JPH051393A - Silver-copper alloy plating bath and silver-copper alloy brazing filler metal - Google Patents
Silver-copper alloy plating bath and silver-copper alloy brazing filler metalInfo
- Publication number
- JPH051393A JPH051393A JP8733991A JP8733991A JPH051393A JP H051393 A JPH051393 A JP H051393A JP 8733991 A JP8733991 A JP 8733991A JP 8733991 A JP8733991 A JP 8733991A JP H051393 A JPH051393 A JP H051393A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- copper alloy
- copper
- plating bath
- alloy plating
- 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.)
- Pending
Links
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 47
- 238000007747 plating Methods 0.000 title claims abstract description 41
- 238000005219 brazing Methods 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 title abstract description 5
- 239000002184 metal Substances 0.000 title abstract description 5
- 239000000945 filler Substances 0.000 title abstract 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 8
- -1 copper complex salt Chemical class 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical group [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical group [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims 1
- 229940098221 silver cyanide Drugs 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 23
- 229910045601 alloy Inorganic materials 0.000 abstract description 23
- 239000000956 alloy Substances 0.000 abstract description 23
- 229910052802 copper Inorganic materials 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000005476 soldering Methods 0.000 abstract 1
- 229920002873 Polyethylenimine Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 239000011888 foil Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- ROJUZFYOCBXBLJ-UHFFFAOYSA-N C1(CCC(N1)=O)=O.[K].[Cu] Chemical compound C1(CCC(N1)=O)=O.[K].[Cu] ROJUZFYOCBXBLJ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- GOBZQAFUBBVPEO-UHFFFAOYSA-N [Cu](C#N)C#N.[K] Chemical compound [Cu](C#N)C#N.[K] GOBZQAFUBBVPEO-UHFFFAOYSA-N 0.000 description 1
- NZWXMOTXTNDNLK-UHFFFAOYSA-N [Cu].[Zn].[Ag] Chemical compound [Cu].[Zn].[Ag] NZWXMOTXTNDNLK-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VPKAOUKDMHJLAY-UHFFFAOYSA-J tetrasilver;phosphonato phosphate Chemical compound [Ag+].[Ag+].[Ag+].[Ag+].[O-]P([O-])(=O)OP([O-])([O-])=O VPKAOUKDMHJLAY-UHFFFAOYSA-J 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は銀銅合金メッキ浴及び
銀銅合金ロウ材に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver-copper alloy plating bath and a silver-copper alloy brazing material.
【０００２】[0002]
【従来の技術】従来より電気・電子工業部品、例えばセ
ラミックパッケージのロウ付け用の銀銅合金層を形成す
るために銀銅合金箔が採用されているが、箔の取扱いが
面倒で位置ズレが生じ易く、コスト的にも不利であると
いう問題点がある。しかも、ロウ材として銀銅合金箔を
採用する場合には、技術的にも３０μｍ以下の薄い箔を
製造するのが困難であるため、一般的に比較的厚い箔が
用いられているが、箔が厚すぎるとロウ付け時にロウが
多く流れすぎによる後工程への障害、電子部品等におけ
るファインピッチ化されたリード同士の短絡等を招くお
それもあった。2. Description of the Related Art Conventionally, silver-copper alloy foil has been used to form a silver-copper alloy layer for brazing of electric / electronic industrial parts, such as ceramic packages, but the foil is troublesome to handle and misaligned. There is a problem in that it is likely to occur and is disadvantageous in terms of cost. Moreover, when a silver-copper alloy foil is used as the brazing material, it is technically difficult to produce a thin foil having a thickness of 30 μm or less, and thus a relatively thick foil is generally used. If it is too thick, too much brazing may flow during brazing, which may lead to problems in subsequent processes, short-circuiting between fine-pitch leads in electronic components, and the like.
