CN1614052A - Softening-resistant copper alloy and method of forming sheet of the same - Google Patents
Softening-resistant copper alloy and method of forming sheet of the same Download PDFInfo
- Publication number
- CN1614052A CN1614052A CN200410090355.0A CN200410090355A CN1614052A CN 1614052 A CN1614052 A CN 1614052A CN 200410090355 A CN200410090355 A CN 200410090355A CN 1614052 A CN1614052 A CN 1614052A
- Authority
- CN
- China
- Prior art keywords
- copper alloy
- rolling
- cold rolling
- annealing
- final
- 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.)
- Pending
Links
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005097 cold rolling Methods 0.000 claims abstract description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005098 hot rolling Methods 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 abstract description 25
- 239000013078 crystal Substances 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001887 electron backscatter diffraction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052726 zirconium 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Conductive Materials (AREA)
- Metal Rolling (AREA)
Abstract
The invention was involved in producing copper alloy with fine heat resisting and its slab. The copper alloy contained ferrum. Bearing density of Cube azimuth was less than 50% after it was annealed for 1 min under 500deg.C and the crystal diameter was under 30um. When producing cold-rolled copper alloy after it was hot rolled, the technology of cold rolling and anneal were done for twice separately between hot rolling and the final cool rolling. At the same time, every cool rolling contained 50%-80% working rate and the final working rate was 30%-80%. The invention provided one method to produce copper alloy with fine heat resisting and its slab and its intensity wasn't mostly decreased under the heat treatment, such as strain relief anneal.
Description
Technical field
Carrying out after the forming process such as being under the heat treated situations such as strain relief annealing even the invention relates to, intensity reduces the copper alloy and the method for making thereof of less and excellent heat resistance, thereby this Albatra metal-, bring into play its excellent heat resistance, can extensively effectively utilize in various fields based on electric and electronic field and mechanical field.
Background technology
In recent years, along with miniaturization and the thin-wall light-weighted progress based on the various device of electronics etc., the miniaturization and that is used as the copper alloy parts of the lead frame that constitutes these equipment and terminal, junctor etc. is also developing rapidly.
For example, as the semiconductor lead frame copper alloy, the general copper alloy that contains small amounts of iron that uses particularly contains Fe:2.1～2.6% and (refers to quality %; Under the situation of chemical ingredients, below identical) copper alloy (CDA 194 alloys) of P:0.015～0.15% and Zn:0.05～0.20%, even in copper alloy, because of it its also outstanding at aspects such as intensity, electroconductibility, heat conductivities, pretend to the international standard copper alloy and be widely used.
When being processed into lead frame etc., generally adopt the copper alloy plate of above-mentioned the sort of chemical constitution, make multitube pin (peen) shape by drawing.Recently for the miniaturization that adapts to foregoing electrical and electronic parts and thin-wall light-weighted, the thin-walled property and the multitube pinization of the copper alloy plate that uses as starting material develop, follow in this, easily residual strain stress is arranged on the processed goods after the drawing, pin irregular tendency that becomes.So usually carry out and the copper alloy plate of the multitube pin shape that obtains with punch process is implemented thermal treatment (elimination strain annealing) eliminate strain.Yet in case carry out such thermal treatment, material promptly is easy to soften, and can not handle physical strength before by maintenance heat.In addition, from the manufacturing process aspect, from the viewpoint of boosting productivity, need with more increase temperature, the short period of time carries out described thermal treatment, still can keep high-strength heat-resistant after the strong request thermal treatment at high temperature.
For such problem, up to the present, make it contain trace additives such as alloying elements such as Fe, P, Zn and other Sn, Mg, Ca, or the countermeasure of improving of adjusting their addition etc. was inquired into.Yet, can not fully adapt to the miniaturization and of copper alloy parts and high-temperature capability characteristic etc. because of only depending on such composition adjustment.Therefore recently in the technology of the set tissue of research control copper alloy etc.
