the foil to roll bonding to the surface of the magnesium plate or foil subjected to sputter-etching to obtain a bi-layer material of the first stainless steel layer/the magnesium layer; a step of subjecting the surface of the magnesium layer of the bi-layer material to sputter-etching; a step of subjecting the second stainless steel plate or foil having surface hardness (Hv) of 300 or less to sputter-etching; and a step of subjecting bi-layer material to roll bonding to the surface of the second stainless steel plate or the foil subjected to sputter-etching to obtain a metal laminate material of a three-layer-structure of the first stainless steel layer/the magnesium layer/the second stainless steel layer.
4. The method for producing the metal laminate material according to claim 3, wherein the surfaces subjected to sputter-etching are subjected to roll bonding at a rolling reduction of 25% or less.
5. A method for producing a metal laminate material comprising a step of subjecting the metal laminate material obtained by the method of production according to claim 3 to heat treatment at 100 C. to 590 C.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
[0029]
DESCRIPTION OF EMBODIMENTS
[0030] Hereafter, the present invention is described in detail.
[0031] As shown in
[0032] The metal laminate material 1 of the present invention has tensile strength (TS) of 200 to 430 MPa and elongation (EL) of 10% or more, and the surface hardness (Hv) of the first stainless steel layer 21 and the second stainless steel layer 22 is 300 or less. The lower limit of TS is preferably 220 or more and the upper limit thereof is preferably 400 or less, more preferably 390 or less, and further preferably 365 or less. EL is preferably 12% or more, and more preferably 20% or more. Hv is preferably 280 or less, and further preferably 249 or less. Within the above range, molding processability of the metal laminate material 1 is sufficient. Specifically, high molding processability, such that the height of bulge determined by the Erichsen test is 3 mm or more, preferably 3.2 mm or more, and more preferably 3.5 mm or more, can be attained. It was impossible to produce a laminate material with hardness (Hv) of 300 or more or TS of 430 MPa or more, as described in the examples below. It is deduced that the stainless steel plate or foil with high hardness and tensile strength could not be bonded to the magnesium with low molding processability because a sufficient contact area could not be formed at the interface between the stainless steel plate or the foil and the magnesium. Even if bonding was sufficiently performed, Ts exceeding 430 MPa would result in improved strength; however, the Erichsen value would not reach 3 mm, and molding processability may not be sufficient. When hardness (Hv) is over 300, also, the whole molding processability is likely to be insufficient due to the causes of high hardness (i.e., solid-solution elements, deposits, and processing strain). In the present invention, tensile strength (TS) and elongation (EL) are measured in accordance with JIS Z2241 (the method of metallic material tensile testing), and surface hardness (Hv) is measured in accordance with JIS Z2244 (the Vickers hardness test, load: 100 gf). The height of bulge determined by the Erichsen test is measured in accordance with JIS Z2247 (the Erichsen test).
[0033] It is preferable for the metal laminate material 1 of the present invention that the average crystal grain size of the first stainless steel layer 21 and the second stainless steel layer 22 be 1.5 m to 10 m and the number of shear bands that cross a 10-m line along the sample coordinate system ND (normal direction) in the image of the cross sectional plane from the sample coordinate system TD (transverse direction) be less than 5. Thus, high molding processability can be achieved. The average crystal grain size is more preferably 1.5 m to 8.0 m, and particularly preferably 2.0 m to 6.0 m. The number of shear bands that cross a 10-m line is more preferably 3 or less, further preferably 1 or less, and particularly preferably 0.
[0034] The average crystal grain size is determined by arbitrarily selecting 30 crystal grains in the image of the cross-sectional plane observed under a scanning electron microscope (SEM) from the sample coordinate system TD of the metal laminate material, measuring the longer diameter and the shorter diameter of each crystal grain, determining the average of the longer diameter and the shorter diameter as a grain size of the crystal grain, and determining the average grain size of the 30 crystal grains. In the present invention, the number of crossing shear bands is determined by drawing ten 10-m lines along the thickness direction (the sample coordinate system ND) of the metal laminate material in the image of the cross-sectional plane observed under SEM from the sample coordinate system TD of the metal laminate material, counting the number of shear bands crossing each line, and determining the average number of the 10 lines.
