CN100530448C - Copper alloy conductor manufacturing method - Google Patents
Copper alloy conductor manufacturing method Download PDFInfo
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- CN100530448C CN100530448C CNB2007101086372A CN200710108637A CN100530448C CN 100530448 C CN100530448 C CN 100530448C CN B2007101086372 A CNB2007101086372 A CN B2007101086372A CN 200710108637 A CN200710108637 A CN 200710108637A CN 100530448 C CN100530448 C CN 100530448C
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Abstract
To provide a copper alloy conductive body provided with both superior strength and high conductivity, and its manufacturing method. Tin is contained in 0.05 to 0.80 wt%, the rest is composed of inevitable impurities and copper, this tin exists in the state of a tin simple substance and tin oxide, and tin component weight of tin oxide/weight of the tin simple substance is 0.3 or less. By making the ratio of tin oxide small, effective amount of tin to contribute to increasing tensile strength is increased, and by making the total amount of tin necessary to obtain the prescribed tensile strength small, reduction of the conductivity is suppressed. Therefore, the conductor can be realized in which both high strength and high conductivity are compatible.
Description
The application is September 24 2003 03157594.3 applying date of original application application number, and denomination of invention is divided an application for " copper alloy conductor ".
Technical field
The present invention is especially in regard to a kind of intensity and good copper alloy conductor and the manufacture method thereof of conductance.
Background technology
As the correlation technique of known copper alloy conductor, in the special public clear 46-32333 communique of Japanese Patent Laid Open Publication, record a kind of so-called tough annealed copper wire.Normally a kind of copper that is no less than 250ppm (0.025%) oxygen that contains of tough copper metallurgy contains impurity such as Ag, Ni, Sb, As, Fe, Sn, Pb, Bi, Si, S.
In addition, also have a kind of spy of Japanese Patent Laid Open Publication to open to be put down in writing in the clear 57-1562 communique, by in copper, add the technology of the fixed element broken string when suppressing wire drawing.
But, the conductor that is difficult to obtain intensity and conductance and deposits by above-mentioned known technology.
When in tough copper metallurgy etc., adding tin, can improve intensity.But the oxygen content in tough copper metallurgy is big, and contained tin is become under the situation of tin oxide, and the contribution that intensity is improved reduces.So, must increase tin concentration for the intensity that needing to obtain.Yet, the problem that when increasing tin concentration, exists conductance to descend and descend as the electrical characteristic of conductor.
Summary of the invention
Therefore, main purpose of the present invention provides a kind of manufacture method that has the copper alloy conductor of good intensity and high conductivity concurrently.
The present invention is by limiting tin concentration, and special provision is present in the tin oxide in the copper alloy and the ratio of tin simple substance, thereby reaches above-mentioned purpose.
That is, main purpose of the present invention provides a kind of manufacture method of copper alloy conductor, comprising:
The engineering that will contain engineering that raw material that the tin of 0.05～0.80 weight %, remaining part is made of unavoidable impurities and copper fuses casting, resulting ingot bar is rolled, it is characterized in that: during the solidifying of the fusion raw material in aforementioned casting engineering, make cooling rate be not less than 3 ℃/second; Cooling rate when making the ingot bar to 200 ℃ after described the solidifying be not less than 10 ℃/.
As mentioned above, the copper alloy conductor that can form intensity and conductance and deposit particularly can be suitable as e-machine and use the conductor of distribution to use with distribution and automobile.
Embodiment
Below the present invention is described in more detail.
When tin concentration during, be difficult to obtain enough hot strengths less than 0.05 weight %.In conductor of the present invention, preferable hot strength is 550N/mm
2More than, be more preferred from 600N/mm
2More than, special good is 700/mm
2More than.
Otherwise, when tin concentration during greater than 0.08 weight %, be difficult to obtain fixed conductance.In conductor of the present invention, preferable conductance is more than 55%, is more preferred from more than 70%, and special good is more than 80%.This conductance is represented with the percentage (%IACS) to the conductance of the standard annealed copper of international annealed copper standard defined 20 ℃ the time.
