TW200948990A - Cu-ni-si alloy to be used in electrically conductive spring material - Google Patents

Abstract

A Cu-Ni-Si base alloy containing Ni in an amount of 1.0 to 4.0 mass% and Si in a concentration of 1/6 to 1/4 of that of Ni, wherein the density of twin boundaries (S3 boundaries) is 15 to 60% of all the grain boundaries. The alloy may further contain Mg: 0.2% or less, Sn: 0.2 to 1%, Zn: 0.2 to 1%, Co: 1 to 1.5%, and/or Cr: 0.05 to 0.2%.

Description

200948990 VI. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to a Cu-NbS! alloy for use in a conductive elastomeric material for electronic parts, and more particularly to a connector, a terminal, and a relay. A Cu-Ni-Si alloy that is excellent in balance of strength, bending workability, and electrical conductivity with electronic components such as switches. [Prior Art]

With the recent reduction in the size and thickness of electronic devices, terminals and connection numbers have become smaller and thinner, and strength and bending workability of Cason (Cu, Si-based) alloys, wrinkles, and shafts have been required. Copper alloy replaces the demand for solid solution-strengthened copper alloy such as phosphor bronze or brass. Among them, the balance between strength and electrical conductivity of Carson alloy is excellent, so the frequency used in electronic parts such as connectors is getting more and more. high. Generally, the strength is opposite to that of the bending processability. In the past, the case of maintaining high strength and improving the bending workability in the Carson alloy has been extensively discussed as follows, that is, by adjusting the manufacturing steps, The crystal grain size, the number and shape of the precipitates, and the aggregate structure are individually or mutually controlled to improve the bending workability. In Patent Document 1, in the Carson alloy in which Co, Zn, Mn, Cr, and A1 are further added, grain growth during dissolution is suppressed, and bending workability is improved. In Patent Document 2, it is preferable that the Carson alloy contains an appropriate amount of Ti, Zr, Hf or Th' to refine the crystal grain size, thereby improving press workability and bending workability. In Patent Document 3, the s content and the cerium content in the Carson alloy are limited to less than 〇0.5 〇, and the Sn content and the Mg content are optimized, and the Zn content is optimized according to 3 200948990, and further The crystal grain size is controlled, thereby improving the bending workability. In Patent Document 4 and Patent Document 5, the content of s in the Carson alloy is limited, and the contents of Mg, Sn, and Zn are optimized, and the crystal grain size and the aspect ratio of the crystal grains are controlled, thereby improving the bending process. Sex and stress mitigation. In the patent document, 'the control organization of the Carson alloy is controlled, and the polar density of the {123} <412> azimuth is controlled within a predetermined range, thereby improving the bending workability. In Patent Document 7, the aggregate structure of the Carson alloy is controlled to satisfy the (I( "u + I (3ΐη) /1 (> 2·〇) method to control the collective weaving, and to improve the bending workability. In Patent Document 8, the conditions of hot rolling and solution treatment in the Carson alloy are adjusted so that the yield strength test does not exhibit a yield p〇int effect, thereby improving bending processing. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2007-169781 [Draft of the Invention] Japanese Patent Laid-Open Publication No. 2007-169781 [Summary of the Invention] 璧L Ming wants to solve the problem, 200948990 With the recent fineness of electronic materials, In the evaluation of workability, in addition to the presence or absence of cracks, The size of the enemy off has become a problem. This is because the curved portion of the case as the electrical connector (eiect_ contact), if the enemy pleats is large, the contact resistance becomes unstable 'to the detriment of the reliability of electrical connection. "

