US20020189729A1 - Copper, copper alloy, and manufacturing method therefor - Google Patents
Copper, copper alloy, and manufacturing method therefor Download PDFInfo
- Publication number
- US20020189729A1 US20020189729A1 US10/105,454 US10545402A US2002189729A1 US 20020189729 A1 US20020189729 A1 US 20020189729A1 US 10545402 A US10545402 A US 10545402A US 2002189729 A1 US2002189729 A1 US 2002189729A1
- Authority
- US
- United States
- Prior art keywords
- copper
- alloy
- copper alloy
- rolling
- manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 43
- 239000010949 copper Substances 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000005097 cold rolling Methods 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 26
- 238000005096 rolling process Methods 0.000 claims abstract description 23
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 238000009864 tensile test Methods 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 31
- 239000000956 alloy Substances 0.000 claims description 31
- 238000000137 annealing Methods 0.000 claims description 23
- 238000001953 recrystallisation Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 claims description 9
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 claims description 9
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 claims description 9
- 238000005452 bending Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 230000035882 stress Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005272 metallurgy Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229910019580 Cr Zr Inorganic materials 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910005487 Ni2Si Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000008207 working material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
Definitions
- the present invention relates to copper and to copper alloys having fine crystal grains, and relates to a manufacturing method therefor, and more particularly, the resent invention relates to a technology for enhancing the characteristics in bending or other working when used for electronic devices such as terminals, connectors, and lead frames for semiconductor integrated circuits.
- the inventors have accumulated extensive research to solve these problems, and they have discovered that fine crystal grains at a level not known thus far can be obtained by controlling the conditions of the rolling process instead of the conditions of the annealing. That is, in the structure of a material cold rolled with an ordinary cold rolling reduction, when recrystallized by subsequent annealing, the decrease in dislocation density occurs discontinuously when the recrystallized grain boundaries pass a cell, and large crystal grains of uneven size are produced intermittently. This is called static recrystallization.
- the present invention is made on the basis of these findings, and provides copper and copper alloy comprising: a structure having fine crystal grains with grain size of 1 ⁇ m or less composed of crystal grain boundaries mainly formed of curved portions after a final cold rolling, the structure obtained by dynamic continuous recrystallization caused by the final cold rolling, and an elongation of 2% or more in a tensile test.
- the present invention also provides a manufacturing method for copper and copper alloy, the method comprising: a final cold rolling with a reduction (true stress) ⁇ , wherein ⁇ is expressed in the following formula and satisfying ⁇ 3, thereby obtaining a structure having fine crystal grains with grain size of 1 ⁇ m or less after the final cold rolling, and
- T 0 plate thickness before rolling
- T 1 plate thickness after rolling.
- a high ductility is essential.
- a fracture elongation in a tensile test is required to be 2% or more at a gauge length of 50 mm.
- the grain size after final cold rolling must be 1 ⁇ m or less.
- the grain size and elongation after final cold rolling vary depending on the cold rolling reduction.
- the cold rolling reduction (true stress) ⁇ by final cold rolling process until reaching the product plate thickness is expressed in the formula below.
- T 0 plate thickness before rolling
- T 1 plate thickness after rolling.
- the value of ⁇ when the value of ⁇ is small, a rolled structure remains, and clear fine crystal grains are not obtained, or if they are obtained, the grain size is large, and the grain boundary sliding does not take place, and favorable ductility is not obtained.
- the value of ⁇ should be 3 or more in order to obtain a fine grain size of 1 ⁇ m or less.
- the structure of a material cold rolled by a conventional ordinary cold rolling reduction sometimes had a cell structure due to mutual entangling of dislocations introduced in the crystal grains. In this case, however, since the misorientation among neighboring cells is small, that is, 15° or less, properties as crystal grain boundary are not realized. Accordingly, as shown in FIG. 1, when recrystallized by annealing after cold rolling, as mentioned above, static crystallization takes place, that is, large crystal grains of uneven size are formed intermittently.
- the crystal grain boundary is largely different from the case of the static recrystallization, and there is no linearity in the grain boundary, and it is a feature that a crystal grain boundary mainly composed of curved portions is formed.
- This dynamic continuous recrystallization is mostly formed in cold rolling. It is also known that a clearer high angle grain boundary is grown by annealing at intentional low temperatures and bringing it into an ordinary recovery regime. In this case, it is found that the ductility is further enhanced as described below.
- cold rolling may be performed by plural rolling machines by exchanging rolling machines depending on the range of plate thickness, or pickling or polishing may be performed in order to control the surface properties.
- the ductility is enhanced, and a further preferable bending properties are obtained.
