EP3400323A2 - Self-lubricating electrolytically deposited phosphate coating - Google Patents
Self-lubricating electrolytically deposited phosphate coatingInfo
- Publication number
- EP3400323A2 EP3400323A2 EP17700126.0A EP17700126A EP3400323A2 EP 3400323 A2 EP3400323 A2 EP 3400323A2 EP 17700126 A EP17700126 A EP 17700126A EP 3400323 A2 EP3400323 A2 EP 3400323A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- workpiece
- solid lubricant
- lubricant particles
- equal
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 22
- 239000011248 coating agent Substances 0.000 title claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 7
- 239000010452 phosphate Substances 0.000 title abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 96
- 239000007787 solid Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 93
- 239000000416 hydrocolloid Substances 0.000 claims description 43
- 238000000151 deposition Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229920000159 gelatin Chemical group 0.000 claims description 11
- 235000019322 gelatine Nutrition 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 108010010803 Gelatin Chemical group 0.000 claims description 10
- 239000008273 gelatin Chemical group 0.000 claims description 10
- 235000011852 gelatine desserts Nutrition 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 108010076876 Keratins Proteins 0.000 claims description 4
- 102000011782 Keratins Human genes 0.000 claims description 4
- 239000005018 casein Substances 0.000 claims description 4
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 4
- 235000021240 caseins Nutrition 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- -1 Bi 2 S 3 Inorganic materials 0.000 claims description 3
- 108010035532 Collagen Chemical group 0.000 claims description 3
- 102000008186 Collagen Human genes 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229920001436 collagen Chemical group 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 229920002717 polyvinylpyridine Chemical group 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Chemical group 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229910052955 covellite Inorganic materials 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052949 galena Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 229910000851 Alloy steel Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 235000003441 saturated fatty acids Nutrition 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- 230000006641 stabilisation Effects 0.000 description 11
- 238000011105 stabilization Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 238000010348 incorporation Methods 0.000 description 8
- 230000001427 coherent effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 7
- 229910000165 zinc phosphate Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002356 laser light scattering Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004141 dimensional analysis Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- YBVAXJOZZAJCLA-UHFFFAOYSA-N nitric acid nitrous acid Chemical compound ON=O.O[N+]([O-])=O YBVAXJOZZAJCLA-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical class OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000010099 solid forming Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- SPDJAIKMJHJYAV-UHFFFAOYSA-H trizinc;diphosphate;tetrahydrate Chemical compound O.O.O.O.[Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SPDJAIKMJHJYAV-UHFFFAOYSA-H 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920002554 vinyl polymer Chemical group 0.000 description 1
- 238000003466 welding Methods 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
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
-
- 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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
Definitions
- the present invention relates to a self-lubricating, electrodeposited phosphating coating on metallic workpieces having stabilized solid lubricants incorporated in the phosphating coating and a method for producing the same.
- Examples of electrolytic coating processes are chromating, galvanizing and phosphating, the latter being used when the corrosion resistance is increased or cold solid forming of the metallic base body is intended.
- Cold forming of metallic workpieces causes high friction between the tool and the workpiece due to the surface pressure and it can be used for local welding of the sliding surfaces and subsequent damage come of the workpiece and / or the tool.
- a phosphating layer is applied before the forming, which usually, in combination with the application of additional lubricants, contributes to a reduction of the friction in the following forming process.
- the lubricating effect of the phosphate layer is itself of only minor importance, more important is that this layer has a crystalline structure with high porosity, which compared to untreated metal surfaces up to 13 times more lubricants, such as oil can accommodate. Solid lubricants also adhere better on a phosphated metal surface than on bare steel.
- Electrolytic deposits of acidic aqueous solutions are disclosed which contain at least zinc and phosphate ions and are carried out with simultaneous use of direct current. Simultaneously with the deposition of the phosphating an electrolytic deposition of zinc takes place in the same electrolyte, wherein the current density is greater than -5 A / dm.
- Another method for phosphating a metal layer by electrolytic deposition of acidic aqueous solutions containing at least zinc and phosphate ions is disclosed in DE 10 2006 035 974 AI. This document discloses metal layers which are covered with a zinc (zinc alloy) / zinc phosphate layer, wherein foreign particles have been incorporated into the zinc (zinc alloy) / zinc phosphate layer.
- DE 164 492 7 discloses a method for the production of particles containing dry lubricant which are to be incorporated by electrodeposition in galvanically suspended metal coatings by placing them in the electrolyte and finely divided powdered dry lubricant optionally together with silicon carbide or alumina particles as wear resistant particles in a resin solution or in a silicate solution optionally as a reaction in sparingly soluble compounds stirring substances are mixed with lime water, aluminum chloride or sulfuric acid, is stirred in that the solvent is driven out of the mixture by evaporation and the residue mechanically comminuted to the desired particle size.
- Another method for double phosphating, optionally with the aid of a polymer in the phosphating solution is described in DE 197 81 959 B4.
- the phosphated workpiece is immersed in a bath of 8.5 to 100 Ca +1 g / l; 0.5 to 100 Zn 2+ g / 1, 5 to 100 P0 4 3 " g / 1, 0 to 100 NO 3" g / 1; 0 to 100 CIO 3 " g / 1 and 0 to 50 F “ or Cl " g / 1, to which polymers and solid lubricants are added to improve the frictional properties of the second phosphating layer.
- an electrolytically deposited phosphating layer comprises at least the elements zinc and phosphorus on a metallic workpiece, wherein the phosphating layer comprises solid particles lubricated by hydrocoids, the stabilized solid lubricant particles being at least partially incorporated in the phosphating layer.
- the additional step of a lubricant or lubricant / lubricant particle order is eliminated by the incorporation of the lubricant particles, so that the fiction, phosphated according to workpieces without further process steps of a mechanical cold forming can be supplied.
- the quality-appropriate deposition and the resulting stability of the additional lubricant-laden phosphating layers results from the presence of the hydrocoids in the phosphating bath.
- These hydrocoids are apparently capable of stabilizing the solid lubricants in the solution in the form of coacervates by attaching to the solid lubricant particles.
- These attachment complexes may appear to contribute to a better distribution of the solid lubricant particles in the solution.
- a phosphating layer according to the invention is an electrodeposited zinc phosphate layer on a metallic workpiece. This can in principle be applied by known methods and is widely used, for example, for the corrosion protection of low-alloyed steels.
- phosphate phosphates precipitate zinc phosphate crystals (hopeite) by exceeding its solubility product on the surface of the component. This can be achieved, for example, by heating the base metal (eg Fe - > Fe 2+ + 2e - ), with the electrons released serving for proton reduction.
- the pH of the aqueous bath solution is shifted to a neutral to basic range and exceeded the solubility of the zinc phosphate.
- the forming layer is usually about 2 to 20 ⁇ strong and may have a coverage sgrad the component surface of about 90% to 95%, sometimes up to 100%.
- the phosphating layer applied according to the invention is deposited electrolytically. This can be done either by applying a direct current or by applying a pulsed direct current. Typical currents are in a range of 0.1 and 250 mA / cm and the bath temperatures can be selected in a range of 20 to 90 ° C. The temperature is preferably between 25 ° C and 80 ° C.
- the Beschich- durations, ie the time in which a current flows through the workpiece and metal ions are deposited from the solution on the workpiece is freely determinable and may conveniently be between a few seconds, for example 1 second and several minutes, such as 5 minutes.
- the coating time as a function of the concentration of the ions to be deposited, the desired Layer thickness and the workpiece geometry selected.
- the treatment times of modern systems for electrolytic galvanizing and phosphating of steel strips are at 90 to 120 m / min. This results in deposition times in the range up to 5 seconds. In general, treatment times of 0.5 to 5 seconds can be used in this coating situation.
- the layer thickness of the phosphating layer can be from 5 ⁇ m to 15 ⁇ m.
- metallic workpieces can be equipped.
- the term of a metallic workpiece is one, two or three-dimensional structures of usually low-alloyed steels. Likewise, however, these layers can also be applied to stainless steels as well as other noble and base metals, such as e.g. Iron, Al, Ti, Cu, Ni, or their alloys, as well as hot-dip galvanized materials are attached.
- the term one-dimensional structures includes, for example, wires, the two-dimensional, for example, bands or sheets, and the three-dimensional, for example, more complex shapes, such as bearing shells.
- the metallic workpieces can be constructed in one or more layers. Thus, it is in particular also within the meaning of the invention that the phosphating layer having stabilized solid lubricant particles can also be applied to a "normal" layer not equipped with stabilized solid lubricant particles.
- the solid lubricant particles are stabilized by hydrocoids both in the solution and, most likely, in the phosphating layer.
- the HydrokoUoide preferably have a chain-like structure of individual, successive building blocks.
- the hydrocoids are capable of forming viscous solutions in water by swelling with addition of water to the hydrocolloid backbone.
- the hydrocoids which can be used according to the invention can be synthesized from one and the same (homopolymer) or else from different building blocks (heteropolymer).
- the HydrokoUoide can have a weight of preferably 1000 to 1,000,000 Da. This particle size has turned out for a effective interaction with the solid lubricant particles proved to be particularly suitable.
- the weight of the hydrocoids can be determined via gel permeation techniques using defined reference samples.
- Suitable HydrokoUoide are in particular the water-soluble, ie swellable HydrokoUoide.
- Examples include phenolsulfonate / formaldehyde condensates, polyvinyl alcohol, polyethers, polyacrylates and methacrylates, polyacrylamides, polyvinylamines, polyamines, polyimines and their quaternary salts, polyvinylpyrrolidone, polyvinylpyridines, polyvinyl phosphonates and their copolymers, and natural HydrokoUoide as collagen, gelatin , Chitosan hydrolyzate, keratin hydrolyzate, casein hydrolyzate, guar, pectins, agar-agar, starch and modified starch, cellulose derivatives such as carboxyalkyl cellulose or cellulose ethers, or mixtures and copolymers thereof.
- the solid lubricant particles are stabilized. This means that the solid lubricant particles in the aqueous solution come into contact with the swollen polymeric hydrocolloids and interact with them on the surface. In principle, it is possible that the solid lubricant particles are stabilized both by interaction with the side chains or else by contact with the backbone of the hydrocolloid. Without being bound by theory, adsorption of the hydrocolloid particles on the lubricant surface occurs, at least partially forming a polymer layer around the solid lubricant. This adherent hydrocolloid layer is capable of mechanically stabilizing the lubricant particle in the solution and in the phosphating layer.
- the deposited phosphating layer it is possible for the deposited phosphating layer to have a proportion of 15 to 60% by weight, more preferably from 20 to 40% by weight, of solid lubricant particles.
- This lubricant content can be sufficient intrinsic lubrication for many applications with simultaneous Maintain good mechanical properties of the phosphating layer.
- the size of the stabilized solid lubricant particles can be in the range between 0.5 ⁇ up to 3 ⁇ , preferably between 1.0 ⁇ and 2 ⁇ .
- the size of the stabilized lubricant particles can be determined by dynamic laser light scattering or by microscopic methods.
- the weight ratio of solid lubricant particle to hydrocolloid can be varied within a wide range without leaving the area of effective stabilization of the solid particle. Conveniently, the ratio can be varied from 100: 1 to 1: 100. This means that effective stabilization of the lubricant particle can be achieved even if only part of its surface is occupied by the hydrocolloids which can be used according to the invention.
- the stabilized lubricant particles are stored, at least partially, in the phosphating layer.
- the stabilized solid lubricant particles are deposited not only on the surface or in the pores of the phosphating layer, but rather also incorporated into the phosphating layer.
- a stabilized solid lubricant particle may be completely or partially surrounded by zinc phosphate.
- the stabilized solid lubricant particles remain after a single immersion of the workpiece without additional mechanical movement in demineralized water at 20 ° C for 1 minute at least 60% by weight, preferably 80% by weight and further preferably at least 90% by weight of the stabilized solid lubricant particles not washable within the layer.
- the total amount of stabilized solid lubricant particles can be determined by dissolution of the material and subsequent quantitative elemental analysis.
- the amount of stabilized solid lubricant particles bonded only superficially can be determined from a determination of the concentration of the stabilized solid lubricant particles in the wash water. ben.
- the proportion can also be determined on the washed / unwashed coated workpieces by means of quantitative X-ray methods such as ED-RFX.
- the hydrocolloid may be a nitrogen-containing hydrocolloid.
- the nitrogen-containing hydrocolloids appear to be capable of forming stable coacervates with the solid lubricant particles. These special coacervates enable a particularly adequate stabilization of the solid lubricant particles in the solution and ensure correct incorporation of the particles into the phosphating layer.
- the nitrogen-containing hydrocolloids in particular, can thus contribute to an effective separation of the solid lubricant particles without the quality of the deposition of the further phosphating constituents being impaired.
- the cationic charge of the N-hydrocolloid which is cationic under the prevailing bath conditions, seems to favor this separation behavior, in which both the stabilization of the lubricant particles in the bath and the incorporation of the latter into the phosphating layer are favored positively influenced.
- the result is a mechanically flexible and sufficiently stable encapsulation of the solid lubricants, which do not disturb the layer structure of the phosphating on the workpiece and can be easily released under mechanical stress in a cold forming.
- the hydrocolloid has the nitrogen either in the side chains, on the hydrocolloid backbone or both.
- the hydrocolloids can have nitrogen atoms both within the chain and on the side groups.
- the nitrogen compounds may also form different organic functional groups known to those skilled in the art.
- the hydrocolloids can be selected from the group comprising polyamines, polyimines and their quaternary salts, polyvinylpyrrolidones, polyvinylpyridines, collagen, gelatin, chitosan hydrolyzate, keratin hydrolyzate, casein hydrolyzate, amidopectins, and copolymers and / or mixtures thereof.
- this group of nitrogen-containing hydrocolloids in combination with the most common solid lubricating material particles to particularly strong interactions and thus to a particularly suitable mechanical stabilization of the solid lubricant particles and / or the resulting phosphating layer.
- this may in particular be due to the molar ratio between nitrogen and the other constituents of said polymers and the swelling behavior of these hydrocolloids with the aqueous bath composition.
- the hydrocolloid may have between 5 and 40 mol, more preferably between 10 and 30 mol of nitrogen. These amounts of nitrogen in the hydrocolloid can lead to a sufficient swelling behavior with unfolding of the hydrocolloid in the phosphating solution and thus contribute to a fast and effective interaction with the solid lubricant particle.
- the hydrocolloids can be selected from the group of vegetable or animal nitrogen-containing hydrocolloids consisting of gelatin, chitosan hydrolyzate, keratin hydrolyzate, casein hydrolyzate or mixtures thereof.
- the hydrocolloid may be gelatin having a molecular weight of greater than or equal to 1000 Da and less than or equal to 100,000 Da.
- Gelatin with a molecular weight in the range given above can form particularly stable complexes with solid lubricant particles. This may be due in particular to the fact that gelatin swells particularly well in acidic phosphating baths and forms an almost completely unfolding chain. This unfolded chain is in turn able to interact with the solid lubricant particles particularly effectively and to stabilize these mechanical ones.
- Another reason for the special stabilization could also be that gelatin carries nitrogen both in the backbone and in the side chains. As a result of this division of the nitrogen, the hydrocolloid chain can bind to the solid lubricant particle particularly quickly and effectively.
- preferred molecular weight ranges for the gelatin are between greater than or equal to 5,000 Da and less than or equal to 75,000 Da, more preferably between greater than or equal to 10000 Da and less than or equal to 50,000 Da. Within these ranges, high quality phosphating layers can be obtained.
- the solid lubricant particles may be selected from the group comprising saturated fatty acid metal and ammonium salts, MoS 2 , h-BN, WS 2 , graphite, oxidized and fluorinated graphite, PTFE, nylon, PE, PP, PVC, PS PET, PUR, clay, talc, TiO 2 , mullite, CuS, PbS, Bi 2 S 3 , CdS or mixtures thereof.
- saturated fatty acid metal and ammonium salts MoS 2 , h-BN, WS 2 , graphite, oxidized and fluorinated graphite, PTFE, nylon, PE, PP, PVC, PS PET, PUR, clay, talc, TiO 2 , mullite, CuS, PbS, Bi 2 S 3 , CdS or mixtures thereof.
- the lubricant particles are particulate.
- the particles without stabilization may have a size (largest distance within the lubricant particle) of greater than or equal to 10 nm and less than or equal to 10 ⁇ m, preferably greater than or equal to 25 nm and less than or equal to 5 ⁇ m, furthermore preferably greater than or equal to equal to 30 nm and less than or equal to 2.5 ⁇ have.
- the size of the lubricant particles can be determined by methods known to those skilled in the art, such as laser light scattering.
- the solid lubricant particles may consist of MoS 2 and have a platelet-shaped geometry.
- Lubricant particles made of molybdenum sulfide can be stabilized particularly effectively by hydrocolloids and provide an incorporation kinetics that can be controlled over a wide range. So even under short energized contact times sufficient amounts of lubricant particles can be installed in layer deposits. An extremely small disturbance of the layer structure The phosphating layer is also obtained in particular if the particles have a platelet-shaped geometry. This geometry can lead to a higher loading of the phosphating layer with lubricant particles and can ensure an immediate lubricating effect during mechanical processing.
- the MoS 2 platelets then have a platelet-shaped geometry if the particle dimensions lie within the following limits: an average length selected from a range with a lower limit of 0.1 ⁇ m and an upper limit of 2 ⁇ m and an average width selected from a range with a lower limit of 0.1 ⁇ and an upper limit of 2 ⁇ and an average height selected from a range with a lower limit of 2 nm and an upper limit of 50 nm.
- Also according to the invention is a process for the preparation of a stabilized solid lubricant particles having phosphating layer, which comprises at least the steps: a) providing a metallic workpiece,
- d) optionally, post-treatment of the electrodeposited phosphating layer optionally, post-treatment of the electrodeposited phosphating layer.
- coherent phosphating layers can be produced, which are provided with a sufficient amount of lubricant and require no additional lubricant addition in the context of a mechanical aftertreatment.
- This process can also be operated with high current densities, so that high deposition rates and thus high layer thicknesses can be achieved with short process times.
- the process can be easily combined with the usual phosphating pretreatment steps such as alkaline cleaning with or without surfactant and with or without intermediate rinsing.
- the bath composition may further comprise accelerators such as urea, nitrates, chlorates, bromates, hydrogen peroxide, ozone, organic nitro bodies, peroxy compounds, hydroxylamine, nitrite nitrate, nitrate perborate or mixtures thereof.
- the coating solution is an emulsion with emulsion droplets in the sub-micron range.
- the zinc phosphate solution can be adjusted to an acidic pH range via acids.
- As a possible after-treatment for example, rinse with demin. Water or Nachpassivi réelle by chromic acid, chromic acid / phosphoric acid solution or an organic Nachpassivitation with poly (vinylphenol) in question.
- Preferred bath parameters may result in:
- the phosphating layer containing stabilized solid lubricant particles can be deposited on a workpiece which has on the surface a phosphating layer with the elements ZnXP, wherein X is selected from the group consisting of Fe, Ni, Ca, Mn.
- the deposition of further metals from the above-mentioned group can contribute to an additional mechanical stabilization of the phosphating layer.
- the lubricant content can be increased, so that it is particularly effective to obtain self-lubricating workpieces.
- the current-carrying contact time of a surface element of the workpiece with the aqueous electrolyte solution may be greater than or equal to 1 second and less than or equal to 100 seconds.
- the method according to the invention is particularly suitable for being able to deposit a sufficiently thick phosphating layer on a metal workpiece within short process times.
- the current-carrying contact time ie the time in which the workpiece is immersed in the bath and the workpiece is flowed through with current, can be kept very short. This is particularly important for wires and tapes which are pulled through the coating baths at high speeds. Specifically, this period of time does not include the time on which constituents of the bath still remain on the surface of the workpiece, but no actual coating (deposition) takes place any more.
- the weight per unit area of the deposited, stabilized solid lubricant particles having phosphating layer determined after
- DIN EN ISO 3892 is greater than or equal to 0.5 g / m 2 and less than or equal to 10 g / m 2.
- the incorporation of stabilized solid lubricant particles can lead to significantly lower basis weights being obtained in comparison with the customary phosphating processes. In this way, for example, costs for the use of coating metals can also be saved.
- These basis weights provide sufficiently coherent and firmly adhering layers, which can be partially destroyed only after significant mechanical stress and release as a result of the lubricant.
- the basis weight may moreover be greater than or equal to 0.75 g / m and less than or equal to 8 g / m 2 and furthermore preferably greater than or equal to 1.0 g / m 2 and less than or equal to 5.0 g / m ,
- the aqueous electrolyte solution may additionally comprise an anionic, cationic, amphoteric or nonionic surfactant in a concentration of greater than or equal to 0.1 and less than or equal to 10 g / 1.
- an anionic, cationic, amphoteric or nonionic surfactant in a concentration of greater than or equal to 0.1 and less than or equal to 10 g / 1.
- the phosphating solution may have a ratio of free acid to total acid (FSV, free acid ratio) of> 2.5 and ⁇ 10, and more preferably of> 5.0 and ⁇ 8.0.
- FSV free acid ratio
- This ratio seems to lead to a particularly effective stabilization of the solid lubricant particles by the hydrocolloids.
- the zeta potential of both the solid lubricant particles and the hydrocolloids such that both a particularly good stabilization of the particles in the solution and a particularly effective incorporation of the stabilized particles in the Phosphating layer results.
- the dimensional analysis of the abovementioned ratio is known to the person skilled in the art.
- metallic, coated workpieces at least comprising a self-lubricating phosphating layer having stabilized by hydrocolloids solid lubricant particles.
- this can also be used for the treatment of pull-peeled workpieces, in particular peeled-off wires.
- the peeled-peeled surface of the workpiece is electrochemical, e.g. by pickling, or mechanically, e.g. by radiation, brushing or grinding, is activated before a coating according to the invention takes place.
- a phosphated cold heading wire is made using a 10 mm diameter steel wire for about 10 seconds through a phosphating solution of the following composition
- Molybdenum disulfide particles (5 ⁇ ) 6.0 g / L is drawn.
- the temperature of the bath is about 55 ° C and the strength of the DC is about 12 A / dm.
- a phosphating layer with an average thickness of 4-8 g / m 2 is deposited, which has embedded molybdenum sulfide particles.
- the phosphated cold upset wire is rinsed with water and then drawn at a rate of 0.06 m / sec in one step to a diameter of 7 mm. The drawing takes place without the addition of another lubricant.
- the wire can be cut at a constant final pull knives without problems and there is no tearing of the wire or other loss of quality.
- a phosphated cold heading wire is produced using a cold heading wire with a diameter of 10 mm for about 2 seconds through a phosphating solution of the following composition:
- Wetting agent (BASF Lutensol ON 110) 0.5 g / L
- Boron nitride particles 1 ⁇ (Hebofill 410) 5.5 g / L is drawn.
- the remaining bath parameters correspond to those of Example 1.
- a phosphating layer with an average thickness of 6 g / m 2 is deposited, which has embedded boron nitride particles.
- the phosphated cold heading wire is rinsed with water and then drawn in one step to a diameter of 7 mm. The drawing takes place without the addition of another lubricant.
- the wire can be pulled without problems at a constant final diameter and there is no tearing of the wire or other loss of quality.
Abstract
Description
Claims
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PL17700126T PL3400323T3 (en) | 2016-01-08 | 2017-01-06 | Self-lubricating electrolytically deposited phosphate coating |
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DE102016100245.3A DE102016100245A1 (en) | 2016-01-08 | 2016-01-08 | Self-lubricating electrodeposited phosphating coating |
PCT/EP2017/050240 WO2017118716A2 (en) | 2016-01-08 | 2017-01-06 | Self-lubricating electrolytically deposited phosphate coating |
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EP3400323B1 EP3400323B1 (en) | 2020-08-19 |
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US (1) | US11078592B2 (en) |
EP (1) | EP3400323B1 (en) |
KR (1) | KR102144494B1 (en) |
DE (1) | DE102016100245A1 (en) |
PL (1) | PL3400323T3 (en) |
RU (1) | RU2702521C1 (en) |
WO (1) | WO2017118716A2 (en) |
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CN109021472B (en) * | 2018-08-09 | 2019-11-05 | 燕山大学 | Molybdenum disulfide-graphite oxide-nickel phosphorus-ptfe composite preparation method |
CN109135137B (en) * | 2018-08-09 | 2020-01-10 | 燕山大学 | Preparation method of graphene-nickel-phosphorus-polytetrafluoroethylene composite material |
CN112210806B (en) * | 2020-08-13 | 2021-10-08 | 法尔胜泓昇集团有限公司 | Anti-corrosion steel wire with molybdenum disulfide coating and preparation process thereof |
Family Cites Families (18)
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US3525651A (en) * | 1966-12-01 | 1970-08-25 | Kenneth A Smith | Coating of metals |
DE1644927B1 (en) | 1967-10-21 | 1971-05-19 | Mahle Kg | Process for the production of particles containing dry lubricants intended for incorporation in electroplated layers |
US4198331A (en) * | 1978-08-28 | 1980-04-15 | Ppg Industries, Inc. | Resinous coating compositions curable by Michael adduct exchange |
CA1235664A (en) | 1984-06-27 | 1988-04-26 | Hendrikus A.B. Van Meegen | Piston-operated machine |
CH667108A5 (en) | 1985-04-22 | 1988-09-15 | Fluehmann Ag Werner | GALVANIC BATHROOM FOR THE COMBINED DEPOSITION OF METAL AND A PERMANENTLY LUBRICATING SOLID LUBRICANT. |
DK173338B1 (en) | 1996-08-29 | 2000-07-31 | Danfoss As | Process for electrochemical phosphating of metal surfaces, especially of stainless steel, with CaZnPO4 by cold flow of metal |
JPH10147886A (en) | 1996-11-15 | 1998-06-02 | Asahi Glass Co Ltd | Conductive film forming coating solution, conductive film and its production |
JP3479609B2 (en) * | 1999-03-02 | 2003-12-15 | 日本パーカライジング株式会社 | Sludge-free zinc phosphate treatment liquid and zinc phosphate treatment method |
JP2002012983A (en) | 2000-06-29 | 2002-01-15 | Nkk Corp | Steel sheet coated with composite phosphate film superior in corrosion resistance, lubricity, and coating material adhesiveness |
DE10348251A1 (en) * | 2003-10-16 | 2005-05-12 | Bosch Gmbh Robert | Electrolytic process for phosphating metal surfaces and phosphated metal layer |
DE102005023023B4 (en) * | 2005-05-19 | 2017-02-09 | Chemetall Gmbh | Method of preparing metallic workpieces for cold forming, process coated workpieces and their use |
JP4419968B2 (en) * | 2005-07-15 | 2010-02-24 | 株式会社デンソー | Electrolytic phosphate chemical treatment method and warm or hot forging method |
DE102006035974A1 (en) | 2006-08-02 | 2008-02-07 | Robert Bosch Gmbh | Process for phosphating a metal layer |
DE102008006147A1 (en) * | 2008-01-26 | 2009-09-10 | Gelita Ag | Cleaning system for metallic and ceramic surfaces |
US7951600B2 (en) * | 2008-11-07 | 2011-05-31 | Xtalic Corporation | Electrodeposition baths, systems and methods |
DE102010022039B3 (en) * | 2010-05-25 | 2011-07-14 | Siemens Aktiengesellschaft, 80333 | Component with a sliding surface for the storage of another component and method for producing a sliding layer |
TR201101163A2 (en) | 2011-02-08 | 2011-10-21 | Bortek Bor Teknoloji̇leri̇ Ve Mekatroni̇k Sanayi̇ Ve Ti̇caret Li̇mi̇ted Şi̇rketi̇ | Method of improving the properties of phosphate coating. |
KR101858143B1 (en) | 2011-12-23 | 2018-05-16 | 두산공작기계 주식회사 | Sliding matrials comprising solid lubricants with nonspherical shape |
-
2016
- 2016-01-08 DE DE102016100245.3A patent/DE102016100245A1/en not_active Withdrawn
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2017
- 2017-01-06 WO PCT/EP2017/050240 patent/WO2017118716A2/en unknown
- 2017-01-06 EP EP17700126.0A patent/EP3400323B1/en active Active
- 2017-01-06 KR KR1020187022008A patent/KR102144494B1/en active IP Right Grant
- 2017-01-06 US US16/066,471 patent/US11078592B2/en active Active
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KR20180099837A (en) | 2018-09-05 |
DE102016100245A1 (en) | 2017-07-13 |
WO2017118716A2 (en) | 2017-07-13 |
PL3400323T3 (en) | 2021-04-06 |
EP3400323B1 (en) | 2020-08-19 |
WO2017118716A3 (en) | 2017-09-14 |
US11078592B2 (en) | 2021-08-03 |
US20190112724A1 (en) | 2019-04-18 |
KR102144494B1 (en) | 2020-08-14 |
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