CN103014409B - The Cu-Ni-Si series copper alloy of projection welding excellent and manufacture method thereof - Google Patents
The Cu-Ni-Si series copper alloy of projection welding excellent and manufacture method thereof Download PDFInfo
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Abstract
The invention provides Cu-Ni-Si series copper alloy and the manufacture method thereof of projection welding excellent, for the circuit substrate etc. of vehicle-mounted driving circuit or engine installation inside.Copper alloy of the present invention has by containing the Ni of 1.0 ~ 4.0 % by weight, Si, the Zn of 0.3 ~ 0.7 % by weight, the Sn of 0.4 ~ 0.8 % by weight of 0.1 ~ 1.0 % by weight, remaining as the composition that Cu and inevitable impurity are formed, mean value in whole crystal grain of the interior GOS by EBSD method mensuration of crystal structure is 2.5 ° ~ 5.0 °, and total special grain boundary length L σ of the special grain boundary measured by EBSD method is 15 ~ 30% relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary.
Description
Technical field
The present invention relates to the Cu-Ni-Si series copper alloy of projection welding excellent, particularly relate to the Cu-Ni-Si series copper alloy for the circuit substrate etc. of vehicle-mounted driving circuit or engine installation inside and manufacture method thereof.
Background technology
Projection welding is the one of resistance welding, because electric current concentrates flowing at salient, so can good welding be carried out, recently in the copper that uses in the circuit substrate of vehicle-mounted driving circuit or engine installation inside or the connection terminal of copper alloy parts and the welding of lead terminal etc.
The driving circuit device that patent documentation 1 is recorded and possess in its engine installation, carries out projection welding to the connection end of terminal and the end of lead terminal.Connection terminal uses fine copper, phosphor bronze etc.The connection terminal 22 extended from circuit substrate 36 is connecting terminal bending part 22A bending, extend upward together with the lead terminal 18 that self-acting control IC44 is extended, and then, the connection end of terminal 22 is engaged by electric welding at weld 16 with the end of lead terminal 18, and connection terminal 22 bends in the mode leaving lead terminal 18 at point of inflection 22B.Therefore, when electric welding, electric current can be suppressed to flow beyond weld 16 and shunt, thus the uneven of welding strength can be suppressed.
In the rectifier of the vehicle-mounted dlternator that patent documentation 2 is recorded, splicing ear 37 branch of circuit board assemblies 32 also exposes in the inner circumferential side of resinite 36 and outer circumferential side, the lead-in wire 33d of+side diode 33 engages by projection welding is integrated with the exposed division 37b of the outer circumferential side of splicing ear 43 branch from outer circumferential side, and then the lead-in wire 34d of-side diode 34 engages by projection welding is integrated with the exposed division 37a of the inner circumferential side of splicing ear 37 branch from inner circumferential side.This lead-in wire is formed by copper.
Patent documentation 1: Japanese Patent Publication 2009-123359 publication
Patent documentation 2: Japanese Patent Publication becomes 11-252877 publication
The brass needing the circuit substrate of projection welding etc. to use in the past or phosphor bronze parts have problems in erosion resistance.Therefore, as these parts, studying the use of copper nisiloy series copper alloy (Cu-Ni-Si series copper alloy) of erosion resistance, excellent heat resistance, but there is shortcoming in projection welding characteristic, therefore expect its solve scheme.
Summary of the invention
The present invention makes in view of these problems, is provided for Cu-Ni-Si series copper alloy and the manufacture method thereof of the projection welding excellent of the circuit substrate of vehicle-mounted driving circuit or engine installation inside etc. especially.
What the present inventor etc. carefully studied found that, copper nisiloy series copper alloy is made to contain the Zn of optimum quantity, make the grain orientation difference (GrainOrientationSpread that the interior Electron Back-Scattered Diffraction of crystal structure (EBSD) method measures, the mean value of whole crystal grain GOS) is 2.5 ° ~ 5.0 °, when total special grain boundary length L σ of the special grain boundary measured by EBSD method is 15 ~ 30% relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary, the leap of projection welding characteristic improves.
