CN103459678A - Sn plating material - Google Patents
Sn plating material Download PDFInfo
- Publication number
- CN103459678A CN103459678A CN201280016466XA CN201280016466A CN103459678A CN 103459678 A CN103459678 A CN 103459678A CN 201280016466X A CN201280016466X A CN 201280016466XA CN 201280016466 A CN201280016466 A CN 201280016466A CN 103459678 A CN103459678 A CN 103459678A
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- CN
- China
- Prior art keywords
- copper
- alloy layer
- tin
- alloy
- exposed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
Abstract
The invention provides a Sn plating material that can suppress occurrences of Sn powder by partially exposing a Cu-Sn alloy layer in a reflow Sn plating layer on the surface of a copper or copper alloy strip. A Sn plating material (10) has a Sn plating layer (6) for which reflow processing has been carried out on the surface of a copper or copper alloy strip (2). The area ratio of a Cu-Sn alloy layer (4a) exposed on the outermost surface is 0.5 - 4%, and viewed from the outermost surface, the number of exposed spots for this Cu-Sn alloy layer is 100 - 900 per 0.033 mm2.
Description
Technical field
The present invention relates to a kind of tin plated materials, it is suitable for use as the conductive elastic materials such as junctor, terminal, rly., switch, has at copper or copper alloy bar surface and has implemented the tin coating that soft heat is processed.
Background technology
Automobile with and various terminals, junctor, rly. or the switch etc. of the terminal used of the people's livelihood, junctor, electric/electronic device in, good soldering wettability, solidity to corrosion, the electrical connectivity of performance tin, implemented zinc-plated (patent documentation 1) on the surface of copper or copper alloy bar.In addition, to more than the melting point of tin and the soft heat of implementing melting is processed, make the raisings such as adaptation or outward appearance at zinc-plated post-heating.
Patent documentation 1: TOHKEMY 2006-283149 communique.
; the copper product to thering is above-mentioned tin coating (below; be called " tin plated materials ") carry out press working and when manufacturing junctor etc.; although press copper product with liner, exist and to contact from the tin coating generation glass putty on copper product surface because of liner with the copper product surface and to sneak into the problem of press.
Summary of the invention
, the present invention proposes in order to solve above-mentioned problem, purpose is to provide a kind of tin plated materials, it is difficult for producing glass putty from the soft heat tin coating on copper or copper alloy bar surface.
The present inventors have carried out various research, found that: if the coating on copper or copper alloy bar surface is carried out after the soft heat processing, the Cu-Sn alloy layer being exposed partly on most surface, the Cu-Sn alloy layer exposed keeps the pure stannum layer of (pin is solid) most surface, suppresses the generation of glass putty.
, tin plated materials of the present invention is the tin plated materials with tin coating of having implemented the soft heat processing on the surface of copper or copper alloy bar, the Area Ratio of the Cu-Sn alloy layer exposed in most surface is 0.5～4%, from most surface, the number of the aforementioned Cu-Sn alloy layer exposed is every 0.033mm
2it is 100～900.
According to the present invention, by making the Cu-Sn alloy layer, at the soft heat tin coating on copper or copper alloy bar surface, expose partly, thereby the Cu-Sn alloy layer exposed can keep the pure stannum layer of (pin is solid) most surface, suppresses the generation of glass putty.
The accompanying drawing explanation
Fig. 1 is the figure that the cross section structure of tin plated materials is shown;
Fig. 2 is SEM picture (reflection electronic picture) that the surface of embodiment 1 is shown and the figure of binary image thereof.
Description of reference numerals:
2: mother metal (copper or copper alloy bar), 4:Cu-Sn alloy layer, 4a: the Cu-Sn alloy layer exposed in most surface, 6: implemented the tin coating that soft heat is processed, 10: tin plated materials, 21: scratch.
Embodiment
Below, the tin plated materials related to embodiments of the present invention describes.In addition, in the present invention, unless otherwise specified, % means quality %.
(1) composition of mother metal
As the copper bar of the mother metal that becomes tin plated materials, can use purity is tough pitch copper, the oxygen free copper more than 99.9%, in addition, as copper alloy bar, can use known copper alloy according to desired intensity or electroconductibility.As known copper alloy, such as enumerating phosphor bronze, brass, titanium copper, corson alloy etc.
(tin coating)
Be formed with on the surface of copper or copper alloy bar and implemented the tin coating that soft heat is processed.Tin coating directly or via plating bottom plating on the surface of copper or copper alloy bar.Enumerate nickel, copper as the plating bottom, can plating a kind of in them, or also can obtain bis-layers of plating bottom of Cu/Ni by the order plating nickel of nickel, copper, copper.
In addition, the related tin plated materials of embodiments of the present invention can be manufactured by following operation usually: in continuous plating production line, degreasing and pickling are carried out in surface to the copper as mother metal or copper alloy bar, then form the plating bottom by electrochemical plating, then by known electrochemical plating, form the tin layer, finally implement the soft heat processing and make the melting of tin layer.Zinc-plated can being undertaken by known method, such as using sulfuric acid bath, sulfonic acid bath, halogen bath etc.
(Cu-Sn alloy layer)
If then implement soft heat at the electroplating surfaces with tin of mother metal (copper or copper alloy bar) 2, process, as shown in Figure 1, the copper in mother metal (copper or copper alloy bar) 2, to 6 diffusions of surperficial tin coating, forms Cu-Sn alloy layer 4 between tin coating 6 and mother metal.Cu-Sn alloy layer 4 has Cu usually
6sn
5and/or Cu
3sn
4composition, but also can comprise the composition of above-mentioned plating bottom or take the interpolation element of copper alloy during as mother metal.
Here, it is to make pure tin stay most surface fully that common soft heat is processed, and Cu-Sn alloy layer 4 does not expose from the teeth outwards, but in the present invention, and the Cu-Sn alloy layer is exposed on most surface with 0.5～4% Area Ratio.Because the Cu-Sn alloy layer is harder than pure tin, the Cu-Sn alloy layer 4a that the scratch 21 that is therefore kept producing when most surface by liner when press working is exposed fixes, and has suppressed to abrade 21 elongations and the pure tin on surface is peeled off the situation of (glass putty).
The Area Ratio of the Cu-Sn alloy layer that order is exposed in most surface is 0.5～4%.If Area Ratio less than 0.5%, do not produce the solid effect of the above-mentioned pin of being realized by the Cu-Sn alloy layer.On the other hand, if Area Ratio surpasses 4%, the pure tin quantitative change on surface is few, and soldering wettability, solidity to corrosion, electrical connectivity etc. are deteriorated, and surface becomes the firecoat shape, and outward appearance is also poor.
The scanning electronic microscope (SEM) that the Area Ratio of Cu-Sn alloy layer is obtained the surface of tin plated materials as the reflection electronic picture.Because the Cu-Sn alloy layer exposed in most surface is compared with tin and is become darker image, so can, this is reversed and convert white image to after as binaryzation, calculate by the area of asking for the Cu-Sn alloy layer.(binaryzation for example is set as 120 in the luminance range 255 of SEM device)
In addition, manage into 0.5～4% method as the Area Ratio by the Cu-Sn alloy layer, enumerate the adjustment of reflowing temperature or Reflowing Time, the adjustment of tin coating thickness.Adjust by these, can control the growth degree of Cu-Sn alloy layer from mother metal one lateral surface, control the ratio of the Cu-Sn alloy layer that arrives most surface (exposing).
For example, the thickness of the tin layer before soft heat is processed can be 0.1～5.0 μ m, and the thickness of the pure stannum layer after the soft heat processing can be also 0.1～4.5 μ m.
From most surface, the number of the Cu-Sn alloy layer exposed is every 0.033mm preferably
2it is 100～900.The number of the Cu-Sn alloy layer more preferably exposed is 200～900.
Only be defined in the Area Ratio of the Cu-Sn alloy layer that most surface exposes, also bag expands for example thick Cu-Sn alloy layer and exposes the situations of few in number, but in this case, is difficult to produce the solid effect of above-mentioned pin, even identical Area Ratio, be dispersed with a plurality of Cu-Sn alloy layers for well in most surface.Stipulate the number of Cu-Sn alloy layer for this reason.If the not enough every 0.033mm of above-mentioned number
2be 100, be difficult to produce the solid effect of above-mentioned pin, if surpass 900, have following situation: the pure tin quantitative change on surface is few, and soldering wettability, solidity to corrosion, electrical connectivity etc. are deteriorated, and surface becomes the firecoat shape, and outward appearance is also poor.
By count the number of the white image that above-mentioned reflection electronic is obtained as binaryzation with computer software, can access the number of the Cu-Sn alloy layer exposed.
Embodiment
Take tough pitch copper as raw material, the ingot casting that casting is added with element shown in table 1～table 5, carrying out hot rolling more than 900 ℃ until thickness is 10mm, removes surperficial oxidation scale, then repeatedly carry out cold rolling and thermal treatment, finally take the final cold rolling plate (mother metal) that thickness is 0.2mm that is finish-machined to.Final cold rolling rolling degree of finish is 10～50%.