However, the bending workability evaluated in the prior art is that the bending crack resistance is hardly considered to be f-curve (four), so that a Cu Ni Si-based alloy excellent in bending flaking resistance cannot be obtained. In Patent Document 3, an invention example in which the (4)' is not evaluated in the evaluation of the actual bending property, but the quantitative evaluation of the f-flicking enemy is not performed, and the wrinkle-free is not obtained. In the patent document, the f-crease evaluation is performed, but in order to obtain a Cu-Ni-Si alloy excellent in strength and bending and securing property, attention is paid to {12/丨' < 412 on the {111} positive dot map. Orientation (Patent Document 6 "〇〇16"), and adjustment of conditions for cold rolling and solution treatment before solution treatment (Patent Document 6 "(9) 19", "Patent Record 8" is also evaluated for bending However, in order to obtain excellent strength and flexural workability &lt; Cu_Nisi alloy, attention is paid to the residual

Nl_S1 (Patent Document 8 "〇〇〇9"), and the amount of Ni, the amount of Si, or the hot rolling and the solution treatment conditions are adjusted (Patent Document 8 "0019"). In order to achieve the above object, the inventors of the present invention have repeatedly studied the bending workability according to the viewpoint of controlling the grain boundary of the polycrystalline metal, which is different from the prior art, and the result is obtained by the Cu_Ni_si alloy. The frequency of occurrence of the annealing twin crystals generated during the processing heat treatment is controlled, and a Cu-Ni-Si alloy having high strength and bending properties is also obtained. 200948990 Effect of tgj The Cu-Ni-si strip of the present invention is excellent in bending workability and can be used as a copper zygoter or a connector which maintains high strength and has a good shrinkage and reduced bending wrinkles. The present invention is applicable to the end [Embodiment] Next, the present invention is made by the condition of [[Ni, Si] ... and the description thereof. In the case of Ni and Si, the fine particles of the intermetallic compound mainly composed of Ni2Si are simultaneously formed, and the conductivity is also increased. The strength of the mouth gold has increased significantly’

Ni is 1. 〇~4. 〇予番0/ *... Preferably, it is in the range of 1.5 to 3 mass%. If Ni is less than 1 〇 〇. / α,. , . ‘Therefore, the law gained sufficient strength. If it exceeds 4.0% by mass, the hot pressing delay will cause cracks.

The added concentration (% by mass) of Si is set to 1/6 to 1/4 of the added concentration (mass 〇/〇) of Ni. If the concentration of Sk added is less than 1/6 of the additive indifference of Ni, the strength will decrease. If more than 1/4 of the added concentration of Ni is not beneficial to the strength, excessive Si will cause a decrease in conductivity. [Mg, Sn, Zn, .Co, Cr]

Although Mg has an effect of improving stress relaxation properties and hot workability, when it exceeds 0.2% by mass, castability (casting surface), hot workability, and plating heat peeling resistance are deteriorated. Therefore, the concentration of Mg is specified to be 〇2% or less.

Sn and Zn have an effect of improving strength and heat resistance, and Sn has an effect of improving stress relaxation resistance, and 211 has an effect of improving solder heat resistance. The Sn is added in the range of % by mass and is added in the range of 〇 2 to ι 200948990% by mass. If it is less than the above range, the desired effect cannot be obtained, and if it is higher than the above range, the conductivity is lowered.