In raising projection welding characteristic, the welding easiness with the metal of electroconductibility and the processibility that can form the protuberance with excellent in shape are important prerequisites, and the result that the present inventor etc. carefully study draws following viewpoint.
(1) Zn is as the addO-on therapy of copper alloy, usually containing it, also contributes to the easiness of welding in order to improve resistance to migration, but is low melting point, if exceed optimum quantity, then usually evaporate when projection welding and make weldability be deteriorated conversely.
(2) the drawing processibility that the mean value in whole crystal grain of the GOS measured by EBSD method in copper alloy tissue, total special grain boundary length L σ of special grain boundary contribute to for the formation of protuberance relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary widely, if exceed optimum value, drawing processibility is deteriorated, and becomes the protuberance being difficult to be formed and having excellent in shape.
That is, there is the mean value in whole crystal grain of best Zn content, best GOS, total special grain boundary length L σ of special grain boundary can play fabulous projection welding relative to the copper nisiloy class copper alloy of the ratio (L σ/L) of total crystal boundary length L of crystal boundary.
In addition, common copper nisiloy series copper alloy is by the sheet material of following process manufacture as the final thickness of slab of target: make ingot bar with proper methods such as continuous castings, this ingot bar is heated to about 850 ~ 950 DEG C and carries out homogenizing annealing, after hot rolling, suppress the precipitation of Ni-Si compound with water cooling, then to this hot rolling material implement (1) cold rolling → the cold rolling and thermal treatment in (2) solution treatment → (3) ageing treatment → (4).In addition, (4) cold rolling after, sometimes also carry out eliminating stress or the process such as short period of time heating, tension leveling for the purpose of straightening.Especially obtain appropriate characteristics, the solution treatment of (2) and the ageing treatment of (3) need select suitable condition.
The present inventor etc. draw following viewpoint, in order to manufacture the copper nisiloy series copper alloy of the drawing processibility with applicable projection welding, do not make compound particles separate out and exist very important with solid solution condition in copper alloy tissue as far as possible.
Namely, do not carry out the solution treatment that compound particles is separated out needed for manufacture and the ageing treatment of copper nisiloy class copper alloy in the past, by selecting top condition to hot rolling, process annealing and low-temperature annealing, the copper nisiloy class copper alloy of projection welding excellence can be manufactured, thus also can cheaply manufacture on cost.
The feature of copper alloy of the present invention is, have by containing the Ni of 1.0 ~ 4.0 % by weight, Si, the Zn of 0.3 ~ 0.7 % by weight, the Sn of 0.4 ~ 0.8 % by weight of 0.1 ~ 1.0 % by weight, remaining as the composition that Cu and inevitable impurity are formed, mean value in whole crystal grain of the interior GOS by EBSD method mensuration of crystal structure is 2.5 ° ~ 5.0 °, and total special grain boundary length L σ of the special grain boundary measured by EBSD method is 15 ~ 30% relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary.
The content of Zn less than 0.3 % by weight time, be unfavorable for improving projection welding characteristic, if exceed 0.7 % by weight, the evaporation when projection welding also makes weldability be deteriorated conversely.
When mean value in whole crystal grain of GOS is less than 2.5 °, the anisotropy grow of crystal structure, causes processibility to reduce, if exceed 5.0 °, the fracture caused by grain-boundary crack easily occurs.
L σ/L less than 15% time, rolling processibility be deteriorated, if exceed 30%, easily there is the fracture caused by grain-boundary crack.
In addition, copper alloy of the present invention can containing at least one in the element be made up of Zr and Cr of 0.01 ~ 0.3 % by weight.
By containing at least one in the element be made up of Zr and Cr of 0.01 ~ 0.3 % by weight, projection welding improves further.
In addition, copper alloy of the present invention can containing the Mg of 0.001 ~ 0.2 % by weight.
By containing the Mg of 0.001 ~ 0.2 % by weight, resistant to mold wear during punch process improves.
