US3663384A - Bath for electroplating tin-bismuth alloy - Google Patents
Bath for electroplating tin-bismuth alloy Download PDFInfo
- Publication number
- US3663384A US3663384A US79272A US3663384DA US3663384A US 3663384 A US3663384 A US 3663384A US 79272 A US79272 A US 79272A US 3663384D A US3663384D A US 3663384DA US 3663384 A US3663384 A US 3663384A
- Authority
- US
- United States
- Prior art keywords
- bismuth
- tin
- bath
- acid
- sulphate
- 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.)
- Expired - Lifetime
Links
- 238000009713 electroplating Methods 0.000 title claims abstract description 16
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910001152 Bi alloy Inorganic materials 0.000 title claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 10
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019256 formaldehyde Nutrition 0.000 claims description 3
- 229960004279 formaldehyde Drugs 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 4
- 229910001451 bismuth ion Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- SFKFRLRQWLYBDM-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Bi+3].[Bi+]=O.S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Bi+3].[Bi+]=O.S(=O)(=O)([O-])[O-] SFKFRLRQWLYBDM-UHFFFAOYSA-J 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- 229960002645 boric acid Drugs 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Definitions
- ABSTRACT Bath for electroplating tin-bismuth alloy upon a metal object such as a frame of a computer, including fluoboric acid in order to maintain the pH acid, tin fluoborate and a bismuth oxide-bismuth sulphate mixture of low quantity.
- the utilized method is of the soluble anode type and the cathode is formed of the object to be coated.
- tin coatings have a drawback. Indeed, at temperatures near the room temperature, a temperature lower than 13 0, tin is submitted to an allotropic transformation: the deposited white tin is changed into a grey tin. This phenomenon is known as tin pest. This tin pest appears as a non-adherent powder which separates from the deposit, thereby exposing the underlying metal to corrosion.
- the prior art has disclosed an electroplating method and bath for electroplating bismuth-tin-alloy.
- the bath is basic and, therefore, bismuth must be introduced in the form of organic bismuthates which are not much soluble.
- the operating temperature is near 90 C. This method is difficult as to its implementation and is relatively expensive and does not make it possible to obtain a sufficient bismuth concentration.
- one object of this invention is to obtain an acid bath for electroplating tin-bismuth alloy.
- Another object of the invention is the implementation of a tin-bismuth electroplating method with which it is possible to obtain a constant bismuth concentration in the tin.
- Another object of the invention is the implementation of a method with which it is possible to obtain a uniform coating of the tin-bismuth alloy upon another metal and this in a simple and cheap manner.
- the object to be coated is immersed into the bath where it acts as a cathode.
- a tin anode is used which is wrapped in a polypropylene bag the texture of which is very close in order to prevent the non ionized metal particles from moving which are pulled out of the anode during dissolution of the anode used to regenerate the tin-contents in the bath.
- the proportion of tin contained in the bath is within 2080 g. of metal tin per liter which is introduced in the form of tin salt, namely, tin fluoborate.
- the concentration of the bismuth ions in the bath which is within 0.0l and 0.05 g. of bismuth per liter, is obtained in the bath by introducing therein from 0.1 to 0.5 g.
- the bath contains also about lg. of formol per liter in order to avoid the anodic oxidation of the stannous ions (Sn* into stannic ions $11 Besides, this bath may include gelatine the proportions of which are 2 to 7 g. per liter and B-naphtol the proportions of which are 0.5 to 1.5 g. per liter in order to improve the quality of the deposit.
- the bath may also contain brighteners in appropriate proportions.
- the so-formed bath has an acid pI-l and its acidity corresponds to the acidity of a solution containing 100 g./liter of sulphuric acid.
- the density is about 13 B.
- the electroplating process is carried out at a temperature within 20-50 C.
- the voltage is between 1 and 3 volts and the current density is between 0.8 and 3A/dm
- the obtained deposit ratio is 0.5 M/mlllllte.
- the anode-cathode surface ratio may be between 1 and 1.5.
- tin fluoborate 30g/liter of metal tin fluoboric acid 130g/liter boric-acid 30g/liter mixture: bismuth sulphate 30% by weight bismuth oxide 70% by weight 0.3g/liter formol lg/liter equivalent acid H IOOg/liter The tests have been made at 25 C. and are gathered in the following table.
- the preferred percentage of bismuth in tin is 0.4 percent.
- An aqueous bath for electroplating tin-bismuth alloy characterized in that it includes acid ions in order to maintain pH acid, and characterized in that the bismuth is inserted in the form of a bismuth sulphate-bismuth oxide mixture, the concentration of which relative to the entire bath is between 0.1 and 0.5 grams per liter and in which the relative proportion of bismuth sulphate to bismuth oxide is in the range between 15/85 and 1.
- tin fluoborate equivalent to 30g/liter of metal tin i oxide is in the range between 15/85 and l. I I 8/ of fluqbfllrif acid 4.
- a tin plating bath according to claim 3 wherein said a bismuth mixture comprises bismuth sulphate and bismuth sulphatemismuth t fggzg the oxide in relative weight proportions of approximately 30 to 70 es tive on s b hts f wh' h 5 Pei-cam lrc 5%-75Z y s.
- a tin plating bath according to claim 4 including approxi- 5.
- lgll 0 f l mately 1 gram per liter of formal as additive to inhibit anodic oxidation of the stannous ions.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR6944284A FR2071199A5 (enrdf_load_stackoverflow) | 1969-12-19 | 1969-12-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3663384A true US3663384A (en) | 1972-05-16 |
Family
ID=9044910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US79272A Expired - Lifetime US3663384A (en) | 1969-12-19 | 1970-10-08 | Bath for electroplating tin-bismuth alloy |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3663384A (enrdf_load_stackoverflow) |
| JP (1) | JPS4931606B1 (enrdf_load_stackoverflow) |
| DE (1) | DE2050145A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2071199A5 (enrdf_load_stackoverflow) |
| GB (1) | GB1299519A (enrdf_load_stackoverflow) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4162205A (en) * | 1978-10-19 | 1979-07-24 | Vulcan Materials Company | Method of electroplating tin and alkaline electroplating bath therefor |
| US4331518A (en) * | 1981-01-09 | 1982-05-25 | Vulcan Materials Company | Bismuth composition, method of electroplating a tin-bismuth alloy and electroplating bath therefor |
| US4565610A (en) * | 1983-12-22 | 1986-01-21 | Learonal, Inc. | Bath and process for plating lead and lead/tin alloys |
| US4565609A (en) * | 1983-12-22 | 1986-01-21 | Learonal, Inc. | Bath and process for plating tin, lead and tin-lead alloys |
| US4599149A (en) * | 1981-09-11 | 1986-07-08 | Learonal, Inc. | Process for electroplating tin, lead and tin-lead alloys and baths therefor |
| US4617097A (en) * | 1983-12-22 | 1986-10-14 | Learonal, Inc. | Process and electrolyte for electroplating tin, lead or tin-lead alloys |
| US4701244A (en) * | 1983-12-22 | 1987-10-20 | Learonal, Inc. | Bath and process for electroplating tin, lead and tin/alloys |
| US4717460A (en) * | 1983-12-22 | 1988-01-05 | Learonal, Inc. | Tin lead electroplating solutions |
| US4749626A (en) * | 1985-08-05 | 1988-06-07 | Olin Corporation | Whisker resistant tin coatings and baths and methods for making such coatings |
| US4871429A (en) * | 1981-09-11 | 1989-10-03 | Learonal, Inc | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
| WO1990004048A1 (en) * | 1988-10-14 | 1990-04-19 | Atochem North America, Inc. | A method, bath and cell for the electrodeposition of tin-bismuth alloys |
| US5039576A (en) * | 1989-05-22 | 1991-08-13 | Atochem North America, Inc. | Electrodeposited eutectic tin-bismuth alloy on a conductive substrate |
| US5066367A (en) * | 1981-09-11 | 1991-11-19 | Learonal Inc. | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
| US5094726A (en) * | 1981-09-11 | 1992-03-10 | Learonal, Inc. | Limiting tin sludge formation in tin or tin-lead electroplating solutions |
| US5391402A (en) * | 1993-12-03 | 1995-02-21 | Motorola | Immersion plating of tin-bismuth solder |
| US5393573A (en) * | 1991-07-16 | 1995-02-28 | Microelectronics And Computer Technology Corporation | Method of inhibiting tin whisker growth |
| US5450784A (en) * | 1993-09-28 | 1995-09-19 | Detroit Diesel Corporation | Electroplated piston skirt for improved scuff resistance |
| WO2003021008A1 (fr) * | 2000-02-29 | 2003-03-13 | Learonal Japan Inc. | Solution galvanoplastique d'etain et procede de galvanoplastie |
| US20090145765A1 (en) * | 2007-12-11 | 2009-06-11 | Enthone Inc. | Composite coatings for whisker reduction |
| US20090145764A1 (en) * | 2007-12-11 | 2009-06-11 | Enthone Inc. | Composite coatings for whisker reduction |
| US20140332393A1 (en) * | 2013-05-09 | 2014-11-13 | Ebara Corporation | Sn ALLOY PLATING APPARATUS AND Sn ALLOY PLATING METHOD |
| US9850588B2 (en) | 2015-09-09 | 2017-12-26 | Rohm And Haas Electronic Materials Llc | Bismuth electroplating baths and methods of electroplating bismuth on a substrate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102579360B1 (ko) * | 2018-12-04 | 2023-09-18 | 현대자동차주식회사 | 차량의 보조 브레이크 제어 시스템 |
| CN111188069A (zh) * | 2019-12-31 | 2020-05-22 | 大连长丰实业总公司 | 一种镀锡铋合金溶液及其制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB526037A (en) * | 1938-03-07 | 1940-09-10 | Remy Van Der Zypen & Co | A method for producing an electroplated tin coating on other metals, particularly iron or steel sheets or strips |
| US3360446A (en) * | 1964-05-08 | 1967-12-26 | M & T Chemicals Inc | Electrodepositing a tin-bismuth alloy and additives therefor |
| US3522155A (en) * | 1964-07-10 | 1970-07-28 | M & T Chemicals Inc | Method of electrodepositing a tinbismuth alloy and compositions therefor |
-
1969
- 1969-12-19 FR FR6944284A patent/FR2071199A5/fr not_active Expired
-
1970
- 1970-10-08 US US79272A patent/US3663384A/en not_active Expired - Lifetime
- 1970-10-13 DE DE19702050145 patent/DE2050145A1/de active Pending
- 1970-11-26 GB GB56352/70A patent/GB1299519A/en not_active Expired
- 1970-11-27 JP JP45104187A patent/JPS4931606B1/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB526037A (en) * | 1938-03-07 | 1940-09-10 | Remy Van Der Zypen & Co | A method for producing an electroplated tin coating on other metals, particularly iron or steel sheets or strips |
| US3360446A (en) * | 1964-05-08 | 1967-12-26 | M & T Chemicals Inc | Electrodepositing a tin-bismuth alloy and additives therefor |
| US3522155A (en) * | 1964-07-10 | 1970-07-28 | M & T Chemicals Inc | Method of electrodepositing a tinbismuth alloy and compositions therefor |
Non-Patent Citations (2)
| Title |
|---|
| Frederick A. Lowenheim, Modern Electroplating, p. 373, (1968) * |
| N. T. Kudryavtsev et al., Trudy MKHTI imenl D. I. Mendeleeva, No. 266, pp. 113 119, (1959) * |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4162205A (en) * | 1978-10-19 | 1979-07-24 | Vulcan Materials Company | Method of electroplating tin and alkaline electroplating bath therefor |
| US4331518A (en) * | 1981-01-09 | 1982-05-25 | Vulcan Materials Company | Bismuth composition, method of electroplating a tin-bismuth alloy and electroplating bath therefor |
| US5094726A (en) * | 1981-09-11 | 1992-03-10 | Learonal, Inc. | Limiting tin sludge formation in tin or tin-lead electroplating solutions |
| US5066367A (en) * | 1981-09-11 | 1991-11-19 | Learonal Inc. | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
| US4599149A (en) * | 1981-09-11 | 1986-07-08 | Learonal, Inc. | Process for electroplating tin, lead and tin-lead alloys and baths therefor |
| US4871429A (en) * | 1981-09-11 | 1989-10-03 | Learonal, Inc | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
| US4701244A (en) * | 1983-12-22 | 1987-10-20 | Learonal, Inc. | Bath and process for electroplating tin, lead and tin/alloys |
| US4717460A (en) * | 1983-12-22 | 1988-01-05 | Learonal, Inc. | Tin lead electroplating solutions |
| US4617097A (en) * | 1983-12-22 | 1986-10-14 | Learonal, Inc. | Process and electrolyte for electroplating tin, lead or tin-lead alloys |
| US4565609A (en) * | 1983-12-22 | 1986-01-21 | Learonal, Inc. | Bath and process for plating tin, lead and tin-lead alloys |
| US4565610A (en) * | 1983-12-22 | 1986-01-21 | Learonal, Inc. | Bath and process for plating lead and lead/tin alloys |
| US4749626A (en) * | 1985-08-05 | 1988-06-07 | Olin Corporation | Whisker resistant tin coatings and baths and methods for making such coatings |
| WO1990004048A1 (en) * | 1988-10-14 | 1990-04-19 | Atochem North America, Inc. | A method, bath and cell for the electrodeposition of tin-bismuth alloys |
| US5039576A (en) * | 1989-05-22 | 1991-08-13 | Atochem North America, Inc. | Electrodeposited eutectic tin-bismuth alloy on a conductive substrate |
| US5393573A (en) * | 1991-07-16 | 1995-02-28 | Microelectronics And Computer Technology Corporation | Method of inhibiting tin whisker growth |
| US5450784A (en) * | 1993-09-28 | 1995-09-19 | Detroit Diesel Corporation | Electroplated piston skirt for improved scuff resistance |
| US5391402A (en) * | 1993-12-03 | 1995-02-21 | Motorola | Immersion plating of tin-bismuth solder |
| US5435838A (en) * | 1993-12-03 | 1995-07-25 | Motorola, Inc. | Immersion plating of tin-bismuth solder |
| WO2003021008A1 (fr) * | 2000-02-29 | 2003-03-13 | Learonal Japan Inc. | Solution galvanoplastique d'etain et procede de galvanoplastie |
| US20090145765A1 (en) * | 2007-12-11 | 2009-06-11 | Enthone Inc. | Composite coatings for whisker reduction |
| US20090145764A1 (en) * | 2007-12-11 | 2009-06-11 | Enthone Inc. | Composite coatings for whisker reduction |
| US8226807B2 (en) | 2007-12-11 | 2012-07-24 | Enthone Inc. | Composite coatings for whisker reduction |
| US8906217B2 (en) | 2007-12-11 | 2014-12-09 | Enthone Inc. | Composite coatings for whisker reduction |
| US20140332393A1 (en) * | 2013-05-09 | 2014-11-13 | Ebara Corporation | Sn ALLOY PLATING APPARATUS AND Sn ALLOY PLATING METHOD |
| US9816197B2 (en) * | 2013-05-09 | 2017-11-14 | Ebara Corporation | Sn alloy plating apparatus and Sn alloy plating method |
| US9850588B2 (en) | 2015-09-09 | 2017-12-26 | Rohm And Haas Electronic Materials Llc | Bismuth electroplating baths and methods of electroplating bismuth on a substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1299519A (en) | 1972-12-13 |
| FR2071199A5 (enrdf_load_stackoverflow) | 1971-09-17 |
| DE2050145A1 (de) | 1971-06-24 |
| JPS4931606B1 (enrdf_load_stackoverflow) | 1974-08-23 |
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