Co and cr have a function of forming a compound with Si and improving the strength by precipitation. Further, C 〇 has a function of preventing coarsening of crystal grains during heat treatment, and Cr has an effect of improving heat resistance. C〇 is added in the range of i to 丨5 mass%, and Cr is added in the range of 0.05 to 0.2 mass%. If it is less than the above range, the desired effect cannot be obtained, and if it is higher than the above range - the conductivity is lowered. 〇曰 [twin boundary] A metal material is usually an aggregate of crystal grains having various crystal orientations, that is, a polycrystal. In a metal material, a boundary exists due to a difference in atom arrangement methods, that is, a crystal. boundary. The grain boundary is divided into a high angle grain boundary, a low angle grain boundary (i〇w_angie grain b〇undary), and a subgrain b〇undary according to the difference in orientation between adjacent grains. The grain boundary refers to the 咼 angle grain boundary where the square Q difference between adjacent crystal grains is 15 or more. On the other hand, the grain boundaries are classified into random grain boundaries and regular grain boundaries according to the consistency between adjacent crystal grains. Due to the regular grain boundary of the annealed bimorph system 产生3 produced by the heat treatment of the Cu-Ni-Si alloy, the uniformity between the grains is high. The Σ value is an index indicating the consistency of the grain boundaries, and when the density ratio of the corresponding lattice points and the lattice points where the phase overlaps when the crystal lattices of the grain boundary are overlapped is 1/η, the relationship is η. Since the atomic consistency of the twin crystal interface is good, uneven deformation is less likely to occur near the boundary, and cracks or wrinkles near the boundary are less likely to occur at the time of bending deformation. Therefore, the bending workability can be improved by controlling the ratio of the twin interface including the total boundary of the B-B and the Shuangyang interface (except for the low-angle grain boundary and the sub-grain boundary). In the Cu_Ni_Si alloy of the present invention, the frequency (ratio) of the double-twisted interface (Σ3 boundary) in the total boundary is controlled to be i5% or more and 6% or less, preferably 30% or more. 6〇% or less, whereby the bending process 14 can be improved, and if it is 15%, the required bending workability cannot be obtained, and if it exceeds 6 〇/〇, the crystal grains at the time of grain formation become coarse, resulting in The strength is reduced. As a method for determining the ratio of the twin crystal interface, for example, an Eeectr〇n Back Scattering Pattern (EBSP) method using a Field Emission Scanning Electron Microscope (FESEM) is known. This method is based on the method of analyzing the crystal orientation based on an electron backscatter diffraction pattern (Kikuchi pattern) generated when the surface of the sample is obliquely irradiated with an electron beam. After analyzing the crystal orientation by the method, the azimuth difference between adjacent crystal orientations is determined to determine the ratio of the random grain boundary and the regular grain boundary (grain boundary characteristic distribution). Since the twin interface is equivalent to a 2:3 regular grain boundary, the ratio of the twin interface can be calculated from (the sum of the lengths of the regular grain boundaries E3) / (the sum of the lengths of the grain boundaries) χ 100. Further, the "grain boundary" means that the difference in orientation between adjacent crystal grains is a boundary of 15 Å or more, excluding a low-angle grain boundary or a subgrain boundary. The twin-crystal annealing twin crystal in the present invention is a twin crystal which is formed by recrystallization due to annealing after rolling. The frequency of twin crystal generation is related to the stacking fault energy. If the stacking energy is low, the twin crystal frequency generated during annealing will rise. If the stacking energy is higher, the frequency will decrease. On the other hand, the difference in stacking energy decreases with increasing amount of solid solution Ni. Si 200948990 (correctly increasing solid solution 81詈). Therefore, in order to increase the bimorphic interface frequency, the stacking energy can be lowered before the final recrystallization annealing (corresponding to the solution treatment in the present invention), and the amount of solid solution state and Si can be increased for this purpose.