The feature of the manufacture method of copper alloy of the present invention is, comprise hot rolling, first cold rolling, process annealing, the second cold rolling and low-temperature annealing successively, during hot rolling, process velocity is in a thickness direction 13.0 ~ 28.0 mm/min, it is 500 ~ 700 DEG C that cooling starts temperature, at 500 ~ 700 DEG C, implement process annealing 20 ~ 60 seconds, at 400 ~ 500 DEG C, implement low-temperature annealing 20 ~ 60 seconds.
Namely, the copper alloy of projection welding excellent of the present invention by do not carry out common copper nisiloy series copper alloy manufacture needed for, solution treatment that compound particles is separated out and ageing treatment, hot rolling, process annealing and low-temperature annealing are selected top condition and are manufactured.
When during hot rolling, process velocity is in a thickness direction less than 13.0 mm/min, tissue becomes uneven, also generate thick precipitate, rolling processibility worsens, when process velocity is larger, tissue becomes even, can suppress the growth of coarse precipitates, but when exceeding 28.0 mm/min, equipment cannot be implemented.
When cooling beginning temperature less than 500 DEG C, tissue becomes uneven, also generates thick precipitate, and rolling processibility worsens, and cooling beginning temperature is higher, organizes and becomes more even, but the energy waste exceeding the setting of 700 DEG C becomes large, uneconomical.
Temperature during process annealing is less than 500 DEG C, and when the time was less than 20 seconds, L σ/L rises and easily produces grain-boundary crack, and rolling processibility worsens, and productivity reduces.In addition, separate out timeliness and occur, electric conductivity rises, and weldability reduces.
Temperature during process annealing exceeds 700 DEG C, when the time exceeds 60 seconds, organizes solid solution, and electric conductivity reduces, but the mean value in whole crystal grain of GOS reduces, and the anisotropy grow of micro organization, processibility reduces.
Temperature during low-temperature annealing is less than 400 DEG C, and when the time was less than 20 seconds, L σ/L rises and easily produces grain-boundary crack, and thus processibility reduces.
Temperature during low-temperature annealing exceeds 500 DEG C, and when the time exceeds 60 seconds, the mean value in whole crystal grain of GOS reduces, thus anisotropy grow, and processibility reduces.
According to the present invention, the Cu-Ni-Si series copper alloy of the projection welding excellent of the circuit substrate being applicable to vehicle-mounted driving circuit or engine installation inside etc. can be obtained.
Embodiment
Below, embodiments of the present invention are described.
The copper alloy of present embodiment has by containing the Ni of 1.0 ~ 4.0 % by weight, Si, the Zn of 0.3 ~ 0.7 % by weight, the Sn of 0.4 ~ 0.8 % by weight of 0.1 ~ 1.0 % by weight, remaining as the composition that Cu and inevitable impurity are formed.
Ni and Si has does not make electric conductivity significantly reduce and improve the effect of intensity.Ni less than 1.0 % by weight or Si less than 0.1 % by weight time, without this effect, Ni exceeds 4.0 % by weight or Si when exceeding 1.0 % by weight, and hot workability significantly reduces.
Zn less than 0.3 % by weight time, be unfavorable for improving projection welding characteristic, if exceed 0.7 % by weight, the evaporation when projection welding also makes weldability worsen conversely.
Sn is component intensity being improved by solution strengthening, less than 0.4 % by weight time, this effect is insufficient, when exceeding 0.8 % by weight, while this effect is saturated, hot workability and cold-workability deterioration.
In addition, this copper alloy containing at least one in the element be made up of Zr and Cr of 0.01 ~ 0.3 % by weight, by containing at least one in these elements of 0.01 ~ 0.3 % by weight, can contribute to the further raising of projection welding.
In addition, this copper alloy containing the Mg of 0.001 ~ 0.2 % by weight, by containing the Mg of 0.001 ~ 0.2 % by weight, can contribute to resistant to mold wear during punch process.
And then, mean value in whole crystal grain of the GOS that this copper alloy measures by EBSD method in crystal structure is 2.5 ° ~ 5.0 °, and the total special grain boundary length L σ of special grain boundary measured by EBSD method is more than 15 ~ 30% relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary.
When mean value in whole crystal grain of GOS is less than 2.5 °, the anisotropy grow of crystal structure, causes processibility to reduce, if exceed 5.0 °, the fracture caused by grain-boundary crack easily occurs.
