WO2011118400A1 - High-strength copper titanium plate and production method therefor - Google Patents
High-strength copper titanium plate and production method therefor Download PDFInfo
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- WO2011118400A1 WO2011118400A1 PCT/JP2011/055599 JP2011055599W WO2011118400A1 WO 2011118400 A1 WO2011118400 A1 WO 2011118400A1 JP 2011055599 W JP2011055599 W JP 2011055599W WO 2011118400 A1 WO2011118400 A1 WO 2011118400A1
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- 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
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- 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
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- the present invention relates to a titanium copper plate and a method of manufacturing the same, and a titanium copper plate suitably used for conductive spring materials such as connectors, terminals, relays and switches, and a method of manufacturing the same.
- Titanium copper specified in JIS alloy No. C1990 is manufactured by performing cold rolling after solution treatment and then aging treatment.
- Patent Document 1 a technique for improving bending workability as well as having high tensile strength and high proof strength by further cold rolling after solution treatment, cold rolling, and aging treatment of titanium copper has been reported.
- the high strength titanium copper plate of the present invention contains 2.5 to 4.0% by mass of Ti, the balance being Cu and unavoidable impurities, and having a tensile strength of 950 MPa or more, 0.2%
- Ratio (MBR / t) is 1.0 or less.
- the average crystal grain size is 3 to 15 ⁇ m
- the aspect ratio of crystal grains is 1.1 to 2.0
- the metallographic structure of the rolling surface Preferably, the area ratio of the second phase particles having a diameter of more than 1 ⁇ m is 0 to 0.2%.
- (MBR / t) is 0.5 or less
- the aspect ratio of the crystal grains is 1.2 to 1.6
- the area ratio of the second phase particles having a diameter of more than 1 ⁇ m is preferably 0 to 0.16%.
- board thickness is 0.15 mm or less.
- the method for producing a high strength titanium copper plate according to the present invention is a method for producing the high strength titanium copper plate, which comprises an ingot containing 2.5 to 4.0% by mass of Ti and the balance being Cu and unavoidable impurities. Hot rolling, cold rolling, solution treatment, aging treatment, and post-aging cold rolling at a working degree of 8 to 25% are performed in this order.
- the solution treatment is preferably performed at 920 to 1050 ° C. for 5 to 50 seconds, and the aging treatment is preferably performed at 380 to 480 ° C. for 3 to 20 hours.
- the post-aging cold rolling it is preferable to carry out strain relief annealing at 200 to 700 ° C. for 0.5 to 15 hours, or 300 to 600 ° C. for 10 to 1000 seconds.
- a high strength titanium copper plate excellent in strength and bending workability can be obtained.
- contact pressure at electrical contacts is obtained by applying elastic deformation of bending to a copper alloy strip.
- the stress generated inside the copper alloy by bending exceeds the yield strength of the copper alloy, plastic deformation (swelling) occurs in the copper alloy, and the contact pressure decreases.
- the higher the load resistance of the material the higher the contact pressure or springiness obtained.
- the higher the tensile strength of the material the lower the bending workability. Therefore, it is necessary to achieve higher proof stress (0.9 times or more of tensile strength) with the same tensile strength.
- the spring strength of the material required for the connector is improved by the level of proof strength rather than tensile strength.
- the present inventors diligently investigate the relationship between the size and shape of crystal grains of the titanium copper plate and the state of the second phase particles (Cu-Ti-based compound) and the strength and bending workability. did. As a result, it was found that high strength and bending workability can be obtained by sequentially performing aging and cold rolling after solution treatment to improve strength and reducing coarse second phase particles.
- the high strength titanium copper plate of the present invention has a tensile strength of 950 MPa or more and a 0.2% proof stress of 0.9 times or more of the tensile strength according to the following composition and other specifications.
- the ratio (MBR / t) of the minimum bending radius (MBR) to the occurrence of cracking to the plate thickness (t) is 1.0 or less It has a characteristic. This can improve, for example, the springability and the bending processability required for a small electronic component.
- the tensile strength is 1000 MPa or more
- (MBR / t) is 0.5 or less
- more preferably (MBR / t) is 0.2 or less.
- the Ti concentration is set to 2.5 to 4.0 mass%. Titanium copper improves strength and conductivity by dissolving Ti into a Cu matrix by solution treatment and dispersing fine precipitates in the alloy by aging treatment. When the Ti concentration is less than 2.5% by mass, precipitation of precipitates is insufficient, and a tensile strength of 950 MPa or more can not be obtained. On the other hand, when the Ti concentration exceeds 4.0% by mass, bending workability deteriorates and (MBR / t) exceeds 1.0. It is preferable to set the Ti concentration to 2.9 to 3.4% by mass because the characteristics of (MBR / t) of 1.0 or less can be stably obtained with a tensile strength of 950 MPa or more.
- 0 to 0.5 mass in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Nb, Ni, P, Si, V and Zr The incorporation of% can further improve the tensile strength.
- the total content of these elements may be zero, that is, it may not contain these elements.
- the total content of these elements exceeds 0.5% by mass, bending workability may be deteriorated, and (MBR / t) may exceed 1.0. More preferably, one or two or more of the above elements are contained in a total amount of 0.05 to 0.4% by mass.
- the thickness of the high-strength titanium copper plate of the present invention is preferably 0.15 mm or less.
- the high strength titanium copper sheet of the present invention tends to improve the bendability as the thickness becomes thinner and the value of (MBR / t) tends to become smaller, and when the thickness becomes 0.15 mm or less, the (MBR / t) becomes 1.0. It is because it becomes easy to achieve the following.
- a more preferable thickness is 0.05 to 0.12 mm.
- the average crystal grain size is 3 to 15 ⁇ m, and the aspect ratio of crystal grains is 1
- the area ratio of second phase particles having a diameter of more than 1 ⁇ m is preferably 0 to 0.2% when the metallographic structure of the rolled surface is observed.
- a cross section parallel to the rolling direction R and the thickness direction T is represented by a symbol S.
- the average grain size is determined as follows. First, in the structure photograph of the cross section S, three straight lines are arbitrarily drawn in the thickness direction T, the number of crystal grains cut by the straight lines is determined, and the length of the straight lines divided by the number of crystal grains is a. . Similarly, three straight lines are drawn arbitrarily in the rolling direction L, the number of crystal grains cut by the straight lines is determined, and the length of the straight line divided by the number of crystal grains is defined as b. And let the value of (a + b) / 2 be an average grain size. Further, the value of b / a is taken as the aspect ratio of the crystal grain.
- the second phase particles refer to a portion having a color tone different from that of the matrix (that is, a composition different from that of the matrix) when observing a secondary electron image of the metal structure after electropolishing the rolled surface.
- This portion is a portion remaining without being dissolved by electrolytic polishing, and represents a second phase particle of Cu-Ti system such as Cu 3 Ti or Cu 4 Ti, and the portion having a diameter of 1 ⁇ m or more is bendable. Degrade the The area ratio of the second phase particles having a diameter of 1 ⁇ m or more is subjected to image analysis of the secondary electron image, and the diameter of the smallest circle including the area is determined for each of the matrix and different color tone areas. Let diameter.
- FIG. 2 is an example of an actual secondary electron image of the metal structure after electropolishing the rolled surface of the high strength titanium copper plate of the invention example 2.
- the average grain size is less than 3 ⁇ m, the solution treatment is insufficient, so non-recrystallized grains may remain locally or coarse second phase grains may remain, so bending workability is possible.
- (MBR / t) may exceed 1.0. When the average grain size exceeds 15 ⁇ m, grain boundaries contributing to the strength may be reduced, and the tensile strength may be less than 950 MPa. Since a tensile strength of 950 MPa or more and (MBR / t) ⁇ 0.5 can be stably obtained, it is more preferable to set the crystal grain size to 3 to 12 ⁇ m.
- the aspect ratio of crystal grains represents the degree of processing of the material, and the higher the aspect ratio, the higher the degree of processing. Therefore, when the aspect ratio of crystal grains is less than 1.1, the tensile strength may be less than 950 MPa. On the other hand, if the aspect ratio of the crystal grain exceeds 2.0, the processing becomes excessive and bending workability deteriorates, and (MBR / t) may exceed 1.0. It is more preferable to set the aspect ratio of the crystal grain to 1.2 to 1.6 because a tensile strength of 950 MPa or more and (MBR / t) ⁇ 1.0 can be stably obtained.
- the area ratio of second phase particles having a diameter of more than 1 ⁇ m exceeds 0.2%, coarse second phase particles are present in the structure, so that bending processability is deteriorated, and (MBR / t) It may exceed 1.0. Since (MBR / t) ⁇ 1.0 is stably obtained, it is more preferable that the area ratio of the second phase particles having a diameter of more than 1 ⁇ m be 0.16% or less.
- the method for producing a high strength titanium copper sheet according to the present invention comprises hot rolling, cold rolling, solution treatment, an ingot containing 2.5 to 4.0 mass% of Ti and the balance being Cu and unavoidable impurities. Aging and cold rolling after aging at a working degree of 8 to 25% are performed in this order. In the present invention, cold rolling is not performed between the solution treatment and the aging treatment. When this cold rolling is performed, although the tensile strength is slightly increased, the bending workability is deteriorated.
- the ingot can be produced by melting and casting the material having the above composition, for example, as an ingot having a thickness of 100 to 300 mm. In order to prevent oxidation damage of titanium, it is preferable to carry out melting and casting in vacuum or in an inert gas atmosphere. Next, the ingot may be heated, for example, at 850 to 1000 ° C. for about 3 to 24 hours to perform hot rolling to a thickness of 3 to 30 mm.
- the solution treatment is preferably performed using a continuous annealing furnace.
- the solution treatment is performed at 920 to 1050 ° C. for 5 to 50 seconds, the above-described average crystal grain size can be adjusted to 3 to 15 ⁇ m.
- the solution treatment conditions are adjusted so that the average grain size immediately after solution treatment becomes 3 to 15 ⁇ m. Good.
- the aspect ratio of crystal grains changes as compared with that immediately after solution treatment. If the solution treatment temperature is less than 920 ° C.
- the solution treatment is insufficient and partially unrecrystallized grains remain, so the average grain size is adjusted to 3 ⁇ m or more It tends to be difficult to adjust the area ratio of second phase particles having a diameter of more than 1 .mu.m to 0.2% or less. As a result, the bending workability of the obtained high strength titanium copper plate may be deteriorated, and (MBR / t) may exceed 1.0.
- the solution treatment temperature exceeds 1050 ° C. or the solution treatment time exceeds 50 seconds, the solution treatment becomes excessive and the crystals grow too much, and the average crystal grain size may be adjusted to 15 ⁇ m or less It tends to be difficult.
- a plurality of preliminary solution treatment may be performed prior to the solution treatment.
- the conditions for the preliminary solution treatment are not particularly limited. If multiple preliminary solution treatments are performed, cold rolling may be performed between each solution treatment.
- the aging treatment is preferably performed using a batch annealing furnace.
- the aging treatment is preferably performed at 380 to 480 ° C. for 3 to 20 hours.
- the aging treatment temperature is less than 380 ° C. or the aging treatment is less than 3 hours, sufficient precipitation (fine particles of Cu 3 Ti or Cu 4 Ti contributing to strength improvement) is not generated due to insufficient aging, and a tension of 950 MPa or more Achieving strength tends to be difficult.
- the aging treatment temperature exceeds 480 ° C. or the aging treatment exceeds 20 hours, the precipitate becomes coarse due to overaging, and the tensile strength becomes less than 950 MPa and (MBR / t) becomes 1.0. May exceed.
- the working ratio of cold rolling after aging is 8 to 25%.
- the working degree is less than 8%, the tensile strength is less than 950 MPa, and the 0.2% proof stress does not reach 0.9 times or more of the tensile strength.
- the degree of processing exceeds 25%, bending workability is poor, and (MBR / t) exceeds 1.0. Since a tensile strength of 950 MPa or more and (MBR / t) ⁇ 1.0 can be stably obtained, and a 0.2% proof stress stably reaches 0.9 times or more of the tensile strength, the processing degree is 10 It is more preferable to set it to -20%.
- strain relief annealing may be performed after cold rolling after aging.
- the strain relief annealing can be performed using a batch annealing furnace or a continuous annealing furnace.
- the material is held in a 200 to 700 ° C. heating furnace for 0.5 to 15 hours. If the temperature of the batch annealing furnace is less than 200 ° C. or the holding time is less than 0.5 hours, it is difficult to sufficiently improve the spring limit value.
- the temperature of the batch annealing furnace exceeds 700 ° C. or the holding time exceeds 15 hours, the tensile strength decreases.
