EP3643799A1 - Titanium copper, method for producing titanium copper and electronic component - Google Patents
Titanium copper, method for producing titanium copper and electronic component Download PDFInfo
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- EP3643799A1 EP3643799A1 EP19202704.3A EP19202704A EP3643799A1 EP 3643799 A1 EP3643799 A1 EP 3643799A1 EP 19202704 A EP19202704 A EP 19202704A EP 3643799 A1 EP3643799 A1 EP 3643799A1
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- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 82
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 238000001887 electron backscatter diffraction Methods 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 19
- 238000004458 analytical method Methods 0.000 claims abstract description 17
- 238000005259 measurement Methods 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 17
- 238000005097 cold rolling Methods 0.000 claims description 16
- 238000005098 hot rolling Methods 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000009864 tensile test Methods 0.000 claims description 2
- 230000035882 stress Effects 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 24
- 229910000881 Cu alloy Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 11
- 238000000137 annealing Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910017945 Cu—Ti Inorganic materials 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 208000037805 labour Diseases 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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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
-
- 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
Definitions
- a compressive strain per pass is from 0.15 to 0.30, and a maximum strain rate at 700 to 900 °C is from 2.0 to 6.0/s, and in a preferred embodiment, from 3.0 to 5.0/s. This can allow the GOS and Schmidt factor to be controlled to the above ranges.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
- Metal Rolling (AREA)
Abstract
Description
- The present invention relates to titanium copper, a method for producing titanium copper, and an electronic component. For example, the present invention relates to titanium copper, a method for producing the titanium copper and an electronic component using the titanium copper, which are suitable for use in electronic components such as connectors, battery terminals, jacks, relays, switches, autofocus camera modules, and lead frames.
- Recently, progressing miniaturization of electronic components such as lead frames and connectors used in electric/electronic devices and on-board components is bringing about remarkable tendencies to narrow a pitch and reduce a height of a copper alloy member forming an electronic component. A smaller connector has a narrower pin width, resulting in a smaller folded shape, so that the copper alloy member to be used is required to have high strength in order to obtain required spring properties. In this respect, a copper alloy containing titanium (hereinafter referred to as "titanium copper") has a relatively high strength and the best stress relaxation resistance among copper alloys. Therefore, the titanium copper has been traditionally used as a signal system terminal member.
- The titanium copper is an age-hardening copper alloy, which has a good balance between strength and bending workability, and additionally exhibits particularly improved characteristics among various copper alloys in terms of stress relaxation resistance. Therefore, developments have been made to improve properties such as strength and bending workability while maintaining the stress relaxation resistance of the titanium copper.
- Japanese Patent Application Publication No.
2014-185370 A - Japanese Patent Application Publication No.
2010-126777 A - Japanese Patent Application Publication No.
2008-308734 A - Japanese Patent Application Publication No.
H07-258803 A -
- Patent Document 1: Japanese Patent Application Publication No.
2014-185370 A - Patent Document 2: Japanese Patent Application Publication No.
2010-126777 A - Patent Document 3: Japanese Patent Application Publication No.
2008-308734 A - Patent Document 4: Japanese Patent Application Publication No.
H07-258803 A - Recently, electronic devices are required to have higher reliability in addition to higher functionality, and electronic components used for the electronic devices are also required to have higher reliability. In particular, heat resistance is one of important indices, which requires a higher level than the prior art. Titanium copper is known to have relatively better stress relaxation resistance. However, the titanium copper alloys disclosed in Patent Documents 1 to 4 still cannot provide sufficient stress relaxation resistance, and so there is a need for further improvement of stress relaxation resistance.
- In view of the above problems, the present disclosure provides titanium copper having improved stress relaxation resistance, a method for producing the titanium copper, and an electronic component using the titanium copper.
- As a result of intensive studies to solve the above problems, the present inventor has found that a titanium copper in which a grain orientation spread (GOS) in crystal grains calculated in an EBSD measurement on a rolled surface, its area ratio, and an area ratio of crystal grains with a certain value of Schmidt factor are within predetermined ranges, respectively, has improved stress relaxation resistance.
