CN113667846A - Copper alloy ingot, copper alloy foil, and method for producing copper alloy ingot - Google Patents
Copper alloy ingot, copper alloy foil, and method for producing copper alloy ingot Download PDFInfo
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- CN113667846A CN113667846A CN202110510662.3A CN202110510662A CN113667846A CN 113667846 A CN113667846 A CN 113667846A CN 202110510662 A CN202110510662 A CN 202110510662A CN 113667846 A CN113667846 A CN 113667846A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 239000011888 foil Substances 0.000 title claims description 33
- 239000011573 trace mineral Substances 0.000 claims abstract description 161
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 161
- 239000010949 copper Substances 0.000 claims abstract description 80
- 239000000654 additive Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 64
- 229910052802 copper Inorganic materials 0.000 claims description 64
- 239000002245 particle Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 239000012768 molten material Substances 0.000 claims description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CWWARWOPSKGELM-SARDKLJWSA-N methyl (2s)-2-[[(2s)-2-[[2-[[(2s)-2-[[(2s)-2-[[(2s)-5-amino-2-[[(2s)-5-amino-2-[[(2s)-1-[(2s)-6-amino-2-[[(2s)-1-[(2s)-2-amino-5-(diaminomethylideneamino)pentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-5-oxopentanoyl]amino]-5 Chemical compound C([C@@H](C(=O)NCC(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCSC)C(=O)OC)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](N)CCCN=C(N)N)C1=CC=CC=C1 CWWARWOPSKGELM-SARDKLJWSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
- B21B1/026—Rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D33/00—Special measures in connection with working metal foils, e.g. gold foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D1/00—Treatment of fused masses in the ladle or the supply runners before casting
- B22D1/007—Treatment of the fused masses in the supply runners
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- 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
- B21B2003/005—Copper or its alloys
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Continuous Casting (AREA)
- Powder Metallurgy (AREA)
- Metal Rolling (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The purpose of the present invention is to provide a copper alloy ingot having further improved uniformity of physical properties. The copper alloy ingot of the present invention has a composition containing at least 1 additive element, and the balance being Cu and unavoidable impurities, wherein the at least 1 additive element is a trace element having a concentration of 10 to 50 mass ppm, and the variation in concentration of the trace element in the longitudinal direction is within a range of + -3.5 mass ppm with respect to the average concentration of the trace element.
Description
Technical Field
The present invention relates to a copper alloy ingot, a copper alloy foil, and a method for manufacturing a copper alloy ingot.
Background
Conventionally, in a copper alloy, physical properties of a copper alloy rolled product (such as a copper alloy foil or sheet) produced from a copper alloy ingot after addition of a small amount of an additive element have been improved by adding a small amount of the additive element to copper or the copper alloy. For example, patent document 1 discloses that In order to obtain a copper alloy foil for a flexible printed circuit board having a fine crystal size and excellent In bendability and etching properties, 1 or more additive elements selected from the group consisting of P, Ti, Sn, Ni, Be, Zn, In, and Mg are added to copper In a total amount of 0.003 to 0.825 mass%.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-141501
Disclosure of Invention
Technical problem to be solved by the invention
Among them, for example, a copper alloy (microalloyed copper alloy) containing a small amount of additive elements as described above can be obtained as follows: a copper alloy in the form of, for example, an ingot is obtained by casting a molten copper material melted in a melting furnace that melts copper as a base material, with a small amount of an additive element being added while supplying the molten copper material into a tundish furnace through a pipe, and the molten copper material being guided from the tundish furnace to a casting facility (continuous casting). By producing an ingot in this manner, the base material can contain the additive elements uniformly, and the ingot can be produced continuously and efficiently.
However, in recent years, in electronic products having as a component a copper alloy rolled product including a copper alloy foil manufactured by rolling a microalloyed copper alloy ingot, a higher performance is required, and along with this, a higher degree of uniformity in physical properties is required for the copper alloy foil and further for the ingot.
Accordingly, an object of one embodiment of the present invention is to provide a copper alloy ingot, a copper alloy foil, and a method for producing a copper alloy ingot, in which uniformity of physical properties is further improved.