- annealing conditions it is necessary to set adequate annealing conditions to such an extent that the product value will not be lost due to extreme decline of strength.
- the annealing condition differs with the alloy system, but by selecting an appropriate annealing condition in a temperature range of 80 to 500° C. and in a range of 5 to 60 minutes, an elongation of 6% or more may be easily obtained, and it is applicable to a severe bend forming.
- Preferred examples of copper alloy of the invention include Cu—Ni—Si alloys having precipitates of intermetallic compounds of Ni and Si such as Ni 2 Si, and the copper alloys comprise Ni: 1.0 to 4.8 mass %, Si: 0.2 to 1.4 mass %, and the balance of Cu.
- the invention also includes Cu—Cr—Zr alloys having precipitates of pure Cr grains and intermetallic compounds of Cu and Zr, and the copper alloys comprise Cr: 0.02 to 0.4 mass %, Zr: 0.1 to 0.25 mass %, and balance of Cu.
- These copper alloy may be added with subsidiary components such as one or more of Sn, Fe, Ti, P, Mn, Zn, In, Mg and Ag in a total amount of 0.005 to 2 mass %.
- copper alloys having second phase particles such as other kinds of precipitates and dispersed particles may be used.
- FIG. 1 is a schematic diagram for explaining the recrystallization process.
- FIG. 2 is a transmission electron microscope photograph showing a structure of an alloy in an example of the invention.
- FIG. 3 is a transmission electron microscope photograph showing a structure of an alloy in a comparative example of the invention.
- the aging temperature was adjusted so that the product strength would be highest in each alloy composition, or in the case of recrystallization, the temperature condition was adjusted so that the grain size would be 5 to 15 ⁇ m.
- the final cold rolling plates of 0.15 mm in thickness were manufactured and obtained as experiment samples for evaluation. The final cold rolling conditions are also shown in Tables 1 to 3.
- Test pieces were sampled from the obtained plates, and the materials were tested to evaluate “grain size”, “strength”, “elongation”, “bending”, and “electrical conductivity”.
- the “grain size” the bright fields were observed by a transmission electron microscope, and it was determined by the cut-off method of JIS H 0501 on the obtained photograph.
- “strength” and “elongation” using No. 5 specimens conforming to the tensile test specified in JIS Z 2241, the tensile strength and rupture elongation were measured.
- “bending” by bend forming using a W-bend testing machine, the bent part was observed by an optical microscope at a magnification of 50 times, and presence or absence of cracking was observed. The mark “o” indicates that cracking is absent, and the mark “x” indicates that cracking is present.
- the “electrical conductivity” was determined by measuring the electrical conductivity according to a four-point method.
- FIG. 2 is a transmission electron microscope photograph of sample No. 12 of the invention, in which the mean grain size of the formed continuous recrystallization is 1 ⁇ m or less, and its crystal grain boundary is mainly composed of curved portions and is round.
- a transmission electron microscope photograph of comparative example No. 6 is shown in FIG. 3, in which the grain size is nearly linear.
Abstract
Description
- 1. Field of the Invention
- The present invention relates to copper and to copper alloys having fine crystal grains, and relates to a manufacturing method therefor, and more particularly, the resent invention relates to a technology for enhancing the characteristics in bending or other working when used for electronic devices such as terminals, connectors, and lead frames for semiconductor integrated circuits.
- 2. Description of the Related Art
- Recently, electronic devices such as terminals and connectors and their parts are reduced in size and thickness, and copper and copper alloy used as materials thereof are demanded to have high strength. In terminal and connector material, the contact pressure must be increased in order to maintain electrical connections, and a high strength material is essential for this purpose. In a lead frame, because the semiconductor circuit is highly integrated, there is an increasing demand for multi-pin structures and thin wall thicknesses. Accordingly, to prevent deformation while conveying or handling the lead frame, the required strength level is progressively increasing.
- Moreover, along with the trend in size-reduction of electronic devices and components, a higher degree of freedom of forming performance is demanded, and workability of connector materials is becoming important, and in particular, an excellent bending properties are required. In the outer lead of the semiconductor lead frame, an excellent bending properties are also needed in the case of gull-wing form bending processes.
- In order to obtain an excellent bending properties not causing cracks in the bent part when a material is bent and deformed, it is necessary to enhance material ductility or to decrease grain size. Furthermore, for the copper alloy used for electronic device, a function for allowing the heat generated during power feed to escape to the outside is needed, aside from a function of transmitting an electric signal, and a high heat conductivity is required in addition to electrical conductivity. In particular, to cope with the recent trend of higher frequency electrical signals, the demand for higher electrical conductivity is mounting.
