CN103429388A - Co-Si-based copper alloy sheet - Google Patents
Co-Si-based copper alloy sheet Download PDFInfo
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- CN103429388A CN103429388A CN2012800153504A CN201280015350A CN103429388A CN 103429388 A CN103429388 A CN 103429388A CN 2012800153504 A CN2012800153504 A CN 2012800153504A CN 201280015350 A CN201280015350 A CN 201280015350A CN 103429388 A CN103429388 A CN 103429388A
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- 229910020711 Co—Si Inorganic materials 0.000 title claims abstract description 23
- 238000005096 rolling process Methods 0.000 claims abstract description 53
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 23
- 230000003746 surface roughness Effects 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 14
- 239000002932 luster Substances 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910000679 solder Inorganic materials 0.000 abstract description 18
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000005554 pickling Methods 0.000 description 46
- 238000005498 polishing Methods 0.000 description 46
- 238000000227 grinding Methods 0.000 description 19
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- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 235000019580 granularity Nutrition 0.000 description 9
- 238000000034 method Methods 0.000 description 9
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- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000021110 pickles Nutrition 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052802 copper 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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
-
- 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
- C22C9/10—Alloys based on copper with silicon as the next major constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
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- Chemical & Material Sciences (AREA)
- 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)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
To provide a Co-Si-based copper alloy sheet which has excellent solder wettability and undergoes the formation of fewer pinholes upon being soldered. A Co-Si-based copper alloy sheet containing 0.5-3.0 mass% of Co and 0.1-1.0 mass% of Si, with the remainder being Cu and unavoidable impurities, wherein a requirement represented by the following formula is fulfilled: [60 degrees specular glossiness G in the direction parallel to the rolling direction (RD)] - [60 degrees specular glossiness G in direction transverse to rolling direction (TD)] >= 90%.
Description
Technical field
The present invention relates to Co-Si series copper alloy plate.
Prior art
Require the electric/electronic device miniaturizations such as connector, and developed the Co-Si series copper alloy (Corson alloy) of excellent strength.Yet Co-Si is Corson alloy, in order by Co and Si, to generate precipitate, and need solid solution or the Ageing Treatment under high temperature, its surface forms firmly oxide scale film, and makes solder wettability deteriorated.In addition, due to the situation of carrying out stress relief annealing after final rolling also being arranged in Corson alloy, thereby oxide scale film is further grown up.Therefore, carry out pickling and oxide scale film is dissolved after final heat treatment, and then grind and remove oxide scale film (below, be called " pickling polishing grinding " more suitable) by polishing.
Based on above-mentioned situation, developed and a kind of surface roughness Ra has been defined as below 0.2 μ m, and Rt has been defined as below 2 μ m, and improved the Cu alloy material (patent documentation 1) of solder wettability.
In addition, develop a kind of Cu alloy material, it reduces owing to producing the concavo-convex solder wettability that makes of the ridge shape caused because of polishing on surface when carrying out above-mentioned pickling polishing grinding, thereby implement pickling or ungrease treatment before finish rolling, and make solder wettability improve (patent documentation 2).If carry out pickling or ungrease treatment before finish rolling, the crest location in the number of degrees distribution map of the concavo-convex composition of presentation surface, can occur in the positive side (protruding composition) of more leaning on of the average line of using than roughness curve (zero position in number of degrees distribution map), can make solder wettability, plating raising.
The prior art document
Patent documentation
Patent documentation 1: International Publication WO2010/13790 communique
Patent documentation 2: Japan's special permission No. 4413992 communique (0013 section).
Summary of the invention
Yet, in the situation that the technology that patent documentation 1 is put down in writing, even solder wettability is good, the oxide scale film of material surface also can't be removed fully, or owing to before final rolling, carrying out pickling, grinding, when foreign matter is pressed into because of rolling, can produce pin hole (pinhole) (part is the zone of attached solder not).If pin hole becomes failure welding easily occurs at most, if especially when Corson alloy is shaped to terminal welding portion produce pin hole, can cause failure welding.