[0035] In the present invention, RD (rolling direction) corresponds to the direction of rolling, TD (transverse direction) corresponds to the direction perpendicular to RD, and ND (normal direction) corresponds to the direction normal to the rolling surface (plate surface).
[0036] Stainless steel materials constituting the first stainless steel layer 21 and the second stainless steel layer 22 are not particularly limited, and plates or foils of, for example, SUS304, SUS210, SUS316, SUS316L, and SUS430, can be used. In order to adjust Hv to 300 or lower after bonding, it is necessary that the surface hardness (Hv) of the plate or foil be 300 or less before bonding. As a result of roll bonding between the stainless steel layer and the magnesium plate or foil, processing strain is introduced into the stainless steel, and the surface hardness (Hv) is generally increased. However, it is preferable that a difference between hardness of the plate or foil before bonding and that after bonding (i.e., the state of the metal laminate material 1 as shown in
[0037] As a magnesium plate or foil, pure magnesium or magnesium alloy can be used without particular limitation. Specific examples include AZ31, AZ61, AZ91, and LZ91. When the surface hardness (Hv) of the magnesium plate or foil is excessively high, molding processability of the metal laminate material is deteriorated after bonding. When Hv is excessively low, in contrast, handling of the metal laminate material becomes difficult. Thus, surface hardness (Hv) should adequately be determined by taking such problems into consideration. While surface hardness (Hv) is preferably 50 to 100, it is not limited thereto. In addition, the magnesium plate or foil with thickness of 0.01 mm or more is generally sufficient. From the viewpoint of mechanical strength and processability of the resulting metal laminate material, thickness is preferably 0.01 mm to 1 mm, although the thickness is not limited thereto.
[0038] When producing the metal laminate material 1, at the outset, a bi-layer material of the first stainless steel layer/the magnesium layer is obtained by a process comprising a step of subjecting the first stainless steel plate or foil (hereafter, it is referred to as plate etc.) to sputter-etching and a step of subjecting the magnesium plate or foil to sputter-etching, followed by roll bonding of the surface of the first stainless steel plate or foil to the surface of the magnesium plate or foil. Subsequently, the metal laminate material 1 having a three-layer structure of the first stainless steel layer 21/the magnesium layer 10/the second stainless steel layer 22 as shown in
[0039] Sputter-etching can be carried out by preparing, for example, the first stainless steel plate etc. and the magnesium plate etc. (the same applies to the case in which a bi-layer material and the second stainless steel plate are subjected to sputter-etching) as a long coil with a width of 100 mm to 600 mm, designating stainless steel connected to magnesium as a ground-connected electrode, applying an alternating current of 1 MHz to 50 MHz to a region between the electrode and the other insulated electrode to generate glow discharge, and adjusting an area of the electrode exposed to the plasma generated by the glow discharge to one third or less of the area of the other electrode. During sputter-etching, the ground-connected electrode is in the form of a cooling roll, which prevents the transfer materials from temperature raising.
[0040] Sputter-etching treatment is intended to completely remove substances adsorbed to the surface and remove a part of or the entire oxide film on the surface by subjecting a surface on which stainless steel is bonded to magnesium to sputtering with inert gas in vacuum. It is not necessary to completely remove the oxide film, and stainless steel can be sufficiently bonded to magnesium in the presence of a remaining part of the oxide film. In the presence of a part of the oxide film remained, the duration of the sputter-etching treatment is shortened to a significant extent, and productivity of metal laminate materials is improved, compared to the case in which the oxide film is completely removed. Examples of inert gas that can be applied include argon, neon, xenon, krypton, and a mixed gas comprising at least one of the inert gases mentioned above. Substances adsorbed to the surface of stainless steel and magnesium can be completely removed with the etching amount of about 1 nm.
[0041] Stainless steel can be subjected to sputter-etching in vacuum at, for example, plasma output of 100 W to 10 kW and a line velocity of 0.5 m/min to 30 m/min. While a higher degree of vacuum is preferable in order to prevent substances from being adsorbed to the surface again, a degree of vacuum of, for example, 110.sup.5 Pa to 10 Pa is sufficient. In sputter-etching, the temperature of stainless steel is preferably maintained at room temperature to 150 C. so as to prevent magnesium from softening.