【０００３】[0003]
【発明が解決しようとする課題】そして、このような銀
銅合金箔の欠点を解決する方法として銀銅合金メッキが
考えれる。しかしながら、このような銀と銅を同時析出
させる銀銅合金メッキを考えた場合、それらの単純塩か
らでは両者の平衡電位の差が大きく且つ分極も小さいた
め、銀と銅との合金を同時に析出させることが大変に困
難である。The silver-copper alloy plating can be considered as a method for solving the drawbacks of the silver-copper alloy foil. However, when considering such a silver-copper alloy plating in which silver and copper are co-precipitated, an alloy of silver and copper is simultaneously deposited because the difference in equilibrium potential between them is large and the polarization is small from simple salts thereof. It is very difficult to get it done.
【０００４】このように、単純塩からの析出が困難な場
合、合金メッキを可能にする一般的な方法としては、錯
イオン化が考えられる。錯イオン化の主な効果は、適当
な錯化剤を選択することによって銀と銅の平衡電位を近
づけ、且つそれと共にカソード分極を大きくすることに
よって銀銅合金析出を可能にすることである。As described above, complex ionization is considered as a general method for enabling alloy plating when precipitation from simple salt is difficult. The main effect of complex ionization is to allow silver-copper alloy precipitation by bringing the equilibrium potentials of silver and copper closer together by increasing the cathodic polarization by choosing an appropriate complexing agent.
【０００５】銀銅合金メッキを可能にする錯化剤として
は、ａ）シアン、ｂ）ヨウ素、ｃ）コハク酸イミド、
ｄ）ピロリン酸、などが考えられる。そこで、代表的な
錯体浴の例として、銀を１０ｇ／ｌ、銅を６０ｇ／ｌ含
有したシアン浴から常温においてメッキを行ったとこ
ろ、電流密度の上昇と共に析出物中の銅の含有率が増加
し、５ＡＳＤの電流密度では、およそ銀７０％、銅３０
％の合金析出物が得られた。しかし、この得られた合金
析出物は、ロウ付けに適した銀：銅比率〔銀：銅＝７０
〜９５：５〜３０〕を一応具備しているものの、外観が
いわゆる「ヤケ」の状態を呈しており、３０μｍのめっ
き厚では析出物が粉状となり、ロウ付け用としての使用
に供することができなかった。この傾向は合金析出物の
銅の含有量が多くなるほど、またメッキが厚くなるほど
顕著になるものであった。Complexing agents that enable silver-copper alloy plating include a) cyanide, b) iodine, c) succinimide,
d) Pyrophosphate, etc. are considered. Therefore, as an example of a typical complex bath, when a cyan bath containing 10 g / l of silver and 60 g / l of copper was plated at room temperature, the copper content in the precipitate increased as the current density increased. However, at a current density of 5 ASD, approximately 70% silver, 30 copper
% Alloy precipitate was obtained. However, the obtained alloy precipitate has a silver: copper ratio [silver: copper = 70] suitable for brazing.
.About.95: 5-30], but the appearance is in a so-called "burnt" state, and a plating thickness of 30 .mu.m causes the precipitate to become powdery, and it can be used for brazing. could not. This tendency became more remarkable as the copper content of the alloy precipitate increased and the plating became thicker.
【０００６】銀銅のシアン浴では、銀及び銅は浴中で、
一般的に「Ag(CN)2 - 」及び「Cu(CN)3 2- （条件によっ
てはCu(CN)2 - 又はCu(CN)4 3- 」の形で存在し、銀のカ
ソード分極は単純塩に比べて大きくなり、合金化にとっ
て好ましい傾向を示す。しかし一方で、平衡電位につい
ては共に卑に移行するが、その差は実用的な範囲で銀銅
濃度、遊離シアン濃度、ｐＨ、温度、をどのように変化
させても、銀は銅に比べて３００ｍＶ以上も貴である。In a silver-copper cyan bath, silver and copper are
Generally, "Ag (CN) 2 -" and "by Cu (CN) 3 2- (Condition Cu (CN) 2 - or Cu (CN) 4 3-" in the form of cathode polarization of silver It becomes larger than that of simple salt and shows a favorable tendency for alloying.On the other hand, both equilibrium potentials shift to base, but the differences are within the practical range of silver-copper concentration, free cyanide concentration, pH, and temperature. , No matter how it is changed, silver is no less than 300 mV more precious than copper.