In addition, in the situation that the technology that patent documentation 2 is put down in writing, owing to before finish rolling, must carrying out pickling or ungrease treatment, thereby operation becomes complicated, the productivity ratio variation.In addition, because Co-Si is that the oxide scale film of Corson alloy is very firm, thereby only with pickling, be difficult for making it to come off, and the technology of putting down in writing due to patent documentation 2 is only carry out pickling after the heat treatment operation of not ground or the operation of not carrying out pickling and grinding, thereby think that it can't remove the oxide scale film of material surface fully, and easily produce pin hole.
That is, the present invention completes in order to address the above problem, the few Co-Si series copper alloy plate of pin hole when its purpose is to provide a kind of solder wettability excellence and welding.
The inventor etc. carry out various research, found that: by the pickling polishing of using the thinner polishing wheel of texture (abrasive grains) to carry out after the final heat treatment of enough number of times, grind, remove the oxide scale film of material surface or the foreign matter be pressed into by rolling, and by making surface for thering is the anisotropic even surface of regulation, thereby the solder wettability excellence, and pin hole reduces.
For reaching above-mentioned purpose, Co-Si series copper alloy plate of the present invention is to contain the Co-Si series copper alloy plate that Co:0.5～3.0 quality %, Si:0.1～1.0 quality % and remainder consist of Cu and unavoidable impurity, and (60 degree mirror surface luster G(RD of rolling parallel direction))-(60 degree mirror surface luster G(TD of rolling vertical direction)) >=90%.
Surface roughness Ra (RD)≤0.07 μ m of preferred rolling parallel direction.
The surface roughness Rz(RD of preferred rolling parallel direction)≤0.50 μ m.
Preferably the crest location in the number of degrees distribution map of the concave-convex surface composition that means the rolling vertical direction, more lean on minus side (being recessed into a minute side) at the average line of using than roughness curve.
Preferably further contain 2.0 quality % following be selected from one kind or two or more in Mn, Fe, Mg, Ni, Cr, V, Nb, Mo, Zr, B, Ag, Be, Zn, Sn, mixed rare earth alloy (ミ ッ シ ュ メ タ Le) and P.
According to the present invention, the few Co-Si series copper alloy plate of pin hole in the time of can obtaining solder wettability excellence and welding.
The accompanying drawing explanation
Fig. 1 is an example of the manufacturing process of the Co-Si series copper alloy plate of expression embodiment of the present invention.
The number of degrees distribution map of the concave-convex surface composition that Fig. 2 is embodiment 4.
The number of degrees distribution map of the concavo-convex composition on the surface that Fig. 3 is embodiment 18.
The specific embodiment
Below, the Co-Si series copper alloy plate of embodiment of the present invention is described.It should be noted that, the % in the present invention means quality % without special instruction the time.
In addition, surface roughness Ra refers to JIS-B0601(2001) center line average roughness of defined, surface roughness Rz refers to the maximum height of this JIS defined.
At first, with reference to Fig. 1, technological thought of the present invention is described.Fig. 1 means an example of the Co-Si series copper alloy plate manufacturing process of embodiment of the present invention.
At first, if the copper alloy plate 2 after final heat treatment is imported to descaling baths 4, carry out pickling, at rolling parallel direction (RD) and the upper oxide scale film of rolling vertical direction (TD), roughly dissolve equably and make the thickness attenuation.Therefore, 60 of rolling parallel direction degree mirror surface luster G(RD after pickling) with 60 degree mirror surface luster G(TD of rolling vertical direction) roughly the same, their difference be G(RD)-G(TD) } ≒ 0(is with reference to Fig. 1 (a)).
Then, if use the copper alloy plate after polishing wheel 6 grinds pickling, can be with the scar of the sleek caused by polishing wheel.Upper in the rolling parallel direction (RD) of the direction of rotation as polishing wheel 6, the carrying out owing to grinding along with material surface, can disappear from material surface by the not consoluet oxide scale film of pickling, thereby material surface becomes smoothly, G(RD) becomes greatly.On the other hand, even also carry out the grinding of material surface on rolling vertical direction (TD), but because the material surface of TD direction is formed with the scar of the sleek caused by polishing wheel, thereby the surface smoothing degree is without large variation, G(TD) without large variation.Therefore, can distinguish, if G(RD)-G(TD)>0, and G(RD)-G(TD) >=90%, carrying out polishing grinding oxide scale film and removed fully, solder wettability improves, and pin hole during welding reduces.Although the upper limit of { G(RD)-G(TD) } does not have special provision, is below 400% in practicality.
