CN102534292A - Copper alloy for electrical and electronic component, and method for producing the same - Google Patents
Copper alloy for electrical and electronic component, and method for producing the same Download PDFInfo
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Abstract
The invention provides copper alloy for electrical and electronic components, and a method for producing the same, wherein a simplified copper alloy manufacturing method is provided and the copper alloy for electrical and electronic components is excellent in strength, electric conductivity and electrical-resistance. The copper alloy contains 2.1-2.6% of Fe by weight, 0.015-0.15% of P by weight, 0.05-0.20% of Zn by weight, and the rest is composed of Cu and unavoidable impurities. In a Fe precipitate dispersed in a Cu master phase, the Fe precipitate with the single area thereof to be within the range of 20 nm2-200 nm2 and the total area of the Fe precipitate is over 0.4 % relative to the whole area of the Cu master phase. When the single area thereof to be within the range of over 200 nm2, the total area of the Fe precipitate is 0.4 < = s1/ s2 < = 1 relative to the whole area of the Cu master phase.
Description
Technical field
The present invention relates to copper alloy and method of manufacture thereof, this copper alloy is as electric, the electronic unit of lead frame, terminal, junctor etc. and the starting material that use, and except intensity with the electroconductibility, superior for heat resistance.
Background technology
To the employed lead frame of the semiconductor product that is used for electronics, along with spininessization, thin-walled property, desired strength, electroconductibility, thermotolerance, and, use CDA Alloy 194 as the material that satisfies these characteristics more well.The structure of CDA Alloy 194 is contain iron (Fe) 2.1～2.6 weight %, phosphorus (P) 0.015～0.15 weight %, zinc (Zn) 0.05～0.20 weight %, and remainder (more than the 97 weight %) to be copper (Cu).
For example; In patent documentation 1; Put down in writing the method for manufacture of the copper base alloy of high-strength and high-conductivity; And this method of manufacture has just been used CDAAlloy 194, and this CDAAlloy 194 contains iron (Fe) 2.3 weight %, phosphorus (P) 0.026 weight %, zinc (Zn) 0.1 weight %, and remainder is copper (Cu).
CDAAlloy 194 has satisfied the above-mentioned requirements characteristic through because of the high strength of work hardening with because of the thermotolerance that Fe is separated out, the improvement of electroconductibility.As the method for manufacture of this copper alloy, known have a following method of manufacture: for example, and will be by the ingot casting of forming the copper base alloy that constitutes of regulation; After 800～1050 ℃ of hot rollings, carry out first cold rolling, keep more than 30 seconds with the temperature more than 900 ℃ after; Be cooled to 50 ℃ with the speed of cooling of PM more than 100 ℃ at once, be cooled to room temperature again, afterwards; Carry out second cold rolling; Annealed 30 minutes～6 hours with 550～650 ℃ temperature, annealed 1～10 hour with 400～525 ℃ temperature again, carry out the 3rd cold rolling back of degree of finish 70～85% then and finish.
Patent documentation 1: the special public clear 52-20404 communique of Japan
Summary of the invention
The method of manufacture of the copper alloy of above-mentioned CDAAlloy 194; Owing to need twice above annealing; Therefore cause not only that operation increases, cost rises, but also cause making the output of the greenhouse oxidizing gases of carbonic acid gas etc. to increase along with the increase of heat treatment time.
So, the objective of the invention is to, use the method for manufacture of the copper alloy of more simplifying, an Albatra metal-is provided, its intensity, electroconductibility, stable on heating characteristic that has than is used for an existing C DAAlloy 194 of lead frame etc. is superior characteristic also.
In order to address the above problem; The present invention provides electric as follows, electronic component-use copper alloy; This is electric, to contain Fe be that 2.1～2.6 weight %, P are that 0.015～0.15 weight %, Zn are 0.05～0.20 weight % to the electronic component-use copper alloy; And remainder is made up of Cu and unavoidable impurities, it is characterized in that: in the Fe precipitate in being scattered in the Cu parent phase, single area is 20nm
2More than and be lower than 200nm
2The total area area occupation ratio S whole of Fe precipitate with respect to the Cu parent phase
1Be more than 0.4%, single area is 200nm
2The total area area occupation ratio S whole of above Fe precipitate with respect to the Cu parent phase
2Satisfy 0.4≤S
1/ S
2≤1.4 relation.