In the chemical composition that forms copper alloy conductor of the present invention, also can contain unavoidable impurities.Unavoidable impurities comprises Ag, Ni, Sb, As, Fe, Pb, Bi, P, Si, Zn, S, Se, Te etc.
And the weight ratio that makes tin composition in the tin oxide and tin simple substance is below 0.3.When this ratio surpasses 0.3, will increase tin concentration in order to obtain enough hot strengths, cause the decline of conductance easily.The total tin weight of Sn among the SnO and Sn is measured by ICP Atomic Emission Spectrophotometer (Emission Spectro-photometric Analysis).The weight of Sn simple substance be by with the sample dissolution of copper alloy conductor in 60% nitric acid and make the SnO precipitate and separate, and the fining end branch imposed atomic absorption analysis (Atimic Absorption Spectrometry), obtain thereby the Sn that is dissolved measured.By from add up to tin weight, deducting the weight of Sn simple substance, can ask among the SnO weight of the tin that is contained.This SnO mainly is in the process of setting in when casting, by with liquid copper in contained combining of oxygen generate.
Forming oxygen concentration in the copper alloy conductor of the present invention, to be no more than 0.08 weight % be good.When oxygen concentration surpassed 0.08 weight %, the amount of SnO increased, and the wire-drawing workability to resulting conductor brings obstacle sometimes.Better oxygen concentration is below the 0.04 weight %.The mensuration of oxygen concentration for example can be utilized, and infrared absorption analysis (Infrared Spectrum Absorbance) carries out.
The mean particle diameter of the tin oxide that in addition, forms in the copper alloy conductor of the present invention to be contained below 10 μ m for good.When mean particle diameter surpasses 10 μ m, sometimes to resulting conductor wire drawing the processability during to thin footpath bring obstacle.The mean particle diameter of tin oxide can utilize scanning electron microscope: SEM (Scanning Electron Microscope) and energy dispersion type x-ray analysis device: EDX (Energy-dispersive X-ray Spectroscopy) to measure.The mean particle diameter of better tin oxide is below 5 μ m.
Above-mentioned copper alloy conductor is fit to utilize following method to make.Promptly, the manufacture method of copper alloy conductor of the present invention comprises that the raw material that the tin that will contain 0.05～0.80 weight %, remaining part are made of unavoidable impurities and copper fuses the engineering of casting and the engineering that resulting ingot bar is rolled, when it is characterized in that the solidifying of fusion raw material in aforementioned casting engineering, make cooling rate be not less than 3 ℃/second.
By utilizing the raw material of above-mentioned tin amount, and the cooling rate when making the solidifying of fusion raw material is not less than 3 ℃/second, and the weight that can access the tin composition weight/tin simple substance in the tin oxide is not more than 0.3 copper alloy conductor.When cooling rate during less than 3 ℃/second, the growing amount of tin oxide increases, and causes the decline of conductance.Usually the upper limit of this cooling rate is about 50 ℃/second.
In general, the engineering that copper alloy conductor can utilize fusion → casting → heat (cold) to roll obtains, in the later stage engineering, carry out wire drawing again and be processed into fixed line footpath.Here, make ingot bar after solidifying when hot rolling reaches 200 ℃ cooling rate or the cooling rate of after casting, carrying out before cold rolling be not less than 10 ℃/second for good.By being controlled at such cooling rate, the growing amount that can make tin oxide is a suitable scope, and keeps higher intensity and conductance.When cooling rate during less than 10 ℃/second, tin spreads the growing amount that makes tin oxide and increases in copper, and causes the decline of conductance.
Form copper alloy conductor of the present invention and have enough intensity, the conductor that particularly can be used as thin footpath utilizes.For example can obtain line like a cork and directly be no more than 1.2mm, even not surpass the conductor of 0.5mm.
Below example of the present invention is described.
(experimental example 1) prepares to contain the copper alloy that the Sn of 0.075 weight %, remaining part are made of Cu and unavoidable impurities, and utilizes the engineering making copper alloy conductor of " fusion → casting → hot rolling → cold rolling ".In casting, utilize the double belt type casting machine.