It should be noted that the state of the material surface of 60 degree mirror surface luster reflection regulation areas.On the other hand, the material surface state on surface roughness (Ra etc.) reflection regulation straight line.Therefore think, 60 degree mirror surface luster specific surface roughness reflect that part is present in the state of the oxide scale film of material surface, foreign matter etc. more well.
It should be noted that, polishing wheel 6 is cylindric, and its surface attachment has abrasive grains.And, forward rotate the surface of the abrasive grains meeting cutting copper alloy plate 2 of polishing wheel 6 in the logical plate direction (Fig. 1 is from left to right) of copper alloy plate 2 by making polishing wheel 6.Therefore, carrying out polishing grinds the rotating speed etc. of the logical plate number of times of particle diameter (granularity) that the degree remove oxide scale film can be by abrasive grains, copper alloy plate 2, plate speed (linear velocity), polishing wheel 6 and is adjusted.
In addition, preferably the surface roughness Ra (RD) of rolling parallel direction is below 0.07 μ m.Ra(RD) be in the following situation of 0.07 μ m, sometimes be stained with the scolder time (zero cross time) and diminish.
In the present invention, also can stipulate the crest location in the number of degrees distribution map of concave-convex surface composition of rolling vertical direction.Herein, 2 records of the number of degrees distribution map of concave-convex surface composition and patent documentation are identical, are height the average line that will use from roughness curve as transverse axis, figure that frequency (determination data number) is drawn as the longitudinal axis.In addition, in the present invention, the height the average line of using from roughness curve take 0.05 μ m as interval (scale) set transverse axis, and the determination data number at each this interval is added up to as frequency, and is drawn.It should be noted that, " average line that roughness curve is used " is the JIS-B0601 defined.
Number of degrees distribution map is particularly to make as follows.(1) at first,, along the rolling vertical direction of sample, measure " height the average line of using from roughness curve ".; due to can each surface location obtain altitude information the average line that use from roughness curve (below; be called " determination data " more suitable), thereby can obtain crest location etc. according to the determination data of gained, and determination data is carried out the numerical value processing and calculates Ra, Rz.(2) height from " average line that roughness curve is used " being take to 0.05 μ m is divided as interval.(3) count this determination data number (number of degrees) at each above-mentioned 0.05 μ m interval.
It should be noted that, determination data with full-length 1.25 mm, cutoff (カ ッ ト オ Off value) 25 mm(according to JIS-B0601), sweep speed 0.1 mm/sec measures.Measure the surface roughness measurement machine (Surfcorder SE3400) that company of the little slope of use research institute manufactures, measured length is 1.25 mm, and the determination data number is 7500.
The concrete assay method of above-mentioned crest location is also identical with patent documentation 2 records, in the gained determination data, the composition that is made as (just) that height from " average line that roughness curve is used " is greater than to 0, will be less than the composition of (bearing) under being categorized as of 0 and the number of degrees are distributed and drawn.If the height (μ m) from " average line that roughness curve is used ", as transverse axis, and, using every 0.05 μ m total number of measurement according to number and the frequency that obtains repaints as the longitudinal axis, can be obtained to Fig. 2 and Fig. 3 (corresponding to Fig. 3 of patent documentation 2).In Fig. 2 and Fig. 3, if the position bracing wire that is 0 μ m at the height from " average line that roughness curve is used " of transverse axis, the crest location that can differentiate frequency is recessed into minute (minus side), or protruding composition (positive side), (or being 0).