[0042] In the present invention, stainless steel comprising an oxide film remaining in a part on its surface can be obtained by adjusting the amount of stainless steel etching to, for example, 1 nm to 10 nm. According to need, the amount of etching may exceed 10 nm.
[0043] Magnesium can be subjected to sputter-etching in vacuum at, for example, plasma output of 100 W to 10 kW and a line velocity of 0.5 m/min to 30 m/min. While a higher degree of vacuum is preferable in order to prevent substances from being adsorbed to the surface again, a degree of vacuum of 110.sup.5 Pa to 10 Pa is sufficient.
[0044] In the present invention, magnesium comprising an oxide film remaining in a part on its surface can be obtained by adjusting the amount of magnesium etching to 1 nm to 10 nm. According to need, the amount of etching may exceed 10 nm.
[0045] A first stainless steel plate etc. can be subjected to roll bonding to a magnesium plate etc. and a bi-layer material can be subjected to roll bonding to a second stainless steel plate etc. A line pressure load for roll bonding is not particularly limited. For example, it can be adjusted to 0.1 to 10 tf/cm. At the time of roll bonding, the temperature is not particularly limited, and it is, for example, room temperature to 150 C.
[0046] If a rolling reduction exceeds 25% at the time of roll bonding, a large amount of processing strain is introduced, and the resulting metal laminate material is likely to suffer from poor molding processability. Accordingly, a rolling reduction is preferably 15% or less, and more preferably 10% or less. It is not necessary that the thickness before roll bonding be different from that after roll bonding. Thus, the lower limit of the rolling reduction is 0%.
[0047] Rolling bonding is preferably carried out in a nonoxidative atmosphere, such as an inert gas atmosphere of Ar, so as to avoid a lowered bonding force between stainless steel and magnesium caused by readsorption of oxygen to the surface of stainless steel and magnesium.
[0048] The average crystal grain size of the stainless steel plate or foil before bonding measured in the same manner as in the case of the metal laminate material is preferably 1.5 m to 10 m, and the number of shear bands crossing a 10-m-long line along the sample coordinate system ND is preferably less than 5. With the use of such stainless steel plate or foil while regulating a rolling reduction within the range described above, the metal laminate material of the three-layer structure, which has tensile strength (TS) of 200 to 430 MPa, elongation (EL) of 10% or more, and surface hardness (Hv) of the stainless steel layer of 300 or less, can be obtained with certainty. When the number of shear bands crossing the line is large or a rolling reduction is high before bonding, the number of shear bands crossing the line remains large after lamination, and molding processability may be lowered, disadvantageously.
[0049] It is preferable that the metal laminate material of the three-layer structure obtained via roll bonding be further subjected to heat treatment, according to need. Through heat treatment, processing strain of the magnesium layer is removed, and adhesion between layers can be improved. It is necessary that the heat treatment be carried out at a temperature lower than the magnesium melting point. For example, the melting point of the magnesium alloy AZ31 is approximately 600 C. Accordingly, heat treatment is carried out at 590 C. or lower, and preferably at 500 C. or lower, so as to prevent magnesium from being molten. The lower limit for heat treatment temperature is preferably 100 C., and more preferably 150 C.
[0050] Further, the heat treatment is preferably carried out at a temperature at which metal elements of stainless steel thermally diffuse to magnesium. A bonding force is improved by thermal diffusion.
[0051] Specifically, heat treatment can be carried out at 100 C. to 590 C. When heat treatment is carried out within such temperature ranges, the metal laminate material resulting from thermal diffusion has a high bonding force and high hardness of the reinforcing material, and magnesium can be prevented from being molten when heated. Heat treatment is preferably carried out at 150 C. to 500 C., so as to further enhance the bonding force and prevent magnesium from being molten. While the duration of heat treatment varies depending on temperature, a duration of 1 second to approximately 240 minutes is sufficient at, for example 300 C. (the duration does not include the temperature-rising time).
