CN101275190A - Copper alloy having superior hot workability and method for producing same - Google Patents
Copper alloy having superior hot workability and method for producing same Download PDFInfo
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- CN101275190A CN101275190A CNA2007100898024A CN200710089802A CN101275190A CN 101275190 A CN101275190 A CN 101275190A CN A2007100898024 A CNA2007100898024 A CN A2007100898024A CN 200710089802 A CN200710089802 A CN 200710089802A CN 101275190 A CN101275190 A CN 101275190A
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Abstract
The present invention provides a copper alloy for an electronic component having excellent hot workability which particularly has excellent strength and electrical conductivity without deteriorating its bending workability. The copper alloy having excellent hot workability has a composition comprising, by mass, 1.0 to 2.0% Ni and 0.1 to 0.5% P, and in which the ratio between the Ni content and the P content, Ni/P is 4.0 to 6.5, and also, comprising 0.03% to 0.45% Cr or 0.005 to 0.070% B, and the balance Cu with inevitable impurities. The copper alloy may further comprise one or more kinds selected from Sn and In by 0.01 to 1.0% in total, preferably, the extension length is over 700 MPa, and the conductive ratio is 40% IACS and excellent hot workability and excellent intensity.
Description
Technical field
The present invention relates to the copper alloy that has superior hot workability that is used for electronic instrument part of high strength, high conductivity, be particularly related to small-sized, highly integrated semiconductor instrument lead-in wire with and terminal connector with in the copper alloy, the electronic component-use copper alloy that can not damage bendability, particularly intensity, excellent electric conductivity, has superior hot workability.
Background technology
The material that copper and copper alloy are used as electronic units such as junctor, lead terminal and flexible circuit base board is widely used in multiple use, in order to adapt to the high performance and the miniaturization shellization of the information instrument that fast-developing ITization causes, to the requirement of copper and the copper alloy higher characteristic of proposition (intensity, bendability, electroconductibility).
In addition, highly integrated along with IC, the a large amount of high semiconductor elements of current consumption that use of beginning are brought into use good Cu-Ni-Si system of exothermicity (electroconductibility) or precipitation type alloys such as Cu-Fe-P, Cu-Cr-Sn, Cu-Ni-P in the lead frame material of semiconductor instrument.Above-mentioned Cu-Ni-P is an alloy because fine the separating out of Ni-P based compound strengthened, and points out in the patent documentation 1, and Ni, P, Mg in the adjustment alloy become component, has obtained possessing the alloy of intensity and electroconductibility, proof stress slackness.
Patent documentation 1 TOHKEMY 2000-273562 communique
Summary of the invention
In general, in the casting of copper alloy, for example continuously or in the semicontinuous casting, ingot casting pulls out heat by mold, except several mm on ingot top layer, just solidify for a moment inside.At this moment, when solidifying and in the process of cooling after solidifying the alloying element that contains of overrun in crystal boundary and intragranular crystallization or separate out.The copper alloy that contains the P more than the Ni and 0.2% more than 1.0%, advantage with high-strength high conductivity, but owing to contain the Ni-P composition more than the solid solution limit in the Cu parent phase under the room temperature in a large number, the Ni-P based compound is usually in the crystal boundary crystallization or separate out when therefore making ingot casting.And, at Cu-Ni-P is that the crystal boundary crystallization of alloy or the Ni-P based compound of separating out are lower than the Cu fusing point of parent phase, thus these copper alloys solidify inhomogeneously, internal modification takes place, because its stress and external force produce destruction in the part of Ni-P based compound, cause cracking at casting, cooling stages.In addition, when hot rolled heats also since the Ni-P based compound prior to parent phase softening or liquid phaseization, ftracture equally.
But, since the Cu-Ni-P of patent documentation 1 be alloy consist of Ni:0.01～1.0%, P:0.01～0.2%, therefore do not recognize the problems referred to above especially.
The object of the present invention is to provide Cu-Ni-P is alloy, the cracking that it can prevent to cast, take place in cooling, hot-work heating or the hot-work, and high temperature ductility excellence, hot workability is good.
The inventor has carried out research repeatedly to achieve these goals, found that, by specific following structure, can obtain having the excellent hot workability and the intensity of excellence and the Cu-Ni-P of electroconductibility is alloy.
The present invention relates to high-strength high conductivity electronic machine copper alloy, this copper alloy is the copper alloy that has superior hot workability, it is characterized in that, contain Ni:1.0%～2.0% (in this specification sheets, the expression component proportions % be quality %.), P:0.10%～0.50%, the content of Ni and P is 4.0～6.5 than Ni/P, and Cr be 0.03%～0.45% or B be 0.005～0.070%, surplus is made of Cu and unavoidable impurities, shows that preferred tensile strength is more than the 700MPa and specific conductivity is having superior hot workability of the above characteristic value of 40%IACS.When in mentioned component is formed, containing 0.01%～1.0% Sn, among the In more than one, show that preferred tensile strength is that the above and specific conductivity of 750MPa is the above characteristic value of 40%IACS.