For example in patent documentation 1, by control final X-ray diffraction intensity after rolling than and final grain size before rolling improve intensity.In addition, in patent documentation 2, the technology that the orientation density of being controlled the Cube orientation outside the X-ray diffraction intensity ratio again improves processibility is disclosed.
[patent documentation 1] spy opens the 2003-96526 communique
[patent documentation 2] spy opens the 2002-339028 communique
Disclosed method in the above-mentioned patent documentation 1, be that the copper alloy that will add small amount of silver in the oxygen free copper is used as raw material, after hot rolling, carry out cold rolling and recrystallization annealing repeatedly, by control final processibility, average crystallite particle diameter after the final recrystallization annealing before cold rolling and the cold rolling processibility before the final annealing in cold rolling control final X-ray diffraction intensity after rolling than and final grain size before rolling, to seek high strength.And according to this document, if cubes set tissue is flourishing, intensity just reduces, and anisotropy occurs aspect corrodibility, even thereby from such viewpoint, think that X-ray diffraction intensity should suitably be controlled.In addition, this Albatra metal-of record also is excellent aspect thermotolerance in the document.Yet, even adopt the rolling and annealing conditions of being recommended in this document in the same old way, also can not obtain to look to the sort of high-level thermotolerance among aftermentioned the present invention, need further to improve.
According to another document 2, wherein record by the X-ray diffraction intensity of proper range control (200) crystal face and (220) crystal face than and the orientation density in Cube orientation, can obtain the electronic component-use copper alloy that processibility and formability have been improved.Yet,, do not reach the high-level thermotolerance of being look among assurance the present invention even adopt this technology yet.
Summary of the invention
The present invention carries out in view of aforesaid well-known technology.Even its objective is to provide and be not equipped with valuable alloying element, and, even particularly for being applicable to that electrical and electronic parts has carried out under the situation of thermal treatment (elimination strain annealing) with the miniaturization and of copper alloy material, also have the copper alloy that can keep high-strength heat-resistant, the method for making this Albatra metal-more reliably also is provided simultaneously.
Can solve the copper alloy of the excellent heat resistance of the present invention of above-mentioned problem, it is characterized in that containing Fe, the orientation density in the Cube orientation after annealing in 1 minute under 500 ℃ is below 50%, it is desirable to the average crystallite particle diameter below 30 μ m.
Copper alloy of the present invention, as mentioned above, as the alloying element of cheapness with a spot of Fe as containing by composition, its content is not done special restriction, but it is desirable to more than 0.01%, below 4%.As some element that often contains in addition, phosphorus (P) following about 0.03% and about 0.1% zinc etc. are arranged, but, should be controlled on the unavoidable impurities amount about other elements.
In addition, method for making of the present invention is to make the method for the copper alloy of above-mentioned excellent heat resistance more reliably, the copper alloy that it is characterized in that containing Fe carries out cold rolling when making cold rolling copper alloy after hot rolling, hot rolling and final cold rolling between, at least cold rolling and annealing respectively to be carried out twice, simultaneously carry out each time cold rolling, final working modulus when cold rolling is decided to be 30～85% with 50～80% working modulus.
According to the present invention, by will below 50%, obtaining the copper alloy of stable and excellent heat resistance through the Cube orientation density control after the annealing in 500 ℃ * 1 minute.Can also reduce pointed in material in the past as far as possible is strength deterioration after the annealing thermal treatment of purpose with the strain relief.Its result, because of such as being that drawing processing etc. causes having strain stress residual, cause under the situation of worrying the dimensional precision reduction, prevent the reduction of dimensional precision when also can reduce, the copper alloy of stay in grade is provided by control intensity such as strain relief annealing.
Description of drawings
Fig. 1 is the cubes orientation mapping graph that the usefulness " the EBSP determination and analysis OIM of system " of prepared copper alloy plate among the embodiment draws.
Fig. 2 be the copper alloy plate that makes equally among the embodiment by the take a picture histogram of the crystallization particle diameter of trying to achieve of SEM.