[0052] The thickness of the metal laminate material of the three-layer structure produced by the procedure described above is not particularly limited. The present invention can provide a thin metal laminate material with high molding processability by regulating tensile strength, elongation, and surface hardness of the stainless steel layer within given ranges. Specifically, the thickness of the metal laminate material can be, for example, 50 m to 800 m, preferably less than 700 m, and further preferably less than 600 m. As the proportion of the stainless steel layer accounting for the metal laminate material of the three-layer structure increases, molding processability is likely to be high. From the viewpoint of weight reduction, however, it is preferable that the proportion of magnesium be greater. When the thickness of the magnesium layer is excessively large compared with the thickness of the stainless steel layer, disadvantageously, molding processability of the metal laminate material is deteriorated.
EXAMPLES
[0053] Hereafter, the present invention is described in greater detail with reference to the examples and the comparative examples provided below, although the scope of the present invention is not limited to these examples.
Examples 1 to 4 and Comparative Example 1
[0054] SUS316 and SUS316L were used as the first stainless steel foil and the second stainless steel foil, and ZA31 was used as a magnesium foil. Table 1 shows characteristic values of the test materials. The hardness was tested using a Micro Vickers Hardness Tester (load: 100 gf), tensile strength and elongation were tested using a tensile tester (Autograph AGS-5kNS, Shimadzu Corporation), and height of bulge was tested using a mechanical Erichsen tester ESM-1 (CAP: 2 mm, Tokyo Koki Testing Machine Co., Ltd.).
TABLE-US-00001 TABLE 1 Height Test Thickness Hardness TS Elongation of bulge material Refining (mm) Hv (Mpa) (%) (mm) Stainless steel foil 1 SUS316 BA 0.0494 200.82 503 8.09 Stainless steel foil 2 SUS316L H 0.0502 257.76 704 45.5 5.98 Stainless steel foil 3 SUS316L H 0.0496 372.4 1095 3.6 2.98 Magnesium foil 1 AZ31 0.495 77.28 319.3 15.0 2.42 Magnesium foil 2 AZ31 0.598 69.66 275.1 16.7 2.12
[0055] Subsequently, the first stainless steel foil and the magnesium foil were subjected to sputter-etching. The first stainless steel foil was subjected to sputter-etching at 0.1 Pa and plasma output of 700 W for 20 minutes. The magnesium foil was subjected to sputter-etching at 0.1 Pa and plasma output of 700 W for 20 minutes. Thus, substances adsorbed to the surfaces of the first stainless steel foil and the magnesium foil were completely removed. After the sputter-etching treatment, the first stainless steel foil was subjected to roll bonding to the magnesium foil at room temperature at a line pressure load of 2 tf/cm. Thus, a bi-layer material was obtained.
[0056] Subsequently, the surface of the magnesium layer and the second stainless steel foil of the bi-layer material were subjected to sputter-etching. The bi-layer material was subjected to sputter-etching at 0.1 Pa and plasma output of 700 W for 20 minutes, the second stainless steel foil was subjected to sputter-etching at 0.1 Pa and plasma output of 700 W for 20 minutes, and substances adsorbed to the surfaces of the magnesium layer and the second stainless steel foil were completely removed. The magnesium layer and the second stainless steel foil of the bi-layer material were subjected to roll bonding to each other via at room temperature and a line pressure load of 2 tf/cm. Thus, a metal laminate material having a three-layer-structure of the first stainless steel layer/the magnesium layer/the second stainless steel layer was produced. The metal laminate materials (as clad materials) correspond to Examples 3 and 4. The reduction of the laminate material obtained in the end was determined in accordance with the formula (1) shown below, the rolling reduction of Example 3 was 8%, and that of Example 4 was 6.3%.
(Total thickness of test materialsthickness of laminate material)/(total thickness of test materials)100(%)Formula (1)
[0057] The metal laminate materials obtained through the procedure described above were further subjected to heat treatment at 300 C. for 30 minutes. The metal laminate materials subjected to the heat treatment correspond to Examples 1 and 2. Table 2 summarizes characteristic values of the metal laminate materials produced.