L σ/L less than 15% time, rolling processibility be deteriorated, if exceed 30%, easily there is the fracture caused by grain-boundary crack.
That is, by the mean value in whole crystal grain of GOS and the L σ/L numerical range in the best, the protuberance with excellent in shape is formed by punch process.
GOS is the crystalline orientation Analytical system by being installed on scanning electron microscope, measure the orientation of each mensuration pixel, the misorientation measured between pixel is considered as crystal boundary more than 15 °, calculate the mean value of a certain pixel in crystal grain and the misorientation between remaining whole pixel, each crystal grain has value.Mean value in whole crystal grain of GOS is the mean value of the GOS of the whole crystal grain calculated in measurement range.
Total special grain boundary length L σ of the interior special grain boundary by EBSD method mensuration of crystal structure is the orientation analysis undertaken by Electron Back-Scattered Diffraction relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary, be as crystal boundary using the misorientation between adjacent measuring point between the measuring point of more than 15 °, measure total crystal boundary length L of crystal boundary, determine that the interface of the crystal grain adjoined forms the grain boundary sites of special grain boundary, calculated by total crystal boundary length L of total special grain boundary length L σ of special grain boundary and the crystal boundary of mensuration.
Like this, the Zn content of the copper alloy of present embodiment is 0.3 ~ 0.7 % by weight, mean value in whole crystal grain of the GOS measured by EBSD method is 2.5 ° ~ 5.0 °, total special grain boundary length L σ of the special grain boundary measured by EBSD method is 15 ~ 30% relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary, has fabulous projection welding.
Below, the embodiment of manufacture method of the present invention is described.
The manufacture method of the copper alloy of present embodiment, when to comprise hot rolling, first cold rolling, process annealing, the second cold rolling and stress relief annealed operation manufactured copper alloy successively, when making hot rolling, process velocity is in a thickness direction 13.0 ~ 28.0 mm/min, it is 500 ~ 700 DEG C that cooling starts temperature, at 500 ~ 700 DEG C, implement process annealing 20 ~ 60 seconds, at 400 ~ 500 DEG C, implement low-temperature annealing 20 ~ 60 seconds and manufacture.
Common copper nisiloy series copper alloy is by the sheet material of following process manufacture as the final thickness of slab of target: make ingot bar with proper methods such as continuous castings, this ingot bar is heated to about 850 ~ 950 DEG C and carries out homogenizing annealing, after hot rolling, suppress the precipitation of Ni-Si compound with water cooling, then cold rolling → solution treatment → ageing treatment → cold rolling processing and thermal treatment are implemented to this hot rolling material.On the other hand, the manufacture method of present embodiment, by the solution treatment not carrying out making compound particles separate out and ageing treatment, is selected top condition to hot rolling, process annealing and low-temperature annealing and is manufactured.
Hot rolling is 13.0 ~ 28.0 mm/min making the process velocity on thickness direction, and it is implement at 500 ~ 700 DEG C that cooling starts temperature.
When process velocity during hot rolling is less than 13.0 mm/min, tissue becomes uneven, also generates thick precipitate, rolling processibility worsens, and when process velocity is larger, tissue becomes even, the growth of coarse precipitates can be suppressed, but when exceeding 28.0 mm/min, equipment cannot be implemented.
When cooling beginning temperature less than 500 DEG C, tissue becomes uneven, also generates thick precipitate, and rolling processibility worsens, and cooling beginning temperature is higher, organizes and becomes more even, but the setting exceeding 700 DEG C makes energy waste become large, uneconomical.
Process annealing is implemented 20 ~ 60 seconds at 500 ~ 700 DEG C.
Temperature during process annealing is less than 500 DEG C, and when the time was less than 20 seconds, L σ/L rises and easily produces grain-boundary crack, and the deterioration of rolling processibility, productivity reduces.In addition, separate out timeliness and occur, electric conductivity rises, and weldability reduces.
Temperature during process annealing exceeds 700 DEG C, when the time exceeds 60 seconds, organizes solid solution, and electric conductivity reduces, but the mean value in whole crystal grain of GOS reduces, and the anisotropy grow of micro organization, processibility reduces.