By the operation result as can be known, the cooling rate when solidifying is 5.77 ℃/second, and the cooling rate (cooling rate that adds man-hour) to 200 ℃ after solidifying is 21 ℃/second.
In the process that engineering is carried out, after rolling end, take off sample and utilize ICP Atomic Emission Spectrophotometer (dry analysis) to ask the full Sn in the alloy to measure.Then by with this sample dissolution in 60% nitric acid, and make the insoluble matter precipitation, and clarification partly carried out atomic absorption analysis, thereby try to achieve the Sn simple substance amount of dissolving.Deduct Sn simple substance amount by full Sn amount, be the amount of the Sn among the SnO.As a result, the value of the Sn/Sn among the SnO is 0.07.And, when utilizing scanning electron microscope (SEM) to observe the sample section after rolling and asking mean particle diameter, be 4 μ m.
When taking another sample and utilize infrared absorption analysis to measure oxygen content, be 0.0230 weight %.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), and finish line directly is 0.4mm.In addition, when this experimental example, comparative example are carried out comprehensively, to the outage in the processing and in the later stage engineering processing difficulty during graph thinning comprehensively judge as processability, and evaluation is divided into 5 levels, by good be 5, difference be 1 when marking, experimental example 1 obtains 5 evaluation.
When utilizing this copper alloy conductor to ask hot strength and conductance, hot strength is 552N/mm
2, conductance is 88.3%IACS.
(experimental example 2) is the copper alloy of 0.624 weight % except utilizing the Sn amount, makes copper alloy conductor by the engineering identical with experimental example 1.Cooling rate when solidifying is 3.2 ℃/second, and the cooling rate that adds man-hour is 23 ℃/second.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), obtains the finish line footpath of 0.4mm.
When same with experimental example 1, engineering ongoing rolling after, when taking sample and measuring Sn/Sn among the SnO, be 0.28, the mean particle diameter of SnO is 12 μ m.And oxygen content is 0.0298 weight %.
The hot strength of resulting copper alloy conductor is 720N/mm
2, conductance is 62.5%IACS.Processability be evaluated as 2, its reason is because the granularity of SnO becomes big.
And, though this experimental example 2 is compared with experimental example 6 with experimental example 5, containing more Sn, hot strength can not be a high value.This also is because the particle diameter of SnO becomes big.
(experimental example 3) is the copper alloy of 0.187 weight % except utilizing the Sn amount, makes copper alloy conductor by the engineering identical with experimental example 1.Cooling rate when solidifying is 3.9 ℃/second, and the cooling rate that adds man-hour is 18 ℃/second.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), obtains the finish line footpath of 0.4mm.
When same with experimental example 1, engineering ongoing rolling after, when taking sample and measuring Sn/Sn among the SnO, be 0.18, the mean particle diameter of SnO is 6 μ m.And oxygen content is 0.0820 weight %.
The hot strength of resulting copper alloy conductor is 595N/mm
2, conductance is 82.6%IACS.Processability be evaluated as 4.
Experimental example 3 is compared with next experimental example 4, contains more Sn, but since oxygen content than experimental example more than 4, so the amount of SnO increases, and the value of hot strength is also less than embodiment 4.
(experimental example 4) is the copper alloy of 0.177 weight % except utilizing the Sn amount, makes copper alloy conductor by the engineering identical with experimental example 1.Cooling rate when solidifying is 5.47 ℃/second, and the cooling rate that adds man-hour is 18 ℃/second.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), obtains the finish line footpath of 0.4mm.
When same with experimental example 1, engineering ongoing rolling after, when taking sample and measuring Sn/Sn among the SnO, be 0.07, the mean particle diameter of SnO is 6 μ m.And oxygen content is 0.0350 weight %.
The hot strength of resulting copper alloy conductor is 610N/mm
2, conductance is 82.8%IACS.Form the very material of balance.And processability is very good, obtains 5 evaluation.