In addition, in above-mentioned electric, all copper alloys of electronic unit, 1.2≤S preferably
1/ S
2≤1.4.
In addition; Method of manufacture electric, the electronic component-use copper alloy is provided; The method of manufacture of this copper alloy is: will contain Fe is that 2.1～2.6 weight %, P are that 0.015～0.15 weight %, Zn are 0.05～0.20 weight %; And the ingot casting that remainder is made up of Cu and unavoidable impurities through hot rolling, first cold rolling, heating solution treatment, second cold rolling, annealing, the 3rd cold rolling operation, is machined to required thickness of slab; It is characterized in that: above-mentioned annealing is with heating below 650 ℃ more than 550 ℃ more than 30 minutes below 4 hours; Afterwards, from this Heating temperature be cooled to 450 ℃ below 1 ℃/minute with average cooling rate more than 0.3 ℃/minute, the above-mentioned the 3rd cold rolling degree of finish with 70～85% carries out cold rolling.
The intensity, electroconductibility, stable on heating characteristic that copper alloy of the present invention has than is used for an existing C DAAlloy 194 of lead frame etc. is superior characteristic also.
Description of drawings
Fig. 1 is the mode chart of the metal structure of an embodiment of the invention.
Fig. 2 is the figure of manufacturing process's flow process of the Cu alloy material of expression an embodiment of the invention.
Fig. 3 is the sketch chart of the annealing operation of an embodiment of the invention.
Nomenclature
The 1-Cu parent phase, 2-Fe phase (20nm
2More than and be lower than 200nm
2), 3-Fe phase (200nm
2More than).
Embodiment
(1) composition of copper alloy
In the present invention, to constituting the composition of copper alloy, the reason of adding is described as follows and is limited reason.
(I) composition of iron (Fe)
The amount of Fe is below the above 2.6 weight % of 2.1 weight % among the present invention, is preferably below the above 2.3 weight % of 2.1 weight %.The reason that contains Fe is: through solid solution in the Cu parent phase or separate out and improve intensity and thermotolerance.If be lower than 2.1 weight %, the solid solution capacity of Fe or separate out quantity not sufficient and can not get intensity and thermotolerance then.On the other hand; If surpass 2.6 weight %, the reduction of the specific conductivity that is then caused by the solid solution of Fe is bigger, and when casting, generates the crystallisate of thick Fe; If the crystallisate of this Fe residues in the product, then possibly become stamping-out and add the crackle in man-hour or the reason of poor plating.
(II) composition of phosphorus (P)
The amount of P is below the above 0.15 weight % of 0.015 weight % among the present invention.P has the effect of the oxygen of in melt-casting, sneaking into molten metal being carried out deoxidation, but if be lower than 0.015 weight %, then is not enough to obtain its effect.Though tendency then on deoxidation effect, occurs if surpass 0.1 weight %, form precipitate with Fe chemical combination, this precipitate also helps intensity or stable on heating raising.Just, if surpass 0.1 weight %, the reason of the intergranular crack when then becoming hot rolling sometimes.And, if surpass 0.15 weight %, deoxidation effect or help the effect of intensity also to become state of saturation not only then, and when casting, separate out in the P of crystal boundary etc. and ftracture the reason of the intergranular crack when becoming hot rolling, generation bad influence with the compound of Fe.According to above situation, be more than the 0.015 weight % below the 0.1 weight % as preferred scope.
(III) composition of zinc (Zn)
The amount of Zn is below the above 0.20 weight % of 0.05 weight % among the present invention, is preferably below the above 0.15 weight % of 0.05 weight %.Zn not only improves the soldering wellability, and has the effect of deoxidation, outgassing and inhibition Cu migration, but if be lower than 0.01 weight %, the effect that then obtains is insufficient.On the other hand, if surpass 0.20 weight %, then cause the reduction of specific conductivity.
(IV) other elemental composition
It is principal constituent that copper alloy of the present invention is gone up with Cu basically, and contains Fe, P, the Zn of specified quantitative.But the situation that exists unescapable other elements to sneak into as impurity contains Mg, Al, Si, Ti, Cr, Mn, Co, Ni, Mn, Zr and Sn etc. sometimes.But, if be lower than 0.1 weight %, then can not bring bad influence to thermotolerance etc., but as unavoidable impurities and permissible scope.