However, in the prior method of manufacturing the Carson alloy, the solid solution of m is usually carried out at the time of the solution treatment, and in the case of the hot calender treatment at a temperature higher than the required temperature, the cost is increased. The risk of cracking during hot pressing will also increase, so it will not be carried out. &amp;, there is also a manufacturing method in which the hot press delay has a solution treatment, but even if it is subjected to hot calendering after annealing corresponding to the solution treatment, the Ni_si crystal formed at the time of casting cannot be completely dissolved. The stacking energy cannot be fully reduced. As a result, the double crystal interface frequency obtained by the prior method was about 12%. On the other hand, in the present invention, the number and particle diameter of the Ni_Si crystals are reduced by increasing the cooling rate during casting, and further, annealing at a high temperature for a long time is not caused in the hot rolling step. Under conditions, the material is cooled, whereby the amount of solid solution Ni is higher than the previous method, thereby obtaining the desired twin interface frequency. [Manufacturing Method] The Carson alloy of the present invention is produced by a general manufacturing process in which a solution treatment, a cold rolling, and an aging treatment are combined after "melting, casting, hot rolling, plane cutting". After the final cold rolling, the case of stress relief annealing or the hot pressing delay is combined with the solution treatment. Since the annealing twin crystal system is generated by recrystallization during the solution treatment, the above casting can be carried out under the following conditions in order to achieve a frequency of the twin crystal interface of 15 Å/〇 or more and 60% or less. The treatment until hot rolling is performed in the final re-deformation 9 200948990 annealing, that is, Ni and Si are sufficiently solid-solved in advance before the solution treatment. The ingot cooling rate at the time of casting is 3 〇〇 5 〇 (rc/min), and the crystallization of coarse Ni-Si particles is suppressed during the cooling of the casting. The cooling rate of the ingot exceeds 500 ° C / min. It is not practical in terms of cost. Then, 'heating temperature is 940 to 1000 ° C, preferably 950 to 980. (: annealing is performed for 3 to 6 h with heating time to solidify Ni-Si particles remaining on the cast bond. After the solution, the hot rolling is carried out. If the heating temperature is less than 940. (: or less than 3 hours, the solid solution of the remaining Ni_Si particles may be insufficient. On the other hand, after the hot pressing delay is exceeded) Annealing at high temperatures increases the risk of hot rolling cracking. Annealing in the above temperature range for more than 6 hours is an excessive annealing for the desired effect, which is not ideal in terms of cost. At the end of the material temperature is 650 ° C or more. If less than 65 〇 t:, the amount of NuSi precipitated during the hot rolling process will increase, and can not ensure a sufficient amount of solid solution state, so the double crystal interface frequency will Decrease. After the plane cutting, 'the cold rolling is performed with a processing degree of 85% or more, at 700~8 After the solution treatment at 5 ° C for 30 sec to 30 min (in this case, the final recrystallization anneal), aging treatment is carried out at 35 〇 to 550 〇 c for 2 to 3 〇h. 5% to 5% by weight is subjected to cold rolling. [Example 1] (Production of sample) The electrolytic copper is melted, and a predetermined amount of the added element is introduced into an atmospheric melting furnace to stir the melt. Thereafter, at a casting temperature of 1250 〇c, the molten metal is injected into the mold to obtain an ingot. By changing the water cooling condition of the mold, the cooling rate of the ingot during casting can be adjusted to the conditions in the table. Casting at the time of casting 200948990. After the solidification of the melt, the temperature of the ingot was reduced to $(eight) c until the average cooling rate rc/min. Then, the ingot was processed and heat-treated in the following R order to obtain a sample having a thickness of 0.25 mm. (1) The ingot is annealed and hot-rolled under the conditions in the table, and the plate thickness is processed to a predetermined thickness, and then water-cooled. (2) The surface oxide is removed by planar cutting. (3) Perform cold rolling until the plate thickness reaches 0.3 mm. ❹ (4) in the table Embodiment 1 minute melt solution treatment at a temperature of (5) to an aging treatment at 45 (condition of TCxl0h.

(6) Perform cold rolling until the aging material reaches 〇.25 melon. For the above materials, the EBSP measurement on the twin crystal interface was carried out according to the following criteria, and the tensile test and the W bending test were carried out. [Dual crystal interface] As a method of determining the ratio of the twin crystal interface, an electron backscatter pattern (EBSP) method using a field emission scanning electron microscope (Field Emission Scanning mectr〇ne Microscope' fmem) is used. . After analyzing the crystal orientation by this method, the azimuth difference between adjacent crystal orientations is determined to determine the grain boundary characteristic distribution. Let the observation magnification be 1000 times and set the total observation field to be 2 mm2. The regular grain boundary is represented by a value of 1: and the twin crystal interface is equivalent to the boundary of the illusion. The ratio (%) of the twin interface can be calculated from (the sum of the lengths of the regular grain boundaries Σ3) / (the sum of the lengths of the grain boundaries) χ 1 0 0 . In addition, the grain boundary of the gossip refers to a difference in orientation between adjacent grains of 15 . The above boundaries do not include low angle grain boundaries or subgrain boundaries. 11 200948990 [Tensile strength] Each of the copper alloy sheets was subjected to a tensile test in a direction parallel to the rolling direction. The tensile strength was determined in accordance with JIS Z2241. In the following examples, the term "south strength" means that the tensile strength is 700 MPa or more in the case of alloy A, and the tensile strength is 65 MPa or more in the case of alloy B, and in the case of alloy C. , means that the tensile strength is 6〇〇Mpa or more. [bending crack]