- Electrical conductivity of copper alloy is inversely related to strength, and when an alloying element is added to enhance the strength, the electrical conductivity is lowered, and therefore alloys which compromise strength and electrical conductivity or price have been used, depending on the application. So far, alloys for enhancing the strength and electrical conductivity have been intensively developed, and generally, copper alloys of precipitation reinforced type containing second phase particles such as Cu—Ni—Si alloy or Cu—Cr—Zr alloy have come to be used as high functional materials which is superior in balance between both.
- Thus, for mechanical characteristics of copper or copper alloys for electronic devices, high strength and excellent workability are desired. However, first of all, strength and ductility are inversely related to each other, and in each alloy system, when rolling is processed in order to increase the strength by work hardening, the ductility declines, and preferable workability is not obtained by rolling alone. On the other hand, by reducing the grain size, increase in strength as indicated by the Hall-Petch relation is expected, and it also leads to improvement of bending properties, and hence it was generally controlled to reduce the grain size during annealing and recrystallization.
- In this method, however, when the annealing temperature is lowered in order to reduce the grain size, non-crystallized grains remain in part, and there is substantially a limit to obtaining recrystallized grains of about 2 to 3 μm, and a technique for further reducing the grain sizes has been demanded. Furthermore, by recrystallization alone, the strength level is usually low, and it is not practical, and therefore a certain rolling process is needed in a later step, which has led to reduction of ductility. Accordingly, generally after rolling process, a process of stress relief annealing was needed to recover the ductility. This process, however, causes lowered strength once obtained in the rolling process, and sufficient ductility is not obtained after stress relief annealing, and it was difficult to satisfy the recent extremely severe demand for bending deformation performance.
- More recently, instead of an annealing process, methods of obtaining fine crystal grains and high ductility by working materials by strong shearing have been studied and reported, for example, by Ito et al. (ARB (Accumulative Roll-Bonding, J. of Japan Society of Metallurgy, 54 (2000), 429), and Hotta et al. (ECAP (Equal-Channel Angular Press), Metallurgy seminar text: Approach to fine crystal grains (2000), Japan Society of Metallurgy, 39). In these processing methods, however, a mass quantity sufficient to be used as materials for electronic devices cannot be manufactured, and there are not suited to industrial production.
- The inventors have accumulated extensive research to solve these problems, and they have discovered that fine crystal grains at a level not known thus far can be obtained by controlling the conditions of the rolling process instead of the conditions of the annealing. That is, in the structure of a material cold rolled with an ordinary cold rolling reduction, when recrystallized by subsequent annealing, the decrease in dislocation density occurs discontinuously when the recrystallized grain boundaries pass a cell, and large crystal grains of uneven size are produced intermittently. This is called static recrystallization. According to the research by the inventors, by extremely increasing the reduction of cold rolling, dynamic recrystallization, usually exhibited in high temperature regions, was also found to occur in cold rolling, and dynamic continuous recrystallization is exhibited as the subgrains formed during processing are transformed into high angle grain boundaries. By making use of this mechanism, round and uniform crystal grains of grain size of 1 μm or less are obtained. According to this method, fine crystal grains can be obtained without sacrificing the strength in order to prevent reduction of ductility, and it is also found that an elongation of 2% or more is obtained even immediately after final cold rolling, and an allowable bending properties are obtained by cold rolling alone. Furthermore, by adding stress relief annealing processing after final cold rolling, the elongation is further enhanced, and thus is applicable also in the case exposed to extremely severe bending. According to such a manufacturing method, moreover, materials for electronic devices can be mass produced industrially. Continuous recrystallization is explained in detail below.
- The present invention is made on the basis of these findings, and provides copper and copper alloy comprising: a structure having fine crystal grains with grain size of 1 μm or less composed of crystal grain boundaries mainly formed of curved portions after a final cold rolling, the structure obtained by dynamic continuous recrystallization caused by the final cold rolling, and an elongation of 2% or more in a tensile test.
- The present invention also provides a manufacturing method for copper and copper alloy, the method comprising: a final cold rolling with a reduction (true stress) η, wherein η is expressed in the following formula and satisfying η≧3, thereby obtaining a structure having fine crystal grains with grain size of 1 μm or less after the final cold rolling, and
- an elongation of 2% or more in a tensile test.
- η=ln(T 0 /T 1)
- T0: plate thickness before rolling, T1: plate thickness after rolling.
- The reasons for setting these numerical values are explained below together with the functions of the invention.