The present invention is by being Cr or the B that adds specified quantitative in the alloy at Cu-Ni-P, suppresses the Ni-P based compound to the crystallization of crystal boundary or separate out, and the speed of cooling during preferably by the control casting suppresses the thick Ni-P-Mg-B system and the generation of P-B based compound.By adopting above-mentioned formation, improve the high-temperature brittleness on grain circle, realize the raising of hot workability.
The copper alloy that has superior hot workability of the present invention is used for the high-strength high conductivity electronic machine can play excellent effect.
Description of drawings
Fig. 1 is the outward appearance photo of the sample edge part after the hot rolling of example 3 of the present invention is tested.
Fig. 2 is the outward appearance photo of the sample edge part after the hot rolling of comparative example 8 is tested.
Fig. 3 is the outward appearance photo of the sample edge part after the hot rolling of comparative example 9 is tested.
Fig. 4 is the outward appearance photo of the sample edge part after the hot rolling of comparative example 10 is tested.
Embodiment
Below, the reason and the effect thereof of the numerical range that the one-tenth that limits copper alloy among the present invention is grouped into together describe.
The Ni amount
Ni has intensity and the stable on heating effect of guaranteeing alloy, and the Ni-P based compound that itself and aftermentioned P are formed is separated out, and helps the raising of alloy strength.But its content can not get ideal intensity less than 1.0% o'clock, and on the contrary, when containing Ni greater than 2.0%, hot workability reduces, and the bendability and the specific conductivity of product obviously reduce simultaneously.And also can increase the big Ni-P of major diameter is the area occupation ratio of precipitate, therefore not preferred.The content of Ni and P and (Ni+P) greater than 2.50% o'clock, the crystallization content of oversize particle increases, and then separating out in the ageing treatment become significantly, and size becomes difficulty for the control of separating out of the following fine Ni-P of 50nm.Therefore, the Ni content of alloy of the present invention is 1.0%～2.0%, is preferably 1.1～1.8%.
The P amount
The compound that P forms itself and Ni is separated out, and improves alloy strength and thermotolerance.When P contained quantity not sufficient 0.10%, separating out of compound was insufficient, so can not obtain ideal intensity.On the contrary, when P content greater than 0.50% the time, hot workability reduces, specific conductivity significantly reduces simultaneously.And also can increase the big Ni-P of major diameter is the area occupation ratio of precipitate, therefore not preferred.Therefore, the P content of alloy of the present invention is 0.1%～0.5%, is preferably 0.2～0.4%.
The Ni/P ratio
Even the content of Ni and P is in above-mentioned limited range, if Ni and P contain suitable stoichiometric composition that ratio Ni/P exceeds the Ni-P based compound than, when being less than 4.0, the solid solution capacity of P increases, and increases greater than the solid solution capacity of Ni under 6.5 the situation, specific conductivity significantly reduces, and is therefore not preferred.Therefore, the Ni/P of alloy of the present invention ratio is 4.0～6.5, preferred 4.5～6.0.
Ni-P is the size and the area occupation ratio of precipitate
If with Ni-P is that the major diameter of precipitate is that a (nm), minor axis are b (nm), final a before cold rolling is less than the precipitate of 20nm, carries out above rolling in machining deformation η=2 and adds man-hour, and precipitate is solid solution again in copper, and specific conductivity is reduced, and is not preferred.On the other hand, final cold rolling preceding a is the above precipitate of 20nm, even carry out the above rolling processing in machining deformation η=2, also is difficult to solid solution again, exists as the precipitate more than the 10nm.Precipitate more than the above-mentioned 20nm is little in the variation of rolling front and back size, major diameter a before particularly rolling keeps the major diameter greater than 50nm after rolling greater than the precipitate of 50nm, but, therefore be difficult to obtain precipitation strength and work strengthening because the dispersion of the precipitate in the alloy becomes excessive at interval.
It should be noted that, along being parallel to rolling direction final cold rolling preceding alloy bar is cut to certain thickness right angle, use image analysis apparatus that major diameter a is measured cross-sectional image as all precipitates more than the 5nm, total the mean value separately of the major diameter of the precipitate that records and minor axis is exactly major diameter a and minor axis b.In addition, establishing rolling preceding thickness of slab is t
0, when the thickness of slab after rolling was t, machining deformation η was with η=ln (t
0/ t) represent.
As mentioned above, the final cold rolling preceding Ni-P of alloy of the present invention is that the preferred major diameter a of size of precipitate is 20nm～50nm.
If represent the long-width ratio of precipitate with a/b, a/b was greater than 5 o'clock, if carry out the above rolling processing in η=2, then precipitate solid solution again in copper reduces specific conductivity.Therefore, the long-width ratio a/b of precipitate is preferably 1～5, and more preferably 1～3.
In order to prevent the reduction of intensity and specific conductivity, final a after cold rolling is that 10nm～50nm and a/b are 1～5.
But, be difficult to make all precipitates in the preferable range of above-mentioned a and a/b, the ratio that the precipitate that therefore is positioned at the scope of above-mentioned a and a/b accounts for total precipitate is important.So, be area occupation ratio C if will be arranged in the ratio of area summation that the area summation of precipitate of the preferable range of above-mentioned a and a/b accounts for total precipitate of alloy, area occupation ratio C then of the present invention is preferably more than 80%.