Then, degreasing and pickling are carried out in the surface of this mother metal, then by electrochemical plating, press the order formation plating bottom of nickel layer, copper plate, then by electrochemical plating, form the tin layer.With sulfuric acid bath, (liquid temperature is about 50 ℃ to nickel plating bottom, and current density is 5A/dm
2) electroplate, making the thickness of nickel plating bottom is 0.3 μ m.With sulfuric acid bath, (liquid temperature is about 50 ℃ to copper plating bottom, and current density is 30A/dm
2) electroplate, making the thickness of copper plating bottom is 0.5 μ m.With the sulfocarbolic acid bath, (liquid temperature is about 35 ℃ to tin coating, and current density is 20A/dm
2) electroplate, the thickness that makes tin coating is 1.2 μ m.The thickness of each coating is measured with the electrolyzing film thickness gauge.
Then, in atmosphere, be in the CO concentration process furnace that is 1.0 volume %, each test portion make the melting of tin layer of packing in 7 seconds, the cooling fluid washing trough that then to pass into liquid temperature be 60 ℃ is carried out cooling, has obtained implementing on surface the end article that soft heat is processed.In addition, as shown in table 1～table 5, the temperature of process furnace and the frequency that blows the fan that comes from the hot gas in process furnace to test portion have been changed.The temperature of process furnace and fan frequency are higher, and test portion is more heated well, and the Cu-Sn alloy layer is grown up.In addition, if improve the fan frequency, by the wind action of brushing to material surface, the karyogenesis of Cu-Sn alloy layer is promoted, and the particle diameter of Cu-Sn alloy layer diminishes.
Each test portion obtained is like this carried out to the evaluation of all characteristics.
(1) Area Ratio of Cu-Sn alloy layer
The scanning electronic microscope (SEM) that obtains the surface of tin plated materials as the reflection electronic picture.Because the Cu-Sn alloy layer exposed in most surface is compared with tin and is become darker image, so can, this is reversed and convert white image to after as binaryzation, by the area of asking for the Cu-Sn alloy layer, calculate Area Ratio.Binaryzation is to be set as 120 to carry out in the luminance range 255 of SEM device.
(2) number of Cu-Sn alloy layer
Resolve software and counted the number that obtains white image that above-mentioned reflection electronic is obtained as binaryzation by being equipped on particle on SEM.
In addition, this number is the area (0.0066mm to the multiplying power of 2000 times
2) carry out 5 visual field countings and average, and be converted into every 0.033mm
2number.
(3) glass putty produces
Test portion is placed in to friction test device and (must congratulates trier Co., Ltd. system, must congratulate wear testing machine) on, to test portion surface mounting felt, on felt under the state of load 30g weight, make felt take the amplitude to-and-fro movement (scanning distance is 15 times as 10mm, sweep velocity as 13mm/s, reciprocal time) of 1cm on the test portion surface.
After this, observe the felt surface of test portion one side, the degree of adhesion of visual valuation tin.Metewand is as follows.If be evaluated as △, mean almost not have the generation of glass putty, no problem in practical, if but zero more preferably.
Zero: have no adhering to of glass putty on felt.
△: be considered on felt have a small amount of glass putty to adhere to.
*: be considered on felt have a large amount of glass puttys to adhere to.
(4) soldering wettability
According to JIS-C0053, measure the soldering wettability of each test portion.If the soldering wettability is practical no problem below 2 seconds.
The result obtained is illustrated in table 1～table 8.
From table 1～table 8, the Area Ratio of the Cu-Sn alloy layer exposed in most surface is 0.5～4%, from most surface, sees that the number of the Cu-Sn alloy layer exposed is every 0.033mm
2be that in the situation of each embodiment of 100～900, the generation of glass putty is few, the soldering wettability is also good.
On the other hand, in the situation that the comparative example 9,10,12,26,27,29,43,44,46,54,59,64,69,74,79,84,89,95,99,104,109,114,119,124,129,134,139,144,149,154,159,164,169,174,179,184,189,195,200,204,209 of the Area Ratio less than 0.5% of the Cu-Sn alloy layer that most surface is exposed, glass putty produces in a large number.
In the situation that the Area Ratio of the Cu-Sn alloy layer that most surface is exposed surpasses 4% comparative example 14,16,17,31,33,34,48,50,51,56,61,66,71,81,86,91,111,121,140,145,151,155,171,175,181,206, the soldering wettability is poor.
In addition, in the situation that the Area Ratio of the Cu-Sn alloy layer that most surface is exposed is 0.5%～4% but the number of the Cu-Sn alloy layer that most surface is exposed surpasses the comparative example 11,28,45,75,94,100,115,130,135,160,165,185,190,194,199 of 900, glass putty produces less, but the soldering wettability is poor.
In addition, in the situation that the Area Ratio of the Cu-Sn alloy layer that most surface is exposed is 0.5%～4% but the comparative example 106,110,211 of 100 of the number deficiencies of the Cu-Sn alloy layer that most surface is exposed, glass putty produces in a large number.
Fig. 2 (a) is the SEM picture (reflection electronic picture) on the surface of embodiment 1, and Fig. 2 (b) is its binary image.