- A. Reduction of Final Cold Rolling, Elongation, and Grain Size
- In order to obtain a favorable bending properties in a material subjected to final cold rolling alone, a high ductility is essential. In order to obtain the favorable bending properties not causing cracking in the bent portion, a fracture elongation in a tensile test is required to be 2% or more at a gauge length of 50 mm. In order to obtain a rupture elongation of 2% or more in the state of final cold rolling, the grain size after final cold rolling must be 1 μm or less. Thus, sufficient elongation is obtained in the cold rolled state by decreasing the grain size, which is because dislocations are piled-up in the grain boundary when continuous recrystallized grains are formed, and a grain boundary structure of a non-equilibrium state is formed and a grain boundary sliding is expressed, thereby enhancing the ductility.
- The grain size and elongation after final cold rolling vary depending on the cold rolling reduction. The cold rolling reduction (true stress) η by final cold rolling process until reaching the product plate thickness is expressed in the formula below.
- η=ln(T 0 /T 1)
- T0: plate thickness before rolling, T1: plate thickness after rolling.
- In this case, when the value of η is small, a rolled structure remains, and clear fine crystal grains are not obtained, or if they are obtained, the grain size is large, and the grain boundary sliding does not take place, and favorable ductility is not obtained. According to the research by the inventors, it is known that the value of η should be 3 or more in order to obtain a fine grain size of 1 μm or less.
- The structure of a material cold rolled by a conventional ordinary cold rolling reduction sometimes had a cell structure due to mutual entangling of dislocations introduced in the crystal grains. In this case, however, since the misorientation among neighboring cells is small, that is, 15° or less, properties as crystal grain boundary are not realized. Accordingly, as shown in FIG. 1, when recrystallized by annealing after cold rolling, as mentioned above, static crystallization takes place, that is, large crystal grains of uneven size are formed intermittently.
- In contrast, by setting the extremely high cold rolling reduction, fine crystal grains are obtained. That is, at a very high cold rolling reduction, numerous regions locally shearing deformed occur in the matrix in the entire material and thus subgrain structures greatly grow. As a result, as shown in FIG. 1, dislocations are introduced in order to compensate the large misorientation between the matrix and the subgrain, and they are piled-up in the grain boundary. In this case, crystal grain boundaries having a large misprientation of 15° or more (high angle grain boundary) are generated. That is, the subgrain structure which has been initially a substructure of crystal grains is directly formed as crystal grains. In this case, the crystal grain boundary is largely different from the case of the static recrystallization, and there is no linearity in the grain boundary, and it is a feature that a crystal grain boundary mainly composed of curved portions is formed. This dynamic continuous recrystallization is mostly formed in cold rolling. It is also known that a clearer high angle grain boundary is grown by annealing at intentional low temperatures and bringing it into an ordinary recovery regime. In this case, it is found that the ductility is further enhanced as described below.
- In this mechanism, if second phase particles such as precipitates and dispersoids are present in the Cu matrix, dislocations introduced by plastic stress due to rolling are accumurated around the second phase particles by forming dislocation loops or the like, and the dislocation density is substantially increased. In this condition, the particle size of the subgrains becomes much finer, and the strength becomes higher. In the final cold rolling, unless recovered or recrystallized by annealing in an intermediate processing, cold rolling may be performed by plural rolling machines by exchanging rolling machines depending on the range of plate thickness, or pickling or polishing may be performed in order to control the surface properties.
- B. Stress Relief Annealing
- When the material after final cold rolling is further annealed for stress relief, the ductility is enhanced, and a further preferable bending properties are obtained. As annealing conditions, it is necessary to set adequate annealing conditions to such an extent that the product value will not be lost due to extreme decline of strength. The annealing condition differs with the alloy system, but by selecting an appropriate annealing condition in a temperature range of 80 to 500° C. and in a range of 5 to 60 minutes, an elongation of 6% or more may be easily obtained, and it is applicable to a severe bend forming.
- Preferred examples of copper alloy of the invention include Cu—Ni—Si alloys having precipitates of intermetallic compounds of Ni and Si such as Ni2Si, and the copper alloys comprise Ni: 1.0 to 4.8 mass %, Si: 0.2 to 1.4 mass %, and the balance of Cu. The invention also includes Cu—Cr—Zr alloys having precipitates of pure Cr grains and intermetallic compounds of Cu and Zr, and the copper alloys comprise Cr: 0.02 to 0.4 mass %, Zr: 0.1 to 0.25 mass %, and balance of Cu. These copper alloy may be added with subsidiary components such as one or more of Sn, Fe, Ti, P, Mn, Zn, In, Mg and Ag in a total amount of 0.005 to 2 mass %. Moreover, copper alloys having second phase particles such as other kinds of precipitates and dispersed particles may be used.
- FIG. 1 is a schematic diagram for explaining the recrystallization process.
- FIG. 2 is a transmission electron microscope photograph showing a structure of an alloy in an example of the invention.