Herein, the differentiation of above-mentioned " crest location " is carried out as follows.At first, the figure (with reference to Fig. 2, Fig. 3) of the height the average line of frequency-use from roughness curve, by value, the highest frequency is made as P1, and will be worth time high frequency and be made as P2.And (1) crest location refers to that for being recessed into minute (minus side) P1 and P2 all are positioned at the situation that the situation of minus side or P2/P1<99% and P1 are positioned at minus side.(2) crest location is that protruding composition (positive side) refers to that P1 and P2 all are positioned at the situation that the situation of positive side or P2/P1<99% and P1 are positioned at positive side.(3) crest location be 0 situation that refers to P2/P1 >=99% (but remove P1 and P2 all be positioned at minus side situation, and P1 and P2 all be positioned at the situation of positive side).
It should be noted that, the line that the height the average line of using from roughness curve is 0 μ m means the average line that roughness curve is used.
It should be noted that, the crest location of trying to achieve respectively according to the result of measuring for 3 times just is scattered in when negative, if measure medium wave peaks for 2 times, appears at (just) composition, regards protruding composition side as.
Fig. 2 is based on the practical measurement data of following embodiment 4, take frequency (%) as the longitudinal axis, the chart that repaints as transverse axis of the height (μ m) of take the average line of using from roughness curve.
In addition, Fig. 3 is based on the practical measurement data of following embodiment 18, take frequency (%) as the longitudinal axis, the chart that repaints as transverse axis of the height (μ m) of take the average line of using from roughness curve.
In the situation that Fig. 3, the average line that crest location in the known distribution map of the number of degrees at the concave-convex surface composition is used than roughness curve is more by positive side (protruding composition side), in the situation that Fig. 2, the average line that known above-mentioned crest location is used than roughness curve is more by minus side (being recessed into a minute side).That is, for example, in the present invention (Fig. 2, embodiment 4), even crest location is minus side (being recessed into a minute side), wetting characteristics is also good, and wetting characteristics be can't help crest location and determined.It should be noted that, pickle when embodiment 18 passes through the change pickling, just become crest location.
2 records of the assay method of above-mentioned surface roughness Ra, Rz and patent documentation are identical, with full-length 1.25 mm, cutoff 25 mm(according to JIS-B0601), sweep speed 0.1 mm/sec measured.Measure the surface roughness measurement machine (Surfcorder SE3400) that company of the little slope of use research institute manufactures, measured length is 1.25 mm, and the determination data number is 7500.It should be noted that, effects on surface roughness Ra, Rz carry out 3 times and measure, and get its mean value.
Then, other regulation and the composition of Co-Si series copper alloy plate of the present invention are described.
<form
Containing Co:0.5～3.0 quality %, Si:0.1～1.0 quality % and remainder is Cu and unavoidable impurity.
If the content of Co and Si is fewer than above-mentioned scope, Co
2The precipitation strength of Si is insufficient, can't realize the raising of intensity.On the other hand, if the content of Co and Si surpasses above-mentioned scope, make electric conductivity deteriorated, also make hot-workability deteriorated.The preferred content of Co is that 1.5～2.5 quality %, preferred content are 1.7～2.2 quality %.The preferred content of Si is that 0.3～0.7 quality %, preferred content are 0.4～0.55 quality %.
The Co/Si mass ratio is preferably 3.5～5.0, more preferably 3.8～4.6.If the Co/Si mass ratio, in this scope, can make Co
2Si separates out fully.
Preferably further contain add up to 2.0 quality % following be selected from one kind or two or more in Mn, Mg, Ag, P, B, Zr, Fe, Ni, Cr, V, Nb, Mo, Be, Zn, Sn and mixed rare earth alloy.If the total amount of above-mentioned element surpasses 2.0 quality %, following effect is saturated, and the productivity ratio variation.But, in the situation that the total amount of above-mentioned element is less than 0.001 quality %, effect is little, thus the total amount of preferred above-mentioned element be 0.001～2.0 quality %, more preferably 0.01～2.0 quality %, most preferably be 0.04～2.0 quality %.
Herein, Mn, Mg, Ag and P, owing to being to add trace, not damaging electrical conductivity ground and improve the article characteristic such as intensity, stress relaxation characteristics.These elements are mainly by the parent phase solid solution, bringing into play above-mentioned effect, but further bring into play effect by containing in second phase particles.