Area occupation ratio is meant that less than 80% situation a is greater than the precipitate of 50nm or less than a large amount of situations about existing of the precipitate of 20nm.The crystallisate that produces when for example a is greater than the precipitate of 50nm or melt-casting before hot rolling heating and solution treatment in not solid solution, the above Ni-P of residual 1000nm is that particle (crystallisate) is when existing in a large number, the size that helps to improve intensity is that the dispersion of fine precipitate of 20～50nm is big at interval, therefore, utilize the processing curing of rolling processing can not obtain ideal intensity.On the other hand, a is less than the precipitate of 20nm, and through rolling processing and solid solution again, so specific conductivity significantly reduces.
The Cr amount
When general speed of cooling when Cu-Ni-P is solidifying of alloy was slow, for example 1100 ℃～950 ℃ speed of cooling was during less than 30 ℃/minute, and the Ni-P based compound is accompanied by intensification, thickization in the crystal boundary crystallization, so not preferred.
Cr suppresses the Ni-P based compound to the crystallization of crystal boundary or separate out when Cu-Ni-P is solidifying of alloy or when process of cooling after solidifying and hot worked heating, improve the hot workability of alloy.But, if its content less than 0.03%, then can't obtain the effect of improving of hot workability, on the other hand, if Cr content greater than 0.45%, then compound such as Ni-P-Cr, Cr-P is in fusing or solidify middle generation or produce the crystallisate of Cr.These contain compound and the crystallisate not solid solution in the Cu parent phase in solution treatment of Cr, so the Ni-P based compound of separating out in ageing treatment minimizing, cause alloy strength to reduce.Compound such as Ni-P-Cr, Cr-P becomes major diameter in product be inclusion more than the 5 μ m, remains in the product, and the rimose root when becoming surface imperfection, the bending machining of product, the root of the defective when plating is handled are therefore not preferred.Therefore, the Cr content of alloy of the present invention is 0.03%～0.45%, is preferably 0.05%～0.30%.
Above-mentioned major diameter is that the existence of inclusiones such as compound such as the above Ni-P-Cr compound of 5 μ m, Cr-P is not preferred, and preferred major diameter is every 1mm greater than the number of the inclusion of 50 μ m
2The number of the inclusion of 0 and major diameter 5～50 μ m is every 1mm
2Below 100, more preferably the number of the inclusion of major diameter 5～50 μ m is every 1mm
2Below 50.It should be noted that the major diameter of precipitate of above-mentioned Ni-P-Cr compound, Cr-P compound and the major diameter that Ni-P is precipitate measure equally.
The B amount
Add B and also can improve hot workability with replaced C r.B suppresses the Ni-P based compound to the crystallization of crystal boundary or separate out when Cu-Ni-P is solidifying of alloy or when process of cooling after solidifying and hot worked heating, improve the hot workability of alloy.But, if its content less than 0.005%, then can't obtain the effect of improving of hot workability, on the other hand, if B content greater than 0.070%, then compound such as Ni-P-B, B-P as inclusion in fusing or solidify middle generation.These compounds that contain B are accompanied by intensification usually, thickization is in the crystal boundary crystallization or separate out, not solid solution in the Cu parent phase in solution treatment, so the Ni-P based compound of separating out in the ageing treatment reduces, and causes alloy strength to reduce.Compound such as Ni-P-B, B-P becomes major diameter in product be inclusion more than the 5 μ m, remains in the product, and the rimose root when becoming surface imperfection, the bending machining of product, the root of the defective when plating is handled are therefore not preferred.Therefore, the B content of alloy of the present invention is 0.005%～0.070%, is preferably 0.007%～0.060%.
Inclusion
" inclusion " of the present invention be meant Cu-Ni-P be crystal boundary in the alloy and/or intragranular crystallization or separate out, be the crystallisate of principal constituent with Ni-P-B compound, B-P compound etc., and the fine Ni-P based compound that is not included in the intragranular crystallization or separates out.The major diameter of inclusion is meant that the size in the rolling parallel cut is the average major diameter of the above inclusion of 5 μ m.
If there be the inclusion of major diameter greater than 50 μ m, the rimose root when then becoming bending machining makes the bendability variation of product.Therefore, the preferred major diameter of copper alloy of the present invention is every 1mm greater than the number of the inclusion of 50 μ m
20.In addition, be the inclusion of 5～50 μ m if there is major diameter, the B that then contains in the inclusion measures increase, can't obtain the adding purpose of B, promptly suppress the crystallization effect of Ni-P based compound to crystal boundary.Therefore, the preferred major diameter of copper alloy of the present invention is that the number of the inclusion of 5～50 μ m is every 1mm
2Below 100, more preferably below 50.
Sn, In amount
The effect of Sn and In amount is that all little amplitude reduces the electroconductibility of alloy, mainly improves intensity by strengthening solid solution.Therefore, add as required these metals more than one, but when the total amount of its content less than 0.01% the time, can not obtain by strengthening the effect that solid solution improves intensity, on the other hand, be 1.0% when above when adding total amount, the specific conductivity and the bendability of alloy significantly reduce.For this reason, two or more Sn and the In amounts of interpolation or compound interpolation is 0.01%～1.0% separately, and preferred total amount is 0.05%～0.8%.It should be noted that these elements are the element that deliberately adds in the present invention, are not considered as unavoidable impurities.