(2) metal structure of copper alloy
Fig. 1 is the mode chart of emphasis of the metal structure of expression copper alloy of the present invention.The metal structure of copper alloy of the present invention is characterised in that in the Fe precipitate in being scattered in the Cu parent phase, single area is 20nm
2More than and be lower than 200nm
2The total area area S whole of Fe precipitate with respect to the Cu parent phase
0Area occupation ratio S
1(S
1=S
01/ S
0) be more than 0.4%, single area is 200nm
2The total area area occupation ratio S whole of above Fe precipitate with respect to the Cu parent phase
2(S
2=S
02/ S
0) satisfied 0.4≤S
1/ S
2≤1.4 relation.Below integrant is detailed.
(I) the Fe precipitate in the Cu parent phase
Copper alloy of the present invention after Fe is separated out in the annealing operation stated.In the Cu of parent phase, the Fe that is separated out helps the raising of specific conductivity.At this, under the many situation of the amount of the separating out solid solution capacity few and in Cu of Fe, to not effect of specific conductivity.Therefore, after in the annealing operation stated, Fe is fully separated out.
On the other hand, if process repeatedly or process with high degree of finish, then the whole thermotolerance of Cu alloy material reduces very big sometimes when rolling.The contriver obtains following opinion: the Fe precipitate is trickle more, and under the situation with identical condition processing, thermotolerance is not easy to reduce more.
According to above-mentioned 2 points,,, obtained very the highland and kept specific conductivity and realize high stable on heating Cu alloy material through the size that is conceived to particle diameter, their ratio again through the result of wholwe-hearted research.Below detail.
(II) single area is 20nm
2More than and be lower than 200nm
2The total area area S whole of Fe precipitate with respect to the Cu parent phase
0Area occupation ratio S
1
In the Fe precipitate in being scattered in the Cu parent phase, making each area that occupies is 20nm
2More than and be lower than 200nm
2Precipitate (below be called precipitate A) disperse.The total area of precipitate A is with respect to the ratio S of entire area
1Be made as more than 0.4%.The reason of each numerical definiteness below is described.
About 20nm
2Lower value
As stated, in order further to improve thermotolerance, specific conductivity, Fe is separated out.But, after cast copper alloy,, carry out processing (rolling) or high degree of finish rolling repeatedly, until reaching the actual shape that can use tensile strength is set at expected value etc. as purpose.At this moment, trickle precipitate is because the passing of dislocation that is caused by processing or crystal boundary (cutting) and solid solution again.Therefore, in through the Fe precipitate after the processing, be lower than 20nm
2Precipitate, its ratio is quite little, can ignore.And, owing to think that the precipitate that helps specific conductivity in fact is 20nm
2More than, therefore its lower limit is made as 20nm
2
About 200nm
2Higher limit
As stated, excessive precipitate when having passed through processing (rolling) or high degree of finish more than three times rolling, brings bad influence to thermotolerance.The contriver is obtaining following opinion in the result through wholwe-hearted research: the size of Fe precipitate that suppresses stable on heating raising is with 200nm
2Size classify, thereby can quantification to stable on heating influence.
About area occupation ratio S
1Be more than 0.4%
Area S with respect to integral body
0, with 20nm
2More than and be lower than 200nm
2The ratio S of total area of precipitate
1The reason that is made as more than 0.4% is, if owing to more than 0.4%, then can access the copper alloy of high conductivity.
(III) S
1And S
2Ratio be 0.4≤S
1/ S
2≤1.4
In the present invention, the total area of precipitate A is with respect to the ratio S of entire area
1, and 200nm
2The total area of above Fe precipitate (below be called precipitate B) is with respect to the ratio S of entire area
2, satisfy 0.4≤S
1/ S
2≤1.4 relational expression.The reason of each numerical definiteness below is described.
About S
1/ S
2Be more than 0.4
As stated, think S
1Amount help very much specific conductivity.Therefore, preferably, help the Fe precipitate A of specific conductivity and the 200nm few to the contribution of specific conductivity
2The ratio of above Fe precipitate B is more than 0.4.