- In one aspect, a titanium copper according to an embodiment of the present invention contains from 2.0 to 4.5% by mass of Ti, and a total amount of from 0 to 0.5% by mass of at least one selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si as a third element, the balance being copper and inevitable impurities, wherein an area ratio of crystal grains with a GOS (Grain Orientation Spread) of from 2 to 6° when an orientation difference of 5° or more is regarded as a crystal grain boundary in crystal orientation analysis in an EBSD measurement on a rolled surface is from 60 to 90%, and an area ratio of crystal grains with a Schmidt factor of 0.35 or less is from 5 to 20%.
- In one aspect, a method for producing titanium copper according to an embodiment of the present invention comprises casting a titanium copper ingot containing from 2.0 to 4.5% by mass of Ti, and a total amount of from 0 to 0.5% by mass of at least one selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si as a third element, the balance being copper and inevitable impurities, and subjecting the cast ingot to hot rolling; and then carrying out a cold rolling step and a subsequent final solutionizing treatment step, wherein the hot rolling step comprises treating the ingot such that a compressive strain per pass is from 0.15 to 0.30 and a maximum strain rate at 700 to 900 °C is from 2.0 to 6.0/s, and wherein the final solutionizing treatment step comprises carrying out a treatment at a heating temperature (°C) of from 52 × X + 610 to 52 × X + 680 in which X is an addition amount (% by mass) of Ti, for a residence time of from 5 to 60 seconds.
- According to the present invention, it is possible to provide titanium copper having improved stress relaxation resistance, a method for producing the titanium copper, and an electronic component using the titanium copper.
-
-
FIG. 1 is a view for explaining a measurement principle of a stress relaxation rate. -
FIG. 2 is a view for explaining a measurement principle of a stress relaxation rate. - Titanium copper according to an embodiment of the present invention has a Ti concentration of from 2.0 to 4.5% by mass. The titanium copper has increased strength and increased electrical conductivity by dissolution of Ti in a Cu matrix with a solutionizing treatment and by dispersion of fine precipitates in the alloy with an aging treatment.
- If the Ti concentration is less than 2.0% by mass, deposition of precipitates is not sufficient and any desired strength cannot be obtained. If the Ti concentration is more than 4.5% by mass, workability is deteriorated and the material is easily cracked during rolling. In terms of a balance between strength and workability, a preferable Ti concentration is from 2.5 to 3.5% by mass.
- The titanium copper according to an embodiment of the present invention contains at least one of third elements selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si, whereby the strength can be further improved. However, if the total concentration of the third elements is more than 0.5% by mass, the workability is deteriorated and the material is easily cracked during rolling. Therefore, these third elements can be contained in a total amount of from 0 to 0.5% by mass, and in view of the balance between strength and workability, the titanium copper preferably contains one or more of the above elements in a total amount of from 0.1 to 0.4% by mass. For each additive element, the titanium copper contains from 0.01 to 0.15% by mass of each of Zr, P, B, V, Mg, and Si, and from 0.01 to 0. 3% by mass of each of Fe, Co, Ni, Cr, Mo, Nb and Mn, and from 0.1 to 0.5% by mass of Zn.
- The titanium copper according to an embodiment of the present invention is characterized in that a grain orientation spread (GOS) quantifying an average orientation difference in crystal grains is controlled within a certain range. More particularly, an area ratio of crystal grains with a GOS of 2 to 6° is from 60 to 90%. The GOS within the above range means that there is fine precipitation in the crystal grains, thereby enabling the stress relaxation resistance to be improved.
- If the area ratio of the crystal grains with a GOS of from 2 to 6° is less than 60%, fine precipitates are insufficient and the stress relaxation resistance is not improved. On the other hand, if the area ratio of the crystal grains with a GOS of from 2 to 6° is higher than 90%, coarse precipitation increases so that the stress relaxation resistance is not improved. The area ratio of crystal grains with a GOS of from 2 to 6° is preferably from 65 to 85%, and more preferably 70 to 80%.