The bending test was parallel to the rolling direction, and a strip test piece having a width mmx length of 3 mm was selected. Perform the boundary bending test of the test piece (JIS H3130)' to set the minimum bending radius without cracking to MBR (Minimum

Bend Radius ) ' and evaluated based on the ratio MBR/t to the plate thickness t (mm). When the MBR/t in the Bad way (BW) direction is 1 or less, the crack of the bending workability is evaluated as good (〇), and the other cases are judged to be bad (χ&gt; 8 and c, when the MBR/t is 0.5 or less, it is judged that the bending workability is good. [Bending fold]

In the above-mentioned w-bending test, a scanning electron microscope (Scamnng Electron Micr〇sc〇py, SEM) image was observed on the surface of the f-curved surface of the piece of the MBR. . The width of the curved pleats was measured on the photograph to determine the width of the largest curvature wrinkles in the test piece. For each of the materials to be fed, the three test pieces were measured and the average value was taken as the width of the curved pleats. When the width of the curved groove in the B w• direction is 30 or less, the wrinkle of the bending workability is evaluated as good (〇), and if it exceeds 3” m ', it is judged to be bad (small, 12, 200948990 An example of the Ni-Si-based copper alloy a (Cu-2% Ni-〇.5% Si-0.1% Mg) of the present invention is shown in Table 1. The Ni-Si-based copper alloy B of the present invention is used. An example of (Cu-1.6% Ni-0.4% Si-0.4% Sn-〇_5% Zn) is shown in Table 2. The Ni-Si-based copper alloy of the present invention cccu-u% Ni_〇4% si) The examples are shown in Table 3. In Comparative Examples 1, 8, and 15, since the cooling rate at the time of casting is less than 300 ° C / mm, the solid solution amount of the coarse Ni Si crystals in the ingot is reduced to the mother phase and the amount of Si dissolved. The difference in energy is not sufficiently reduced, so the double crystal interface frequency is less than 15%. In Comparative Examples 2 to 4, 9 to 11 and 16 to 18, the hot rolling conditions did not satisfy 940 C or more and 3 h or more, and the end temperature was 65 Torr. . In any of the above, the Ni-Si particles are not sufficiently solid-solved, and the stacking energy is not lowered, so the twin-crystal interface frequency is less than 15 〇/〇. ▲ In Comparative Examples 5, 12 and _ φ, since the degree of cold working is 85% or less,

Therefore, recrystallization at the time of solution formation was insufficient, and the bimorphic interface frequency was less than L. In Comparative Examples 6, 13 &amp; 20, the solution temperature was 7 Å. . Below, the recrystallization is not sufficient, and the twins see this *, ^ double-day interface frequency is less than 1 5%, and the strength also decreases. In Comparative Examples 7, 14, and 21 Φ, Shan # &amp; because the solution temperature exceeded 820. (:, therefore, the double-crystal interface frequency exceeds 60%, and the 砝y α and 'α crystal grain sizes increase, so the curved wrinkle width increases. 13 200948990 [I ί Alloy A ( Cu-2% Ni-0.5% Si- 0.1% Mg ) Bending workability pleats XXXX 1 XX m 〇〇〇〇〇〇〇〇X 〇〇 Tensile strength (MPa) 1 712 1 1 722 1 [739 1 1 742 1 1 730 1 728 | 738 I 683 760 Double crystal interface frequency (%) 00 Ο 00 CO C\ CN o Solution temperature (°c) 720 730 750 750 750 750 750 750 __Z5〇__ 680 850 Cold rolling I Processing degree (%) 00 00 925 ON o I ΐ shock 〇Ο uS 10.0 Ο in Ο Ο o iri ooo ι fire, hot rolling end temperature (0 〇 650 650 700 650 650 650 650 600 650 650 650 annealing time (8) inch inch inch inch inch inch inch annealing Temperature (°C) 1 950 1 950 1 950 1 970 950 900 960 960 960 960 950 Cooling rate during casting (°C/min) 300 350 400 420 200 350 Ο in cn 350 350 I 350 I 350 (N ΓΟ inch ( Ν ro 寸 卜 invention example comparison example 200948990 ο