About S
1/ S
2Be below 1.4
Surpassing 200nm
2Fe precipitate B situation about not having fully under, in annealing operation, show the Fe precipitate and fail fully to grow up.In the case, thermotolerance reduces.In order to give full play to thermotolerance, also need there be S
2But, if too much, then thermotolerance is brought bigger bad influence.The contriver obtains following opinion: at ratio S
1/ S
2Be under the situation more than 1.4, thermotolerance reduces very big.Therefore, preferred proportion S
1/ S
2Be below 1.4.
(3) method of manufacture of copper alloy
Fig. 2 representes an example of manufacturing process's flow process of copper alloy of the present invention.The copper alloy of mode of the present invention is made as follows, at first, prepares the ingot casting (formation with Cu alloy material of predetermined composition: step 1 below is expressed as step " S ") of Cu alloy material as starting material.To have the ingot casting that above-mentioned copper alloy is formed, through hot rolling (S2), first cold rolling (S3), heating solution treatment (perhaps fluidization processing) (S4), second cold rolling (S5), annealing (S6), the 3rd cold rolling process (S7), be machined to required thickness of slab.In the manufacturing process of above-mentioned copper alloy; Carry out anneal as follows; Heat with the temperature below 650 ℃ more than 550 ℃ and with the time below 10 hours more than 30 minutes, afterwards, cool off below 1 ℃/second more than 0.3 ℃/second with average cooling rate from Heating temperature to 450 ℃; Afterwards, cold rolling with 70～85% degree of finish.Below, the manufacturing process of copper alloy is elaborated by each operation.
(I) fusing and casting, hot rolling, first cold rolling (S1～S3)
In the present invention, melting and casting and after forming Cu alloy material (S1), this copper alloy is carried out hot rolling (S2) with the temperature below 1050 ℃ more than 800 ℃ with predetermined composition.If be lower than 800 ℃, then the amount of separating out of Fe is many, and when hot rolling, is easy to generate crackle.Then, carry out cold rolling (S3), but thickness of slab is become below the 3mm in order starting material integral body evenly to be transmitted heat effectively when the solution treatment of proceeding, preferably relative reduction in area to be set for.
(II) (S4) handled in heating solid solution (fluidization)
Above-mentioned hot rolling, cold rolling after, after keeping more than 30 seconds, be cooled to 300 ℃ with the speed of cooling of PM more than 100 ℃ immediately with the temperature more than 900 ℃, be cooled to room temperature again.The heating solution treatment is carried out in order to make the Fe precipitate solid solution of separating out when the hot rolling.If omit this operation, then can not obtain intensity and thermotolerance as target.
(III) second cold rolling (S5)
After above-mentioned solution treatment, carry out cold rolling.The cold rolling relative reduction in area that is carried out to becomes more than 50% to preferred.Separating out in the annealing that can successfully explain below thus.
(IV) annealing (S6)
Shown in the sketch chart of the annealing operation of Fig. 3, in the present invention, will anneal with heating below 650 ℃ more than 550 ℃ more than 30 minutes below 4 hours, preferably with heating below 600 ℃ more than 550 ℃ more than 1 hour below 4 hours.This operation is to be mainly used in the operation that precipitate B is separated out.This is being lower than under 550 ℃ the situation, and separating out and growing up of Fe needs the longer time, and to manufacturing process simple, the shorteningization effect is little.Under than 650 ℃ of high situation, the Fe precipitate becomes also thicker than suitable size, and this also becomes the reason that thermotolerance reduces.If the time is also departed from specialized range, then the precipitate size departs from suitable size, becomes the reason that thermotolerance and/or specific conductivity reduce.
In the present invention; With more than 550 ℃ below 650 ℃ the heating after; To be made as more than 0.3 ℃/minute from the average cooling rate of Heating temperature to 450 ℃ and cool off below 1 ℃/minute, preferably will be made as more than 0.5 ℃/minute and cool off below 0.8 ℃/minute from the average cooling rate of Heating temperature to 450 ℃.This operation is to be mainly used in the operation that precipitate A is separated out.Being set at average cooling rate from the scope of Heating temperature to 450 ℃ is because Fe separates out hardly when being lower than 450 ℃.In addition, with average cooling rate be set at more than 0.3 ℃/minute below 1 ℃/minute be because, if be lower than 0.3 ℃/minute, then to manufacturing process simple, the shorteningization effect is little.With than 1 ℃ of/minute fast speed of cooling, separating out of Fe can not fully be carried out, and can not obtain the specific conductivity of target.At this, average cooling rate (℃/minute) can be obtained by following formula (several 1).