(experimental example 5) is the copper alloy of 0.315 weight % except utilizing the Sn amount, makes copper alloy conductor by the engineering identical with experimental example 1.Cooling rate when solidifying is 5.47 ℃/second, and the cooling rate that adds man-hour is 8 ℃/second.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), obtains the finish line footpath of 0.4mm.
When same with experimental example 1, engineering ongoing rolling after, when taking sample and measuring Sn/Sn among the SnO, be 0.11, the mean particle diameter of SnO is 5 μ m.And oxygen content is 0.0410 weight %.
The hot strength of resulting copper alloy conductor is 700N/mm
2, conductance is 76.8%IACS.Processability be evaluated as 3.This is because add the cooling rate in man-hour.
And in this experimental example 5, although the amount of Sn is slightly little than next experimental example 6, conductance is big unlike embodiment 6.Its reason is that Sn diffuses to form SnO in Cu because adding the cooling rate in man-hour is no more than 10 ℃/second, thereby conductance is descended.
(experimental example 6) is the copper alloy of 0.338 weight % except utilizing the Sn amount, makes copper alloy conductor by the engineering identical with experimental example 1.Cooling rate when solidifying is 5.47 ℃/second, and the cooling rate that adds man-hour is 23 ℃/second.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), obtains the finish line footpath of 0.4mm.
When same with experimental example 1, engineering ongoing rolling after, when taking sample and measuring Sn/Sn among the SnO, be 0.07, the mean particle diameter of SnO is 4 μ m.And oxygen content is 0.0215 weight %.
The hot strength of resulting copper alloy conductor is 710N/mm
2, conductance is 78.0%IACS.Processability be evaluated as 4.
(comparative example 1) is the copper alloy of 0.030 weight % except utilizing the Sn amount, makes copper alloy conductor by the engineering identical with experimental example 1.Cooling rate when solidifying is 5.47 ℃/second, and the cooling rate that adds man-hour is 18 ℃/second.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), obtains the finish line footpath of 0.4mm.
When same with experimental example 1, engineering ongoing rolling after, when taking sample and measuring Sn/Sn among the SnO, be 0.03, the mean particle diameter of SnO is 3 μ m.And oxygen content is 0.0240 weight %.
The hot strength of resulting copper alloy conductor is 535N/mm
2, conductance is 97.8%IACS.Owing to adopt the raw material near fine copper, the conductance performance is bigger value, but hot strength can not get enough intensity.Processability is no problem, is evaluated as 5.
(comparative example 2) is the copper alloy of 0.680 weight % except utilizing the Sn amount, makes copper alloy conductor by the engineering identical with experimental example 1.Cooling rate when solidifying is 2.1 ℃/second, and the cooling rate that adds man-hour is 23 ℃/second.
Degree of finish after wire drawing finishes is 99.75% (section reduction rate), obtains the finish line footpath of 0.4mm.
When same with experimental example 1, engineering ongoing rolling after, when taking sample and measuring Sn/Sn among the SnO, be 0.37, the mean particle diameter of SnO is bigger, reaches 20 μ m.And oxygen content is 0.0850 weight %.
The hot strength of resulting copper alloy conductor is 710N/mm
2, but conductance is lower, is 52.5%IACS.This raw material is owing to Sn content height, so hot strength is big, but conductance has deficiency slightly.And processability is evaluated as 1 because the outage in the later stage engineering increases.Consideration is because the SnO particle diameter becomes big cause.
Shown in above-mentioned experimental example and comparative example, arbitrary experimental example all possesses high tensile and conductance simultaneously.And, shown in comparative example 1, when the Sn content in the raw material itself during not a preferred range, no matter processing conditions how, all can't make hot strength and conductance and deposit.Even the Sn/Sn among the SnO above 0.3, can not make hot strength and conductance too and deposit.
As described above, form copper alloy conductor of the present invention, increase effective tin amount that the increase of hot strength is made contributions by reducing the ratio of tin oxide, and by be reduced to obtain the fixed required total tin amount of hot strength suppress the decline of conductance.So, the conductor that can realize making high strength and conductance and deposit.
And the manufacture method that forms copper alloy conductor of the present invention is a kind of manufacture method that is suitable for making copper alloy conductor of the present invention.
