EP2085502A1 - Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zinn-Zink-Legierung - Google Patents
Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zinn-Zink-Legierung Download PDFInfo
- Publication number
- EP2085502A1 EP2085502A1 EP08001614A EP08001614A EP2085502A1 EP 2085502 A1 EP2085502 A1 EP 2085502A1 EP 08001614 A EP08001614 A EP 08001614A EP 08001614 A EP08001614 A EP 08001614A EP 2085502 A1 EP2085502 A1 EP 2085502A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte composition
- tin
- electrolyte
- zinc
- deposition
- 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.)
- Withdrawn
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 25
- 230000008021 deposition Effects 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 22
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 7
- 238000005282 brightening Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 3
- 235000021317 phosphate Nutrition 0.000 claims abstract description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims abstract description 3
- 239000000080 wetting agent Substances 0.000 claims abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910002065 alloy metal Inorganic materials 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- -1 mercapto-glycollates Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052961 molybdenite Inorganic materials 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical class ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical class CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 229910003465 moissanite Inorganic materials 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910010271 silicon carbide Inorganic materials 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 238000007747 plating Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 229940071182 stannate Drugs 0.000 description 3
- 125000005402 stannate group Chemical group 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- 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
- the present invention relates to an electrolyte composition for the deposition of a tin-zinc alloy on a substrate surface. Furthermore, the invention relates to a method for the deposition of a tin-zinc alloy layer on a substrate surface.
- Tin-zinc alloy electroplating methods have come to be widely used as an industrial plating method in various industries like automobile industries, fitting industries or electronic industries. Tin-zinc alloy layers on substrate surfaces deposited by electroplating methods have excellent corrosion resistance and good solder abilities.
- US 6,436,269 B1 discloses an aqueous plating bath for the electrodeposition of a tin-zinc alloy comprising at least one bath soluble stannous salt, at least one bath soluble zinc salt, and a quaternary ammonium polymer selected from a ureylene quaternary ammonium polymer, an iminoureylene quaternary ammonium polymer or a thioureylene quaternary ammonium polymer.
- the plating bath disclosed in US 6,436,269 B1 may also contain hydroxy polycarboxylic acids like citric acid, ammonium salts, conducting salts, aromatic carbonyl-containing compounds, polymers of aliphatic amines or hydroxyalkyl substituted diamines as metal complexing agents. From such an aqueous plating bath bright and level layers can be deposited.
- a tin-zinc alloy electroplating bath comprising an amphoteric surfactant , a water soluble stannous salt, a water soluble zinc salt and balance water.
- an electrolyte composition for the deposition of a tin-zinc alloy on a substrate surface, wherein tin is comprised in the electrolyte composition in oxidation state +4 (Sn 4+ ) and wherein the electrolyte composition has a pH-value in the range of about pH 9 to about pH 11.
- the electrolyte composition according to the invention comprises at least zinc in form of a soluble zinc compound, tin in form of a water soluble stannate and an complexing agent.
- the electrolyte composition can comprise zinc hydroxide which, under the conditions of the electrolyte composition, reacts to oxyl or hydroxyl acids of zinc, known as zincates.
- the electrolyte composition can comprise stannic acid or derivatives of stannic acid like salts.
- the inventive electrolyte composition comprises at least one of the group consisting of carboxylates, amino derivatives, phosphates and hydroxides.
- a preferred complexing agent in the inventive electrolyte composition is 1-hydroxyethylene-1, 1-diphosphonic acid.
- the inventive electrolyte composition may further comprise a brightening agent for the deposition of bright tin-zinc layers.
- a brightening agent the electrolyte composition may comprise at least one of the group consisting of aldehydes, ketones, mercapto-glycollates, benzalacetone derivatives, orthochlorobenzaldehyde derivatives, unsaturated ethane alkyl carboxylates, multiple unsaturated alkanes extended with amine or carboxyl groups and metal cations acting as grain refiners such as iron, cobalt or nickel.
- a preferred brightening agent within this group is methacrylic acid.
- the electrolyte may further comprise alkaline hydroxides, sulphates or chlorides.
- the pH-value of the composition can be maintained within a range from about pH 9 to about pH 11 for the deposition of tin-zinc alloy layers on substrate surfaces having excellent corrosion resistance, good mechanical properties and an adequate appearance.
- the electrolyte composition when set to a pH-value in the range from about pH 9 to about pH 11, the electrolyte composition is less aggressive in comparison to the plating compositions known from the state of the art and can easily be handled. Also, the inventive electrolyte composition is less aggressive to the plating equipment, thereby reducing the need for maintenance of the plating equipment.
- the crystal structure of the tin-zinc alloy layer deposited from the inventive electrolyte composition allows the inclusions of further compounds or elements within the crystal lattice. This allows the deposition of composite layers enclosing a composite material within the crystal lattice, thereby forming a surface layer with advanced properties.
- the enclosure of silicon within the tin-zinc alloy lattice is possible.
- the composite layers will have enhanced physical and chemical properties. Depending on the co-deposited material corrosion resistance, hardness, wear-resistance and friction can be improved.
- the object of the invention is solved by a method for the deposition of a tin-zinc alloy layer on a substrate surface, the method comprising the steps:
- Zinc is preferably pre-dissolved in alkaline or acidic medium to form water soluble salts resulting in zinc ions or zincate.
- zinc may be added as zinc hydroxide to the inventive electrolyte.
- Tin is pre-dissolved in alkaline media to form stannate ions (Sn 4+ ). This solution should be used fresh to avoid formation of meta stannates.
- alkaline hydroxides can be added. It was found that the addition of potassium hydroxide to the inventive electrolyte composition further improves the solubility of the bath chemicals, compared to the use of other alkaline hydroxides.
- the bath performs at different temperatures and cathodic current densities to give an alloy deposition targeted at 70 - 80% by weight Sn and 30 - 20% by weight zinc for optimal corrosion resistance.
- a true 98,5% by weight tin alloy can be obtained next to deposition of pure tin and zinc crystals in the deposited layer.
- the element to be deposited together with the alloy metals can be added to the inventive electrolyte composition as a water soluble or water dispersible compound.
- the element to be deposited together with the alloy metals can be comprised in the electrolyte composition in an amount up to 100 g/I.
- an inert carbon/graphite anode can be used as counter electrode.
- one of the main features of the inventive electrolyte composition is to be applicable at a pH from about pH 9 to about pH 11, the control of the pH-value is important.
- alkaline hydroxides like potassium hydroxide or acids like hydrochloric acid can be added to the electrolyte composition in order to set the pH level in the inventive range.
- a steel substrate was contacted with an electrolyte comprising 7 g/I zinc as zincate, 42 g/I tin as stannate, 230 g/l of an complexing agent based on organophosphonate and hydroxyl carboxy alkanes, 0,8 g/I methylmethacrylate, 0,8 g/I fluoro-aliphatic ammonium surfactant and potassium hydroxide as well as hydrochloric acid to set the pH-value to pH 10.
- the substrate was contacted with the electrolyte at a temperature of 55°C.
- a cathodic current density of 0,8 A/dm 2 was conducted between the substrate surface and a carbon/graphite inert anode for 20 minutes.
- a uniform semi-bright tin-zinc deposit was obtained; containing 25-30% zinc, remainder tin.
- colloidal silica dispersion was added to the electrolyte descripted in example 1.
- Plating conditions were the same as in example 1.
- the addition of a colloidal silica dispersion allowed a co-deposition of silica particles.
- a tin-zinc-SiO 2 composite was obtained, having a composition of 87% tin, 8% zinc and 5% SiO 2 .
- the composition of the composite could be controlled by varying the concentrations and conditions.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08001614A EP2085502A1 (de) | 2008-01-29 | 2008-01-29 | Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zinn-Zink-Legierung |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08001614A EP2085502A1 (de) | 2008-01-29 | 2008-01-29 | Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zinn-Zink-Legierung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2085502A1 true EP2085502A1 (de) | 2009-08-05 |
Family
ID=39315134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08001614A Withdrawn EP2085502A1 (de) | 2008-01-29 | 2008-01-29 | Elektrolytzusammensetzung und Verfahren zur Abscheidung einer Zinn-Zink-Legierung |
Country Status (1)
| Country | Link |
|---|---|
| EP (1) | EP2085502A1 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757672A (zh) * | 2014-01-20 | 2014-04-30 | 广州市海科顺表面处理有限公司 | 一种锌锡合金电镀方法 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992004485A1 (en) * | 1990-08-31 | 1992-03-19 | Barry, Beresford, Thomas, Kingcome | Electroplating |
| EP0636713A2 (de) * | 1993-07-26 | 1995-02-01 | Degussa Aktiengesellschaft | Cyanidisch-alkalische Bäder zur galvanischen Abscheidung von Kupfer-Zinn-Legierunsüberzügen |
| EP0666342A1 (de) * | 1994-02-05 | 1995-08-09 | W.C. Heraeus GmbH | Bad zum galvanischen Abscheiden von Silber-Zinn-Legierungen |
| US5618402A (en) | 1992-09-25 | 1997-04-08 | Dipsol Chemicals Co., Ltd. | Tin-zinc alloy electroplating bath and method for electroplating using the same |
| EP0921211A1 (de) * | 1997-12-06 | 1999-06-09 | Federal-Mogul Wiesbaden GmbH | Schichtverbundwerkstoff für Gleitlanger mit bleifreier Gleitschicht |
| WO2002022913A2 (de) * | 2000-09-16 | 2002-03-21 | Degussa Galvanotechnik Gmbh | Ternäre zinn-zink legierungen enthaltend eisen, kobalt oder nickel, galvanische bäder und galvanisches verfahren zu ihrer erzeugung |
| US6436269B1 (en) | 2000-10-19 | 2002-08-20 | Atotech Deutschland Gmbh | Plating bath and method for electroplating tin-zinc alloys |
| US20030150743A1 (en) * | 2001-09-20 | 2003-08-14 | Daiwa Fine Chemicals Co., Ltd. | Tin or tin alloy plating bath, tin salt solution and acid or complexing agent solution for preparing or controlling and making up the plating bath, and electrical and electric components prepared by the use of the plating bath |
| WO2006063469A1 (en) * | 2004-12-17 | 2006-06-22 | Integran Technologies, Inc. | Article comprising a fine-grained metallic materal and a polymeric material |
-
2008
- 2008-01-29 EP EP08001614A patent/EP2085502A1/de not_active Withdrawn
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992004485A1 (en) * | 1990-08-31 | 1992-03-19 | Barry, Beresford, Thomas, Kingcome | Electroplating |
| US5618402A (en) | 1992-09-25 | 1997-04-08 | Dipsol Chemicals Co., Ltd. | Tin-zinc alloy electroplating bath and method for electroplating using the same |
| EP0636713A2 (de) * | 1993-07-26 | 1995-02-01 | Degussa Aktiengesellschaft | Cyanidisch-alkalische Bäder zur galvanischen Abscheidung von Kupfer-Zinn-Legierunsüberzügen |
| EP0666342A1 (de) * | 1994-02-05 | 1995-08-09 | W.C. Heraeus GmbH | Bad zum galvanischen Abscheiden von Silber-Zinn-Legierungen |
| EP0921211A1 (de) * | 1997-12-06 | 1999-06-09 | Federal-Mogul Wiesbaden GmbH | Schichtverbundwerkstoff für Gleitlanger mit bleifreier Gleitschicht |
| WO2002022913A2 (de) * | 2000-09-16 | 2002-03-21 | Degussa Galvanotechnik Gmbh | Ternäre zinn-zink legierungen enthaltend eisen, kobalt oder nickel, galvanische bäder und galvanisches verfahren zu ihrer erzeugung |
| US6436269B1 (en) | 2000-10-19 | 2002-08-20 | Atotech Deutschland Gmbh | Plating bath and method for electroplating tin-zinc alloys |
| US20030150743A1 (en) * | 2001-09-20 | 2003-08-14 | Daiwa Fine Chemicals Co., Ltd. | Tin or tin alloy plating bath, tin salt solution and acid or complexing agent solution for preparing or controlling and making up the plating bath, and electrical and electric components prepared by the use of the plating bath |
| WO2006063469A1 (en) * | 2004-12-17 | 2006-06-22 | Integran Technologies, Inc. | Article comprising a fine-grained metallic materal and a polymeric material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757672A (zh) * | 2014-01-20 | 2014-04-30 | 广州市海科顺表面处理有限公司 | 一种锌锡合金电镀方法 |
| CN103757672B (zh) * | 2014-01-20 | 2016-06-29 | 广州市海科顺表面处理有限公司 | 一种锌锡合金电镀方法 |
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