- As used herein, the "GOS" refers to an average value of orientation differences between all pixels within each crystal grain when an orientation difference of 5° or more is regarded as a crystal grain boundary, in crystal orientation analysis in EBSD (Electron Back Scatter Diffraction) measurement on a rolled surface, using an analysis software (for example, OIM Analysis available from TSL Solutions, Inc.) attached to the EBSD. The "GOS" is determined by calculating the average value of the orientation differences between pixels within the crystal grains and all the remaining pixels, and performing this procedure for all crystal grains.
- In this embodiment, the following conditions are adopted for EBSD measurement:
- (a) SEM conditions
- Beam Conditions: an acceleration voltage of 15 kV and an irradiation current of 5 × 10-8 A;
- Work Distance: 25mm;
- Observation Field: 150 µm × 150 µm;
- Observation Surface: rolled surface;
- Pre-treatment of Observation Surface: The structure is allowed to appear by electropolishing in a solution of 67% phosphoric acid + 10% sulfuric acid + water under conditions of 15V for 60 seconds.
- (b) EBSD conditions
- Measurement Program: OIM Data Collection;
- Data analysis Program: OIM Analysis (Ver. 5.3); and
- Step Width: 0.25 µm.
- In the titanium copper according to the present invention, the area ratio of the crystal grains with a Schmidt factor of 0.35 or less is controlled to 5 to 20%. When the area ratio of the crystal grains with a Schmidt factor of 0.35 or less is 5 to 20%, the stress relaxation resistance of the titanium copper according to the present invention can be improved, in combination with the area ratio of the crystal grains with a GOS of from 2 to 6°.
- A shear stress τ required when slip deformation occurs in the material can be expressed as τ = σ cos ϕ cos λ. Here, σ is a tensile stress, ϕ is an angle formed by a tensile axis and a normal line of a sliding surface, λ is an angle formed by the tensile axis and the sliding direction, and the portion of cos ϕ cos λ is a Schmidt factor. The Schmidt factor takes a value from 0 to 0.5 and represents ease of deformation. That is, the Schmidt factor means that if it is lower it is difficult to deform, and if it is higher it is easy to deform. If the area ratio of the crystal grains with a Schmidt factor of 0.35 or less is more than 20%, the resistance is increased when stress is applied and the strain tends to accumulate. As a result, the stress relaxation resistance is not improved. Although the stress relaxation resistance is improved as the area ratio of the crystal grains with Schmid factor of 0.35 or less is lower, it is practically difficult to control the area ratio of the crystal grains with a Schmid factor of 0.35 or less to less than 5% in a completely recrystallized state. From this viewpoint, the area ratio of the crystal grains with a Schmidt factor of 0.35 or less is preferably from 6 to 18%, and more preferably 7 to 16%.
- In the present embodiment, the "Schmidt factor" refers to a result calculated for individual crystal grains when an orientation difference of 5° or more is regarded as a crystal grain boundary, in crystal orientation analysis in EBSD (Electron Back Scatter Diffraction) measurement on a rolled surface, using an analysis software (for example, OIM Analysis available from TSL Solutions, Inc.) attached to the EBSD. The following conditions are adopted for EBSD measurement:
- (a) SEM conditions
- Beam Conditions: an acceleration voltage of 15 kV and an irradiation current of 5 × 10-8 A;
- Work Distance: 25mm;
- Observation Field: 150 µm × 150 µm;
- Observation Surface: rolled surface;
- Pre-treatment of Observation Surface: The structure is allowed to appear by electropolishing in a solution of 67% phosphoric acid + 10% sulfuric acid + water under conditions of 15V for 60 seconds.
- The titanium copper according to an embodiment of the present invention can have improved stress relaxation resistance. In one Embodiment, it has a feature that a stress relaxation rate is 10% or less after maintaining the titanium copper at 300 °C for 10 hours.
- In one embodiment of the titanium copper according to the present invention, it is preferable to control an average crystal grain size on the rolled surface to a range of from 2 to 30 µm, more preferably to a range of from 2 to 15 µm, and even more preferably a range of from 2 to 10 µm, from the viewpoint of improving the strength, bending workability and fatigue characteristics with a good balance.
- The average crystal grain size refers to an average crystal grain size in a case where an orientation difference of 5° or more is regarded as a crystal grain boundary by a crystal orientation analysis in EBSD (Electron Back Scattering Diffraction) measurement on the rolled surface using an analysis software (e.g.,, OIM Analysis available from TSL Solutions) attached to the EBSD, as with the average crystal grain size used for calculating the coefficient of variation of the crystal grain size as described above.
- In one embodiment, the titanium copper according to the embodiment of the present invention can achieve a 0.2% yield strength of 800 MPa or more in a direction parallel to the rolling direction. The 0.2% yield strength of the titanium copper according to the present invention is 850 MPa or more in a preferred embodiment, 900 MPa or more in a more preferred embodiment, and 950 MPa or more in an even more preferred embodiment.
- The upper limit value of the 0.2% yield strength is not particularly limited from the viewpoint of the intended strength of the present invention. However, in terms of labors and costs, the upper limit is typically 1200 MPa or less, and more typically 1100 MPa or less.
- In the present invention, the 0.2% yield strength of titanium copper in the direction parallel to the rolling direction is measured in accordance with JIS-Z2241 (2011) (Metal Material Tensile Test Method).
- In one embodiment, the titanium copper according to the present invention can have a thickness of 1.0 mm or less, and in a typical embodiment, it can have a thickness of from 0.02 to 0.8 mm, and in a more typical embodiment, it can have a thickness of from 0.05 to 0.5 mm.
- The titanium copper according to the present invention can be processed into various copper products, such as plates, strips, tubes, bars and wires. The titanium copper according to the present invention can preferably be used as a conductive material or a spring material in electronic parts including, but not limited to, switches, connectors, autofocus camera modules, jacks, terminals (particularly battery terminals), and relays. These electronic components can be used, for example, as on-board components or components for electric/electronic devices.
- Hereinafter, the method for producing the titanium copper according to an embodiment of the present invention includes casting an titanium copper ingot containing from 2.0 to 4.5% by mass of Ti, a total amount of from 0 to 0.5% by mass of at least one selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si as a third element, the balance being copper and inevitable impurities, and subjecting the cast ingot to hot rolling, and then carrying out a cold rolling step and a subsequent final solutionizing treatment step. Hereinafter, a suitable production example of the titanium copper according to this embodiment is sequentially described for each step.
- Production of the ingot by melting and casting is basically carried out in a vacuum or in an inert gas atmosphere. If the additive element remains un-melted during melting, it does not effectively act on improvement of strength. Therefore, in order to eliminate un-melted residue, a high melting point third element such as Fe and Cr should be sufficiently agitated after being added, and then maintained for a certain period of time. On the other hand, since Ti is relatively easily dissolved in Cu, it may be added after the third element is melted. Therefore, to Cu is added at least one selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si so as to contain them in a total amount of from 0 to 0. 5% by mass and then added Ti so as to contain it in an amount of from 2.0 to 4.5% by mass to produce the ingot.
- Since solidifying segregation and crystallized matters produced during the production of the ingot are coarse, it is desirable to dissolve them in the parent phase as much as possible to decrease them, and eliminate them as much as possible, by homogenized annealing. This is because it is effective in preventing cracks due to bending. More particularly, after the ingot production step, homogenized annealing is preferably carried out by heating at 900 to 970 °C for 3 to 24 hours, and the hot rolling is then preferably carried out. In order to prevent liquid metal embrittlement, it is preferable that a temperature before and during the hot rolling is preferably 960 °C or less, and that a temperature is preferably 800 °C or more for a pass from an original thickness to an entire working ratio of 80%.
- In the present embodiment, a compressive strain per pass is from 0.15 to 0.30, and a maximum strain rate at 700 to 900 °C is from 2.0 to 6.0/s, and in a preferred embodiment, from 3.0 to 5.0/s. This can allow the GOS and Schmidt factor to be controlled to the above ranges. The compressive strain per pass can be calculated by dividing a compressive strain η = In {(cross-sectional area before hot rolling) / (cross-sectional area after hot rolling)} by the total number of passes in hot rolling. Further, the strain rate ε (/s) is calculated from the following equation (1):
[Equation 1] - After the hot rolling, cold rolling is carried out. The working ratio of the cold rolling is typically 60% or more. The working ratio per pass can be obtained according to the following Equation (2), where T0 is a thickness of the ingot before rolling by the pass and T is a thickness of the ingot at the end of rolling by the pass:
- Annealing can be then carried out. The annealing is typically carried out at 900 °C for 1 to 5 minutes. The cold rolling and annealing can be repeated as needed.
- A first solutionizing treatment is preferably carried out after repeating the cold rolling and annealing as needed. Here, the reason why the solutionizing treatment is carried out in advance is to reduce burdens in a final solutionizing treatment. That is, in the final solutionizing treatment, it is not a heat treatment for dissolving second phase grains and solutionizing is already achieved, so it is sufficient to cause recrystallization while maintaining that state and thus to be a light heat treatment. More particularly, the first solutionizing treatment may be carried out at a heating temperature of from 850 to 900 °C for 2 to 10 minutes. In this case, it is preferable to increase the heating rate and the cooling rate as much as possible so that the second phase grains do not precipitate. It should be noted that the first solutionizing treatment may not be carried out.
- Intermediate rolling is then carried out. The working ratio of the intermediate rolling is typically 60% or more.
- In the final solution treatment, it is desirable to dissolve precipitates completely. However, if heating is carried out at an elevated temperature until the precipitates are completely eliminated, the crystal grains tends to coarsen. Therefore, the heating temperature is near a solid solution limit of the second phase grain composition. More particularly, the heating temperature (°C) is in a range of from 52 × X + 610 to 52 × X + 680 where X is an addition amount (% by mass) of Ti.
- In a case where the heating temperature is lower than 52 × X + 610 °C, it causes non-recrystallization, and in a case where the heating temperature is higher than 52 × X + 680, the crystal grain size becomes coarse. In both cases, the strength of titanium copper finally obtained is decreased.
- The GOS and Schmidt factor can be controlled by adjusting a heating time in the final solutionizing treatment. The heating time can be, for example, from 5 to 60 seconds, and typically from 20 to 45 seconds.
- Final cold rolling is carried out following the final solutionizing treatment. The final cold rolling can increase the strength. In order to obtain good stress relaxation resistance, the working ratio is preferably from 5 to 50%, and more preferably from 20 to 40%.
- An aging treatment is carried out following the final cold rolling. Preferably, it is carried out by heating at a material temperature of from 300 to 500 °C for 1 to 50 hours, and more preferably heating at a material temperature of from 350 to 450 °C for 10 to 30 hours. The aging treatment is preferably carried out in an inert atmosphere such as Ar, N2 and H2 in order to suppress generation of an oxide film.
- In summary, the method for producing the titanium copper according to the embodiment of the present invention includes:
- a step of casting a titanium copper ingot containing from 2.0 to 4.5% by mass of Ti, and a total amount of from 0 to 0.5% by mass of at least one selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si as a third element, the balance being copper and inevitable impurities;
- a hot rolling step of treating the cast ingot such that a compressive strain per pass is from 0.15 to 0.30 and a maximum strain rate at 700 to 900 °C is from 2.0 to 6.0/s; and a final solutionizing treatment of treating the ingot at a heating temperature (°C) in a range of from 52 × X + 610 to 52 × X + 680 for a retention time of from 5 to 50 seconds,
- It will be appreciated by a person skilled in the art that steps such as grinding, polishing, and shot blast pickling for removing oxide scales on the surface may be carried out between the above steps.
- Hereinafter, while Examples of the present invention are shown below together with Comparative Examples, these are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
- Each alloy containing the alloy components as shown in Table 1, the balance being copper and inevitable impurities, was used as an experimental material to investigate effects of production conditions of the alloy components, hot rolling and final solutionizing treatment on the 0.2% yield strength, average crystal grain size, GOS, Schmidt factor and stress relaxation resistance.
- First, 2.5 kg of electrolytic copper was melted in a vacuum melting furnace, and each third element was added at each mixing ratio as shown in Table 1, and Ti was then added at each mixing ratio as shown in Table 1. After sufficient consideration was given to the retention time after the addition such that there was no un-melted residue of the added elements, these were injected into a mold in an Ar atmosphere to produce about 2 kg of each ingot.
