CN103459678B - Tin plated materials - Google Patents

Tin plated materials Download PDF

Info

Publication number
CN103459678B
CN103459678B CN201280016466.XA CN201280016466A CN103459678B CN 103459678 B CN103459678 B CN 103459678B CN 201280016466 A CN201280016466 A CN 201280016466A CN 103459678 B CN103459678 B CN 103459678B
Authority
CN
China
Prior art keywords
copper
alloy layer
tin
plated materials
alloy
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.)
Active
Application number
CN201280016466.XA
Other languages
Chinese (zh)
Other versions
CN103459678A (en
Inventor
原田宏司
金滨庆太郎
Original Assignee
JX Nippon Mining and Metals Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by JX Nippon Mining and Metals Corp filed Critical JX Nippon Mining and Metals Corp
Publication of CN103459678A publication Critical patent/CN103459678A/en
Application granted granted Critical
Publication of CN103459678B publication Critical patent/CN103459678B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

A kind of tin plated materials being provided, by making Cu-Sn alloy layer expose partly on the soft heat tin coating on copper or copper alloy bar surface, the generation of glass putty can being suppressed.Implement in the tin plated materials (10) of the tin coating (6) of mild melt treatment having the surface at copper or copper alloy bar (2), the area ratio of the Cu-Sn alloy layer (4a) 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.