Embodiment
The copper alloy of excellent heat resistance of the present invention, be to make as mentioned above with the copper alloy that contains small amount of Fe, what it had first is characterised in that under 500 ℃ that the orientation density in the Cube orientation after annealing in 1 minute is below 50%, better is outside this orientation density, what it had second is characterised in that, the average crystallite particle diameter under 500 ℃ after annealing in 1 minute is below 30 μ m.
As mentioned above, will be set in below 50% in the orientation density in the Cube orientation after annealing in 1 minute under 500 ℃, according to following reason.Promptly confirm following true by various experiment: under the situation of the copper alloy that contains small amount of Fe according to present inventors, the orientation density in Cube orientation is big more behind the heating anneal, then the intensity reduction degree that causes because of thermal treatment is just big more, this orientation is close more little, then the intensity reduction degree that causes because of thermal treatment is just more little, is the copper alloy of excellent heat resistance; Cube orientation density when the quantitative benchmark of this orientation density can be set in [500 ℃ * 1 minute] with heating anneal in addition after the annealing is that benchmark is done evaluation, if surpass 50%, then the intensity that causes because of thermal treatment reduces degree and will obviously become big, this orientation density is 50% when following, better is 40% when following, demonstrates stable and good thermotolerance.
Also have, outside Cube orientation density, above-mentioned also have high correlation with thermotolerance at the average crystallite particle diameter after annealing in 1 minute under 500 ℃.This average crystallite particle diameter is 30 μ m when following, confirms that it demonstrates better thermotolerance.
Moreover so-called Cube orientation is crystalline＜001〉direction and rolling direction, rolling surface normal and width become parallel orientation, on rolling surface by (100) face orientation.Along with the prosperity in Cube orientation, the ratio that exists with the crystal grain in this Cube orientation just becomes big, and the Cube orientation is once excessive prosperity, and the intensity of this copper alloy will reduce.So if the orientation density in Cube orientation is controlled at below 50%, the high-caliber thermotolerance that just can guarantee among the present invention to be look to.
Here, the orientation density in Cube orientation can use EBSP (Electron Back-Scatterdiffraction Pattern) to measure, promptly in the EBSP method, make electron beam incident on the test portion surface, the reflection electronic that takes place in the time of thus can obtain Kikuchi pattern (Cube orientation map) as shown in fig. 1.If the Kikuchi pattern is analyzed, i.e. the crystal orientation of electron impact position as can be known.Make this electron beam carry out two-dimensional scan then on the test portion surface, if all determine crystal orientation by every section prescribed distance, the orientation that can measure the test portion surface distributes.
But strain field that causes owing to the processing of thin-walled property and drawing etc. and defectives such as slip line, dislocation boundary are present under the situation in the test portion in a large number, are difficult to obtain the Kikuchi pattern.Copper alloy of the present invention as will describing in detail subsequently, owing to be to process at last by cold rolling suppressing under, therefore is the orientation density that can not estimate the Cube orientation with the EBSP method under the script state of final cold-reduced sheet.Therefore, in the present invention, be to stipulate with the Cube orientation density after annealing in 1 minute under 500 ℃.
Again, along with the prosperity in Cube orientation, the increasing proportion of Qu Xiang crystal grain in the same direction, thereby the disorderly degree of atom diminishes on the grain boundary, the tendency of obvious thickization of crystal grain can be observed.This crystallization particle diameter is below 30 μ m, and better is when 25 μ m are following, even still keeping high strength also to be confirmed after annealing in 1 minute under 500 ℃.
Among the present invention employed copper alloy with Fe as must composition and contain, comprise this Fe content, the one-tenth of this copper alloy is grouped into do not do special restriction, but effect of the present invention is more effectively brought into play, various characteristics as copper alloy is more effectively manifested, wish to use Fe content more than 0.01%, below 4.0%.By the way, if when Fe contains quantity not sufficient 0.01%, the Fe in the copper alloy matrix or the amount of separating out of Fe base intermetallic compound are less, thereby will be not enough as lead frame and desired intensity such as terminal, junctor, and in addition, thermotolerance is not much of that yet.But, the effect of such Fe is promptly saturated about 4.0% o'clock greatly, can not get further improving intensity and stable on heating effect, and the coarse grain and the precipitate that on the contrary contain Fe generate in a large number, processibility when understanding castibility and hot rolling causes detrimentally affect, thereby preferably is controlled at below 4.0%.Intensity and thermotolerance and castibility and hot workability are reached and deposit, better Fe content is more than 0.03%, below 3.5%, further it is desirable to more than 0.05%, below 3.0%.