Claims (1)
1. the manufacture method of a copper alloy conductor comprises:
The engineering that will contain engineering that raw material that the tin of 0.05～0.80 weight %, remaining part is made of unavoidable impurities and copper fuses casting, resulting ingot bar is rolled, it is characterized in that: during the solidifying of the fusion raw material in aforementioned casting engineering, make cooling rate be not less than 3 ℃/second; Make the cooling rate of ingot bar when being hot-rolled down to 200 ℃ after described the solidifying be not less than 10 ℃/second.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002329628 | 2002-11-13 | ||
| JP2002329628 | 2002-11-13 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031575943A Division CN100347790C (en) | 2002-11-13 | 2003-09-24 | Copper alloy conductor and method of fabricating the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101071661A CN101071661A (en) | 2007-11-14 |
| CN100530448C true CN100530448C (en) | 2009-08-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101086372A Expired - Lifetime CN100530448C (en) | 2002-11-13 | 2003-09-24 | Copper alloy conductor manufacturing method |
| CNB031575943A Expired - Lifetime CN100347790C (en) | 2002-11-13 | 2003-09-24 | Copper alloy conductor and method of fabricating the same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031575943A Expired - Lifetime CN100347790C (en) | 2002-11-13 | 2003-09-24 | Copper alloy conductor and method of fabricating the same |
Country Status (3)
| Country | Link |
|---|---|
| CN (2) | CN100530448C (en) |
| HK (1) | HK1064796A1 (en) |
| TW (1) | TWI291994B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4479510B2 (en) * | 2005-01-17 | 2010-06-09 | 日立電線株式会社 | Copper alloy conductor, trolley wire / cable using the same, and method for producing copper alloy conductor |
| CN100538917C (en) * | 2005-12-26 | 2009-09-09 | 云南铜业股份有限公司 | A kind of production method of copper-tin alloy conducting wire |
| CN103421982A (en) * | 2013-07-15 | 2013-12-04 | 徐高磊 | Copper alloy band used on auto radiator |
| CN103602851B (en) * | 2013-11-08 | 2015-10-28 | 浙江八达铜业有限公司 | Copper alloy and manufacture method thereof |
| CN107723504B (en) * | 2017-10-09 | 2019-08-09 | 中国西电集团有限公司 | A kind of contact line of bronze in use for electrified railroad in and its method for continuous production |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4632333Y1 (en) * | 1971-02-13 | 1971-11-09 | ||
| EP0039503B1 (en) * | 1980-05-05 | 1984-03-21 | Olin Corporation | Method of processing copper base alloys and cast copper base alloys produced in accordance with this method |
| US4822560A (en) * | 1985-10-10 | 1989-04-18 | The Furukawa Electric Co., Ltd. | Copper alloy and method of manufacturing the same |
| JPS6345338A (en) * | 1986-04-10 | 1988-02-26 | Furukawa Electric Co Ltd:The | Copper alloy for electronic and electric appliance and its production |
| JPH03219033A (en) * | 1990-01-22 | 1991-09-26 | Toyama Pref Gov | Copper alloy for metallic art castings having pear-skin tone |
| CN1032824C (en) * | 1993-09-06 | 1996-09-18 | 铁道部科学研究院机车车辆研究所 | Copper alloy contact wire |
-
2003
- 2003-09-01 TW TW92124073A patent/TWI291994B/en not_active IP Right Cessation
- 2003-09-24 CN CNB2007101086372A patent/CN100530448C/en not_active Expired - Lifetime
- 2003-09-24 CN CNB031575943A patent/CN100347790C/en not_active Expired - Lifetime
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2004
- 2004-10-04 HK HK04107594A patent/HK1064796A1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW200407441A (en) | 2004-05-16 |
| TWI291994B (en) | 2008-01-01 |
| CN1501409A (en) | 2004-06-02 |
| CN100347790C (en) | 2007-11-07 |
| CN101071661A (en) | 2007-11-14 |
| HK1064796A1 (en) | 2005-02-04 |
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