- FIG. 3 is a transmission electron microscope photograph showing a structure of an alloy in a comparative example of the invention.
- (Embodiments)
- Effects of the invention are more specifically described below by referring to preferred embodiments. First, using electric copper or oxygen-free copper as material, a specified amount of the material was put in a vacuum melting furnace, together with other additive elements, if necessary, and ingots of the chemical composition shown in Tables 1 to 3 were obtained by casting at the molten metal temperature of 1250° C. Table 1 shows the compositions of Cu—Ni—Si alloys, Table 2 shows the Cu—Cr—Zr alloys, and Table 3 shows other copper alloys.
TABLE 1 Cu—Ni—Si alloy Final Rolling Condition Product Properties Chemical composition Original Plate Final Plate Tensile Rupture Cu and Thickness Thickness Cold Rolling Grain Size Strength Elongation Bending Conductivity Ni Si Impurities (mm) (mm) Reduction (μm) (MPa) (%) Properties (% IACS) Example of Invention 1 3.02 0.67 Balance 3.30 0.15 3.1 0.20 820 3.7 ◯ 48 2 2.75 0.59 Balance 3.80 0.15 3.2 0.15 810 3.8 ◯ 50 3 3.18 0.62 Balance 3.65 0.15 3.2 0.15 830 4.5 ◯ 49 4 3.30 0.70 Balance 3.40 0.15 3.1 0.20 820 3.8 ◯ 48 5 2.60 0.55 Balance 3.00 0.15 3.0 0.40 800 2.3 ◯ 51 Comparative Example 6 3.21 0.59 Balance 1.85 0.15 2.5 2.00 800 1.2 X 48 7 2.80 0.58 Balance 1.10 0.15 2.0 Rolled Structure 790 0.8 X 50 8 3.15 0.64 Balance 2.50 0.15 2.8 1.35 800 1.8 X 47 -
TABLE 2 Cu—Cr—Zr alloy Final Rolling Condition Product Properties Chemical Composition Original Plate Final Plate Cold Tensile Rupture Cu and Thickness Thickness Rolling Grain Size Strength Elongation Bending Conductivity Cr Zr Zn Impurities (mm) (mm) Reduction (μm) (MPa) (%) Properties (% IACS) Example of Invention 9 0.21 0.08 — Balance 3.25 0.15 3.1 0.30 610 3.5 ◯ 80 10 0.18 0.10 — Balance 3.50 0.15 3.1 0.30 600 3.9 ◯ 82 11 0.23 0.14 — Balance 3.80 0.15 3.2 0.25 620 4.8 ◯ 79 12 0.18 0.07 0.22 Balance 3.75 0.15 3.2 0.25 610 5.0 ◯ 78 13 0.24 0.11 0.18 Balance 3.10 0.15 3.0 0.35 620 2.8 ◯ 77 Comparative Example 14 0.20 0.11 — Balance 1.15 0.15 2.0 Rolled 590 0.8 X 80 Structure 15 0.18 0.08 — Balance 2.60 0.15 2.9 1.20 600 1.7 X 81 16 0.23 0.09 0.19 Balance 1.50 0.15 2.3 1.40 590 1.3 X 78 -
TABLE 3 Manufacturing conditions of other alloys of the invention and comparative examples Final Rolling Condition Original Cold Chemical Composition (w %) Plate Final Plate Rolling Cu and Thickness Thickness Reduc- Sn Cr Zr Ni Si Fe Ti P Mn Zn In Mg Ag Impurities (mm) (mm) tion Example of Invention 17 — — — — — — — — — — — — — Tough 3.80 0.15 3.2 Pitch Copper 18 — — — — — — — — — — — — — Oxygen- 3.40 0.15 3.1 free Copper 19 — — — — — — — — — — — — 0.03 Balance 3.50 0.15 3.1 20 5.12 — — — — — — 0.02 — — — — — Balance 3.10 0.15 3.0 21 — 0.18 — — — — — — — — — — — Balance 3.25 0.15 3.1 22 0.22 0.28 — — — — — — — 0.19 — — — Balance 3.75 0.15 3.2 23 — — 0.08 — — — — — — — — — — Balance 3.65 0.15 3.2 24 — 0.18 0.11 — — 0.61 0.37 — — — — — — Balance 3.00 0.15 3.0 25 — 0.22 0.13 — — — — — — — 0.04 — — Balance 3.10 0.15 3.0 26 — 0.26 0.11 — 0.02 — — — — — — 0.04 — Balance 3.75 0.15 3.2 27 — — — 2.61 0.51 — — — — 0.29 — — — Balance 3.70 0.15 3.2 28 0.51 — — 2.11 0.48 — — — — 0.48 — — — Balance 3.65 0.15 3.2 29 — — — — — 1.81 — 0.15 — — — 0.02 — Balance 3.30 0.15 3.1 30 — — — — — 2.43 — 0.03 — 0.12 — — — Balance 3.75 0.15 3.2 31 — — — — 0.04 3.01 — 0.26 0.03 — — — — Balance 3.80 