Several 1
After above-mentioned timeliness, carry out cold working with the degree of finish below 85% more than 70% with rolling.Can not obtain the intensity of target when being lower than 70% degree of finish, thermotolerance reduces during than 85% big degree of finish, can not obtain the thermotolerance of target.In addition, after this, also can carry out low-temperature annealing in order to improve elongation or elimination distortion.
Embodiment
Below, to the present invention is based on the embodiment further explain, still the invention is not restricted to this.
To contain 2.2% Fe, 0.03% P, 0.1% Zn with weight %; And the copper alloy that remainder is formed by Cu and inevitable impurity; After the high-frequency induction crucible melting; Carry out semicontinuous casting with the copper mold, made the ingot casting of the rectangular parallelepiped of xsect 200mm * 450mm, length 4000mm.5mm is cut on the surface of this ingot casting respectively, keep carrying out hot rolling afterwards in 2 hours, make thickness of slab 12mm with 950 ℃.And, after 1mm is cut respectively in surface and the back side, through the first cold rolling thickness of slab 2.5mm that makes.
Then, be controlled in top temperature and be to the maximum in 950 ℃, copper coin is walked in the heating zone of continuous annealing furnace material.After the heating zone, then make it pass through cooling zone and water-cooled pond, carry out chilling and carry out solution treatment.And, after the lapped face and the back side, through the second cold rolling thickness of slab 0.7mm that makes.Then, with electric furnace in nitrogen atmosphere with 550 ℃ annealing temperature (heating in the annealing operation) 3 hours, be cooled to 450 ℃ with 0.5 ℃/minute of speed of cooling from 550 ℃ of Heating temperatures.Afterwards, with the cold room temperature that drops to of stove.
Table 1 is the table of each condition (Heating temperature, heat-up time, cooling range, annealing time, speed of cooling) in the expression annealing operation.
Table 1
With the form record of " Heating temperature * heat-up time ", be because under the big situation of the product of Heating temperature and heat-up time, separate out and carry out.Actual Heating temperature produces some inequalities in temperature sometimes, but makes the temperature of sample become Heating temperature with the mode that is not less than 550 ℃ of lowest temperatures.
" cooling range " expression is from 450 ℃ of the temperature of the lower limit of the temperature of the cooling beginning speed of cooling that to be above-mentioned Heating temperature state after be used to calculate.In addition, be lower than after 450 ℃, be positioned in the stove and cool off.
450 ℃ of used cooling times of temperature of the lower limit of the speed of cooling that " annealing time " expression is stated after be used to calculate from above-mentioned Heating temperature.
" speed of cooling " is temperature head that " cooling range " the put down in writing number divided by " annealing time " shown in formula (several 1).In addition, using 450 ℃ reason is that the end of separating out of Fe precipitate is roughly since 450 ℃.
Then, through the 3rd cold rolling thickness of slab 0.14mm that makes, make in its heating zone that walks in continuous annealing furnace with the purpose that improves elongation at last.The raw-material temperature of this moment is maximum 400 ℃, and it is below 5 minutes through the time.For the plate of this 0.14mm thickness, metal structure, machinery and electric characteristic, thermotolerance have been estimated.Evaluation method is following.
About metal structure, to will having carried out the sample of filmization, use to have and to have carried out surface analysis with the EDS of the visual field of 100,000 times of observations of transmission electron microscope to the Fe element with the vertical face of rolling direction.Utilize the result that the image analysis software analysis obtains thus (detecting the area of Fe), estimated precipitate A and B are added the total area 8 together
01+ 8
02Area occupation ratio, the total area S of precipitate A
01, precipitate B total area S
02
About the characteristic of machinery, tensile strength, elongation, specific conductivity, Vickers' hardness (tensile strength, elongation (elongation at break) are measured based on JIS Z2241, and Vickers' hardness is measured based on JISZ2244) have been estimated with electricity.In addition,, measure the 3rd Vickers' hardness and the Vickers' hardness after the 3rd applies 450 ℃ * 5 minutes thermal treatment after cold rolling after cold rolling, estimate with (Vickers' hardness after the thermal treatment) ÷ (thermal treatment Vickers' hardness before) about thermotolerance.Thermotolerance is the scope of being allowed more than 90%.