TABLE-US-00002 TABLE 2 Height Thickness Hardness TS Elongation of bulge No. Constitution (mm) Hv (MPa) (%) (mm) Ex. 1 Stainless steel foil 1/Magnesium foil 1/ 0.541 227.1 351.5 27 4.2 Stainless steel foil 1 Ex. 2 Stainless steel foil 2/Magnesium foil 1/ 0.558 265.3 357.6 23 3.4 Stainless steel foil 2 Ex. 3 Stainless steel foil 1/Magnesium foil 1/ 0.541 233.44 376.0 17 3.8 Stainless steel foil 1 Ex. 4 Stainless steel foil 2/Magnesium foil 1/ 0.558 258.5 381.3 14 3.3 Stainless steel foil 2 Comp. Ex. 1 Stainless steel foil 3/Magnesium foil 1/ Impossible to bond Stainless steel foil 3 Ex. 1 and Ex. 2: after heat treatment (300 C. 30 min); Ex. 3 and Ex. 4: as clads
[0058] When tensile strength (TS) was 200 to 430 MPa, elongation (EL) was 10% or more, and surface hardness (Hv) was 300 or less (Examples 1 to 4), as shown in Table 2, the height of bulge was found to be 3 mm or more and high molding processability was achieved. When test materials SUS316U (H materials) having surface hardness (Hv) exceeding 300 were used as the first and the second stainless steel foils (Comparative Example 1), it was not possible to bond the stainless steel foils to the magnesium foil. While the reason why the stainless steel foils were not bonded to the magnesium foil is not apparent, it is assumed that bonding cannot take place because of lack of a sufficient area of contact at the interface of the surfaces to be bonded when the stainless steel foils with high hardness are to be bonded to magnesium with poor molding processability.
[0059] The results of comparison of Example 3 and Example 1 and comparison of Example 4 and Example 2 also demonstrate that the height of bulge would be improved via heat treatment and more sufficient molding processability would be achieved.
(Evaluation of Average Crystal Grain Size)
[0060] The average crystal grain sizes of the stainless steel layers of the metal laminate materials of Examples 1 to 3 were determined in the manner described below. At the outset, samples of the metal laminate materials were soaked in aqua regia diluted to about one third as corrosive liquids for about 10 to 15 minutes, and the stainless steel layers were subjected to etching. Thereafter, the stainless steel layers of the samples subjected to etching were observed at the cross sectional plane from the sample coordinate system TD using an SEM (the field-emission scanning electron microscope SU8020, Hitachi High Technologies). On the basis of the observation images, the average crystal grain size was determined in accordance with the definition above. For comparison, the average crystal grain size of the stainless steel foil 1 and that of the stainless steel foil 2 before bonding were measured. The results of measurement are shown in Table 3.
TABLE-US-00003 TABLE 3 Test material alone After bonding (as clads) After heat treatment Stainless steel foil 1 2.6 Ex. 3 2.9 Ex. 1 2.9 (SUS316, BA) Stainless steel foil 2 5.5 Ex. 2 6.5 (SUS316L, H) Unit: m
[0061] As shown in Table 3, the average crystal grain size of the stainless steel layers of the metal laminate materials of Examples 1 to 3 with sufficient molding processability was within the range of 1.5 m to 10 m. Concerning the stainless steel foil 3 (SUS316L, H material), it was difficult to determine the crystal grain size due to the presence of shear bands.
(Evaluation of Shear Band)
[0062] Regarding the metal laminate materials of Examples 1 to 3, subsequently, the number of shear bands crossing a 10-m line along the sample coordinate system ND in the cross-sectional observation image from the sample coordinate system TD was determined in accordance with the definition above. The apparatuses used to evaluate the average crystal grain size above were used for measurement. For comparison, the number of shear bands of the stainless steel foil 1 and that of the stainless steel foil 3 before bonding were measured. The results of measurement are shown in Table 4.
TABLE-US-00004 TABLE 4 Test material alone After bonding (as clads) After heat treatment Stainless steel foil 1 0 Ex. 3 0 Ex. 1 0 SUS316 (BA) Stainless steel foil 3 6 Comp. Ex. 1 Impossible SUS316L (H) to bond Numerical values in the tables indicate the numbers of shear bands crossing the line
[0063] As shown in Table 4, no shear bands crossing the line were observed in the stainless steel layer of Example 3. In addition, no shear bands were observed in the stainless steel foil 1 before bonding (
DESCRIPTION OF NUMERAL REFERENCES
[0064] 1: Metal laminate material [0065] 10: Magnesium layer [0066] 21: First stainless steel layer [0067] 22: Second stainless steel layer
[0068] All publications, patents, and patent applications cited herein are incorporated herein by reference in their entirety.