r-lfNd alloy B (Cu-1.6%Ni-0.4% Si-0.4% Sn-0.5% Zn) Bending process folds XXXX 1 XX Electric Weng t» 〇〇〇〇〇〇〇〇X 〇〇 « £ ^ § | 664 | |676 IL—697一I [702 I | 684 I 1678 J 1 687 | 696 as VO [640 1 CO Bu-double interface frequency (%) Bu 〇 solution temperature (0〇720 730 750 750 750 750 750 750 ο 680 ο 00 |Cold calendering | Machining degree (%) 00 00 1 92·5 1 a\ 13 13 13⁄4 1 q Ο 10.0 〇〇IT) 〇〇in Ο ^Η Ο »〇ο Annealing, hot calendering end temperature (°C) 650 1 650 700 1 650 1 650 650 | 650 I 600 1 650 1 650 650 1 Annealing time (h) Inch inch inch inch inch annealing temperature (°C) 950 950 950 970 950 900 960 960 960 〇 \ 1 When casting | Cooling rate (°C/min) 300 | 350 | 400 420 200 350 350 350 1 350 1 1 350 1 | 350 I VO 00 00 〇 〇 〇ra cn inch invention example Comparative Example 200948990 [e ί Alloy C (Cu-l.6% Ni-0.4% Si) 1 Bending workability I pleats XXXX 1 XX 〇〇〇〇〇〇 〇X 〇〇 tensile strength (MPa) S 602 1 622 I | 626 I 1 612 1 605 ro S 1 623 1 1 627 1 CN ί 637 I Double crystal interface frequency (%) 00 CN (X 5 inch 〇cn CN 1-H iH 溶 Solution temperature (°C) 720 730 __750 Ί 750 750 750 ο 750 750 680 850 | Cold rolling | Processing degree (%) 00 00 Bu 2_5 1 o Cloud rj q inch · 〇1 lo. o 1 〇〇ο in o in qo 退火 Annealing, hot rolling end temperature (°C) “650 1 650 1 700 1 650 1 | 650 I | 650 | 650 600 650 | 650 I 1 650 1 Annealing time (8) inch inch Annealing temperature (°C) 950 1 950 1 1 950 | 970 1 950 1 900 960 960 960 960 950 Cooling rate during casting (°C/nim) 300 350 400 420 200 | 350 — 1 350 350 350 350 350 〇\ 〇vr) OO On Inventive Example Comparative Example 200948990 [Example 2] (Production of Sample) The electrolytic copper was melted, and a predetermined amount of additive element 'in the atmospheric melting furnace was introduced to achieve the desired composition shown in Table 4, Stir the melt. Thereafter, the molten metal was poured into the mold at a casting temperature of 1,250 ° C, and the cooling rate was adjusted to 400 ° C / min to obtain an ingot. Next, the ingot was processed and heat-treated in the following order to obtain a sample having a thickness of 0.25 mm. (1) After the casting bond was annealed at 950C for 4 hours, hot rolling was performed so that the temperature after the end of the dust extension reached 700 °C. (2) Plane cutting the rust scale of the surface layer and machine the thickness to 5 mm. (3) Perform cold rolling until the sheet thickness reaches 0.3 mm. (4) The solution treatment was carried out at 750 ° C for 1 minute. (5) Aging treatment is carried out at 450 ° C x l 〇 h. (6) Perform cold rolling until the aging material reaches 〇 25 mm. For the above materials, EBSP measurement, tensile test, conductivity and trade bending test on the twin interface were carried out. The evaluation of the twin-crystal interface frequency and the w-bending test was carried out in the same manner as in the above-described Example 1, and the tensile strength was greatly affected by the composition, so that it was judged that the strength was 600 MPa or more. 17 200948990 [Table 4] Composition (wt%) Ni Si Mg Sn Zn Mn Co Cr Inventive