- the material is held in a heating furnace at 300 to 600 ° C. for 10 to 1000 seconds. If the temperature of the continuous annealing furnace is less than 300 ° C. or the holding time is less than 10 seconds, it is difficult to sufficiently improve the spring limit value. When the temperature of the continuous annealing furnace exceeds 600 ° C. or the holding time exceeds 1000 seconds, the tensile strength decreases.
- processes such as grinding, polishing, shot blasting and pickling for removing oxide scale on the surface can be appropriately performed between the above respective processes.
- Electrolytic copper was melted in a vacuum melting furnace, and Ti and other elements (subcomponents of Tables 1 and 2) were added in the proportions shown in Tables 1 and 2. This molten metal was cast to obtain a rectangular ingot having a thickness of 150 mm, a width of 600 mm, and a length of 6000 mm. The ingot was heated at 950 ° C. for 3 hours, and hot rolled into a hot-rolled sheet with a thickness of 10 mm.
- strain relief annealing was performed at 300 ° C. for 3 hours in a batch annealing furnace, or at 500 ° C. for 10 seconds in a continuous annealing furnace. The following characteristic evaluation was performed about the sample after cold rolling after aging (after strain relief annealing after strain relief annealing).
- the spring limit value in the direction parallel to the rolling direction was measured by a moment test prescribed in JIS-H3130. (Average grain size and aspect ratio) After finishing the rolling direction and parallel to the cross section of the sample (S in FIG. 1) to a mirror surface by mechanical polishing, water (100mL) -FeCl 3 (5g) grain boundaries by etching using a-HCl (10 mL) solution of the current The tissue was photographed using an optical microscope. On the photograph of the structure, three straight lines are arbitrarily drawn in the thickness direction T, the number of crystal grains cut by the straight line is determined, and a value obtained by dividing the length of the straight line by the number of crystal grains is a.
- the lightness of the observation field of view is binarized with the threshold value 60, and the diameter of the smallest circle including the area is determined for each of the matrix and different areas of color tone. It was the diameter of the two-phase particle. And the value which divided the total area of the 2nd phase particle of diameter 1 micrometer or more by the total area of the observation visual field was made into the area ratio.
- the tensile strength is 950 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 1 .0 or less, and both strength and bending workability were excellent.
- the tensile strength is 1000 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 0.5 or less It was excellent in both strength and bending workability.
- Comparative Example 1 In the case of Comparative Example 1 in which the Ti concentration is less than 2.5%, the tensile strength is less than 950 MPa. On the other hand, in the case of Comparative Example 2 in which the Ti concentration exceeded 4.0%, bending workability decreased and (MBR / t) exceeded 1.0. In the case of Comparative Example 3 in which the plate thickness is more than 0.15 mm, bending workability is reduced, and (MBR / t) exceeds 1.0.
- Comparative Example 4 In the case of Comparative Example 4 in which the working ratio of cold rolling after aging is less than 8%, the aspect ratio of the crystal grains is less than 1.1, the tensile strength is reduced to less than 950 MPa, and the 0.2% proof stress is tensile strength Less than 0.9 times the
- Comparative Example 5 in which the working ratio of cold rolling after aging exceeded 25%, the aspect ratio exceeded 2.0, the bending workability decreased, and (MBR / t) exceeded 1.0. .
- Comparative Example 11 In the case of Comparative Example 11 in which cold rolling before aging was performed between solution treatment and aging treatment in addition to cold rolling after aging, bending formability was reduced, and (MBR / t) was It exceeded 1.0. Comparative Example 11 was manufactured under the same conditions as Inventive Example 2 except that cold rolling before aging was performed, and although the tensile strength was slightly increased (20 MPa), the bending workability decreased. It can be seen that
- Comparative Example 12 in which cold rolling before aging was performed between solution treatment and aging treatment in addition to cold rolling after aging, bending formability is reduced (MBR / t) exceeded 1.0.
- Comparative Example 12 was manufactured under the same conditions as Inventive Example 11 except that cold rolling before aging was performed, and although the tensile strength was slightly increased (11 MPa), the bending workability decreased. It can be seen that Moreover, the total processing degree ( ⁇ (plate thickness at the time of solution treatment)-(final plate thickness)) / (plate thickness at the time of solution treatment ⁇ 100) of Comparative Example 12 is 20%, and the total processing rate is It can be seen that the bending workability is deteriorated even in comparison with the same invention example 12.
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Abstract
Disclosed are a copper titanium plate with excellent strength, conductivity, and bendability, and a production method therefor. The high-strength copper titanium plate includes 2.5 to 4.0 mass% Ti, with the remainder comprising Cu and unavoidable impurities, wherein the tensile strength is at least 950 MPa, the 0.2% proof stress is 0.9 times the tensile strength, and the ratio (MBR/t) between the plate thickness (t) and the minimum bending radius (MBR) at which breaking does not occur is no more than 1.0 when a W bending test is performed in a manner such that the bending axis becomes parallel with the rolling direction.
Description
本発明はチタン銅板及びその製造方法に関し、コネクタ、端子、リレ－、スイッチ等の導電性ばね材に好適に用いられるチタン銅板及びその製造方法に関する。
The present invention relates to a titanium copper plate and a method of manufacturing the same, and a titanium copper plate suitably used for conductive spring materials such as connectors, terminals, relays and switches, and a method of manufacturing the same.
電子機器の各種端子、コネクタ、リレー、スイッチなどの電気伝導性及びばね性が必要な材料として、製造コストを重視する場合には低廉な黄銅が用いられ、ばね性が重視される場合にはりん青銅が用いられ、ばね性及び耐食性が重視される場合には洋白が用いられてきた。しかしながら、近年、電子機器類及びその部品の軽量化、薄肉化および小型化に伴い、これらの材料では強度を十分に向上させることが難しいため、チタン銅などのいわゆる高級ばねの需要が増大している。
ＪＩＳ合金番号Ｃ１９９０に規定されるチタン銅は、溶体化処理の後に冷間圧延を行ない、次いで時効処理を行うことにより製造される。溶体化処理では、鋳造や熱間圧延の際に生成した粗大なＣｕ－Ｔｉ化合物をＣｕ母地に固溶させると同時にＣｕ母地を再結晶させ、再結晶粒の結晶粒径を調整する。時効処理においてはＣｕ３ＴｉまたはＣｕ４Ｔｉの微細粒子を析出させ、これらの微細粒子が引張り強さ、耐力、ばね限界値などの強度特性の向上に寄与する。 As materials requiring electrical conductivity and springiness, such as various terminals of electronic devices, connectors, relays and switches, inexpensive brass is used when importance is placed on manufacturing costs, and phosphorus is considered when springiness is important. Bronze has been used, and nickel and white have been used where springability and corrosion resistance are important. However, in recent years, with the reduction in weight, thickness and size of electronic devices and their parts, it is difficult to sufficiently improve the strength of these materials, so the demand for so-called high-grade springs such as titanium copper increases. There is.
Titanium copper specified in JIS alloy No. C1990 is manufactured by performing cold rolling after solution treatment and then aging treatment. In the solution treatment, coarse Cu—Ti compounds generated during casting or hot rolling are dissolved in a Cu matrix simultaneously with recrystallization of the Cu matrix to adjust the crystal grain size of recrystallized grains. In the aging treatment, fine particles of Cu 3 Ti or Cu 4 Ti are precipitated, and these fine particles contribute to the improvement of strength characteristics such as tensile strength, proof stress, and spring limit value.
ＪＩＳ合金番号Ｃ１９９０に規定されるチタン銅は、溶体化処理の後に冷間圧延を行ない、次いで時効処理を行うことにより製造される。溶体化処理では、鋳造や熱間圧延の際に生成した粗大なＣｕ－Ｔｉ化合物をＣｕ母地に固溶させると同時にＣｕ母地を再結晶させ、再結晶粒の結晶粒径を調整する。時効処理においてはＣｕ３ＴｉまたはＣｕ４Ｔｉの微細粒子を析出させ、これらの微細粒子が引張り強さ、耐力、ばね限界値などの強度特性の向上に寄与する。 As materials requiring electrical conductivity and springiness, such as various terminals of electronic devices, connectors, relays and switches, inexpensive brass is used when importance is placed on manufacturing costs, and phosphorus is considered when springiness is important. Bronze has been used, and nickel and white have been used where springability and corrosion resistance are important. However, in recent years, with the reduction in weight, thickness and size of electronic devices and their parts, it is difficult to sufficiently improve the strength of these materials, so the demand for so-called high-grade springs such as titanium copper increases. There is.
Titanium copper specified in JIS alloy No. C1990 is manufactured by performing cold rolling after solution treatment and then aging treatment. In the solution treatment, coarse Cu—Ti compounds generated during casting or hot rolling are dissolved in a Cu matrix simultaneously with recrystallization of the Cu matrix to adjust the crystal grain size of recrystallized grains. In the aging treatment, fine particles of Cu 3 Ti or Cu 4 Ti are precipitated, and these fine particles contribute to the improvement of strength characteristics such as tensile strength, proof stress, and spring limit value.
そして、電子機器類及びその部品の軽量化などがさらに進み、材料の高強度化の要求は一層厳しくなっているため、チタン銅の製造プロセスの改良が進められている。例えば、チタン銅の溶体化処理、冷間圧延、時効処理後にさらに冷間圧延することで、高引張強度及び高耐力を有すると共に曲げ加工性を向上させる技術が報告されている（特許文献１）。
Then, as the weight reduction of electronic devices and parts thereof and the like are further progressed, and the demand for high strength of materials is becoming more severe, improvement of the manufacturing process of titanium copper is being promoted. For example, a technique for improving bending workability as well as having high tensile strength and high proof strength by further cold rolling after solution treatment, cold rolling, and aging treatment of titanium copper has been reported (Patent Document 1). .
しかしながら、本発明者らが検討した結果、特許文献１に記載されたチタン銅の場合、強度は高いものの、曲げ性の改善が十分とはいえないことが判明した。
このように、強度及び曲げ加工性を共に改善させ、小型コネクタに適したチタン銅は未だ開発されていない。
すなわち、本発明は上記の課題を解決するためになされたものであり、強度及び曲げ加工性に優れた高強度チタン銅板及びその製造方法の提供を目的とする。 However, as a result of examinations by the present inventors, it was found that titanium copper described in Patent Document 1 has high strength but the improvement of bendability is not sufficient.
Thus, titanium copper that improves both strength and bendability and is suitable for a small connector has not been developed yet.
That is, the present invention was made in order to solve the above-mentioned subject, and an object of the present invention is to provide a high-strength titanium copper plate excellent in strength and bending workability, and a method of manufacturing the same.
このように、強度及び曲げ加工性を共に改善させ、小型コネクタに適したチタン銅は未だ開発されていない。
すなわち、本発明は上記の課題を解決するためになされたものであり、強度及び曲げ加工性に優れた高強度チタン銅板及びその製造方法の提供を目的とする。 However, as a result of examinations by the present inventors, it was found that titanium copper described in Patent Document 1 has high strength but the improvement of bendability is not sufficient.
Thus, titanium copper that improves both strength and bendability and is suitable for a small connector has not been developed yet.
That is, the present invention was made in order to solve the above-mentioned subject, and an object of the present invention is to provide a high-strength titanium copper plate excellent in strength and bending workability, and a method of manufacturing the same.
本発明者らは種々検討した結果、溶体化処理後に時効、冷間圧延を順次行って強度を向上するとともに、粗大な第二相粒子を減少させることで、優れた強度及び曲げ加工性が得られることを見出した。
すなわち本発明は、本発明の高強度チタン銅板は、２．５～４．０質量％のＴｉを含有し、残部がＣｕ及び不可避不純物からなり、引張強さが９５０ＭＰａ以上で、０．２％耐力が引張り強さの０．９倍以上であり、曲げ軸が圧延方向と平行になるようにＷ曲げ試験を行ったとき、割れの発生しない最小曲げ半径（ＭＢＲ）と板厚（ｔ）との比（ＭＢＲ／ｔ）が１．０以下である。 As a result of various investigations by the present inventors, it is possible to improve strength by sequentially performing aging and cold rolling after solution treatment, and to obtain excellent strength and bendability by reducing coarse second phase particles. Found out that
That is, according to the present invention, the high strength titanium copper plate of the present invention contains 2.5 to 4.0% by mass of Ti, the balance being Cu and unavoidable impurities, and having a tensile strength of 950 MPa or more, 0.2% The minimum bending radius (MBR) and plate thickness (t) where no cracking occurs when a W bending test is conducted so that the proof stress is 0.9 times or more of the tensile strength and the bending axis is parallel to the rolling direction. Ratio (MBR / t) is 1.0 or less.