The O amount
O reacts with Cr easily in alloy, when O exists with the state of oxide compound in alloy, can't obtain the additive effect of Cr.P, B also are easy to oxidized, if particularly P is oxidized, then the precipitate of Ni-P reduces, and cause intensity to reduce.Therefore, the O content of alloy of the present invention is below 0.0050%, and is preferred below 0.0030%.
Tensile strength and specific conductivity
Having superior hot workability of copper alloy of the present invention more has excellent electroconductibility, tensile strength, bendability concurrently.The tensile strength of copper alloy of the present invention is preferably more than the 700MPa, and more preferably more than the 750MPa, its upper limit is generally about 950MPa.In addition, specific conductivity is preferably more than the 40%IACS, and more preferably more than the 45%IACS, its upper limit is generally about 65%IACS.
The speed of cooling when solidifying and the size of inclusion
The Cu-Ni-P that satisfies the invention described above important document is an alloy, can cast at the ingot casting that those skilled in the art adopt usually in the mill, hot rolling, solution treatment, middle cold rolling, ageing treatment, finally cold rolling, in the elimination strain annealing etc., by selecting suitably to select Heating temperature, time, speed of cooling, manufacturings such as rolling degree of finish, but for the Cu-Ni-P-B that adds 0.005～0.070% B is alloy, usually the device that the setting rate in the continuous or semicontinuous casting of carrying out adopts according to solidification stages, mode and difference, and when not adopting the situations such as the formula that pours of cooling homogenization method, in the outside and the inboard difference that produces of ingot casting.For example, (inject molten copper among the Φ 700 * h1500mm) and under the situation of the formula that pours of solidifying, 1100 ℃～950 ℃ speed of cooling are about 1 ℃/minute at mold made of iron.
Solidification temperature range during the casting of copper alloy of the present invention is preferably 1100 ℃～950 ℃, if the speed of cooling in this cooling temperature scope is slow, then Ni-P-B system and/or P-B based compound are easy to generate in solidification stages thickly, might can't see the raising of adding the hot rolling that B causes.
Above-mentioned is as seen following relevant in inclusion number and the hot rolling of principal constituent with Ni-P-B system and/or P-B based compound.Will cast, among the instrumentation result of the inclusion of sample that 1100 ℃～950 ℃ speed of cooling in the solidification stages obtains in 850 ℃ of heating after 1 hour, water-cooled less than 20 ℃/minute ingot casting, major diameter is that the number of the inclusion of 5～50 μ m is every 1mm
2More than 100 or major diameter be every 1mm greater than the number of the inclusion of 50 μ m
21 when above, under 850 ℃ hot rolling, also ftracture even if added the alloy of the B of specified amount.Therefore, 1100 ℃～950 ℃ speed of cooling in casting, the solidification stages is preferably more than 20 ℃/minute.In addition, in order not make the bendability deterioration of alloy, owing to can suppress thick the separating out of Ni-P-B based compound and/or P-B based compound, 1100 ℃～950 ℃ speed of cooling in preferred casting, the solidification stages is more than 30 ℃/minute.It should be noted that the defective that pore causes increases owing to be unable to catch up with the supply of molten copper to solidification shrinkage portion greater than 1500 ℃/minute speed of cooling, therefore not preferred.
When having added the casting of copper alloy of the present invention of Cr, solidification temperature range is preferably 1100 ℃～950 ℃, if the speed of cooling in this cooling temperature scope is slow, then Ni-P system and/or Ni-P-Mg based compound are easy to generate in solidification stages thickly, might can't see the raising of adding the hot rolling that Cr causes.
Embodiment
Cu-Ni-P-Cr is alloy (table 1)
The manufacturing of sample
With electrolytic copper or oxygen free copper is main raw material, with nickel (Ni), 15%P-Cu mother alloy (P), 10%Cr-Cu mother alloy (Cr), tin (Sn), to plug with molten metal (In) be auxiliary material, utilize high frequency melting furnace, melt in a vacuum or in the argon gas, make cast iron mold, be cast as the ingot casting of 45 * 45 * 90mm.Carry out the hot rolling test of ingot casting, for the rimose ingot casting does not take place under the hot rolling, according to hot rolling and solution treatment, ageing treatment, middle cold rolling, ageing treatment, finally order cold rolling, that eliminate strain annealing is implemented to handle, and makes the flat board of thickness 0.15mm.The different plates test film that collects is tested, and carries out the evaluation of " intensity " and " specific conductivity ".
The hot workability evaluation of ingot casting:
By hot rolling evaluation " hot workability ".That is, ingot casting is cut to 45 * 45 * 25mm, 850 ℃ of heating were carried out the hot rolling test of 3 passages after 1 hour, thickness were rolled by 25mm be 5mm.For the surface and the edge of the sample after the hot rolling, visual visible rimose situation note is done " cracking is arranged ", there are not cracking, level and smooth situation note to do " not having cracking " on surface and edge.