【０００７】そのため、低い電流密度では銅が析出する
電位に達せず、銀が優先的に析出する。また、銅が析出
する条件になると、銀はすでに限界電流に達しており、
濃度律速で析出が進み、いわゆる「デンドライト」或い
は「粉状」の析出物になってしまう。この傾向はシアン
浴以外の錯塩についても同様である。従って、従来はロ
ウ付けに適した良好な銀銅合金被膜をメッキにより得る
ことはできなかった。Therefore, at a low current density, the potential at which copper is deposited does not reach, and silver is deposited preferentially. In addition, under the condition that copper is deposited, silver has already reached the limit current,
Precipitation proceeds at a concentration-controlled rate, resulting in so-called "dendrites" or "powdered" precipitates. This tendency is the same for complex salts other than the cyan bath. Therefore, conventionally, it was not possible to obtain a good silver-copper alloy coating suitable for brazing by plating.
【０００８】この発明はこのような従来の技術に着目し
てなされたものであり、外観が良好で且つ銅の含有比率
が高く、更に厚さが２０〜１００μｍ程度の良好な合金
析出被膜を得ることができる銀銅合金メッキ浴を提供
し、且つこの銀銅合金メッキ浴を使用した銀銅合金メッ
キにより電気・電子工業部品のロウ付けの好適な銀銅合
金ロウ材を得んとするものである。The present invention has been made by paying attention to such a conventional technique, and obtains a good alloy deposition film having a good appearance, a high copper content, and a thickness of about 20 to 100 μm. The present invention provides a silver-copper alloy plating bath that can be used, and obtains a silver-copper alloy brazing material suitable for brazing of electric / electronic industrial parts by silver-copper alloy plating using this silver-copper alloy plating bath. is there.
【０００９】[0009]
【課題を解決するための手段】この発明に係る銀銅合金
メッキ浴は、上記の目的を達成するために、可溶性の銀
錯塩及び銅錯塩を含み、且つ添加剤としてポリイミン及
び／又はポリアミンを含んでいるものである。また、こ
の発明に係る銀銅合金ロウ材は、前記銀銅合金メッキ浴
を使用した銀銅メッキにより得られるものである。The silver-copper alloy plating bath according to the present invention contains a soluble silver complex salt and a copper complex salt and a polyimine and / or polyamine as an additive in order to achieve the above object. It is what you are leaving. The silver-copper alloy brazing material according to the present invention is obtained by silver-copper plating using the silver-copper alloy plating bath.
【００１０】可溶性の銀錯塩としては、具体的にはシア
ン化銀カリウム、ヨウ化銀、ピロリン酸銀、銀カリウム
スクシンイミドなどが好適であり、その含有量としては
１〜２００ｇ／ｌが好ましい。As the soluble silver complex salt, specifically, potassium cyanide, silver iodide, silver pyrophosphate, silver potassium succinimide and the like are preferable, and the content thereof is preferably 1 to 200 g / l.
【００１１】また、可溶性の銅錯塩としては、具体的に
はシアン化第一銅、シアン化銅カリウム、ヨウ化銅、ピ
ロリン酸銅、銅カリウムスクシンイミドなどが好適であ
り、その含有量としては１〜４００ｇ／ｌが好ましい。As the soluble copper complex salt, specifically, cuprous cyanide, potassium copper cyanide, copper iodide, copper pyrophosphate, copper potassium succinimide and the like are preferable, and the content thereof is 1 It is preferably 400 g / l.
【００１２】そして、ポリイミン及び／又はポリアミン
の含有量としては０．０１〜２００ｇ／ｌが好ましい。
これらポリイミン及び／又はポリアミンを浴中に添加す
ることにより、外観が良好で且つ銅の含有率の高い合金
析出被膜を得ることができるようになる。なぜならば、
これらポリイミン及び／又はポリアミンの存在により、
銀のカソード分極が更に大きくなり、銀の限界電流にな
るカソード電流を更に卑にもって行くことができるた
め、結果として銀の限界電流が現れる前に、銅を析出さ
せることが可能となるからである。The content of polyimine and / or polyamine is preferably 0.01 to 200 g / l.