Table 2 is the ratio S with respect to the area of the total of precipitate A in expression embodiment and the comparative example
1, with respect to the ratio S of the area of the total of precipitate B
2, their the ratio S of area occupation ratio
1/ S
2, tensile strength, elongation, specific conductivity, Vickers' hardness, stable on heating table.
Table 2
As shown in table 2, with regard to the copper alloy plate among the embodiment 1, the ratio S of Fe precipitate A with respect to the area that adds up to
1Be 0.6%, the ratio S of Fe precipitate B with respect to the area that adds up to
2Be 0.5%, the ratio S of their area occupation ratio
1/ S
2Be 1.2.In addition, tensile strength is that 531MPa, elongation are 7%, specific conductivity is that 66%IACS, Vickers' hardness are 159Hv, and thermotolerance keeps 95%.In addition, the copper coin material is warming up to and heats 3 hours after 550 ℃, and to be cooled to 450 ℃ of needed time as shown in table 1 be 320 minutes.
In embodiment 2～5, also with the annealing conditions manufacturing shown in the table 1.Under situation about annealing conditions being set in the specialized range, can access good characteristic with embodiment 1 identical ground.
The method of present embodiment does not need the annealing more than 2 grades, therefore can reduce operation and reduce cost.In addition, can reduce the increase of output of the greenhouse oxidizing gases of carbonic acid gas of causing along with the increase of heat treatment time etc.
According to table 2, in embodiment 2, S
1Ratio be 0.4%, S
2Ratio be 0.7%, the ratio S of their area occupation ratio
1/ S
2Be 0.6.In addition, tensile strength is that 532MPa, elongation are 5%, specific conductivity is that 64%IACS, Vickers' hardness are 159Hv, and thermotolerance keeps 94%.
In embodiment 3, S
1Ratio be 0.7%, S
2Ratio be 0.5%, the ratio S of their area occupation ratio
1/ S
2Be 1.4.In addition, tensile strength is that 534MPa, elongation are 6%, specific conductivity is 65%IACS, is 159Hv with embodiment 2 identical ground Vickers' hardnesses, and thermotolerance keeps 94%.
In embodiment 4, S
1Ratio be 0.4%, S
2Ratio be 0.4%, the ratio (S of their area occupation ratio
1/ S
2) be 1.0.This be Fe precipitate A be equal example with respect to the ratio of the area that adds up to and the ratio of Fe precipitate B with respect to the area that adds up to.In addition, tensile strength is that 546MPa, elongation are 5%, specific conductivity is that 60%IACS, Vickers' hardness are 156Hv, and thermotolerance is 91%.
In embodiment 5, with embodiment 4 identical ground, S
1Ratio be 0.4%, S
2Ratio be 0.4%, the ratio S of their area occupation ratio
1/ S
2Be 1.0.In addition, tensile strength is that 535MPa, elongation are 5%, specific conductivity is that 60%IACS, Vickers' hardness are 157Hv, and thermotolerance is 92%.
Relatively the foregoing description 1～3 can know that with embodiment 4,5 embodiment 1～3 compares S
1And S
2Ratio better for embodiment 4,5 characteristics (tensile strength, elongation, specific conductivity, Vickers' hardness, thermotolerance) that equate.
Embodiment 6
Embodiment 6 is with the condition manufacturing identical with embodiment 1, but is 12 hours and longer heat-up time.According to table 2, S
1Ratio be 0.4%, S
2Ratio be 1.1%, the ratio S of their area occupation ratio
1/ S
2Be 0.4.In addition, tensile strength is that 547MPa, elongation are 7%, specific conductivity is that 67%IACS, Vickers' hardness are 159Hv, and thermotolerance is 93%.Considering that more preferably embodiment 1～3 under manufacturing time and the condition of cost.
Embodiment 7
Embodiment 7 except annealing conditions to make identically with embodiment 1 identical composition.In embodiment 7, after the second cold rolling operation, use electric furnace in nitrogen atmosphere with 600 ℃ annealing temperature 2 hours, be cooled to 500 ℃ with 5 ℃/minute of speed of cooling, annealed afterwards 2 hours.