The evaluation of physical property of test film:
For " intensity ", use No. 13 B test films by the tension test of JIS Z 2241 regulations, measure tensile strength.
" specific conductivity " uses the resistance of 4 terminal method determination test sheets, represents with %IACS.
" bendability " estimated with 90 degree W pliability tests.Test uses the anchor clamps of R=0.1mm to carry out 90 degree bending machining under the loading of 50kN based on CES-M0002-6.For the evaluation of bend, with the situation of observation by light microscope central part angle surface, the rimose note will take place do *, the note that fold takes place is △, and good note does zero.Bending axis and rolling direction meet at right angles (Good Way).
Ni-P is the evaluation of precipitate:
Use scanning electronic microscope and transmission electron microscope, final cold rolling preceding alloy bar is parallel to rolling direction is cut to certain thickness right angle, observe the precipitate in cross section from 10 visuals field.When the precipitate size is 5～50nm with 500,000 times～700,000 times the visual field (about 1.4 * 10
10～2.0 * 10
10Nm
2) take pictures, when the precipitate size is 100～2000nm with 50,000 times～100,000 times the visual field (about 1.0 * 10
13～2.0 * 10
13Nm
2) take pictures.Image to the photo taken uses image analysis apparatus (Nireco of Co., Ltd. system, trade(brand)name Luzex), is that precipitate more than the 5nm is measured its major diameter a, minor axis b and area respectively to all major diameter a.Select 100 at random by these precipitates, obtain average ata and the average bta of minor axis and the mean aspect ratio ata/bta that obtains by them of the major diameter of total precipitate, respectively as major diameter a, minor axis b and long-width ratio a/b.With major diameter a is the total area of the area summation of all precipitates more than the 5nm as total precipitate.With major diameter a is that 10nm～50nm, long-width ratio a/b are that the ratio of the area summation of 1～5 the precipitate total area that accounts for this total precipitate is as area occupation ratio C (%).
It should be noted that, by finally cold rolling (usually machining deformation η=more than 2), confirm major diameter be the following Ni-P of 20nm be precipitate or major diameter greater than 20nm but long-width ratio greater than 3 precipitate solid solution, but 20nm is above and long-width ratio to be 1～3 precipitate also keep its major diameter, minor axis and long-width ratio final after cold rolling.In addition, the area occupation ratio C of precipitate is also because greater than the not solid solution of precipitate of 200nm, and is therefore final also almost constant after cold rolling.
The copper alloy that is grouped into for the one-tenth shown in the table 1 describes the embodiment of the high-strength high-conductive copper alloy that has superior hot workability that the present invention relates to comparative example.Alloy embodiment 1～9 of the present invention does not ftracture when hot rolling, has excellent intensity and specific conductivity.On the other hand, if the result of research comparative example 10～22 then for comparative example 10～13, does not add or adds the Cr less than specified amount, so under the hot rolling cracking taken place.The P addition of comparative example 14 is greater than 0.50%, and the addition summation of the Sn of comparative example 15 and In is greater than 1.0%, and the addition of the Sn of comparative example 16 amounts to greater than 1.0%, therefore ftractures when hot rolling respectively.The scope that the Ni addition of comparative example 17, the P addition of comparative example 18 exceed the present invention's regulation is lower, so intensity is low.The Ni/P ratio of comparative example 19 exceeds higher, so the increase of the solid solution capacity of Ni, and the reduction of specific conductivity takes place, and the amount of precipitate is few, and intensity is also low.The Ni/P of comparative example 20 relatively exceeds suitable ratio of components in the lowland, and the solid solution capacity of P increases, and the reduction of specific conductivity takes place.The Ni addition of comparative example 21 is greater than 2.0%, and the addition of P is greater than 0.50%, so ftractures during hot rolling.The Cr addition of comparative example 22 is greater than 0.45%, compound such as Ni-P-Cr, Cr-P or Cr crystallization or separate out when solidifying, and the precipitate amount of Ni-P system reduces thus, and intensity and specific conductivity are low, and bendability is poor.
Cu-Ni-P-B is an alloy
The present invention's example and comparative example 1～18 (table 2)
The manufacturing of sample (a):
With electrolytic copper or oxygen free copper is main raw material, with nickel (Ni), 15%P-Cu mother alloy (P), 2%B-Cu mother alloy (B), tin (Sn), indium (In) is auxiliary material, utilize high frequency melting furnace, melt in a vacuum or in the argon gas, use the mold of material cast iron, be cast as the ingot casting of 45 * 45 * 90mm.Carry out the hot rolling test of ingot casting, for the rimose ingot casting does not take place under the hot rolling, according to hot rolling and solution treatment, ageing treatment, middle cold rolling, ageing treatment, finally order cold rolling, that eliminate strain annealing is implemented to handle, and makes the flat board of thickness 0.15mm.The different plates test film that collects is tested, and carries out the evaluation of " intensity ", " specific conductivity ", " bendability ".