By adding these polyimines and / or polyamines to the bath, it becomes possible to obtain an alloy deposit film having a good appearance and a high copper content. because,
Due to the presence of these polyimines and / or polyamines,
Since the cathodic polarization of silver is further increased and the cathodic current, which becomes the limiting current of silver, can be made more base, as a result, it becomes possible to deposit copper before the limiting current of silver appears. is there.
【００１３】この銀銅合金メッキ浴は上記成分の他に、
電導塩としてホウ酸、クエン酸、酒石酸、リン酸などを
０．１〜２００ｇ／ｌ含有して良く、またその他に各種
光沢剤やｐＨ調製剤などを添加してもよい。This silver-copper alloy plating bath contains, in addition to the above components,
As the conductive salt, boric acid, citric acid, tartaric acid, phosphoric acid, etc. may be contained in an amount of 0.1 to 200 g / l, and various brightening agents, pH adjusting agents and the like may be added.
【００１４】更に、この銀銅合金メッキ浴にシアン化亜
鉛、ヨウ化亜鉛などの可溶性の亜鉛錯塩を１〜４００ｇ
／ｌ添加して、銀−銅−亜鉛合金を析出させることも可
能である。Further, 1 to 400 g of a soluble zinc complex salt such as zinc cyanide and zinc iodide is added to the silver-copper alloy plating bath.
It is also possible to precipitate silver-copper-zinc alloy by adding 1 / l.
【００１５】前記銀銅合金メッキ浴を使用した銀銅合金
メッキにより得られる銀銅合金被膜は、電気・電子工業
部品のロウ材として大変好適である。たとえば、セラミ
ックパッケージ、真空封入遮断器、センサー等の、メタ
ライズしたセラミックスと金属をロウ付けするのに最適
である。また、この他にも、工業用部品で従来銀ロウに
て接着していた部品のロウ付けに好適である。The silver-copper alloy coating obtained by silver-copper alloy plating using the silver-copper alloy plating bath is very suitable as a brazing material for electric and electronic industrial parts. For example, it is suitable for brazing metallized ceramics and metals such as ceramic packages, vacuum-sealed circuit breakers, and sensors. In addition to this, it is also suitable for brazing of industrial parts that have conventionally been bonded with silver brazing.
【００１６】[0016]
【実施例】実施例１ ＊銀銅合金メッキ浴組成： ・シアン化銀カリウム（Ａｇ量）─────────１０ｇ／ｌ ・シンア化銅（Ｃｕ量）────────────１００ｇ／ｌ ・ポリエチレンイミン（ＰＥＩ）─────────１０ｇ／ｌ[Examples] Example 1 * Silver-copper alloy plating bath composition: -Silver potassium cyanide (Ag amount) ───────── 10 g / l-Copper cyanide (Cu amount) ────── ────── 100g / l ・ Polyethyleneimine (PEI) ───────── 10g / l
【００１７】 ＊操作条件： ・メッキ方式─────────────────浸漬メッキ ・浴温度─────────────────────２５℃ ・ｐＨ──────────────────────８．０ ・電流密度───────────────１、２、３ＡＳＤ ・メッキ時間───────────８０、４０、３０ｍｉｎ[0017] * Operating conditions: ・ Plating method ───────────────── immersion plating ・ Bath temperature ─────────────────────25 ℃ ・ PH──────────────────────8.0 ・ Current density ─────────────── 1,2,3ASD ・ Plating time ─────────── 80, 40, 30min
【００１８】上記の合金メッキ浴を使用して、４２合金
製のテストピースの表面に銀銅合金の析出層を形成する
メッキ試験を行った。そして、比較例として、上記合金
浴組成からポリエチレンイミン（ＰＥＩ）を抜いた組成
の合金浴を用いて同様のメッキ試験を行った。Using the above alloy plating bath, a plating test was carried out to form a silver-copper alloy precipitation layer on the surface of the 42 alloy test piece. Then, as a comparative example, the same plating test was performed using an alloy bath having a composition obtained by removing polyethyleneimine (PEI) from the above alloy bath composition.