Afterwards, be cooled to 450 ℃ with 5 ℃/minute, kept 2 hours with this temperature.After 450 ℃ of maintenances, with the cold room temperature that drops to of stove.The annealing conditions of table 1 expression embodiment 7.Then, through the 3rd cold rolling thickness of slab 0.14mm that makes, make in its heating zone that walks in continuous annealing furnace with the purpose that improves elongation at last.The raw-material temperature of this moment is maximum 400 ℃, and it is below 5 minutes through the time.The characteristic of the copper coin in the present embodiment 7 is: tensile strength is that 543MPa, elongation are 5%, specific conductivity is that 66%IACS, Vickers' hardness are 158Hv, and thermotolerance keeps 91%.
In addition, after being warmed up to 600 ℃, to keep finishing the needed time in two hours with 450 ℃ be 380 minutes to the copper coin material.Present embodiment can access the performance with embodiment 1 to 3 same degree, but spended time.
In addition, in the Fe of above-mentioned each embodiment precipitate, be lower than 20nm
2Be below 0.02%.
Comparative example 1～6
Comparative example 1～6 also is to make with embodiment 1 identical condition identically except annealing conditions.Annealing conditions is as shown in table 1.
Comparative example 1 is the example that was made as than the specialized range shortening 10 minutes heat-up time.As shown in table 2, thermotolerance is 62% and not enough.Think that its reason is: S
1Ratio be 0.7%, S
2Ratio be 0.1%, the ratio S of their area occupation ratio
1/ S
2Be 7.0, S
2With respect to S
1Ratio little, in annealing operation, the Fe precipitate fails fully to grow up.
Comparative example 2 is that Heating temperature is also lower and be made as 500 ℃ example than specialized range.In this case, even carry out the 6 hour thermal treatments also longer than the specified time, thermotolerance is 62% and not enough.This be because: because Heating temperature is low, do not promote separating out of Fe, so 200nm
2Above Fe precipitate is not enough, the ratio S of area occupation ratio
1/ S
2Become 2.3, cause thermotolerance not enough.
Comparative example 3 is that Heating temperature is also higher and be made as 700 ℃ example than specialized range.Surpass 200nm
2Thick precipitate increase the ratio S of area occupation ratio
1/ S
2Become 0.3 and be lower than 0.4.Therefore, specific conductivity be 43%IACS and lower, thermotolerance drops to 61% greatly.
Comparative example 4 is that speed of cooling also is made as 0.1 ℃/minute slowly than specialized range, and the annealing time lengthening is made as 1030 minutes example.Though guaranteed S
1Area occupation ratio be 1.2% and higher, and specific conductivity is 73%IACS, but the ratio S of area occupation ratio
1/ S
2Be 4.0 and higher.Therefore, thermotolerance is 62% and lower, can not guarantee thermotolerance.
To be heat-up times than specialized range also long and be made as 6 hours for comparative example 5, and the speed of cooling in the annealing operation is made as 5 ℃/minute the example also faster than specialized range.In this case, thermotolerance is 90% and higher, but S
1Area occupation ratio be actually zero, specific conductivity drops to 53%IACS.
Comparative example 6 is with after 550 ℃ of heating 4 hours, carries out the example of water-cooled immediately.In this case, S
2Ratio be 0.8%, the major part that obtains the size of a lot of precipitates is 200nm
2Therefore above precipitate accesses the characteristic of 91% in the specialized range about resistance toheat, but S
1Be lower than 0.4%, specific conductivity is 54% and not enough.
Comparative example 7 is to be warming up to after 550 ℃, carries out the refrigerative example with 0.3 ℃/minute immediately.In this case, S
2(0.1%) with respect to S
1(0.3%) little, so the ratio S of area occupation ratio
1/ S
2Become 3.0 and surpass 1.4, thermotolerance is 60% and lower, breaks away from specialized range.
In addition, if be conceived to comparative example 7 and embodiment 3, then their difference is 550 ℃ * 30 minutes hold-time.We can say, separating out during for the cooling in the annealing operation, the hold-time influence of heated condition before is bigger.
More than, to embodiments of the invention 1～7 and comparative example 1～7, their condition and evaluation result is illustrated.According to the evaluation result of table 2, especially in embodiment 1 and embodiment 3, can access superior elongation, specific conductivity, Vickers' hardness, thermotolerance.In embodiment 1 and embodiment 3, the ratio S of area occupation ratio
1/ S
2Be 1.2 and 1.4, therefore in copper alloy of the present invention, 1.2≤S more preferably
1/ S
2≤1.4.
According to the embodiment of the invention described above, can provide to have HS, high conductivity, and the copper alloy of superior for heat resistance.In addition, can simplify working process, and can suppress manufacturing cost.Thus, can shorten the treatment time, and can reduce the output of the greenhouse oxidizing gases of carbonic acid gas etc.
Claims (3)
1. electric, electronic component-use copper alloy, containing Fe is that 2.1～2.6 weight %, P are that 0.015～0.15 weight %, Zn are 0.05～0.20 weight %, and remainder is made up of Cu and unavoidable impurities, it is characterized in that,
In the Fe precipitate in being scattered in the Cu parent phase, single area is 20nm
2More than and be lower than 200nm
2The total area area occupation ratio S whole of Fe precipitate with respect to the Cu parent phase
1Be more than 0.4%,
Single area is 200nm
2The total area area occupation ratio S whole of above Fe precipitate with respect to the Cu parent phase
2Satisfy 0.4≤S
1/ S
2≤1.4 relation.
2. electric, electronic component-use copper alloy according to claim 1 is characterized in that,
1.2≤S
1/S
2≤1.4。
3. the method for manufacture of electric, an electronic component-use copper alloy; To contain Fe is that 2.1～2.6 weight %, P are that 0.015～0.15 weight %, Zn are 0.05～0.20 weight %; And the ingot casting that remainder is made up of Cu and unavoidable impurities through hot rolling, first cold rolling, heating solution treatment, second cold rolling, annealing, the 3rd cold rolling operation, is machined to required thickness of slab; It is characterized in that
Above-mentioned annealing is with heating below 650 ℃ more than 550 ℃ more than 30 minutes below 4 hours, afterwards, more than 0.3 ℃/minute below 1 ℃/minute, is cooled to 450 ℃ from this Heating temperature with average cooling rate,
The above-mentioned the 3rd cold rolling degree of finish with 70～85% carries out cold rolling.
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| JP2010290659A JP5555154B2 (en) | 2010-12-27 | 2010-12-27 | Copper alloy for electrical and electronic parts and method for producing the same |
| JP2010-290659 | 2010-12-27 |
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| CN102534292A true CN102534292A (en) | 2012-07-04 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104073677B (en) * | 2013-03-27 | 2017-01-11 | 株式会社神户制钢所 | Copper alloy strip for lead frame of led |
| CN106591623A (en) * | 2016-12-05 | 2017-04-26 | 宁波博威合金板带有限公司 | High-temperature-resisting ferro-bronze and preparing method and application of high-temperature-resisting ferro-bronze |
| CN112585699A (en) * | 2018-08-21 | 2021-03-30 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
| CN113278828A (en) * | 2021-04-13 | 2021-08-20 | 太原晋西春雷铜业有限公司 | Preparation process for homogenizing C19400 copper alloy cast ingot structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016211053A (en) | 2015-05-12 | 2016-12-15 | 株式会社神戸製鋼所 | Copper alloy excellent in heat resistance |
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| JPH02111829A (en) * | 1988-10-20 | 1990-04-24 | Sumitomo Metal Mining Co Ltd | Copper alloy for lead frame |
| JP2004099978A (en) * | 2002-09-10 | 2004-04-02 | Kobe Steel Ltd | Copper alloy having high strength and high conductivity |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073677B (en) * | 2013-03-27 | 2017-01-11 | 株式会社神户制钢所 | Copper alloy strip for lead frame of led |
| CN106591623A (en) * | 2016-12-05 | 2017-04-26 | 宁波博威合金板带有限公司 | High-temperature-resisting ferro-bronze and preparing method and application of high-temperature-resisting ferro-bronze |
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| CN112585699A (en) * | 2018-08-21 | 2021-03-30 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
| CN112585699B (en) * | 2018-08-21 | 2022-05-13 | 住友电气工业株式会社 | Covered electric wire, electric wire with terminal, copper alloy wire, copper alloy stranded wire, and method for producing copper alloy wire |
| CN113278828A (en) * | 2021-04-13 | 2021-08-20 | 太原晋西春雷铜业有限公司 | Preparation process for homogenizing C19400 copper alloy cast ingot structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5555154B2 (en) | 2014-07-23 |
| JP2012136746A (en) | 2012-07-19 |
| CN102534292B (en) | 2015-09-09 |
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