Again, in the copper alloy of the present invention, except that above-mentioned Fe, phosphorus (P) and zinc also can be sneaked into, but in order to restrain the reduction that generates the castibility that causes because of thick crystalline, preferably are controlled at below about 0.1%.In addition, zinc is effective elements preventing aspect the peeling off of tin and welding agent, but if its effect will be saturated too much the time, and what make molten tin and welding agent on the contrary soaks the extendability deterioration, thereby wishes to be controlled at below about 1.0%.About other element, then needn't make energetically it contain into, but in not overslaugh above-mentioned action effect scope of the present invention, for example inevitable impurity level such as Pb, Ni, Mn, Cr, Al, Mg, Ca, Be, Si, Zr, In is sneaked into and also is fine, and it also is possible perhaps adding on a small quantity energetically.These situations also all are included in the technical scope of the present invention.
Below describe about the method for making of the copper alloy of the excellent heat resistance that obtains to satisfy above-mentioned Cube orientation density and average crystal grain footpath.
When making copper alloy of the present invention, after hot rolling,, at least respectively carry out twice repeatedly with cold rolling with annealing, after the cold rolling specific thickness that is processed into to carrying out in the last cold rolling process.In method in the past, general what adopt is from productivity and cost cold rolling after the hot rolling and annealing to be controlled at the method that necessary minimum (for example, hot rolling-cold rolling-annealing-finally cold rolling) carries out.But according to the situation that present inventors confirmed, if the working modulus when will be each time cold rolling improves excessively, the karyomorphism that just has the Cube orientation becomes, and when fabricated product was annealed, the Cube orientation was just flourishing easily.Otherwise, if the working modulus when cold rolling each time is low excessively, then the prosperity of the rolling set tissue in B orientation ({ 011}＜211 〉) and S orientation ({ 123}＜634 〉) etc. just is suppressed, become cold rolling before (being the hot rolling finish time) a large amount of residual the states of residual Cube orientation and nuclear thereof.
Hot rolling and final cold rolling between, if will be cold rolling in suitable working modulus scope and annealing each carries out twice repeatedly at least, then the formation flourishing and that examine in Cube orientation is just suppressed significantly.By the way, if make the working modulus less than 50% when cold rolling each time or surpass 80%, then when goods anneals, the Cube orientation is growth significantly easily, can surpass above-mentioned OK range in the Cube orientation density after annealing in 1 minute under 500 ℃.But along with the prosperity in Cube orientation, crystal grain is grown up unusually, and the average crystallite particle diameter also surpasses 30 μ m, and then becomes the reason that makes the thermotolerance deterioration.So in the present invention, each cold rolling working modulus is decided to be 50～80%, and must cold rollingly at least respectively carries out twice with annealing.
Again, by the above-mentioned cold rolling and annealed repeatable operation of after hot rolling, being carried out, the prosperity that fully suppresses the Cube orientation becomes with karyomorphism, though with size adjusting attach most importance to final cold rolling the time the permission work range can obtain some expansions, but reliably suppress if the prosperity in Cube orientation in the final cold rolling process will be become with karyomorphism also, then preferably final working modulus when cold rolling is suppressed at more than 30% below 85%, more better is is suppressed at more than 35% below 80%.
The present invention constitutes as described above, by will under the prescribed condition heating after Cube orientation density specific for below 50%, intensity in the time of can obtaining heating anneal reduces less and the copper alloy of excellent heat resistance, and, can make the copper alloy of high heat resistance reliably by suitable control in cold rolling and annealed repeatable operation that is hot-rolled down to final regulation working modulus of being carried out between cold rolling and final working modulus when cold rolling.