すなわち本発明は、本発明の高強度チタン銅板は、２．５～４．０質量％のＴｉを含有し、残部がＣｕ及び不可避不純物からなり、引張強さが９５０ＭＰａ以上で、０．２％耐力が引張り強さの０．９倍以上であり、曲げ軸が圧延方向と平行になるようにＷ曲げ試験を行ったとき、割れの発生しない最小曲げ半径（ＭＢＲ）と板厚（ｔ）との比（ＭＢＲ／ｔ）が１．０以下である。 As a result of various investigations by the present inventors, it is possible to improve strength by sequentially performing aging and cold rolling after solution treatment, and to obtain excellent strength and bendability by reducing coarse second phase particles. Found out that
That is, according to the present invention, the high strength titanium copper plate of the present invention contains 2.5 to 4.0% by mass of Ti, the balance being Cu and unavoidable impurities, and having a tensile strength of 950 MPa or more, 0.2% The minimum bending radius (MBR) and plate thickness (t) where no cracking occurs when a W bending test is conducted so that the proof stress is 0.9 times or more of the tensile strength and the bending axis is parallel to the rolling direction. Ratio (MBR / t) is 1.0 or less.
圧延方向及び厚み方向に平行な断面の金属組織を観察したとき、平均結晶粒径が３～１５μmであり、結晶粒のアスペクト比が１．１～２．０であり、且つ圧延面の金属組織を観察したとき、直径が１μmを超える第二相粒子の面積率が０～０．２％であることが好ましい。
（ＭＢＲ／ｔ）が０．５以下であり、圧延方向及び厚み方向に平行な断面の金属組織を観察したとき、結晶粒のアスペクト比が１．２～１．６であり、且つ圧延面の金属組織を観察したとき、直径が１μmを超える第二相粒子の面積率が０～０．１６％であることが好ましい。
Ａｇ、Ｂ、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎｉ、Ｐ、Ｓｉ、Ｖ及びＺｒからなる群から選択される１種又は２種以上を合計で０～０．５質量％含有することが好ましい。
板厚が０．１５ｍｍ以下であることが好ましい。 When a metallographic structure of a cross section parallel to the rolling direction and thickness direction is observed, the average crystal grain size is 3 to 15 μm, the aspect ratio of crystal grains is 1.1 to 2.0, and the metallographic structure of the rolling surface Preferably, the area ratio of the second phase particles having a diameter of more than 1 μm is 0 to 0.2%.
(MBR / t) is 0.5 or less, and when observing a metallographic structure of a cross section parallel to the rolling direction and thickness direction, the aspect ratio of the crystal grains is 1.2 to 1.6, and When the metallographic structure is observed, the area ratio of the second phase particles having a diameter of more than 1 μm is preferably 0 to 0.16%.
0 to 0.5 mass% in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Nb, Ni, P, Si, V and Zr It is preferable to contain.
It is preferable that board thickness is 0.15 mm or less.
（ＭＢＲ／ｔ）が０．５以下であり、圧延方向及び厚み方向に平行な断面の金属組織を観察したとき、結晶粒のアスペクト比が１．２～１．６であり、且つ圧延面の金属組織を観察したとき、直径が１μmを超える第二相粒子の面積率が０～０．１６％であることが好ましい。
Ａｇ、Ｂ、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎｉ、Ｐ、Ｓｉ、Ｖ及びＺｒからなる群から選択される１種又は２種以上を合計で０～０．５質量％含有することが好ましい。
板厚が０．１５ｍｍ以下であることが好ましい。 When a metallographic structure of a cross section parallel to the rolling direction and thickness direction is observed, the average crystal grain size is 3 to 15 μm, the aspect ratio of crystal grains is 1.1 to 2.0, and the metallographic structure of the rolling surface Preferably, the area ratio of the second phase particles having a diameter of more than 1 μm is 0 to 0.2%.
(MBR / t) is 0.5 or less, and when observing a metallographic structure of a cross section parallel to the rolling direction and thickness direction, the aspect ratio of the crystal grains is 1.2 to 1.6, and When the metallographic structure is observed, the area ratio of the second phase particles having a diameter of more than 1 μm is preferably 0 to 0.16%.
0 to 0.5 mass% in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Nb, Ni, P, Si, V and Zr It is preferable to contain.
It is preferable that board thickness is 0.15 mm or less.
本発明の高強度チタン銅板の製造方法は、前記高強度チタン銅板の製造方法であって、２．５～４．０質量％のＴｉを含有し、残部がＣｕ及び不可避不純物からなる鋳塊を熱間圧延、冷間圧延、溶体化処理、時効処理、加工度８～２５％での時効後冷間圧延の順で行う。
The method for producing a high strength titanium copper plate according to the present invention is a method for producing the high strength titanium copper plate, which comprises an ingot containing 2.5 to 4.0% by mass of Ti and the balance being Cu and unavoidable impurities. Hot rolling, cold rolling, solution treatment, aging treatment, and post-aging cold rolling at a working degree of 8 to 25% are performed in this order.
前記溶体化処理を９２０～１０５０℃で５～５０秒間行い、前記時効処理を３８０～４８０℃で３～２０時間行うことが好ましい。
前記時効後冷間圧延の後に、２００～７００℃で０．５～１５時間、又は３００～６００℃で１０～１０００秒間の歪み取り焼鈍を行うことが好ましい。 The solution treatment is preferably performed at 920 to 1050 ° C. for 5 to 50 seconds, and the aging treatment is preferably performed at 380 to 480 ° C. for 3 to 20 hours.
After the post-aging cold rolling, it is preferable to carry out strain relief annealing at 200 to 700 ° C. for 0.5 to 15 hours, or 300 to 600 ° C. for 10 to 1000 seconds.
前記時効後冷間圧延の後に、２００～７００℃で０．５～１５時間、又は３００～６００℃で１０～１０００秒間の歪み取り焼鈍を行うことが好ましい。 The solution treatment is preferably performed at 920 to 1050 ° C. for 5 to 50 seconds, and the aging treatment is preferably performed at 380 to 480 ° C. for 3 to 20 hours.
After the post-aging cold rolling, it is preferable to carry out strain relief annealing at 200 to 700 ° C. for 0.5 to 15 hours, or 300 to 600 ° C. for 10 to 1000 seconds.
本発明によれば、強度及び曲げ加工性に優れた高強度チタン銅板が得られる。
According to the present invention, a high strength titanium copper plate excellent in strength and bending workability can be obtained.
以下、本発明の実施形態に係る高強度チタン銅板及びその製造方法について説明する。なお、本発明において％とは、特に断らない限り、質量％を示すものとする。
Hereinafter, a high strength titanium copper plate and a method of manufacturing the same according to an embodiment of the present invention will be described. In the present invention,% indicates mass% unless otherwise specified.
コネクタなどの電子部品では、曲げの弾性変形を銅合金条に与えることで、電気接点における接圧を得ている。曲げにより銅合金内部に生じる応力が、銅合金の耐力を超えると、銅合金に塑性変形（へたり）が生じ、接圧が低下する。従って、材料の耐力が高いほど、より高い接圧、すなわちばね性が得られる。一方、材料の引張り強さが高くなるほど、曲げ加工性が低下する。したがって、同じ引張り強さで、より高い耐力（引張り強さの０．９倍以上）を達成することが必要となる。なお、コネクタに要求される材料のバネ強度は、引張り強さよりも耐力の高さによって向上する。
In electronic parts such as connectors, contact pressure at electrical contacts is obtained by applying elastic deformation of bending to a copper alloy strip. When the stress generated inside the copper alloy by bending exceeds the yield strength of the copper alloy, plastic deformation (swelling) occurs in the copper alloy, and the contact pressure decreases. Thus, the higher the load resistance of the material, the higher the contact pressure or springiness obtained. On the other hand, the higher the tensile strength of the material, the lower the bending workability. Therefore, it is necessary to achieve higher proof stress (0.9 times or more of tensile strength) with the same tensile strength. In addition, the spring strength of the material required for the connector is improved by the level of proof strength rather than tensile strength.
このようなことから、本発明者らは、チタン銅板の結晶粒の大きさ、形態、及び第二相粒子（Ｃｕ－Ｔｉ系化合物）の状態と、強度及び曲げ加工性との関係を鋭意調査した。その結果、溶体化処理後に時効、冷間圧延を順次行って強度を向上するとともに、粗大な第二相粒子を減少させることで、高い強度及び曲げ加工性が得られることを見出した。
具体的には、以下の組成及びその他の規定により、本発明の高強度チタン銅板は、引張強さが９５０ＭＰａ以上で、０．２％耐力が引張り強さの０．９倍以上であり、曲げ軸が圧延方向と平行になるようにＷ曲げ試験を行ったとき、割れの発生しない最小曲げ半径（ＭＢＲ）と板厚（ｔ）との比（ＭＢＲ／ｔ）が１．０以下であるという特性を有する。これにより、例えば小型電子部品に要求されるばね性および曲げ加工性を向上させることができる。
好ましくは、引張り強さが１０００ＭＰａ以上で、（ＭＢＲ／ｔ）が０．５以下であり、さらに好ましくは（ＭＢＲ／ｔ）が０．２以下である。 From the above, the present inventors diligently investigate the relationship between the size and shape of crystal grains of the titanium copper plate and the state of the second phase particles (Cu-Ti-based compound) and the strength and bending workability. did. As a result, it was found that high strength and bending workability can be obtained by sequentially performing aging and cold rolling after solution treatment to improve strength and reducing coarse second phase particles.
Specifically, the high strength titanium copper plate of the present invention has a tensile strength of 950 MPa or more and a 0.2% proof stress of 0.9 times or more of the tensile strength according to the following composition and other specifications. When a W bending test is performed so that the axis is parallel to the rolling direction, the ratio (MBR / t) of the minimum bending radius (MBR) to the occurrence of cracking to the plate thickness (t) is 1.0 or less It has a characteristic. This can improve, for example, the springability and the bending processability required for a small electronic component.
Preferably, the tensile strength is 1000 MPa or more, (MBR / t) is 0.5 or less, and more preferably (MBR / t) is 0.2 or less.
具体的には、以下の組成及びその他の規定により、本発明の高強度チタン銅板は、引張強さが９５０ＭＰａ以上で、０．２％耐力が引張り強さの０．９倍以上であり、曲げ軸が圧延方向と平行になるようにＷ曲げ試験を行ったとき、割れの発生しない最小曲げ半径（ＭＢＲ）と板厚（ｔ）との比（ＭＢＲ／ｔ）が１．０以下であるという特性を有する。これにより、例えば小型電子部品に要求されるばね性および曲げ加工性を向上させることができる。
好ましくは、引張り強さが１０００ＭＰａ以上で、（ＭＢＲ／ｔ）が０．５以下であり、さらに好ましくは（ＭＢＲ／ｔ）が０．２以下である。 From the above, the present inventors diligently investigate the relationship between the size and shape of crystal grains of the titanium copper plate and the state of the second phase particles (Cu-Ti-based compound) and the strength and bending workability. did. As a result, it was found that high strength and bending workability can be obtained by sequentially performing aging and cold rolling after solution treatment to improve strength and reducing coarse second phase particles.
Specifically, the high strength titanium copper plate of the present invention has a tensile strength of 950 MPa or more and a 0.2% proof stress of 0.9 times or more of the tensile strength according to the following composition and other specifications. When a W bending test is performed so that the axis is parallel to the rolling direction, the ratio (MBR / t) of the minimum bending radius (MBR) to the occurrence of cracking to the plate thickness (t) is 1.0 or less It has a characteristic. This can improve, for example, the springability and the bending processability required for a small electronic component.
Preferably, the tensile strength is 1000 MPa or more, (MBR / t) is 0.5 or less, and more preferably (MBR / t) is 0.2 or less.
次に、本発明の高強度チタン銅板の組成及びその他の規定について説明する。
（１）組成
Ｔｉ濃度を２．５～４．０質量％とする。チタン銅は、溶体化処理によりＣｕマトリックス中へＴｉを固溶させ、時効処理により微細な析出物を合金中に分散させることにより、強度及び導電率を向上させる。
Ｔｉ濃度が２．５質量％未満になると、析出物の析出が不充分となり９５０ＭＰａ以上の引張り強さが得られない。一方、Ｔｉ濃度が４．０質量％を超えると、曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える。
Ｔｉ濃度を２．９～３．４質量％とすると、引張強さ９５０ＭＰａ以上で、（ＭＢＲ／ｔ）が１．０以下の特性が安定して得られるので好ましい。 Next, the composition and other specifications of the high-strength titanium copper plate of the present invention will be described.