【００１９】 [0019]
【００２０】得られた析出層はＰＥＩを添加したもの
は、優れた外観品質を呈し、いわゆる「ヤケ」などの発
生は全くなかった。一方、ＰＥＩを添加しない浴からは
「ヤケ」の発生が見られ、その傾向は電流密度の増加と
共に顕著になった。When the PEI was added to the obtained deposited layer, excellent appearance quality was exhibited, and so-called "burn" was not generated at all. On the other hand, the occurrence of “burning” was observed from the bath to which PEI was not added, and this tendency became remarkable as the current density increased.
【００２１】また、得られた合金被膜中の銀と銅の含有
比率は、上記第１表に示す如く、ＰＥＩを添加した方が
銅の含有比率が高かった。Regarding the content ratio of silver and copper in the obtained alloy film, as shown in Table 1 above, the content ratio of copper was higher when PEI was added.
【００２２】そして、ＰＥＩを添加した浴から得られた
合金被膜の厚さは、平均して５０μｍあり、ロウ付け用
の合金被膜として使用可能なものであった。The thickness of the alloy coating obtained from the PEI-added bath was 50 μm on average, and it was usable as an alloy coating for brazing.
【００２３】そして、前記のようにして銀銅合金被膜を
下面に施した４２合金製のテストピースを上にして、該
銀銅合金被膜をサンドイッチする状態で、別の４２合金
製のテストピースを下側へ重ね合わせた。そして、重ね
合わせた一対の各テストピースを、それぞれ還元雰囲気
中において前記第１表に記載した加熱温度でもってロウ
付けしてみた。結果は全て良好なロウ付け性を示した。
ロウ付けしたテストピース同士をペンチで引きはがして
みたところ、合金箔を使用した場合と同等のロウ付け強
度が得られていることもわかった。Then, another test piece made of 42 alloy is placed with the test piece made of 42 alloy having the silver-copper alloy coating on the lower surface as described above on top and sandwiching the silver-copper alloy coating. Stacked down. Then, the pair of test pieces thus stacked were brazed in the reducing atmosphere at the heating temperatures shown in Table 1 above. The results all showed good brazeability.
When the brazed test pieces were peeled off with pliers, it was also found that brazing strength equivalent to that when alloy foil was used was obtained.
【００２４】実施例２
先の実施例で示したＰＥＩを添加した銀銅合金メッキ浴
と、添加しない銀銅合金メッキ浴の両方を使用して、温
度３６℃、電流密度１０、１２、１５ＡＳＤ、メッキ時
間８、７、６ｍｉｎ、流速１００ｍ／ｍｉｎ、で噴射式
高速メッキを行った。 Example 2 Using both the silver-copper alloy plating bath containing PEI and the silver-copper alloy plating bath containing no PEI shown in the previous example, a temperature of 36 ° C., a current density of 10, 12, 15 ASD, The jet high-speed plating was performed at a plating time of 8, 7 and 6 min and a flow rate of 100 m / min.
【００２５】 [0025]
【００２６】この実施例２で得られた析出層も、ＰＥＩ
を添加した方は全て優れた外観品質を呈し、いわゆる
「ヤケ」などの発生は全くなかった。一方、ＰＥＩを添
加しない方は「ヤケ」等の発生が見られた。The deposited layer obtained in this Example 2 is also PEI
All of the products with the addition of B exhibited excellent appearance quality, and so-called "burn" did not occur at all. On the other hand, in the case where PEI was not added, the occurrence of “burn” and the like were observed.
【００２７】また、得られた合金被膜中の銀と銅の含有
比率を調べたところ、上記第２表に示す如く、先の実施
例と同様に、ＰＥＩを添加した方が銅の含有比率が高か
った。Further, when the content ratio of silver and copper in the obtained alloy coating film was examined, as shown in Table 2 above, the content ratio of copper was smaller in the case where PEI was added, as in the previous example. it was high.
【００２８】そして、得られた合金被膜の厚さは、平均
して５０μｍあり、ロウ付け用の合金被膜として使用可
能なものであった。The resulting alloy coating film had an average thickness of 50 μm, and could be used as an alloy coating film for brazing.