The copper alloy of the present invention that obtains like this has good thermotolerance as mentioned above, even thermal treatment such as strain relief annealing in addition, it is also less that intensity reduces, thereby can be used as effectively such as resembling IC lead frame, terminal, connector etc. and will carry out the raw material of heat treated copper alloy products such as strain relief annealing for final finished size adjustment.
[embodiment]
Below for stating embodiment and comparative example is described more specifically the present invention.The present invention surely not is restricted because of following embodiment, and in the scope of described aim, it also is possible suitably being changed enforcement before and after being fit to.These situations are also included within the technical scope of the present invention certainly.
Embodiment
Copper alloy melting in coreless furnace respectively with chemical ingredients shown in the following table 1 comes agglomeration with the semicontinuous casting method, makes the ingot bar of thick 50mm * wide 200mm * long 500mm.With being hot-rolled down to thickness 12mm after prepared each ingot bar heating, carry out surfacing afterwards, and then repeat cold rolling and annealing, carry out finally rollingly at last, make the copper alloy plate of thick about 0.2mm.
With prepared copper alloy plate in 500 ℃ salt bath furnace after annealing in 1 minute, the test film that the selecting and purchasing structure observation is used after carrying out mechanical mill and polishing and grinding, is done electrolytic polishing and is adjusted the surface.About prepared each test film, utilize the SEM (model " JEOL JSM5410 ") of NEC society manufacturing and the EBSP determination and analysis OIM of system (Orientation ImagingMacrograph) of TSL society manufacturing in the scope of 500 μ m * 500 μ m, to measure with the interval of 1 μ m.Then, try to achieve the orientation density (starting within 15 °) and the average crystal grain footpath in Cube orientation by desirable orientation with the analysis software (software name " OIM Analysis ") of same system.
Fig. 1 is the Cube orientation mapping graph that has utilized the sample determination of the symbol 1 shown in above-mentioned " the EBSP determination and analysis OIM of system " his-and-hers watches 1 to obtain, and the field that is black is the Cube orientation.Thereby, can try to achieve Cube orientation density if such Cube orientation mapping graph is carried out image with above-mentioned analysis software resolves.In addition, Fig. 2 is the histogram of crystallization particle diameter that the sample of symbol 1 is tried to achieve with same analysis software equally.From the such crystallization particle diameter and the histogram of each area ratio, can try to achieve the average crystallite particle diameter.
In addition, the thermotolerance of each examination material that provides is to estimate according to the hardness reduction degree that is caused by annealing.The mensuration of hardness is by the copper alloy plate goods after the final rolling completion with its any selecting and purchasing test film (thick 0.2mm * wide 10mm * long 10mm) respectively in the plate after annealing in 1 minute under 500 ℃, with the micro-DPH meter (trade(brand)name " micro-hardness tester ") of loose damp smart machine society manufacturing in addition the loading of 0.5kg carry out.
The result gathered be shown in table 1.