By adding B, Zr and Fe, also can improve the article characteristic such as intensity, electrical conductivity, stress relaxation characteristics, plating.These elements are mainly by the parent phase solid solution, bringing into play above-mentioned effect, but further bring into play effect by containing in second phase particles or by the second phase particles that forms new composition.
Ni, Cr, V, Nb, Mo, Be, Zn, Sn and mixed rare earth alloy are supplied characteristic mutually, and, not only to intensity, electrical conductivity, the manufacturing of improvement of the hot-workability that also counter stress relaxation property, bendability, plating, the miniaturization organized by ingot bar realize and so on is improved.
It should be noted that, cause in dysgenic scope in the characteristic to alloy of the present invention not, also can add in this specification the element of concrete record.
Then, an example of the manufacture method of Co-Si series copper alloy plate of the present invention described.At first, after the ingot bar that hot rolling is formed by copper, essential alloying element and then unavoidable impurity, carry out that face is cut and cold rolling, after carrying out solution treatment, carry out Ageing Treatment and make Co
2Si separates out.Then, by the final cold rolling specific thickness that is refined to, further carry out as required stress relief annealing, finally carry out pickling and carry out at once the polishing grinding.
Solution treatment for example can selected in the scope below 1000 ℃ more than 700 ℃.In addition, Ageing Treatment for example can be carried out 1～20 hour under 400 ℃～650 ℃.
In addition, final rolling degree of finish is preferably 5～50% and then be preferably 20%～30%.The crystal particle diameter of alloy material of the present invention is not particularly limited, and is generally below 3～20 μ m.The particle diameter of precipitate is 5 nm～10 μ m.
Embodiment
The ingot formed shown in casting table 1, being hot-rolled down to thickness 10 mm more than 960 ℃, after face is cut surperficial oxide skin, carry out cold rollingly, after more than 700 ℃, below 1000 ℃, carrying out solution treatment, under 400 ℃～650 ℃, implements the Ageing Treatment of 1～20 hour.Then, with working modulus 5%～40%, by the final cold rolling specific thickness that is refined to, and then carry out the stress relief annealing of 0.05～3 hour under 300～600 ℃, finally with the condition shown in table 1, carry out pickling and carry out at once the polishing grinding.It should be noted that, the pickle of the pickling before grinding for polishing is concentration 20～30 quality %, the aqueous solution of dilute sulfuric acid, hydrochloric acid or rare nitric acid below pH=1, and the dip time of pickling is made as to 60～180 seconds.Polishing is ground polishing material used and is the abrasive grains of using the oxidation aluminum, makes in nylon nonwoven fabrics to contain the material that aluminium oxide forms.And, use the polishing material that makes respectively sleek roughness (granularity of abrasive grains) change.The granularity of abrasive grains means the mesh quantity of every 1 inch of abrasive grains, by JIS R6001, is stipulated.For example, if granularity is 1000, the average grain diameter of abrasive grains is 18～14.5 μ m.It should be noted that, in embodiment 18, identical with other embodiment except the pickling that working concentration 40～50 quality %, aqueous solution of nitric acid below pH=1 grind as the pickling polishing.
Each sample of gained like this is carried out to the evaluation of each characteristic.
(1) Ra and Rz
According to JIS-B0601(2001), measure center line average roughness Ra and maximum height Rz.Mensuration is measured respectively rolling parallel direction (RD) and rolling vertical direction (TD).In mensuration, established standards length is that 1.25 mm, cutoff are that 0.25 mm(is according to above-mentioned JIS), sweep speed is 0.1 mm/sec, and the surface roughness measurement machine (Surfcorder 5E3400) that uses company of little slope research institute to manufacture, measured length is 1.25 mm, and the determination data number is 7500.
(2) number of degrees distribution map
Determination data for the rolling vertical direction of (1) gained, in determination data, being categorized as from " average line that roughness curve is used " the composition of (just) with under the composition of (bear), the height the average line that will use from roughness curve be take 0.05 μ m as scale drafting number of degrees distribution map.According to determination data, take frequency (%) as the longitudinal axis, the height (μ m) of take the average line of using from roughness curve repaints as transverse axis, and obtains Fig. 2 and Fig. 3.In Fig. 2 and Fig. 3, if the position bracing wire that the height the average line of using from roughness curve of transverse axis is 0 μ m, the crest that can differentiate frequency is recessed into minute (minus side), or protruding composition (positive side), (also or be 0).