(1) Composition The Ti concentration is set to 2.5 to 4.0 mass%. Titanium copper improves strength and conductivity by dissolving Ti into a Cu matrix by solution treatment and dispersing fine precipitates in the alloy by aging treatment.
When the Ti concentration is less than 2.5% by mass, precipitation of precipitates is insufficient, and a tensile strength of 950 MPa or more can not be obtained. On the other hand, when the Ti concentration exceeds 4.0% by mass, bending workability deteriorates and (MBR / t) exceeds 1.0.
It is preferable to set the Ti concentration to 2.9 to 3.4% by mass because the characteristics of (MBR / t) of 1.0 or less can be stably obtained with a tensile strength of 950 MPa or more.
（１）組成
Ｔｉ濃度を２．５～４．０質量％とする。チタン銅は、溶体化処理によりＣｕマトリックス中へＴｉを固溶させ、時効処理により微細な析出物を合金中に分散させることにより、強度及び導電率を向上させる。
Ｔｉ濃度が２．５質量％未満になると、析出物の析出が不充分となり９５０ＭＰａ以上の引張り強さが得られない。一方、Ｔｉ濃度が４．０質量％を超えると、曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える。
Ｔｉ濃度を２．９～３．４質量％とすると、引張強さ９５０ＭＰａ以上で、（ＭＢＲ／ｔ）が１．０以下の特性が安定して得られるので好ましい。 Next, the composition and other specifications of the high-strength titanium copper plate of the present invention will be described.
(1) Composition The Ti concentration is set to 2.5 to 4.0 mass%. Titanium copper improves strength and conductivity by dissolving Ti into a Cu matrix by solution treatment and dispersing fine precipitates in the alloy by aging treatment.
When the Ti concentration is less than 2.5% by mass, precipitation of precipitates is insufficient, and a tensile strength of 950 MPa or more can not be obtained. On the other hand, when the Ti concentration exceeds 4.0% by mass, bending workability deteriorates and (MBR / t) exceeds 1.0.
It is preferable to set the Ti concentration to 2.9 to 3.4% by mass because the characteristics of (MBR / t) of 1.0 or less can be stably obtained with a tensile strength of 950 MPa or more.
更にＡｇ、Ｂ、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎｉ、Ｐ、Ｓｉ、Ｖ及びＺｒからなる群から選択される１種又は２種以上を合計で０～０．５質量％含有させることにより、引張強さを更に向上させることができる。これら元素の合計含有量が０、つまり、これらの元素を含まなくてもよい。一方、これら元素の合計含有量が０．５質量％を超えると、曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える場合がある。
より好ましくは、上記元素の１種又は２種以上を合計で０．０５～０．４質量％含有させる。 Furthermore, 0 to 0.5 mass in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Nb, Ni, P, Si, V and Zr The incorporation of% can further improve the tensile strength. The total content of these elements may be zero, that is, it may not contain these elements. On the other hand, when the total content of these elements exceeds 0.5% by mass, bending workability may be deteriorated, and (MBR / t) may exceed 1.0.
More preferably, one or two or more of the above elements are contained in a total amount of 0.05 to 0.4% by mass.
より好ましくは、上記元素の１種又は２種以上を合計で０．０５～０．４質量％含有させる。 Furthermore, 0 to 0.5 mass in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Nb, Ni, P, Si, V and Zr The incorporation of% can further improve the tensile strength. The total content of these elements may be zero, that is, it may not contain these elements. On the other hand, when the total content of these elements exceeds 0.5% by mass, bending workability may be deteriorated, and (MBR / t) may exceed 1.0.
More preferably, one or two or more of the above elements are contained in a total amount of 0.05 to 0.4% by mass.
（２）板厚
本発明の高強度チタン銅板の板厚が０．１５ｍｍ以下であることが好ましい。本発明の高強度チタン銅板は厚みが薄くなるほど曲げ性が向上し、（ＭＢＲ／ｔ）の値が小さくなる傾向があり、厚みが０．１５ｍｍ以下になると、（ＭＢＲ／ｔ）を１．０以下に達成しやすくなるためである。より好ましい板厚は０．０５～０．１２ｍｍである。 (2) Plate Thickness The thickness of the high-strength titanium copper plate of the present invention is preferably 0.15 mm or less. The high strength titanium copper sheet of the present invention tends to improve the bendability as the thickness becomes thinner and the value of (MBR / t) tends to become smaller, and when the thickness becomes 0.15 mm or less, the (MBR / t) becomes 1.0. It is because it becomes easy to achieve the following. A more preferable thickness is 0.05 to 0.12 mm.
本発明の高強度チタン銅板の板厚が０．１５ｍｍ以下であることが好ましい。本発明の高強度チタン銅板は厚みが薄くなるほど曲げ性が向上し、（ＭＢＲ／ｔ）の値が小さくなる傾向があり、厚みが０．１５ｍｍ以下になると、（ＭＢＲ／ｔ）を１．０以下に達成しやすくなるためである。より好ましい板厚は０．０５～０．１２ｍｍである。 (2) Plate Thickness The thickness of the high-strength titanium copper plate of the present invention is preferably 0.15 mm or less. The high strength titanium copper sheet of the present invention tends to improve the bendability as the thickness becomes thinner and the value of (MBR / t) tends to become smaller, and when the thickness becomes 0.15 mm or less, the (MBR / t) becomes 1.0. It is because it becomes easy to achieve the following. A more preferable thickness is 0.05 to 0.12 mm.
（３）結晶粒及び組織
上記した特性を達成するため、圧延方向及び厚み方向に平行な断面の金属組織を観察したとき、平均結晶粒径が３～１５μmであり、結晶粒のアスペクト比が１．１～２．０であり、且つ圧延面の金属組織を観察したとき、直径が１μmを超える第二相粒子の面積率が０～０．２％であることが好ましい。 (3) Crystal grains and structure In order to achieve the above-mentioned characteristics, when observing a metal structure of a cross section parallel to the rolling direction and thickness direction, the average crystal grain size is 3 to 15 μm, and the aspect ratio of crystal grains is 1 The area ratio of second phase particles having a diameter of more than 1 μm is preferably 0 to 0.2% when the metallographic structure of the rolled surface is observed.
上記した特性を達成するため、圧延方向及び厚み方向に平行な断面の金属組織を観察したとき、平均結晶粒径が３～１５μmであり、結晶粒のアスペクト比が１．１～２．０であり、且つ圧延面の金属組織を観察したとき、直径が１μmを超える第二相粒子の面積率が０～０．２％であることが好ましい。 (3) Crystal grains and structure In order to achieve the above-mentioned characteristics, when observing a metal structure of a cross section parallel to the rolling direction and thickness direction, the average crystal grain size is 3 to 15 μm, and the aspect ratio of crystal grains is 1 The area ratio of second phase particles having a diameter of more than 1 μm is preferably 0 to 0.2% when the metallographic structure of the rolled surface is observed.
ここで、図１に示すように、圧延方向Ｒ及び厚み方向Ｔに平行な断面は符合Ｓで表される。又、平均結晶粒径は以下のようにして定める。まず、断面Ｓの組織写真において、厚み方向Ｔに直線を任意に３本引き、直線によって切断される結晶粒の個数を求め、直線の長さを結晶粒の個数で割った値をａとする。同様に、圧延方向Ｌに直線を任意に３本引き、直線によって切断される結晶粒の個数を求め、直線の長さを結晶粒の個数で割った値をｂとする。そして、（ａ＋ｂ）／２の値を平均結晶粒径とする。また、ｂ／ａの値を結晶粒のアスペクト比とする。
Here, as shown in FIG. 1, a cross section parallel to the rolling direction R and the thickness direction T is represented by a symbol S. Further, the average grain size is determined as follows. First, in the structure photograph of the cross section S, three straight lines are arbitrarily drawn in the thickness direction T, the number of crystal grains cut by the straight lines is determined, and the length of the straight lines divided by the number of crystal grains is a. . Similarly, three straight lines are drawn arbitrarily in the rolling direction L, the number of crystal grains cut by the straight lines is determined, and the length of the straight line divided by the number of crystal grains is defined as b. And let the value of (a + b) / 2 be an average grain size. Further, the value of b / a is taken as the aspect ratio of the crystal grain.
又、第二相粒子は、圧延面を電解研磨した後の金属組織の２次電子像を観察したとき、マトリクスと異なる色調（つまり、マトリックスと異なる組成）の部分をいう。この部分は、電解研磨で溶解せずに残存した部分であり、Ｃｕ３ＴｉやＣｕ４Ｔｉ等のＣｕ－Ｔｉ系の第二相粒子を表し、この部分が直径１μm以上のものは曲げ加工性を劣化させる。
直径が１μm以上の第二相粒子の面積率は、上記２次電子像を画像解析し、マトリックスと異なる色調領域のそれぞれについてその領域を含む最小円の直径を求め、それを第二相粒子の直径とする。そして直径１μm以上の第二相粒子の合計面積を観察視野の総面積で割った値を面積率とする。
図２は、本発明例２の高強度チタン銅板の圧延面を電解研磨した後の金属組織の実際の２次電子像の例である。 Further, the second phase particles refer to a portion having a color tone different from that of the matrix (that is, a composition different from that of the matrix) when observing a secondary electron image of the metal structure after electropolishing the rolled surface. This portion is a portion remaining without being dissolved by electrolytic polishing, and represents a second phase particle of Cu-Ti system such as Cu 3 Ti or Cu 4 Ti, and the portion having a diameter of 1 μm or more is bendable. Degrade the
The area ratio of the second phase particles having a diameter of 1 μm or more is subjected to image analysis of the secondary electron image, and the diameter of the smallest circle including the area is determined for each of the matrix and different color tone areas. Let diameter. Then, a value obtained by dividing the total area of second phase particles having a diameter of 1 μm or more by the total area of the observation field of view is taken as the area ratio.
FIG. 2 is an example of an actual secondary electron image of the metal structure after electropolishing the rolled surface of the high strength titanium copper plate of the invention example 2.
直径が１μm以上の第二相粒子の面積率は、上記２次電子像を画像解析し、マトリックスと異なる色調領域のそれぞれについてその領域を含む最小円の直径を求め、それを第二相粒子の直径とする。そして直径１μm以上の第二相粒子の合計面積を観察視野の総面積で割った値を面積率とする。
図２は、本発明例２の高強度チタン銅板の圧延面を電解研磨した後の金属組織の実際の２次電子像の例である。 Further, the second phase particles refer to a portion having a color tone different from that of the matrix (that is, a composition different from that of the matrix) when observing a secondary electron image of the metal structure after electropolishing the rolled surface. This portion is a portion remaining without being dissolved by electrolytic polishing, and represents a second phase particle of Cu-Ti system such as Cu 3 Ti or Cu 4 Ti, and the portion having a diameter of 1 μm or more is bendable. Degrade the
The area ratio of the second phase particles having a diameter of 1 μm or more is subjected to image analysis of the secondary electron image, and the diameter of the smallest circle including the area is determined for each of the matrix and different color tone areas. Let diameter. Then, a value obtained by dividing the total area of second phase particles having a diameter of 1 μm or more by the total area of the observation field of view is taken as the area ratio.
FIG. 2 is an example of an actual secondary electron image of the metal structure after electropolishing the rolled surface of the high strength titanium copper plate of the invention example 2.
平均結晶粒径が３μm未満であるものは、溶体化処理が不十分であるため、局所的に未再結晶粒が残存したり、粗大な第二相粒子が残存したりするため、曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える場合がある。平均結晶粒径が１５μmを超えると、強度に寄与する粒界が減少し、引張り強さが９５０ＭＰａ未満となる場合がある。９５０ＭＰａ以上の引張り強さ、及び（ＭＢＲ／ｔ）≦０．５が安定して得られるため、結晶粒径を３～１２μmとするとより好ましい。
If the average grain size is less than 3 μm, the solution treatment is insufficient, so non-recrystallized grains may remain locally or coarse second phase grains may remain, so bending workability is possible. (MBR / t) may exceed 1.0. When the average grain size exceeds 15 μm, grain boundaries contributing to the strength may be reduced, and the tensile strength may be less than 950 MPa. Since a tensile strength of 950 MPa or more and (MBR / t) ≦ 0.5 can be stably obtained, it is more preferable to set the crystal grain size to 3 to 12 μm.