Claims (1)
1. a tin plated materials, have and implemented the tin coating that soft heat is processed on the surface of copper or copper alloy bar, it is characterized in that, the Area Ratio of the Cu-Sn alloy layer exposed in most surface is 0.5～4%, from most surface, the number of aforementioned Cu-Sn alloy layer is every 0.033mm
2it is 100～900.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-080394 | 2011-03-31 | ||
| JP2011080394 | 2011-03-31 | ||
| JP2011086947A JP5389097B2 (en) | 2011-03-31 | 2011-04-11 | Sn plating material |
| JP2011-086947 | 2011-04-11 | ||
| PCT/JP2012/057877 WO2012133378A1 (en) | 2011-03-31 | 2012-03-27 | Sn PLATING MATERIAL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103459678A true CN103459678A (en) | 2013-12-18 |
| CN103459678B CN103459678B (en) | 2016-04-13 |
Family
ID=46931095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280016466.XA Active CN103459678B (en) | 2011-03-31 | 2012-03-27 | Tin plated materials |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5389097B2 (en) |
| KR (1) | KR101457321B1 (en) |
| CN (1) | CN103459678B (en) |
| WO (1) | WO2012133378A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114424413A (en) * | 2019-09-19 | 2022-04-29 | 株式会社自动网络技术研究所 | Pin terminal, connector, harness with connector, and control unit |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5587935B2 (en) * | 2012-03-30 | 2014-09-10 | Ｊｘ日鉱日石金属株式会社 | Sn plating material |
| JP2015225704A (en) * | 2014-05-26 | 2015-12-14 | 矢崎総業株式会社 | Terminal |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614328A (en) * | 1995-01-19 | 1997-03-25 | The Furukawa Electric Co. Ltd. | Reflow-plated member and a manufacturing method therefor |
| JPH11140569A (en) * | 1997-11-04 | 1999-05-25 | Mitsubishi Shindoh Co Ltd | Sn or sn alloy plated copper sheet alloy, and connector made of the sheet |
| JP2006283149A (en) * | 2005-04-01 | 2006-10-19 | Nikko Kinzoku Kk | Surface treatment method for copper or copper alloy, surface-treated material, and electronic component using the same |
| CN100583309C (en) * | 2004-09-10 | 2010-01-20 | 株式会社神户制钢所 | Conductive material for connecting part and method for manufacturing the conductive material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3378717B2 (en) * | 1995-01-19 | 2003-02-17 | 古河電気工業株式会社 | Method for manufacturing reflow plated member |
-
2011
- 2011-04-11 JP JP2011086947A patent/JP5389097B2/en active Active
-
2012
- 2012-03-27 WO PCT/JP2012/057877 patent/WO2012133378A1/en active Application Filing
- 2012-03-27 KR KR1020137024130A patent/KR101457321B1/en active IP Right Grant
- 2012-03-27 CN CN201280016466.XA patent/CN103459678B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614328A (en) * | 1995-01-19 | 1997-03-25 | The Furukawa Electric Co. Ltd. | Reflow-plated member and a manufacturing method therefor |
| JPH11140569A (en) * | 1997-11-04 | 1999-05-25 | Mitsubishi Shindoh Co Ltd | Sn or sn alloy plated copper sheet alloy, and connector made of the sheet |
| CN100583309C (en) * | 2004-09-10 | 2010-01-20 | 株式会社神户制钢所 | Conductive material for connecting part and method for manufacturing the conductive material |
| JP2006283149A (en) * | 2005-04-01 | 2006-10-19 | Nikko Kinzoku Kk | Surface treatment method for copper or copper alloy, surface-treated material, and electronic component using the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114424413A (en) * | 2019-09-19 | 2022-04-29 | 株式会社自动网络技术研究所 | Pin terminal, connector, harness with connector, and control unit |
| CN114424413B (en) * | 2019-09-19 | 2023-12-08 | 株式会社自动网络技术研究所 | Pin terminal, connector, wire harness with connector, and control unit |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012133378A1 (en) | 2012-10-04 |
| KR101457321B1 (en) | 2014-11-05 |
| JP5389097B2 (en) | 2014-01-15 |
| KR20130124384A (en) | 2013-11-13 |
| CN103459678B (en) | 2016-04-13 |
| JP2012214864A (en) | 2012-11-08 |
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Address after: Tokyo, Japan, Japan Patentee after: JX NIPPON MINING & METALS CORPORATION Address before: Tokyo, Japan, Japan Patentee before: JX Nippon Mining & Metals Co., Ltd. |
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Address after: No. 10-4, erdingmu, tiger gate, Tokyo port, Japan Patentee after: JKS Metal Co.,Ltd. Address before: Tokyo, Japan Patentee before: JKS Metal Co.,Ltd. |