Table 1
| ????No. | Chemical ingredients | Cold rolling number of times between hot rolling-final is cold rolling | The highest cold rolling working modulus (%) | Cold rolling minimum working modulus (%) | Final cold rolling working modulus (%) | Product initial stage hardness (Hv) | After the 500 ℃ * 1min annealing | |||||
| ????Fe | ????P | ????Zn | Hardness (Hv) | Hardness reduction amount (Hv) | Cube orientation density (%) | Average crystallite particle diameter (μ m) | ||||||
| ????1 | ????1.8 | ????- | ????- | ??2 | ????70 | ??60 | ??60 | ??128 | ????105 | ????23 | ??19 | ??12 |
| ????2 | ????0.5 | ????- | ????- | ??2 | ????75 | ??55 | ??70 | ??123 | ????96 | ????27 | ??31 | ??19 |
| ????3 | ????2.1 | ????0.03 | ????- | ??2 | ????65 | ??60 | ??50 | ??140 | ????120 | ????20 | ??7 | ??9 |
| ????4 | ????2.1 | ????0.03 | ????- | ??2 | ????75 | ??60 | ??75 | ??156 | ????123 | ????33 | ??34 | ??21 |
| ????5 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????78 | ??55 | ??83 | ??159 | ????121 | ????38 | ??43 | ??26 |
| ????6 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????70 | ??60 | ??65 | ??148 | ????122 | ????26 | ??22 | ??15 |
| ????7 | ????2.1 | ????0.03 | ????0.1 | ??3 | ????70 | ??60 | ??55 | ??143 | ????126 | ????17 | ??5 | ??7 |
| ????8 | ????1.6 | ????- | ????- | ??2 | ????88 | ??60 | ??55 | ??124 | ????72 | ????52 | ??57 | ??34 |
| ????9 | ????0.3 | ????- | ????- | ??2 | ????93 | ??60 | ??88 | ??130 | ????70 | ????60 | ??70 | ??42 |
| ????10 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????95 | ??60 | ??60 | ??147 | ????90 | ????57 | ??64 | ??38 |
| ????11 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????70 | ??30 | ??80 | ??151 | ????96 | ????55 | ??61 | ??36 |
| ????12 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????70 | ??60 | ??95 | ??157 | ????99 | ????58 | ??65 | ??40 |
| ????13 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????92 | ??60 | ??90 | ??161 | ????99 | ????62 | ??72 | ??43 |
| ????14 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????50 | ??20 | ??20 | ??125 | ????65 | ????60 | ??69 | ??42 |
| ????15 | ????2.1 | ????0.03 | ????0.1 | ??2 | ????90 | ??40 | ??90 | ??160 | ????95 | ????65 | ??75 | ??46 |
| ????16 | ????2.1 | ????0.03 | ????0.1 | ??1 | ????75 | ??70 | ??50 | ??142 | ????94 | ????48 | ??52 | ??31 |
As shown in Table 1, symbol 1-7 is the embodiment that satisfies prescribed condition of the present invention, and each all is that 500 ℃ * 1 minute Cube orientation density after the annealing is below 50%, and the average crystallite particle diameter is below the 30 μ m, and the hardness reduction amount before and after the annealing has excellent heat resistance all below 40Hv.
Compare with these situations, symbol 8-16 is the comparative material that lacks a certain prescribed condition of defined among the present invention as described below, each Cube orientation density is all above 50%, simultaneously the average crystallite particle diameter surpasses 30 μ m, and the big and not talkative thermotolerance of the intensity reduction amount before and after the annealing is sufficient.
Symbol 8: the highest cold rolling working modulus of being carried out during final rolling after the hot rolling surpasses 80%.
Symbol 9: the highest cold rolling working modulus of being carried out during final rolling after the hot rolling surpasses 80%, and in addition, final working modulus when rolling also surpasses 85%.
Symbol 10: the highest cold rolling working modulus of being carried out during final rolling after the hot rolling surpasses 80%.
Symbol 11: the highest cold rolling working modulus less than 50% of being carried out during final rolling after the hot rolling.
Symbol 12: final working modulus when rolling surpasses 85%.
Symbol 13: the highest cold rolling working modulus of being carried out during final rolling after the hot rolling surpasses 80%, and in addition, final working modulus when rolling also surpasses 85%.
Symbol 14: the cold rolling minimum working modulus of being carried out during final rolling after the hot rolling is less than 50% not only, and final working modulus when rolling does not reach 30% yet.
Symbol 15: the cold rolling minimum working modulus less than 50% of being carried out during final rolling after the hot rolling, in addition, final working modulus when rolling surpasses 85%.
Symbol 16: the cold rolling and annealed multiplicity of being carried out during final rolling after the hot rolling only once.
Claims (5)
1, a kind of copper alloy of excellent heat resistance is characterized in that: contain iron, the orientation density in the Cube orientation after annealing in 1 minute under 500 ℃ is below 50%.
2, a kind of copper alloy of excellent heat resistance is characterized in that: containing iron, is below 50% in the orientation density in Cube orientation after annealing in 1 minute under 500 ℃, and is below the 30 μ m at the average crystallite particle diameter after annealing in 1 minute under 500 ℃.