又、結晶粒のアスペクト比は材料の加工度を表し、アスペクト比が高いほど、加工度も高い。従って、結晶粒のアスペクト比が１．１未満であると、引張り強さが９５０ＭＰａ未満となる場合がある。一方、結晶粒のアスペクト比が２．０を超えると、加工が過度になって曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える場合がある。９５０ＭＰａ以上の引張り強さ、及び（ＭＢＲ／ｔ）≦１．０が安定して得られるため、結晶粒のアスペクト比を１．２～１．６とするとより好ましい。
In addition, the aspect ratio of crystal grains represents the degree of processing of the material, and the higher the aspect ratio, the higher the degree of processing. Therefore, when the aspect ratio of crystal grains is less than 1.1, the tensile strength may be less than 950 MPa. On the other hand, if the aspect ratio of the crystal grain exceeds 2.0, the processing becomes excessive and bending workability deteriorates, and (MBR / t) may exceed 1.0. It is more preferable to set the aspect ratio of the crystal grain to 1.2 to 1.6 because a tensile strength of 950 MPa or more and (MBR / t) ≦ 1.0 can be stably obtained.
又、直径が１μmを超える第二相粒子の面積率が０．２％を超えると、粗大な第二相粒子が組織中に存在するため、曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える場合がある。
（ＭＢＲ／ｔ）≦１．０が安定して得られるため、直径が１μmを超える第二相粒子の面積率が０．１６％以下であるとより好ましい。 In addition, when the area ratio of second phase particles having a diameter of more than 1 μm exceeds 0.2%, coarse second phase particles are present in the structure, so that bending processability is deteriorated, and (MBR / t) It may exceed 1.0.
Since (MBR / t) ≦ 1.0 is stably obtained, it is more preferable that the area ratio of the second phase particles having a diameter of more than 1 μm be 0.16% or less.
（ＭＢＲ／ｔ）≦１．０が安定して得られるため、直径が１μmを超える第二相粒子の面積率が０．１６％以下であるとより好ましい。 In addition, when the area ratio of second phase particles having a diameter of more than 1 μm exceeds 0.2%, coarse second phase particles are present in the structure, so that bending processability is deteriorated, and (MBR / t) It may exceed 1.0.
Since (MBR / t) ≦ 1.0 is stably obtained, it is more preferable that the area ratio of the second phase particles having a diameter of more than 1 μm be 0.16% or less.
次に、本発明の高強度チタン銅板の製造方法について説明する。
本発明の高強度チタン銅板の製造方法は、２．５～４．０質量％のＴｉを含有し、残部がＣｕ及び不可避不純物からなる鋳塊を熱間圧延、冷間圧延、溶体化処理、時効処理、加工度８～２５％での時効後冷間圧延の順で行う。
なお、本発明では、溶体化処理と時効処理の間で冷間圧延を行わない。この冷間圧延を行うと、引張り強さはわずかに増加するものの、曲げ加工性が劣化するためである。 Next, the manufacturing method of the high strength titanium copper plate of the present invention is explained.
The method for producing a high strength titanium copper sheet according to the present invention comprises hot rolling, cold rolling, solution treatment, an ingot containing 2.5 to 4.0 mass% of Ti and the balance being Cu and unavoidable impurities. Aging and cold rolling after aging at a working degree of 8 to 25% are performed in this order.
In the present invention, cold rolling is not performed between the solution treatment and the aging treatment. When this cold rolling is performed, although the tensile strength is slightly increased, the bending workability is deteriorated.
本発明の高強度チタン銅板の製造方法は、２．５～４．０質量％のＴｉを含有し、残部がＣｕ及び不可避不純物からなる鋳塊を熱間圧延、冷間圧延、溶体化処理、時効処理、加工度８～２５％での時効後冷間圧延の順で行う。
なお、本発明では、溶体化処理と時効処理の間で冷間圧延を行わない。この冷間圧延を行うと、引張り強さはわずかに増加するものの、曲げ加工性が劣化するためである。 Next, the manufacturing method of the high strength titanium copper plate of the present invention is explained.
The method for producing a high strength titanium copper sheet according to the present invention comprises hot rolling, cold rolling, solution treatment, an ingot containing 2.5 to 4.0 mass% of Ti and the balance being Cu and unavoidable impurities. Aging and cold rolling after aging at a working degree of 8 to 25% are performed in this order.
In the present invention, cold rolling is not performed between the solution treatment and the aging treatment. When this cold rolling is performed, although the tensile strength is slightly increased, the bending workability is deteriorated.
鋳塊は、上記組成の材料を溶解及び鋳造し、例えば厚み１００～３００ｍｍのインゴットとして製造することができる。チタンの酸化損耗を防止するため、溶解及び鋳造を真空中又は不活性ガス雰囲気中で行うことが好ましい。次に、鋳塊を例えば８５０～１０００℃で３～２４時間程度加熱し、３～３０ｍｍの厚みまで熱間圧延を行うことができる。
The ingot can be produced by melting and casting the material having the above composition, for example, as an ingot having a thickness of 100 to 300 mm. In order to prevent oxidation damage of titanium, it is preferable to carry out melting and casting in vacuum or in an inert gas atmosphere. Next, the ingot may be heated, for example, at 850 to 1000 ° C. for about 3 to 24 hours to perform hot rolling to a thickness of 3 to 30 mm.
溶体化処理は連続焼鈍炉を用いて行うことが好ましい。溶体化処理を９２０～１０５０℃で５～５０秒間行うと、上記した平均結晶粒径を３～１５μmに調整することができる。ここで、溶体化処理後に時効後冷間圧延をしても平均結晶粒径はほぼ変わらないので、溶体化処理直後の平均結晶粒径が３～１５μmになるよう溶体化処理条件を調整すればよい。なお、時効後冷間圧延をすると、溶体化処理直後に比べて結晶粒のアスペクト比は変化する。
溶体化処理温度が９２０℃未満または溶体化処理時間が５秒未満の場合、溶体化処理が不十分であり、部分的に未再結晶粒が残存するため、平均結晶粒径を３μm以上に調整することが困難になり、また直径が１μmを超える第二相粒子の面積率を０．２％以下に調整することが困難になる傾向にある。その結果、得られた高強度チタン銅板の曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える場合がある。一方、溶体化処理温度が１０５０℃を超え、または溶体化処理時間が５０秒を超える場合、溶体化処理が過度になって結晶が成長し過ぎ、平均結晶粒径を１５μm以下に調整することが困難になる傾向にある。
溶体化処理に先立ち、複数回の予備の溶体化処理を行っても良い。予備の溶体化処理の条件は、特に限定されない。複数回の予備の溶体化処理を行う場合、各溶体化処理の間に冷間圧延を行うとよい。 The solution treatment is preferably performed using a continuous annealing furnace. When the solution treatment is performed at 920 to 1050 ° C. for 5 to 50 seconds, the above-described average crystal grain size can be adjusted to 3 to 15 μm. Here, even if cold rolling after aging after solution treatment does not substantially change the average grain size, if the solution treatment conditions are adjusted so that the average grain size immediately after solution treatment becomes 3 to 15 μm. Good. In addition, when cold rolling is performed after aging, the aspect ratio of crystal grains changes as compared with that immediately after solution treatment.
If the solution treatment temperature is less than 920 ° C. or the solution treatment time is less than 5 seconds, the solution treatment is insufficient and partially unrecrystallized grains remain, so the average grain size is adjusted to 3 μm or more It tends to be difficult to adjust the area ratio of second phase particles having a diameter of more than 1 .mu.m to 0.2% or less. As a result, the bending workability of the obtained high strength titanium copper plate may be deteriorated, and (MBR / t) may exceed 1.0. On the other hand, when the solution treatment temperature exceeds 1050 ° C. or the solution treatment time exceeds 50 seconds, the solution treatment becomes excessive and the crystals grow too much, and the average crystal grain size may be adjusted to 15 μm or less It tends to be difficult.
A plurality of preliminary solution treatment may be performed prior to the solution treatment. The conditions for the preliminary solution treatment are not particularly limited. If multiple preliminary solution treatments are performed, cold rolling may be performed between each solution treatment.
溶体化処理温度が９２０℃未満または溶体化処理時間が５秒未満の場合、溶体化処理が不十分であり、部分的に未再結晶粒が残存するため、平均結晶粒径を３μm以上に調整することが困難になり、また直径が１μmを超える第二相粒子の面積率を０．２％以下に調整することが困難になる傾向にある。その結果、得られた高強度チタン銅板の曲げ加工性が劣化し、（ＭＢＲ／ｔ）が１．０を超える場合がある。一方、溶体化処理温度が１０５０℃を超え、または溶体化処理時間が５０秒を超える場合、溶体化処理が過度になって結晶が成長し過ぎ、平均結晶粒径を１５μm以下に調整することが困難になる傾向にある。
溶体化処理に先立ち、複数回の予備の溶体化処理を行っても良い。予備の溶体化処理の条件は、特に限定されない。複数回の予備の溶体化処理を行う場合、各溶体化処理の間に冷間圧延を行うとよい。 The solution treatment is preferably performed using a continuous annealing furnace. When the solution treatment is performed at 920 to 1050 ° C. for 5 to 50 seconds, the above-described average crystal grain size can be adjusted to 3 to 15 μm. Here, even if cold rolling after aging after solution treatment does not substantially change the average grain size, if the solution treatment conditions are adjusted so that the average grain size immediately after solution treatment becomes 3 to 15 μm. Good. In addition, when cold rolling is performed after aging, the aspect ratio of crystal grains changes as compared with that immediately after solution treatment.
If the solution treatment temperature is less than 920 ° C. or the solution treatment time is less than 5 seconds, the solution treatment is insufficient and partially unrecrystallized grains remain, so the average grain size is adjusted to 3 μm or more It tends to be difficult to adjust the area ratio of second phase particles having a diameter of more than 1 .mu.m to 0.2% or less. As a result, the bending workability of the obtained high strength titanium copper plate may be deteriorated, and (MBR / t) may exceed 1.0. On the other hand, when the solution treatment temperature exceeds 1050 ° C. or the solution treatment time exceeds 50 seconds, the solution treatment becomes excessive and the crystals grow too much, and the average crystal grain size may be adjusted to 15 μm or less It tends to be difficult.
A plurality of preliminary solution treatment may be performed prior to the solution treatment. The conditions for the preliminary solution treatment are not particularly limited. If multiple preliminary solution treatments are performed, cold rolling may be performed between each solution treatment.
時効処理はバッチ焼鈍炉を用いて行うことが好ましい。時効処理を３８０～４８０℃で３～２０時間行うことが好ましい。時効処理温度が３８０℃未満または時効処理が３時間未満の場合、時効不足により充分な析出物（強度向上に寄与するＣｕ３ＴｉまたはＣｕ４Ｔｉの微細粒子）が生成せず、９５０ＭＰａ以上の引張り強さを達成することが困難になる傾向にある。一方、時効処理温度が４８０℃を超え、または時効処理が２０時間を超える場合、過時効により析出物が粗大化し、引張り強さが９５０ＭＰａ未満となるとともに、（ＭＢＲ／ｔ）が１．０を超える場合がある。
The aging treatment is preferably performed using a batch annealing furnace. The aging treatment is preferably performed at 380 to 480 ° C. for 3 to 20 hours. When the aging treatment temperature is less than 380 ° C. or the aging treatment is less than 3 hours, sufficient precipitation (fine particles of Cu 3 Ti or Cu 4 Ti contributing to strength improvement) is not generated due to insufficient aging, and a tension of 950 MPa or more Achieving strength tends to be difficult. On the other hand, when the aging treatment temperature exceeds 480 ° C. or the aging treatment exceeds 20 hours, the precipitate becomes coarse due to overaging, and the tensile strength becomes less than 950 MPa and (MBR / t) becomes 1.0. May exceed.
時効後冷間圧延の加工度は８～２５％とする。加工度が８％未満であると、引張り強さが９５０ＭＰａ未満となるとともに、０．２％耐力が引張り強さの０．９倍以上に達しない。一方、加工度が２５％を超えると、曲げ加工性が劣り、（ＭＢＲ／ｔ）が１．０を超える。
９５０ＭＰａ以上の引張り強さ、及び（ＭＢＲ／ｔ）≦１．０が安定して得られ、０．２％耐力が引張り強さの０．９倍以上に安定して達するため、加工度を１０～２０％とするとより好ましい。 The working ratio of cold rolling after aging is 8 to 25%. When the working degree is less than 8%, the tensile strength is less than 950 MPa, and the 0.2% proof stress does not reach 0.9 times or more of the tensile strength. On the other hand, when the degree of processing exceeds 25%, bending workability is poor, and (MBR / t) exceeds 1.0.
Since a tensile strength of 950 MPa or more and (MBR / t) ≦ 1.0 can be stably obtained, and a 0.2% proof stress stably reaches 0.9 times or more of the tensile strength, the processing degree is 10 It is more preferable to set it to -20%.
９５０ＭＰａ以上の引張り強さ、及び（ＭＢＲ／ｔ）≦１．０が安定して得られ、０．２％耐力が引張り強さの０．９倍以上に安定して達するため、加工度を１０～２０％とするとより好ましい。 The working ratio of cold rolling after aging is 8 to 25%. When the working degree is less than 8%, the tensile strength is less than 950 MPa, and the 0.2% proof stress does not reach 0.9 times or more of the tensile strength. On the other hand, when the degree of processing exceeds 25%, bending workability is poor, and (MBR / t) exceeds 1.0.
Since a tensile strength of 950 MPa or more and (MBR / t) ≦ 1.0 can be stably obtained, and a 0.2% proof stress stably reaches 0.9 times or more of the tensile strength, the processing degree is 10 It is more preferable to set it to -20%.
ばね限界値の改善を図るため、時効後冷間圧延の後に歪取り焼鈍を行っても良い。歪取り焼鈍はバッチ焼鈍炉又は連続焼鈍炉を用いて行うことができる。バッチ焼鈍炉では、２００～７００℃の加熱炉中に材料を０．５～１５時間保持する。バッチ焼鈍炉の温度が２００℃未満または保持時間が０．５時間未満の場合、ばね限界値を十分に改善することが難しい。バッチ焼鈍炉の温度が７００℃を超え、又は保持時間が１５時間を超える場合、引張り強さが低下する。
一方、連続焼鈍炉では、３００～６００℃の加熱炉中に材料を１０～１０００秒間保持する。連続焼鈍炉の温度が３００℃未満または保持時間が１０秒未満の場合、ばね限界値を十分に改善することが難しい。連続焼鈍炉の温度が６００℃を超え、又は保持時間が１０００秒を超える場合、引張り強さが低下する。 In order to improve the spring limit value, strain relief annealing may be performed after cold rolling after aging. The strain relief annealing can be performed using a batch annealing furnace or a continuous annealing furnace. In the batch annealing furnace, the material is held in a 200 to 700 ° C. heating furnace for 0.5 to 15 hours. If the temperature of the batch annealing furnace is less than 200 ° C. or the holding time is less than 0.5 hours, it is difficult to sufficiently improve the spring limit value. When the temperature of the batch annealing furnace exceeds 700 ° C. or the holding time exceeds 15 hours, the tensile strength decreases.
On the other hand, in the continuous annealing furnace, the material is held in a heating furnace at 300 to 600 ° C. for 10 to 1000 seconds. If the temperature of the continuous annealing furnace is less than 300 ° C. or the holding time is less than 10 seconds, it is difficult to sufficiently improve the spring limit value. When the temperature of the continuous annealing furnace exceeds 600 ° C. or the holding time exceeds 1000 seconds, the tensile strength decreases.
一方、連続焼鈍炉では、３００～６００℃の加熱炉中に材料を１０～１０００秒間保持する。連続焼鈍炉の温度が３００℃未満または保持時間が１０秒未満の場合、ばね限界値を十分に改善することが難しい。連続焼鈍炉の温度が６００℃を超え、又は保持時間が１０００秒を超える場合、引張り強さが低下する。 In order to improve the spring limit value, strain relief annealing may be performed after cold rolling after aging. The strain relief annealing can be performed using a batch annealing furnace or a continuous annealing furnace. In the batch annealing furnace, the material is held in a 200 to 700 ° C. heating furnace for 0.5 to 15 hours. If the temperature of the batch annealing furnace is less than 200 ° C. or the holding time is less than 0.5 hours, it is difficult to sufficiently improve the spring limit value. When the temperature of the batch annealing furnace exceeds 700 ° C. or the holding time exceeds 15 hours, the tensile strength decreases.
On the other hand, in the continuous annealing furnace, the material is held in a heating furnace at 300 to 600 ° C. for 10 to 1000 seconds. If the temperature of the continuous annealing furnace is less than 300 ° C. or the holding time is less than 10 seconds, it is difficult to sufficiently improve the spring limit value. When the temperature of the continuous annealing furnace exceeds 600 ° C. or the holding time exceeds 1000 seconds, the tensile strength decreases.
なお、上記各工程の間に適宜、表面の酸化スケール除去のための研削、研磨、ショットブラスト酸洗等の工程を行なうこともできる。
In addition, processes such as grinding, polishing, shot blasting and pickling for removing oxide scale on the surface can be appropriately performed between the above respective processes.
以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。
真空溶解炉にて電気銅を溶解し、表１、表２に示す割合でＴｉおよびその他の元素（表１、表２の副成分）を添加した。この溶湯を鋳造し、厚み１５０ｍｍ、幅６００ｍｍ、長さ６０００ｍｍの直方体のインゴットを得た。このインゴットを９５０℃で３時間加熱し、熱間圧延により厚み１０ｍｍの熱延板とした。面削によるスケール除去後、中間冷間圧延、溶体化処理、時効および時効後冷間圧延の順で加工し、表１、表２に示す厚みの板試料を得た。
一部の試料では、時効後冷間圧延の後に、バッチ焼鈍炉で３００℃、３時間、又は連続焼鈍炉で５００℃、１０秒間の歪取り焼鈍を施した。
時効後冷間圧延の後（歪取り焼鈍を行ったものでは歪取り焼鈍後）の試料につき、以下の特性評価を行った。 Examples of the present invention are given below together with comparative examples, but these examples are provided to better understand the present invention and its advantages, and are not intended to limit the invention.
Electrolytic copper was melted in a vacuum melting furnace, and Ti and other elements (subcomponents of Tables 1 and 2) were added in the proportions shown in Tables 1 and 2. This molten metal was cast to obtain a rectangular ingot having a thickness of 150 mm, a width of 600 mm, and a length of 6000 mm. The ingot was heated at 950 ° C. for 3 hours, and hot rolled into a hot-rolled sheet with a thickness of 10 mm. After removing the scale by facing, it was processed in the order of intermediate cold rolling, solution treatment, aging and cold rolling after aging to obtain plate samples having thicknesses shown in Table 1 and Table 2.
For some samples, after cold rolling after aging, strain relief annealing was performed at 300 ° C. for 3 hours in a batch annealing furnace, or at 500 ° C. for 10 seconds in a continuous annealing furnace.
The following characteristic evaluation was performed about the sample after cold rolling after aging (after strain relief annealing after strain relief annealing).
真空溶解炉にて電気銅を溶解し、表１、表２に示す割合でＴｉおよびその他の元素（表１、表２の副成分）を添加した。この溶湯を鋳造し、厚み１５０ｍｍ、幅６００ｍｍ、長さ６０００ｍｍの直方体のインゴットを得た。このインゴットを９５０℃で３時間加熱し、熱間圧延により厚み１０ｍｍの熱延板とした。面削によるスケール除去後、中間冷間圧延、溶体化処理、時効および時効後冷間圧延の順で加工し、表１、表２に示す厚みの板試料を得た。
一部の試料では、時効後冷間圧延の後に、バッチ焼鈍炉で３００℃、３時間、又は連続焼鈍炉で５００℃、１０秒間の歪取り焼鈍を施した。
時効後冷間圧延の後（歪取り焼鈍を行ったものでは歪取り焼鈍後）の試料につき、以下の特性評価を行った。 Examples of the present invention are given below together with comparative examples, but these examples are provided to better understand the present invention and its advantages, and are not intended to limit the invention.
Electrolytic copper was melted in a vacuum melting furnace, and Ti and other elements (subcomponents of Tables 1 and 2) were added in the proportions shown in Tables 1 and 2. This molten metal was cast to obtain a rectangular ingot having a thickness of 150 mm, a width of 600 mm, and a length of 6000 mm. The ingot was heated at 950 ° C. for 3 hours, and hot rolled into a hot-rolled sheet with a thickness of 10 mm. After removing the scale by facing, it was processed in the order of intermediate cold rolling, solution treatment, aging and cold rolling after aging to obtain plate samples having thicknesses shown in Table 1 and Table 2.
For some samples, after cold rolling after aging, strain relief annealing was performed at 300 ° C. for 3 hours in a batch annealing furnace, or at 500 ° C. for 10 seconds in a continuous annealing furnace.
The following characteristic evaluation was performed about the sample after cold rolling after aging (after strain relief annealing after strain relief annealing).
（引張り強さ、０．２％耐力）
引張方向が圧延方向と平行になるように、プレス機を用いてＪＩＳ１３Ｂ号試験片を作製した。ＪＩＳ－Ｚ２２４１に従ってこの試験片の引張試験を行ない、圧延平行方向の引張り強さおよび０．２％耐力を測定した。
（曲げ加工性）
ＪＩＳ－Ｈ３１３０に従って、Ｂａｄｗａｙ（曲げ軸が圧延方向と同一方向）のＷ曲げ試験を行い、割れの発生しない最小半径（ＭＢＲ）と板厚（ｔ）との比である（ＭＢＲ／ｔ）値を測定した。試料の幅は１０ｍｍとした。 (Tensile strength, 0.2% proof stress)
A JIS13B test piece was produced using a press so that the tensile direction was parallel to the rolling direction. The tensile test of this test piece was carried out according to JIS-Z2241, and the tensile strength in the rolling parallel direction and the 0.2% proof stress were measured.
(Bendability)
Conduct a W bending test of Badway (the bending axis is the same direction as the rolling direction) according to JIS-H3130, and calculate the ratio of the minimum radius (MBR) where the crack does not occur to the thickness (t) to the plate thickness (t). It was measured. The width of the sample was 10 mm.
引張方向が圧延方向と平行になるように、プレス機を用いてＪＩＳ１３Ｂ号試験片を作製した。ＪＩＳ－Ｚ２２４１に従ってこの試験片の引張試験を行ない、圧延平行方向の引張り強さおよび０．２％耐力を測定した。
（曲げ加工性）
ＪＩＳ－Ｈ３１３０に従って、Ｂａｄｗａｙ（曲げ軸が圧延方向と同一方向）のＷ曲げ試験を行い、割れの発生しない最小半径（ＭＢＲ）と板厚（ｔ）との比である（ＭＢＲ／ｔ）値を測定した。試料の幅は１０ｍｍとした。 (Tensile strength, 0.2% proof stress)
A JIS13B test piece was produced using a press so that the tensile direction was parallel to the rolling direction. The tensile test of this test piece was carried out according to JIS-Z2241, and the tensile strength in the rolling parallel direction and the 0.2% proof stress were measured.
(Bendability)
Conduct a W bending test of Badway (the bending axis is the same direction as the rolling direction) according to JIS-H3130, and calculate the ratio of the minimum radius (MBR) where the crack does not occur to the thickness (t) to the plate thickness (t). It was measured. The width of the sample was 10 mm.
（ばね限界値）
ＪＩＳ－Ｈ３１３０に規定されているモーメント式試験により圧延方向と平行な方向のばね限界値を測定した。
（平均結晶粒径およびアスペクト比）
試料の圧延方向と平行な断面（図１のＳ）を機械研磨により鏡面に仕上げた後、水（１００ｍＬ）－ＦｅＣｌ３（５ｇ）－ＨＣｌ（１０ｍＬ）水溶液を用いたエッチングにより結晶粒界を現出させ、光学顕微鏡を用い組織写真を撮影した。組織写真上において、厚み方向Ｔに直線を任意に３本引き、直線によって切断される結晶粒の個数を求め、直線の長さを結晶粒の個数で割った値をａとしｔ。同様に、圧延方向Ｌに直線を任意に３本引き、直線によって切断される結晶粒の個数を求め、直線の長さを結晶粒の個数で割った値をｂとした。そして、（ａ＋ｂ）／２の値を平均結晶粒径とする。また、ｂ／ａの値を結晶粒のアスペクト比とした。 (Spring limit value)
The spring limit value in the direction parallel to the rolling direction was measured by a moment test prescribed in JIS-H3130.
(Average grain size and aspect ratio)
After finishing the rolling direction and parallel to the cross section of the sample (S in FIG. 1) to a mirror surface by mechanical polishing, water (100mL) -FeCl 3 (5g) grain boundaries by etching using a-HCl (10 mL) solution of the current The tissue was photographed using an optical microscope. On the photograph of the structure, three straight lines are arbitrarily drawn in the thickness direction T, the number of crystal grains cut by the straight line is determined, and a value obtained by dividing the length of the straight line by the number of crystal grains is a. Similarly, three straight lines are drawn arbitrarily in the rolling direction L, the number of crystal grains cut by the straight line is determined, and the length of the straight line divided by the number of crystal grains is defined as b. And let the value of (a + b) / 2 be an average grain size. Further, the value of b / a was taken as the aspect ratio of crystal grains.