(3) glossiness
60 degree mirror surface lusters, used Grossmeters according to JIS Z8741 (Japanese electric look industry is manufactured, trade name " PG-1M "), respectively rolling parallel direction RD, and rolling vertical direction TD on incidence angle 60 degree, measured.
Fig. 2 is the practical measurement data to embodiment 4, take frequency (%) as the longitudinal axis, the chart that repaints as transverse axis of the height (μ m) of take the average line of using from roughness curve.
In addition, Fig. 3 is the practical measurement data to following embodiment 18, take frequency (%) as the longitudinal axis, the chart that repaints as transverse axis of the height (μ m) of take the average line of using from roughness curve.
(3) scolder characteristic
(3-1) pinhole number
Pinhole number refers to, nonwetting scolder and in the quantity in the observable hole of substrate (Cu alloy material).If pinhole number becomes, failure welding easily occurs at most, the test of pinhole number, at dilute sulfuric acid aqueous solution pickling 10 mm with 10 quality % after wide sample, it be impregnated in to scolder is bathed with impregnating depth 12 mm, impregnating speed 25 mm/s, dip time 10 sec and while lifting, observe positive and negative with light microscope (50 times of multiplying powers), the pin hole quantity of the substrate that counting is visually observed, good by being made as below 5.
The scolder test is implemented according to JIS-C60068-2-54.Scolder is bathed consists of tin 60 wt%, plumbous 40 wt%, and then adds in right amount flux (flux) (rosin 25 wt%, ethanol 75 wt%), and to make solder temperature be 235 ℃ ± 3 ℃.
(3-2) be stained with the scolder time (T2 value)
Be stained with the time of scolder time (T2 value) till for wetting stress value vanishing, be stained with the scolder time shorter, scolder is more wetting.Test, after the dilute sulfuric acid aqueous solution pickling sample with 10 wt%, with impregnating depth 4 mm, impregnating speed 25 mm/s, dip time 10 sec, sample be impregnated in during the above-mentioned scolder of 235 ℃ ± 3 ℃ bathes, implemented according to JISC60068-2-54, and be stained with solder method (メ ニ ス コ グ ラ Off method) with arc surfaced and obtain and be stained with the scolder time.To be stained with the scolder time and be below 2.0 seconds to be made as solder wettability good.
Acquired results is shown in to table 1～table 3.It should be noted that, in " pre-treatment of finish rolling " of table 1, table 2, A method, B method are to utilize following condition to carry out the method for pickling polishing grinding.For example, embodiment 9 carries out pickling polishing grinding before finish rolling, and then also carries out pickling polishing grinding after finish rolling.Pickling polishing before finish rolling grind in pickling pickle used and the pickling polishing after above-mentioned finish rolling to grind pickle used identical.
The A method: number of times 1 time, plate speed 40 m/min, sleek roughness (abrasive grains) 1000 granularities, polishing wheel rotating speed 500 rpm are ground in polishing
The B method: number of times 3 times, plate speed 10 m/min, sleek roughness (abrasive grains) 2000 granularities, polishing wheel rotating speed 1400 rpm are ground in polishing.
It should be noted that, for a part of sample, before finish rolling, only made it impregnated in 10% aqueous sulfuric acid the pickling of 30 seconds.In addition, for a part of sample, before finish rolling, only made it impregnated in hexane the degreasing of 30 seconds.In addition, for other sample, do not carry out any processing before finish rolling.
From table 1～table 3: use the thinner polishing wheel of texture (abrasive grains) to carry out in the situation of each embodiment that the pickling polishing after the final heat treatment (stress relief annealing) of sufficient number of times grinds, the solder wettability excellence, and pin hole reduces.Each embodiment is { (60 degree mirror surface luster G(RD of rolling parallel direction))-(60 degree mirror surface luster G(TD of rolling vertical direction)) } >=90%, can think being pressed into of the oxide scale film of fully having removed material surface, foreign matter, and surface becomes level and smooth.