3, according to the copper alloy of being put down in writing in the claim item 1, iron level is 0.01～4 quality %.
4, according to the copper alloy of being put down in writing in the claim item 2, iron level is 0.01～4 quality %.
5, a kind of method for making of copper alloy of excellent heat resistance, it is characterized in that, to contain carry out after the copper alloy hot rolling of Fe cold rolling when making cold rolling copper alloy, hot rolling and final cold rolling between, cold rolling and annealing are at least respectively carried out twice, simultaneously carry out each time cold rolling with 50～80% working modulus, final working modulus when cold rolling is set at 30～85%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003376122A JP4041452B2 (en) | 2003-11-05 | 2003-11-05 | Manufacturing method of copper alloy with excellent heat resistance |
| JP2003376122 | 2003-11-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1614052A true CN1614052A (en) | 2005-05-11 |
Family
ID=34544313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410090355.0A Pending CN1614052A (en) | 2003-11-05 | 2004-11-04 | Softening-resistant copper alloy and method of forming sheet of the same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20050092404A1 (en) |
| JP (1) | JP4041452B2 (en) |
| KR (1) | KR20050043655A (en) |
| CN (1) | CN1614052A (en) |
| DE (1) | DE102004053346B4 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4441467B2 (en) * | 2004-12-24 | 2010-03-31 | 株式会社神戸製鋼所 | Copper alloy with bending workability and stress relaxation resistance |
| CN101693960B (en) * | 2005-06-08 | 2011-09-07 | 株式会社神户制钢所 | Copper alloy, copper alloy plate, and process for producing the same |
| EP2439296B1 (en) | 2005-07-07 | 2013-08-28 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy having high strength and superior bending workability, and method for manufacturing copper alloy plates |
| EP2426225B1 (en) | 2006-05-26 | 2015-12-02 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy with high strength, high electrical conductivity, and excellent bendability |
| WO2008010378A1 (en) | 2006-07-21 | 2008-01-24 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy sheets for electrical/electronic part |
| JP4950584B2 (en) | 2006-07-28 | 2012-06-13 | 株式会社神戸製鋼所 | Copper alloy with high strength and heat resistance |
| WO2008041584A1 (en) | 2006-10-02 | 2008-04-10 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy plate for electrical and electronic components |
| EP2695958B1 (en) | 2007-08-07 | 2018-12-26 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy sheet |
| JP4630323B2 (en) | 2007-10-23 | 2011-02-09 | 株式会社コベルコ マテリアル銅管 | Copper alloy tube for heat exchangers with excellent fracture strength |
| JP2009179864A (en) * | 2008-01-31 | 2009-08-13 | Kobe Steel Ltd | Copper alloy sheet superior in stress relaxation resistance |
| JP5312920B2 (en) * | 2008-11-28 | 2013-10-09 | Ｊｘ日鉱日石金属株式会社 | Copper alloy plate or strip for electronic materials |
| JP5436349B2 (en) * | 2010-01-30 | 2014-03-05 | 三菱伸銅株式会社 | Bonding method of LED chip and lead frame |
| JP5525369B2 (en) * | 2010-03-11 | 2014-06-18 | 三菱伸銅株式会社 | Cu-Fe-P copper alloy strips for electronic equipment with excellent resin adhesion |
| JP4608025B1 (en) * | 2010-06-03 | 2011-01-05 | 三菱伸銅株式会社 | Copper alloy strip for electronic equipment with excellent heat dissipation and resin adhesion |
| JP5690170B2 (en) * | 2011-02-25 | 2015-03-25 | 株式会社神戸製鋼所 | Copper alloy |
| JP6696895B2 (en) | 2014-03-31 | 2020-05-20 | 古河電気工業株式会社 | Rolled copper foil, rolled copper foil manufacturing method, flexible flat cable, flexible flat cable manufacturing method |
| JP6172368B1 (en) | 2016-11-07 | 2017-08-02 | 住友電気工業株式会社 | Covered wire, wire with terminal, copper alloy wire, and copper alloy twisted wire |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522112A (en) * | 1967-06-26 | 1970-07-28 | Olin Corp | Process for treating copper base alloy |
| JP4329967B2 (en) * | 2000-04-28 | 2009-09-09 | 古河電気工業株式会社 | Copper alloy wire suitable for IC lead pins for pin grid array provided on plastic substrate |
| JP2002226929A (en) * | 2001-01-30 | 2002-08-14 | Nippon Mining & Metals Co Ltd | Copper alloy foil for high frequency circuit |
| JP3798260B2 (en) * | 2001-05-17 | 2006-07-19 | 株式会社神戸製鋼所 | Copper alloy for electric and electronic parts and electric and electronic parts |
| JP3962291B2 (en) * | 2001-07-17 | 2007-08-22 | 日鉱金属株式会社 | Rolled copper foil for copper clad laminate and method for producing the same |
-
2003
- 2003-11-05 JP JP2003376122A patent/JP4041452B2/en not_active Expired - Fee Related
-
2004
- 2004-11-01 US US10/976,818 patent/US20050092404A1/en not_active Abandoned
- 2004-11-04 KR KR1020040089127A patent/KR20050043655A/en active Search and Examination
- 2004-11-04 CN CN200410090355.0A patent/CN1614052A/en active Pending
- 2004-11-04 DE DE102004053346.6A patent/DE102004053346B4/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP4041452B2 (en) | 2008-01-30 |
| DE102004053346A1 (en) | 2005-07-21 |
| DE102004053346B4 (en) | 2017-12-28 |
| US20050092404A1 (en) | 2005-05-05 |
| KR20050043655A (en) | 2005-05-11 |
| JP2005139501A (en) | 2005-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1614052A (en) | Softening-resistant copper alloy and method of forming sheet of the same | |
| EP2695956B1 (en) | Copper alloy sheet | |
| CN101605917B (en) | Copper alloy sheet for electrical and electronic parts excelling in strength and formability | |
| KR101419149B1 (en) | Copper alloy sheet | |
| CN101166840B (en) | Copper alloy | |
| KR101113356B1 (en) | Copper alloy material, electric and electronic parts, and copper alloy material manufacturing method | |
| EP1967599B1 (en) | Aluminum alloy sheet with excellent formability and paint bake hardenability and method for production thereof | |
| CN1269979C (en) | High-strength high-conductivity copper alloy | |
| CN110506132B (en) | Cu-Co-Si-based copper alloy plate material, method for producing same, and member using same | |
| JP7202121B2 (en) | Cu-Ni-Al-based copper alloy plate material, manufacturing method thereof, and conductive spring member | |
| JP3717321B2 (en) | Copper alloy for semiconductor lead frames | |
| KR20170125805A (en) | Copper alloy material and method for producing same | |
| WO2022024891A1 (en) | Cu-ni-al-based copper alloy plate material, method for manufacturing same, and electroconductive spring member | |
| JP3748859B2 (en) | High-strength copper alloy with excellent bendability | |
| CN1297674C (en) | Copper alloy and producing method therefor | |
| CN108796296B (en) | One Albatra metal and its application | |
| JP4280287B2 (en) | Copper alloy for electrical and electronic parts with excellent heat resistance | |
| JP2004027253A (en) | Aluminum alloy sheet for molding, and method of producing the same | |
| CN109937262B (en) | Copper alloy strip with high heat resistance and heat dissipation | |
| CN100545282C (en) | Copper alloy | |
| CN111971406A (en) | Copper alloy sheet material, method for producing copper alloy sheet material, and connector using copper alloy sheet material | |
| EP1967596B1 (en) | Cu-Ni-Si-based copper alloy sheet material and method of manufacturing same | |
| KR102021442B1 (en) | A method of manufacturing a copper alloy sheet material excellent in strength and conductivity and a copper alloy sheet material produced therefrom | |
| JPH03294445A (en) | High strength aluminum alloy having good formability and its manufacture | |
| KR20240074759A (en) | Copper alloy sheet and its manufacturing method, as well as electronic components and drawing products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |