EP1319093B1 - Galvanische elektrolytbäder zur erzeugung von ternären zinn-zink-kobalt legierungsschichten - Google Patents
Galvanische elektrolytbäder zur erzeugung von ternären zinn-zink-kobalt legierungsschichten Download PDFInfo
- Publication number
- EP1319093B1 EP1319093B1 EP01969597A EP01969597A EP1319093B1 EP 1319093 B1 EP1319093 B1 EP 1319093B1 EP 01969597 A EP01969597 A EP 01969597A EP 01969597 A EP01969597 A EP 01969597A EP 1319093 B1 EP1319093 B1 EP 1319093B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- zinc
- tin
- cobalt
- alloy layer
- 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
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- SDRDGBIYJHUXJX-UHFFFAOYSA-N [Co].[Zn].[Sn] Chemical compound [Co].[Zn].[Sn] SDRDGBIYJHUXJX-UHFFFAOYSA-N 0.000 title claims description 7
- 229910000531 Co alloy Inorganic materials 0.000 title claims description 6
- 238000009713 electroplating Methods 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims description 38
- 239000000956 alloy Substances 0.000 claims description 38
- 239000003792 electrolyte Substances 0.000 claims description 32
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 12
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000000080 wetting agent Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 238000002161 passivation Methods 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims 6
- 239000010410 layer Substances 0.000 description 39
- 229910052718 tin Inorganic materials 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 15
- 238000000151 deposition Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910001297 Zn alloy Inorganic materials 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 230000008021 deposition Effects 0.000 description 10
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 238000005275 alloying Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 238000004532 chromating Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910005728 SnZn Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000011787 zinc oxide Substances 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 241000288113 Gallirallus australis Species 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000005612 glucoheptonate group Chemical group 0.000 description 1
- 125000005611 glucoheptonic acid group Chemical group 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- KIMPPGSMONZDMN-UHFFFAOYSA-N sodium;dihydrogen phosphite Chemical compound [Na+].OP(O)[O-] KIMPPGSMONZDMN-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000002347 wear-protection layer Substances 0.000 description 1
- 230000004580 weight loss 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
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- 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 invention relates to galvanic electrolyte baths and their use.
- Higher requirements such as resistance to salt spray testing up to the first occurrence of red rust of up to 1000 hours, may be met by coating with zinc alloys containing nickel, cobalt or iron as the alloying component followed by chromating.
- the proportion of alloying elements may be less than 1% by weight, for example 0.4-0.6% by weight of Fe in the ZnFe system, up to 15% by weight, for example 12-15% by weight of Ni in the ZnNi system ( Zinc alloy process: properties and applications in the art , Dr. A. Jiménez, B. Kerle and H. Schmidt, Galvanotechnik 89 (1998) 4 ).
- Tin-zinc alloy layers can also be used as anti-corrosion layers for iron.
- values of up to 1000 hours are achieved with chromated SnZn layers until the first appearance of red rust.
- the most favorable alloy composition is 70% by weight of Sn and 30% by weight of Zn.
- the disadvantage seen is the low hardness of SnZn layers of only about 50 HV ( Tin-Zinc-Plating, E. Budmann and D. Stevens, Trans. IMF 76 (1998) 3 ).
- the invention therefore an object of the invention to find galvanic electrolyte baths for the deposition of alloy systems with particularly high corrosion resistance, which meet the future requirements in terms of corrosion protection.
- the above electrolytic baths can be used for electroplating a ternary tin-zinc-cobalt alloy layer consisting of 30 to 65% by weight of tin, 30 to 65% by weight of zinc and 0.1 to 15% by weight of cobalt.
- the alloy layer consists of 40 to 55 wt.% Tin, 45 to 55 wt.% Zinc and 1 to 5 wt.% Cobalt.
- the alloy layer can serve as a corrosion protection layer, as a solderable layer or as a decorative final layer. Furthermore, it can be used with a subsequent passivation as a corrosion protection layer on a ferrous material.
- ternary tin-zinc alloys according to the invention which consist of 30 to 65 wt.% Tin, 30 to 65 wt.% Zinc and 0.1 to 15 wt.% Cobalt, as a third alloy component, the requirements meet with regard to corrosion resistance excellent.
- the alloy layers are produced by electroplating, namely by electrolytic deposition from aqueous electrolytic electrolyte baths containing the alloy components in dissolved form.
- the tin-zinc ternary alloys can be deposited on substrates from alkaline or neutral galvanic electrolyte baths.
- An alkaline electrolyte is understood here to mean an electrolyte having a pH greater than 10.
- the neutral electrolyte is an electrolyte with a pH of 6 - 10.
- the alloy components are added to the aqueous electrolyte bath in the form of their respective medium soluble ionic compounds.
- Tin is preferably used as sulfate, chloride, sulfonate, oxalate or in the form of sodium or potassium stannate.
- Zinc is preferably added as sulfate, chloride, hydroxide, sulfonate or oxide.
- cobalt is preferably added as each of sulfate, chloride, hydroxide or carbonate.
- the galvanic electrolytes according to the invention for the production of ternary tin-zinc alloy layers may further contain customary and known additives and auxiliaries in electroplating.
- additives and auxiliaries may be alkalis for pH adjustment, such as sodium, potassium or ammonium hydroxide, or inorganic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, alkali metal salts of these acids as buffer and / or conductive salts, organic acids such as hydroxycarboxylic acids and / or salts thereof, for example citric acid, complexing agents such as EDTA, wetting agents, brighteners, etc.
- citric acid complexing agents
- complexing agents such as EDTA
- wetting agents wetting agents
- brighteners etc.
- the ratio of the metals in the electrodeposited alloy layer can be influenced in a known manner by the ratio of the metals in the bath composition, by the nature and amount of the other bath components and by the deposition parameters.
- the substrate to be coated for example a component to be protected from corrosion from an iron material
- the substrate to be coated is immersed in a corresponding galvanic bath and wired as a cathode.
- Anodes can be used as counterelectrodes of insoluble or, preferably in the case of neutral electrolytes, soluble materials.
- Insoluble anodes are usually made of graphite or platinized titanium.
- Soluble anodes suitably consist of the metals of the alloy layer to be deposited, preferably in the desired composition.
- a temperature of about 20 - 70 ° C and a current density of about 0.1 - 5 A / dm 2 are considered, with deposition rates of about 0, 05 - 1 ⁇ m / minute.
- the galvanic deposition of the alloy takes place at temperatures between 40-70 ° C at current densities of 1 - 5 A / dm 2 with deposition rates of 0.15 - 0.3 microns / minute.
- As anodes graphite or platinized titanium can be used.
- organic acids and their salts organic acids and their salts, phosphonic acids, phosphonates, gluconates, glucoheptonic acids, glucoheptonates and ethylenediaminetetraacetic acid can be used.
- Suitable wetting agents and brighteners can be used in the appropriate media resistant surfactants, polyhydric alcohols and betaines.
- the alloy composition of the layer can be varied.
- an increase in the hydroxide content causes a reduction in the tin content and a corresponding increase in the other two metals in the layer.
- An increase in the amount of complexing agent causes a decrease in the zinc content and an increase in the tin content in the layer.
- these changes have virtually no influence.
- the galvanic deposition of the alloy is carried out at temperatures between 40-70 ° C at current densities of 0.5 - 3 A / dm 2 with deposition rates of 0.05 - 0.3 microns / minute.
- As anodes graphite or platinized titanium can be used. The use of soluble anodes is also possible.
- the ratio of the alloy composition can be varied by varying the coating parameters.
- the ternary tin-zinc alloys have very advantageous material properties, due to which they can be used both as an independent material, and in particular in the form of coatings on substrates in different ways.
- the ternary tin-zinc alloys have a particularly high corrosion resistance. Therefore, these alloys are particularly suitable as corrosion protection coatings on iron materials. Accordingly, the corresponding galvanic electrolytes can preferably be used to produce corrosion protection coatings on iron materials.
- coated iron sheets in combination with the usual passivation by chromating or chromitization readily achieve a resistance to the occurrence of red rust of over 3000 hours.
- the properties of the ternary tin-zinc alloy layers can be optimized depending on the choice of the third alloy element.
- Table 1 gives an overview of the influence of the third alloying element when either good corrosion resistance, hardness, abrasion or solderability are desired.
- the nickel and iron alloys are given as comparative examples. ⁇ b> ⁇ u> Table 1 ⁇ / u> ⁇ /b> corrosion hardness abrasion solderability SnZnNi + - + - SnZnFe - + - + SnZnCo + + - +
- the SnZnFe and SnZnCo alloy layers achieve the highest hardness values.
- the highest abrasion resistance is exhibited by SnZnNi layers.
- Such alloy layers can therefore be used advantageously as wear protection layers under mechanical stress.
- SnZnFe and SnZnCo layers are particularly easy to solder and are therefore excellently suited in electronics as solderable layers and as contact surfaces.
- Table 2 shows the corresponding data for exemplarily selected alloy systems.
- the ternary tin-zinc alloys can also be used as decorative end layers.
- the three alloy systems depending on the choice of the third alloy element, interesting and appealing, lying in the blue range colors.
- the above-mentioned layer composition can be obtained with this electrolyte at a temperature of 60 ° C and current densities of 1-2 A / dm 2 . In this case, about 0.2 microns alloy layer are built up per minute. The density of the alloy layer is 7.27 g / cm 3 .
- the above-mentioned layer composition can be obtained with this electrolyte at a temperature of 60 ° C and current densities of 0.5 - 1 A / dm 2 . 0.15 ⁇ m layer is built up per minute.
- the density of the alloy layer is 7.27 g / cm 3 .
- the above-mentioned layer composition can be obtained with this electrolyte at a temperature of 40 ° C and current densities of 1.5 A / dm 2 . In this case, about 0.4 microns alloy layer are built up per minute. The density of the alloy layer is 7.2 g / cm 3 .
- the above-mentioned layer composition can be obtained with this electrolyte at a temperature of 40 ° C and current densities of 1.5 A / dm 2 . In this case, about 0.4 microns alloy layer are built up per minute. The density of the alloy layer is 7.25 g / cm 3 .
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10045991A DE10045991A1 (de) | 2000-09-16 | 2000-09-16 | Ternäre Zinn-Zink-Legierungen, galvanische Bäder und galvanisches Verfahren zur Erzeugung von ternären Zinn-Zink-Legierungsschichten |
| DE10045991 | 2000-09-16 | ||
| PCT/EP2001/009452 WO2002022913A2 (de) | 2000-09-16 | 2001-08-16 | Ternäre zinn-zink legierungen enthaltend eisen, kobalt oder nickel, galvanische bäder und galvanisches verfahren zu ihrer erzeugung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1319093A2 EP1319093A2 (de) | 2003-06-18 |
| EP1319093B1 true EP1319093B1 (de) | 2008-12-31 |
Family
ID=7656548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01969597A Expired - Lifetime EP1319093B1 (de) | 2000-09-16 | 2001-08-16 | Galvanische elektrolytbäder zur erzeugung von ternären zinn-zink-kobalt legierungsschichten |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20040091385A1 (enExample) |
| EP (1) | EP1319093B1 (enExample) |
| JP (1) | JP4817352B2 (enExample) |
| CN (1) | CN1239751C (enExample) |
| DE (2) | DE10045991A1 (enExample) |
| WO (1) | WO2002022913A2 (enExample) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3878978B2 (ja) | 2002-10-24 | 2007-02-07 | コーア株式会社 | 鉛非含有はんだ、および鉛非含有の継手 |
| JP2005026188A (ja) | 2003-07-03 | 2005-01-27 | Koa Corp | 電流ヒューズ及び電流ヒューズの製造方法 |
| JP4901120B2 (ja) * | 2005-03-29 | 2012-03-21 | 兵庫県 | 亜鉛を含むめっき皮膜 |
| CN100554528C (zh) * | 2006-03-29 | 2009-10-28 | 哈尔滨工业大学 | 具有良好耐化学性及粘结力的电解铜箔镀层表面处理方法 |
| EP2085502A1 (en) * | 2008-01-29 | 2009-08-05 | Enthone, Incorporated | Electrolyte composition and method for the deposition of a tin-zinc alloy |
| KR20110028010A (ko) * | 2009-09-11 | 2011-03-17 | 삼성전기주식회사 | 미립 주석 분말 및 그 제조 방법 |
| CN102791902B (zh) * | 2010-02-01 | 2015-04-08 | 科卢斯博知识产权有限公司 | 镍基热喷涂粉末和涂层及其制备方法 |
| CN102212809B (zh) * | 2011-05-12 | 2012-07-18 | 北京化工大学 | 一种镍基合金加热管的防腐蚀方法 |
| US20130098691A1 (en) | 2011-10-25 | 2013-04-25 | Longyear Tm, Inc. | High-strength, high-hardness binders and drilling tools formed using the same |
| CN102690975B (zh) * | 2012-06-11 | 2014-12-03 | 东莞市闻誉实业有限公司 | 一种三元锡-锌合金及其电镀方法 |
| CN103849912A (zh) * | 2012-11-29 | 2014-06-11 | 沈阳工业大学 | 一种电镀光亮锡锌镍合金工艺 |
| RU2654030C2 (ru) | 2012-12-18 | 2018-05-15 | Лэнксесс Бутил Пте. Лтд. | Электронные устройства, содержащие бутилкаучук |
| CN103436825A (zh) * | 2013-08-23 | 2013-12-11 | 哈尔滨理工大学 | 纳米氧化锡涂覆陶瓷相增强体/铝基复合材料的制备方法 |
| CN106521580A (zh) * | 2016-11-02 | 2017-03-22 | 苏州市汉宜化学有限公司 | 四价锡Sn‑Co‑Zn三元合金代铬电镀液及电镀方法 |
| CN112779576B (zh) * | 2020-12-25 | 2022-06-21 | 南通正海磁材有限公司 | 一种钕铁硼磁体复合镀层及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH103474A (fr) * | 1923-04-13 | 1924-02-16 | Enrico Scala Giuseppe | Soudure pour aluminium et procédé de fabrication de celle-ci. |
| US3791801A (en) * | 1971-07-23 | 1974-02-12 | Toyo Kohan Co Ltd | Electroplated steel sheet |
| US3881919A (en) * | 1974-01-07 | 1975-05-06 | Whyco Chromium Co | Ternary alloys |
| JPS51131427A (en) * | 1975-05-05 | 1976-11-15 | Whyco Chromium Co | Ternary alloy |
| SU670638A1 (ru) * | 1977-02-14 | 1979-06-30 | Ярославский политехнический институт | Электролит дл нанесени покрытий из сплавов на основе олова |
| CA1193222A (en) * | 1981-02-25 | 1985-09-10 | Wim M.J.C. Verberne | Electroplating cobalt alloy with zinc or tin from amine bath |
| JPS5848694A (ja) * | 1981-09-16 | 1983-03-22 | Nippon Steel Corp | アルコ−ルを含有もしくはアルコ−ル系燃料容器用Ｓｎ−Ｚｎ系合金電気メツキ鋼板 |
| JPS58153796A (ja) * | 1982-03-05 | 1983-09-12 | Sumitomo Metal Ind Ltd | 電気メツキ鋼板 |
| JPS59170289A (ja) * | 1983-03-15 | 1984-09-26 | Sumitomo Metal Ind Ltd | 鉄系電気メツキ法 |
| US4488942A (en) * | 1983-08-05 | 1984-12-18 | Omi International Corporation | Zinc and zinc alloy electroplating bath and process |
| JPS63186860A (ja) * | 1987-01-27 | 1988-08-02 | Nippon Steel Corp | 耐錆性、溶接性に優れた表面処理鋼板の製造方法 |
| JPH01172593A (ja) * | 1987-12-25 | 1989-07-07 | Kawasaki Steel Corp | 塗装後密着性が優れたＺｎ−Ｎｉ−Ｓｎ合金めっき鋼板の製造方法 |
| US5429882A (en) * | 1993-04-05 | 1995-07-04 | The Louis Berkman Company | Building material coating |
| DE19644235C1 (de) * | 1996-10-24 | 1998-02-12 | Grillo Werke Ag | Schrot für Munitionszwecke |
-
2000
- 2000-09-16 DE DE10045991A patent/DE10045991A1/de not_active Ceased
-
2001
- 2001-08-16 US US10/380,212 patent/US20040091385A1/en not_active Abandoned
- 2001-08-16 DE DE50114623T patent/DE50114623D1/de not_active Expired - Lifetime
- 2001-08-16 CN CN01816986.4A patent/CN1239751C/zh not_active Expired - Fee Related
- 2001-08-16 WO PCT/EP2001/009452 patent/WO2002022913A2/de not_active Ceased
- 2001-08-16 JP JP2002527347A patent/JP4817352B2/ja not_active Expired - Fee Related
- 2001-08-16 EP EP01969597A patent/EP1319093B1/de not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE50114623D1 (de) | 2009-02-12 |
| WO2002022913A3 (de) | 2002-07-25 |
| CN1239751C (zh) | 2006-02-01 |
| CN1468327A (zh) | 2004-01-14 |
| HK1054576A1 (zh) | 2003-12-05 |
| JP2004509229A (ja) | 2004-03-25 |
| JP4817352B2 (ja) | 2011-11-16 |
| US20040091385A1 (en) | 2004-05-13 |
| DE10045991A1 (de) | 2002-04-04 |
| WO2002022913A2 (de) | 2002-03-21 |
| EP1319093A2 (de) | 2003-06-18 |
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