0.15 3.2 32 — — — — — — 2.95 — — — — — — Balance 3.50 0.15 3.1 Com- parative Example 33 — 0.18 0.09 — — — — — — 0.12 — — — Balance 1.10 0.15 2.0 34 — — — 3.12 0.67 — — — — 0.14 — — — Balance 2.50 0.15 2.8 - These ingots were hot rolled at a temperature of 950° C. into plates of 10 mm in thickness. The oxide layer of the surface layer was removed by mechanical scalping, and the plates were cold rolled to a thickness of 5 mm, and a solid solution treatment was applied in the case of age precipitation type copper alloy, and recrystallization annealing was applied once in the others. By further cold rolling, plates of an intermediate thickness of 1.1 to 3.8 mm were obtained, and at this plate thickness, further, aging treatment or second recrystallization annealing was performed. In the case of aging treatment, the aging temperature was adjusted so that the product strength would be highest in each alloy composition, or in the case of recrystallization, the temperature condition was adjusted so that the grain size would be 5 to 15 μm. By the final cold rolling, plates of 0.15 mm in thickness were manufactured and obtained as experiment samples for evaluation. The final cold rolling conditions are also shown in Tables 1 to 3.
- Test pieces were sampled from the obtained plates, and the materials were tested to evaluate “grain size”, “strength”, “elongation”, “bending”, and “electrical conductivity”. To evaluate the “grain size”, the bright fields were observed by a transmission electron microscope, and it was determined by the cut-off method of JIS H 0501 on the obtained photograph. As for “strength” and “elongation”, using No. 5 specimens conforming to the tensile test specified in JIS Z 2241, the tensile strength and rupture elongation were measured. As for “bending”, by bend forming using a W-bend testing machine, the bent part was observed by an optical microscope at a magnification of 50 times, and presence or absence of cracking was observed. The mark “o” indicates that cracking is absent, and the mark “x” indicates that cracking is present. The “electrical conductivity” was determined by measuring the electrical conductivity according to a four-point method.
- Evaluation results are shown in Tables 1, 2, and 4. The alloys of the invention are known to have excellent strength, elongation and bending properties. By contrast, in comparative examples 6 to 8, 14 to 16, 33, and 34, since the reduction of final rolling was low, the desired structure was not obtained, the ductility dropped, and favorable bending properties were not achieved. FIG. 2 is a transmission electron microscope photograph of sample No. 12 of the invention, in which the mean grain size of the formed continuous recrystallization is 1 μm or less, and its crystal grain boundary is mainly composed of curved portions and is round. By way of comparison, a transmission electron microscope photograph of comparative example No. 6 is shown in FIG. 3, in which the grain size is nearly linear.
- The materials manufactured in embodiments 9, 22, 26, and 30 of the invention and comparative examples 33, and 34 were further annealed for stress relief, and tensile tests were conducted. Results are shown in Table 5. In the alloys of the invention, by stress relief annealing, elongation is further enhanced as compared with that of the alloys of the comparative examples. Hence, it is expected to be able to withstand further more severe working.