- The ingot was subjected to homogenized annealing at 950 °C for 3 hours, followed by hot rolling at 900 to 950 °C to obtain a hot rolled sheet having a thickness of 10 mm. After descaling by chamfering, cold rolling and annealing were repeated to obtain a raw strip thickness (2.0 mm), and a first solutionizing treatment was carried out for the raw strip. The first solutionizing treatment was carried out by heating at 850 °C for 10 minutes, and then cooling in water. The intermediate cold rolling was then carried out, followed by the final solution treatment, and followed by cooling in water. Then, after descaling by pickling, the final cold rolling was carried out at a working ratio of 25% to obtain a sheet thickness of 0.1 mm, and finally the aging treatment was carried out under conditions of 400 °C for 15 hours to prepare each sample for Examples and Comparative Examples.
- The following evaluations were conducted for the produced samples:
- Each JIS 13B sample was prepared, and the 0.2% yield strength in the direction parallel to the rolling direction was measured using a tensile tester according to the measurement method as described above.
- After a sheet surface (rolled surface) of each sample was polished and etched, each sample was measured for an average crystal grain size in the case where an orientation difference of 5° or more was regarded as a crystal grain boundary, by crystal orientation analysis in EBSD (Electron Back Scatter Diffraction) measurement (e.g., OSL Analysis available from TSL Solutions) using an analysis software attached to the EBSD.
- The sheet surface (rolled surface) of each sample was polished and then etched, and the sample was subjected to crystal orientation analysis in EBSD measurement. An analysis software (e.g., OIM Analysis available from TSL Solutions) was used to show an average value of orientation differences between all pixels in each crystal grain when an orientation difference of 5° or more was regarded as a grain boundary, and an average value of orientation differences between the pixels in the crystal grains and all the remaining pixels was calculated, which were carried out for all crystal grains to calculate an average value.
- The sheet surface (rolled surface) of each sample was polished and then etched, and the sample was subjected to crystal orientation analysis in EBSD measurement. An analysis software (e.g., OIM Analysis available from TSL Solutions) was used to calculate the Schmidt factors of individual crystal grains when an orientation difference of 5° or more was regarded as a crystal grain boundary.
- The stress relaxation rate after maintaining each sample at 300 °C for 10 hours was measured. Each strip-shaped sample having a width of 10 mm and a length of 100 mm was collected such that a longitudinal direction of the sample was parallel to the rolling direction. As shown in
FIG. 1 , a deflection of y0 was applied to the sample at a position of I = 50 mm as a working point to apply a stress (s) corresponding to 80% of the 0.2% yield strength in the rolling direction. The y0 was determined by the following equation: y0 = (2/3)·I2·s/(E·t), in which:
E is a Young's modulus in the rolling direction, and t is a thickness of the sample. The load was removed after heating at 300 °C for 10 hours, and an amount of permanent deformation (height) y was measured as shown inFIG. 2 to calculate the stress relaxation rate {[y (mm) / y0 (mm)] × 100 (%)}. - When the stress relaxation rate was 10% or less, the stress relaxation resistance was considered to be good (○).