It should be noted that, in each embodiment, in abrasive grains be more than 2000 granularities, logical plate number of times more than 2 times, below plate speed 10 mpm, under the condition of rotating speed more than 1200 rev/mins, carry out pickling polishing grinding, certainly according to manufacturing installation, their most preferred range also can change.
On the other hand, fully do not carry out pickling polishing grinding in each comparative example, can't remove fully the oxide scale film of material surface or being pressed into of foreign matter.Therefore, in each comparative example, (60 degree mirror surface luster G(RD of rolling parallel direction))-(60 degree mirror surface luster G(TD of rolling vertical direction))<90%, pin hole increases, and oxide scale film is more residual, causes solder wettability deteriorated.
These worsening reasons, in the situation that comparative example 1,2,15,17,19 can think that the plate speed ground due to the pickling polishing surpasses the cause of 20 mpm.
In the situation that comparative example 3,5,8,20, can think that the logical plate number of times that grinds due to the pickling polishing is lower than the cause of 2 times.It should be noted that comparative example 20 has been implemented the pickling grinding with above-mentioned A method after final rolling.
In the situation that comparative example 13, can although think owing to having carried out pickling, but the cause of not carrying out the polishing grinding.
In the situation that comparative example 6,7, can think therefore almost can't be ground because the abrasive grains that the pickling polishing is ground is that 4000 granularities cause abrasive grains meticulous, cause Ra(RD) to reduce effect few.
In the situation that comparative example 11,12, can think that the rotating speed that grinds due to the pickling polishing is lower than the cause of 1200 rev/mins.
In the situation that comparative example 9,10, the too coarse pickling polishing abradant surface that causes of abrasive grains is coarse, and (60 degree mirror surface luster G(RD of rolling parallel direction))-(60 degree mirror surface luster G(TD of rolling vertical direction))<90%, pin hole increases, and is stained with scolder time variation.Can think that this is is 500 granularities owing to making the abrasive grains that the pickling polishing is ground, thus abrasive grains too coarse due to.
In the situation that comparative example 4,14,16,18,21, can think owing to after final rolling, not carrying out pickling polishing grinding, thereby the oxide scale film on not removed surface, being pressed into of foreign matter and maintain the surface state of rolling originally.It should be noted that, comparative example 21, except the roughness of the roller that makes final rolling attenuates, is manufactured in the same manner with each embodiment.
It should be noted that, in the situation that comparative example 16,18, owing to having carried out processing (pickling or degreasing) before finish rolling, and do not carry out pickling polishing grinding, thereby the average line used than roughness curve of crest location (in the number of degrees distribution map of the concavo-convex composition of presentation surface zero position) is more by positive side (protruding composition side).That is, these comparative examples mean the copper alloy plate of patent documentation 2.
In addition, in the situation that comparative example 4,13,16,21 was stained with the scolder time over 2.0 seconds, solder wettability is also deteriorated, and its reason can be thought to grind owing to once also carrying out pickling and polishing, thereby oxide scale film more residues in the cause of metal surface.(it should be noted that, comparative example 16 is equivalent to the condition of patent documentation 2 records).
Claims (5)
1.Co-Si the series copper alloy plate, it is to contain the Co-Si series copper alloy plate that Co:0.5～3.0 quality %, Si:0.1～1.0 quality % and remainder consist of Cu and unavoidable impurity,
(60 degree mirror surface luster G(RD of rolling parallel direction))-(60 degree mirror surface luster G(TD of rolling vertical direction)) >=90%.
2. Co-Si series copper alloy plate as claimed in claim 1, wherein, the surface roughness Ra of rolling parallel direction (RD)≤0.07 μ m.
3. Co-Si series copper alloy plate as claimed in claim 2, wherein, the surface roughness Rz(RD of rolling parallel direction)≤0.50 μ m.