The hot workability evaluation (a) of ingot casting:
By hot rolling evaluation " hot workability ".That is, ingot casting is cut to 45 * 45 * 25mm, 850 ℃ of heating were carried out the hot rolling test of 3 passages after 1 hour, thickness were rolled by 25mm be 5mm.For the surface and the edge of the sample after the hot rolling, visual visible rimose situation note is done " cracking is arranged ", there are not cracking, level and smooth situation note to do " not having cracking " on surface and edge.
The evaluation of physical property of test film (a):
For " intensity ", use No. 13 B test films by the tension test of JIS Z 2241 regulations, measure tensile strength.
" specific conductivity " uses the resistance of 4 terminal method determination test sheets, represents with %IACS.
" bendability " estimated with 90 degree W pliability tests.Test uses the anchor clamps of R=0.1mm to carry out 90 degree bending machining under the loading of 50kN based on CES-M0002-6.For the evaluation of bend, with the situation of observation by light microscope central part angle surface, the rimose note will take place do *, the note that fold takes place is △, and good note does zero.Bending axis and rolling direction meet at right angles (Good Way).
Ni-P is the evaluation (a) of precipitate:
Use scanning electronic microscope and transmission electron microscope, final cold rolling preceding alloy bar is parallel to rolling direction is cut to certain thickness right angle, observe the precipitate in cross section from 10 visuals field.When the precipitate size is 5～50nm with 500,000 times～700,000 times the visual field (about 1.4 * 10
10～2.0 * 10
10Nm
2) take pictures, when the precipitate size is 100～2000nm with 50,000 times～100,000 times the visual field (about 1.0 * 10
13～2.0 * 10
13Nm
2) take pictures.Image to the photo taken uses image analysis apparatus (Nireco of Co., Ltd. system, trade(brand)name Luzex), is that precipitate more than the 5nm is measured its major diameter a, minor axis b and area respectively to all major diameter a.Select 100 at random by these precipitates, obtain average ara and the average bta of minor axis and the mean aspect ratio ata/bta that obtains by them of the major diameter of total precipitate, respectively as major diameter a, minor axis b and long-width ratio a/b.With major diameter a is the total area of the area summation of all precipitates more than the 5nm as total precipitate.With major diameter a is that 10nm～50nm, long-width ratio a/b are that the ratio of the area summation of 1～5 the precipitate total area that accounts for this total precipitate is as area occupation ratio C (%).
It should be noted that, by finally cold rolling (usually machining deformation η=more than 2), confirm major diameter be the following Ni-P of 20nm be precipitate or major diameter greater than 20nm but long-width ratio greater than 3 precipitate solid solution, but 20nm is above and long-width ratio to be 1～3 precipitate also keep its major diameter, minor axis and long-width ratio final after cold rolling.In addition, the area occupation ratio C of precipitate is also because greater than the not solid solution of precipitate of 200nm, and is therefore final also almost constant after cold rolling.
The copper alloy that is grouped into for the one-tenth shown in the table 2 describes the embodiment of the high-strength high-conductive copper alloy that has superior hot workability that the present invention relates to comparative example.
Alloy embodiment 1～6 of the present invention does not ftracture when hot rolling, has excellent intensity and specific conductivity.
On the other hand, for comparative example 7～18, be the alloy of the composition that exceeds alloy composition scope of the present invention or Ni/P ratio.Comparative example 7～10 does not add or adds the B less than specified amount, so under the hot rolling cracking has taken place.The Ni addition of comparative example 11 is greater than 2.0%, and the P addition of comparative example 12 is greater than 0.50%, and the addition summation of the Sn of comparative example 13 and In is greater than 1.0%, and therefore the summation of the addition of the Sn of comparative example 14 ftractures when hot rolling respectively greater than 1.0%.The Ni/P of comparative example 15 relatively exceeds suitable ratio of components in the lowland, so the solid solution capacity of P increases the reduction of generation specific conductivity.The Ni/P of comparative example 16 relatively exceeds suitable ratio of components in the highland, so the increase of the solid solution capacity of Ni, and the reduction of specific conductivity takes place, and the amount of separating out is few, and intensity is also low.The B addition of comparative example 17 is greater than 0.070%, the crystallization or separate out when solidifying of compounds such as Ni-P-B, B-P, and the precipitate amount of Ni-P system reduces thus, and intensity and specific conductivity are low, and bendability is poor.The Ni of comparative example 18 and the addition of P exceed specialized range of the present invention than the lowland, so intensity is low.
Outward appearance photo after the hot rolling test is shown in Fig. 1～4.Fig. 1 is that example 3 of the present invention, Fig. 2 are that comparative example 8, Fig. 3 are the sample of comparative example 10 for comparative example 9, Fig. 4.