Example 13 1.60 0.40 Inventive Example 14 2.50 0.45 Inventive Example 15 3.00 0.50 Inventive Example 16 3.20 0.70 Inventive Example 17 1.60 0.40 0.20 0.30 Inventive Example 18 1.60 0.40 0.50 0.40 Inventive Example 19 2.30 0.50 0.10 Inventive Example 20 2.60 0.60 0.50 0.40 Inventive Example 21 2.80 0.68 0.50 0.40 Inventive Example 22 3.00 0.50 0.15 Inventive Example 23 3.00 0.50 0.20 Inventive Example 24 2.00 0.50 1.50 0.12 Comparative Example 22 0.80 0.20 Comparative Example 23 4.20 1.00 The results are shown in Table 5. As shown in Table 5, in the inventive examples 13 to 24, the desired twin-crystal interface frequency was obtained, the bending workability was good, and the strength was also good. In Comparative Example 22, the amount of Ni was less than a predetermined amount, and the bending workability was good, but the tensile strength was lowered. In Comparative Example 23, the amount of Ni was higher than the predetermined amount, and hot rolling cracking occurred, and the sample could not be produced. 18 200948990 【二】 Bending workability 1 pleats 热 L hot rolling cracks, can not make samples through stretching Strength (MPa) 1615 I | 723 I 1 754 1 1—Η Os 646 m 1 716 | 820 | 739 I L731 I 1 526 | Double crystal interface frequency (%) 〇\ CO Ο fΗ $ Solution temperature (° C) 750 750 750 750 750 750 750 750 750 750 750 750 750 L cold rolling | Machining degree (%) 5 butyl w after the thickness Ο 〇〇Ο *〇〇Ο Ο uS 〇to 〇〇uS 〇〇〇 Annealing, hot rolling end temperature (°C) 700 700 700 700 700 Ο ο 700 ο ο 700 700 700 700 700 ^71 Annealing time (8) inch inch inch inch inch inch inch inch annealing temperature (°C) 950 950 1 950 | 1 950 1 1 950 | 950 1 950 1 950 950 950 950 1 950 1 Γ 950 1 | Casting | Cooling rate (°C/min) 400 400 400 400 400 400 400 400 400 400 400 400 400 1 Inventive Example 13 | Example 14|Inventive Example 15 | Inventive Example 16 | Inventive Example 17 | 1 Inventive Example 18 | 1 Inventive Example 19 1 invention example 2 〇 | invention example 21 | invention example 22| | invention example 23| | invention example 24| | comparison example 22| comparison example 23 200948990 [Simple description of the diagram] None [Description of main component symbols] None

20

Claims (1)

200948990 VII. Patent application scope: 1. A Cu-Ni-Si alloy containing: 1.0 to 4.0% by mass of Ni, a concentration of Si of 1/6 to 1/4 of the mass percentage relative to Ni, and The remainder is composed of Cu and unavoidable impurities. As a result of observation of the aggregate structure by EBSP measurement, the frequency of the double-day a interface (Σ3 boundary) in the total grain boundary is controlled to be 15% or more and below. ❹ 2· The Cu_Ni_Si-based alloy according to the first item of the patent application, which further contains 0.2% by mass or less of Mg. The card is 3 right as / please (4) (4) 1 item of CHSi alloy, which has 2 2 to 1% by mass, such as, and 〇. 2 to 1% by mass. An alloy which has a 0.2% by mass of Cr. The step contains 1 to 1.5% by mass of c〇, and 〇 〇5 as CU-N of the first application of the patent scope "Si VIII, schema: (none) 21