Means for solving the problems
In one embodiment, the copper alloy ingot of the present invention has a composition containing at least 1 additive element, and the balance being Cu and unavoidable impurities, wherein the at least 1 additive element is a trace element having a concentration of 10 to 50 mass ppm, and the variation in concentration of the trace element in the longitudinal direction is within a range of ± 3.5 mass ppm with respect to the average concentration of the trace element.
In one embodiment, the copper alloy foil of the present invention is obtained by rolling the above-described copper alloy ingot.
In one embodiment, a method for producing a copper alloy ingot according to the present invention is a method for producing a copper alloy ingot, including: and a step of adding the trace element to a molten copper material containing Cu while causing the molten copper material to flow in one direction, wherein when a desired concentration of the trace element in the copper alloy ingot is denoted as a concentration D, in the step of adding, an addition amount M1 for 1 second is adjusted to be less than 2 times a theoretical addition amount M2 of the trace element per 1 second, the theoretical addition amount M2 being calculated using the concentration D and a flow rate F per 1 second of the molten copper material flowing in one direction.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a copper alloy ingot, a copper alloy foil, and a method for producing a copper alloy ingot, in which uniformity of physical properties is further improved, can be provided.
Detailed Description
Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail, but the present invention is not limited to the embodiment.
The copper alloy ingot of the present embodiment is an ingot of a micro-alloyed copper alloy (micro copper alloy), and has a composition containing at least 1 kind of additive element and the balance being Cu and unavoidable impurities, wherein the at least 1 kind of additive element is a trace element (trace elements) having a concentration of 10 to 50 mass ppm, and a variation in concentration of the trace element in the longitudinal direction is within a range of ± 3.5 mass ppm with respect to an average concentration of the trace element. The copper alloy ingot according to the present embodiment is not particularly limited, and can be used for applications in which copper alloy rolled products (for example, copper alloy sheets and foils) are produced by a rolling step. The copper alloy foil produced from the ingot can be used for flexible printed circuit boards, for example.
The copper alloy ingot according to the present embodiment (hereinafter, simply referred to as "ingot") has the above-described composition, and thus can have a high degree of uniformity of physical properties.
More specifically, since the ingot of the present embodiment contains trace elements at a concentration of 10 to 50 mass ppm, for example, when the ingot is processed in a rolling step, crystal grains in the composition can be suitably refined, and a copper alloy rolled product having strength and high bending resistance can be obtained.
In the case of using the copper alloy rolled product as a copper alloy rolled product, there is a possibility that a user may heat-treat the copper alloy rolled product during use (for example, heat treatment when laminating a copper alloy foil and a resin in the case of a copper alloy foil), and the variation in concentration of trace elements in the longitudinal direction of the ingot is within a range of ± 3.5 mass ppm with respect to the average concentration of trace elements, whereby recrystallization can be appropriately performed after the heat treatment.
That is, a user of a copper alloy rolled product produced from an ingot generally sets heat treatment conditions for the entire copper alloy rolled product to be used, with reference to a certain portion (for example, a portion where trace elements have an average concentration) in the copper alloy rolled product. However, if the concentration of the trace element is higher than the upper limit value or lower than the lower limit value in a certain portion of the copper alloy rolled product in the longitudinal direction, it is difficult to sufficiently adapt the predetermined heat treatment conditions to the portion in the copper alloy rolled product. As a result, when the concentration exceeds the upper limit, recrystallization is less likely to occur, and when the concentration is lower than the lower limit, recrystallized grains are coarsened.
Therefore, by setting the variation in the concentration of the trace element in the longitudinal direction of the ingot to be within the range of ± 3.5 mass ppm with respect to the average concentration of the trace element, for example, in a copper alloy rolled product produced from the ingot, the nonuniformity of the physical properties in the longitudinal direction of the copper alloy rolled product can be sufficiently reduced, and therefore, in the case where a user performs a heat treatment under a predetermined condition using the copper alloy rolled product, it is possible to avoid a portion that does not conform to the predetermined heat treatment condition and does not perform recrystallization appropriately in the copper alloy rolled product.
The trace elements In the composition of the copper alloy ingot of the present embodiment are not particularly limited, and may Be any elements, but are preferably elements capable of refining crystal grains, and more preferably 1 or more selected from the group consisting of P, Zr, Cr, Ti, Sn, Ni, Be, Zn, In, Mg, V, Mo, W, Ba, Sr, and Y, and even more preferably P. These elements can make it easier to refine crystal grains in a copper alloy rolled product obtained by working a copper alloy ingot.
The concentration of the trace element in the ingot is 10 to 50 mass ppm. When the concentration of the trace element is in such a range, for example, in the case of working as a copper alloy rolled product by a rolling process, crystal grains in the composition can be suitably refined. Specifically, by setting the concentration to 10 mass ppm, crystal grains in the composition can be made fine, and the strength and bending resistance of the copper alloy rolled product can be improved. Further, since the concentration is 50 mass ppm or less, the recrystallization temperature does not increase excessively, and recrystallization can be caused when the copper alloy rolled product is heat-treated, it is possible to prevent the strength from becoming excessively high, and to ensure the bending resistance.
When the ingot contains a plurality of trace elements, the concentrations of the respective trace elements are within the above-described ranges (for example, 10 to 50 mass ppm).
The variation in the concentration of the trace element in the longitudinal direction is within a range of. + -. 3.5 mass ppm, more preferably within a range of. + -. 2 mass ppm, and still more preferably within a range of. + -. 1 mass ppm with respect to the average concentration of the trace element. By setting the deviation to the range of ± 3.5 mass ppm, for example, in a copper alloy rolled product produced from an ingot, since the nonuniformity of physical properties in the longitudinal direction of the copper alloy rolled product can be sufficiently small, in the case where a user performs a heat treatment under a predetermined condition using the copper alloy rolled product, it is possible to avoid generation of a portion in which a desired physical property cannot be obtained due to the heat treatment condition not being suitable for the predetermined condition in the copper alloy rolled product.
When the ingot contains a plurality of trace elements, the concentration of each trace element varies within the above range (for example, within a range of ± 3.5 mass ppm).
Here, the concentration of a trace element in an ingot is a value obtained by sampling the surface of the ingot at every 1m point in the longitudinal direction of the ingot at the center in the width direction of the ingot (except for a range of 2.25cm from both ends in the longitudinal direction of the ingot), measuring each obtained sample by ICP emission spectrometry, and averaging the measured values (and this value is referred to as the average concentration of a trace element in the ingot). The deviation of the concentration within the range of ± 3.5 mass ppm with respect to the average concentration of the trace elements means that the concentration of each sample sampled and measured by the above-described method falls within the range between a concentration (upper limit) 3.5 mass ppm higher than the concentration (average value) of the trace elements obtained by the above-described method and a concentration (lower limit) 3.5 mass ppm lower than the average concentration.
In the present embodiment, the copper alloy contains trace elements and at least 1 additional element. When an element other than a trace element is contained as an additive element, the additive element other than the trace element is not particularly limited, and examples thereof include Ag, Sn, and Zr. The concentration of the additive elements other than the trace elements is not particularly limited, and may be 0.01 to 0.2 mass%.
In the present embodiment, the balance is made up of Cu and unavoidable impurities. Here, the inevitable impurities are impurity elements inevitably mixed into the material in the manufacturing step.
The ingot of the present embodiment is not particularly limited, and may have a thickness of 150 to 220mm, a length of 3 to 6m, and a width of 500 to 700mm, for example. The shape of the ingot is not particularly limited, and may be, for example, a rectangular parallelepiped shape.
As described above, the ingot of the present embodiment is preferably used for applications (for copper alloy sheets, copper alloy foils, and the like) in which a copper alloy rolled material is produced by a rolling step, and particularly preferably used for copper alloy foils.
Specifically, the copper alloy rolled product produced from the ingot of the present embodiment is not particularly limited, and the ingot can be rolled and produced by a known method. The copper alloy rolled product preferably has the same composition as an ingot, specifically, a composition containing at least 1 additive element and the balance being Cu and inevitable impurities, wherein the at least 1 additive element is a trace element having a concentration of 10 to 50 mass ppm, and the variation in concentration of the trace element in the longitudinal direction is within ± 3.5 mass ppm with respect to the average concentration of the trace element.
The concentration of the trace element in the copper alloy rolled product is a value obtained by sampling the surface of the copper alloy rolled product at every 10000m in the longitudinal direction at the center in the width direction (excluding the range of 1m from both ends in the longitudinal direction), measuring each obtained sample by the same method as the ingot, and averaging the measured values (this value is referred to as the average concentration of the trace element in the copper alloy rolled product). The variation in concentration within the range of ± 3.5 mass ppm with respect to the average concentration of the trace element means that the concentration of each sample obtained by sampling and measuring by the above-described method falls within the range between a concentration (upper limit) 3.5 mass ppm higher than the concentration (average) of the trace element and a concentration (lower limit) 3.5 mass ppm lower than the concentration (average) of the trace element.
When a copper alloy foil is produced from the ingot according to the present embodiment, the thickness of the copper alloy foil is preferably 0.003 to 0.017 mm.
Next, a method for producing a copper alloy ingot according to the present embodiment will be described.
The method for producing a copper alloy ingot according to the present embodiment (hereinafter also referred to as an ingot production method) is a method for producing a copper alloy ingot according to the above-described embodiment of the present invention, and includes a step of adding a trace element to a molten copper material containing Cu while flowing the molten copper material in one direction.
More specifically, the ingot manufacturing method according to the present embodiment can use a manufacturing apparatus including: a melting furnace for melting a material (for example, copper) before adding a trace element as a base material; a pipe through which a copper melt (molten copper) melted in the melting furnace flows in one direction; a tundish furnace to which a copper molten material is supplied through the pipe; and a casting device for introducing the molten copper material from the tundish furnace into the casting device. Further, the manufacturing apparatus includes: and an addition path which communicates with the duct and extends upward in the vertical direction, wherein the top end of the belt conveyor is positioned at an opening part on the upper side in the vertical direction of the addition path.
In the case of using such a manufacturing apparatus, an ingot is manufactured by allowing a trace element conveyed by a belt conveyor to fall from the tip of the belt conveyor while flowing a copper molten material in one direction (from one end of the pipe to the other end) in a pipe and by being thrown into an opening portion on the upper side in the vertical direction of an addition path, thereby adding the trace element to the copper molten material.
In the above-described manufacturing apparatus, a low-frequency induction furnace can be used as the melting furnace, and the melting is preferably performed in an oxygen-free state.
The pipe may be a cylindrical passage, and in order to prevent oxidation of the molten copper (molten copper) flowing through the pipe, it is preferable that the inside of the pipe is filled with an inert gas such as nitrogen (the molten copper flows below the inside of the pipe, and the space above the molten copper is filled with the inert gas).
The addition path may be a cylindrical passage that communicates with the duct and extends upward in the vertical direction (may be inclined), and may have an opening portion on the upper side in the vertical direction of the addition path. In order to make the trace elements conveyed by the belt conveyor fall and easily enter the inside of the addition path, the opening portion may be made to have an expanded shape, or a funnel may be mounted at the opening portion.
The belt conveyor can be used for automatically conveying the trace elements, and the conveyed trace elements fall from the top end of the belt conveyor and are thrown into the opening of the adding path. In order to quantitatively convey and charge the trace elements by using the belt conveyor, the belt conveyor preferably has a metering function capable of measuring the weight of the trace elements before and after dropping. Such a belt conveyor having a metering function can adjust the amount of trace elements to be fed by measuring the amount of change in the mass of the trace elements carried on the belt, for example, in order to feed a predetermined amount of trace elements per unit time; specifically, when the actual amount of trace elements to be charged (the amount of mass change) exceeds a predetermined amount, the feeding by the belt conveyor is stopped for a certain period of time, and the amount of trace elements to be charged can be adjusted.
The tundish furnace is a furnace in which the molten copper material is temporarily stored, and the molten copper material is stirred in the furnace and impurities and the like can be removed. The trace element is preferably added to the copper molten material flowing through the pipe in the present embodiment, but may be added to the copper molten material in the tundish furnace.
The casting facility is capable of producing an ingot by introducing a predetermined amount of a copper molten material from a tundish furnace and cooling the copper molten material.
Here, in the method of manufacturing an ingot according to the present embodiment, in the step of adding a trace element to the copper molten material, the amount of addition M1 of the trace element in 1 second can be adjusted to be less than 2 times the theoretical amount of addition M2 of the trace element per 1 second, the theoretical amount of addition M2 being calculated using the concentration D (the required concentration of the trace element in the ingot) and the flow rate F per 1 second of the copper molten material flowing in one direction.
The "amount of trace element added per 1 second M1" means the mass of trace element actually added to the copper melt within 1 second, and means the mass of the trace element itself in the diluted particles.
The "theoretical amount of trace element added M2 per 1 second" is calculated using the concentration D of trace elements in the ingot and the flow rate F per 1 second of the copper molten material flowing in one direction, in other words, the mass of trace elements to be added to the copper molten material per 1 second calculated so that the concentration of trace elements in the copper alloy becomes the desired concentration D. That is, when a trace element is directly added (as a simple substance) to a copper melt, the concentration D of the trace element in the ingot can be determined by the theoretical addition amount M2 of the trace element per 1 second, which is M2 — D × F/(1-D), as D2/(F + M2). Therefore, the amount of trace element added M1 in 1 second was M1 < 2 × M2 — 2 × D × F/(1-D).
When the concentration of the trace element in the ingot is defined as "D", the theoretical amount of the trace element added per 1 second of M2 is defined as "M2" × F/(1-D/D) "as" D2/(F + M2/D "), as" D "when the concentration of the trace element in the ingot is defined as" D ". Therefore, the amount of trace element added per 1 second of M1 was M1 < 2 × M2 — 2 × D × F/(1-D/D).
The flow rate F of the copper molten material can be obtained by, for example, the amount of the copper molten material supplied from the melting furnace and the supply time thereof, and can be calculated by an arbitrary method.
In the present embodiment, the variation in the concentration of the trace element in the longitudinal direction of the ingot can be reduced by adjusting the amount of addition M1 of the trace element within 1 second to be less than 2 times the theoretical amount of addition M2 of the trace element per 1 second. That is, when the amount of addition M1 in 1 second is more than 2 times the theoretical amount of addition M2 per 1 second, an excessively high concentration of trace elements is generated in the copper melt. At the same time, if the amount of addition M1 in 1 second is too large, the amount of addition M1 of the trace element in the next 1 second is adjusted to 0, or the amount of addition M1 of the trace element is continuously decreased in the next several seconds, and the amount of addition M1 is decreased, then in the copper molten material, in addition to the above-described portion where the concentration of the trace element is too large, a portion where the concentration of the trace element is too low may be generated. Therefore, by adjusting the amount of addition of the trace element M1 in 1 second to be less than 2 times the theoretical amount of addition M2 per 1 second, the unevenness of such trace element in the copper molten material can be reduced, and therefore the variation in the concentration of the trace element in the longitudinal direction of the ingot can be reduced.
Here, in the method for producing an ingot according to the present embodiment, as a method for adjusting the amount of the trace element added in 1 second to be less than 2 times the theoretical amount of the trace element added M2 per 1 second, the following method can be exemplified.
That is, as a method of adjusting the amount of addition of the trace element M1 in 1 second to less than 2 times the theoretical amount of addition of M2 per 1 second, the following methods are exemplified: in the ingot manufacturing apparatus, the height (thickness) of the additive element carried on the belt conveyor for throwing the copper molten material flowing into the pipe through the additive path is made relatively small. That is, when the height (thickness) of the additive element carried on the belt conveyor is large, the trace element is carried while being carried in a large amount in the height direction, and thus the trace element tends to fall more from the tip of the belt conveyor toward the opening of the additive path (the trace element accumulated in the height direction tends to fall more from the tip). On the contrary, by reducing the height of the additive element carried on the conveyor belt, the amount of the trace element falling from the tip of the belt conveyor to the opening of the additive path can be reduced, and the amount of the trace element added M1 in 1 second can be easily adjusted. In addition, the adjustment can be performed by changing the conveying speed of the belt conveyor itself.
In addition, as methods other than the above methods, there can be mentioned: in the ingot manufacturing apparatus, a belt width (a length in a direction orthogonal to a belt traveling direction) of a belt conveyor for throwing a molten copper material flowing through an addition path into a pipe is made relatively small. That is, when the belt width of the belt conveyor is large, the trace elements are conveyed while being carried in a state of being widely spread in the width direction, and thus the amount of the trace elements added per one time of dropping from the tip of the belt conveyor to the opening portion of the addition path tends to be large (the trace elements stacked in the width direction tend to drop from the tip frequently). Conversely, by reducing the belt width, the trace elements falling from the tip of the belt conveyor to the opening of the addition path can be reduced, and the amount of addition M1 of the trace elements in 1 second can be easily adjusted.
In addition to the above-mentioned methods, when the trace element is in a particle form as described below, a method of making the particle diameter of the trace element relatively small can be mentioned. By reducing the particle diameter of the trace element, the trace element gradually falls down little by little (the trace element does not fall down a large amount from the tip at a time) when the trace element falls down from the tip of the belt conveyor to the opening of the addition path, and therefore the amount of addition M1 of the trace element within 1 second can be easily adjusted.
Further, as a method other than the above method, there is a method of blowing a gas, more preferably an inert gas such as nitrogen gas, into the opening of the addition path when dropping and charging the trace elements conveyed by the belt conveyor. Specifically, when a trace element is thrown into a copper molten material flowing in a pipe through an addition path, heat of the copper molten material causes an updraft to be generated in the addition path, and therefore unevenness is generated in the dropping in the trace element addition path. However, the trace elements can be more stably dropped by blowing the gas toward the opening of the addition path. In particular, in the ingot production method of the present embodiment, when the molten copper material flows in a state in which the inside of the pipe is filled with the inert gas, the gas may flow back in the addition path, and therefore the trace elements can be more stably dropped by blowing the gas toward the opening of the addition path. In addition, in the case of using an inert gas, oxidation of the trace elements can be prevented.
In the method for producing an ingot according to the present embodiment, the method of adjusting the amount of addition of the trace element M1 in 1 second to less than 2 times the theoretical amount of addition M2 per 1 second has been described above, but the method of adjustment in the method for producing an ingot according to the present embodiment is not limited to the above, and any method or combination of the above may be used.
In the method for producing an ingot according to the present embodiment, the trace element is preferably added using a particulate trace element, and more preferably, diluted particles in which the trace element is diluted in copper (specifically, a product of mixing the trace element with copper) are added. By using the particulate trace element, the amount of the trace element M1 added in 1 second can be easily adjusted to an appropriate amount, and by using the diluent particles, the amount of the trace element M1 added in 1 second can be more easily adjusted by increasing the amount of the trace element to be added. In addition, chemical changes such as oxidation of the trace elements can be suppressed, and the handleability of the trace elements can be improved.
The particle diameter is preferably 2.0 to 4.0 mm. The particle diameter means a volume average particle diameter, that is, a value (D) of 50% of a volume particle diameter distribution50)。
When the particle diameter is less than 2.0mm, although it is advantageous in that it can be dissolved in the molten copper quickly, it is liable to become a lump during transportation, and it is difficult to adjust the amount of M1 added within 1 second. In addition, when the particle diameter is less than 1.0mm, it may be oxidized and may be affected by the gas flow. On the other hand, when the particle diameter is larger than 4.0mm, the handling is easy, but it tends to be difficult to adjust the amount of M1 added within 1 second.
The concentration d of the trace element is preferably 50% by mass or less, and more preferably 20% by mass or less. Within such a range, the amount of addition M1 in 1 second can be adjusted by increasing the amount of input.
Further, in the case where the ingot contains an additive element other than a trace element, the additive element other than a trace element may be added by using an addition route in the method for producing an ingot of the present embodiment, as in the method for adding a trace element, or the additive element may be contained in the material itself melted in the melting furnace, or the additive element may be added in the tundish furnace.
In the method for producing an ingot according to the present embodiment, when the trace element is P, it is preferable to use diluent particles containing 8 mass% or more of P in Cu (specifically, a product obtained by mixing P with Cu). This enables production of a copper alloy ingot having further improved uniformity of physical properties.
More specifically, by using the diluent particles, the addition amount is increased as compared with the addition of the elemental substance P, and the addition rate of P can be easily adjusted to an appropriate rate. Further, chemical changes such as oxidation of P can be suppressed, and the handleability of P can be improved.
Further, since P contains 10 mass% or more of diluent particles in Cu and the melting point is high and close to the melting point of Cu, when P is added using the diluent particles, P is slowly dissolved in the copper melt (the dissolution rate is decreased), and P can be easily dispersed in the copper melt. When the concentration of P is 13 mass% or more, the hardness of the diluted particles is relatively high, and it is difficult to generate fine powder in the diluted particles in the process of producing the diluted particles. In the case where the amount of fine powder in the diluent particles is large, when P is added, the fine powder is rapidly dissolved in the copper melt (the dissolution rate increases), P is locally present in the copper melt, and the generation of the fine powder is suppressed, whereby the local presence of P can be suppressed.
Therefore, by adding P using diluted particles in which P is contained in Cu by 8 mass% or more, the addition of P can be more easily adjusted, and the dispersibility of P in the copper molten material can be improved, and as a result, a copper alloy ingot with further improved uniformity of physical properties can be produced.
The concentration of P in the diluted particles is preferably 8 to 16 mass%, more preferably 14 to 16 mass%.
Although the embodiments of the present invention have been described above, the copper alloy ingot, the copper alloy foil, and the method for producing a copper alloy ingot according to the present invention are not limited to the above examples, and can be modified as appropriate.
Examples
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to the following examples.
(Experimental example 1)
In experimental example 1, a copper alloy ingot was produced as follows, and the concentration of trace elements and the variation thereof of the ingot were measured.
The copper alloy ingot of example 1 was produced while adding trace elements to a molten copper material while allowing the molten copper material to flow, and the amount of trace elements added in 1 second at this time, M1, was adjusted to be less than 2 times the theoretical amount of trace elements added per 1 second, M2.
Specifically, the composition of the copper alloy ingot was copper and phosphorus as a trace element, and 5 tons of copper was used for producing the copper alloy ingot. The trace elements were added using diluted particles (product name 15PCuA, phosphorus concentration 15 mass%, particle diameter 2.0 to 3.7mm, Osaka alloy industries, Ltd.) diluted in copper.
A manufacturing apparatus for manufacturing an ingot, comprising: a melting furnace; a pipe through which a copper molten material melted in the melting furnace passes; a tundish furnace to which a copper molten material is supplied through the pipe; a casting device for introducing a molten copper material from the tundish furnace into the casting device; an addition path which communicates with the duct and extends upward in the vertical direction; and a belt conveyor having an opening at a distal end thereof located at a vertically upper side of the addition path. In addition, in the belt conveyor of the manufacturing apparatus, the height of the trace element (diluted particles) carried on the belt conveyor is adjusted so that the addition amount M1 of the trace element in 1 second is less than 2 times the theoretical addition amount M2 per 1 second.
The ingot produced as described above had a thickness of 178mm, a width of 635mm and a length of 5 m.
Further, 5 samples were taken from the ingot, and the phosphorus concentration of the ingot was measured by the ICP emission spectrometry. As a result, the calculated phosphorus concentration (average value) is within the range of 10 to 50 mass ppm. Further, the difference between the phosphorus concentration of each sample and the phosphorus concentration (average value) of the ingot was-0.2 mass ppm, +0.8 mass ppm, -1.2 mass ppm, and +0.8 mass ppm, and the deviation was within a range of. + -. 3.5 mass ppm with respect to the average concentration of the trace elements.
Further, copper alloy ingots of comparative examples 1 and 2 were produced in the same manner as in example 1, except that the amount of trace element added in 1 second, M1, was 2 times or more the theoretical amount of addition, M2, per 1 second. Specifically, the addition amount is adjusted by changing the conveying speed of the belt conveyor itself.
5 samples were sampled from the ingots of comparative examples 1 and 2, and the calculated phosphorus concentration (average value) was within the range of 10 to 50 mass ppm.
Further, the phosphorus concentrations of the samples of comparative example 1 were-6.0 mass ppm, -2.0 mass ppm, +3.0 mass ppm, +4.0 mass ppm and +1.0 mass ppm, and the deviations were out of the range of. + -. 3.5 mass ppm relative to the average concentration of trace elements. The phosphorus concentrations of the samples of comparative example 2 were-5.4 mass ppm, -2.4 mass ppm, +1.6 mass ppm, +3.6 mass ppm, and +2.6 mass ppm, and the deviations were out of the range of. + -. 3.5 mass ppm relative to the average concentration of trace elements.
(Experimental example 2)
In experimental example 2, the influence of the variation of the elements on the copper alloy foil was confirmed. Specifically, the following example 2 and comparative examples 3 and 4 were examined as to whether or not a copper alloy foil produced by rolling a copper alloy ingot and a resin were laminated under heating and then recrystallized appropriately in the composition of the copper alloy foil.
In example 2, the copper alloy foil was 0.012mm thick, and the copper alloy foil produced from the copper alloy ingot of example 1 was used. The resin material was polyimide (Pixio FRS manufactured by KANEKA, K.) having a thickness of 25 μm. The copper alloy foil, the resin, and the copper alloy foil were stacked and pressed by using a 350 ℃ roller, thereby performing lamination.
Next, comparative examples 3 and 4 were performed in the same manner as in example 2, except that copper alloy foils were produced from the copper alloy ingots of comparative examples 1 and 2, respectively.
As a result, in example 2, recrystallization in the copper alloy foil was suitable, the average crystal size was 2.5 μm, and coarse particles having 10 times or more the average crystal size were not observed. In comparative examples 3 and 4, there were portions in which recrystallization was not completed in the copper alloy foil, and even when recrystallization was completed and the average crystal grain size was 2.5 μm, there were portions in which coarse grains of 10 times or more the average crystal grain size existed, and recrystallization did not proceed properly.
The average crystal particle size was determined by observing the surface of each copper alloy foil using sem (scanning Electron microscope) and was calculated according to JIS H0501. Wherein twin crystals are measured as different crystal grains. The measurement area is 100 μm × 100 μm on the surface.
Based on the results of experimental example 1 described above, it was found that, in the method for producing a copper alloy ingot, by adjusting the amount of addition M1 of a trace element in 1 second to be less than 2 times the theoretical amount of addition M2 of the trace element per 1 second, the variation in the concentration of the trace element in the ingot in the longitudinal direction was within a range of ± 3.5 mass ppm with respect to the average concentration of the trace element. Further, it is understood from the above-mentioned experimental example 2 that the copper alloy foil produced from the copper alloy ingot having a small variation in trace elements has high uniformity of physical properties.
Industrial applicability of the invention
According to the present invention, a copper alloy ingot, a copper alloy foil, and a method for producing a copper alloy ingot, in which uniformity of physical properties is further improved, can be provided.
Claims (7)
1. A copper alloy ingot is provided, which comprises a copper alloy ingot,
has a composition containing at least 1 additive element and the balance of Cu and inevitable impurities,
the at least 1 additive element is a trace element with a concentration of 10-50 mass ppm,
the variation in the concentration of the trace element in the longitudinal direction is within a range of. + -. 3.5 mass ppm relative to the average concentration of the trace element.
2. The copper alloy ingot according to claim 1, wherein the trace element is phosphorus.
3. A copper alloy foil obtained by rolling the copper alloy ingot according to claim 1 or 2.
4. A method for producing a copper alloy ingot according to claim 1 or 2, wherein,
comprising the step of adding the trace element to a molten copper material containing Cu in a molten state while allowing the molten copper material to flow in one direction,
when the desired concentration of the trace element of the copper alloy ingot is denoted as concentration D,
in the adding step, an addition amount M1 of the trace element in 1 second is adjusted to be less than 2 times a theoretical addition amount M2 of the trace element per 1 second, the theoretical addition amount M2 being calculated using the concentration D and the flow rate F per 1 second of the copper molten material flowing in one direction.
5. The method of producing a copper alloy ingot according to claim 4, wherein the trace element is added using diluent particles obtained by diluting the trace element in Cu.
6. A method for producing a copper alloy ingot according to claim 5, wherein the diluent particles are formed by adding 8 mass% or more of phosphorus to Cu.
7. The method of producing a copper alloy ingot according to any one of claims 4 to 6, wherein in the step of adding,
the copper molten material flows in one direction in a pipe filled with an inert gas,
the trace element is added by dropping the trace element conveyed by the belt conveyor from the tip end of the belt conveyor into a vertically upper opening of an addition path communicating with the duct and extending toward the vertically upper side.
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