The present invention's example and comparative example 19～39 (table 3)
The manufacturing of sample (b):
With electrolytic copper or oxygen free copper is main raw material, with nickel (Ni), 15%P-Cu mother alloy (P), 2%B-Cu mother alloy (B), tin (Sn), indium (In) is auxiliary material, utilize high frequency melting furnace, melt in a vacuum or in the argon gas, be cast as the ingot casting of 45 * 45 * 90mm or Φ 50 * 90mm.In order to change casting, speed of cooling when solidifying, the material that makes mold is cast iron, aluminum oxide, silicon-dioxide system.Central part at mold inserts thermopile, measures casting, 1100～950 ℃ speed of cooling when solidifying, and the cast iron mold is 340 ℃/minute as a result, and the aluminum oxide mold is 85 ℃/minute, and the silicon-dioxide mold is 33 ℃/minute.In order to prepare speed of cooling is ingot casting below 20 ℃/minute, makes the ingot casting of 20 ℃/minute, 15 and 10 ℃/minute speed of cooling with the unidirectional solidification device.Carry out ingot casting hot rolling test, for the rimose ingot casting does not take place under the hot rolling, according to hot rolling and solution treatment, ageing treatment, middle cold rolling, ageing treatment, finally order cold rolling, that eliminate strain annealing is implemented to handle, and makes the flat board of thickness 0.10mm.The different plates test film that collects is tested, and carries out the evaluation of " intensity ", " specific conductivity ", " bendability ".
The hot workability evaluation (b) of ingot casting:
Ingot casting is cut to 45 * 45 * 45mm or Φ 50 * 45mm, and 850 ℃ of heating were carried out the hot rolling test of 4 passages after 1 hour, thickness were rolled by 45mm be 12mm, in addition estimated A with the hot workability of above-mentioned ingot casting and similarly estimated.
The inclusion evaluation (b) of test film:
For the inclusion evaluation in the sample, according to hot rolling and solution treatment, ageing treatment, middle cold rolling, ageing treatment, finally order cold rolling, that eliminate strain annealing is implemented to handle to ingot casting, the rolling parallel cut of the dull and stereotyped sample of mirror polish thickness 0.10mm is with 500 times of 5 visual field (about 0.35mm of inclusion that observe more than the big or small 5 μ m of electron microscope SEM picture
2), calculate every 1mm
2The inclusion number.On the other hand, for the rimose ingot casting takes place 850 ℃ of heating after 1 hour in the hot workability of ingot casting is estimated, water-cooled is carried out the evaluation of inclusion to sample.The mirror polish sample is similarly used the electron microscope observation inclusion with above-mentioned dull and stereotyped sample, calculates every 1mm
2The inclusion number.For the good alloy of hot workability, 850 ℃ of heated plate samples and ingot casting be after 1 hour, water-cooled, and the number of inclusion in the duplicate, the result has obtained roughly the same result.
The evaluation of physical property of test film (b):
For " intensity ", use No. 13 B test films by the tension test of JIS Z 2241 regulations, measure tensile strength." specific conductivity " uses the resistance of double bridge method determination test sheet, represents with %IACS." bendability " estimated with 90 degree W pliability tests.Test uses the anchor clamps of R=0.1mm to carry out 90 degree bending machining under the loading of 50kN based on CES-M0002-6.For the evaluation of bend, with the situation of observation by light microscope central part angle surface, the rimose note will take place do *, the note that fold takes place is △, and good note is O.Bending axis and rolling direction meet at right angles (Good Way).
The copper alloy that is grouped into for the one-tenth shown in the table 3 describes the embodiment of the high-strength high-conductive copper alloy that has superior hot workability that the present invention relates to comparative example.
Alloy embodiment 19～26 of the present invention does not ftracture when hot rolling, has excellent intensity and specific conductivity.Speed of cooling during the casting of example 22 is 20 ℃/minute, and is slower, therefore compares with other example of the present invention, and the inclusion number is many, and bendability is poor slightly.
On the other hand, for comparative example 27～39, be the alloy of the composition that exceeds alloy composition scope of the present invention or Ni/P ratio.Comparative example 27～29 does not add or adds the B less than specified amount, so under the hot rolling cracking has taken place.The addition of the Ni of comparative example 30 is greater than 2.0%, and the P addition of comparative example 31 is greater than 0.50%, and the addition summation of the Sn of comparative example 32 and In is greater than 1.0%, and therefore the addition summation of the Sn of comparative example 33 ftractures when hot rolling respectively greater than 1.0%.The Ni/P of comparative example 34 relatively exceeds suitable ratio of components in the lowland, so the solid solution capacity of P increases the reduction of generation specific conductivity.The Ni/P of comparative example 35 relatively exceeds suitable ratio of components in the highland, so the increase of the solid solution capacity of Ni, and the reduction of specific conductivity takes place, and the amount of separating out is few, and intensity is also low.The B addition of comparative example 36 is greater than 0.070%, so the crystallization or separate out when solidifying of compounds such as Ni-P-B, B-P, and the precipitate amount of Ni-P system reduces thus, and intensity and specific conductivity are low, and bendability is poor.The speed of cooling of comparative example 37～39 when casting is less than 20 ℃/minute, and be slower than prescribed value, so hot rolling is ftractureed down.
Claims (12)
1. the copper alloy that has superior hot workability is characterized in that, by quality ratio, contain Ni:1.0%～2.0%, P:0.10%～0.50%, the content of Ni and P is 4.0～6.5 than Ni/P, and Cr is 0.03%～0.45%, and surplus is made of Cu and unavoidable impurities.
2. the copper alloy that has superior hot workability, it is characterized in that, by quality ratio, contain Ni:1.0%～2.0%, P:0.10%～0.50%, the content of Ni and P is 4.0～6.5 than Ni/P, and Cr is 0.03%～0.45%, also contains among Sn and the In more than one and amounts to 0.01%～1.0%, and surplus is made of Cu and unavoidable impurities.