Description

Tin plated materials
Technical field
The present invention relates to a kind of tin plated materials, it is suitable for use as the conductive elastomeric material such as junctor, terminal, rly., switch, has the tin coating implementing mild melt treatment at copper or copper alloy bar surface.
Background technology
Automobile with and the terminal of the people's livelihood, junctor, the various terminals of electric/electronic device, junctor, rly. or switch etc. in, play excellent soldering wettability, solidity to corrosion, the electrical connectivity of tin, implement zinc-plated (patent documentation 1) on the surface of copper or copper alloy bar.In addition, more than zinc-plated post-heating to the melting point of tin, implement the mild melt treatment of melting, make the raising such as adaptation or outward appearance.
Patent documentation 1: Japanese Unexamined Patent Publication 2006-283149 publication.
; (following to the copper product with above-mentioned tin coating; be called " tin plated materials ") carry out press working and when manufacturing junctor etc.; although with liner pressing copper product, exist because liner contacts with copper product surface and produce glass putty from the tin coating on copper product surface and be mixed into the problem of press.
Summary of the invention
Namely, the present invention proposes to solve above-mentioned problem, and object is to provide a kind of tin plated materials, and it not easily produces 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 make Cu-Sn alloy layer expose partly in most surface after carrying out mild melt treatment to the coating on copper or copper alloy bar surface, the pure stannum layer of most surface that the Cu-Sn alloy layer then exposed keeps (pin is solid), suppresses the generation of glass putty.
Namely, tin plated materials of the present invention has the tin plated materials implementing the tin coating of mild melt treatment 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 Cu-Sn alloy layer expose partly at the soft heat tin coating on copper or copper alloy bar surface, thus the Cu-Sn alloy layer exposed can keep the pure stannum layer of (pin is solid) most surface, suppresses the generation of glass putty.
Accompanying drawing explanation
Fig. 1 is the figure of the cross section structure that tin plated materials is shown;
Fig. 2 is the SEM picture (reflection electronic picture) on the surface that 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: the tin coating implementing mild melt treatment, 10: tin plated materials, 21: scratch.
Embodiment
Below, the tin plated materials involved by embodiments of the present invention is described.In addition, in the present invention, unless otherwise specified, % represents quality %.
(1) composition of mother metal
As the copper bar of mother metal becoming tin plated materials, can use purity be more than 99.9% tough pitch copper, oxygen free copper, in addition, as copper alloy bar, known copper alloy can be used according to required intensity or electroconductibility.As known copper alloy, such as, can enumerate phosphor bronze, brass, titanium copper, corson alloy etc.
(tin coating)
The tin coating implementing mild melt treatment is formed on the surface of copper or copper alloy bar.Tin coating is directly or via plating bottom plating on the surface of copper or copper alloy bar.Nickel, copper is enumerated as plating bottom, can the one of plating in them, or also can by the order plating nickel of nickel, copper, copper and obtain Cu/Ni bis-layers of plating bottom.
In addition, tin plated materials involved by embodiments of the present invention can be manufactured by following operation usually: in continuous plating lines, degreasing and pickling is carried out to as the copper of mother metal or the surface of copper alloy bar, then plating bottom is formed by electrochemical plating, then form tin layers by known electrochemical plating, finally implement mild melt treatment and make tin layers melting.Zinc-platedly can be undertaken by known method, such as, can use sulfuric acid bath, sulfonic acid bath, halogen bath etc.
(Cu-Sn alloy layer)
If then implement mild melt treatment at the electroplating surfaces with tin of mother metal (copper or copper alloy bar) 2, then as shown in Figure 1, copper in mother metal (copper or copper alloy bar) 2 spreads to the tin coating 6 on surface, 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 be mother metal with copper alloy time Addition ofelements.
Here, common mild melt treatment makes pure tin stay most surface completely, and Cu-Sn alloy layer 4 does not expose from the teeth outwards, but in the present invention, make Cu-Sn alloy layer with 0.5 ~ 4% area ratio expose in most surface.Because Cu-Sn alloy layer is harder than pure tin, the scratch 21 produced when therefore keeping most surface when press working by liner is fixed by the Cu-Sn alloy layer 4a exposed, and inhibits scratch 21 to extend and the situation of the pure tin on surface stripping (glass putty).
The area ratio making the Cu-Sn alloy layer exposed in most surface is 0.5 ~ 4%.If area ratio is less than 0.5%, then do not produce the solid effect of the above-mentioned pin realized by Cu-Sn alloy layer.On the other hand, if area ratio is more than 4%, then the pure tin quantitative change on surface is few, the deteriorations such as soldering wettability, solidity to corrosion, electrical connectivity, and surface becomes firecoat shape, and outward appearance is also poor.
The scanning electronic microscope (SEM) that the area ratio of Cu-Sn alloy layer obtains the surface of tin plated materials as reflection electronic picture.Because the Cu-Sn alloy layer exposed in most surface becomes darker image compared with tin, thus can by this as binaryzation after carry out reversing and convert white image to, calculate by asking for the area of Cu-Sn alloy layer.(binaryzation is such as set as 120 in the luminance range 255 of SEM device)
In addition, as the method area ratio of Cu-Sn alloy layer being managed into 0.5 ~ 4%, the adjustment of the adjustment of reflowing temperature or Reflowing Time, tin coating thickness is enumerated.By these adjustment, can control Cu-Sn alloy layer from the growth degree of mother metal one lateral surface, control the ratio of the Cu-Sn alloy layer arriving most surface (exposing).
Such as, the thickness of the tin layers before mild melt treatment can be 0.1 ~ 5.0 μm, and the thickness of pure stannum layer after mild melt treatment also can be 0.1 ~ 4.5 μm.
From most surface, number preferably every 0.033mm of the Cu-Sn alloy layer exposed 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 is exposed, also bag expands the situation that such as thick Cu-Sn alloy layer exposes few in number, but in this case, is difficult to produce the solid effect of above-mentioned pin, even if identical area ratio, be dispersed with multiple Cu-Sn alloy layer as well in most surface.Specify the number of Cu-Sn alloy layer for this reason.If the every 0.033mm of above-mentioned number deficiency 2be 100, be then difficult to produce the solid effect of above-mentioned pin, if more than 900, then there is following situation: the pure tin quantitative change on surface is few, the deteriorations such as soldering wettability, solidity to corrosion, electrical connectivity, and surface becomes firecoat shape, and outward appearance is also poor.
By counting the number of the white image obtained as binaryzation by above-mentioned reflection electronic with computer software, the number of the Cu-Sn alloy layer exposed can be obtained.
Embodiment
Take tough pitch copper as raw material, casting is added with the ingot casting of element shown in table 1 ~ table 5, carries out hot rolling until thickness is 10mm more than 900 DEG C, removes the oxidation scale on surface, then repeatedly carry out cold rolling and thermal treatment, be finally finish-machined to finally cold rolling the plate (mother metal) that thickness is 0.2mm.Finally cold rolling rolling degree of finish is 10 ~ 50%.
Then, degreasing and pickling are carried out to the surface of this mother metal, then press the order formation plating bottom of nickel layer, copper plate by electrochemical plating, then form tin layers by electrochemical plating.With sulfuric acid bath, (liquid temperature is about 50 DEG C to nickel plating bottom, and current density is 5A/dm 2) plating, the thickness making nickel plate bottom is 0.3 μm.With sulfuric acid bath, (liquid temperature is about 50 DEG C to copper plating bottom, and current density is 30A/dm 2) plating, the thickness making copper plate bottom is 0.5 μm.With sulfocarbolic acid bath, (liquid temperature is about 35 DEG C to tin coating, and current density is 20A/dm 2) plating, make the thickness of tin coating be 1.2 μm.The thickness of each coating measures with electrolyzing film thickness gauge.
Then, be CO concentration be in the process furnace of 1.0 volume % in atmosphere, load each test portion and make tin layers melting in 7 seconds, then passing into liquid temperature is that the cooling fluid washing trough of 60 DEG C cools, and obtains the end article implementing mild melt treatment on surface.In addition, as shown in table 1 ~ table 5, the frequency of the temperature changing process furnace and the fan blowing the hot gas come from process furnace to test portion.Temperature and the fan frequency of process furnace are higher, then test portion is more heated well, and Cu-Sn alloy layer is grown up.In addition, if improve fan frequency, then 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.
The each test portion obtained like this is carried out to the evaluation of all characteristics.
(1) area ratio of Cu-Sn alloy layer
The scanning electronic microscope (SEM) obtaining the surface of tin plated materials as reflection electronic picture.Because the Cu-Sn alloy layer exposed in most surface becomes darker image compared with tin, thus can by this as binaryzation after carry out reversing and convert white image to, calculate area ratio by asking for the area of Cu-Sn alloy layer.Binaryzation is in the luminance range 255 of SEM device, be set as that 120 carry out.
(2) number of Cu-Sn alloy layer
Undertaken counting by the particle parsing software be equipped on SEM and obtain the number of the white image obtained as binaryzation by above-mentioned reflection electronic.
In addition, this number is the area (0.0066mm to the multiplying power of 2000 times 2) carry out 5 visual field countings and be averaged, and be converted into every 0.033mm 2number.
(3) glass putty produces
Test portion is placed in friction test device (Xu He trier Co., Ltd. system, must wear testing machine be congratulated) on, to test portion surface mounting felt, on felt load 30g weight state under, make felt on test portion surface with the amplitude to-and-fro movement of 1cm (scanning distance is 10mm, sweep velocity is 13mm/s, reciprocal time be 15 times).
After this, the felt surface of test portion side is observed, the degree of adhesion of visual valuation tin.Metewand is as follows.If be evaluated as △, then represent the generation almost not having glass putty, no problem in practical, but if zero more preferably.
Zero: attachment felt having no glass putty.
△: be considered to felt has a small amount of glass putty adhere to.
×: be considered to felt has a large amount of glass putty adhere to.
(4) soldering wettability
According to JIS-C0053, measure the soldering wettability of each test portion.If soldering wettability is below 2 seconds, then practical no problem.
The result obtained is represented 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%, the number of Cu-Sn alloy layer exposed viewed from most surface is every 0.033mm 2when being each embodiment of 100 ~ 900, the generation of glass putty is few, and soldering wettability is also excellent.
On the other hand, when the area ratio of the Cu-Sn alloy layer that most surface is exposed less than 0.5% 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, glass putty produces in a large number.
When the area ratio of the Cu-Sn alloy layer that most surface is exposed more than 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, soldering wettability is poor.
In addition, when the area ratio of the Cu-Sn alloy layer that most surface is exposed be 0.5% ~ 4% but the number of Cu-Sn alloy layer exposed of most surface more than 900 comparative example 11,28,45,75,94,100,115,130,135,160,165,185,190,194,199, glass putty produces less, but soldering wettability is poor.
In addition, when the area ratio of the Cu-Sn alloy layer that most surface is exposed be 0.5% ~ 4% but the number of Cu-Sn alloy layer exposed of most surface less than 100 comparative example 106,110,211, 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 the tin coating implementing mild melt treatment 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.
CN201280016466.XA 2011-03-31 2012-03-27 Tin plated materials Active CN103459678B (en)

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 CN103459678A (en) 2013-12-18
CN103459678B true 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)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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
JP7226210B2 (en) * 2019-09-19 2023-02-21 株式会社オートネットワーク技術研究所 Pin terminals, connectors, wire harnesses with connectors, and control units

Citations (3)

* Cited by examiner, † Cited by third party
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
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 (2)

* Cited by examiner, † Cited by third party
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
JP4308931B2 (en) * 1997-11-04 2009-08-05 三菱伸銅株式会社 Sn or Sn alloy-plated copper alloy thin plate and connector manufactured with the thin plate

Patent Citations (3)

* Cited by examiner, † Cited by third party
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
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

Also Published As

Publication number Publication date
CN103459678A (en) 2013-12-18
KR101457321B1 (en) 2014-11-05
JP2012214864A (en) 2012-11-08
JP5389097B2 (en) 2014-01-15
KR20130124384A (en) 2013-11-13
WO2012133378A1 (en) 2012-10-04

Similar Documents

Publication Publication Date Title
KR101203438B1 (en) Tin-plated material for electronic part
CN101981234B (en) Tinned copper alloy bar with excellent abrasion resistance, insertion properties, and heat resistance
JP5002407B2 (en) Tin-plated copper or copper alloy strip with excellent tin plating wear resistance
CN100576366C (en) Zinc-plated Cu-Ni-Si-Zn-Sn is alloy bar and zinc-plated
US10982345B2 (en) Tin-plated product and method for producing same
WO2007126011A1 (en) TIN-PLATED Cu-Ni-Si ALLOY STRIP
CN103459678B (en) Tin plated materials
JP5692799B2 (en) Sn plating material and method for producing the same
CN102482794B (en) Tin-plated cu-ni-si-based alloy strip having excellent resistance to heat separation of the tin-plating
CN103361693B (en) Sn-plated material
JP2011214066A (en) Glossy nickel plating material, electronic component comprising glossy nickel plating material, and process for production of glossy nickel plating material
JP6086531B2 (en) Silver plating material
KR20170120547A (en) Sn-PLATED MATERIAL FOR ELECTRONIC COMPONENT
JP2011099128A (en) Plated member and method for manufacturing the same
JP4611419B2 (en) Copper alloy tin plating strip with excellent solder wettability and insertability
TW201634706A (en) Sn plating material for electronic parts
JP6793618B2 (en) Sn plating material and its manufacturing method
KR101175092B1 (en) Cu ALLOY Sn-PLATED STRIP HAVING EXCELLENT SOLDER WETTABILITY AND INSERTABILITY/EXTRABILITY
JPH0467725B2 (en)
JP2647657B2 (en) Method of manufacturing contacts
TW202406735A (en) Surface-coated material for electrical contacts, and electrical contact, switch and connector terminal each using same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

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.

CP02 Change in the address of a patent holder
CP02 Change in the address of a patent holder

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.