Low-temperature annealing is implemented 20 ~ 60 seconds at 400 ~ 500 DEG C.
Temperature during low-temperature annealing is less than 400 DEG C, and when the time was less than 20 seconds, L σ/L rises and easily produces grain-boundary crack, and thus processibility reduces.
Temperature during low-temperature annealing exceeds 500 DEG C, and when the time exceeds 60 seconds, the mean value in whole crystal grain of GOS reduces, anisotropy grow, and processibility reduces.
The Zn content of the copper alloy manufactured according to this manufacture method is 0.3 ~ 0.7 % by weight, mean value in whole crystal grain of the GOS measured by EBSD method is 2.5 ° ~ 5.0 °, total special grain boundary length L σ of the special grain boundary measured by EBSD method is 15 ~ 30% relative to the ratio (L σ/L) of total crystal boundary length L of crystal boundary, has fabulous projection welding.
[embodiment]
Below, to embodiments of the invention, comprise comparative example and be described in detail.
Dissolve the copper alloy (component beyond Addition ofelements is Cu and inevitable impurity) of composition shown in following table 1 with electric furnace, make the ingot bar of thickness 175mm, width 500mm, length 4m.After this ingot bar is heated to 950 DEG C, carry out hot rolling with the process velocity of the thickness direction of 13.6 ~ 27.2 mm/min, carry out water cooling rapidly from 500 ~ 700 DEG C, obtain the rolled stock of thickness of slab 12mm.Then, after surfacing cut being carried out to the oxide film on its surface with milling cutter, carry out first cold rolling, carry out the process annealing of 20 ~ 60 seconds at 500 ~ 700 DEG C.And then, carry out second cold rolling, be refined to thickness 0.25mm, carry out the low-temperature annealing of 20 ~ 60 seconds at 400 ~ 500 DEG C, obtain the copper alloy thin plate shown in embodiment 1 ~ 9 of table 1.In addition, change component composition, hot-rolled condition, process annealing condition and low-temperature annealing condition at comparative example 1 ~ 9 to make.The low-temperature annealing hurdle "-" of comparative example 9 represents does not implement low-temperature annealing.
[table 1]
The test film of structure observation is gathered by the copper alloy thin plate obtained, after carrying out mechanical mill and polishing, carry out ion milling (Hitachi Ha イ テ ク System Off ラ Star ト ミ リ Application グ: to the input angle 90 ° of test portion, acceleration voltage 6kV, 10 minutes) adjustment surface, the EBSD that the SEM (model " S-3400N ") using ハイテク company of Hitachi to manufacture and TSL company manufacture measures, analytical system OIM (OrientationImagingMicrograph), respectively measures the orientation of pixel in the regions of 300 μm × 300 μm with the measuring space of 0.5 μm.Afterwards, use the analysis software (software name " OIMAnalysis ") of identical systems that the misorientation measured between pixel is considered as crystal boundary more than 15 °, calculate the mean value of a certain pixel in crystal grain and the misorientation between remaining whole pixel, obtain the GOS of whole crystal grain, calculate the mean value in whole crystal grain of GOS.
In addition, each test film on surface was adjusted for carrying out ion milling, use above-mentioned machine, for the region of 300 μm × 300 μm, be as crystal boundary using the misorientation between adjacent measuring point between the measuring point of more than 15 °, total crystal boundary length L of the crystal boundary measured in region is measured, determine that the interface of the crystal grain adjoined forms the grain boundary sites of special grain boundary, the crystal boundary length of the total special grain boundary length L σ and total crystal boundary length L of the crystal boundary of said determination that simultaneously obtain special grain boundary is than L σ/L.
What table 2 showed these copper alloy thin plate measures mean value in whole crystal grain of the GOS obtained and L σ/L based on EBSD.
In addition, table 2 shows the measurement result of the deep drawing processibility of these test portions, electric conductivity, weldability.
The trier that deep drawing processibility uses エ リ Network セ Application company to manufacture, punching hole diameter be Φ 10mm, lubricant makes cup under being the condition of lubricating grease, observe outward appearance, what outward appearance was good is expressed as zero, runs through ear, crack be expressed as ×.