【００２９】そして、このようにして銀銅合金被膜を片
面に施した４２合金製のテストピースを、第２表に記載
した加熱温度でもって、別の４２合金製のテストピース
と先の実施例と同じ要領でロウ付けしてみた。結果は先
の実施例と同様に優れたロウ付け性及びロウ付け強度を
示した。Then, the test piece made of 42 alloy having the silver-copper alloy coating film on one side thereof was used at the heating temperature shown in Table 2 and another test piece made of 42 alloy and the above-mentioned example. I tried brazing in the same way as. The results showed excellent brazing property and brazing strength as in the previous examples.
【００３０】[0030]
【発明の効果】この発明に係る銀銅合金メッキ浴は、以
上説明してきた如き内容のものなので、外観が良好で且
つ銅の含有比率が高く、更に厚さが十分なロウ材として
好適な合金析出被膜を得ることができる。また、この発
明に係る銀銅合金ロウ材は、電気・電子工業部品のロウ
付け、特にセラミックパッケージ、真空封入遮断器、セ
ンサー等の、メタライズしたセラミックスと金属とのロ
ウ付けに最適である。Since the silver-copper alloy plating bath according to the present invention has the contents described above, it is an alloy suitable for a brazing material having a good appearance, a high copper content, and a sufficient thickness. A deposited film can be obtained. Further, the silver-copper alloy brazing material according to the present invention is most suitable for brazing of electric / electronic industrial parts, particularly brazing of metallized ceramics and metal such as ceramic packages, vacuum-sealed circuit breakers, and sensors.
Claims (5)
添加剤としてポリイミン及び／又はポリアミンを含んで
いることを特徴とする銀銅合金メッキ浴。1. A silver-copper alloy plating bath comprising a soluble silver complex salt and a copper complex salt, and containing polyimine and / or polyamine as an additive.
請求項１記載の銀銅合金メッキ浴。2. The silver-copper alloy plating bath according to claim 1, wherein the soluble silver complex salt is silver cyanide.
請求項１記載の銀銅合金メッキ浴。3. The silver-copper alloy plating bath according to claim 1, wherein the soluble copper complex salt is copper cyanide.
載の銀銅合金メッキ浴。4. The silver-copper alloy plating bath according to claim 1, wherein a soluble zinc complex salt is added.
キ浴を使用した銀銅合金メッキにより得られる電気・電
子工業部品用の銀銅合金ロウ材。5. A silver-copper alloy brazing material for electric / electronic industrial parts, which is obtained by silver-copper alloy plating using the silver-copper alloy plating bath according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8733991A JPH051393A (en) | 1990-07-19 | 1991-03-28 | Silver-copper alloy plating bath and silver-copper alloy brazing filler metal |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-189322 | 1990-07-19 | ||
| JP18932290 | 1990-07-19 | ||
| JP8733991A JPH051393A (en) | 1990-07-19 | 1991-03-28 | Silver-copper alloy plating bath and silver-copper alloy brazing filler metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH051393A true JPH051393A (en) | 1993-01-08 |
Family
ID=26428630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8733991A Pending JPH051393A (en) | 1990-07-19 | 1991-03-28 | Silver-copper alloy plating bath and silver-copper alloy brazing filler metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH051393A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012214899A (en) * | 2011-03-31 | 2012-11-08 | Swatch Group Research & Development Ltd | 18-carat 3-n gold alloy and its precipitation method |
| KR101403456B1 (en) * | 2012-05-17 | 2014-06-03 | 서울대학교산학협력단 | THE FABRICATION METHOD OF Cu-Ag ALLOY COATING AND INTERCONNECTION USING ELECTRODEPOSITION |
| CN107962317A (en) * | 2017-10-31 | 2018-04-27 | 常州菲胜图自动化仪器有限公司 | A kind of water base type scaling powder free of cleaning |
| CN109545696A (en) * | 2018-11-28 | 2019-03-29 | 哈尔滨工业大学 | A method of law temperature joining high-temperature service connector is prepared using single phase nano yellow gold soldering paste |
| JP2020097213A (en) * | 2018-09-21 | 2020-06-25 | ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド | Method for producing materials by adhering layer for protection of silver against tarnishing on substrate comprising silver surface |
| DE102020112059A1 (en) | 2020-05-05 | 2021-11-11 | Dr. Ing. H.C. F. Porsche Aktiengesellschaft | Banjo bolt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55134191A (en) * | 1979-04-04 | 1980-10-18 | Engelhard Min & Chem | Silver or silver alloy plating bath |
| JPS573773A (en) * | 1980-06-11 | 1982-01-09 | Hitachi Ltd | Manufacture of ceramic sealed structure |
| JPS60248893A (en) * | 1984-05-23 | 1985-12-09 | Kaoru Aotani | Silver-copper-zinc alloy plating bath |
-
1991
- 1991-03-28 JP JP8733991A patent/JPH051393A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55134191A (en) * | 1979-04-04 | 1980-10-18 | Engelhard Min & Chem | Silver or silver alloy plating bath |
| JPS573773A (en) * | 1980-06-11 | 1982-01-09 | Hitachi Ltd | Manufacture of ceramic sealed structure |
| JPS60248893A (en) * | 1984-05-23 | 1985-12-09 | Kaoru Aotani | Silver-copper-zinc alloy plating bath |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012214899A (en) * | 2011-03-31 | 2012-11-08 | Swatch Group Research & Development Ltd | 18-carat 3-n gold alloy and its precipitation method |
| KR101403456B1 (en) * | 2012-05-17 | 2014-06-03 | 서울대학교산학협력단 | THE FABRICATION METHOD OF Cu-Ag ALLOY COATING AND INTERCONNECTION USING ELECTRODEPOSITION |
| CN107962317A (en) * | 2017-10-31 | 2018-04-27 | 常州菲胜图自动化仪器有限公司 | A kind of water base type scaling powder free of cleaning |
| JP2020097213A (en) * | 2018-09-21 | 2020-06-25 | ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド | Method for producing materials by adhering layer for protection of silver against tarnishing on substrate comprising silver surface |
| CN109545696A (en) * | 2018-11-28 | 2019-03-29 | 哈尔滨工业大学 | A method of law temperature joining high-temperature service connector is prepared using single phase nano yellow gold soldering paste |
| DE102020112059A1 (en) | 2020-05-05 | 2021-11-11 | Dr. Ing. H.C. F. Porsche Aktiengesellschaft | Banjo bolt |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB2287717A (en) | Palladium-gold alloy electroplating compositions | |
| WO1999041433A1 (en) | Electrolyte and tin-silver electroplating process | |
| MY129655A (en) | Solder powder and method for preparing the same and solder paste | |
| US5391402A (en) | Immersion plating of tin-bismuth solder | |
| JP3303594B2 (en) | Heat-resistant silver-coated composite and method for producing the same | |
| JPH0216172A (en) | Solderable conductive paint | |
| US5783059A (en) | Electrodeposition bath | |
| JPH10245693A (en) | Electroplating bath for nickel and nickel alloy and electroplating method | |
| JP3711141B1 (en) | Method for forming Sn-Ag-Cu ternary alloy thin film | |
| JPS59500475A (en) | chelated metal | |
| JPWO2005085498A1 (en) | Metal surface treatment agent | |
| JP3662577B1 (en) | Method for forming Sn-Ag-Cu ternary alloy thin film | |
| US4586990A (en) | Chelating metals | |
| JP3373356B2 (en) | Discoloration preventing liquid and method for preventing discoloration of copper or copper alloy, and electronic component material using the same | |
| WO2006043578A1 (en) | METHOD FOR FORMING Sn-Ag-Cu THREE-ELEMENT ALLOY THIN FILM ON BASE | |
| JP2001200323A (en) | Electronic component lead material and electronic component using the lead material | |
| JPS5865597A (en) | Ag alloy brazing filler metal having excellent surface characteristic of brazed part | |
| JP4014739B2 (en) | Reflow Sn plating material and terminal, connector, or lead member using the reflow Sn plating material | |
| JP4728462B2 (en) | Tin electroplating solution and plating method | |
| JP3741709B1 (en) | Method for forming Sn-Ag-Cu ternary alloy thin film | |
| JP3173982B2 (en) | Lead-free solder plating bath and solder plating film obtained thereby | |
| JP2003328182A (en) | Tin-silver alloy plating bath for rackless plating | |
| JP2005220374A (en) | Terminal, and component and product having the same | |
| JPS6238435B2 (en) | ||
| JPS628261B2 (en) |