[Table 1] Examples Production Conditions Final Characteristics Component (% by mass) Hot Rolling Final Solutionizing Treatment Ti Third Element Compressive Strain per Pass (-) Maximum Strain Rate at 700 to 900°C (/s) Temperature (°C) Retention Time (s) 0.2% Yield Strength (MPa) Average Grain Size (µm) Area Ratio of Crystal Grain with GOS of 2 to 6° (%) Area Ratio (%) of Crystal Grain with Schmidt Factor of 0.35 or less Stress Relaxation Property after 300 °C × 10h Example 1 3.1 0.2Fe 0.20 4.0 800 30 912 5 72 13 ○ Example 2 3.1 0.2Fe 0.16 4.0 800 30 906 5 63 14 ○ Example 3 3.1 0.2Fe 0.28 4.0 800 30 920 5 87 14 ○ Example 4 3.1 0.2Fe 0.20 2.2 800 30 905 3 74 18 ○ Example 5 3.1 0.2Fe 0.20 5.8 800 30 929 4 73 17 ○ Example 6 3.1 0.2Fe 0.20 4.0 775 30 917 3 70 12 ○ Example 7 3.1 0.2Fe 0.20 4.0 830 30 896 10 76 13 ○ Example 8 3.1 0.2Fe 0.20 4.0 800 9 915 4 73 13 ○ Example 9 3.1 0.2Fe 0.20 4.0 800 56 897 18 74 12 ○ Example 10 3.1 - 0.20 4.0 800 30 885 25 83 16 ○ Example 11 2.0 - 0.20 4.0 745 30 808 23 72 18 ○ Example 12 4.5 - 0.20 4.0 875 30 1042 16 88 12 ○ Example 13 3.1 0.2Zn-0.1 Mo-0.05P 0.23 4.3 800 30 931 11 81 12 ○ Example 14 3.1 0.2Cr-0.05Zr 0.24 4.3 780 30 917 4 76 11 ○ Example 15 3.1 0.1Co-0.1 Mn 0.19 4.9 810 30 886 6 67 16 ○ Example 16 3.1 0.2Ni-0.05B 0.18 3.2 820 30 914 15 76 16 ○ Example 17 3.1 0.05V-0.05Nb-0.05Ma 0.18 2.8 780 30 920 7 70 17 ○ Example 18 3.1 0.2Si 0.19 5.5 795 30 923 6 73 17 ○ Comparative Example 1 3.1 0.2Fe 0.13 4.0 800 30 904 7 56 13 × Comparative Example 2 3.1 0.2Fe 0.34 Not Produced - - - - - - Comparative Example 3 3.1 0.2Fe 0.20 1.7 800 30 923 7 75 24 × Comparative Example 4 3.1 0.2Fe 0.20 6.3 800 30 921 5 73 24 × Comparative Example 5 3.1 0.2Fe 0.20 4.0 765 30 851 Non-recrvstallized - - × Comparative Example 6 3.1 0.2Fe 0.20 4.0 840 30 834 36 95 12 × Comparative Example 7 3.1 0.2Fe 0.20 4.0 800 2 929 Mixed Grain 32 2 × Comparative Example 8 3.1 0.2Fe 0.20 4.0 800 68 846 33 93 11 × Comparative Example 9 3.1 0.3Si-0.3Mo Not Produced - - - - - Comparative Example 10 1.8 0.2Fe 0.20 4.0 735 30 789 16 68 24 × Comparative Example 11 4.8 0.2Fe Not Produced - - - - - - In each of Examples 1 to 18, the stress relaxation rate after maintaining at 300 °C for 10 hours was 10% or less, indicating improved stress relaxation resistance.
- On the other hand, in Comparative Example 1, the compressive strain per pass was too low, so that fine precipitates were not sufficiently obtained, and the area ratio of the crystal grains with GOS of 2 to 6° was lower than 60%, whereby an improved stress relaxation resistance as compared with Examples 1 to 18 could not be obtained.
- In Comparative Example 2, the compression strain per pass was too high and the shape during rolling was poor, so that production was impossible. In each of Comparative Examples 3 and 4, the maximum strain rate at 700 to 900 °C was not appropriate, so that the area ratio of crystal grains with a Schmidt factor of 0.35 or less was higher, and an improved stress relaxation resistance as compared with Examples 1 to 18 could not be obtained.
- In Comparative Example 5, the temperature of the final solutionizing treatment was too low, so that an improved stress relaxation resistance as compared with Examples 1 to 18 could not be obtained. In Comparative Example 6, the temperature of the final solutionizing treatment temperature was too high, so that the area ratio of the crystal grains with GOS of 2 to 6° was higher than 90%, and an improved stress relaxation resistance as compared with Examples 1 to 18 could not be obtained.
- In Comparative Example 7, the retention time of the final solutionizing treatment was too short, so that the crystal grain size was of mixed grain type, the area ratio of the crystal grains with GOS of 2 to 6° was lower than 60%, and the area ratio of crystal grains with a Schmidt factor of 0.35 or less was decreased, whereby an improved stress relaxation resistance as compared with Examples 1 to 18 could not be obtained. In Comparative Example 8, the retention time of the final solutionizing treatment was too long, the crystal grain size was coarsened, and the area ratio of crystal grains with GOS of 2 to 6° was higher than 90%, whereby an improved stress relaxation resistance as compared with Examples 1 to 18 could not be obtained.
- Comparative Examples 9 to 11 show cases where the addition amount of titanium or the third element was not appropriate. In Comparative Example 9, the amount of the additive element was too large, so that cracking occurred during hot rolling, and production was thus impossible. In Comparative Example 10, the addition amount of Ti was too low, so that the area ratio of crystal grains with a Schmidt factor of 0.35 or less was increased, whereby an improved stress relaxation resistance as compared with Examples 1 to 18 could not be obtained. In Comparative Example 11, the addition amount of Ti was too high, so that cracking occurred during hot rolling, whereby production was impossible.
Claims (6)
- A titanium copper, the titanium copper containing from 2.0 to 4.5% by mass of Ti, and a total amount of from 0 to 0.5% by mass of at least one selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si as a third element, the balance being copper and inevitable impurities, wherein an area ratio of crystal grains with a GOS (Grain Orientation Spread) of from 2 to 6° when an orientation difference of 5° or more is regarded as a crystal grain boundary in crystal orientation analysis in an EBSD measurement on a rolled surface is from 60 to 90%, and an area ratio of crystal grains with a Schmidt factor of 0.35 or less is from 5 to 20%.
- The titanium copper according to claim 1, wherein the titanium copper has a stress relaxation rate of 10% or less after maintaining the titanium copper at 300 °C for 10 hours.
- The Titanium copper according to claim 1 or 2, wherein in crystal orientation analysis in the EBSD measurement on a rolled surface, an average crystal grain size when an orientation difference of 5° or more is regarded as a grain boundary is from 2 to 30 µm.
- The titanium-copper according to any one of claims 1 to 3, wherein a 0.2% proof stress in a direction parallel to a rolling direction is 800 MPa or more when a tensile test is carried out according to JIS-Z2241 (2011).
- An electronic component comprising the titanium copper according to any one of claims 1 to 4.
- A method for producing titanium copper, the method comprising casting a titanium copper ingot containing from 2.0 to 4.5% by mass of Ti, and a total amount of from 0 to 0.5% by mass of at least one selected from the group consisting of Fe, Co, Ni, Cr, Zn, Zr, P, B, Mo, V, Nb, Mn, Mg, and Si as a third element, the balance being copper and inevitable impurities, and subjecting the cast ingot to hot rolling; and then carrying out a cold rolling step and a subsequent final solutionizing treatment step,
wherein the hot rolling step comprises treating the ingot such that a compressive strain per pass is from 0.15 to 0.30 and a maximum strain rate at 700 to 900 °C is from 2.0 to 6.0/s, and
wherein the final solutionizing treatment step comprises carrying out a treatment at a heating temperature (°C) of from 52 × X + 610 to 52 × X + 680 in which X is an addition amount (% by mass) of Ti, for a residence time of from 5 to 60 seconds.
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CN111733372A (en) * | 2020-08-27 | 2020-10-02 | 宁波兴业盛泰集团有限公司 | Elastic copper-titanium alloy and preparation method thereof |
CN114152638A (en) * | 2021-11-29 | 2022-03-08 | 宁波江丰电子材料股份有限公司 | Sample preparation method for MoNb target EBSD detection |
CN116024444A (en) * | 2022-12-28 | 2023-04-28 | 付亚波 | High-strength high-conductivity high-elasticity titanium bronze alloy, preparation method thereof and vacuum melting solidification device |
CN114152638B (en) * | 2021-11-29 | 2024-05-14 | 宁波江丰电子材料股份有限公司 | Sample preparation method for EBSD detection of MoNb target material |
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CN116024444B (en) * | 2022-12-28 | 2024-04-26 | 付亚波 | High-strength high-conductivity high-elasticity titanium bronze alloy, preparation method thereof and vacuum melting solidification device |
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