For electric conductivity, the rectangle test film of processing 25mm × 150mm, measures resistance with quadripolar mesh procedure, is calculated by average cross section method.
For weldability, prepare the thin rectangle test film of two 25mm × 150mm, make two overlapping in the longitudinal direction 25mm, use the welding source (NT-8A) that Japanese ア PVC オ ニ Network ス company manufactures, welding timer (NRW-25A) and soldering tip (NA-72), be chromium-copper by material, diameter 16mm, the electrode of front end flat pattern is with plus-pressure 294N (30kgf), turn on angle 80%, center implementation spot welding to the lap of test film under the condition of 60 circulations (1.2 seconds), what test film engaged is expressed as zero, test film is unassembled to be expressed as ×.
[table 2]
Inferred by table 2, compared with comparative example, the Cu-Ni-Si series copper alloy containing the Zn of 0.3 ~ 0.7 % by weight of embodiment is owing to having excellent deep drawing processibility and weldability, so the projection welding of needs two characteristics is excellent.
In addition, for each embodiment, respectively with the test film B comprising weld part, tension test is carried out to the test film A not containing weld part of copper alloy plate, the tensile strength obtained is obtained to the ratio of (tensile strength of test film B)/(tensile strength of test film A), acetonideexample 3 and 4 is the ratio close to 90%.It can thus be appreciated that the Cu-Ni-Si series copper alloy of Zr, Cr particularly containing specified amount, welding property excellent, is applicable to the circuit substrate etc. of vehicle-mounted driving circuit or engine installation inside.
Above, embodiments of the present invention are illustrated, but the invention is not restricted to this record, various change can be applied without departing from the scope of the subject in the invention.
Claims (5)
1. an Albatra metal-, it is characterized in that, Ni by 1.0 ~ 4.0 % by weight, 0.1 ~ 1.0 % by weight Si, 0.3 ~ 0.7 % by weight Zn, the Sn of 0.4 ~ 0.8 % by weight, remaining Cu and inevitably impurity form, the mean value of whole crystal grain of the interior grain orientation difference by Electron Back-Scattered Diffraction method mensuration of crystal structure is 2.5 ° ~ 5.0 °, and total special grain boundary length L σ of the special grain boundary measured by Electron Back-Scattered Diffraction method is 15 ~ 30% relative to the ratio L σ/L of total crystal boundary length L of crystal boundary.
2. copper alloy according to claim 1, is characterized in that, at least one in the element be made up of Zr and Cr containing 0.01 ~ 0.3 % by weight.
3. copper alloy according to claim 1, is characterized in that, containing the Mg of 0.001 ~ 0.2 % by weight.
4. copper alloy according to claim 2, is characterized in that, containing the Mg of 0.001 ~ 0.2 % by weight.
5. the manufacture method of an Albatra metal-, it is characterized in that, for the manufacture method of the copper alloy in Claims 1-4 described in any one, comprise hot rolling, first cold rolling, process annealing, the second cold rolling and low-temperature annealing successively, during described hot rolling, process velocity is in a thickness direction 13.0 ~ 28.0 mm/min, it is 500 ~ 700 DEG C that cooling starts temperature, implements described process annealing 20 ~ 60 seconds, implement described low-temperature annealing 20 ~ 60 seconds at 400 ~ 500 DEG C at 500 ~ 700 DEG C.
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| CN1600881A (en) * | 2003-07-31 | 2005-03-30 | 日矿金属加工株式会社 | Cu-Ni-Si alloy having good performance against fatigure |
| CN1841570A (en) * | 2005-03-29 | 2006-10-04 | 日矿金属加工株式会社 | Thermal resistant tinned Cu-Ni-Si-Zn-Sn sieries alloy bar with excellent stripping character and tinned bar |
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| CN1841570A (en) * | 2005-03-29 | 2006-10-04 | 日矿金属加工株式会社 | Thermal resistant tinned Cu-Ni-Si-Zn-Sn sieries alloy bar with excellent stripping character and tinned bar |
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