4. Co-Si series copper alloy plate as described as any one in claim 1～3, wherein, the crest location in the number of degrees distribution map of the concave-convex surface composition that means the rolling vertical direction, the average line of using than roughness curve more by minus side (being recessed into a minute side).
5. as the Co-Si series copper alloy plate of any one in claim 1～4, its further contain 2.0 quality % following be selected from one kind or two or more in Mn, Fe, Mg, Ni, Cr, V, Nb, Mo, Zr, B, Ag, Be, Zn, Sn, mixed rare earth alloy and P.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-070183 | 2011-03-28 | ||
| JP2011070183A JP4831552B1 (en) | 2011-03-28 | 2011-03-28 | Co-Si copper alloy sheet |
| PCT/JP2012/055830 WO2012132805A1 (en) | 2011-03-28 | 2012-03-07 | Co-Si-BASED COPPER ALLOY SHEET |
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| Publication Number | Publication Date |
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| CN103429388A true CN103429388A (en) | 2013-12-04 |
| CN103429388B CN103429388B (en) | 2016-10-05 |
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| CN201280015350.4A Active CN103429388B (en) | 2011-03-28 | 2012-03-07 | Co-Si series copper alloy plate |
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|---|---|
| US (1) | US20140065441A1 (en) |
| EP (1) | EP2679341B1 (en) |
| JP (1) | JP4831552B1 (en) |
| KR (1) | KR101569262B1 (en) |
| CN (1) | CN103429388B (en) |
| TW (1) | TWI450985B (en) |
| WO (1) | WO2012132805A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI621719B (en) * | 2015-11-04 | 2018-04-21 | Jx Nippon Mining & Metals Corp | Metal mask material and metal mask |
| CN109593989A (en) * | 2017-10-03 | 2019-04-09 | Ｊｘ金属株式会社 | Cu-Ni-Sn series copper alloy foil, the camera model for stretching copper product, electronic equipment part and auto-focusing |
| CN109698299A (en) * | 2017-10-20 | 2019-04-30 | 住友化学株式会社 | Nonaqueous electrolytic solution secondary battery spacer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6126791B2 (en) | 2012-04-24 | 2017-05-10 | Ｊｘ金属株式会社 | Cu-Ni-Si copper alloy |
| TWI612691B (en) * | 2013-09-02 | 2018-01-21 | Furukawa Electric Co Ltd | Substrate for lead frame for optical semiconductor device, manufacturing method thereof, lead frame for optical semiconductor device therefor, method for manufacturing the same, and optical semiconductor device |
| KR20160117210A (en) | 2015-03-30 | 2016-10-10 | 제이엑스금속주식회사 | Cu-Ni-Si BASED ROLLED COPPER ALLOY AND METHOD FOR MANUFACTURING THE SAME |
| US20170208680A1 (en) * | 2016-01-15 | 2017-07-20 | Jx Nippon Mining & Metals Corporation | Copper Foil, Copper-Clad Laminate Board, Method For Producing Printed Wiring Board, Method For Producing Electronic Apparauts, Method For Producing Transmission Channel, And Method For Producing Antenna |
| JP7296757B2 (en) * | 2019-03-28 | 2023-06-23 | Ｊｘ金属株式会社 | Copper alloys, copper products and electronic equipment parts |
| CN112695219A (en) * | 2020-12-11 | 2021-04-23 | 中南大学 | Method for improving strength and conductivity of Cu-Cr-Nb alloy for smelting and casting |
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Also Published As
| Publication number | Publication date |
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| KR20130122667A (en) | 2013-11-07 |
| TW201245471A (en) | 2012-11-16 |
| CN103429388B (en) | 2016-10-05 |
| WO2012132805A1 (en) | 2012-10-04 |
| EP2679341A4 (en) | 2014-12-24 |
| EP2679341B1 (en) | 2016-07-27 |
| TWI450985B (en) | 2014-09-01 |
| JP2012201963A (en) | 2012-10-22 |
| KR101569262B1 (en) | 2015-11-13 |
| EP2679341A1 (en) | 2014-01-01 |
| US20140065441A1 (en) | 2014-03-06 |
| JP4831552B1 (en) | 2011-12-07 |
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