ＪＩＳ－Ｈ３１３０に規定されているモーメント式試験により圧延方向と平行な方向のばね限界値を測定した。
（平均結晶粒径およびアスペクト比）
試料の圧延方向と平行な断面（図１のＳ）を機械研磨により鏡面に仕上げた後、水（１００ｍＬ）－ＦｅＣｌ３（５ｇ）－ＨＣｌ（１０ｍＬ）水溶液を用いたエッチングにより結晶粒界を現出させ、光学顕微鏡を用い組織写真を撮影した。組織写真上において、厚み方向Ｔに直線を任意に３本引き、直線によって切断される結晶粒の個数を求め、直線の長さを結晶粒の個数で割った値をａとしｔ。同様に、圧延方向Ｌに直線を任意に３本引き、直線によって切断される結晶粒の個数を求め、直線の長さを結晶粒の個数で割った値をｂとした。そして、（ａ＋ｂ）／２の値を平均結晶粒径とする。また、ｂ／ａの値を結晶粒のアスペクト比とした。 (Spring limit value)
The spring limit value in the direction parallel to the rolling direction was measured by a moment test prescribed in JIS-H3130.
(Average grain size and aspect ratio)
After finishing the rolling direction and parallel to the cross section of the sample (S in FIG. 1) to a mirror surface by mechanical polishing, water (100mL) -FeCl 3 (5g) grain boundaries by etching using a-HCl (10 mL) solution of the current The tissue was photographed using an optical microscope. On the photograph of the structure, three straight lines are arbitrarily drawn in the thickness direction T, the number of crystal grains cut by the straight line is determined, and a value obtained by dividing the length of the straight line by the number of crystal grains is a. Similarly, three straight lines are drawn arbitrarily in the rolling direction L, the number of crystal grains cut by the straight line is determined, and the length of the straight line divided by the number of crystal grains is defined as b. And let the value of (a + b) / 2 be an average grain size. Further, the value of b / a was taken as the aspect ratio of crystal grains.
（第二相粒子）
試料の圧延面を電解研磨（電解液：水（２５０ｍＬ）＋りん酸（１２５ｍＬ）＋尿素（２．５ｇ）＋エタノール（１２５ｍＬ）＋プロパノール（２５ｍＬ）、１２Ａ、１分間）した後、電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ；日本ＦＥＩ社製の型番ＸＬ３０ＳＦＥＧ）を用いて、７５０倍の倍率で０．０１７ｍｍ２の視野の２次電子像を視野を変えて１２箇所観察した。その後、画像解析装置を使用して、観察視野の濃淡の明度をしきい値６０で二値化後、マトリックスと色調の異なる領域のそれぞれについてその領域を含む最小円の直径を求め、それを第二相粒子の直径とした。そして直径１μm以上の第二相粒子の合計面積を、観察視野の総面積で割った値を面積率とした。 (Second phase particles)
The field emission type after electrolytic polishing of the rolled surface of the sample (electrolytic solution: water (250 mL) + phosphoric acid (125 mL) + urea (2.5 g) + ethanol (125 mL) + propanol (25 mL), 12 A, 1 minute) Using a scanning electron microscope (FE-SEM; model No. XL30SFEG manufactured by Japan FEI), secondary electron images of a field of view of 0.017 mm 2 were observed at 12 points with a magnification of 750 times. After that, using the image analysis device, the lightness of the observation field of view is binarized with the threshold value 60, and the diameter of the smallest circle including the area is determined for each of the matrix and different areas of color tone. It was the diameter of the two-phase particle. And the value which divided the total area of the 2nd phase particle of diameter 1 micrometer or more by the total area of the observation visual field was made into the area ratio.
試料の圧延面を電解研磨（電解液：水（２５０ｍＬ）＋りん酸（１２５ｍＬ）＋尿素（２．５ｇ）＋エタノール（１２５ｍＬ）＋プロパノール（２５ｍＬ）、１２Ａ、１分間）した後、電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ；日本ＦＥＩ社製の型番ＸＬ３０ＳＦＥＧ）を用いて、７５０倍の倍率で０．０１７ｍｍ２の視野の２次電子像を視野を変えて１２箇所観察した。その後、画像解析装置を使用して、観察視野の濃淡の明度をしきい値６０で二値化後、マトリックスと色調の異なる領域のそれぞれについてその領域を含む最小円の直径を求め、それを第二相粒子の直径とした。そして直径１μm以上の第二相粒子の合計面積を、観察視野の総面積で割った値を面積率とした。 (Second phase particles)
The field emission type after electrolytic polishing of the rolled surface of the sample (electrolytic solution: water (250 mL) + phosphoric acid (125 mL) + urea (2.5 g) + ethanol (125 mL) + propanol (25 mL), 12 A, 1 minute) Using a scanning electron microscope (FE-SEM; model No. XL30SFEG manufactured by Japan FEI), secondary electron images of a field of view of 0.017 mm 2 were observed at 12 points with a magnification of 750 times. After that, using the image analysis device, the lightness of the observation field of view is binarized with the threshold value 60, and the diameter of the smallest circle including the area is determined for each of the matrix and different areas of color tone. It was the diameter of the two-phase particle. And the value which divided the total area of the 2nd phase particle of diameter 1 micrometer or more by the total area of the observation visual field was made into the area ratio.
得られた結果を表１～表４に示す。
The obtained results are shown in Tables 1 to 4.
表１～表４から明らかなように、発明例１～２６の場合、引張強さが９５０ＭＰａ以上で、０．２％耐力が引張り強さの０．９倍以上、（ＭＢＲ／ｔ）が１．０以下となり、強度と曲げ加工性にともに優れた。
特に発明例２～７、１２、１４、２０、２４～２６は引張強さが１０００ＭＰａ以上、０．２％耐力が引張り強さの０．９倍以上、（ＭＢＲ／ｔ）が０．５以下となり、強度と曲げ加工性にともに優れた。 As is apparent from Tables 1 to 4, in the case of Inventive Examples 1 to 26, the tensile strength is 950 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 1 .0 or less, and both strength and bending workability were excellent.
In particular, in the invention examples 2 to 7, 12, 14, 20 and 24 to 26, the tensile strength is 1000 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 0.5 or less It was excellent in both strength and bending workability.
特に発明例２～７、１２、１４、２０、２４～２６は引張強さが１０００ＭＰａ以上、０．２％耐力が引張り強さの０．９倍以上、（ＭＢＲ／ｔ）が０．５以下となり、強度と曲げ加工性にともに優れた。 As is apparent from Tables 1 to 4, in the case of Inventive Examples 1 to 26, the tensile strength is 950 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 1 .0 or less, and both strength and bending workability were excellent.
In particular, in the invention examples 2 to 7, 12, 14, 20 and 24 to 26, the tensile strength is 1000 MPa or more, the 0.2% proof stress is 0.9 times or more of the tensile strength, and (MBR / t) is 0.5 or less It was excellent in both strength and bending workability.
Ｔｉ濃度が２．５％未満である比較例１の場合、引張強さが９５０ＭＰａ未満になった。一方、Ｔｉ濃度が４．０％を超えた比較例２の場合、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。
板厚が０．１５ｍｍ超である比較例３の場合、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。 In the case of Comparative Example 1 in which the Ti concentration is less than 2.5%, the tensile strength is less than 950 MPa. On the other hand, in the case of Comparative Example 2 in which the Ti concentration exceeded 4.0%, bending workability decreased and (MBR / t) exceeded 1.0.
In the case of Comparative Example 3 in which the plate thickness is more than 0.15 mm, bending workability is reduced, and (MBR / t) exceeds 1.0.
板厚が０．１５ｍｍ超である比較例３の場合、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。 In the case of Comparative Example 1 in which the Ti concentration is less than 2.5%, the tensile strength is less than 950 MPa. On the other hand, in the case of Comparative Example 2 in which the Ti concentration exceeded 4.0%, bending workability decreased and (MBR / t) exceeded 1.0.
In the case of Comparative Example 3 in which the plate thickness is more than 0.15 mm, bending workability is reduced, and (MBR / t) exceeds 1.0.
時効後冷間圧延の加工度が８％未満である比較例４の場合、結晶粒のアスペクト比が１．１未満となり、引張強さが９５０ＭＰａ未満に低下し、０．２％耐力が引張り強さの０．９倍未満となった。一方、時効後冷間圧延の加工度が２５％を超えた比較例５の場合、アスペクト比が２．０を超え、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。
In the case of Comparative Example 4 in which the working ratio of cold rolling after aging is less than 8%, the aspect ratio of the crystal grains is less than 1.1, the tensile strength is reduced to less than 950 MPa, and the 0.2% proof stress is tensile strength Less than 0.9 times the On the other hand, in the case of Comparative Example 5 in which the working ratio of cold rolling after aging exceeded 25%, the aspect ratio exceeded 2.0, the bending workability decreased, and (MBR / t) exceeded 1.0. .
溶体化処理温度が９２０℃未満である比較例６の場合、結晶粒径が３μm未満で、直径１μmを超える第二相粒子の面積率が０．２％を超え、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。一方、溶体化処理時間が５０秒を超えた比較例７の場合、結晶粒径が１５μmを超え、引張強さが９５０ＭＰａ未満に低下した。
板厚が０．１５ｍｍを超えたと共に、溶体化処理温度が９２０℃未満で、時効後冷間圧延の加工度が２５％を超えた比較例８の場合、直径１μmを超える第二相粒子の面積率が０．２％を超え、アスペクト比が２．０を超えた。そのため曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。 In the case of Comparative Example 6 in which the solution treatment temperature is less than 920 ° C., the area fraction of the second phase particles having a crystal grain size of less than 3 μm and a diameter of more than 1 μm exceeds 0.2%, and the bending workability decreases. (MBR / t) exceeded 1.0. On the other hand, in the case of Comparative Example 7 in which the solution treatment time exceeded 50 seconds, the crystal grain size exceeded 15 μm, and the tensile strength decreased to less than 950 MPa.
In the case of Comparative Example 8 in which the plate thickness exceeds 0.15 mm, the solution treatment temperature is less than 920 ° C., and the degree of working of cold rolling after aging exceeds 25%, the second phase particles exceeding 1 μm in diameter The area ratio exceeded 0.2% and the aspect ratio exceeded 2.0. Therefore, bending workability decreased and (MBR / t) exceeded 1.0.
板厚が０．１５ｍｍを超えたと共に、溶体化処理温度が９２０℃未満で、時効後冷間圧延の加工度が２５％を超えた比較例８の場合、直径１μmを超える第二相粒子の面積率が０．２％を超え、アスペクト比が２．０を超えた。そのため曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。 In the case of Comparative Example 6 in which the solution treatment temperature is less than 920 ° C., the area fraction of the second phase particles having a crystal grain size of less than 3 μm and a diameter of more than 1 μm exceeds 0.2%, and the bending workability decreases. (MBR / t) exceeded 1.0. On the other hand, in the case of Comparative Example 7 in which the solution treatment time exceeded 50 seconds, the crystal grain size exceeded 15 μm, and the tensile strength decreased to less than 950 MPa.
In the case of Comparative Example 8 in which the plate thickness exceeds 0.15 mm, the solution treatment temperature is less than 920 ° C., and the degree of working of cold rolling after aging exceeds 25%, the second phase particles exceeding 1 μm in diameter The area ratio exceeded 0.2% and the aspect ratio exceeded 2.0. Therefore, bending workability decreased and (MBR / t) exceeded 1.0.
時効処理温度が３８０℃未満である比較例９の場合、引張強さが９５０ＭＰａ未満に低下した。一方、時効処理温度が４８０℃を超えた比較例１０の場合、引張強さが９５０ＭＰａ未満に低下したと共に、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。
In the case of the comparative example 9 whose aging treatment temperature is less than 380 degreeC, tensile strength fell to less than 950 Mpa. On the other hand, in the case of Comparative Example 10 in which the aging treatment temperature exceeded 480 ° C., the tensile strength decreased to less than 950 MPa, the bending workability decreased, and (MBR / t) exceeded 1.0.
時効後冷間圧延に加え、溶体化処理と時効処理との間に加工度２０％の時効前冷間圧延を行った比較例１１の場合、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。なお、比較例１１は時効前冷間圧延を行ったこと以外は発明例２と同一の条件で製造されたものであり、引張強さがわずかに（２０ＭＰａ）増加したが、曲げ加工性の低下を招いたことがわかる。
In the case of Comparative Example 11 in which cold rolling before aging was performed between solution treatment and aging treatment in addition to cold rolling after aging, bending formability was reduced, and (MBR / t) was It exceeded 1.0. Comparative Example 11 was manufactured under the same conditions as Inventive Example 2 except that cold rolling before aging was performed, and although the tensile strength was slightly increased (20 MPa), the bending workability decreased. It can be seen that
時効後冷間圧延に加え、溶体化処理と時効処理との間に加工度１１．２％の時効前冷間圧延を行った比較例１２の場合も、曲げ加工性が低下し、（ＭＢＲ／ｔ）が１．０を超えた。なお、比較例１２は時効前冷間圧延を行ったこと以外は発明例１１と同一の条件で製造されたものであり、引張強さがわずかに（１１ＭＰａ）増加したが、曲げ加工性の低下を招いたことがわかる。
また、比較例１２の総加工度（｛（溶体化処理時の板厚）―（最終板厚）｝／（溶体化処理時の板厚×１００））は２０％であり、総加工度が同一の発明例１２と比較しても曲げ加工性が劣化したことがわかる。
なお、比較例１１及び１２は、時効前冷間圧延を行ったために時効処理時に析出物の粗大化を促進し、直径１μmを超える第二相粒子の面積率が０．２％を超え、曲げ加工性が劣化したと考えられる。 Also in the case of Comparative Example 12 in which cold rolling before aging was performed between solution treatment and aging treatment in addition to cold rolling after aging, bending formability is reduced (MBR / t) exceeded 1.0. Comparative Example 12 was manufactured under the same conditions as Inventive Example 11 except that cold rolling before aging was performed, and although the tensile strength was slightly increased (11 MPa), the bending workability decreased. It can be seen that
Moreover, the total processing degree ({(plate thickness at the time of solution treatment)-(final plate thickness)) / (plate thickness at the time of solution treatment × 100) of Comparative Example 12 is 20%, and the total processing rate is It can be seen that the bending workability is deteriorated even in comparison with the same invention example 12.
In Comparative Examples 11 and 12, since the cold rolling before aging was performed, coarsening of precipitates was promoted at the time of aging treatment, and the area ratio of the second phase particles exceeding 1 μm in diameter exceeded 0.2%, and bending was caused. It is considered that the processability has deteriorated.
また、比較例１２の総加工度（｛（溶体化処理時の板厚）―（最終板厚）｝／（溶体化処理時の板厚×１００））は２０％であり、総加工度が同一の発明例１２と比較しても曲げ加工性が劣化したことがわかる。
なお、比較例１１及び１２は、時効前冷間圧延を行ったために時効処理時に析出物の粗大化を促進し、直径１μmを超える第二相粒子の面積率が０．２％を超え、曲げ加工性が劣化したと考えられる。 Also in the case of Comparative Example 12 in which cold rolling before aging was performed between solution treatment and aging treatment in addition to cold rolling after aging, bending formability is reduced (MBR / t) exceeded 1.0. Comparative Example 12 was manufactured under the same conditions as Inventive Example 11 except that cold rolling before aging was performed, and although the tensile strength was slightly increased (11 MPa), the bending workability decreased. It can be seen that
Moreover, the total processing degree ({(plate thickness at the time of solution treatment)-(final plate thickness)) / (plate thickness at the time of solution treatment × 100) of Comparative Example 12 is 20%, and the total processing rate is It can be seen that the bending workability is deteriorated even in comparison with the same invention example 12.
In Comparative Examples 11 and 12, since the cold rolling before aging was performed, coarsening of precipitates was promoted at the time of aging treatment, and the area ratio of the second phase particles exceeding 1 μm in diameter exceeded 0.2%, and bending was caused. It is considered that the processability has deteriorated.
Claims (8)
- ２．５～４．０質量％のＴｉを含有し、残部がＣｕ及び不可避不純物からなり、引張強さが９５０ＭＰａ以上で、０．２％耐力が引張り強さの０．９倍以上であり、曲げ軸が圧延方向と平行になるようにＷ曲げ試験を行ったとき、割れの発生しない最小曲げ半径（ＭＢＲ）と板厚（ｔ）との比（ＭＢＲ／ｔ）が１．０以下である高強度チタン銅板。 Containing 2.5 to 4.0% by mass of Ti, the balance being Cu and unavoidable impurities, having a tensile strength of 950 MPa or more, and a 0.2% proof stress of 0.9 times or more of the tensile strength, When the W bending test is performed so that the bending axis is parallel to the rolling direction, the ratio (MBR / t) of the minimum bending radius (MBR) to the occurrence of cracking to the plate thickness (t) is 1.0 or less High strength titanium copper plate.
- 圧延方向及び厚み方向に平行な断面の金属組織を観察したとき、平均結晶粒径が３～１５μmであり、結晶粒のアスペクト比が１．１～２．０であり、
且つ圧延面の金属組織を観察したとき、直径が１μmを超える第二相粒子の面積率が０～０．２％である請求項１記載の高強度チタン銅板。 When a metallographic structure of a cross section parallel to the rolling direction and thickness direction is observed, the average crystal grain size is 3 to 15 μm, and the aspect ratio of crystal grains is 1.1 to 2.0,
The high-strength titanium copper plate according to claim 1, wherein the area ratio of second phase particles having a diameter of more than 1 μm is 0 to 0.2% when the metal structure of the rolled surface is observed. - （ＭＢＲ／ｔ）が０．５以下であり、
圧延方向及び厚み方向に平行な断面の金属組織を観察したとき、結晶粒のアスペクト比が１．２～１．６であり、
且つ圧延面の金属組織を観察したとき、直径が１μmを超える第二相粒子の面積率が０～０．１６％である請求項１記載の高強度チタン銅板。 (MBR / t) is less than 0.5,
When observing the metallographic structure of a cross section parallel to the rolling direction and thickness direction, the aspect ratio of the crystal grains is 1.2 to 1.6,
The high strength titanium copper plate according to claim 1, wherein the area ratio of the second phase particles having a diameter of more than 1 μm is 0 to 0.16% when observing the metal structure of the rolled surface. - Ａｇ、Ｂ、Ｃｏ、Ｃｒ、Ｆｅ、Ｍｇ、Ｍｎ、Ｍｏ、Ｎｂ、Ｎｉ、Ｐ、Ｓｉ、Ｖ及びＺｒからなる群から選択される１種又は２種以上を合計で０～０．５質量％含有する請求項１～３のいずれか記載の高強度チタン銅板。 0 to 0.5 mass% in total of one or more selected from the group consisting of Ag, B, Co, Cr, Fe, Mg, Mn, Mo, Nb, Ni, P, Si, V and Zr The high strength titanium copper plate according to any one of claims 1 to 3, which contains it.
- 板厚が０．１５ｍｍ以下である請求項１～４のいずれか記載の高強度チタン銅板。 The high-strength titanium copper plate according to any one of claims 1 to 4, which has a thickness of 0.15 mm or less.
- 請求項１～５のいずれか記載の高強度チタン銅板の製造方法であって、
２．５～４．０質量％のＴｉを含有し、残部がＣｕ及び不可避不純物からなる鋳塊を熱間圧延、冷間圧延、溶体化処理、時効処理、加工度８～２５％での時効後冷間圧延の順で行う高強度チタン銅板の製造方法。 The method for producing a high strength titanium copper plate according to any one of claims 1 to 5, comprising:
Hot rolling, cold rolling, solution treatment, aging treatment, ingot containing 2.5 to 4.0% by mass of Ti and the balance being Cu and unavoidable impurities, and aging at a working degree of 8 to 25% A method of manufacturing a high strength titanium copper plate which is performed in the order of post cold rolling. - 前記溶体化処理を９２０～１０５０℃で５～５０秒間行い、前記時効処理を３８０～４８０℃で３～２０時間行う請求項６記載の高強度チタン銅板の製造方法。 The method according to claim 6, wherein the solution treatment is performed at 920 to 1050 ° C for 5 to 50 seconds, and the aging treatment is performed at 380 to 480 ° C for 3 to 20 hours.
- 前記時効後冷間圧延の後に、２００～７００℃で０．５～１５時間、又は３００～６００℃で１０～１０００秒間の歪み取り焼鈍を行う請求項６又は７記載の高強度チタン銅板の製造方法。 The high strength titanium copper plate according to claim 6 or 7, wherein the post-aging cold rolling is followed by strain relief annealing at 200 to 700 ° C for 0.5 to 15 hours, or 300 to 600 ° C for 10 to 1000 seconds. Method.
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| JP5718443B1 (en) | 2013-12-27 | 2015-05-13 | Jx日鉱日石金属株式会社 | Titanium copper for electronic parts |
| CN104372234B (en) * | 2014-10-29 | 2017-01-11 | 嵊州市博纳五金机械厂 | High-wear-resistance titanium-copper nickel-silicon alloy composite material and preparation method thereof |
| CN105149570A (en) * | 2015-08-31 | 2015-12-16 | 苏州莱特复合材料有限公司 | Ferronickel base antifriction powder metallurgy composite material and preparation method thereof |
| CN107267799B (en) * | 2017-06-22 | 2019-03-08 | 安徽晋源铜业有限公司 | A kind of chrome zirconium copper alloy material and preparation method thereof |
| CN108559859B (en) * | 2018-05-15 | 2020-06-26 | 西安理工大学 | High-strength conductive Cu-Ti-Ni-Si alloy and preparation method thereof |
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| CN108950292B (en) * | 2018-07-24 | 2020-07-24 | 西安理工大学 | Conductive elastic Cu-Ti-Ni-Al alloy and preparation method thereof |
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| CN113278844B (en) * | 2021-05-18 | 2022-05-27 | 国工恒昌新材料沧州有限公司 | High-strength high-elasticity copper-titanium alloy and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63143230A (en) * | 1986-12-08 | 1988-06-15 | Nippon Mining Co Ltd | Precipitation strengthening high tensile copper alloy having high electrical conductivity |
| JP2004091871A (en) * | 2002-08-30 | 2004-03-25 | Yamaha Metanikusu Kk | High strength copper alloy and its production method |
| JP2004143469A (en) * | 2002-08-30 | 2004-05-20 | Nikko Metal Manufacturing Co Ltd | High strength copper alloy excellent in bendability |
| JP2006283142A (en) * | 2005-03-31 | 2006-10-19 | Nikko Kinzoku Kk | High-strength copper alloy superior in bending workability |
| JP2008081767A (en) * | 2006-09-26 | 2008-04-10 | Nikko Kinzoku Kk | Titanium-copper for electronic part |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60114558A (en) * | 1983-11-22 | 1985-06-21 | Ngk Insulators Ltd | Production of elongated material consisting of age hardenable titanium-copper alloy |
| JPS60114542A (en) * | 1983-11-22 | 1985-06-21 | Ngk Insulators Ltd | Age hardenable titanium-copper alloy material |
| JPH04136142A (en) * | 1990-09-25 | 1992-05-11 | Ngk Insulators Ltd | Manufacture of age hardening copper alloy |
| JP4001491B2 (en) * | 2001-02-20 | 2007-10-31 | 日鉱金属株式会社 | High-strength titanium-copper alloy, manufacturing method thereof, and terminal / connector using the same |
| CN1930314A (en) * | 2004-03-12 | 2007-03-14 | 住友金属工业株式会社 | Copper alloy and process for producing the same |
-
2010
- 2010-03-25 JP JP2010069470A patent/JP4761586B1/en active Active
-
2011
- 2011-03-10 WO PCT/JP2011/055599 patent/WO2011118400A1/en active Application Filing
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- 2011-03-10 CN CN201180015912.0A patent/CN102822362A/en active Pending
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63143230A (en) * | 1986-12-08 | 1988-06-15 | Nippon Mining Co Ltd | Precipitation strengthening high tensile copper alloy having high electrical conductivity |
| JP2004091871A (en) * | 2002-08-30 | 2004-03-25 | Yamaha Metanikusu Kk | High strength copper alloy and its production method |
| JP2004143469A (en) * | 2002-08-30 | 2004-05-20 | Nikko Metal Manufacturing Co Ltd | High strength copper alloy excellent in bendability |
| JP2006283142A (en) * | 2005-03-31 | 2006-10-19 | Nikko Kinzoku Kk | High-strength copper alloy superior in bending workability |
| JP2008081767A (en) * | 2006-09-26 | 2008-04-10 | Nikko Kinzoku Kk | Titanium-copper for electronic part |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021258747A1 (en) * | 2020-06-24 | 2021-12-30 | 宁波博威合金板带有限公司 | Titanium bronze alloy strip containing nb and al and preparation method therefor |
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