3. the copper alloy that has superior hot workability is characterized in that, by quality ratio, contain Ni:1.0%～2.0%, P:0.1%～0.5%, the content of Ni and P is 4.0～6.5 than Ni/P, and B is 0.005%～0.070%, and surplus is made of Cu and unavoidable impurities.
4. the copper alloy that has superior hot workability, it is characterized in that, by quality ratio, contain Ni:1.0%～2.0%, P:0.1%～0.5%, the content of Ni and P is 4.0～6.5 than Ni/P, and B is 0.005%～0.070%, also contains among Sn and the In more than one and amounts to 0.01%～1.0%, and surplus is made of Cu and unavoidable impurities.
5. claim 3 or the 4 described copper alloys that have superior hot workability, wherein, the number of the inclusion of major diameter 5～50 μ m is every 1mm
2Below 100, and major diameter is every 1mm greater than the number of the inclusion of 50 μ m
20.
6. claim 1 or the 2 described copper alloys that have superior hot workability, wherein, the major diameter a that final Ni-P before cold rolling is a precipitate is that 20nm～50nm, long-width ratio a/b are 1～5.
7. claim 3 or the 4 described copper alloys that have superior hot workability, wherein, the major diameter a that final Ni-P before cold rolling is a precipitate is that 20nm～50nm, long-width ratio a/b are 1～5.
8. be used for the described copper alloy that has superior hot workability of claim 5 of high-strength high conductivity electronic machine, wherein, tensile strength is more than the 700MPa, and specific conductivity is more than the 40%IACS.
9. the described copper alloy that has superior hot workability of claim 6, wherein, tensile strength is more than the 700MPa, and specific conductivity is more than the 40%IACS.
10. the described copper alloy that has superior hot workability of claim 7, wherein, tensile strength is more than 700 MPa, and specific conductivity is more than the 40%IACS.
11. the manufacture method of the described copper alloy that has superior hot workability of claim 5, wherein, 1100 ℃～950 ℃ average cooling rate during casting is more than 20 ℃/minute.
12. the manufacture method of the described copper alloy that has superior hot workability of claim 5, wherein, 1100 ℃～950 ℃ average cooling rate during casting is more than 30 ℃/minute.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006-097728 | 2006-03-31 | ||
| JP2006097677A JP4750601B2 (en) | 2006-03-31 | 2006-03-31 | Copper alloy excellent in hot workability and manufacturing method thereof |
| JP2006-097677 | 2006-03-31 |
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| CN101275190A true CN101275190A (en) | 2008-10-01 |
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|---|---|---|---|
| CNA2007100898024A Pending CN101275190A (en) | 2006-03-31 | 2007-03-30 | Copper alloy having superior hot workability and method for producing same |
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| CN (1) | CN101275190A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603253A (en) * | 2016-01-15 | 2016-05-25 | 宁波博威合金材料股份有限公司 | Copper alloy material containing nickel-phosphorus phase and nickel-boron phase and production method thereof |
| CN109022900A (en) * | 2018-08-17 | 2018-12-18 | 宁波博威合金材料股份有限公司 | A kind of copper alloy of excellent combination property and its application |
| WO2021077241A1 (en) * | 2019-10-24 | 2021-04-29 | 宁波博威合金材料股份有限公司 | Copper alloy with excellent anti-bending performance, preparation method therefor and use thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS613857A (en) * | 1984-06-18 | 1986-01-09 | Furukawa Electric Co Ltd:The | Copper alloy for wiring connector |
| JPH0219433A (en) * | 1988-07-05 | 1990-01-23 | Mitsubishi Electric Corp | Copper alloy for electronic equipment |
| JPH04231444A (en) * | 1990-12-27 | 1992-08-20 | Nikko Kyodo Co Ltd | Production of electrifying material |
| JPH04231432A (en) * | 1990-12-27 | 1992-08-20 | Nikko Kyodo Co Ltd | Electrifying material |
| JP4257668B2 (en) * | 1998-10-15 | 2009-04-22 | Ｄｏｗａホールディングス株式会社 | Copper alloy for lead frame with excellent etching processability and its manufacturing method |
-
2006
- 2006-03-31 JP JP2006097677A patent/JP4750601B2/en not_active Expired - Fee Related
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2007
- 2007-03-30 CN CNA2007100898024A patent/CN101275190A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603253A (en) * | 2016-01-15 | 2016-05-25 | 宁波博威合金材料股份有限公司 | Copper alloy material containing nickel-phosphorus phase and nickel-boron phase and production method thereof |
| CN109022900A (en) * | 2018-08-17 | 2018-12-18 | 宁波博威合金材料股份有限公司 | A kind of copper alloy of excellent combination property and its application |
| WO2021077241A1 (en) * | 2019-10-24 | 2021-04-29 | 宁波博威合金材料股份有限公司 | Copper alloy with excellent anti-bending performance, preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4750601B2 (en) | 2011-08-17 |
| JP2007270269A (en) | 2007-10-18 |
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