TABLE 4 Characteristic evaluation results of alloys of the invention and comparative examples Tensile Rupture Grain size strength elongation Bending Conductivity (μm) (MPa) (%) Properties (% IACS) Example of Invention 17 0.40 420 2.5 ◯ 100 18 0.45 410 2.7 ◯ 100 19 0.30 420 2.8 ◯ 98 20 0.25 630 2.1 ◯ 15 21 0.45 590 2.9 ◯ 78 22 0.35 610 2.2 ◯ 74 23 0.25 550 3.6 ◯ 87 24 0.15 670 2.3 ◯ 69 25 0.30 580 3.8 ◯ 80 26 0.30 590 3.9 ◯ 52 27 0.15 790 3.6 ◯ 50 28 0.20 780 2.6 ◯ 52 29 0.35 570 2.9 ◯ 60 30 0.20 540 2.5 ◯ 63 31 0.35 590 2.8 ◯ 56 32 0.40 1020 2.4 ◯ 11 Comparative Example 33 Rolled 590 1.2 X 80 Structure 34 1.35 800 0.9 X 50 -
TABLE 5 Characteristic evaluation results after stress relief annealing Stress Relief Annealing Conditions Tensile Rupture Temperature Time Strength Elongation Conductivity Alloy name (° C.) (min) (MPa) (%) (% IACS) Example of Invention 9 400 15 570 8.2 82 22 400 15 590 8.9 75 26 450 15 740 9.5 52 30 400 15 520 7.5 65 Comparative Example 33 400 15 570 5.1 81 34 450 15 740 4.5 50
Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/134,043 US20080277032A1 (en) | 2001-03-27 | 2008-06-05 | Copper, copper alloy, and manufacturing method therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001091179 | 2001-03-27 | ||
JP2001-91179 | 2001-03-27 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/134,043 Continuation US20080277032A1 (en) | 2001-03-27 | 2008-06-05 | Copper, copper alloy, and manufacturing method therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
US20020189729A1 true US20020189729A1 (en) | 2002-12-19 |
Family
ID=18945850
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/105,454 Abandoned US20020189729A1 (en) | 2001-03-27 | 2002-03-26 | Copper, copper alloy, and manufacturing method therefor |
US12/134,043 Abandoned US20080277032A1 (en) | 2001-03-27 | 2008-06-05 | Copper, copper alloy, and manufacturing method therefor |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/134,043 Abandoned US20080277032A1 (en) | 2001-03-27 | 2008-06-05 | Copper, copper alloy, and manufacturing method therefor |
Country Status (5)
Country | Link |
---|---|
US (2) | US20020189729A1 (en) |
EP (1) | EP1245690B1 (en) |
KR (1) | KR100513943B1 (en) |
CN (1) | CN1223690C (en) |
DE (1) | DE60215240T2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104087768A (en) * | 2014-06-25 | 2014-10-08 | 盐城市鑫洋电热材料有限公司 | Method for improving performance of nickel-chromium-iron electrothermal alloy |
CN105291891A (en) * | 2015-11-25 | 2016-02-03 | 北京力鑫科技有限公司 | Production method of reinforced dropper and electrified railway contact network |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4087307B2 (en) * | 2003-07-09 | 2008-05-21 | 日鉱金属株式会社 | High strength and high conductivity copper alloy with excellent ductility |
JP4809602B2 (en) * | 2004-05-27 | 2011-11-09 | 古河電気工業株式会社 | Copper alloy |
JP5306591B2 (en) * | 2005-12-07 | 2013-10-02 | 古河電気工業株式会社 | Wire conductor for wiring, wire for wiring, and manufacturing method thereof |
JP5355865B2 (en) * | 2006-06-01 | 2013-11-27 | 古河電気工業株式会社 | Copper alloy wire manufacturing method and copper alloy wire |
US8876990B2 (en) * | 2009-08-20 | 2014-11-04 | Massachusetts Institute Of Technology | Thermo-mechanical process to enhance the quality of grain boundary networks |
JP6617313B2 (en) * | 2017-08-03 | 2019-12-11 | Jx金属株式会社 | Copper foil for flexible printed circuit board, copper-clad laminate using the same, flexible printed circuit board, and electronic device |
CN109338314A (en) * | 2018-12-04 | 2019-02-15 | 有研亿金新材料有限公司 | A kind of processing method of Ultra-fine grain copper manganese alloy target |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6251199B1 (en) * | 1999-05-04 | 2001-06-26 | Olin Corporation | Copper alloy having improved resistance to cracking due to localized stress |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08960B2 (en) * | 1989-03-15 | 1996-01-10 | 日本碍子株式会社 | Beryllium copper alloy hot forming method and hot forming product |
JPH09256084A (en) * | 1996-03-19 | 1997-09-30 | Hitachi Cable Ltd | Bending resistant copper alloy wire |
JP3510469B2 (en) * | 1998-01-30 | 2004-03-29 | 古河電気工業株式会社 | Copper alloy for conductive spring and method for producing the same |
JP2000038628A (en) * | 1998-07-22 | 2000-02-08 | Furukawa Electric Co Ltd:The | Copper alloy for semiconductor lead frame |
JP3856582B2 (en) * | 1998-11-17 | 2006-12-13 | 日鉱金属株式会社 | Rolled copper foil for flexible printed circuit board and method for producing the same |
JP2000256766A (en) * | 1999-03-05 | 2000-09-19 | Sanyo Special Steel Co Ltd | HOT WORKING METHOD FOR CuNiFe ALLOY |
JP4345075B2 (en) * | 1999-03-26 | 2009-10-14 | Dowaホールディングス株式会社 | Copper and copper-based alloy excellent in wire bonding property and die bonding property and manufacturing method thereof |
-
2002
- 2002-03-25 KR KR10-2002-0016015A patent/KR100513943B1/en not_active IP Right Cessation
- 2002-03-26 DE DE60215240T patent/DE60215240T2/en not_active Expired - Lifetime
- 2002-03-26 EP EP02006886A patent/EP1245690B1/en not_active Expired - Lifetime
- 2002-03-26 US US10/105,454 patent/US20020189729A1/en not_active Abandoned
- 2002-03-27 CN CNB021192707A patent/CN1223690C/en not_active Expired - Fee Related
-
2008
- 2008-06-05 US US12/134,043 patent/US20080277032A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6251199B1 (en) * | 1999-05-04 | 2001-06-26 | Olin Corporation | Copper alloy having improved resistance to cracking due to localized stress |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104087768A (en) * | 2014-06-25 | 2014-10-08 | 盐城市鑫洋电热材料有限公司 | Method for improving performance of nickel-chromium-iron electrothermal alloy |
CN105291891A (en) * | 2015-11-25 | 2016-02-03 | 北京力鑫科技有限公司 | Production method of reinforced dropper and electrified railway contact network |
Also Published As
Publication number | Publication date |
---|---|
CN1223690C (en) | 2005-10-19 |
EP1245690A1 (en) | 2002-10-02 |
KR20020076139A (en) | 2002-10-09 |
CN1386873A (en) | 2002-12-25 |
DE60215240D1 (en) | 2006-11-23 |
US20080277032A1 (en) | 2008-11-13 |
KR100513943B1 (en) | 2005-09-09 |
EP1245690B1 (en) | 2006-10-11 |
DE60215240T2 (en) | 2007-05-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20080277032A1 (en) | Copper, copper alloy, and manufacturing method therefor | |
JP5312920B2 (en) | Copper alloy plate or strip for electronic materials | |
JP4255330B2 (en) | Cu-Ni-Si alloy member with excellent fatigue characteristics | |
KR101331339B1 (en) | Cu-ni-si-co based copper ally for electronic materials and manufacturing method therefor | |
KR100515804B1 (en) | Titanium copper alloy having high strength and method for producing the same, and terminal?connector using the titanium copper alloy | |
JP4494258B2 (en) | Copper alloy and manufacturing method thereof | |
KR101114116B1 (en) | Copper Alloy Material for Electric and Electronic Apparatuses, and Electric and Electronic Components | |
KR101917416B1 (en) | Copper-cobalt-silicon alloy for electrode material | |
KR102005332B1 (en) | Method for manufacturing Cu-Co-Si-Fe-P alloy having Excellent Bending Formability | |
KR20130109209A (en) | Cu-si-co-base copper alloy for electronic materials and method for producing same | |
JP3408021B2 (en) | Copper alloy for electronic and electric parts and method for producing the same | |
JP3717321B2 (en) | Copper alloy for semiconductor lead frames | |
KR20160003555A (en) | Copper alloy material, method for producing copper alloy material, lead frames and connectors | |
JP4225733B2 (en) | Terminal, connector, lead frame material plate | |
KR102421870B1 (en) | Cu-Ni-Si-Mn-Sn based Copper alloy material with excellent strength, electrical conductivity and bendability, and method for preparing the same | |
KR101875806B1 (en) | Method for manufacturing copper-titanium-based copper alloy material for automobile and electronic parts and copper alloy material therefrom | |
JPH10287939A (en) | Copper alloy for electric and electronic equipment, excellent in punchability | |
JP4175920B2 (en) | High strength copper alloy | |
JPH10265873A (en) | Copper alloy for electrical/electronic parts and its production | |
JP2002194461A (en) | Copper alloy for lead frame and its production method | |
JP3941308B2 (en) | Copper alloy with excellent hot workability | |
JP6246454B2 (en) | Cu-Ni-Si alloy and method for producing the same | |
JP7311651B1 (en) | Copper alloys for electronic materials and electronic parts | |
JP2016211078A (en) | Cu-Ni-Si-BASED ALLOY AND MANUFACTURING METHOD THEREFOR | |
JP4679040B2 (en) | Copper alloy for electronic materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: NIPPON MINING & METALS CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TOMIOKA, YASUO;MIYAKE, JUNJI;REEL/FRAME:012738/0932 Effective date: 20020225 |
|
AS | Assignment |
Owner name: NIKKO METAL MANUFACTURING CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NIPPON MINING & METALS CO., LTD.;REEL/FRAME:014636/0211 Effective date: 20040427 |
|
AS | Assignment |
Owner name: NIPPON MINING & METALS CO., LTD., JAPAN Free format text: MERGER AND CHANGE OF NAME;ASSIGNOR:NIKKO METAL MANUFACTURING CO., LTD.;REEL/FRAME:017710/0231 Effective date: 20060403 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |